特征谱区筛选在多元混合物的太赫兹光谱定量分析中的应用

用特征谱区筛选法结合太赫兹时域光谱(THz-TDS)技术对多元混合物成分含量进行了定量分析研究。实验利用太赫兹时域光谱系统测量了由乳糖一水合物(LAC)、对乙酰氨基酚(APAP)、可溶性淀粉(starch)以及微晶纤维素(MCC)四种材料组成的混合物样品的太赫兹吸收光谱,并分别尝试采用常规区间偏最小二乘(iPLS)、向后区间偏最小二乘(biPLS)、联合区间偏最小二乘(siPLS)和移动窗口偏最小二乘(mwPLS)四种特征谱区筛选法对多元混合物的太赫兹吸收光谱进行特征子区间优选,建立了太赫兹吸收谱与四元混合物中乳糖一水合物含量之间的定量回归模型。通过比较四种谱区筛选算法模型及全光谱偏最小二乘(PLS)模型所得结果,表明采用移动窗口偏最小二乘法建立的谱区筛选模型得到的结果相对最优,其交互验证均方根误差(RMSECV)、预测均方根误差(RMSEP)、校正集相关系数(R_C)和预测集相关系数(R_P)分别为0.980 3,1.114 1,0.996 0和0.995 1。实验结果表明,采用特征谱区筛选方法可以有效选择多元混合物太赫兹吸收光谱的特征区间,提高模型精度和降低模型复杂性,为实现多元混合物成分含量的快速检测提供了一种有效的方法。     

基于植被光谱监测喀斯特异质性生境可行性研究

选取喀斯特与非喀斯特典型植被及共生植被,基于植被光谱分析和典范对应分析(CCA)探讨喀斯特植被光谱与喀斯特生境的关系。结果表明：在可见光波段范围(400～680 nm)的一阶导数光谱和短波红外波段(1 300～2 500 nm)的反射率光谱,喀斯特与非喀斯特植被光谱具有显著的差异特征;土壤水分含量和钙含量对喀斯特植被光谱特征具有较大影响,CCA二维排序图能够成功地将喀斯特植被与非喀斯特植被区分开。研究表明植被光谱特征与其生境条件密切相关,基于植被光谱特征来监测喀斯特异质性生境是可能的。     

On self-organized shell formation by bovine carbonic anhydrase II, and soluble protein extracted from regenerated shell

The soluble protein of hemocytes from diseased shell (HDS) of oyster, Crassostrea gigas, was shown to play a key role in the rapid growth of calcium carbonate crystals. In this study, we compared HDS extracted from regenerated (or diseased) shell with bovine carbonic anhydrase II in terms of their ability to promote the growth of calcium carbonate crystals. On the basis of scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) analysis, a high growth rate of calcium carbonate crystals was identified under artificial seawater and atmospheric temperature. The function and role of HDS extracted from regenerated shell are discussed at the molecular point as compared to aragonite-specific soluble proteins. Our findings suggest that hemocytes function as a soluble protein, with repeated GX (G: Gly, X: Asp, Asn or Glu) or negative charged amino acid domains binding calcium and specific surface features for catalyzing rapid shell regeneration.     

碳酸钙在水溶性甲壳素溶液中的结晶行为

依据生物矿化基本原理,以甲壳素作为有机基质,探讨了在不同浓度甲壳素溶液中CaCO3晶体的生长情况;同时研究了生长体系的pH值和温度对生成CaCO₃晶体的影响。通过傅里叶红外光谱、扫描电子显微镜进行表征的结果表明,甲壳素溶液中形成的CaCO₃晶体完全不同于纯水中形成的晶体;而且甲壳素溶液的浓度不同,形成的CaCO₃晶体的晶型也有较大差别。在CaCO₃结晶过程中,CaCO₃对甲壳素也有影响,即晶体与甲壳素之间存在相互作用。     

