RESOLUTION OF MULTICOMPONENT FLUORESCENT MIXTURES BY ANALYSIS OF THE EXCITATION-EMISSION-FREQUENCY ARRAY

Fluorescence lifetime provides a third independent dimension of information for the resolution of totalluminescence spectra of multicomponent mixtures.The incorporation of this parameter into theexcitation-emission matrix(EEM)by the phase modulation technique results in a three-dimensionalexcitation-emission-frequency array (EEFA).Multicomponent analysis based on the three-dimensionalEEFA brings a qualitative change for the resolved spectra,i.e.individual spectra can be uniquely resolved,which is impossible with any two-dimensional analysis.In this paper we present a method for analyzingthe EEFA.We show mathematically that with the three-dimensional analysis of the EEFA individualspectra and lifetimes can be obtained.Our algorithm is developed in mathematical detail and isdemonstrated by its application to a two-component mixture.     

SHORT COMMUNICATION THE RELATIONSHIP OF CLOSURE,MEAN CENTERING AND MATRIX RANK INTERPRETATION

This paper describes an investigation into the relationship of closure,a baseline offset and mean centeringto the interpretation of matrix rank.The equivalence of a certain type of closure to a constant baseline(i.e.a simple numerical offset which may vary between response channels but is constant over all samples)is demonstrated.A systematic approach to the interpretation of the rank of a matrix is given.     

PRINCIPAL COMPONENT ANALYSIS APPLIED TO THE STUDY OF SUCCESSIVE COMPLEX FORMATION DATA IN CU(II)-ETHANOLAMINE SYSTEMS

Application of principal component analysis to Cu(II)-ethanolamine complex formation data is shown.Determination of the number of complex species is obtained from the rank of the matrix of spectral datausing either Gauss elimination or factorial analysis.Relevant information concerning species distributionversus pH is obtained from the plot of the signficant factors upsurging from the evolution of spectraltitration data.     

A weighted-averaging regression and calibration model for inferring lakewater salinity using chrysophycean stomatocysts from lakes in western Canada

Chrysophycean stomatocysts were identified and enumerated from the surface sediments of 60 lakes located on the Interior Plateau of British Columbia. The lakes span a salinity gradient from freshwater to hypersaline (0.0–92.4 g L^–1), with the majority being fresh to hyposaline. One hundred and ten stomatocyst morphotypes, almost all of which were previously described, were identified from the lake sediments. The first axis of direct gradient analysis, which was highly significant, was essentially a salinity axis (i.e. [Ca], [Mg], [K], [Na], [SO₄], [DIC], and [Cl]). Most cysts were found to have fairly broad tolerances, with the narrowest tolerances occurring among morphotypes with the lowest salinity optima. Weighted-averaging regression and calibration techniques were used to develop an inference model to measure the relationship between measured average lakewater salinity and stomatocyst inferred salinity (apparent r²=0.80). Simple weighted-averaging produced a model with a lower bootstrapped RMSE of prediction than weighted-averaging with tolerance downweighting. These data indicate that chrysophyte stomatocysts are useful quantitative indicators of past lakewater salinity (in the freshwater to hyposaline range) in B.C. lakes, and can be used to strengthen the interpretations from diatom-inference models already developed from the same region.     

两株极地真菌次级代谢产物的研究

采用硅胶柱层析、凝胶柱层析和HPLC等色谱技术,对极地真菌Articulospora sp.Z1-1和Penicilliumsp.S-1-10的发酵液提取物进行分离纯化,共得到9个化合物,通过理化性质及波谱学分析并与相关文献比对,确定化合物结构为3,7-二羟基-9-甲氧基-1-甲基-苯并[c]色烯-6-酮(1),1,4-二羟基甲苯(2),间羟基苄醇(3),对羟基苯乙醇(4),邻苯二甲酸二丁酯(5),1,7-二羟基-3-羟甲基-8-甲氧基-二苯并[b,e]氧杂卓-13,14-二酮(6),邻苯二甲酸二(2-乙基己)酯(7),4-十三烷基-苯甲醛(8)和(Z)-7-十四烯酸(9)。其中,化合物1—6首次从Articulospora sp.属真菌中获得,化合物8为新天然产物。化合物1和4被证明具有抑制稻瘟霉的作用,化合物2有较好的抗菌和细胞毒活性,化合物3有较强的抗氧化活性。     

