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2018 Vol. 38, No. 11 Published: 2018-11-01

	3321	Research on Preparation Process Optimization and Surface Enhanced Raman Spectroscopy (SERS) of Graphene-Silver Nanoparticle Composites
		GONG Tian-cheng^1,2, ZHU Yong^1*, WANG Xin-yu^1,3, WANG Ning¹, ZHANG Jie¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3321-07
		Based on general preparation process of surface-enhanced Raman scattering (SERS) substrate of graphene-silver nanoparticles composites, the coupling agent has been used to improve the uniformity of silver nanoparticles adsorbed on the target substrates; bilayer of polymethylmethacrylate (PMMA) has been used to transfer graphene in order to reduce the defects of graphene; annealing treatment has been used to reduce the Raman background noise and improve the contrast of Raman spectra. The experimental results indicate that using the optimized preparation process can improve the uniformity of SERS substrate. The contrast of graphene Raman signal at G and 2D peak increased by 54.9% and 64.3%, respectively. The goodness of fit (R²) on the relationship between Raman intensities of Rhodamine 6G (R6G, at 774 and 1 363 cm^-1) and concentration achieved 0.997 5 and 0.986 7, respectively.
		2018 Vol. 38 (11): 3321-3327 [Abstract] ( 173 ) RICH HTML PDF (4058 KB) ( 179 )

	3328	Research on Wavelength Shift Correction Algorithm for Tunable Laser Absorption Spectrum
		TANG Qi-xing^{1, 2}, ZHANG Yu-jun^1*, CHEN Dong^{1, 3}, ZHANG Kai^{1, 2}, HE Ying¹, YOU Kun¹, LIU Guo-hua^{1, 2}, LU Yi-bing^{1, 2}, FAN Bo-qiang^{1, 2}, YU Dong-qi^{1, 2}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3328-06
		Tunable semiconductor laser is featured by narrow bandwidth, fast wavelength scanning, and room temperature working temperature, etc. The laser absorption spectroscopy gas measurement system based on tunable diode laser is widely applied in atmospheric environmental monitoring and on-line industrial production process detection. In the actual measurement system, the center wavelength of the tunable semiconductor laser is affected by temperature and other factors. If the center wavelength is not corrected, the spectral data will be overlapped and the processed spectral line will be widened, which will affect the subsequent spectral line fitting and affect the accuracy of gas concentration inversion. Generally, the reference spectrum absorption line peak-finding method is used to align the offset of the spectral data. However, the accuracy of the peak wavelength in the spectral data is affected the random noise, the background and drift noise. In order to reduce the side effects mentioned above, an improved algorithm of the time domain correlation is proposed. Firstly, the autocorrelation of the spectral signal is carried out to improve the spectral signal-to-noise ratio to a certain extent, then the time-domain cross-correlation processing is applied, which can accurately calculate the laser wavelength offset, reduce the influence of spectral broadening, and improve the concentration inversion accuracy and measurement stability. Experiments have been carried out in the detection experimental system of gas concentration based on laser absorption. Experimental results show that the standard deviation of the original data is 1.482 8 while the standard deviation of data correction is 0.433 9 and 0.293 6, respectively. The corrected standard deviation of improved method of time domain correlation correction is 0.132 5 with the correlation coefficient higher than 0.992. The standard deviation of Euclidean distance is 1.726 4. The system stability evaluation indicates that the modified standard deviation of the wavelength drift correction is up to 0.144 3.
		2018 Vol. 38 (11): 3328-3333 [Abstract] ( 209 ) RICH HTML PDF (2097 KB) ( 218 )

	3334	Heterogeneous Adsorption Behaviors of Humic Acid Light-Absorbing Components on Multiple-Walled Carbon Nanotubes by Two-Dimensional Correlation Absorption Spectroscopy
		YANG Cheng-hu¹, LIU Yang-zhi², SUN Xiu-mei¹, LIU Qin¹, LI Tie-jun¹, GUO Yuan-ming^1*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3334-07
		Dissolved Organic Matter (DOM) is a heterogeneous mixture of dissolved material found ubiquitously in aquatic systems. DOM not only influences greatly the fate and the bioavailability of pollutants in natural waters, but also belongs to the precursor of the Disinfection Byproducts (DBPs). Therefore, how to effectively remove DOM from water has become one of the most popular issues in the research of environmental pollution control and management technology. In this study, adsorption behaviors of the commercial humic acid (HA) light-absorbing components on pristine multiple-walled carbon nanotube (MWCNT), hydroxylated MWCNT (MWCNT-OH) and carboxylated MWCNT (MWCNT-COOH) were investigated using two-dimensional correlation spectroscopy (2D-COS) based on the ultraviolet-visible absorption spectra. The kinetics, isotherms and thermodynamics of adsorption of the HA light-absorbing components on the three MWCNTs were the focus of the present study. 2D-COS could enhance the resolution of the HA one-dimensional absorption spectra. Two types of absorption bands for the HA light-absorbing components were distinguished by two-dimensional correlation absorption spectra, which changed sequentially in the order of 275 nm→400 nm. Thus, the 2D-COS revealed that heterogeneous adsorption behaviors of the HA light-absorbing components on MWCNTs. The adsorption kinetic rate of the HA light-absorbing component at 275 nm was higher than that of the HA light-absorbing component at 400 nm, suggesting that the HA light-absorbing component at 275 nm was preferentially adsorbed to MWCNTs. The adsorption isotherms of MWNCTs and the HA light-absorbing components were nonlinear under 25 ℃ and 35 ℃. In comparison, the adsorption isotherms between the HA light-absorbing components and MWCNTs were fitted better to the Freundlich model than the Langmuir model by higher correlation coefficient R². Furthermore, the saturation adsorption capacity (qmax) and the single point adsorption coefficient Kd of the HA light-absorbing component at 275 nm were higher than those of the HA light-absorbing component at 400 nm, further suggesting that the interaction of MWCNTs and the HA light-absorbing components was heterogeneous adsorption. In addition, the adsorption affinity between MWCNTs and the HA light-absorbing component was stronger when the given equilibrium concentration (c_e=0.5 cm^-1 and c_e=1.5 cm^-1) was lower, indicating that the HA light-absorbing component tended to occupy high energy adsorption sites on MWCNTs at lower HA concentration. The adsorption affinity sequence was in order of MWCNT8>MWCNT8-OH>MWCNT8-COOH when at the same equilibrium concentration and the specific HA light-absorbing component, demonstrating that various functional groups could contribute to different adsorption characteristics between MWCNTs and the HA light-absorbing component. Furthermore, an insignificant correlation between the surface area of MWCNTs and the Kd values under the same conditions suggested that the surface area is not the major factor that makes the adsorption differences between MWCNTs and the specific HA light-absorbing component. Meso-pores of MWCNTs presented a significantly positive correlation with the Kd values, but micro-pores of MWCNTs showed an insignificant correlation with the Kd values, which could be due to the fact that HA light-absorbing component molecules can enter meso-pores in MWCNTs, while it was difficult for the HA light-absorbing molecules to enter micro-pores in MWCNTs due to large molecular size. Finally, thermodynamic analysis showed that the HA light-absorbing components adsorption on MWCNTs occurred spontaneously due to the negative values of Gibbs free energy change (ΔG⁰). The positive values of enthalpy change (ΔH⁰) indicated that the adsorption of the HA light-absorbing components on MWCNTs is an endothermic reactions, while the positive values of entropy change (ΔS⁰) reflected an increase in the randomness at the solid-solution interface during the adsorption process. The ΔG⁰ values of MWCNT8-OH and MWCNT8-COOH for the same HA light-absorbing component and temperature were higher than those of MWCNT8, further suggesting that the adsorption affinities of MWCNT8-OH and MWCNT8-COOH were lower than those of MWCNT8. This study proves that 2D-COS could differentiate the various HA light-absorbing components with different adsorption behaviors, and two-dimensional correlation absorption spectroscopy could be successfully applied to investigate the heterogeneous adsorption behaviors of the HA light-absorbing components on MWCNTs. The conclusion of the present study could provide a deep understanding of the characteristics and mechanisms of the interactions between MWCNTs and DOM. These results have implications for eliminating DOM in the aquatic environment, and the findings obtained in this research are helpful to better predict the transport and fate of both DOM and MWCNTs in the natural environment.
		2018 Vol. 38 (11): 3334-3340 [Abstract] ( 207 ) RICH HTML PDF (2720 KB) ( 183 )

	3341	Misjudgment Elimination Method on Identification of Thin Film Damage by Plasma Flash Method
		WANG Gui-xia, SU Jun-hong^*, XU Jun-qi, SHI Kai
		DOI: 10.3964/j.issn.1000-0593(2018)11-3341-06
		Based on whether the detector receives a flash signal emitted from surrounding of the thin film sample, the traditional plasma flash method can evaluate whether the thin film is damaged, while it can be easy to confuse plasma flash of air and with that of thin film and make a misjudgment. The elimination of misjudgment on traditional plasma flash method can be realized through comparing the ignition time of the plasma flash of the air and thin film and using the difference of time between them to eliminate this misjudgment. In order to verify the reliability of the new method, a model for calculating the ignition time of air plasma was established by means of the theory of multiphoton absorption and cascade ionization. On the other hand, a calculation model of the same kind was established when the thin film was broken through, and the plasma flash ignition time of air and thin film was calculated to be 1.856 and 7.843 ns respectively by using these established model simulations. The experimental device was set up to update the traditional plasma flash method, and three photodetectors were set up at different positions in the device to collect incident laser signals, air and thin film plasma flash signals, respectively, and the photodetector collecting the incident laser signal was placed on the side of the focusing lens, and the other two detectors were placed around the thin film sample and stay bilateral symmetry, which were used to collect the plasma flash signal of the film and the air, respectively. The signals collected by all photoelectric detectors were converted into electrical signals and sent to oscilloscope synchronously, with the incident laser signal taken as the reference signal, the difference between the initial time of the incident laser signal and the flash signal of air and thin film plasma was the flash ignition time of air and thin film plasma, respectively. When the Nd∶YAG pulse laser, whose pulse width is 10 ns and the wavelength is 1 064 nm, with a radius of 0.015 cm and incident energy of 82.4 mJ laser acts on the sample of single layer Aluminum trioxide film with the optical thickness λ/4 and the diameter of 20 mm. Acquiring various signals under the above laser action, the measured values of plasma flash ignition time for air and thin film after treatment were 2.7 and 7.8 ns respectively. The theoretical calculations and experimental results showed that the ignition time of air is always smaller than that of the film, which is in good agreement with each other. The results showed that the flash of air plasma is earlier than that of thin film when strong laser acts on the surface of single layer Aluminum trioxide film. This difference between the plasma flashes ignition time of air and thin film can be used to accurately identify whether the film is damaged and obtain the criterion to identify if the film is damaged or not . This new method for identifying the flash damage of thin film plasma from time difference provides a technical basis for the elimination of misjudgment in conventional plasma flash method both theoretically and experimentally.
		2018 Vol. 38 (11): 3341-3346 [Abstract] ( 154 ) RICH HTML PDF (1942 KB) ( 48 )

	3347	Study and Determination of Nitriding Salt with Salt Bath Heat Treatment Technology
		WU Xin^1，2, LI Guang-lin^1*, WEN Zhi-yu³
		DOI: 10.3964/j.issn.1000-0593(2018)11-3347-07
		Salt bath compound heat treatment technology is a new kind of metal surface treatment technology, which can enhance the wearability, corrosion and fatigue resistance of workpiece, and it is widely used. In order to guarantee the quality of metal surface treatment, it is very important to accurately determine the content of the Cyanate, Cyanide and Iron ion in nitriding salt. At present, it is difficult for the chemical titration method adopted by industry to satisfy the requirements for the automated analysis. Based on the spectrophotometric method, a semi-automatic nitriding salt parameter detection setup using 510, 620 and 697 nm of three different wavelengths of monochromatic LED light source, a coupling optical fiber and three photodiodes, which can fastly and exactly test the content of the Cyanate, Cyanide and Iron ion. The semi-automatic nitriding salt parameter detection setup includes the Optical system, mixing control system, constant temperature control system and data acquisition circuit. By the indirect method determining the content of Cyanate, converting the Cyanate ions into ammonium ions by chemical method, and then measuring the content of ammonium ions in water according to the national standard GB 7481—1987 Water quality-Determination of ammonium-Spectrophotometric method with salicylic acid, the characteristic absorption wavelength of ammonium is 697 nm. Determining the content of Cyanide according to the national standard HJ 484—2009 Water quality-Determination of Cyanide-Volumetric and Spectrophotometry method, the characteristic absorption wavelength of Cyanide is 620 nm. Determining the content of iron according to the national standard HJ 345—2007 Water quality-determination of Iron-phenanthroline spectrophotometry, the characteristic absorption wavelength of ammonium is 510 nm. In this setup, the light intensity stability of LED light source is tested, and the LED light intensity is a stable value when it starts working. Testing the influence of the coupled optical fibers, the spectrum of the monochromic LED light has not changed between through a coupling fiber and a single fiber, and just the optical intensity decreases a little when the light through the coupling fiber. Testing the stability of the LED light by stirring, the data showed the mixing control system has no effect on the optical system. Using the experimental device to measure the absorbance of Cyanate standard sample-potassium cyanate, Cyanide standard sample-potassium cyanide and iron standard sample-ferrous sulfate, based on the lambert beer’s law, establishing a Cyanate, Cyanide and Iron standard sample fitting curve, whose linear correlation R² is 0.990 7, 0.999 6, 0.998 1, respectively, which has high linearity. The maximum mean relative error and maximum relative standard deviation of Cyanate, Cyanide and Iron in predicted samples were 4.53% and 1.04%, 2.29% and 0.79%, 4.2% and 0.7%, respectively. The limit of detection of Cyanate, Cyanide and Iron were 0.017, 0.009 and 0.005 mg·L^-1, respectively. By contrasting the traditional chemical test method, the experiment setup test the Cyanate, Cyanide and Iron ion in nitriding salt, the test result of the detection system is superior to the traditional chemical titration method, and the maximum mean relative error and maximum relative standard deviation of Cyanate, Cyanide and Iron in nitriding salt sample were 4.17% and 0.69%, 1% and 0.58%, 4% and 0.29%, respectively. The results of these tests meet the design requirements and provide theoretical and technical support for the tri-component semi-automatic analyzer for salt bath compound heat treatment technology. The optical path system of experiment setup includes three monochromatic LEDs light source and a coupling fiber, which realizes the rapid and accurate detection and multi-parameter detection of the light source spectral. The whole optical inspection system has no moving parts, which greatly reduces the system error brought by the optical detection system, which guarantees the accuracy and repeatability of the analyzer test.
		2018 Vol. 38 (11): 3347-3353 [Abstract] ( 174 ) RICH HTML PDF (2832 KB) ( 46 )

