Structure and Two-dimensional Correlation Infrared Spectroscopy Study of a New One-dimensional Chain Compound: (4,4’-Hbpy)_3[NaMo_8O_(26)](4,4’- bpy)_2(H_2O)_4 (bpy = Bipydine)

A novel compound, （4,4＇-Hbpy）3[NaMo8O26]（4,4＇-bpy）2（H2O）4 1 （bpy=bipydine）, was synthesized by the hydrothermal method. Single-crystal X-ray diffraction shows that compound 1 belongs to the monoclinic system, space group C2/m with a=19.1921（5）, b=18.6931（6）, c=9.3821（3） A° β=104.8020（11）°, V=3254.22（17）A°^3 C50H51Mo8N10NaO30, Mr=2062.52, Z=2, F（000）=2016, μ=1.591 mm^-1 and Dc=2.105 g/cm^3. The final R=0.0283 and wR=0.0912 for 3118 observed reflections （I〉20（I））. Compound 1 contains the β-[Mo8O26]^4-anion, sodium ion, 4,4＇-bpy and lattice crystalline water molecules. The β-[MosO26] units link the sodium ion to form a chain structure. The infinitechains of [Na（Mo8O26）]^3- blocks are surrounded by protonized 4,4＇-bpy cations, 4,4＇-bpy and lattice crystalline water molecules. The 2D-IR correlation spectroscopy study indicates that the stretching vibrations of Mo=O occur more preferentially due to the thermal effect. The TGA analysis shows that compound 1 has high thermal stability.

Study on the Hydrogen Bond Interaction Between Soy Protein Isolate and Glycerol Using Two-Dimensional Correlation Fourier-Transform Infrared Spectroscopy

A series of soy protein isolate(SPI)films plasticized by glycerol(Gly)were studied using attenuated total reflectance-Fourier transform infrared spectroscopy(ATR/FTIR).Perturbation-correlation movingwindow two-dimensional(PCMW2D)and two-dimensional correlation(2DCOS)analyses were applied to the amideⅠband and thus the hydrogen bond interaction between SPI and Gly was systematically investigated.When Gly concentrations were in the range 0~35%,the hydrogen bond amongβ-sheets was replaced by the one between SPI chain and Gly molecule,which caused these protein chains being changed toα-helix.However,the transformation ofβ-sheet toα-helix was saturated and both of them tend to change to random coil when Gly concentrations were in the range 35%~60%.

Application of Two-Dimensional Correlation UV-Vis Spectroscopy in Chinese Liquor Moutai Discrimination

Chinese liquor Moutai is the “National alcoholic drink” in China and plays a very important role of social activities in Chinese people’s life. In pursuit of high profits, some illegal counterfeit Moutai liquors have begun to appear in the market. Therefore, it is an urgent need for new techniques to discriminate the genuine and counterfeit Moutai liquor. In this work, the conventional Ultraviolet-Visible (UV-Vis) spectroscopy and two-dimensional correlation UV-Vis spectroscopy are applied to obtain the UV-Vis characteristic of Moutai liquor and counterfeit one, respectively. The experimental results reveal that the conventional UV-Vis spectra of the genuine and counterfeit Moutai liquor are similar. However, the two-dimensional correlation UV-Vis spectra of them are different and this method would be applied to differentiate the counterfeit Moutai liquor from the genuine Moutai liquor. Compared with conventional methods, this novel method has the advantages of easy operation, simple instrumentation and direct recognition, which make it a potential tool in the fields of food safety.

Evolution of Two-Dimensional Correlation Spectroscopy

A number of useful techniques associated with two-dimensional correlation spectroscopy(2DCOS)to improve its performance and utility have been developed in the last 30years.Evolution of these 2DCOS techniques,including some of the very recent developments,is reviewed with examples.Topics include merged or modified asynchronous 2Dcorrelation spectrum,two-dimensional codistribution spectroscopy(2DCDS),Pareto scaling,and null-space projection treatment of spectral dataset.