Li2SO4溶液中离子间的缔合相互作用:基于密度泛函理论和分子动力学模拟的研究

基于密度泛函理论,使用B3LYP/aVDZ方法对[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇的结构和性质进行了系统地研究,并结合Car-Parrinello分子动力学(CPMD)模拟了不同浓度的Li_2SO_4溶液结构,目的在于理解在Li_2SO_4溶液中离子间缔合相互作用及可能存在的物种。研究发现,对于[Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇,双配位单齿螯合接触离子对结构比双配位双齿螯合接触离子对结构更稳定,溶剂共享离子对结构最不稳定。同时,CPMD模拟结果表明,在3.09和3.17 mol/kg的Li_2SO_4溶液中,双配位单齿螯合接触离子对结构仍然是主要物种。以上结果表明在饱和的Li_2SO_4溶液(3.16 mol/kg)中,Li~+和SO_4~(2-)离子间的相互缔合作用主要以双配位单齿螯合接触离子对结构的物种存在,而具有双配位双齿螯合离子对结构的物种占少数,溶剂共享离子对结构几乎不存在。     

样方形状对空间点格局的性能影响分析——以天目山阔叶林为例

利用浙西天目山常绿阔叶林样地调查数据,在随机样方点格局分析基础上,提出样方形状对点格局分析性能影响差异性问题。结果表明:(1)在最优样方面积相同条件下,通过配对t检验得出圆形与正方形、圆形与正六边形和正方形与正六边形样方性能对比的配对t检验概率P分别为0.249、0.043和0.023,表明样方形状对点格局分析性能影响具有差异性,圆形样方和正方形样方之间没有显著差异,正六边形样方与圆形样方、正方形样方之间差异显著;(2)圆形～正六边形和正方形～正六边形样方间VMR差值的95%置信区间分别为[-0.429,-0.010]和[-0.196,-0.021],其区间值上界均小于0,表明正六边形样方分析性能为最优,其性能高于圆形样方和正方形样方;(3)随机样方法在样本量较小时,点格局分析结果不稳定,但随着采样数目逐步增大到90以上时,其VMR值和P值趋于稳定。     

TENSORIAL RESOLUTION:A DIRECT TRILINEAR DECOMPOSITION

Modern instrumentation in chemistry routinely generates two-dimensional(second-order)arrays of data.Considering that most analyses need to compare several samples,the analyst ends up with a three-dimensional(third-order)array which is difficult to visualize or interpret with the conventional statisticaltools.Some of these data arrays follow the so-called trilinear model,(?)These trilinear arrays of data are known to have unique factor analysis decompositions which correspondto the true physical factors that form the data,i.e.given the array (?),a unique solution can be found inmany cases for each order X,Y and Z.This is in contrast to the well-known second-order bilinear datafactor analysis,where the abstract solutions obtained are not unique and at best cannot be easilycompared with the underlying physical factors owing to a rotational ambiguity.Trilinear decompositions have had the disadvantage,however,that a non-linear optimization withmany parameters is necessary to reach a least-squares solution.This paper will introduce a method forreducing the problem to a rectangular generalized eigenvalue-eigenvector equation where the eigenbectorsare the contravariant form(pseudo-inverse)of the actual factors.It is shown that the method works wellwhen the factors are linearly independent in at least two orders(e.g.X_(jr),and Y_(jr) are full rank matrices).Finally,it is shown how trilinear decompositions relate to multicomponent calibration,curve resolutionand chemical analysis.     