	3354	Effects of Nitrogen on the Degradation of Methyl Blue by Corona Discharge Plasma
		LI Miao^{1, 2}, DONG Fa-qin^2*, HUO Ting-ting^{2, 3}, ZHOU Lei^{2, 3}, LI Gang^{2, 3}, ZHOU Shi-ping^{3, 4}, WANG Bin^{2, 3}, HE Ping¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3354-08
		The corona discharge plasma technology is a new type of advanced oxidation processes (AOPs) which has developed in recent years. Corona discharge plasma technology, which has characteristics such as high degradation efficiency, simple operation and less occupied area, has been widely used in the field of printing and dyeing wastewater treatment. At present, little is known about most of the organic pollutants degradation mechanism, hence this technology in the field of printing and dyeing wastewater treatment is still in the exploratory stage. Therefore, in order to apply the corona discharge plasma technology to the treatment of industry printing and dyeing wastewater as soon as possible, the exploration of different pollutants degradation mechanism is of great significance to the industrialization and industrial application of this technology. Up to now, corona discharge plasma technology has good degradation efficiency on the dyes which had been studied. However, the suitability of this technique for the degradation of all dyes remains to be further researched. In this paper, choosing methyl blue which is of triphenylmethane dye as a target contaminant, corona discharge plasma technology was used to degrade it. The impact of the initial concentration of methyl blue solution on the degradation rate of aromatic ring (314 nm) and the change of chromophore group (603 nm) absorbance in the ultraviolet visible spectra (UV-Vis) were investigated. The changes of the solution concentration, total organic carbon (TOC), total nitrogen (TN) and the pH values of the methyl blue solution were measured with the discharge time increased, and the correlation between them were analyzed. In this paper, three kinds of spectroscopy methods, based on ultraviolet visible spectra (UV-Vis), three dimensional fluorescence spectrum (3-D fluorescence) and Fourier transform infrared spectroscopy (FTIR), were used to analyze the changes of color, varieties of fluorescent substance and functional groups of methyl blue solution during the degradation process by corona discharge plasma. And the intermediate products generated after the methyl blue was degraded by corona discharge for 30 minutes were analyzed. The experimental results showed that the concentration of methyl blue in the solution decreased gradually with the increase of discharge time in the degradation process of methyl blue by corona discharge plasma, which indicated that the technology has a certain ability in the degradation of methyl blue solution. In the degradation process of the methyl blue solution by corona discharge plasma technology, turn on the high-voltage power supply, and the high voltage electrodes penetrate the air containing a large amount of nitrogen between the high voltage electrode and liquid surface to produce N, NO·, N⁺₂ and other nitrogen-containing high activity particles, these particles migrate to the liquid phase through diffusion, which leads to the TN content in the solution to gradually increase throughout the degradation process. In addition, another part of the nitrogen-containing high-activity particles and the C element dissolved from tungsten needle electrode bonding to generate CN double bound, which is of chromophore group in organic matter, so that total organic carbon in the solution increased at the discharge time of 5 minutes. More highly active particles generated by extending the discharge time reacted with the residual organic matter (methyl blue and intermediate products) in the solution, and some organisms were mineralized to form CO₂ with the discharge time increasing, which caused a drop in the TOC content of the solution. The parameters of the corona discharge plasma reactor without any change throughout the degradation process, hence the number of active species generated within the same time frame was identical in the degradation process of methyl blue by corona discharge. Increasing the initial concentration of methyl blue solution is, the more methyl blue molecules are not degraded, which induces the reduction of the degradation rate of methyl blue. The chromophoric group absorbance got the maximum value when the discharge time was 5 minutes, which resulted from the polymerization between methyl blue molecules in the process of corona discharge and the formation of chromophore group of CN double bonds. In addition, the higher the initial concentration of methyl blue solution, the more the absorbance increases between the discharge time of 5 minutes and 0 minutes (A₅-A₀). It can also be observed from the experimental phenomenon that the methyl blue sample in discharge time of 5 minutes had the deepest color in all the samples and then gradually became lighter, further confirming the formation of the CN bound during the discharging process. In general, nitrogen in the air has an important effect on the degradation of methyl blue by corona discharge plasma, which is mainly attributed to the CN chromophore group in chemical structure of methyl blue, and the main reason of the solution color deepens and then lighter in the degradation process of methyl blue by corona discharge is that the existence of CN chromophore group. Moreover, the consumption of the hydroxyl free radicals, which is a kind of active species, generated hydroxyl ions, resulting in the increase of the pH value at the discharge time of 5 minutes. With the progress of the degradation reaction, nitric acid and small molecule acids generated in the solution enhance the acidity of the solution, resulting in a decrease in pH value of the methyl blue solution. It can be seen from the three-dimensional fluorescence spectrum of dissolved organic compounds (DOM) that there exists three kinds of obvious fluorescence peaks in degradation process of methyl blue solution at different times by corona discharge plasma technology. These fluorescence peaks, which are located at E_X/E_M=310~320/430~450，E_X/E_M=240~250/320~340 and E_X/E_M=280/340，representing humic acid, aromatic proteins and soluble microbial metabolites, respectively. Three-dimensional fluorescence spectrum results showed that the fluorescent substances in methyl blue solution before degradation are mainly humic acids, with the prolongation of the degradation time, the humic acid was first degraded to aromatic protein, which could further degrade to the soluble microbial metabolic by-product. After the corona discharge time of 30 minutes, compared the infrared spectra and the fitting curves of infrared spectra (1 750~1 540 cm^-1) of the methyl blue solution before and after corona discharge, the FTIR Spectra of the degraded samples changed obviously. The asymmetric stretching vibration peak at 3 432.8 cm^-1 of N—H bond is red-shifted by 0.3 cm^-1. The stretching vibration peak at 2 975.9 cm^-1 of C—H bond on the olefin and benzene ring is shifted by 0.5 cm^-1, the stretching vibration of the double bond of RCHCHR at 1 638.7 cm^-1 shifts blue-shifted by 3.2 cm^-1. The C—N stretching vibration peak of aromatic amine 1 341.6 cm^-1 shifts to 1.3 cm^-1. The stretching vibration peaks at 1 121.1 and 1 034.3 cm^-1 of SO are red shifted by 3.8 and 13 cm^-1, respectively. Furthermore, the absorption peaks situate at 1 657.9 and 1 676.9 cm^-1 of CC and the CN outside the ring in the chemical structure of methyl blue all disappear after the corona discharge for 30 minutes. It showed that the corona discharge plasma discharge effectively destroys these two bonds, and stretching vibration absorption peaks of CO and NO appear at 1 692.4 and 1 400.4 cm^-1, respectively. Additionally, its degradation products might be 2,5-cyclohexadiene-1,4-diketone, sodium p-nitrobenzene sulfonate and ketones and other intermediates. The results showed that the research has important theoretical significance and practical value in Methyl Blue treatment by Corona discharge plasma technology.
		2018 Vol. 38 (11): 3354-3361 [Abstract] ( 233 ) RICH HTML PDF (4529 KB) ( 61 )

	3362	The Study of Fast Localization Method of Anomaly Block in Tissue Based on Differential Optical Density
		WANG Hui-quan^{1, 2}, REN Li-na¹, ZHAO Zhe^{1, 2}, WANG Jin-hai^{1, 2*}, CHEN Hong-li^{1, 2}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3362-06
		The position of the source-detector (S-D) relative to the anomaly had an important influence on the detection effect when the detection of the anomaly in tissues was non-invasive based on near-infrared spectroscopy. In this study, a Single-Source Multi-Detectors structure was designed in order to realize the rapid localization of anomaly within the organization. This method was for finite element analysis of optical density distribution for different horizontal positions, depths and diameters of anomaly. Then calculated the difference in optical density between the detectors. The simulation results showed that the horizontal position of the anomaly in the tissue could be quickly located according to the differential optical density difference curves formed by the multiple detectors. The Gaussian fitting feature of these curves has a strong correlation with the horizontal positions, depths and diameters of the anomaly. Through the differential optical density difference curves, rapid localization could be achieved within the region of interest in the organization. It provides an important reference for the sources and detectors location in terms of tumor detection, brain function optical imaging and other fields using near infrared spectroscopy, which can improve its detection accuracy.
		2018 Vol. 38 (11): 3362-3367 [Abstract] ( 194 ) RICH HTML PDF (4662 KB) ( 160 )

	3368	Research on Efficiency Improvement of Inverted PTB7∶PC₇₀BM Solar Cells Using ZnO Nanofibers Prepared by Electrospinning as Electron Transport Layer
		SUN Qin-jun^, SHI Xiao-lei, GAO Li-yan, ZHOU Shao-long, WU Jun, HAO Yu-ying^
		DOI: 10.3964/j.issn.1000-0593(2018)11-3368-06
		In this paper, the effects of different diameters of ZnO nanofibers prepared by electrospinning on the conversion efficiency of organic solar cells were studied. First of all, ZnO nanofibers with diameters ranging from 43 to 110 nm were prepared by electrospinning technique. Then, ZnO nanofibers with different diameters were added to inverted organic solar cells (ITO/ZnO∶ZnO nanofiber/PTB7∶PC₇₀BM/MoO₃/Al) as electron transport layer. Compared to the planar ZnO electron transport layer, ZnO nanofibers have the advantages of large specific surface area, increasing the ability of electron transfer and extraction and improving the photoelectric conversion efficiency of the device. It was found that the smaller the diameter of ZnO nanofibers is, the greater the efficiency of the cells will be. When the diameter of ZnO nanofibers was (46±5) nm and the receiving time was 30 s, conversion efficiency of the cell increased by 8%.
		2018 Vol. 38 (11): 3368-3373 [Abstract] ( 148 ) RICH HTML PDF (2861 KB) ( 48 )

	3374	Investigation of Bovine Serum Albumin at Different Temperatures by Terahertz Time-Domain Spectroscopy
		TAN Hong-ying
		DOI: 10.3964/j.issn.1000-0593(2018)11-3374-05
		As the temperature changes, the stability of bovine serum albumin (BSA) molecules’ interior structure may change. We measured the low frequency spectra of BSA’s solid sample heated to 298, 308, 328 and 348 K based on the technology of Terahertz Time-Domain Spectroscopy. According to refractive index curve and absorption coefficient curve, the refractive index of samples at different temperatures changes obviously, showing that the interior structure of samples changes; as temperature goes up, samples’ absorptive capacity has an obvious increase, but the sample at 348 K has a sudden decrease in absorption coefficient on average, showing that the samples have a denaturation. At the main time, using the theory of THz-TDS, we can get the relation that BSA’s imaginary part of dielectric coefficient and dielectric loss tangent change with frequency. Using Principal Component Analysis to reduce dimensionality, when the first three principal components reach to 98.69% of the amount of information of original data, we found that compared to refractive index, absorption coefficient, imaginary part of dielectric coefficient, dielectric loss tangent is most relevant to the temperature of the samples of BSA, with correlation coefficient reaching 99.76%. Combine PCA and fuzzy recognition, build BSA’s recognition models, and we gain a method to judge BSA’s temperature.
		2018 Vol. 38 (11): 3374-3378 [Abstract] ( 198 ) RICH HTML PDF (1880 KB) ( 193 )

	3379	Analysis of Measurement Uncertainty in THz-TDS Carried by Delay-Line Position Deviation
		DONG Hai-long, WANG Jia-chun^*, ZHAO Da-peng, CHEN Zong-sheng, LIU Rui-huang, SHI Jia-ming
		DOI: 10.3964/j.issn.1000-0593(2018)11-3379-06
		Terahertz time-domain spectroscopy can extract the optical constants of materials in the terahertz region rapidly and accurately. However, the errors of various components in the control precision, response error, system noise, experiment operation and data processing will affect the accuracy of the extracted optical constants of materials. Based on the measurement principle of transmission terahertz time domain spectroscopy, the influence on the accuracy of the system delay-line position deviation on extracting the complex index of refraction of materials was analysed in this paper, and the error on propagation through the measurement process was modeled. Simulation was carried out to illustrate the relation between the error and the uncertainty in the extracted complex index of refraction of materials. The results showed that the uncertainty of complex index of refraction of the sample is influenced by the system delay-line position. The larger the system delay-line position deviation is, the greater the uncertainty of the extraction in the complex index of refraction of the sample will be. Meanwhile, compared to coefficient of light extinction, the system delay-line position deviation has greater influence on the uncertainty of refractive index of the sample. The model has some practical significance and theoretical reference value, which can analyze the influence of the system delay-line position deviation on extracting the optical constants of materials, and provide theoretical suggestions for the optimization of terahertz time-domain spectroscopy.
		2018 Vol. 38 (11): 3379-3384 [Abstract] ( 186 ) RICH HTML PDF (2495 KB) ( 206 )

	3385	A Quantitative Analysis Method for GCB as Rubber Additive by Terahertz Spectroscopy
		YIN Xian-hua^{1, 2}, WANG Qiang^{1, 2}, MO Wei¹, CHEN Tao^{1, 2*}, SONG Ai-guo³
		DOI: 10.3964/j.issn.1000-0593(2018)11-3385-05
		Gas carbon black (GCB) is one of the important additives in rubber. Its content has an important influence on the performance of rubber. Nitrile butadiene rubber (NBR) is a synthetic rubber used widely in industrial production. It is important to study the content of GCB in NBR. In this paper, the content of GCB in eight kinds of samples consisted of GCB and NBR with different proportion is detected via terahertz time-domain spectroscopy (THz-TDS). Absorption spectra data of these samples is obtained in the frequency ranging from 0.3 to 1.4 THz. Two quantitative analysis models of GCB are established respectively using partial least squares (PLS) method and support vector regression (SVR) method. The uniform gradient method is used to select the calibration set and the prediction set of two models. The correlation coefficient (r) and the root mean square error (RMSE) of two models were calculated. The r and RMSE for the prediction set of PLS model were 0.985 8 and 2.098 9%. The r and RMSE for the prediction set of SVR model were 0.998 0 and 0.785 4%. Experimental results showed that the predictive result of SVR model was better than that of PLS model. In order to prove the stability of the SVR model, we used the random selection method several times to select its calibration set and prediction set, and got their r and RMSE. The results showed that all the r and RMSE of SVR model are better than that of PLS model, whether the uniform gradient method or the random selection method is used to select the calibration set and the prediction set of the SVR model.
		2018 Vol. 38 (11): 3385-3389 [Abstract] ( 181 ) RICH HTML PDF (2394 KB) ( 49 )