利用光谱吸收深度定量反演碳酸盐矿物的影响因素及应用分析

光谱吸收特征是矿物识别与定量反演的重要指标。为提高利用光谱吸收特征定量反演矿物精度,以方解石为代表,以线性混合光谱模型与连续统去除方法为基础,以连续统去除吸收深度(CRBD)为分析对象,按端元光谱在2.33 μm附近有无吸收特征对光谱进行分类,并分析每类数据与方解石混合光谱CRBD随丰度、反射率以及光谱特征等影响因素的变化规律,进而非线性拟合其变化范围并提出一种新的矿物含量表示方法。研究结果表明,端元丰度对CRBD值影响较大,方解石丰度越大,吸收特征越明显,CRBD值越大。同样,混合端元反射率与光谱特征对混合光谱CRBD值影响也较明显,当混合端元光谱在2.33 μm附近为无特征时,端元光谱反射率越小,CRBD随碳酸盐丰度变化上凸越明显,为反射峰特征时,端元光谱反射率越大,下凹越明显;混合端元在2.33 μm附近为吸收谷特征时,CRBD随碳酸盐丰度接近线性变化。通过交叉分析与多端元混合光谱CRBD变化分析发现,混合光谱CRBD随碳酸盐矿物丰度及混合端元反射率变化受限于一定范围,其上限拟合方程满足指数函数变化,下限拟合方程为三次多项式函数,且拟合精度较高,R2均高于0.99,RMSE低于0.005。为实现矿物含量的精确预测,根据拟合方程提出一种以变化范围替代定量值来表示碳酸盐矿物丰度分布的方法,实现碳酸盐矿物含量反演的范围表示。通过影响因素分析及范围表示法可为矿产监测、定量评估等提供新的表达方法,为建立具有普适性的地物定量反演模型提供理论参考。     

Nonlinear joint fractional Fourier transform correlation for target detection in hyperspectral image

In this paper, we present a spectral joint fractional Fourier transform correlation (SJFRTC) for detecting and identifying very small target with only a few pixels using reflectance spectral information in the hyperspectral imagery. In this technique, fractional correlation (FC) between input spectral signature and known reference spectral signature is performed digitally or optically. Binary differential technique is utilized to enhance the performance of the SJFRTC, resulting in delta-function-like correlation peaks without dc interference. Distinctive and distinguishable correlation performance is obtained using peak-to-clutter ratio (PCR) instead of absolute correlation peak value, which makes the proposed technique independent from the intensity variation of the spectral signature. Simulation results using real-life hyperspectral images show that the binary SJFRTC can detect both single or/and multiple targets successfully with excellent detection capability, as compared to the other traditional hyperspectral detection algorithms.     

Experimental and theoretical investigations of absorbance spectra for edge-plasma monitoring in fusion reactors

This present paper deals with the spectral characterization of dusty plasmas such as those produced during ITER fusion experiments. Such plasma formed in a small radio frequency plasma reactor with acetylene was characterized using in situ Fourier transform infrared (FTIR) absorption spectroscopy and laser scattering, and ex situ transmission electron microscopy (TEM). The plasma absorbance spectra thus obtained in the visible and infrared wavelengths exhibit special features associated with the dust particle growth which absorbs and scatters IR light. This experimental absorbance behavior is reproduced using a dedicated radiation modeling based on the Mie theory and the Monte Carlo simulation. The bimodal distribution assumed for particle sizes brings the model-determined optical properties closer to the experimental dust absorbance than the normal and uniform distributions. Dust formation mechanism is further discussed comparing the experimental and simulated absorbance.     

Generalized biaxial shearing of MQMAS NMR spectra

Two dimensional multiple quantum (MQ) MAS NMR experiments have become popular due to the wide applicability of this technique to structural questions in materials science, the abundance of half-integer spin nuclei in the periodic table, and the ease of implementation on typical solid state NMR instruments. In spite of the high-resolution theoretically possible from such experiments, the homogeneous and inhomogeneous broadening factors inherent in many samples of interest can make spectral analysis challenging. We present several possible spectral shearing schemes that may be useful for spectral analysis, and in particular we introduce shearing in the directly detected dimension. We suggest that for amorphous or disordered samples that give broad spectral features, shearing may be used as a general tool for optimal positioning of these features relative to one another and for the characterization of isotropic chemical and quadrupolar shifts.     

Absorptivity of nitric oxide in the fundamental vibrational band

From observations of the spectral absorbance of mixtures of nitric oxide in nitrogen at room temperature, we derive an integrated absorptivity for the NO fundamental band of 137.3±4.6 cm^-2 atm^-1 at 0°C. The indicated uncertainty is the estimated maximum error.     

Emission spectra simulation of calcium plasmas in non-local thermodynamic equilibrium

We use previous high-quality experimental spectra to test the accuracy of atomic data and the validity of the collisional－radiative (CR) model used in this paper. The synthetic spectrum with electron temperature log T_e(K)=6.745 and electron density n_e=6.0×10^{13}cm^{-3}, which almost reproduces the experimental spectra, is presented. Nearly all the features of the experimental spectra were identified. The results of the CR modelling for the emission spectra of calcium plasmas all agree well with the measured spectral line intensities within the experimental error for most of the lines. Furthermore, we make the electron temperature diagnostic through the synthetic spectrum and population fractions of every ionization state as a function of charge state at different electron temperatures, as well as the electron density diagnostic through the intensity ratios of two lines of Be-like calcium and three lines of C-like calcium. A good agreement between the calculated values and the measured ones is found.     

