基于CARS和K-S的马拉硫磷农药浓度吸收光谱预测模型研究

利用马拉硫磷在紫外/可见光波长范围内的不同浓度梯度的吸光度光谱数据,建立其快速有效的定量预测分析模型。在预测模型的建立过程中,参与建模的波长变量和校正集样本的优劣对定量分析模型的预测能力有着决定性作用。首先对实验样本是否存在异常样本进行检查,然后将200.08~750.04 nm波长范围的光谱数据采用不同预处理方法并建立PLS模型,进而将预处理结果最优(均值中心化)的光谱数据采用竞争性自适应重加权采样(CARS)算法和蒙特卡洛无消息变量消除法(MC-UVE)分别筛选出关键波长变量并建立相应的PLS预测模型,模型结果表明,CARS算法在关键变量筛选的性能上优于MC-UVE算法;再将CARS算法筛选出的18个波长变量(为原来变量数的1.1378%)结合Kennard-Stone(K-S)算法和蒙特卡洛交叉验证(MCCV)分别优选出的44个建模样本(原来样本数的88%)建立CARS-K-Ss-PLS和CARS-CCVs-PLS定量预测模型,R^2p分别为0.9982和0.9989,RMSEP分别为0.8634和1.0262,RPD分别为24.1635和20.3301,CARS-K-Ss-PLS模型略优于CARS-CCVs-PLS模型。结果表明,CARS算法能够淘汰与样本浓度相关性较弱的变量,同时有效剔除无关光谱信息,K-S算法能帮助选择更优的建模样本集,马拉硫磷农药的紫外/可见光吸收光谱结合CARS算法和K-S算法所建立的CARS-K-Ss-PLS模型能够用来定量预测马拉硫磷农药浓度。研究工作为利用光谱技术快速检测有机磷农药浓度提供一定的理论依据和实验基础,在有机磷农药快速检测领域具有良好的应用前景。

苯并咪唑的三维荧光光谱与三维室温磷光光谱

测量了浓度为 1× 1 0 - 4 mol/L苯并咪唑水溶液的三维荧光光谱 ,三维室温磷光光谱和紫外 /可见吸收光谱 ,还测量了苯并咪唑固体紫外 /可见吸收光谱 对化合物的荧光和室温磷光进行了分析、比较 ,发现苯并咪唑在 2 90nm、5 80nm和 870nm区域均有强而丰富的荧光谱线 ,而室温磷光谱线 (RTP)单一地出现在 2 90nm区域 ,且强度很小 ;

邻位甲基红水溶液的光谱性质随pH值的变化:含时密度泛函理论计算与实验研究（英文）

探明影响甲基红光谱性质的各种因素,有助于拓宽偶氮苯衍生物在有机光电器件中的应用。采用密度泛函理论和实验相结合的方法研究了溶液酸碱性和溶剂水对邻位甲基红水溶液光谱的影响。溶液pH从13.1逐渐降低至0.5,邻位甲基红水溶液的最大吸收波长从430 nm红移至520 nm。在不同酸碱条件下,主要有三种物种共存于甲基红水溶液中,它们分别是双质子化的甲基红o-H_2MR+(强酸性条件下),单质子化的甲基红oHMR(弱酸条件下)和碱性甲基红o-MR–(碱性条件下),通过密度泛函理论计算研究了三种不同形式的电子结构特征。采用含时密度泛函理论计算了甲基红偶极跃迁允许的最低激发能,分别采用连续介质模型和分子簇模型研究水溶剂对甲基红电子结构和光谱性质的影响。在酸性条件下,o-H_2MR+和o-HMR分子内氢键导致π共轭体系平面性增强,因而光谱红移。而在碱性条件下,溶剂对o-MR–的光谱有显著影响:极性o-HMR和o-MR–与水分子的偶极–偶极相互作用导致光谱进一步红移。