	3390	The Application of Raman Shift of Sulfate in Temperature Detection of Deep-Sea Hydrothermal Fluid
		XI Shi-chuan^{1, 3}, ZHANG Xin^{1, 2, 3*}，DU Zeng-feng¹, LUAN Zhen-dong¹, LI Lian-fu^{1, 3}, WANG Bing¹, LIANG Zheng-wei^{1, 3}, LIAN Chao¹, YAN Jun¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3390-05
		Hydrothermal field is a typical deep-sea extreme environment where there are various sulfide minerals and special ecological communities. The research on the physicochemical characters of hydrothermal fluid is essential to the understanding of hydrothermal activities. The laser Raman spectroscopy has been used both at the qualitative and quantitative analysis, especially the in situ detections in the deep sea. In this paper, we simulated the hydrothermal fluid environment characterized by high temperature and high pressure, and discussed the availability of the Raman shifts of water and sulfate for detecting the temperature of the deep-sea hydrothermal fluids. The experiment results showed that the Raman shifts of the ν₁(H₂O) and ν₁(SO^2-₄) were sensitive to the temperature. However, the Raman shifts of the ν₁（H₂O） are also affected by the concentration of sulfate obviously, which is an obstacle to calculating the temperature of the hydrothermal fluid. On the contrary, the Raman shift of the ν₁(SO^2-₄) is insensitive to the concentration of sulfate and fluid pressure, which makes it a good choice to calculate the temperature of the hydrothermal fluid. Therefore, we established the liner relationship equationof the ν₁(SO^2-₄) Raman shift with temperature: Rν₁(SO^2-₄)=-0.03T+980.69, R²=0.998 6, which is also suitable for the in situ measurements of the hydrothermal fluid in the deep sea.
		2018 Vol. 38 (11): 3390-3394 [Abstract] ( 194 ) RICH HTML PDF (3295 KB) ( 184 )

	3395	Application of Raman Spectroscopy in Rapid Detection of New-Type Drugs
		SUI Cheng-hua^{1, 2*}，TU Qian¹，YAN Bo^{1, 2}，CHEN Nai-bo^{1, 2}，LU Zhong^{1, 2}，Lü Bin^{1, 2}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3395-06
		The increasing spread and rapid updating of new-type drugs have put forward higher and higher requirements for the rapid detection by law enforcement departments. In this paper, Raman spectroscopy in the rapid detection of new-type drugs was studied by theoretical calculation and experimental detection of three typical new-type drugs. The molecules of the three drugs were optimized and calculated by B3LYP hybrid functional and 6-31G basis set. The Raman spectrometer was used for the experimental detection. The results indicated that the theoretical Raman spectra tallies with the experimental Raman spectra, and can be used for providing a reference for the attribution of experimental spectral peaks. The Raman peak positions of the three drugs are significantly different. The characteristic Raman peaks of methamphetamine are located at 837 and 1 003 cm^-1. Those of ketamine are located at 463，659 and 1 046 cm^-1. And the most obvious characteristic peaks of Ma Gu are located at 556, 1 329 and 1 699 cm^-1. Clearly the Raman spectra can be used for the identification of drugs. The Raman spectra of methamphetamine and ketamine residues tally with those obtained from the constant samples, which just shows that drug residues can be accurately identified by Raman spectroscopy. The characteristic Raman peak of pseudomethamphetamine (N-benzylisopropylamine) 853 cm^-1 is significantly different from that of methamphetamine 837 cm^-1. Therefore the Raman spectra can also be used to identify the authenticity of new-type drugs. Moreover, transparent packaging has a great influence on the Raman spectrum of Ma Gu which has strong fluorescence interference.
		2018 Vol. 38 (11): 3395-3400 [Abstract] ( 242 ) RICH HTML PDF (2742 KB) ( 169 )

	3401	A Study of the Adsorption Property of Dispersant of Polycarboxylate onto Pyraclostrobin Particle Surfaces by Using FT-IR, XPS and SEM
		WANG Li-ying^1,2，XU Yan³，JIANG Zhen-dong²，XU Yong²，XIANG Sheng²，GUO Xin-yu²，WU Xue-min^2*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3401-06
		The main methods in performing the study of the adsorption properties of polycarboxylate onto pyraclostrobin particle surfaces were FTIR, XPS and SEM from the microscopic view, and the study results provided the theory basis for the application of dispersant polycarboxylate in pyraclostrobin suspension concentrate. The results showed: Infrared spectra is not a new adsorption peak after pyraclostrobin adsorbed polycarboxylate dispersant; the results suggested that physical adsorption is mainly between pyraclostrobin and polycarboxylate dispersant; van der Waals force is the main force. After adsorption of polycarboxylate dispersant by pyraclostrobin particles, the peak intensity of N and Cl of the interface of pyraclostrobin particle decreased sharply, while the adsorption of C and O of the interface of pyraclostrobin particle increased, the Na peak appeared also after pyraclostrobin adsorbed the dispersant. This is mainly the polycarboxylate dispersant C, O and Na contribution, which indicates that polycarboxylate dispersant was adsorbed on the surface of pyraclostrobin. The calculating thickness of the adsorption was 1.22 nm by the characterized element Cl. The morphology of the sample was investigated by scanning electron microscopy. After the polycarboxylate dispersant was adsorbed, many fine particles were adsorbed on the surface of the original smooth pyraclostrobin particles, which were distributed in an orderly manner. This was attributed to the fact that dispersant hydrophobic group formed a coating for pyraclostrobin particles, then hydrophilic groups were fully exposed, thus effectively blocking the pyraclostrobin agglomeration between particles and thereby enhancing the physical stability of pyraclostrobin suspension.
		2018 Vol. 38 (11): 3401-3406 [Abstract] ( 221 ) RICH HTML PDF (2877 KB) ( 92 )

	3407	Analysis and Identification of Integral Structure of Dendrobium officinale Kimura et Migo, Dendrobium nobile Lindl. and Dendrobium chrysotoxum Lindl. and Their Extracts by Infrared Spectroscopy
		ZHU Nan-nan^1，2，SUN Zhi-rong^1*，QU Ji-xu¹，HE Yu-xin¹，MA Fang³，SUN Su-qin³
		DOI: 10.3964/j.issn.1000-0593(2018)11-3407-07
		To analyze and identify the Dendrobium officinale Kimura et Migo., Dendrobium nobile Lindl. and Dendrobium chrysotoxum Lindl. as well as their two extracts by using the Fourier transform infrared spectroscopy (FTIR). Fourier transform infrared spectroscopy (FTIR) was used to analyze and identify the structures of Dendrobium officinale Kimura et Migo., Dendrobium nobile Lindl., and Dendrobium chrysotoxum Lindl. as well as their extracts. The structural information of samples showed that all the Dendrobium officinale Kimura et Migo., Dendrobium nobile Lindl., and Dendrobium chrysotoxum Lindl. contained the characteristic absorption peaks in the range of 2 920, 2 852, 1 737 and 1 509 cm^-1. Additionally, the presence of characteristic absorption peaks in the range of 1 000～1 200 cm^-1 presumed that lipids, aromatics and starches were contained in all of these three Dendrobium samples. The above results were confirmed by the secondary derivative infrared spectra (SD-IR). In addition, according to the peak strength determine the difference in compound content contained in the three kinds of Dendrobium, and the secondary derivative infrared spectra also showed that the contents of lipids and starches were higher in the Dendrobium officinale Kimura et Migo. and Dendrobium nobile Lindl. than those in the Dendrobium chrysotoxum Lindl.. The content of lipids in the Dendrobium nobile Lindl. and the content of polysaccharides in the Dendrobium officinale Kimura et Migo were higher than those in the other two samples. Meanwhile, the characteristic absorption peaks of the calcium oxalate at 1 318 and 782 cm^-1 were observed in the secondary derivative infrared spectra (SD-IR). The component and content of both two extracts were different from each corresponding samples, and the differences of peak shape, peak location and peak strength in different Dendrobium samples were also observed. The characteristic absorption peaks of lipids, aromatics and polysaccharides were observed in both water extraction and alcohol precipitation extract and anhydrous ethanol extract. Further comparison with the standard substance indicated that the main polysaccharides in Dendrobium nobile Lindl., and Dendrobium chrysotoxum Lindl. were starches which were mucopolysaccharide in Dendrobium officinale Kimura et Migo. The lipide and aromatic series were confirmed by infrared spectrum, and the aromatic series in the Dendrobium chrysotoxum Lindl was higher. Integral structure analysis based on infrared spectrum contributed to the identification of differences in the Dendrobium officinale Kimura et Migo., Dendrobium nobile Lindl., and Dendrobium chrysotoxum Lindl. The method is suitable to be used for rapid identification, quality evaluation and control for various cultivars, which provides the foundation for systemic identification of Dendrobium.
		2018 Vol. 38 (11): 3407-3413 [Abstract] ( 152 ) RICH HTML PDF (3884 KB) ( 80 )

	3414	Measurement of Moisture Content and Viscosity of HFC Based on Mid Infrared Spectroscopy
		YU Liang-wu^1，2, LIU Dong-feng^1，2*, CHEN Cong³, FANG You-long^1，2
		DOI: 10.3964/j.issn.1000-0593(2018)11-3414-06
		For water glycol fire-resistant hydraulic fluids (HFC), the commonly used methods for measuring the moisture content and viscosity present problems such as complicated operation, long time-consuming, high measurement cost, etc. The application of mid-infrared spectroscopy to HFC moisture content and viscosity measurement was studied. The sample set consisted of 85 actual in-use oil samples. The moisture content and kinematic viscosity were measured by traditional coulometric method and capillary method. The mid-infrared spectra of samples was collected using an ATR liquid pool. Spectra pretreatments such as spectra correction, background subtraction, Savitzky-Golay (SG) smoothing and baseline correction were performed. During the process of constructing the moisture content measurement model, strong influence points were searched by student residuals-leverage method, which were determined as abnormal samples and removed. Mahalanobis distance SPXY method was used to divide the sample set into modeled samples and verification samples. According to the Beer-Lambert law, the moisture content was directly proportional to the infrared absorbance. So a linear method should be used to construct the relationship between the moisture content and the infrared absorbance. At the same time, the no information variables, redundant information and noise in the spectrum need to be eliminated to improve the model robustness and generalization ability. By the backward interval partial least squares method (BiPLS), the moisture content measurement feature bands were optimized, and a linear calibration analysis model was established. The results showed that the minimum root mean square error of cross validation (RMSECV) was obtained when the bands of 3 526~3 354, 1 790~1 618, 3 005~2 660 and 1 096~924 cm^-1 remained. The preferred feature bands can be explained as that, and the OH amount in moisture was calculated by subtracting the OH amount in ethylene glycol converted by the 3 005~2 660 and 1 096~924 cm^-1 bands from the all OH amount in the HFC system converted by the 3 526~3 354 cm^-1 band, and then the moisture content was calculated. In order to improve the accuracy, the 1 790~1 618 cm^-1 band, corresponding to the moisture OH swing vibration absorption peak, was used as an auxiliary wave for measuring the moisture content. The independent verification samples were used to test the model. The results showed that the correlation coefficient (r) of the established linear model was 0.989 5 and the root mean square error of prediction (RMSEP) was 0.405 2, which met the accuracy requirement for moisture content measurement in HFC. During the process of constructing the viscosity measurement model, the outlier samples were searched by Mahalanobis distance method, which were determined as abnormal samples and removed. Mahalanobis distance SPXY method was used to divide the sample set into modeled samples and verification samples. Viscosity was a physicochemical index that had complex relationships with multiple factors, and was nonlinear to the infrared spectrum. Based on principal component analysis combined with BP neural network method (PCA-BPNN), a nonlinear viscosity correction analysis model was established. The first 10 principal components with a cumulative contribution rate of 95.12% were extracted as input, and the measured viscosity values were treated as output. A single hidden layer BP neural network was created and trained. The training result correlation coefficient r was 0.996 8. The independent verification samples were used to test the model. The results showed that the r of the established nonlinear model was 0.984 3 and the RMSEP was 0.615 1, which met the accuracy requirement for HFC viscosity measurement and were superior to the ones obtained by the BiPLS linear model. Four mid-infrared bands were identified and can be used for moisture content measurement in HFC, which could provide basis for narrowband infrared spectroscopy or other similar studies. The research results showed that the mid-infrared spectroscopy combined with BiPLS and PCA-BPNN analysis method can be applied to the measurement of moisture content and viscosity of HFC, and the accuracy meets the monitoring requirements. Compared with the traditional measurement methods, a new test method is provided with the features of being fast, non-destructive and low-cost.
		2018 Vol. 38 (11): 3414-3419 [Abstract] ( 174 ) RICH HTML PDF (3056 KB) ( 243 )

	3420	Study on the Intermolecular Interaction of Icarrin with Human Serum Albumin Based on Fluorescence Spectrometry and Physical Modeling
		ZHAO Xiao-xue¹, GUO Ming^{1, 2*}, WANG Yan¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3420-08
		The intermolecular interaction between Icarrin (ICA) and Human Serum Albumin (HSA) was investigated by spectral method and building molecular model to explore ICA-HSA mechanism of interaction. And the intermolecular interaction model of ICA-HSA was described by using a variety of theoretical equations to compare and discuss their usability. The results showed that the fluorescence intensity of HSA in the fluorescence spectra showed regular decrease, indicating that HSA did interact with ICA. The synchronous fluorescence spectrum showed that micro-conformation of HSA changed due to the intermolecular interaction between ICA and HSA. The intermolecular interactions of ICA-HSA were described using Stern-Volmer equation, Lineweaver-Burk equation, double logarithmic regression equation, Scatchard series equation, Lehrer-Fasman equation and Tachiya model respectively. The results showed that the theoretical model was different and the results were different from ICA-HSA. There are two quantitative kinds of trends based on the differences between hypothesis and experimental conditions. In this paper, physical model was built to assist the intermolecular interaction mode of ICA-HSA.The optimal mode of ICA-HSA intermolecular interaction was the double logarithmic equation. Meanwhile, the ICA-HSA intermolecular interaction was analyzed by physical modeling, indicating that the ICA tend to occurr in active site Sudlow’s sites I and ICA-HSA system mainly has van der Waals force, hydrophobic interaction and hydrogen bonding. These results obtained in this paper serves to provide a reference for the comprehensive analysis of ICA-HSA intermolecular interaction, as well as the theoretical description of the intermolecular interactions between small molecules and biomacromolecules.
		2018 Vol. 38 (11): 3420-3427 [Abstract] ( 153 ) RICH HTML PDF (3591 KB) ( 94 )

