裂解毛细管柱气相色谱－傅里叶变换红外光谱的剖析应用

 采用裂解气相色谱－傅里叶变换红外光谱（ＰｙＧＣ／ＦＴＩＲ）技术，使用大口径毛细管柱，分析了一未知进口涂料，对其主要裂解碎片峰进行了定性，进而从特征碎片的产生推出该涂料的成分。并同常规红外光谱差减法进行了比较，结果表明ＰｙＧＣ／ＦＴＩＲ具有简便、快速、全面和无需标样等优点，有广泛的应用价值。     

裂解气相色谱—红外光谱联用分析聚合物结构（II）

采用国产ＳＣ－７型色谱以及ＪＰ－０１型居里点裂解器，Ｎｉｃｏｌｅｔ１７０ＳＸ红外光谱仪及接口组成的裂解色相色谱－傅里叶变换红外光谱（ＰＧＣ／ＦＴＩＲ）分析仪，ＨＰ－１７型大口径毛细管色谱柱，分析了两个复杂组成的聚合物样品。从主要裂解碎片峰的定性结果及形成机理出发，逐步推出了原样品的组成和结构，常规红外光谱分析方法被用来作为对比，但它获得的信息有限，无法得到能与ＰＷＢＣＧＣ／ＦＴＩＲ分析结果和媲美的     

裂解气相色谱－红外光谱联用分析聚合物结构（Ⅱ）

采用国产ＳＣ－７型色谱仪及ＪＰ－０１型居里点裂解器、Ｎｉｃｏｌｅｔ１７０ＳＸ红外光谱仪及接口组成的裂解气相色谱－傅里叶变换红外光谱（ＰＧＣ／ＦＴＩＲ）分析仪、ＨＰ－１７型大口径毛细管色谱柱，分析了两个复杂组成的聚合物样品。从主要裂解碎片峰的定性结果及形成机理出发，逐步推出了原样品的组成和结构。常规红外光谱分析方法被用来作为对比，但它获得的信息有限，无法得到能与ＰＷＢＣＧＣ／ＦＴＩＲ分析结果相媲美的结论，充分显示了ＰＷＢＣＧＣ／ＦＴＩＲ用于聚合物分析的优越性。     

芳香烃异构体的毛细管柱气相色谱—傅里叶变换红外光谱联用技术分析

采用国产色谱仪与进口红外光谱仪及接口组成的气相色谱－傅里叶变换红外光谱（ＧＣ／ＦＴＩＲ）分析仪，使用大口径毛细管柱，分析了乙苯与苯乙烯固相催化反应液的复杂芳香烃异构体组成，讨论了ＧＣ／ＦＴＩＲ分析中随机噪声和基线漂的去除方法。采用等高线图９ＣＴＤ）分析技术得混合液中各组分的纯气相红外光谱图，最后了１４个气相色谱峰中的９个，占整个色谱峰面积９９５以上。     

芳香烃异构体的毛细管柱气相色谱－傅里叶变换红外光谱联用技术分析

采用国产色谱仪与进口红外光谱仪及接口组成的气相色谱－傅里叶变换红外光谱（ＧＣ／ＦＴＩＲ）分析仪，使用大口径毛细管柱，分析了乙苯与苯乙烯固相催化反应液的复杂芳香烃异构体组成，讨论了ＧＣ／ＦＴＩＲ分析中随机噪声和基线漂移的去除方法。采用等高线图（ＣＴＤ）分析技术得到了混合液中各组分的纯气相红外光谱图，最后鉴定了１４个气相色谱峰中的９个，占整个色谱峰面积９９％以上。     

用色谱联用技术分析桂腈和溴代苏合香烯顺反异构体

应用气相色谱／红外光谱（ＧＣ／ＦＴＩＲ）、核磁共振（ＮＭＲ）等技术快速分离、鉴定了桂腈和溴代苏合香烯的顺反异构体,解决了气相色谱／质谱（ＧＣ／ＭＳ）分析时出现的保留行为不同的顺反异构体因为质谱图类似而导致谱库检索鉴别困难的问题。从而,可将保留指数与质谱数据相结合,互补各自在鉴定上的局限性。     

傅里叶变换红外光谱和核磁共振法对土壤中腐殖酸的表征

采用氢氧化钠碱提法提取和纯化了我国４种典型土壤中腐殖酸,分别用元素分析、傅里叶变换红外光谱（ＦＴＩＲ）、固仿核磁共振（ＮＭＲ）等方法对提取腐殖酸进行了表征。结果表明,４种土壤中腐殖酸原ＦＴＩＲ图谱相似,含有相同类型的官能团。对ＮＭＲ不同化学位移域的谱峰积分获得４种土壤腐殖酸的各组成比例,组成中以烷氧基Ｃ的含量最高,脂类Ｃ略高于芳香Ｃ含量。     

