小波变换方法的比较──红外光谱数据压缩

介绍了小波变换和多分辨分析的基本理论以及常用小波变换压缩数据的3种方法:(1)只保留模糊信号;(2)全部保留模糊信号及锐化信号中的较大值;(3)保留模糊信号及锐化信号中的较大值.将紧支集小波和正交三次B-样条小波压缩4-苯乙炔基-邻苯二甲酸酐的红外光谱数据进行了对比,计算表明正交三次B-样条小波变换方法效果较好,而在全部保留模糊信号及只保留锐化信号中数值较大的系数时,压缩比大而重建光谱数据与原始光谱数据间的均方差较小.     

离散小波变换-遗传算法-交互检验法用于近红外光谱数据的高倍压缩与变量筛选

用遗传算法(GA)与交互检验(CV)相结合建立了一种用于对近红外光谱(NIR)数据及其离散小波变换(DWT)系数进行变量筛选的方法，并应用于烟草样品中总挥发碱和总氮的同时测定。结果表明：NIR数据经DWT压缩为原始大小的3．3％时基本没有光谱信息的丢失；有效的变量筛选可以极大地减少模型中的变量个数，降低模型的复杂程度，改善预测的准确度。     

自适应小波算法用于近红外光谱的多元校正

实现了一种构建自适应小波滤波器的方法,并将其用于近红外光谱数据的多元校正。该方法根据一定的目标函数,针对信号的特性自适应地构造小波滤波器。用该法构建的滤波器对烟草样品的近红外光谱进行压缩,并将压缩后的数据采用偏最小二乘法建模,实现了烟草样品常规组分的定量分析。     

小波包压缩-RBF网络同时测定润滑油中铁、铜、锌

将小波包压缩-RBF网络方法用于润滑油中铁铜锌三组分分光光度同时测定该方法采用小波包函数对光谱数据进行压缩处理，用较大的小波色系数构成新的校正集和预测集代替原始的校正集和预测集，然后用RBF网络进行数据解析。研究表明，用bior2．4小波包处理原始测定数据，最佳小波基用logenerge熵标准，选择适当阈值将变量数由46个压缩成25个（压缩比为0．54），整体预测效果最好。将此方法用于合成样预测．预测结果与实际浓度的相对误差绝对值在2．50％～9．40％之间；用于实际润滑油样品中铁、铜和锌的同时测定，解析值与原子吸收法（AAS）的测定值的相对误差绝对值作3．55％～7．86％之间。应用结果令人满意。     

基于OSC–WT–PLS近红外光谱法测定烟草中芸香苷

采用正交信号校正(OSC)结合小波变换(WT)对烟草光谱进行光谱预处理,将预处理后的烟草光谱结合偏最小二乘法(PLS)建立了烟草光谱对芸香苷的预测模型。利用OSC滤除光谱中与芸香苷含量无关的光谱信息,确定OSC提取的最佳主成分数为7,再选择WT中的最佳小波基函数bior1.1对OSC预处理后的光谱进行压缩及进一步滤噪,然后进行PLS建模,OSC–WT–PLS所建模型决定系数r~2=0.874,校正标准偏差RMSEC=0.85,预测均方根误差RMSEP=0.743,交互验证系数Q_(ext)~2=0.887。结果表明,用OSC–WT–PLS可滤除光谱信息中与待测样品含量无关的信息、减少光谱数据量,降低建立模型的复杂度、提高建模速度及模型的预测能力、准确度。     

红外光谱数据的小波压缩和重建

介绍了小波变换及多分辨分析理论，并利用Ｄａｕｂｅｃｈｉｅｓ的正交紧支集小波基和Ｍａｌｌａｔ算法实现了对红外光谱数据的压缩和重建。计算表明，即使对原始数据压缩５倍，仍能很好地重建原有图谱，重建光谱数据与原始光谱数据之间的均方差为０．２６０。这为光谱数据的存储、检索和处理带来了方便。     

基于独立分量和神经网络的近红外多组分分析方法

采用小波变换对光谱数据进行压缩,用独立分量分析(ICA)方法提取近红外光谱数据矩阵的独立成分和相应的混合矩阵,再用BP神经网络对混合矩阵和实测浓度矩阵进行建模,提出了基于独立分量分析-神经网络回归(ICA-NNR)的近红外分析建模方法。进一步研究了独立分量数和网络中间隐层的神经元数对模型性能的影响,经优化后的ICA-NNR模型在相关系数与均方根误差两个指标上均优于直接用光谱矩阵作为输入所建立的模型。本方法用于玉米中水分、淀粉、蛋白质3种主要成分含量的同时测定,检验样品集的化学检测值与近红外预测值的相关系数分别达到:淀粉r=0.971,蛋白质r=0.976,水分r=0.975。     

基于小波变换的航空润滑油酸值红外光谱分析

为利用红外光谱分析技术快速、准确测定在用航空润滑油酸值,将小波变换用于润滑油红外光谱预处理中,结合均值中心化法,提取光谱有效信息建模。光谱的小波变换选择符合光谱特征的db4小波为基函数,在分解尺度9下进行光谱分解,利用软阈值法滤除各层干扰噪声,重构消噪信号。该光谱预处理法与传统的Savitzky-Golay平滑导数结合均值中心化法相比,滤噪效果好,有效压缩了建模数据量。采用偏最小二乘法,选择最佳主因子数5,建立酸值模型,并对10个在用航空润滑油油样进行了分析。     

基于主成分分析和小波神经网络的近红外多组分建模研究

将小麦叶片原始光谱经过预处理后,采用主成分分析(PCA)对数据进行降维,取前3个主成分输入小波神经网络,建立了基于主成分分析和小波神经网络的近红外多组分预测模型(WNN);进一步研究了小波基函数个数的选取(WNN隐层节点数)对小波神经网络模型性能的影响,并将WNN模型与偏最小二乘法(PLS)和传统的反向传播神经网络(BPNN)模型进行了比较.结果表明,所建立的WNN模型能用于同时预测小麦叶片全氮和可溶性总糖两种组分含量,其预测均方根误差(RMSEP)分别为0.101%和0.089%,预测相关系数(R)分别为0.980和0.967.另外,在收敛速度和预测精度上,WNN模型明显优于BPNN和PLS模型,从而为将小波神经网络用于近红外光谱的多组分定量分析奠定了基础.     

基于料酒的三维同步荧光光谱模式识别研究

提出了一种应用同步荧光光谱技术无损快速鉴别料酒品牌的新方法.利用主成分分解法和小波变换法对料酒样品的同步荧光光谱信号进行了压缩处理,分别采用同步荧光光谱数据的第一主成分和小波细节系数为特征变量进行主成分分析和聚类分析,分类结果表明小波系数作为料酒的特征变量对料酒品牌分类正确率更高.利用偏最小二乘和径向基人工神经网络方法...     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.