	3428	Preparation and Application of Fluorescent Cystine Aggregated Nanoclusters
		WENG Wen-ting, CAI Lu, HAN Ji-yu, MAO Ke-jun, XIE Xiao-lan
		DOI: 10.3964/j.issn.1000-0593(2018)11-3428-06
		We first reported a strategy for promoting fluorescent aggregation nanocluster of cystine molecule by heating in constant temperature bath and this performance could be used for detecting quantity of cystine. The effects of pH value, reaction time and temperature on the system were investigated and the mechanism of photoluminescence was discussed. The results suggested that the non-fluorescent molecule was assembled to form Fluorescent Aggregated Nanoclusters (FANC) by heating the pH 9.0 0.01 mol·L^-1 cystine solution at 90 ℃ for 12 hours, and its aqueous solution showed a maximum absorption at 410 nm and a fluorescence emission at 508 nm. The fluorescence performance and structure of FANC were characterized by fluorescence spectroscopy (FL), transmission electron microscopy (TEM) and mass spectrometry (MS). The average fluorescence lifetime of the FANC aqueous system is 6.028 ns and the fluorescence quantum yield is 8.48%. Moreover, FANC has stable photobleaching, acid-base stability and spectral dependence in aqueous solution. TEM images showed that the fluorescent FANC has a size of 12.5 nm, however, DLS size distribution of FANC is about 150 nm, suggesting that the aggregates of cystine has a hydrophilic surface. Zeta potential result is -57 mV, demonstrating that the nanocluster has a negative charge. Additionally, the results of mass spectrometry showed that there are molecular fragments formed by the intermolecular dehydration of cystine in the system. Therefore, we can further speculate that FANC is an inner molecular aggregation of cystine to form the supramolecular vesicles in the aqueous solution environment due to intermolecular forces. The relative fluorescence peak intensity of FANC and the concentration of cystine showed a good linear relationship in a certain range of 1.0×10^-5～6.0×10^-4 mol·L^-1, and the detection limit of 4.559×10^-9 mol·L^-1(3S₀/K). The proposed method was applied to the quantitative analysis of cystine tablet. The results were consistent with the titration result of Chinese Pharmacopoeia. Compared with other detection methods, this new method has the advantages of simple operation, low detection limit and high precision.
		2018 Vol. 38 (11): 3428-3433 [Abstract] ( 154 ) RICH HTML PDF (2816 KB) ( 113 )

	3434	Characterization of Chilled Pork with Three-Dimensional Fluorescence Spectroscopy
		REN Meng-jia^{1, 2}, DING Cheng-qiao^{1, 2}, Naoshi Kondo³, WU Hua-lin^{1, 2}, CUI Di^{1, 2*}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3434-05
		Three-dimensional fluorescence spectroscopy was employed to investigate the fluorescence characteristic of chilled pork stored at different temperatures in this research. The locations of fluorescence peaks were identified and the changes in the average intensity values of two fluorescence peaks in their respective regions during storage were traced. Initially the fluorescent substances were determined as a basis for realizing rapid non-destructive detection of chilled pork freshness with three-dimensional fluorescence spectroscopy. The results showed that three-dimensional fluorescence spectra of chilled pork samples showedfluorescence peaks of two types (Peak A and Peak B) regardless of the storage temperature. The excitation wavelength (λ_ex)/emission wavelength (λ_em) of Peak A was 250～310 nm/300～400 nm, whereas of Peak B was 300～450 nm/400～550 nm. Peak A and Peak B represented protein-like fluorescence and lipid oxidation products fluorescence, respectively. Moreover, the location of the maximum of Peak A was at λ_ex/λ_em=290 nm/335 nm during storage, while that of Peak B shifted from λ_ex/λ_em=320 nm/470 nm to λ_ex/λ_em=390 nm/470 nm. The results also indicated that the average intensity values of two fluorescence peaks in their respective regions had the same trend regardless of the storage temperature: the average intensity values of Peak A in the region of λ_ex/λ_em=250～310 nm/300～400 nm (I_A) was gradually declined, while that of Peak B in the region of λ_ex/λ_em=300~450 nm/400~550 nm (I_B) was gradually increased as time went by. However, the storage temperature determined the change rate of I_A and I_B: the samples stored at 20 ℃ had higher the rate of change than those stored at 4 ℃.
		2018 Vol. 38 (11): 3434-3438 [Abstract] ( 196 ) RICH HTML PDF (3404 KB) ( 72 )

	3439	Determination of Phenols in Water by Three Dimensional Fluorescence Spectroscopy Combined with APTLD
		WANG Yu-tian, SHANG Feng-kai^*, WANG Jun-zhu, BIAN Xu, SUN Yang-yang, YANG Zhe
		DOI: 10.3964/j.issn.1000-0593(2018)11-3439-08
		Phenols have serious harm to animals and plants. The experiment is a direct, rapid and accurate method for the qualitative and quantitative analysis of phenols in the case of interference and no interference by the method of fluorescence spectrometer combined with APTLD algorithm. The effects of temperature on the fluorescence intensity of thymol, hydroquinone and phenol were studied. After the comprehensive consideration, the experiment was carried out at 20 degrees centigrade. The obtained spectral data array is processed by eliminating scattering and correction. The original spectrum information is preserved to avoid the serious distortion of spectrum. APTLD algorithm is compared with PARAFAC and ATLD algorithm, highlighting the advantages of the algorithm. Experimental results showed that the APTLD algorithm can well analyze the overlapped peaks of the fluorescence spectrum data and obtain the fluorescence spectra of three target analytes respectively, achieving rapid qualitative analysis; the average recovery rate of the quantitative analysis is 97.4%±4.5%~103.1%±3%; The root mean square error of prediction is less than 1.664×10^-2 g·mL^-1, and the detection limit is lower than the national standard; The treatment process is simple and rapid, which provides a powerful basis for on-site detection and on-line real-time monitoring of phenolic compounds in water environment.
		2018 Vol. 38 (11): 3439-3446 [Abstract] ( 203 ) RICH HTML PDF (5719 KB) ( 74 )

	3447	Functional Nucleic Acid Based Fluorescent Biosensing Method for Hg²⁺ Detection in Water Samples
		ZHU Xi-yu^{1, 2}, WANG Ruo-yu², ZHOU Xiao-hong^2, TAN Ai-juan^1, WEN Xiao-gang^3*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3447-05
		As an important environmental contaminant, mercury(Ⅱ) has caused worldwide concern. The T-T mismatch based detection for Hg²⁺ greatly depends on the design of mercury specific oligonucleotide (MSO). This paper optimized the currently reported MSOs by using SYBR Green I. Based on the binding response analysis between several MSOs and Hg²⁺and further discussion on the secondary structure of sequences, the optimum T-rich sequences was proposed. Hence a fluorescent detection method towards Hg²⁺ in water samples based on SYBR Green Ⅰ was established. Consequently, the recovery ratios in spiked real water samples ranged from 82.8% to 101.8% with the relative standard derivation of less than 15%. Results show that this method was slightly affected by the environmental matrix, providing accurate detection of mercury ions in real water samples.
		2018 Vol. 38 (11): 3447-3451 [Abstract] ( 167 ) RICH HTML PDF (2129 KB) ( 48 )

	3452	Quantitative Inversion for Wind Injury Assessment of Rubber Trees by Using Mobile Laser Scanning
		YUN Ting^{1, 3}, ZHANG Yan-xia¹, WANG Jia-min¹, HU Chun-hua¹, CHEN Bang-qian², XUE Lian-feng^1*, CHEN Fan-di¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3452-12
		The light detection and ranging (LiDAR) technique, which has the advantages of high efficiency and high accuracy in forest survey and is superior to the traditionalinformation acquisitionmethods, can be used to quickly obtain high-resolution mapping of morphological structures of forest. In this paper, two rubber forest plots (forest plot 1, clonePR107; forest plot 2, clone CATAS7-20-59) are taken as the study subjects, which are under the long-term impact of wind-induced disturbance severity and located in Danzhou city, the largest rubber production base of Hainan Island, China. First, point cloud of the forest plots through man-loaded mobile LiDAR was collectedand Ruili entropy method was designed to process the scanned data for calculating the slope angle of tree trunk (typhoon-induced) in order to find the canopy centre of each tree. Second, after the vertical projection of scanned forest points, Watershed and Mean shift algorithm were adopted to realize individual tree canopy delineation. Finally, many tree parameters, such as crown breadth, Diameter at Breast Height (DBH), crown volume, leaf area density, leaf distribution and included angle between trunk and main branches, were deduced automatically for analyzing the impact of typhoon disturbance on the two forest plots. Overall parameters obtained from our methods were compared with manual field measurements. The calculated average crown diameter in west-east direction of rubber trees in forest plot 1 and plot 2 using our method were 3.95 and 3.73 m, respectively, with false rate of 1.74% for forest plot 1 and 6.27% for plot 2. The calculated average crown diameter in north-south direction of rubber trees in forest plot 1 and plot 2 using our method were 6.47 and 6.51 m, respectively, with false rate of 4.02% for forest plot 1 and 2.54% for plot 2. The calculated average diameter at breast height (DBH) for forest plot 1 and plot 2 using our method were 5.20 and 4.73 cm, respectively, with false rate of 2.44% for forest plot 1 and 0.64% for plot 2. The calculated average crown volume for forest plot 1 and plot 2 using our method were 168.01 and 141.80 m³, respectively, with false rate of 0.67% for forest plot 1 and 0.85% for plot 2. The calculated average inclination angle of rubber trunk for forest plot 1 and plot 2 using our method were 18.80° and 13.11°, respectively, with false rate of 5.53% for forest plot 1 and 7.09% for plot 2. The calculated average included angle between trunk and branch for forest plot 1 ranged from 45.21° to 69.23°, and the calculated average included angle between trunk and branch for forest plot 2 ranged from 10.63° to 32.14°. Thedifference in the included angles of two forest plots was nearly 62.63%. Meanwhile, the leaf area index (LAI) of forest plot 1 derived fromhemispherical photos of various zenith angles was generally higher than forest plot 2. Compared with the in-situ measurements, the forest parameters from the subsample (scanned data of 150 trees per forest plot) were accurately retrieved using our method with a deviation of less than 8%. A variety of disturbance, such as the perspective occlusion caused by closed forest canopies, the error produced by multi-scan registration, vegetative elements moved by wind during the scanning process, beam divergence and scanning range constraint of the scanner, hampers the accurate scanned data acquisition and generates computer errors in the algorithm. Meanwhile, the included angle between trunks and branches, canopy volume and leaf area index of rubber tree clone PR107 (in forest plot 1) were overall higher than the parameters of rubber tree clone CATAS7-20-59 (in forest plot 2), resulting in the existence of higher vulnerability of clone PR107 than clone CATAS7-20-59 when wind damage propagation occurred in the forest plots. Thus, our research can be used to study the effects of wind disturbance on different forest plots and to quantify ecological instability of the forest in response to wind excitation. Our method makes a contribution to solving the problem of tree canopy delineation and forest parameter retrieval using man-loaded laser scanning technique, showing promise for further exploration of utilizing mobile terrestrial LiDAR as an effective tool for the applications in forest survey.
		2018 Vol. 38 (11): 3452-3463 [Abstract] ( 159 ) RICH HTML PDF (15394 KB) ( 62 )

	3464	Aerosol Optical Depth Retrieval over Beijing Using MODIS Satellite Images
		YANG Dong-xu^1,2, WEI Jing^3,4, ZHONG Yong-de^1
		DOI: 10.3964/j.issn.1000-0593(2018)11-3464-06
		Atmospheric aerosol is one of the most important factors that affect air quality of urban environment, meanwhile, it has important effects on human health. Traditional aerosol optical depth (AOD) retrieval algorithms are always suitable for dark areas with low surface reflectance including ocean and densely vegetated areas, however, for bright urban areas, surface reflectance is high and difficult to be determined, leading to great challenges. Aiming at this problem, a new improved approach of surface reflectance estimation is proposed and the underlying surfaces are divided into dark and bright areas. Surface reflectance is determined using the simulated relationships between the surface reflectance between visible and short-wave infrared channels and a priori surface reflectance dataset constructed with long time series of MODIS apparent reflectance images using the minimum value synthesis technology. Then aerosol retrieval is performed based on the radiative transfer theory with pre-calculated Look-up Tables. Beijing, which features complex surfaces and serious air pollution, is selected as the study area and the proposed algorithm is applied to the MODIS data for aerosol retrieval experiments. Four AErosol RObotic NETwork (AERONET) AOD ground-measured stations, Beijing, Xianghe, Beijing_CAMS and Beijing_RADI, and operational MODIS aerosol product (MOD04) are selected for validation and comparison purposes. Results showed that AOD retrievals are highly consistent with AERONET AOD ground measurements (R²=0.902) and showed overall higher accuracy with more detailed spatial distribution compared to MOD04 AOD products over bright urban areas.
		2018 Vol. 38 (11): 3464-3469 [Abstract] ( 158 ) RICH HTML PDF (2961 KB) ( 93 )

	3470	Spectral Inversion and Characteristics of NO₂ Column Density at Shangdianzi Regional Atmospheric Background Station
		CHENG Si-yang¹, MA Jian-zhong^1*, ZHOU Huai-gang², JIN Jun-li³, LIU Yan⁴, DONG Fan², ZHOU Li-yan², YAN Peng^{1, 3}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3470-06
		In order to explore the variation characteristics of significant air pollutant NO₂ in the Beijing-Tianjin-Hebei background region, the Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) was used to record solar scattering spectra at Shangdianzi regional atmospheric background station and retrieve the NO₂ column densities. Quantitative spectral analysis was carried out in the characteristic wavelength of NO₂ 405～430 nm. The NO₂ tropospheric vertical column densities (VCD_trop) from July 2009 to September 2009 were calculated through geometric approximation. The mean and maximum value of NO₂ VCD_trop were 5.43×10¹⁵ and 7.15×10¹⁶ molec·cm^-2 during the observation period, respectively. The daily NO₂ VCD_trop was lower, but there was an upward trend as a whole. The variation of NO₂ VCD_trop was closely related to wind speed and direction: NO₂ VCD_trop concentration was lower when southwesterly wind was weaker, and the northeasterly wind was conducive to the NO₂ diffusion. Generally, diurnal variations of NO₂ VCD_trop showed the characteristics of being low at noon and high in the morning and evening, and the evening peak was slightly higher than the morning one. The level and diurnal range of NO₂ VCD_trop at Shangdianzi station were significantly smaller than the results in the Beijing city over the same period. These variation characteristics were consistent with the ones at the mild pollution stations of Xianghe and Gucheng in Hebei. In a word, reginal background atmospheric NO₂ VCD_trop can be effectively monitored by MAX-DOAS, although the characteristics were related to complex factors such as industrial and traffic emission, photochemical reaction and atmospheric transport. More data are necessary for further study.
		2018 Vol. 38 (11): 3470-3475 [Abstract] ( 167 ) RICH HTML PDF (3884 KB) ( 100 )