K2B4O7和KBO2溶液pH和拉曼光谱研究

用合成的水合四硼酸钾和偏硼酸钾晶体,配制一系列溶液,研究了pH与浓度变化的关系,并计算硼酸根离子的摩尔分数-浓度(δ-c)关系图。用拉曼光谱方法研究四硼酸钾和偏硼酸钾溶液,给出其拉曼光谱图,并对各峰进行了归属。研究表明,四硼酸钾溶液中存在的物种主要有[B4O5(OH)4]2-、[B3O3(OH)4]-和[B(OH)4]-,而其它物种所占摩尔分数很小;在偏硼酸钾水溶液中,[B(OH)4]-占绝大多数,有很少量H3BO3、[B4O5(OH)4]2-和[B3O3(OH)4]3-。硼酸盐离子浓度越低,越容易水解为聚合度较低的简单物种。     

用差示FT—Raman和^11B NMR光谱学研究四硼酸锂水溶液的结构

用差示 FT- Raman和 1 1 B NMR光谱学研究了四硼酸锂过饱和溶液的结构机理 ,结果表明硼酸盐过饱和溶液中存在的粒子有 :B(OH) 3、B(OH) 4- 、B3O3(OH) 4- 、B4O5 (OH ) 42 - 和 B5 O6 (OH) 4- ,其结构机理类似于四硼酸锂饱和溶液和其他碱金属四硼酸盐溶液的结构机理     

Demographic response to rural restructuring and counterurbanisation in South Australia, 1981-1991

"Using South Australia as a case study, this paper seeks to trace and demonstrate two processes (counterurbanisation and rural restructuring) whose effects overlap to differentiate and characterise the population geography of...two zones, separated by a transition along the outer fringe of Adelaide's urban field.... In the demographic core zone [rural restructuring] has been partly offset by continued counterurbanisation, resulting in demographic mixing and rural dilution. The 1981-91 population growth in rural communities is shown to be more a function of population density at the outset of the period than of initial population size. Demographic growth...is shown to conform to a simple unidimensional scale, allowing the production of a clear, easily interpretable typology of rural demographic change with few non-conforming statistical areas. At a local level within individual rural communities, demographic decline is shown to be accompanied by increased concentration of the population into small towns, while demographic growth is associated with deconcentration."     

CHARACTERIZATION OF THE EFFECT OF PEAK SHIFTS ON THE PERFORMANCE OF THE KALMAN FILTER IN MULTICOMPONENT ANALYSES

The effect of peak shifts on the performance of a Kalman filter multicomponent analysis algorithm hasbeen investigated.A series of Gaussian test systems were employed to characterize the concentrationestimation errors and the morphology of the on-line residuals(the innovations sequence).Both forwardand reverse filters were used in the generation of the innovations sequences.It was found that thedifference between the forward and reverse innovations sequences gave an accurate indication of thedirection and magnitude of the peak shift.A series of overlapped two-component systems were alsoinvestigated.Again,a correlation between the difference innovations and the degree of the responseshift was observed.The behavior of the Katman filter in fitting the shifted fluorescence emissionspectrum of benzo[a]pyrene was also examined.The response for henzo[a]pyrene in cyclohexanesolution was compared to that obtained on the surface of a reversed phase thin layer chromatographyplate.A red shift of 4 nm was detected for the surface spectrum by observing the difference innovationssequence.This approach holds promise for correction of response shifts in multicomponent systems.     

滇西北亚高山草甸退化梯度上马蹄黄地上形态特征变化

马蹄黄(Spenceria ramalana)是滇西北亚高山草甸的旅游景观资源,其地上形态特征随草甸退化梯度的变化趋势尚少见报道。于2018年7月在香格里拉市调查、对比了3个退化梯度(一级退化,DI;二级退化,DII;无退化对照,CK)上马蹄黄的植株高度、展度、叶片数量、叶片长度、叶片宽度、叶面积、叶片长宽比和生存状态。结果表明:(1)与CK相比,DI和DII梯度上马蹄黄的植株高度、展度、叶片数量、叶片长度、叶片宽度和叶面积均显著减小(P<0.05);(2)DII梯度上马蹄黄的叶片长度、叶片宽度和叶面积显著高于DI梯度(P<0.05);(3)CK、DI和DII中马蹄黄的叶片长宽比分别为3.5±0.3、2.9±0.4和2.3±0.1,叶片形状由倒披针形向倒卵形过渡;(4)DI、DII和CK中马蹄黄的生存状态指数分别是0.12、0.23和0.63。     