繁峙煤镜质组的生烃特征与热解产物生成动力学研究

本文利用付立叶红外光谱（ＦＴＩＲ），热解气相色谱（Ｐｙ－ＧＣ）及热解气相色谱质谱（Ｐｙ－ＧＣ－ＭＳ）联用技术等分析手段，探讨了我国山西繁峙煤镜质组的生烃特征，鉴定了如气体烃、正构脂肪烃、苯酚、单环芳烃以及甲氧基酚类等热解产物６７种化合物。用相继等温热解法一级反应动力学模型，求取了热解产物如气体组分（Ｃ１￣Ｃ６）、轻烃（Ｃ７￣Ｃ１４）、重烃（Ｃ１５￣Ｃ３０）、正构脂肪烃（ｎＣｉ）、烷基芳烃、苯酚等的     

气相催化氟化合成的1,1,1,2—四氟乙烷及其相关副产物组分的气相色谱

本文报道了用ＧＣ／ＦＴＩＲ方法分析相催化氟合成的ＣＦＣ１２的替代物ＨＦＣ１３４ａ粗产品、中间体及副产笺的化学组成。该法选择石英ＰＬＯＴＡｌ２Ｏ３柱分离 、ＦＩＤ检测。     

侧基上带有C60基因的聚苯乙烯的表征

用ＵＶ、ＦＴＩＲ、ＤＳＣ、ＴＧ和ＤＴＡ及ＧＰＣ等方法证明了通过三步反应（氯甲基化，叠氮化，环加成反应）确实将Ｃ６０引入到聚苯乙烯的侧基上，Ｃ６０基本上以单取代的方式存在，并通过ＴＧ和ＤＴＡ方法估算了Ｃ６０在聚苯乙烯Ｃ６０衍生物中的含量。     

紫外分光光度法同时测定硝酸盐氮和亚硝酸盐氮

提出了用均匀设计安排ＢＰ网络运行参数以进行优化的方法。研究了硝酸盐和亚硝酸盐在紫外区的吸收光谱。利用ＢＰ算法的人工神经网络处理光谱数据,提出了关于同时测定水样中的硝酸盐氮和亚硝酸盐氮的新方法。对实际水样进行了测定,结果满意。     

Comparisons between LIBS and ICP/OES

In the framework of the development of new techniques, the ability of laser-induced breakdown spectroscopy (LIBS) to analyse remotely complex aqueous solutions was investigated. The jet configuration with a collimated gas stream was chosen because it appeared to be the most promising method for the LIBS probe, particularly in terms of sensitivity and repeatability. For emission collection, the echelle spectrometer offers a simultaneously recorded wavelength range from the UV to the near IR and is interesting for multielemental analysis for LIBS and also for inductively coupled plasma (ICP) optical emission spectroscopy (OES). The importance of parameters influencing the quantitative results of LIBS such as multispecies analysis, sheath gas, use of an internal standard and temporal parameters for analysis is described. LIBS quantitative data have been directly compared with results from the more standard ICP/OES technique.     

Hydrogen bonding interaction between N-methylformamide and alcohols

The hydrogen bonding interactions between N-methylformamide and primary, secondary, and tertiary alcohols have been studied using the FTIR spectroscopic method. The most likely association complex between alcohol and N-methylformamide is the 1:1 stoichiometric complex formed between the hydroxyl group of alcohol and the carbonyl group of N-methylformamide. The formation constant of the 1:1 complexes has been calculated using the Nash method. It appears that the primary alcohols have larger formation constant compared with the secondary and tertiary alcohols. The results showed that the proton-donating ability of the alcohols decreased in the order: primary>secondary>tertiary, and that the association constant increased with the increase in carbon chain of the alkyl group of alcohols.     

Raman scattering from La-substituted BiFeO3-PbTiO3

Polycrystalline samples of pure BiFeO₃-PbTiO₃ (BF-PT) and those upon substituting Bi by La up to 50% (x≤0.5) were synthesized using a solid-state reaction method. A composition-driven tetragonal-cubic transition, identified from X-ray diffraction, was found to occur at x=0.4. We report the phonon spectra of pure and La-substituted BF-PT and its assignment. From the behavior of total Raman intensity, the origin of the symmetry-forbidden Raman spectra is identified to lie in substitutional disorder. The dependence of splitting of A₁-E modes and that of the LO-TO modes on composition are obtained and their consequences on ionicity are discussed.     