	3476	A Visualization Evaluation Method for Blue Light Hazard and Circadian Effect of Light Source
		YANG Chao-pu^1,2, FANG Wen-qing^3*, LIU Ming-bao^1,2, LI Chun^1,2, ZHANG Mei-li^1,2, HAN Xi^1,2, LIU Yan-feng^1,2, DAI Wei-li^1,2
		DOI: 10.3964/j.issn.1000-0593(2018)11-3476-07
		In order to provide general consumers with a convenient and direct method for evaluating blue light hazard and circadian effect of light source, the spectra distributions of six common artificial illumination and three displays were measured. The spectra distributions of the nine light sources going through QB5 cobalt blue glass were calculated and analyzed, combined with the transmittance of the adopted glass. The relationship between blue light hazard factor, circadian factor, and chromaticity coordinate Z value of 1931 CIE-XYZ was investigated, as well as the relationship between dominant wavelength of the glass and luminous flux through the glass. Based on the resolution of wavelength and brightness variation by human eyes to visible light through the glass, the feasibility of evaluating blue light hazard and circadian effect in visualization way was demonstrated where candlelight was the reference. Results showed that blue light hazard factor and circadian factor of nine light source increase with the increase of the chromaticity coordinate Z value of 1931 CIE-XYZ, the dominant wavelength and the luminous flux through the glass, which verified the feasibility of this method. The research method and the obtained results can provide reference for the evaluation of photobiological safety and the development of related devices.
		2018 Vol. 38 (11): 3476-3482 [Abstract] ( 157 ) RICH HTML PDF (2682 KB) ( 78 )

	3483	*Reflectance Analysis of Coral, Padina Pavonica* and Coral Sand at Luhuitou of Sanya Bay**
		CHEN Yong-qiang^1,2, CHEN Biao³, LEI Xin-ming¹, XIE Qiang⁴，HUANG Hui^1,2*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3483-06
		Reflectance spectra of eight common scleractinian coral species were chosed to represent the reflectance of corals in the sea area of Luhuitou, Sanya Bay in the north-western South China Sea (SCS). Reflectance spectra of these scleractinian corals, Padina Pavonicaand coral sand were measured using a fiber spectrometer. Then spectral reflectance analysis and derivative spectroscopy were used to study the diference of the reflectance spectrum of reef building scleractinian coral, Padina Pavonica and coral sand in this sea area. The results showed that reflectance difference of Padina Pavonica and scleractinian coral is very significant in 500～700 nm; reflectance of coral sand is significantly higher than that of coral reflectance spectrum with significant differences. Derivative analysis results showed that the distinguishable bands of scleractinian coral, Padina Pavonica and coral sand are as follows: scleractinian coral and Padina Pavonica, first order derivatives are mainly in 415.1～425.6，482～487，514.5～529，577～587.6 and 631.9～644 nm bands. The second order derivatives are mainly in 413～418.7，427.4～432.5，462.3～470.6，494.4～503.6，551.6～561.4，590～594 and 639～643 nm bands. The fourth order derivatives are mainly in 412.2～418.4，420.5～425.3，470.9～480.2，481.3～486.9，540.8～545.7，560～568.3 and 635.6～639.6 nm bands. First order derivatives of scleractinian coral and coral sand are mainly in 400～413.7，514.5～529.6，576.9～587.6 and 602.7～667 nm bands. The second order derivatives are mainly in 420.5～430.7，446.9～458.8，467.3～472.3，537～544.3，556.8～561.4，582.8～587.2 and 637.6～649.4 nm. The fourth order derivatives are mainly in 414.4～418.7，419.5～430.3，486.9～495.8，534.2～540.1，579～583.1，622.7～627.5，640～645 and 665.4～672.8 nm bands.
		2018 Vol. 38 (11): 3483-3488 [Abstract] ( 169 ) RICH HTML PDF (3164 KB) ( 43 )

	3489	Characterization of the Interactions between Alpha Arbutin and Human Serum Albumin with Spectroscopic Method and Molecular Docking
		XIONG Shi-peng, CHEN Jian-bo^*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3489-06
		Alpha arbutin is a botanical extract which can relieve cough and asthma, and its effects on protein and the mechanism of action are poorly reported. This paper studied the interaction between alpha arbutin and human serum albumin (HSA) under different temperature conditions with fluorescence spectroscopy. With the increasing of alpha arbutin concentration, the fluorescence intensity of HSA was significantly enhanced with the occurrence of blue shift of fluorescence spectrum. By using fluorescence enhancement effect equations, we can obtain the binding constants of alpha arbutin and HSA. Thermodynamic parameters were obtained using the van’t Hof equation, resulting in the main type of molecular force between alpha arbutin and HSA. The thermodynamic parameters(ΔH=-23.29 kJ·mol^-1 and ΔS=40.96 J·mol^-1·K^-1) indicated that hydrogen bond and hydrophobic were the intermolecular force. UV-Vis, Synchronous fluorescence spectrometry and Three-dimensional fluorescence spectra were utilized to explore the effects of arbutin and HSA interactions on the secondary structure of protein. The circular two color spectrometry can conclude the protein secondary structure, which indicated the loss of helical stability after the interaction of arbutin and HSA. The binding details between arbutin and HSA were confirmed by molecular docking, which revealed alpha arbutin was bound at siteⅡ (subdomain IIIA) via multiple interactions, such as hydrogen bond, hydrophobic. The full basic data in the work is to clarify the binding mechanism of alpha arbutin with HSA and is useful for understanding its effect on protein function during the blood transportation process.
		2018 Vol. 38 (11): 3489-3494 [Abstract] ( 138 ) RICH HTML PDF (3404 KB) ( 76 )

	3495	A Research into the Nonthermal Effect of Thiophenic Sulfur Structure in the Coking Coal under Mocrowave Radiation
		GE Tao, MIN Fan-fei, ZHANG Ming-xu
		DOI: 10.3964/j.issn.1000-0593(2018)11-3495-07
		With the adoption of XANES and XPS, an analysis of occurrence characteristics in the organic sulfur of coking coal in Shanxi Province is conducted, with the choice of model compounds of thiophenic sulfur that matches the structure in the coal for the microwave radiation and water bath heating. Through a comparison of Raman Spectrum, a research is carried out into the action of mechanism of sulfur-bearing structure in the model compounds from what is mentioned above, with Materials Studio in place to construct and optimize the structure of model compounds and the application of the theory of density function to conduct computational simulation of the parameters of molecular configuration of model compounds in the microwave field to analyze the response mechanism of sulfur-bearing structure to the microwave. The outcome has established that thiophene is the main occurrence of organic sulfur in the coking coal. After the microwave radiation, there comes a red shift of the absorption peak of Raman regarding carbon-sulfur bonds and sulfur-sulfur bonds in the model compounds, with a comparatively smaller shift with respect to the model compounds that have a rapid temperature rise. There is almost no shift after the water bath heating under the same temperature. The microwave energy is not powerful enough to break carbon-sulfur bonds and sulfur-sulfur bonds in the model compounds, but with a change in the molecular configuration. It is likely that the sulfur-bearing bonds in the model compounds have a transition state in the microwave field. As a result, the existence of the nonthermal effect in the thiophenic sulfur structure under the microwave.
		2018 Vol. 38 (11): 3495-3501 [Abstract] ( 146 ) RICH HTML PDF (4166 KB) ( 38 )

	3502	Spectroscopic Analysis of Weak Acid Modified Steel Slag Powder
		ZHANG Hao^{1, 2, 3}, ZHANG Xin-yu³, LONG Hong-ming^{1, 2, 3*}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3502-05
		Taking steel slag powder as the object of study, weak acid modified steel slag powder was prepared by phosphoric acid modified steel slag powder. Weak acid modified steel slag powder was characterized by X-ray diffractometer, specific surface area and aperture meter and environmental scanning electron microscope. Composition, pore structure, microstructure and element composition of weak acid modified steel slag powder were researched. The results showed that the proper phosphate solution can effectively remove the f-CaO in the steel slag powder and improve pore structure of weak acid modified steel slag powder. The excess phosphate solution reacts with Ca(OH)₂ in steel slag powder, causing structure of weak acid modified steel slag powder to collapse, and showing fleeciness as a whole. When steel slag powder is 80 g and phosphate solution is 1.6~3.2 mL, weak acid modified steel slag powder has low f-CaO content and good pore structure. It provides technical support and theoretical basis for further expanding the utilization methods of steel slag.
		2018 Vol. 38 (11): 3502-3506 [Abstract] ( 160 ) RICH HTML PDF (2822 KB) ( 52 )

	3507	Hyperspectral Image Anomaly Detection Based on Laplasse Constrained Low Rank Representation
		WANG Jie-chao^{1, 2, 3}, SUN Da-peng^{1, 2, 3}, ZHANG Chang-xing¹, XIE Feng¹, WANG Jian-yu^1*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3507-09
		With the widespread use of hyperspectral images, hyperspectral image technology has made considerable progress, of which hyperspectral image anomaly detection technology has received more and more attention. In order to solve the problem of poor practicability and poor detection effect of traditional hyperspectral image anomaly detection techniques, this paper presents a novel low rank representation detection algorithm. For hyperspectral images, most of the background pixels can be approximated by a small number of major background pixel combinations, and their representation coefficients will be located in a low-rank space. While the remaining anomalous pixels in the sparse part that can not be represented by the main background pixels can be extracted by the detection algorithm. In low-rank representations, the construction of the background pixel dictionary will affect the representation of the background pixels in the hyperspectral image. When extracting the background pixels directly from the existing hyperspectral image to construct the dictionary, this process will lead to the contamination of the background pixel dictionary by the abnormal pixels. So in this paper, the background pixel dictionary is constructed by using the observed data on the hyperspectral image to be detected and the potential unobserved data that can be synthesized by the principle of spectral composition, and the main features of the background pixels are extracted, helping to better separate the sparse anomalous pixel Information. Hyperspectral image data is characterized by high-dimensional geometry. In this paper, we introduce a Laplacian matrix to constrain the representation of locally similar pixels in the space to be detected, and get a closer representation of the true representation coefficients. The experimental results are validated respectively on the simulation data and the real data, showing that the proposed method reduces the false detection rate by effectively highlighting the abnormal pixels and improves the detection rate by suppressing the background pixels.
		2018 Vol. 38 (11): 3507-3515 [Abstract] ( 151 ) RICH HTML PDF (4479 KB) ( 58 )

	3516	Rapid Quantification of Iron Oxides in Red Paleosols in Yuanmou Basin Using Diffuse Reflectance Spectroscopy
		LIU Yan-guo^{1, 2}, LIU Yan-qiu¹, OUYANG Li-li¹, CAI Yuan-feng³, HUANG Cheng-min^1*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3516-05
		Iron oxide is one of important minerals in modern soils and red paleosols, while the quantity and morphology of iron oxides are the critical indicators for soil-formation and weathering development. However, identification of iron oxides in soils and sediments is challenged by its small size, poor crystallinity, low content, close bond with clay minerals and the effect of soil matrix. Here the diffuse reflectance spectroscopy (DRS) method was adopted to quantify and semi-quantify iron oxides of red paleosols in Yuanmou Basin, southwest China. The spectral reflectance of paleosols was about 45%, measured over the range of 400～2 500 nm at an interval of 2 nm with a total of 1 061 bands. Nearly all samples exhibited the similar spectral reflectance, while the first and secondary derivative curve peaks occurred at 575 nm for hematite and 435 nm for goethite, respectively. Combination of CBD method and DRS technique the concentrations of hematite and goethitethe in red paleosols in Yuanmou Basin were 3~5 and 5~10 g·kg^-1, respectively. The estimate on goethite and hematite using DRS was supported by the X-ray diffraction method.
		2018 Vol. 38 (11): 3516-3520 [Abstract] ( 159 ) RICH HTML PDF (1933 KB) ( 180 )

	3521	Quantitative Inversion of Soil Organic Matter Content Based on Continuous Wavelet Transform
		WANG Yan-cang^{1, 3}, ZHANG Lan^{1, 3}, WANG Huan^{1, 3}, GU Xiao-he^{2, 4*}, ZHUANG Lian-ying^{1, 3}, DUAN Long-fang^{1, 3}, LI Jia-jun^{1, 3}, LIN Jing^{1, 3}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3521-07
		In this study, the data sourced from hyperspectral data of 96 tidal soil samples in Miyun, Tongzhou and Shunyi Districts of Beijing are processed and analyzed by means of continuous wavelet multiscale analysis technique. Firstly, the hyperspectral data are decomposed to generate wavelet coefficients and the correlation between the coefficients and soil organic matter content is analyzed, and the characteristic band is selected. Finally, the model to estimate soil organic matter content is constructed by using the characteristic band. The research results show that the estimation of soil organic matter by the reflectivity of soil spectrum is better than that of the traditional spectral transformation technology after continuous wavelet transformation. The ability of estimating soil organic matter by continuous wavelet decomposition decreases first and then increases with the reduction of spectral resolution. The results of continuous wavelet analysis can improve the ability to estimate the content of organic matter by the soil spectrum. Compared with the high spectral reflectivity of soil, the accuracy of soil organic content based on continuous wavelet is improved by 19%. Since the model accuracy is higher when built with the spectral resolution of 80 nm, its R² reaches 0.632, which indicates that the wide band data can be used for the monitoring of soil organic matter content by using the continuous wavelet technique.
		2018 Vol. 38 (11): 3521-3527 [Abstract] ( 181 ) RICH HTML PDF (3565 KB) ( 168 )

	3528	Accurate Evaluation of Regional Soil Salinization Using Multi-Source Data
		WU Ya-kun^{1, 2}, LIU Guang-ming^2, SU Li-tan^3, YANG Jin-song²
		DOI: 10.3964/j.issn.1000-0593(2018)11-3528-06
		Due to its negative impacts on land productivity and plant growth, soil salinization is a tough problem, particularly in arid and semi-arid regions of the world. Therefore, monitoring, mapping and predicting soil salinization are of utmost importance regarding lessening and/or preventing further increase in soil salinity through some protective measures. The current study proposes an evaluating and predicting approach that is based on remote sensing (e.g., Landsat TM images), near sensing technologies (e.g., electromagnetic induction device, EM38) and soil sampling data in typical zone of Xinjiang Automonous region. Firstly, maps of soil salinity were obtained from accurate interpretation model of soil salinity using multiple regression method in study area. The uniform distribution of 3D scatter data was modelled by grid sampling point on map of soil salinity. Then, a three-dimensional soil salt distribution was characterized by inverse distance weighting method. The results showed that the coefficient of variation of soil salinity, an indicative of strength intensity variation for different seasons, ranging from 1.281 to 1.527. The soil salinity remained at a low level and it decreased with increase of depth in the study area. Map of three-dimensional distribution of the regional soil salt demonstrated that severe soil salinity located in Midwestern region of the studied area. The synthesized method based spectral indices from remote sensing, soil apparent electrical conductivity from electromagnetic induction device and data of soil sampling in this study had 0.908 of high correlation coefficient for assessment of regional soil salinity. Thus the application of this technique provides a new method to interpret and evaluate regional soil salinity in the three-dimensional spatial distribution characteristics in Xinjiang.
		2018 Vol. 38 (11): 3528-3533 [Abstract] ( 164 ) RICH HTML PDF (3947 KB) ( 182 )