Experimental Consideration of Two-Dimensional Fourier Transform Spectroscopy

Two-dimensional Fourier transform(2D FT) spectroscopy is an important technology that developed in recent decades and has many advantages over other ultrafast spectroscopy methods. Although 2D FT spectroscopy provides great opportunities for studying various complex systems, the experimental implementation and theoretical description of 2D FT spectroscopy measurement still face many challenges, which limits their wide application.Recently, the 2D FT spectroscopy reaches maturity due to many new developments which greatly reduces the technical barrier in the experimental implementation of the 2D FT spectrometer. There have been several different approaches developed for the optical design of the 2D FT spectrometer, each with its own advantages and limitations. Thus, a procedure to help an experimentalist to build a 2D FT spectroscopy experimental apparatus is needed.This tutorial review is intending to provide an accessible introduction for a beginner to build a 2D FT spectrometer.

Docosahexaenoic Acid Ester Degradation Measured by FTIR-ATR with Correlation Spectroscopy

Highly unsaturated fatty acids such as docosahexaenoic acid and linolenic acid are prone to oxidation with a resulting loss of bioactivity and generation of malodorous degradation compounds. Degradation proceeds by formation of the corresponding hydroperoxyl free radical with subsequent oxidative cleavage at the double bond site. FTIR-ATR was used to detect degradation through spectral changes that were correlated to oxidative degradation. The spectrometer was equipped with a heated stage so that a series of spectra could be collected while the sample was exposed to elevated temperatures. The appearance of new bands at 972.8 cm﹣1, 2934 cm﹣1, and 3498 cm﹣1 with the disappearance of bands at 703.6 cm﹣1 and 3013 cm﹣1 were observed after heating and these spectral changes were evaluated by correlation spectroscopy analysis. These results provide a method to quickly detect the oxidative degradation of polyunsaturated fats. This approach is expected to be applied for the quality assessment of feed formulations fortified with omega-3 fatty acids.

Application of Grey-correlated Spectral Region Selection in Analysis of Near-infrared Spectra

The optimal selection method of spectral region based on the grey correlation analysis was applied in the analysis of near-infrared（NIR） spectra. In order to compute ＂characteristic＂ spectral region, 160 samples of tobacco were surveyed by NIR. Next, the whole spectral region was randomly divided into six regions, and the values of association coefficients and correlation orders of different regions were computed for total sugar, reducing sugar and nicotine. Moreover, two regions that owned the largest value of association coefficient were regarded as ＂characteristic＂ spectral region of a model. Finally, the quantitative analysis models of different components were established via the partial least squares method, and the common selection methods of spectral region were compared. The simulation results indicate that the models to choose the spectral region based on grey correlation analysis are more effective than the common selection methods of spectral region, the optimized time of algorithm is shorter, the prediction precision of the models is higher and generalization ability for quantitative analysis results is stronger. This research can provide the support for the quantitative analysis models of NIR spectra and new idea for commercial analysis software of NIR. So, it has a high application value in the analysis of NIR spectra.

Generalized two-dimensional correlation near-infrared spectroscopy and principal component analysis of the structures of methanol and ethanol

Liquid state methanol and ethanol under different temperatures have been investigated by FT-NIR(Fourier transform nearinfrared) spectroscopy,generalized two-dimensional(2D) correlation spectroscopy,and PCA(principal component analysis) . First,the FT-NIR spectra were measured over a temperature range of 30-64(or 30-71) °C,and then the 2D correlation spectra were computed.Combining near-infrared spectroscopy,generalized 2D correlation spectroscopy,and references,we analyzed the molecular structures(especially the hydrogen bond) of methanol and ethanol,and performed the NIR band assignments. The PCA method was employed to verify the results of the 2D analysis.This study will be helpful to the understanding of these reagents.

Solvent effects on infrared spectra of 2-methyl-4,5-dimethoxy-3-oxo-2H-pyridizine： Part 1. Single solvent systems

Infrared spectroscopy studies of 2 methyl 4,5 dimethoxy 3 oxo 2H pyridizine (MDOP) in 12 pure organic solvents were undertaken to investigate the solvent solute interactions. The frequencies of the carbonyl (C=O) of MDOP were correlated with solvent properties such as solvent acceptor number (AN) and the linear solvation energy relationships (LSER). These frequencies showed a good correlation with the solvent acceptor number (AN) and the LSER.