RANK-ORDER ANALYSIS FOR ROBUST MULTIRESPONSE,MULTIBLOCK COMPARISONS:EVALUATION OF HERBICIDE INTERACTIONS

Studies of interactions among bioactive compounds are often difficult to interpret unambiguously.A priori assumptions about the nature of such interactions can seriously distort analysis of the data.Byapplying a rank order analysis appropriate to the naturally ordinal scale of response to xenobiotic insult,several co-herbicides were successfully identified from among numerous candidates in an experimentinvolving multiple blocks,rates and species.Moreover,underlying herbicide interactions weresubstantiated and identified which were not apparent by more traditional parametric analysis.     

非晶态镍硼酸盐的制备和表征

由摩尔比分别为1:2和1:8的六水氯化镍和硼砂反应得到两种镍硼酸盐样品1.25NiO·B_2O_3·4.5H_2O和NiO·B_2O_3·3.1H_2O。用XRD、TG-DSC、FT-IR和Raman等实验方法对其进行表征,样品为非晶态,确定了样品中的阴离子等,并结合化学分析结果近似确定了上述两种非晶态镍硼酸盐样品的结构组成式,前者为三元复盐,结构式为Ni[B_3O_3(OH)_5]·0.5Ni[B_2O(OH)_6]·Ni(OH)_2·4H_2O,后者结构式为Ni[B_2O(OH)_6]。     

Microstructure of NiSO4 Solution:A Combined DFT and EXAFS Study

The microhydration structure of nickel sulfate aqueous solution has been determined via density functional theory( DFT) calculation and extended X-ray absorption fine structure( EXAFS) spectroscopy. The geometric optimization and energy calculation of nickel sulfate hydrated clusters of the molecular formula [NiSO_4( H_2 O)_n]~0( n = 1-12) were determined via DFT using the B3 LYP method. Several possible initial structures were considered for clusters of each size to locate the equilibrium geometry.Based on the DFT calculation,the favorable structure of Ni~(2+)includes the six-coordinated form of [NiSO_4( H_2 O)_n]~0 clusters. The results of hydration energy calculation suggest that the six-coordinated contact ion pair( CIP) is the stable configuration for small hydration clusters( n≤5),while the solventshared ion pair( SSIP) represents the favorable structure for medium hydration clusters( 6≤n≤10).The solvent is separated by x water molecules( xSIP,x ≥2 is the number of water molecule between Ni~(2+)and SO_4~(2-)) in larger hydration clusters( n≥11). The EXAFS analysis of the NiSO_4 aqueous solutions and NiSO_4·6 H_2 O solid established that Ni~(2+)was surrounded by six water molecules tightly forming an octahedral structure in the first hydration shell,and no CIP was found from 0. 70 mol/L to 2. 22 mol/L( near saturation). The Ni-O distance and coordinated number were 2. 040 ± 0. 020 ? and 6. 0 ± 1. 0,respectively. These results are consistent with the DFT calculations for [NiSO_4( H_2 O)_n]~0 clusters. DFT and EXAFS are powerful techniques that can be used to enhance the resolution of NiSO_4 solution microstructure.     