	3534	Relationships between Characteristics of Wheat Canopy and Leaf Spectral Reflectance and Yield under Different Nitrogen Treatments
		GENG Shi-ying, SUN Hua-lin, WANG Xiao-yan^, XIONG Qin-xue^, ZHANG Jing-lin
		DOI: 10.3964/j.issn.1000-0593(2018)11-3534-07
		The use of remote sensing spectroscopy in predicting the application of nitrogen fertilizer is of great importance in protecting the environment and improving fertilizer use efficiency and grain yiled. In this study, we used the FieldSpec 4 Wide-Res Field Spectrum radiometer to measure the spectral characteristics and red-edge parameters of wheat canopies and leaves under different nitrogen applications. We proposed a new spectral index - the Normalized Difference Maximum Index. We analyzed the correlations between Normalized Difference Maximum Index and leaf area index (LAI), SPAD (Soil and Plant Analyzer Development) value, MDA (Malondialdehyde) content, nitrogen content in flag leaf and yield. Twenty six days after flowering, the original spectrum of the spectral reflectance of leaves was the highest in the range of 800～1 330 nm for the N3 (1/3 starter fertilizer+1/3 pre-winter topdressing + 1/3 jointing stage topdressing) treatment, followed by the N1 treatment (1/2 starter fertilizer+1/2 pre-winter topdressing). The application of one-third of nitrogen fertilizer in both pre-winter and jointing stages enhanced the photosynthetic capacity of the leaves. The original spectrum of the spectral reflectance of canopies in the range of 400～700 nm was the lowest for the N2 (1/2 starter fertilizer+1/2 jointing stage topdressing) treatment. The spectral reflectance of the N1 treatment was the highest in the range of 760～1 368 nm followed by the N3 freatment. The canopy spectral reflectance of the N3 treatment was the highest at 26 d and 33 d after flowering. It is recommended to use the canopy raw spectral data in the ranges of 400～700 nm and 760～1 368 nm to measure flag leaf nitrogen content and to decide fertilizer application model. Two peaks were found in the range of 500～750 nm in the first-order differential spectrum of the leaf. The model of nitrogen application could be estimated by the degree of positional shift of the peaks and the offset periods. Of the canopy, the first-order differential spectral value in the range of 670～740 nm was the highest in flowering stage, and the lowest at 10th day after flowering. The first-order differential spectral value of the N1 treatment was higher than that of the N3 treatment for the first 10 days after flowering, but lower than the N3 treatment at late grain filling stage. Our results indicated that the first-order differential maximum value can be used to predict the growth stages and efficient fertilizer application. From flowering stage to mid-grain-filling stage, the highest first-order derivative (FD-Max) of canopy reflectance was the highest in the N1 treatment, followed by the N3 treatment 26 to 33d after flowering, the population structure of the N3 treatment is denser than the other treatments, resulting in the highest first-order derivation maximum. Less differences among different treatments were found on the maximum value of the first derivative of leaves. The red boundary position (REP_FD-Max) of the N1, N3 canopy shifted significantly after the mid-grain-filling stage. 26 d to 33 d after flowering, the N3 treatment ended up with a dense upper structure and wide and thick leaves. Applying nitrogen fertilizer before winter affected the REP_FD-Max migration. Based on the NDVI, we have developed a new index-the Normalized Difference Maximum Index (NDMI). The maximum canopy normalized index (CNDMI) showed a better correlation with agrochemical parameters than the leaf maximum normalized index (LNDMI). Similarly, a better correlation was also found between CNDMI and yiled. The maximum index of normalized canopy differences was significantly correlated with nitrogen content (r=0.81), SPAD value (r=0.92) and MDA content (r=-0.72) in flag leaves. In summary, the spectral data and red edge parameters can be used to predict nitrogen levels in leaves, growth stages and the model of nitrogen fertilizer application. It provides a basis for filed fertilization management and fertilization diagnosis. CNDMI has a better correlation with wheat yiled. CNDMI with a spectrum band falling into China’s resource satellites can be practically used in the diagnosis and management of fertilizer application.
		2018 Vol. 38 (11): 3534-3540 [Abstract] ( 162 ) RICH HTML PDF (2229 KB) ( 199 )

	3541	Study on LIF Emission Characteristics of Petroleum Pollutants in Different Soil Physical Properties
		WANG Xiang^{1, 2}, ZHAO Nan-jing^1*, YU Zhi-min², MENG De-shuo^{1, 3}, XIAO Xue¹, MA Ming-jun^{1, 3}, YANG Rui-fang¹, HUANG Yao¹, LIU Jian-guo^{1, 3}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3541-05
		The petroleum pollutants in soil can be rapidly detected with laser induced fluorescence technique. However, the fluorescence emission characteristic of each pollutant would be different under different soil physical properties. In order to prepare suitable soil samples rapidly in the field, the relationship between fluorescence intensity and spectral stability of soil organic pollutants, soil bulkiness, particle size and moisture was studied in this paper. The stability of the fluorescence spectra of the soil samples was better when the pressure was greater than 2 MPa, and the relative standard deviation of the fluorescence intensity of the nine soil samples with different porosity was 3.51%. The fluorescence intensity difference of the oil soil samples with different particle sizes was small, and the fluorescence spectrum RSD of 100-mesh soil samples was 2.25%. The results shows that the fluorescence spectrum is stable when the surface of the soil sample is flat and clean. The bulkiness and particle size of soil have little influence on fluorescence emission. When the soil moisture is less than 10%, the changes of fluorescence intensity is less significant , but when the humidity range is greater than 10%, the fluorescence intensity changes greatly. This paper provides references for the rapid and effective pretreatment and accurate measurement of petroleum contaminated soil samples in the field.
		2018 Vol. 38 (11): 3541-3545 [Abstract] ( 183 ) RICH HTML PDF (2159 KB) ( 156 )

	3546	Study on Self-Absorption of Cu Plasma Spectrum by Laser Induced Breakdown in Alloy at Different Pressure
		NING Ri-bo, LI Chuan-xiang, LI Qian, YUAN Bei, XU Song-ning^*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3546-04
		The self-absorption of copper alloy plasma spectrum was studied by using 532 nm laser (pulse width of 8 ns) under the laser energy of 100, 80, 60 and 40 mJ. The effects at low ambient pressure on the self-absorption and spectral characteristics of copper alloy plasma were studied under the laser energy of 100 and 40 mJ. The research showed that the characteristic line (Cu Ⅰ 324.754 nm) has a serious self-absorption at standard atmospheric pressure, and the degree of self-absorption reduced with the decrease of laser energy. By reducing the environmental pressure properly, the degree of self-absorption greatly reduced, the SBR(Signal-to-Back Ratio) increased, and the self-absorption phenomenone liminated under a certain low pressure. Under the pressure of 5.0×10⁴ Pa, the SBR under two laser energy reached its maximum value, which were 8.90 and 8.66 respectively, 11.23 and 12.62 times higher than the SBR at normal pressure, and the RSD （Relative Standard Deviation） were 2.9%, 1.3% at present. The spectral widths of two laser energy decreased rapidly with the decrease of ambient pressure. The spectral widths were 0.08 and 0.06 nm at the pressure of 5.0×10⁴ Pa, which were 19% and 20% with the value of widths under normal pressurere spectively. The results showed that sensitivity and precision in spectral analysis can be significantly improved under low-pressure. It indicates that to select the element sensitive spectral line as analysis line is possible when analyzing higher content elements, and provides an effective method for the determination of high content elements in material accurately by LIBS.
		2018 Vol. 38 (11): 3546-3549 [Abstract] ( 195 ) RICH HTML PDF (1920 KB) ( 131 )

	3550	High Sensitive Determination of Pb and Zn in Refined Copper Ores Samples Using Liquid Cathode Glow Discharge-Atomic Emission Spectrometry
		YU Jie¹, ZHU Shu-wen¹, LU Quan-fang^{1, 2*}, ZHANG Zhi-chao¹, ZHANG Xiao-min¹, WANG Xing¹, YANG Wu¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3550-08
		Monitoring of trace heavy metal ions in ores samples before the mining, smelting and processing is of great importance due to it high toxicity and gradual accumulation in the environment as well as in animal or human organs. The well-known atomic spectrometry analytical instruments, such as atomic fluorescence spectrometry (AFS), atomic absorption spectrometry (AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES), have been extensively employed for the determination of metal elements in various complex samples. However, these analytical instruments require bulky and costly devices, high power and large gases consumption. These shortcomings restrict their use within laboratory, preventing their use for field measurement and continuous monitoring. To meet the trend of miniaturization in analytical instrumentation and the requirements of on-line detection in field, electrolyte cathode discharge (ELCAD) has been developed by Cserfalvi in 1993 as an important tool in atomic spectrum analysis for element determination of liquid samples. In the original apparatus of ELCAD, the sample solution is acted as cathode, which overflows with typical flow rate of 8～10 mL·min^-1 from a pipette into about 35 mL reservoir completely filled with electrolyte solution, and a counter-electrode (mostly W or Ti rod) above it (2～4 mm) is the anode. The pipette is immersed into electrolyte solution and then curved upwards about 1～3 mm from the reservoir containing a grounded graphite electrode to make it electrically conductive. Since then, in order to improve the emission efficiency and discharge stability, many improvements for excitation source of ELCAD have been developed. In the present work, a novel liquid cathode glow discharge (LCGD) was successfully constructed based on the principle of ELCAD, in which the glow discharge plasma was generated between the needle-like Pt anode (diameter 0.5 mm) and electrolyte (served as the liquid cathode) overflowing from a quartz capillary (1.0 mm inner diameter). The vertical gap between capillary and pointed Pt wire is 2 mm. The quartz capillary was inserted into a graphite tube and protruded from the graphite tube about 2.5 mm. The sample solution was introduced through the quartz capillary with the aid of a peristaltic pump at flow rate 4.5 mL·min^-1, and then flowed over the top of capillary into the grooves on the graphite tube. This device can offer several advantages over conventional ELCAD. For example, sealed Pt wire into a quartz tube can form a Pt tip discharge and make the energy focus on a very tiny spot, which has lower energy consumption (<60 W) and higher excitation efficiency. In addition, several knots in peristaltic-pump tubing can reduce signal fluctuations of discharge induced by the peristaltic pump and improve the stability of discharge plasma. Furthermore, inserted the quartz capillary into graphite tube is excluded the reservoir of ELCAD, which can reduce the consumption of solution samples. To evaluate the analytical performance of LCGD, the simultaneous determination of Pb and Zn in digested refined copper ores samples with HNO₃-HCl was carried out. The stability of LCGD and the effects of discharge condition, supporting electrolyte, solution pH and solution flow rate on emission intensity were systematically investigated. The limits of detections (LODs) of Pb and Zn were compared with those measured by closed-type ELCAD. In addition, the measured results of samples using LCGD were verified by ICP. Moreover, a t-test between the analytical results obtained by LCGD-AES and ICP-AES was also used for estimating the uncertainty in analytical measurements. The results showed that the emission intensities increase markedly with the increase of the discharge voltage from 620 to 680 V. This is because a higher discharge voltage creates more high-energy electrons which collide with gaseous water and metal vapor in the excitation source, thus improving the excitation efficiency of metal. Considering the discharge stability, excitation efficiency and lifetime of the electrodes, 650 V was selected as the optimal discharge voltage. The emission intensities are increased when the flow rate increases from 2.5 to 4.5 mL·min^-1 before slightly reducing over 4.5 mL·min^-1. The increase of the emission intensity may be assigned to increasing the amounts of analytes which entered into the discharge region. The reduction of emission intensity over 4.5 mL·min^-1 may be ascribed to too much water loading and evaporating, which can consume the energy in the discharge region and reduce the efficiency of exciting the atoms. Therefore, 4.5 mL·min^-1 was selected as the optimal flow rate. It is observed that pH=1 HNO₃ has higher emission intensities. Hence, pH=1.0 HNO₃ was selected as the optimum solution pH. Under the best analyzing conditions, the limits of detections (LODs) of Pb and Zn obtained from this method are 0.38 and 0.59 mg·L^-1, respectively. The relative standard deviation (RSD) is 0.9% for Pb and 1.2% for Zn. The power consumption is below 60 W. LOD of this method has higher than that of other ELCAD. This may be associated with the selected spectrometer. The emission intensity remains almost unchanged under the same discharge condition, suggesting that the glow plasma is very stable. The recoveries of Pb and Zn are in the range of 87.6%~107.4%. The results of refined copper ores samples using LCGD are well consistent with the comparing values of ICP and there is no significant difference between the two methods. Compared with ICP, LCGD has several advantages, such as low power consumption, high excitation efficiency and easy miniaturization. It may be developed as a miniaturized analytical instrument for on-site, real-time and on-line determination of metal elements with further improvement.
		2018 Vol. 38 (11): 3550-3557 [Abstract] ( 211 ) RICH HTML PDF (2692 KB) ( 70 )

	3558	*Identification of Fritillaria thunbergii* Treated by Sulfur Fumigation Using Laser-Induced Breakdown Spectroscopy**
		ZHAO Yi-ying¹, ZHU Su-su¹, HE Juan³, ZHANG Chu¹, LIU Fei^1,2, HE Yong^1,2*, FENG Lei^1,2
		DOI: 10.3964/j.issn.1000-0593(2018)11-3558-05
		The paper discusses the feasibility of identifying Fritillaria thunbergii treated by sulfur fumigation using laser-induced breakdown spectroscopy (LIBS) technology with the combination of chemometric methods. Spectral data of Fritillaria thunbergii samples of no sulfur fumigation (no SF), mild sulfur fumigation (mild SF) and severe sulfur fumigation (severe SF) were collected and preprocessed by wavelet transform and normalization. Discrimination models of support vector machine (SVM), extreme learning machine (ELM) and random forest (RF) were developed on full spectra (400.41～871.65 nm) and characteristic wavebands (400.41～600.02 nm), respectively. Results showed that three models developed on characteristic wavebands all obtained the same or even better performance than the corresponding models developed on full spectra, indicating the effectiveness of extracting characteristic wavebands. Among the models developed on characteristic wavebands, SVM model obtained the optimal performance, with calibration and prediction accuracy reaching 100% and 95.83% respectively. The overall results demonstrated that LIBS technology with a combination of characteristic wavebands extraction and chemometric methods could be used for identifying Fritillaria thunbergii treated by sulfur fumigation. This study provides an instruction for identifying traditional Chinese medicine and can help to establish a quality detecting and grading evaluating system for traditional Chinese medicine.
		2018 Vol. 38 (11): 3558-3562 [Abstract] ( 165 ) RICH HTML PDF (2497 KB) ( 189 )