光谱技术结合化学计量学分析方法快速检测阿维菌素的试验研究

生物农药阿维菌素是一种微溶于水的高毒杀虫剂,有广谱、高效等特点,在防治水稻螟虫,稻纵卷叶螟方面表现优异,但对水生生物高毒。为了探讨利用光谱技术现场快速检测水体中生物农药阿维菌素的可能性,测定了其在紫外/可见光波长范围内的不同浓度吸光度光谱数据,建立其快速有效的定量分析模型。使用不同光程比色皿采集一定浓度范围的阿维菌素农药样本光谱数据进行对比,得到最佳光谱数据用于后续定量处理分析。将波长范围为200~500 nm的光谱数据采用Savitzky-Golay卷积平滑法(S-G平滑法)进行数据预处理,将原始光谱数据和S-G平滑法预处理后的光谱数据校正集和预测集分别按不同比例采用Sample set partitioning based on joint x-y distance(SPXY)算法进行样本集划分,并分别建立PLS模型进行比较。再将划分样本集后优选出的光谱数据采用主成分分析(Principle component analysis,PCA)结合马氏距离阈值法(Mahalanobis Distance,MD),即PCAMD算法剔除异常样本,再将剔除异常样本后的光谱数据采用竞争性自适应重加权采样法(Competitive adaptive reweighted sampling,CARS)筛选特征波长变量,建立S-G平滑-SPXY-(PCA-MD)-CARS-PLS定量分析模型。结果表明,100 mm光程比色皿获得的光谱数据最佳,245.4 nm处为阿维菌素特征吸收峰。原始数据经S-G平滑法预处理、SPXY划分样本集、PCA-MD剔除异常样本以及CARS筛选特征波长变量后建立的定量模型最优,模型评价系数R2p为0.9988,预测集均方根误差为0.0611,剩余预测残差为29.5894,该方法有效简化了模型并提高了模型精度和稳健性。研究表明,生物农药阿维菌素的紫外/可见光吸收光谱数据结合化学计量学分析方法能够用来定量分析生物农药阿维菌素浓度。

光谱检测水体中磷酸三钠浓度的实验研究

以不同浓度的磷酸三钠溶液为研究对象,探究紫外/可见吸收光谱用于检测水体中磷酸三钠溶液浓度的可行性。使用不同光源和不同光程组合的3套吸光度测量装置采集不同浓度下磷酸三钠样液的光谱数据,进而分别对三组实验数据采用不同预处理方法进行预处理,偏最小二乘(PLS)模型结果表明三次实验均采用Savitzky-Golay(S-G)卷积平滑预处理方法效果最好;接着采用蒙特卡洛交叉验证(MCCV)算法对校正集中奇异样本进行剔除,对剔除奇异样本后的全波段数据建立PLS模型,模型结果表明MCCV法有助于提高PLS模型的预测性能;最后采用相关系数法三种实验选取的主要特征波长分别为214.0998,218.8371和204.66 nm,为了建立一个精度较高且具有普适性的模型,依据以上三个主要特征波长选取磷酸三钠的特征波段为200~222 nm,并建立相应特征波段PLS模型,结果表明该模型可用于磷酸三钠溶液浓度的定量分析和预测。所以采用光谱技术快速检测水体中磷酸三钠溶液浓度具有一定的可行性,该研究为开发快速检测水体中无机磷浓度的仪器设备提供一定的理论基础。

混凝沉淀及高级氧化工艺处理嘧啶废水的研究

采用混凝沉淀及高级氧化两步工艺对嘧啶废水进行了处理研究。结果表明,在反应温度20℃,pH为3.5,Fe2+的投加量为64mmol·L-1时,Fenton试剂对的嘧啶转化率达74.89%,COD去除率达42.16%;而混凝工艺及H2O2氧化工艺的最高嘧啶去除率分别仅为21.59%和20.20%。通过处理前后的UV/Vis吸收光谱图比较,进一步表明Fenton试剂对嘧啶废水有理想的处理效果。

Isolation of a Prodigiosin-producing Strain and Analysis of It's Pigments

[Objective] The aim was to isolate a prodigiosin producing strain and study its pigment fractions.[Method] Red pigment-producing bacteria was identified by physiological and biochemical characteristics after isolation in plate.By using column chromatography and thin-layer chromatography,pigment fractions were separated and purified from the extractives of the strain after fermentation in flask,and then pigment fractions were analyzed via UV-Vis and LC/MS.[Result] A red pigment-producing Serratia marcescens strain NS-17 sampled from soil of Nanchang was isolated and identified.2 pigment fractions showing similar UV-Vis and LC/MS characters were separated and purified,the characters of fraction 1 were identical to those of prodigiosin,while fraction 2 showed a special UV-Vis absorption spectrum that had not been reported.[Conclusion] A prodigiosin-producing Serratia marcescens strain NS-17 and its 2 pigment fractions were isolated.