From Ultrafast Structure Determination to Steering Reactions: Mixed IR/Non‐IR Multidimensional Vibrational Spectroscopies

Ultrafast multidimensional infrared spectroscopy is a powerful method for resolving features of molecular structure and dynamics that are difficult or impossible to address with linear spectroscopy. Augmenting the IR pulse sequences by resonant or nonresonant UV, Vis, or NIR pulses considerably extends the range of application and creates techniques with possibilities far beyond a pure multidimensional IR experiment. These include surface‐specific 2D‐IR spectroscopy with sub‐monolayer sensitivity, ultrafast structure determination in non‐equilibrium systems, triggered exchange spectroscopy to correlate reactant and product bands, exploring the interplay of electronic and nuclear degrees of freedom, investigation of interactions between Raman‐ and IR‐active modes, imaging with chemical contrast, sub‐ensemble‐selective photochemistry, and even steering a reaction by selective IR excitation. We give an overview of useful mixed IR/non‐IR pulse sequences, discuss their differences, and illustrate their application potential.     

A study of electronic structure of SbCl5.L and SnCl4.L2 complexes by the PM3 method

Electronic structures of SbCl₅.L and SnCl₄.L₂ complexes were studied by the semiempirical PM3 method. The results were compared with the data from ³⁵Cl NQR and ¹²¹Sb NQR studies and Mössbauer spectra.

A good correlation was obtained between the calculated and experimental values of quadrupole coupling constants. The calculated energies of the donor-acceptor bond formation were compared with the degree of electron density transfer. The derived correlation dependences between the above two parameters suggest different properties for cis and trans complexes.     

A study of electronic structure of SbCl5.L and SnCl4.L2 complexes by the PM3 method

Electronic structures of SbCl₅.L and SnCl₄.L₂ complexes were studied by the semiempirical PM3 method. The results were compared with the data from ³⁵Cl NQR and ¹²¹Sb NQR studies and Mössbauer spectra.

A good correlation was obtained between the calculated and experimental values of quadrupole coupling constants. The calculated energies of the donor-acceptor bond formation were compared with the degree of electron density transfer. The derived correlation dependences between the above two parameters suggest different properties for cis and trans complexes.     

High-Resolution,Higher-Order UV/VIS Derivative Spectrophotometry

Derivative spectrophotometry has gained increasing importance in the past two years and is currently experiencing vigorous development. Following and introduction the present article provides a review of this extremely effective method. In particular, the advantages of higher-order derivative spectrophotometry (HODS method, n > 2) are discussed on the basis of practical examples from a wide range of analytical fields. The results are achieved with the aid of a newly developed analog computer unit, whereby for the first time readily reproducible, low-noise, on-line spectra can be obtained up to the 7th order and even, in favorable cases, up to the 9th order. In practice it has proved valuable to work with spectra of the 3rd to 5th order; but even higher derivations could be profitable for the separation of strongly superposed signals or for “fingerprinting”.     

The support and characterization of C60 and MoO3 on Al2O3

A new type of catalyst from supporting C₆₀ on MoO₃ and Al₂O₃ has been prepared. The effect of different order of impregnation and calcination atmosphere on catalyst are investigated by the solution test in toluene, UV-VIS spectroscopy and temperature programmed reduction (TPR). The results show that when the catalyst was prepared by supporting MoO₃ on C₆₀/Al₂O₃ and calcined in N₂, there is a stronger interaction between C₆₀, MoO₃ and Al₂O₃, but when supporting C₆₀ on MoO₃/Al₂O₃, the interaction is relatively weak. We consider that in the former method a new complex, Mo–C₆₀–O–Al, is formed.     

A study of the intermolecular interactions of tolmetin/N-acetyl-l-tyrosine ethyl ester complex

The formation of tolmetin/N-acetyl-l-tyrosine ethyl ester (ATEE) complex has been reported by means of both theoretical and experimental studies, including quantum mechanical calculations as well as UV–vis absorption, fluorescence and time-resolved spectroscopy measurements. It has been found that the fluorescence of ATEE is quenched due to the formation of a non-fluorescent complex between ATEE and tolmetin in the ground state. The geometrical parameters of ATEE/tolmetin complex have been determined with the use of the DFT method applying the B3LYP correlation-exchange functional and 6-31G(d) basis set. The results of experiments indicated the static ATEE quenching by tolmetin. Additionally, the experimental and theoretically predicted Gibbs free energy of complexation has been calculated.