	3563	Comparison of Mineral Element Contents in Silky Fowl and Non-Medicinal Chicken
		TIAN Ying-gang, HU Qing-qing, XIE Ming-yong
		DOI: 10.3964/j.issn.1000-0593(2018)11-3563-04
		Analysis and comparison of mineral and microelement contents in Silky Black-bone Silky fowl (BSF) is a traditional Chinese edible chicken that is endemic to China. In generally Lingnan Yellow Chinken (LNYC) and Chongren Chicken (CRC) are not used medicinally in traditional Chinese medicine, but they belong to two high quality chicken breeds with a wide range of aquaculture. In addition to the content of mineral elements and distribution characteristics and chicken-related, but also with the breeding conditions, especially feed and water are closely related. Therefore, two kinds of non-medicinal chicken breeds raised under the same conditions as mentioned above can eliminate the experimental error and enhance the reliability of experimental results. In this paper, inductively coupled plasma atomic emission spectrometry (ICP-AES) has been used to determine the effect of two kinds of chicken on the basis of the advantages of fast analysis, wide range of measurement, high accuracy and precision, good selectivity and simultaneous determination of multiple elements The content of eight kinds of mineral elements in different species can better compare the differences of the content of mineral elements contained in different kinds of chicken breeds and more accurately reflect the nutritional value of silky fowls. Under the same feeding, drinking water and feeding environment, two kinds of non-medicinal chicken were used as control. ICP-AES method was used to determine the P, Ca, Na, K, Mg, Fe, Cu and Zn in BSF, LNYC, CRC. Take their skin, bones, chicken breasts, chicken thighs as a sample (n=8), cut and dried until constant weight, weighing. Take the above samples for each of the three parallel samples, each weighing about 2 g precision, were added 10ml mixed acid (HClO₄∶HNO₃=1∶4), heat digestion. After cooling, the sample was dissolved in 2% HNO₃, and a blank test solution was prepared with distilled water as the sample. The sample was determined under the selected working conditions. The main working conditions of ICP-AES are set as follows: RF power 1.2 kW; auxiliary gas flow 0.2 L·min^-1; atomizing gas flow 0.8 L·min^-1; plasma gas flow 15 L·min^-1; solution lift 1.5 mL·min^-1; Cooling air flow 15 L·min^-1. The determination of all samples had been repeated for three times. All data are expressed as mea±standard deviation (x±s). Significance analysis using SPSS20.0 statistical software test for evaluation. Univariate analysis of variance was used to study variables in different groups, assuming a significant difference of p<0.05. The correlation coefficient r>0.999 54 and the limit of detection (0.01～3.90 μg·g^-1) of the standard curve were measured experimentally, which showed that there was a good linear relationship between the concentration of each element and the absorbance within the concentration range studied, ensure the accuracy of the experiment. Compared with other two non-medicinal breeds, BSF’s skin shows much higher concentrations in all of the eight mineral elements content (p＜0.01); Ca，Fe，Na, Zn in the bone of BSF are higher than that of the others too（Ca，Fe：p＜0.01, Na，Zn：p＜0.05). Interestingly, Ca and Fe in BSF’s breast are higher than others’ (Ca：p＜0.05, Fe：p＜0.01), while BSF’s Mg are the lowest among the three breeds (p＜0.01); Fe and Cu in BSF’s leg are the highest (p＜0.01), while Na，K，Mg，Zn in BSF’s leg are very low (p＜0.05). On the other hand, CRC and LNYC show similar results in the eight mineral elements contents. In summary, the high contents of Ca and Fe are the most remarkable characteristics of BSF, and BSF’s hematinics function might be relating to its Fe content. Therefore, this study helps to reveal the BSF’s hematinics theory.
		2018 Vol. 38 (11): 3563-3566 [Abstract] ( 147 ) RICH HTML PDF (803 KB) ( 44 )

	3567	Accurate Determination of Calcium and Chlorine in Food with Inductively Coupled Plasma Tandem Mass Spectrometry
		ZHOU Xue-zhong, LIU Hong-wei^*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3567-05
		An analytical method for the determination of Ca and Cl elements in food was established with inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). The most abundant isotope ⁴⁰Ca of Ca is suffering from intense interferences from the ⁴⁰Ar among the argon plasma gas, and ³⁵Cl is subjected to interference from ¹⁶O¹⁸OH. To avoid the interference, in the MS/MS mode, collision/reaction cell (CRC) was adopted using H₂ as the reaction gas, so that H₂ will reach with ⁴⁰Ar⁺ instead of ⁴⁰Ca⁺, A H₂ on-mass method was used to eliminate the interference of ⁴⁰Ar⁺ on ⁴⁰Ca⁺. As mass shift reaction could take place between ³⁵Cl⁺ and H₂ to generate H₂³⁵Cl⁺, thus the interference of ¹⁶O¹⁸OH⁺ on ³⁵Cl⁺ can be eliminated by determining H₂³⁵Cl⁺. Ca and Cl showed good linearity in the concentration range of 0.0～100.0 μg·L^-1 with linear correlation coefficient (R²)≥0.999 9, and the detection limits of Ca and Cl were 0.061 and 2.32 μg·L^-1, respectively. The accuracy and precision of this method were verified by series of national standard materials. The results of this method were basically consistent with the certified values of the reference materials, indicating that the method of good accuracy and high precision. The new method can be used to achieve the accurate determination of Ca and Cl in food.
		2018 Vol. 38 (11): 3567-3571 [Abstract] ( 167 ) RICH HTML PDF (1825 KB) ( 210 )

	3572	Impurity Elements Analysis of Catalyst Precursor Ruthenium Nitrosyl Nitrate Using Inductively Coupled Plasma Tandem Mass Spectrometry
		FU Liang^1,3, ZHAO Feng-xuan², WANG Hai-yan³, WANG Huan-zhe², CHEN Tao², XU Jian-hua¹, LI Bing¹, XIE Hua-lin^1*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3572-06
		Ruthenium catalyzed precursor is the most principal factor affecting the catalytic performance of the supported ruthenium catalyst. Some impurities in the ruthenium catalyzed precursor can inhibit the catalytic performance. In particular, the high content of impurities (such as S, P, Cl and As) reduces activity of the catalyst. In severe cases, the catalyst can be poisoned, thus the level of impurities in the catalytic precursor must be controlled. In this paper, we report an analytical method for rapid and accurate determination of impurity elements in ruthenium nitrosyl nitrate (Ru(NO)(NO₃)₃) precursor. After dissolved by nitric acid, the impurities (such as P, S, Ti, V, Cr, Mn, Fe and As) were directly determined by inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). In order to prevent the hydrolysis of Ru(NO)(NO₃)₃ into Ru(NO)(NO₃)_x(OH)_3-x, we used diluted nitric acid to dissolve the samples while retaining their stability. In the MS/MS mode, the first quadrupole mass filter (Q₁) controlled the collision/reaction cell (CRC) ions, only allowing analytes with the same mass charge ratio (m/z) into the CRC. It prevented the interfering ions from the sample matrix and plasma Ar from traveling outside of the CRC, eliminating a significant mass spectral interference. The reaction of target ions P⁺, S⁺, Ti⁺, V⁺ and As⁺ with O₂ (added into the CRC as a reaction gas) was an exothermic process, which could spontaneously produce corresponding oxides (³¹P⁺+O₂→³¹P¹⁶O⁺+O，ΔH_r=-3.17 eV；³²S⁺+O₂→³²S¹⁶O⁺+O，ΔH_r=-0.34 eV；⁴⁸Ti⁺+O₂→⁴⁸Ti¹⁶O⁺+O，ΔH_r=-1.63 eV；⁵¹V⁺+O₂→⁵¹V¹⁶O⁺+O，ΔH_r=-0.85 eV；⁷⁵As⁺+O₂→⁷⁵As¹⁶O⁺+O，ΔH_r=-0.63 eV). The reaction of Cr⁺ and Mn⁺ target ions with O₂ was an endothermic process (⁵²Cr⁺+O₂→⁵²Cr¹⁶O⁺+O，ΔH_r=+1.38 eV；⁵⁵Mn⁺+O₂→⁵⁵Mn¹⁶O⁺+O，ΔH_r=+2.15 eV). In order to promote this endothermic reaction, we adjusted parameters of the CRC, in particular, by setting the octopole bias voltage to a negative voltage. Under these conditions, kinetic energy of Cr⁺ and Mn⁺ increased and the ions accelerated before the reaction with O₂. However, the P⁺, S⁺, Ti⁺, V⁺, Cr⁺, Mn⁺ and As⁺ ions did not react with O₂ in CRC, but still maintained the original m/z. The second quadrupole mass filters (Q₂) could block out these interfering ions allowing the oxide-forming ions to enter the detector. This technique eliminated almost all interference from P, S, Ti, V, Cr, Mn and As. NH₃ has high reactivity and a pair of lone pairs of electrons, therefore it reacts with many metal ions forming cluster ions. By adding NH₃/He as a reactant gas into the CRC, the mass shift reaction of the target Fe⁺ ions with NH₃ occurred. Among the multiple cluster ions, content of Fe(NH₃)⁺₂ was the highest and no interference was observed. Thus, we eliminated the interference by the NH₃ mass shift method. All 8 elements had a good linear relationship in the range of 0～500 μg·L^-1 with the correlation coefficient R²≥0.999 8. The instrumental limit of detection (LOD) of analyte ranged from 0.29 to 485 ng·L^-1. According to the established method, the contents of impurity elements in the samples were analyzed. The spiked recovery of the analyte ranged from 93.2% to 107.5%, and the relative standard deviations (RSDs) were less than 3.9%. The proposed method has the advantages of simple sample processing, high speed of analysis and high precision, and is suitable for accurate determination of impurities in Ru(NO)(NO₃)₃, thereby providing a quality guarantee for preparing the supported ruthenium catalysts.
		2018 Vol. 38 (11): 3572-3577 [Abstract] ( 158 ) RICH HTML PDF (1130 KB) ( 40 )

	3578	FI-KR-FAAS Twice Gas Isolation Elution Method for the Determination of Trace Lead in Marine Biological Samples
		WANG Zhong-yuan¹, ZHANG Hong-kang^2*, NI Zhi-xin¹, LIU Jing-qin¹, CHEN Xin¹, LI Sheng-yong¹, YANG Qi-jin², ZHANG Can¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3578-05
		In this paper, trace lead in marine biological samples was determined by using flow injection ( FI ) air mixture adsorption preconcentration and twice gas isolation elution method in knotted reactor (KR) coupled with flame atomic absorption spectrometry (FAAS) . Air, complexing reagent and lead solution were mixed on-line during the preconcentration step, and the introduction of air greatly improved the adsorption effects of the lead chelate on the inner walls of KR. By the introduction of air flow before elution and adding part of air flow during elution, through these two parts of the introduction of air flow bubble partition, the dispersion of the lead chelate in KR was greatly reduced, and the peak of the atomic absorption signal was increased, and the enhancement factor (Enhancement factor, EF) was increased. By the combination with the KR of the air mixing sorption preconcentration and twice gas isolation elution method, the KR adsorption effect and elution effect reached a higher level, and compared with high back pressure and short lifetime of the micro column, KR has the characteristics such as acid and alkali resistance, low back pressure and almost unlimited lifetime. What’s more, it has no critical requirement for the peristaltic pump and is not easy to cause leakage of the solution. In the elution process, 1 s air flow was used as a spacer at the fifth second, instead of entering the air flow after the entire elution process was completed. The advantage of this method is not only being eluted completely, but also greatly reducing the dispersion of the analyte during the elution process, and the value of the absorption signal is greatly increased. If the elution time is simply put down to 5 s, then the elution will be very incomplete, the tube being not clean, a large number of analytes still remaining in the tube, and the remnants of the analyte were brought into the analysis of the next sample. All the experimental data will be inaccurate, and the value of data utilization will be lost. So complete elution is necessary and must ensure a certain elution time. As for the elution process, the elution of the analyte decreased gradually, in the past elution method, until the entire process is performed after elution, the analyte in the elution dispersion has been quite serious, which leads to the great reduction of absorption signal value. Operational parameters such as types, concentration and pH of complexing agents, sample preconcentration time and flow rate, flow rate and time of air mixing sorption process, the first ventilation time, pre elution time, the second ventilation time were optimized for the purpose of determining trace lead. Using the optimized conditions, a linear relationship existed between the peak absorbance and the concentrations of lead in the range of 0.005～0.6 mg·L^-1 respectively. The method was applied in the determination of trace lead in marine biological samples with a detection limit（3σ） of 2.2 μg·L^-1. In this paper, the detection results of FAAS method, traditional FI-KR-FAAS air mixing sorption preconcentration method and normal elution method were compared with this method, and it showed that the new method obtained the highest enhancement factor value. This method was applied to detect the trace lead in biological samples such as eel, pawn, slipper lobster, sturgeon, tonguefish and mussel. The trace lead content in these biological samples were among 0.34~1.92 μg·g^-1. When the 1.0 μg·g^-1 standard Lead solution was added, the recovery was 93.5%~96.4%, and the relative standard deviation (RSD) was 0.52%~2.94%. The method of FI-KR-FAAS twice gas isolation elution for the determination of trace lead in marine biological samples obtains several merits. It has good preconcentration effect, high precision，high degree of accuracy and high enhancement factor. This method can satisfy the analysis requirement for the marine biological samples.
		2018 Vol. 38 (11): 3578-3582 [Abstract] ( 195 ) RICH HTML PDF (1427 KB) ( 57 )

	3583	Synthesis of Hyperbranched Polyamidoamine (PAMAM) Grafted Chitosan and Its Adsorption for Heavy Metal and Dyes Studied with Spectroscopy
		LINGYUN Xia-fei^{1, 2}, GAO Chao^{1, 2}, FAN Jing-shuang^{1, 2}, Lü Hai-xia^{1, 2*}, YU Yan^{1, 2}
		DOI: 10.3964/j.issn.1000-0593(2018)11-3583-05
		A new type of hyperbranched polyamide grafted chitosan (CS-PAMAM) adsorbent was synthesized using glutaraldehyde (GLA) as the crosslinker. The adsorbent wascharacterized with Field Emission Scanning Electron Microscope and Fourier Transform Infrared. Combined with flame atomic absorption spectroscopy (FAAS) and UV-Vis spectrophotometry, the adsorption of Malachite green (MG), Sunset yellow (SY) and Cu(Ⅱ) by adsorbent were investigated. Experimental conditions affecting the adsorption percentage were discussed and the experimental operation parameters were optimized (pH value were 7.0，2.0 and 6.0, respectively; adsorption time were 60，60 and 30 min, respectively). Under the optimal condition, the maximum adsorption capacity of MG, SY and Cu(Ⅱ) on CS-PAMAM was found to be 515.30, 201.79 and 80.00 mg·g^-1, respectively. The advantages are obvious. The adsorption process for MG, SY and Cu(Ⅱ) obeyed Langmuir isother mequation.
		2018 Vol. 38 (11): 3583-3587 [Abstract] ( 177 ) RICH HTML PDF (1835 KB) ( 62 )