Identification of Superoxide O2^- during KNO3-NaNO2-NaNO3 Salt by Electron UV-Vis Absorption Spectroscopy Thermal Decomposition of Molten Paramagnetic Resonance and

On account of excellent thermal physical properties, molten nitrates/nitrites salt has been widely employed in heat transfer and thermal storage industry, especially in concentrated solar power system. The thermal stability study of molten nitrate/nitrite salt is of great importance for this system, and the decomposition mechanism is the most complicated part of it. The oxide species O2^2- and O2^- were considered as intermediates in molten KNO3-NaNO3 while hard to been detected in high temperature molten salt due to their trace concentration and low stability. In this work, the homemade in situ high temperature UV- Vis instrument and a commercial electron paramagnetic resonance were utilized to supply evidence for the formation of superoxide during a slow decomposition process of heat transfer salt （HTS, 53 wt% KNO3/40 wt% NaNO2/7 wt% NaNO3）. It is found that the superoxide is more easily generated from molten NaNO2 compared to NaNO3, and it has an absorption band at 420-440 nm in HTS which red shifts as temperature increases. The band is assigned to charge-transfer transition in NaO2 or KO2, responsible for the yellow color of the molten nitrate/nitrite salt. Furthermore, the UV absorption bands of molten NaNO2 and NANO3 are also obtained and compared with that of HTS.

Adsorption properties of CFBC ash-cement pastes as compared with PCC fly ash-cement pastes

Circulating fluidized bed combustion （CFBC） ash can be potentially used as supplementary cementitious materials for concrete production due to its desirable pozzolanic activity. The adsorption properties of CFBC ash-cement pastes were studied, and ordinary pulverized coal combustion （PCC） fly ash-cement pastes were used as control. The water-adsorption and superplasticizer （SP）-adsorption properties of the pastes were evaluated by water demand and UV-visible absorption spectroscopy respectively. The results show that CFBC ash-cement system has greater compressive strength as compared with PCC fly ash-cement system at a given curing age, although the water demand of the former is significantly higher than that of the latter. CFBC ash-cement pastes possess higher adsorption ability of aliphatic SP than PCC fly ash-cement pastes and the adsorption amount increases with an increase in ash replacement ratio. CFBC ash- cement pastes exhibit lower workability with higher slump loss. It is concluded that CFBC ash can be potentially used as supplementary cementitious material in concrete production, but the mix design of CFBC ash concrete needs to be appropriately adjusted. It is suggested that CFBC ash is used for the production of the concrete needing low flowability.

Iron(Ⅱ) tetrasulfophthalocyanine mimetic enzymatic synthesis of conducting polyaniline in micellar system

Iron(Ⅱ) tetrasulfophthalocyanine(FeTSPc) ,as a novel mimetic enzyme of peroxidase,was used in the synthesis of a conducting polyaniline(PANI) /sodium dodecylsulfate(SDS) complex in SDS aqueous micellar solutions. The effects of pH,concentrations of aniline,SDS and H2O2,and reaction time on polymerization of aniline were studied in this case as shown by UV-Vis absorption spectroscopy. The results show that a wide range of pH(0.5-4.0) is required to produce the conducting PANI,and the optimal pH is 1.0 in SDS micelle. The optimal concentrations of aniline,SDS and H2O2 in feed,and reaction time in this case for the production of conducting PANI are respectively 10 mmol/L,10 mmol/L,25 mmol/L,and 15 h. FT-IR spectrum,elemental analysis,conductivity,cyclic voltammetry and thermogravimetric analysis confirm the thermal stability and electroactive form of PANI.

Kinetics Study on Reaction between Dihydroartemisinic Acid and Singlet Oxygen: An Essential Step to Photochemical Synthesis of Artemisinin

Artemisinin is an excellent antimalarial drug widely used in clinical medicine.However,due to the limitation of natural source of artemisinin,the chemical synthesis of artemisinin has achieved substantial attention.Dihydroartemisinic acid is a key precursor for the synthesis of artemisinin.The reaction of dihydroartemisinic acid with singlet oxygen to form peroxide is a pivotal step in the photochemical preparation of artemisinin.Nevertheless,the reaction kinetics of dihydroartemisinic acid with singlet oxygen has not been investigated previously.Herein,we report the rate constants of the reaction between dihydroartemisinic acid and singlet oxygen.By directly detecting the luminescence decay kinetics of singlet oxygen at 1270 nm at room temperature,the reaction rate constants of singlet oxygen and dihydroartemisinic acid in different solvents are obtained to be 1.81×10^5(mol/L)^-1·s^-1 in CCl4,5.69×10^5(mol/L)^-1·s^-1 in CH3CN,and 3.27×10^6(mol/L)^-1·s^-1 in DMSO,respec-tively.It is found that the reaction rate constants of dihydroartemisinic acid with singlet oxygen increase as polarity of the solvent increases among the three solvents.These results provide fundamental knowledge to optimize experiment conditions of photochemical synthesis of artemisinin for improving the yields of artemisinin.