祁连山大野口流域青海云杉种群结构和空间分布格局

青海云杉（Picea crassifolia）是祁连山亚高寒山地森林植被的建群种之一。应用“相邻格子法”获得100 m×100 m样方内所有个体的调查资料,采用种群动态和胸径、树高和冠幅级频率分布及6种聚集强度指数分析了青海云杉的种群结构和空间分布格局。结果表明：（1）青海云杉种群动态分析表明,种群表现为增长型种群。（2）青海云杉种群胸径级频率分布呈“倒J”型,胸径级随个体数的变化符合对数方程y=-219.32ln(x)+482.67(R²=0.963 8,P＜0.01),胸径分异指数为0.48,种群个体胸径差异属明显分异;树高级频率分布呈“间歇”型,不同高度级与个体数之间可用二次方程y=0.795x²-31.23x+285.1(R²=0.603,P＜0.01)进行较好的描述,树高分异指数为0.55,高度差异属明显分异;胸径和树高两者之间符合对数方程y=5.912ln(x)-4.249 3(R²=0.603,P＜0.01);冠幅级与个体数之间可用三次方程y=5.317 6x³ -91.759x²+408.88x-173.87(R²=0.8355,P＜0.01)进行很好的拟合[WTBZ],冠幅分异指数为0.53,种群个体冠幅差异亦属明显分异。总体上看,青海云杉幼苗较为丰富,天然更新能力强,目前表现为成熟稳定型种群。（3）在空间分布格局上,青海云杉种群空间分布格局呈斑块状聚集分布,其扩散系数、丛生指标、聚块性指数、平均拥挤度指数、负二项式分布参数、Cassie指标分别为1.162、2.285、0.162、85.802、1.002和0.026。在不同发育阶段的分布格局有所差异,Ⅰ级幼苗和Ⅱ级幼苗为聚集分布,小树、中树和大树为均匀分布,随着龄级的增大,种群的聚集程度减小,即由聚集分布变为均匀分布,该种群表现出明显的扩散趋势。研究结果可为青海云杉的管理和经营提供理论依据。     

DETERMINATION OF A MULTIVARIATE DETECTION LIMIT AND LOCAL CHEMICAL RANK BY DESIGNING A NON-PARAMETRIC TEST FROM THE ZERO-COMPONENT REGIONS

In this paper we redefine the term detection limit to embrace the inherent multivariate nature of samples,instrumental measurements and chemometrics resolution procedures. The so-called zero-componentregions, i.e. parts with no chemical components eluting, are used as repeated analytical blanks to estimatea statistical multivariate detection limit for determining the number of chemical species in local regionsof a single two-way chromatogram or a collection of synchronized one-way chromatograms. For two-waychromatography the detection limit is determined from the distribution of the first eigenvalues obtainedfrom all possible combinations of spectra in the zero-component regions. The number of spectra in eachcalculation should correspond to the number included in the later examination of the local retention timeregions. For one-way chromatography on a collection of samples with similar chemical components atvarying concentrations the same procedure is used, with the samples taking the role of the spectra intwo-way chromatography. The detection limit can be chosen at various confidence levels depending onwhether false positive or negative detection of minor components is most critical. The results obtainedfrom the zero-eigenvalue distribution are more robust than those obtained by a previously developedF-test.     

FACTOR ANALYSIS OF A SIMULATED DATA MATRIX INVOLVING AQUEOUS COMPLEX EQUILIBRIA

Abstract factor analyses were performed on databases consisting of simulated samples from aqueousequilbria.The program COMPLEX was used to generate equilibrium species in a system of three reactantmetals and five reactant bases.Reactant concentrations and pH were drawn from random-normaldistributions so that sample data vectors comprised a multivariate log-normal distribution of equilibriumconcentrations.In addition,sample groups were created containing different distributions for pH andreactant concentrations.Equilibrium species were shown to contain variance contributed by change in pH among samples aswell as change in reactant concentrations.Factor modelling revealed the qualitative relationships amongthe species and how the relationships change with pH.Factors also revealed those reactants containingvariance in the data matrix.In some cases,reactant variance obscured relationships between pH and theequilibrium species.Since factor modelling of a simulated data matrix revealed the expected chemical equilibriuminteractions,a potentially powerful tool exists for investigating the effects of outliers and error.     

城市体系时空演化的广义维数分析——刻划城市资源分享空间的理论基础、计算方法与应用实例

根据城市组成元素和城市体系构成要素的异速生长性质发展了一套城市体系时空演化的广义维数分析方法。只要城市和城市体系满足异速生长或准异速生长关系,就可以据之建立基于广义维数比值的分享系数矩阵,通过矩阵的特征向量计算出城市元素和各个城市在某种测度下的相对发展速度权重,进而利用先前的结果算出综合权重数值。将有关数值予以适当的处理可以揭示城市体系时空演化的复杂动态,从而借之实现城市体系的功能调控和结构优化。本方法的数学处理过程与Saaty的递阶分析方法(AHP)异曲同工,但其理论前提、建模技巧和应用方向等等都与后者具有严格的本质性区别。