	3588	XRD and SEM Analyses of Molybdenite with Different Particle Sizes and Its Floatability Difference
		LI Hui¹, HE Ting-shu^1*, WANG Yu-bin¹, JIN Jian-ping², YUAN Hang¹
		DOI: 10.3964/j.issn.1000-0593(2018)11-3588-05
		In the process of flotation, the recovery of micro-particle molybdenite is difficult, and it is easy to lose in the tailings. In order to analyze the flotability difference of molybdenite with different particle sizes and to reveal the reasons for the flotability of fine-grained molybdenite, using four particle sizes molybdenite respectively -150+74, -74+45, -45+38 and -38 μm as the research object, through molybdenite flotation tests of pure minerals, first by means of X ray diffraction analysis (XRD) and scanning electron microscopy (SEM) analysis，the floatability of particle size molybdenite and its crystalline characteristics, external morphology and variation were systematically studied and compared. The results showed that the floatability of molybdenite decreased with the decrease of particle size, and the flotation effect deteriorated. The floatability of molybdenite was determined by the area ratio of non-polar, low energy, hydrophobic “surface”and lively, hydrophilic “edge”. In the process of transformation from coarse to fine particle size under the action of external force, firstly, it mainly broke along the cleavage plane, and then broke more along the fracture surface, resulting in the decrease of the area ratio of “surface” and “edge”, and the decrease of the floatability. Meanwhile, the crystalline structure of molybdenite changed from 3R type to 2H type. In addition, compared with 3R type coarse particle size molybdenite, fine particle size molybdenite was mainly 2H type and the surface spacing of (002) crystal surface increased gradually. So water molecules was easy to enter the crystal structure and formed hydrated film on the mineral surface, resulting in an increase of the hydrophilicity of molybdenite. The physical properties of molybdenite with different particle sizes changed by different crystal types. The increase of the distance between the surfaces made the number of hydrophilic molybdenum sulfur bonds exposed to the fracture surface of molybdenite increase, which was the essential reason for the enhancement of hydrophilicity and the decrease of floatability of fine grained molybdenite.
		2018 Vol. 38 (11): 3588-3592 [Abstract] ( 182 ) RICH HTML PDF (2047 KB) ( 147 )

	3593	Study of the False Peak Eliminating Algorithm in Fine EDXRF
		ZHOU Wei, LIU Ze-wei^*, ZHOU Hang, LIANG Fei-xi, ZHANG Rong-zhou
		DOI: 10.3964/j.issn.1000-0593(2018)11-3593-05
		In the background of high counting rate, the full-energy peak of X-rays fluorescence is seriously disturbed by the false peak whichis caused by the charge sensitive preamplifier in High Performance Silicon Drift Detector and slow digital shaping algorithm. In this paper, a novel method of false peak eliminating is presented. And some technical points are also introduced in details such asdigital triangleshaping, signal screening and peak discrimination. Taking ⁵⁵Fe nuclide and rock samples as experimentations, the spectrum before and after the false peak eliminating are compared. And the results showed that the false peak can availably be eliminated. Therefore, the performance of fine X-rays fluorescence will be improved such as peak to background ratio and accuracy of trace elements analysing.
		2018 Vol. 38 (11): 3593-3597 [Abstract] ( 166 ) RICH HTML PDF (2819 KB) ( 75 )

	3598	Component Analysis of Various China Clays Nearby Fanchang Kiln
		CUI Ming-fang¹, ZHU Jian-hua^2*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3598-09
		The formula process of bluish white porcelain body is still in the speculation stage. There exist no tangible proofs and simulated experiments to clarify the underlying craft. In order to explore the formula process, various china clays near the Fanchang Kiln have been characterized, and simulative firing experiments in the virtue of ancient porcelain technology have also been performed. Different characterizations including wavelength-dispersive X-ray fluorescence (WDXRF) XRD and FT-IR spectra was applied to determine the composition of the several china clays nearby the Fanchang Kiln. Meanwhile, the firing temperature was explored by TG-DSC analysis. Based on the above analysis, simulation firing was performed to study the possible firing process. And the microstructures of resultant samples were characterized by optical microscopy. Experiments evidences indicated that these china clays can be used as the raw material to fire bluish white porcelain body of the Fanchang Kiln. Considering aluminum content of these china clays is lower than that of the bluish white porcelain body, some materials containing high alumina component may be introduced in the production of the bluish white porcelain. This research has huge academic significance in understanding the production technology and promoting the status of the Fanchang Kiln in the development history of Chinese ceramic technology. This research also is helpful to improve the modern ceramic technology.
		2018 Vol. 38 (11): 3598-3606 [Abstract] ( 165 ) RICH HTML PDF (4614 KB) ( 53 )

	3607	Spectral Analysis of the Effects of γ-Irradiation on Gadolinium-Containing Barium Phosphate Glass
		YU Tao^{1, 2, 3}, WANG Jun-xia³, LIU Hai-feng², LIANG Xiao-feng^{1, 2, 3*}, YANG Shi-yuan³, LUO Qing³
		DOI: 10.3964/j.issn.1000-0593(2018)11-3607-04
		The xGd₂O₃-(50-x)BaO-50P₂O₅ (0≤x≤7 mol%) series of glass samples were prepared with melt quenching method to develop new γ-ray shielding materials and irradiated with ⁶⁰Co irradiation source. The light transmission characteristics and microstructure of the glass were studied by UV-Vis-nir and Raman. γ-ray irradiation makes the glass produce phosphorus oxygen hole center (class Ⅰ color), presenting brown. The resistance of phosphate glass to γ irradiation was enhanced by Gd₂O₃. The higher the content of Gd₂O₃ in glass, the lower the number of color centers caused by γ-ray irradiation. The transmittance on visible and near infrared light regions were reduced with the addition of Gd₂O₃. γ-ray irradiation causes the glass to exhibit optical absorption band loss, and the transmittance of the glass in the ultraviolet to visible region is reduced. The glass samples are mainly based on Q² partial phosphate structure, accompanied by Q¹ pyrophosphate and Q⁰ orthophosphate glass structure, and γ-ray irradiation has little effect on the microstructure of glass.
		2018 Vol. 38 (11): 3607-3610 [Abstract] ( 166 ) RICH HTML PDF (2682 KB) ( 123 )

	3611	DNA Binding and Antitumor Activity of a New Fluorescent Probe Eu(Ⅲ)-Complex Containing 4-Methyl-Coumarin Moiety
		Belal H M Hussein^1,2*, Mostafa A Gouda^1,3, Omer Sakin¹, Abdulla Faluji⁴, Mohamed Gomaa⁵, Hassan A Azab², Walid Fathalla⁶, Sherin Arabi⁷, Sawsan Mosa⁸
		DOI: 10.3964/j.issn.1000-0593(2018)11-3611-11
		A new europium (Ⅲ) complex containing (4-Methyl-2-oxo-2H-chromen-7-yloxy)-acetic acid moiety (CMMC) was synthesized, characterized, and confirmed as antitumor agent and fluorescent probe. The spectroscopic measurements of Eu(Ⅲ) in the presence of CMMC were obtained in different solvents. The results show that the strongest Eu(Ⅲ) emission bands were monitored in iso-propyl alcohol while the weakest Eu(Ⅲ) emission band was observed in acetonitrile. The interaction of Eu(Ⅲ)-(CMMC)₂ complex with DNA was monitored using absorption and emission techniques. From fluorescence titration measurements, the binding constants of DNA with Eu(Ⅲ)-(CMMC)₂ complex were found to be 1.04×10⁵ L·mol^-1 in Tris-HCl and 1.17×10⁷ L·mol^-1 in DMSO-Tris-HCl buffer (9∶1 V/V). Hypochromism was observed from the absorption titration experiment which indicates the intercalation of Eu(Ⅲ)-complex between the base pair of DNA. This result further confirmed by fluorescent Ethidium bromide displacement assay. The fluorescence calibration curve was used for the determination of DNA with LOD of 1.2 ng in DMSO-Tris-HCl buffer (9∶1 V/V) and 5 ng in Tris-HCl buffer. The preliminary antitumor investigation shows promising cytotoxicity against MDA-MB-231, MCF-7 (mammary cancer), and PC-3 (prostate carcinoma) cell lines with IC₅₀ values of 40.63, 25.42 and 30.25 μmol·L^-1, respectively.
		2018 Vol. 38 (11): 3611-3621 [Abstract] ( 179 ) RICH HTML PDF (6458 KB) ( 60 )

	3622	Estimation of Metformin Drug for the Diabetes Patients by Simple, Quick and Cheap Techniques within the Formation of Colored Charge Transfer Complexes
		Omar B. Ibrahim¹, El-Sayed A. Manaaa^2,3, M.M. AL-Majthoub¹, Ahmed M. Fallatah¹, Abdel Majid A. Adam¹, Mha M. Alatibi¹, Jehan Y. Al-Humaidi⁴, Moamen S. Refat^1,5*
		DOI: 10.3964/j.issn.1000-0593(2018)11-3622-09
		Metformin (Met) is a drug developed for the treatment of patients with type Ⅱ diabetes. Recently, Met estimation in pharmaceutical formulations and human fluids has gained a growing interest. To extend requisite data that can be used to assessment of Met quantitatively based on charge-transfer (CT) complexation, the present study describes the synthesis and characterization of CT complexes that formed between drug Met and the organic π-acceptors picric acid (PA), chloranilic acid (CLA), chloranil (CHL), 7,7’,8,8’-tetracyanoquinodimethane (TCNQ), and dichlorodicyanobenzoquinone (DDQ). The properties of the formed CT complexes were investigated by elemental, spectral (UV-visible, IR, and Raman spectroscopies), thermal (TG) and morphological (SEM) studies. IR results indicated that the complexation of Met with either PA or CLA acceptors occurs through proton transfer interaction, whereas its complexation with CHL, TCNQ, or DDQ acceptors occurs through n→π^* interaction.
		2018 Vol. 38 (11): 3622-3630 [Abstract] ( 151 ) RICH HTML PDF (2425 KB) ( 55 )

	3631	Quantum Chemical Calculations on 4-[2-(Tert-Butylamino)-1-Hydroxyethyl]-2-(Hydroxymethyl) Phenol by Density Functional Theory
		Rubarani P Gangadharan^1*, S Sampath Krishnan²
		DOI: 10.3964/j.issn.1000-0593(2018)11-3631-07
		Density functional theory (DFT) calculations have been carried out for the compound 4-[2-(tert-butylamino)-1-hydroxyethyl]-2-hydroxymethyl) phenol (4BAHEHMP) by using the B3LYP method at the 6-311++G (d,p) basis set level. The electric dipole moment (μ) and the first hyperpolarizability (α) values of the investigated molecule were computed. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis were presented. HOMO and LUMO energies confirm that charge transfer occurs within the molecule. In addition Molecular Electrostatic Potential (MEP), Natural Bond Orbital analysis (NBO) and Non- Linear Optical (NLO) properties are studied.
		2018 Vol. 38 (11): 3631-3637 [Abstract] ( 171 ) RICH HTML PDF (2231 KB) ( 59 )

	3638	A Study of the Terahertz Time-Domain Spectroscopy for Qualitative Identification of Alfalfa Forages from Different Varieties
		WANG Fang^1,2, GUO Shuai^1,2, ZHAO Jing-feng³, XIA Hong-yan³, BAO Ri-ma^1,2, ZHAN Hong-lei^1,2, WANG Jia-ni^1,2
		DOI: 10.3964/j.issn.1000-0593(2018)11-3638-07
		In this study, terahertz time-domain spectroscopy (THz-TDS) and multivariate statistical methods were used to demonstrate the feasibility of identifying fourteen alfalfa forage varieties that look extremely similar. THz spectra parameters, such as refractive index and absorption coefficient, were calculated from 0.1 to -1.5 THz, and the test spectrum revealed that different kinds of alfalfa grass seeds are different in time delay, absorption intensity and average refractive index. Although these characteristics differences mentioned above mean that the THz-TDS are feasible to identify alfalfa forage varieties, the statistical methods, including cluster analysis (CA) and principal component analysis (PCA), were used to build models between THz parameters and different alfalfa forage varieties because there was no characteristics absorption peak as fingerprint identification basis. The Euclidean distances of CA between forage grasses, and the scores of the first principal component (PC1) in PCA method reflect the forage-dependent differences, indicating the consistency between CA and PCA. Consequently, the combination of THz technology and statistical methods can be an effective method for the rapid identification of alfalfa forage with different properties. Furthermore, this combination method also provides a favorable basis for establishing the THz spectrum database of forage species in the future.
		2018 Vol. 38 (11): 3638-3644 [Abstract] ( 240 ) RICH HTML PDF (2794 KB) ( 90 )

	3645	Blurred Infrared Image Segmentation Using New Immune Algorithm with Minimum Mean Distance Immune Field
		YU Xiao¹, ZHOU Zi-jie¹, Kamil Ríha²
		DOI: 10.3964/j.issn.1000-0593(2018)11-3645-08
		Criminals tend to use various methods to cope with the traditional forensic image technologies, so infrared image is becoming an effective means for obtaining crime scene traces. However, segmentation targets from infrared image shoot in crime scene is a challenging task as these images are target weakened infrared images. Previous studies about immune algorithms do not describe immune variation and immune recognition distance in the network and algorithm. In opposition to segment these target weakened traces infrared images, we propose a new immune framework with immune variation and minimum mean immune recognition distance, and construct a new immune segmentation algorithm with minimum mean distance immune field. According to the distinguishing feature of infrared images, this method use multi-step classification algorithm, immune variation and adaptive immune minimum mean distance recognition to achieve optimal classification based on the overall statistical properties of target areas and background areas. Experimental results show that the proposed immune algorithm with minimum mean distance can segment target weakened infrared images efficiently. Compared with classical edge template and conventional region template methods, the proposed algorithm has better segmentation results, especially the boundaries of five fingers.
		2018 Vol. 38 (11): 3645-3652 [Abstract] ( 176 ) RICH HTML PDF (1712 KB) ( 54 )

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