Introducing a Novel Approach for Oil-Oil Correlation based on Asphaltene Structure: X-ray Diffraction

Asphaltenes have always been an attractive subject for researchers.However,the application of this fraction of the geochemical field has only been studied in a limited way.In other words,despite many studies on asphaltene structure,the application of asphaltene structures in organic geochemistry has not so far been assessed.Oil-oil correlation is a wellknown concept in geochemical studies and plays a vital role in basin modeling and the reconstruction of the burial history of basin sediments,as well as accurate characterization of the relevant petroleum system.This study aims to propose the Xray diffraction(XRD)technique as a novel method for oil-oil correlation and investigate its reliability and accuracy for different crude oils.To this end,13 crude oil samples from the Iranian sector of the Persian Gulf region,which had previously been correlated by traditional geochemical tools such as biomarker ratios and isotope values,in four distinct genetic groups,were selected and their asphaltene fractions analyzed by two prevalent methods of XRD and Fouriertransform infrared spectroscopy(FTIR).For oil-oil correlation assessment,various cross-plots,as well as principal component analysis(PCA),were conducted,based on the structural parameters of the studied asphaltenes.The results indicate that asphaltene structural parameters can also be used for oil-oil correlation purposes,their results being completely in accord with the previous classifications.The average values of distance between saturated portions(d_(r))and the distance between two aromatic layers(d_(m))of asphaltene molecules belonging to the studied oil samples are 4.69Aand 3.54A,respectively.Furthermore,the average diameter of the aromatic sheets(L_(a)),the height of the clusters(L_(c)),the number of carbons per aromatic unit(C_(au)),the number of aromatic rings per layer(R_(a)),the number of sheets in the cluster(M_(e))and aromaticity(f_(a))values of these asphaltene samples are 10.09A,34.04A,17.42A,3.78A,10.61Aand 0.26A,respectively.The results of XRD parameters indicate that plots of dr vs.d_(m),d_(r) vs.M_(e),d_(r) vs.f_(a),d_(m) vs.L_(c),L_(c) vs.L_(a),and f_(a) vs.L_(a) perform appropriately for distinguishing genetic groups.A comparison between XRD and FTIR results indicated that the XRD method is more accurate for this purpose.In addition,decision tree classification,one of the most efficacious approaches of machine learning,was employed for the geochemical groups of this study for the first time.This tree,which was constructed using XRD data,can distinguish genetic groups accurately and can also determine the characteristics of each geochemical group.In conclusion,the obtaining of structural parameters for asphaltene by the XRD technique is a novel,precise and inexpensive method,which can be deployed as a new approach for oil-oil correlation goals.The findings of this study can help in the prompt determination of genetic groups as a screening method and can also be useful for assessing oil samples affected by secondary processes.

基于反向比例解析的近红外光谱定量模型快速构建方法

为解决光谱漂移问题,该研究设计了一种基于反向比例解析的近红外光谱定量模型方法。以烟叶近红外光谱和烟碱含量为研究对象,将数据划分为训练集和测试集。通过计算训练集光谱与测试集光谱的相关性并按照高低排序,选择前20%的光谱,运用约束规划的方法,计算测试集的拟合系数,得到测试集光谱的估计值。结果显示,使用反向比例解析法建立的模型的平均绝对误差为0.3466,预测标准偏差为0.4252,相关系数为0.7932,优于PLS模型。反向光谱比例解析可以有效解决光谱漂移问题,实现烟草中烟碱含量的准确预测,为烟碱的有效测量提供参考。