Adsorption of Cationic Laser Dye onto Polymer/Surfactant Complex Film

Fabrication of complex molecular films of organic materials is one of the most important issues in modern nanoscience and nanotechnology. Soft materials with flexible properties have been given much attention and can be obtained through bottom up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and technologies. In this work, we report the successful incorporation of cationic laser dye rhodamine 6G abbreviated as R6G into the pre-assembled polyelectrolyte/surfactant complex film onto quartz substrate by electrostatic adsorption technique. Poly（allylamine hydrochloride） （PAH） was used as polycation and sodium dodecyl sulphate （SDS） was used as anionic surfactant. UV-Vis absorption spectroscopic characterization reveals the formation of only H-type aggregates of R6G in their aqueous solution and both H- and J-type aggregates in PAH/SDS/R6G complex layer-bylayber films as well as the adsorption kinetics of R6G onto the complex films. The ratio of the absorbance intensity of two aggregated bands in PAH/SDS/R6G complex fihns is merely independent of the concentration range of the SDS solution used to fabricate PAH/SDS complex self-assembled films. Atomic force microscopy reveals the formation of R6G aggregates in PAH/SDS/R6G complex films.

Reaction Kinetics between Thiobases and Singlet Oxygen Studied by Direct Detection of the 1O2 Luminescence Decay

Thiobase derivatives have received important investigations due to their wide usage as phototherapeutic agents and their potential carcinogenic side effects as immunosuppressants. The substitution of oxygen atom by the sulfur atom makes the ultraviolet absorption of thiobases redshifted and absorbs UVA light (>300 nm), resulting in unusual high quantum yield of triplet state to generate the singlet oxygen (1O2) through photosensitization. As a type of reactive oxygen species, 1O2 is highly reactive toward thiobases. Herein, we report the measurements of reaction rate constants between di erent thiobases and 1O2 in different solvents through the direct detection of 1O2 luminescence decay kinetics at 1270 nm. The rate constants of thiouracils with 1O2 are five times smaller than that of thioguanine with 1O2, which suggests that thiopurines are more reactive than thiopyrimidines and thus less suitable to be a photosensitive drug on the application of photodynamic therapy. Additionally, the rate constants of thiobases and 1O2 were found to be obviously influenced by the solvent polarity. With the increase of solvent polarity, the rate constants of thiobases and 1O2 decrease.

Spectroscopic Studies of the Interaction of Silver Nanoparticles with Methylene Blue

The interaction between silver nanoparticles and Methylene Blue （MB） is studied by UV-Vis spectroscopy and fluorescence spec- trometry. The UV-Vis absorption of the silver nanoparticles changes dramatically with the addition of MB. However, no obvious changes of absorption spectra of MB are observed when silver colloids are added into the MB solution. In the presence of surfactant SDS, the catalysis of the silver nanoparticles in the reduction of MB by sodium borohydride is exhibited by UV-Vis and fluorescence spectrosopy of MB displaying faster response compared with the absence of the silver nanoparticles. The results show that the activity of surfactant SDS modified silver nanoparticles is great and a strong physical adsorption to MB exists.

Optical Absorption and Refractive Index Study of Ti： Al2O3 Single Crystal

The optical absorption of Ti：Al2O3 single crystal has been measured at room temperature, in the wavelength region between 200 nm and 800 nm. The main absorption peaks at 491 nm and 562 nm, the weak infrared absorption band with a peak at 650 nm and the strong UV absorption band below 300 nm were observed. The refractive index is discussed by using Fresnel＇s equation. In particular, the Sellmeier equation was determined in the visible region by means on non-conventional method based on the measurement of refraction by using UV-visible spectroscopy. The refractive indices decreased from 3.71 to 1.28 with wavelength in the range 400-800 nm.

Aroma Properties of Selected Local Spices of Akwa Ibom State of Nigeria

Some famous local spices were selected to determine their potentials in terms of their aroma and utilization. They included Tea Bush （Ocimum basilicum）, Guinea Black Pepper （Piper guineense）, African Pepper （Xylopia aethiopica）, Alden Tree （Tetrapleura tetraptera） and the African Meg Nut or Onion Tree （Blighia unijugata）. Essential oils were extracted from the samples and used for aroma absorption test in a uv-visible spectrometer V2.03. The intensity of aroma was indicated at some peak values of absorption at particular wavelengths. The compounds responsible for the aroma at this peak values were identified by matching their wavelengths with those of known compounds at similar wavelengths of absorption. Thus, a compound such as Quinoline that has hot strong aroma and little bleaching effect was proved to be present in Guinea black pepper ;at the wavelength of 313.0 nm. Benzene with hot strong aroma and flammable effect was also indicated in this spice at the wavelength of 253.0 rim. Proximate analysis carried out showed that these spices have high nutritive values. Some of them such as Guinea black pepper, African Nutmeg and Ethiopian （African） pepper had high ether extract of 20.01, 25.97 and 31.25 respectively, and could be regarded as oil seeds, they contain much of essential oils.