Hydrophobic Interactions in Donor-Disulphide-Acceptor (DSSA) Probes Looking Beyond Fluorescence Resonance Energy Transfer Theory

Donor –linker –acceptor (DSSA) is a concept in fluorescence chemistry with acceptor being a fluorescent compound (FRET) or quencher. The DSSA probes used to measure thiol levels in vitro and in vivo. The reduction potential of these dyes are in the range of ?0.60 V, much lower than the best thiol reductant reported in literature, the DTT (?0.33 V). DSSA disulphide having an unusually low reduction potential compared to the typical thiol reductants is a puzzle. Secondly, DSSA probes have a cyclized rhodamine ring as acceptor which does not have any spectral overlap with fluorescein, but quenches its absorbance and fluorescence. To understand the structural features of DSSA probes, we have synthesized DSSANa and DSSAOr. The calculated reduction potential of these dyes suggest that DSSA probes have an alternate mechanism from the FRET based quenching, namely hydrophobic interaction or dye to dye quenching. The standard reduction potential change with increasing complexity and steric hindrance of the molecule is small, suggesting that ultra- low Eo’ has no contribution from the disulphide linker and is based on structural interactions between fluorescein and cyclized rhodamine. Our results help to understand the DSSA probe quenching mechanism and provide ways to design fluorescent probes.     

东北黑土的光谱特性及其与土壤参数的相关性分析

选取我国东北黑土作为研究对象,研究其光谱特性并分析黑土主要参数与近红外光谱的相关性。通过比较东北黑土和北方潮土光谱特征的差异,显示当水分含量较高时,两种土壤的光谱特性差别不是很明显,当水分含量较低时,受土壤质地的影响,两种土壤的吸光度光谱及微分光谱均有很大差异。土壤水分值和吸收光谱有很大相关系数,土壤全氮与光谱呈现出了一定的相关性,提高土样全氮含量的方差,可以获得高的相关系数;由于黑土中有机质的含量很高,使基于土壤有机质的光谱吸收达到饱和,二者之间呈现较低的相关性。     

中药重楼及其伪品开口箭的FTIR分析与鉴别

本文采用傅里叶变换红外光谱方法(FTIR)对中药材重楼及其伪品开口箭的红外光谱进行了测试及对比分析。研究表明,重楼和开口箭各自有其独特的红外光谱特征,二者各自所包含的红外吸收峰的峰位明显不同,二者的红外光谱的峰形整体上有非常明显的区别,特别是在1650cm-1处及1405～1258cm-1范围这两个地方二者的峰形有非常明显的区别。采用傅里叶变换红外光谱方法可对重楼及其伪品开口箭加以鉴别和区分。     

Free radical EPR spectroscopy analysis using blind source separation

In this paper, we propose a novel approach for electron paramagnetic resonance (EPR) mixture spectra analysis based on blind source separation (BSS) technique. EPR spectrum of a free radical is often superimposed by overlapping spectra of other species. It is important and challenging to accurately identify and quantify the 'pure' spectra from such mixtures. In this study, an automated BSS method implementing independent component analysis is used to extract the components from mixed EPR spectra that contain overlapping components of different paramagnetic centers. To apply this method, there is no requirement to know the component spectra or the number of components in advance. The method is applied to analyze free radical EPR spectra which are collected from standard chemical system, cultured cell suspense, and ex vivo rat kidneys by spin trapping EPR technique. Results show that the BSS method proposed here is capable of identifying the component EPR spectra from mixtures with unknown compositions. The BSS technique can offer powerful aids in resolving spectral overlapping problems in general EPR spectroscopy analysis.     

基于中红外光谱分析的微水对绝缘油电气性能影响研究

微量水分对绝缘油的介质损耗因数、电阻率等电气性能指标有明显的影响,探讨绝缘油受微量水分的影响规律,对于采取有效措施监控绝缘油的运行状态具有重要意义。首先对配制不同微水含量的绝缘油经过超声波振荡8h后再进行显微图像观察,得到该油水分散系中游离水和乳化水相对均匀程度在25 min内其分散状态较为稳定;在此基础上对油水分散系的介质损耗因数、电阻率指标进行了实验测试,得到了微水对绝缘油的电气性能指标的影响规律;然后对不同微水含量的绝缘油进行中红外光谱分析,得到不同微水含量的绝缘油在1 640,3 400,3 450,3 615 cm-1波数处的吸光度值。结合绝缘油中红外光谱分析的吸光度值变化以及实验测试结果表明油样在1 640,3 400,3 450,3 615 cm-1水分的特征波数处吸光度值数据随水分含量不同而产生明显变化,且吸光度值与水分含量的皮尔逊相关系数分别为0.964 1,0.984 8,0.984 5,0.944 0,油样中水分在相应特征波数处的吸光度值能够较好的反映出油样中水分含量的变化趋势;微水对绝缘油介质损耗因数的影响和水分子在3 400和3 450 cm-1特征波数处的吸光度值变化趋势之间的相关系数较大,分别为0.860 6和0.863 6;微水对绝缘油介质损耗因数的影响和水分子在1 640和3 615 cm-1特征波数处的吸光度值变化趋势之间的相关系数分别为-0.931 5和-0.9680,从而为绝缘油中微水的监测奠定了前期研究基础。     