基于光谱特征的多重金属离子与DOM结合特性

通过淬灭滴定实验,文章采用同步荧光光谱和傅里叶红外光谱(FTIR)结合二维相关光谱分析,探究Cu^(2+)和Cd^(2+)多重离子与溶解态有机质(DOM)结合特性。研究结果表明,(1)DOM与Cu^(2+)和Cd^(2+)结合稳定常数(lg KM)分别为4.75~5.18和3.71~4.12,Cu^(2+)与DOM的结合能力要强于Cd^(2+)。(2)Cd^(2+)浓度为0和100μmol/L时,DOM点位与Cu^(2+)的结合顺序均为430~500 nm>330~420 nm,且Cd^(2+)存在时Cu^(2+)与DOM的lg KM为4.56~4.95。对比结果表明Cd^(2+)的存在并未影响DOM点位与Cu^(2+)的结合顺序,但减弱了DOM与Cu^(2+)的结合能力。(3)FTIR结果表明,Cd^(2+)浓度为0和100μmol/L时DOM官能团与Cu^(2+)结合顺序依次为酚类C-O>酰胺N-H>酰胺C=O>羧基C=O>芳香族C-H>多糖C-O和酰胺N-H>酰胺C=O>酚类C-O>芳香族C-H>多糖C-O。Cd^(2+)与酚类C-O结合后影响了Cu^(2+)与DOM中酚类C-O和羧基C=O官能团的结合。水环境中多重金属离子共存时的生物有效性和生态风险应受到关注。

基于二维相关红外光谱对pH值影响大豆分离蛋白二级结构含量的快速分析

为满足不同种类食品对大豆分离蛋白(soybean protein isolate,SPI)不同功能性的需求,本研究利用红外光谱快速采集70组不同pH值处理后SPI的数据,探讨pH值变化对SPI结构含量的影响。使用均值中心化、多元散射校正、标准正态变量变换和归一化算法对红外光谱数据进行预处理,基于二维相关红外光谱提取特征波段,再利用偏最小二乘(partial least square,PLS)法和算术优化算法-随机森林(arithmetic optimization algorithm-random forests,AOA-RF)建立不同pH值条件下SPI结构及含量的预测模型。结果表明,经均值中心化和多元散射校正结合处理后,α-螺旋、β-折叠、β-转角和无规卷曲模型的相对标准偏差分别为1.29%、1.60%、1.37%、7.28%,两者结合对光谱数据的预处理效果最佳。预测α-螺旋和β-折叠含量最优模型为AOA-RF(特征波段),校正集决定系数为0.9350和0.9266,预测集决定系数为0.8568和0.8701;预测β-转角和无规卷曲含量最优模型为PLS(特征波段),校正集决定系数为0.9154和0.8817,预测集决定系数为0.8913和0.7843。本研究结果可为工业生产过程中产品质量快速检测和工艺条件控制提供理论支撑。

Solriamfetol的二维相关红外光谱分析

利用红外光谱及二维相关光谱进行了Solriamfetol进行了结构分析。检测Solriamfetol 20~150℃范围内(每隔5℃)的近红外光谱,结合红外光谱、二维相关光谱及相关文献,分析Solriamfetol分子内变化。观察分析了温度对Solriamfetol分子的羰基、脂肪胺基和酰胺基的氢键和自由基之间的影响,明确了因温度扰动,引起羰基氢键的断裂及变化规律,分析了胺基与酰胺氢键的不同,确定了不同分结构之间的变化先后顺序,并进行了红外峰的归属。联合使用二相关光谱,提高了Solriamfetol红外光谱的分辨率和可解释性。

Generalized two-dimensional correlation spectroscopy——Theory and applications in analytical field

Since the theory of generalized two-dimensional (2-D) correlation spectroscopy was proposed, it has been keenly concerned in scientific research and its analytical method has been widely applied in various analytical fields. The mathematical process to construct generalized 2-D correlation spectroscopy and the physical meaning of 2-D correlation spectral map are described, and three examples in the fields of chemical analysis and molecular biology are provided, such as the component analysis of organic solvent, the analysis of biological molecules in the solvent with different pH values and structural analysis of protein. The theory and analytical method of generalized 2-D correlation spectroscopy are also detailedly commented.

Spectral Insights into Microdynamics of Thermoresponsive Polymers from the Perspective of Two-dimensional Correlation Spectroscopy

Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.