Coumarin-derived azolyl ethanols:synthesis,antimicrobial evaluation and preliminary action mechanism

A series of coumarin-derived azolyl ethanols including imidazolyl,triazolyl,tetrazolyl,benzotriazolyl,thiol-imidazolyl and thiol-triazolyl ones were conveniently synthesized and characterized by IR,~1H NMR,^(13)C NMR and high-resolution mass spectra(HRMS) spectra.Some of the prepared compounds showed appropriate logP_(ow) values and effective antibacterial and antifungal activities.Noticeably,compound 14 with bis-triazolyl ethanol group exhibited low minimal inhibitory concentration(MIC)value of 8 μg/mL against MRSA,which was comparable or even superior to reference drugs Norfloxacin(MIC=8μg/mL)and Chloramphenicol(MIC=16μg/mL).It could also effectively inhibit the growth of the tested fungal strains compared to Fluconazole.Further binding studies of coumarin 14 with calf thymus DNA were investigated by UV-Vis absorption and fluorescence spectroscopy.It was found that compound 14 could interact with calf thymus DNA by groove binding to form14-DNA complex via both hydrogen bonds and van der Waals force,which might be the factor to exert the powerful antimicrobial activity.

Inorganic cesium lead halide CsPbX_3 nanowires for long-term stable solar cells

ABX3-type organic-inorganic hybrid halide perovskite materials have been recognized as promising candidates for optoelectronic applications. However, poor stability of organic-inorganic hybrid perovskite hinders their forward long-term utilization and hence an effective strategy is needed to replace the organic part with an inorganic cation. Herein, all inorganic CsPbI3 nanowires with a di- ameter of 50-100 nm are synthesized on fluorine-doped tin oxide glass via a simple solution-dipping process, which are further transformed into CsPbBr3 nanowires through a so- lution-phase halide exchange method. A phase change from non-perovskite to perovskite structure is observed during the ion substitution process of I- by Br-, which is elaborated by X-ray diffraction, absorption and photoluminescence spectra. We for the first time apply the as-formed CsPbI3 and CsPbBr3 nanowires into perovskite solar cells, yielding power conversion efficiency of 0.11% and 1.21%, respectively. The inorganic CsPbBr3 nanowire solar cell shows impressive sta- bility which still remains 99% of the initial power conversion efficiency even after 5500 h aging.

Synthesis of cell-penetrated nitrogen-doped carbon dots by hydrothermal treatment of eggplant sepals

Novel nitrogen doped carbon quantum dots were successfully fabricated by a hydrothermal method wxth eggplam sepals as carbon source. The carbon materials were characterized by transmission electron microscopy （TEM）, UV-Vis adsorption, Fourier-transformed infrared spectroscopy （FTIR）, fluorescence and the X-ray photoelectron spectroscopy （XPS） measurements, respectively. The carbon quantum dots showed excellent photoluminescence property with high stability in phosphate buffer solution with different pH values from 5 to 9, even in the cell culture medium supplied with the fetal bovine serum. Meanwhile, we also studied the interaction of carbon quantum dots with living HeLa cells with confocal microscopy. Our results indicated that the carbon quantum dots can enter the living HeLa cells by cellular penetration.

Investigation of nitroxoline-human serum albumin interactions by spectroscopic methods

Nitroxoline is a wide spectrum antibacterial and is one of the most important urinary antiseptics.The interaction between nitroxoline and human serum albumin(HSA)has been investigated systematically by fluorescence spectroscopy,synchronous fluorescence,three-dimensional fluorescence,CD spectroscopy and UV-Vis absorption spectroscopy.The results indicated that the quenching of HSA by nitroxoline was static.The corresponding thermodynamic parameters △H,△S and △G calculated according to van’t Hoff equation revealed that the intermolecular forces acting between nitroxoline and HSA were mainly hydrogen bonding and van der Waals forces.The conformational changes in the interaction were studied by synchronous fluorescence,CD spectroscopy and three-dimensional fluorescence spectra which showed changes in the microenvironment and conformation of HSA.