改善光源光谱特性提高光学多道分析器用于吸收光谱测量的信噪比

本文报道通过改善热辐射光源光谱特性,相对提高短波辐射光强,以提高ＣＣＤ光学多道分析器在可见区特别是短波段吸收光谱的信噪比。改善后光源的短波辐射信噪比比一般热辐射光源提高约８倍。实验证实用此光源易在整个可见光区得到高信噪比的吸收光谱曲线。     

Validation of TPEN as a Zinc Chelator in Fluorescence Probing of Calcium in Cells with the Indicator Fura-2

Fura-2 is widely used as a fluorescent probe to monitor dynamic changes in cytosolic free calcium in cells, where Ca²⁺ can enter through several types of voltage-operated or ligand-gated channels. However, Fura-2 is also sensitive to other metal ions, such as zinc, which may be involved in ionic channels and receptors. There is interest, in particular, in studying the synapses between mossy fibers and CA3 pyramidal cells which contain both calcium and high quantities of free or loosely bound zinc. We have found, through fluorescence probing, that endogenous zinc inhibits mossy fiber calcium transients. However, since these results might be explained by an effect of the zinc chelator N,N,N’,N’-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) on the spectral properties of Fura-2, we have carried out a validation of the method through fluorescence excitation spectra of the complex Fura-2/calcium, and show that TPEN does not affect these spectra. This supports the idea that the observed calcium enhancement is related to a zinc inhibition of presynaptic calcium mechanisms, and confirms the use of the chelator TPEN as a general procedure for the biophysical study of Ca(II) in the presence of Zn(II) using Fura-2.     

Investigation of inter-molecular hydrogen bonding in the binary mixture (acetone + water) by concentration dependent Raman study and ab initio calculations

This paper reports that vibrational spectroscopic analysis on hydrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6-311+G(d,p) basis set. Changes in wavenumber position and linewidth (fullwidth at half maximum) have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.     

Integration approach for developing a high-performance biointerface: Sequential formation of hydroxyapatite and calcium carbonate by an improved alternate soaking process

Biointerfaces are crucial for regulating biofunctions. An effective method of producing new biomaterials is surface modification, in particular, the hybrid organic-inorganic approach. In this paper, we propose a method for the sequential formation of hydroxyapatite and calcium carbonate on porous polyester membranes by using an improved alternate soaking process. The resulting hybrid membranes were characterized in terms of their calcium and phosphorus ion contents; further, their structure was analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), and infrared spectroscopy (IR). As a typical biofunction, protein adsorption by these hybrid membranes was investigated. Sequential hydroxyapatite and calcium carbonate formation on the membranes was successfully achieved, and the total amounts of hydroxyapatite and calcium carbonate formed were precisely regulated by the preparative conditions. The SEM and XRD characterizations were verified by comparing with the IR results. The amount of adsorbed protein correlated well with not only the amount of hydroxyapatite formed but also the combined amounts of hydroxyapatite and calcium carbonate formed. The results indicate that the hybrid membranes can function as high-performance biointerfaces that are capable of loading biomolecules such as proteins.     

Density functional theory calculations for ethylene carbonate-based binary electrolyte mixtures in lithium ion batteries

The density functional theory (DFT) calculations have been performed to investigate the interaction of Li⁺ with various organic solvents widely used as Li ion rechargeable battery electrolytes such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC); and their EC-based binary mixtures at the level of B3LYP/6-31G (d). The interaction of Li⁺ with these solvents has been calculated in terms of electronic structures of clusters of the mixtures of organic solvents including a lithium ion. The main objective of our investigation is to help in understanding a stable and enhancing ionic transfer at graphite/electrolyte interface assisted by the mixtures of the solvents. The calculated results favor the stability of EC-based binary mixtures and high EC-content binary mixture systems. In infrared (IR) vibrational spectra, the IR active modes of the solvent show significant changes due to the cation-solvent interaction.