Recent developments in two-dimensional (2D) correlation spectroscopy

Recent noteworthy developments in the field of two-dimensional（2D） correlation spectroscopy are reviewed.2D correlation spectroscopy has become a very popular tool due to its versatility and relative ease of use.The technique utilizes a spectroscopic or other analytical probe from a number of selections for a broad range of sample systems by employing different types of external perturbations to induce systematic variations in intensities of spectra.Such spectral intensity variations are then converted into2 D spectra by a form of correlation analysis for subsequent interpretation.Many different types of 2D correlation approaches have been proposed.In particular,2D hetero-correlation and multiple perturbation correlation analyses,including orthogonal sample design scheme,are discussed in this review.Additional references to other important developments in the field of 2D correlation spectroscopy,such as projection correlation and codistribution analysis,were also provided.

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al（OH）3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH〉 COO-〉NH deformation of amide Ⅱ〉 aliphatic hydroxyl C／OH at p H 5, and COO-〉aliphatic hydroxyl C／OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.

基于近红外光谱技术的南荻生物质品质快速分析

为快速分析洞庭湖南荻的生物质品质(可溶物、纤维素、半纤维素、木质素、灰分含量和纤维素结晶度、聚合度),以采集的126份种质资源为材料,分别采用2种光谱预处理方法和3种特征光谱筛选方法优化原始光谱,基于不同组合方式优化光谱及原始光谱,结合偏最小二乘法构建近红外光谱分析模型,筛选针对7个品质指标的双重优化模型,基于灰色关联度法对126份种质资源进行工业化潜力评估。结果表明:洞庭湖南荻可溶物、纤维素、半纤维素、木质素、灰分含量及纤维素结晶度、聚合度均存在丰富的多样性,且大致呈正态分布,符合近红外建模的要求;基于直接差分法(DD)结合竞争性自适应重加权算法(CARS)优化的PLS模型对南荻可溶物含量的预测结果表现优异,其校正集的均方根误差(RMSEC)为0.27,决定系数(R_(C)^(2))为0.99;交叉验证集的均方根误差(RMSECV)为0.77,决定系数(R^(2)_(CV))为0.97,预测集的相对分析误差为5.07,相关系数(R_(V)^(2))为0.88;基于DD结合变量组合集群分析混合迭代保留信息变量(VCPA–IRIV)优化的PLS模型在南荻的纤维素、半纤维素、木质素、灰分含量和结晶度、聚合度的预测中表现优异,模型的RMSEC为0.14~10.20,R_(C)^(2)为0.98~0.99,RMSECV为0.28~19.46,R^(2)_(CV)为0.94~0.98,R_(V)^(2)为0.87~0.98,相对分析误差(RPD)为4.84~15.65;表明基于双重优化光谱子集建立的近红外光谱模型能较好地预测南荻的生物质品质,且具有较高的稳定性;通过灰色关联度法对126份南荻种质资源进行评估,发现126个样本的工业化利用潜力分数大致呈正态分布,其利用潜力分数的均值为54.4,一级种质资源4个,二级种质资源40个,三级种质资源63个,四级种质资源14个,五级种质资源5个。

土壤有机质可见-近红外反射光谱特性研究

为优化土壤有机质含量预测模型运算速度,以50份土壤有机质为例,利用Pearson相关系数分析法对土壤有机质的特征波段进行提炼筛选。结果表明,土壤样品的反射光谱与土壤有机质含量在555~662 nm波段范围内呈较强负相关,显著特征波段为601 nm;经过不同预处理后的土壤反射光谱与土壤有机质含量呈较强的相关性,显著特征波段增加,主要体现在601、1221、1410、1665、1880、2110、2200 nm波段附近。对不同土壤含水率的反射光谱与土壤有机质含量之间的Pearson相关曲线进行分析发现,显著特征波段主要体现在601、1450、1930、2200 nm波段附近,随着土壤含水率的增加,土壤有机质的特征波段601 nm的相关性逐渐减弱,土壤水分的特征波段1450、1930、2200 nm的相关性逐渐加强;土壤含水率超过10%,土壤反射光谱与土壤有机质含量呈正相关。研究获取的土壤有机质特征波段和土壤水分影响波段,为土壤有机质快速检测模型的建立提供理论支撑。