Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

Variable temperature13C MAS NMR of KFe2Mn(CO)12 in the solid state and as aCatalyst precursor on a carbon support

Variable temperature¹³C MAS NMR spectra are reported for¹³CO-enriched KFe₂Mn(CO)₁₂ as a solid and also as dispersed clusters on a carbon support. The spectrum of KFe₂Mn(CO)₁₂ at 300 K agrees with the proposed structure for this cluster and shows that the cluster is static. Two bridging carbonyl resonances are clearly resolved and, by comparison with¹³C MAS NMR spectra of Mn₂(CO)₁₀ and Fe₂(CO)₉, all terminal resonances for the cluster can be assigned. When the cluster is supported on carbon, two broad resonances are observed at room temperature which are assignable to KFe₂Mn(CO)₁₂ and a decomposition product, Mn₂(CO)₁₀. The carbonyl ligands in both supported clusters are completely averaged, and KFe₂Mn(CO)₁₂ on the carbon surface demonstrates fluxional behavior similar to that observed for the cluster in solution. For this fluxional process, activation energies of 0.6 kcal/mol and 0.5 kcal/mol are estimated for carbon-supported KFe₂Mn(CO)₁₂ and Mn₂(CO)₁₀, respectively.     

双水解法制备SO4^2-/SnO2·SiO2固体超强酸及其结构表征

用双水解法合成了SO24-/SnO2-SiO2固体超强酸催化剂。采用FTIR、TG-DTA和XRD技术研究了SO24-/SnO2-SiO2的结构,其测试结果表明:SO42-/SnO2-SiO2的结构与其催化活性存在很好的一致性。     

二苯并噻吩合成方法的改进

对文献报道的由联苯和硫在AlCl3催化下反应合成二苯并噻吩(DBT方法中的提纯过程作了改进，大大简化了提纯步骤，使制备DBT的时间缩短了一半，产率为63．4％，经提纯后的成品含量达99．7％，其纯度、外观、晶相均优于进口试剂，但成本远低于进口试剂。产品用FT-IR、LRS、XRD和^1H NMR表征结果与文献报道完全相符合。     

水性UV图案化功能涂膜技术研究

研究了一种新型水性UV涂料制备技术,可得到用传统方法无法获得的图案化涂膜。利用扫描电镜、DSC、凝胶渗透色谱等对该图案化聚合物进行分析表征;考察了不同功能添加剂对涂膜形貌的影响;并讨论了光照时间、光引发剂用量与聚合物相对分子质量间的关系。     

尼龙66/乙烯-醋酸乙烯酯共聚物接枝马来酸酐共混体系的研究(Ⅰ)乙烯-醋酸乙烯酯共聚物熔融接枝马来酸酐的制备与表征

以马来酸酐为单体、过氧化物为引发剂，采用熔融挤出法制备了乙烯-醋酸乙烯酯共聚物接枝马来酸酐(EVA-g-MAH)。重点讨论了不同型号的EVA、过氧化物引发剂品种及用量、单体MAH用量和加工工艺条件等因素时接枝反应的影响。通过化学滴定法和傅立叶红外光谱法(FTlR)证实部分马来酸酐确实以化学键连接到EVA分子链上。与聚乙烯(PE)、聚丙烯(PP)相比，EVA中由于含有醋酸乙烯(VA)基团，极性较大，与MAH的相客性较好，因而在相同的条件下接枝效率也更大；而且VA含量越大，越有利于接枝反应。比较不同的过氧化物引发剂BPO和DCP。发现DCP的引发效果更好。实验结果还表明，在EVA进行接枝反应的同时存在着交联反应，引发剂DCP的用量不宜过高，为得到接枝率适中，交联度很小的接枝产物，还要选择合适的MAH与DCP的用量。     

噻吩类导电高聚物的研究进展

噻吩类聚合物是研究较为广泛的功能高分子材料。详述了通过化学氧化聚合法和电化学氧化聚合法所合成的噻吩类导电聚合物的性能和用途,常用的结构与性能表征方法以及噻吩类导电聚合物在光、电、磁等各种领域中的应用。     

Structural characterization of Ti centres in Ti-silicalite and reaction mechanisms in cyclohexanone ammoximation

The main results obtained by means of many physical methods (IR, Raman, UV-Vis and XAFS spectroscopies) concerning the structure of the Ti centre in titanium silicalite and the reaction intermediates in the ammoximation of cyclohexanone are concisely reviewed.

The Ti is in tetrahedral coordination in vacuo and expands its coordination sphere upon interaction with adsorbates. In the presence of H₂O and H₂O/H₂O₂ solutions one of the SiOTi bridges is hydrolyzed with formation of (SiO)₃L₂TiOH (LH₂O) and (SiO)₃L₂TiOOH species, respectively. When NH₃ is dosed on (SiO)₃L₂TiOOH structures (SiO)₃L₂TiOO⁻NH₄⁺ species are formed. These species are thought to play an important role in the ammoximation reaction. The geometries of the peroxidic species (open or bridged) are discussed also on the basis of ab initio calculations.     

Classification of vegetable oils by high-resolution <Superscript>13</Superscript>C NMR spectroscopy using chromatographically obtained oil fractions

¹³C NMR spectra of oil fractions obtained chromatographically from 109 vegetable oils were obtained and analyzed to evaluate the potential use of those fractions in the classification of vegetable oils and to compare the results with the NMR analysis of complete oils. The oils included the following: virgin olive oils from different cultivars and regions of Europe and north Africa; “lampante” olive, refined olive, refined olive pomace, hazelnut, rapeseed, high-oleic sunflower, corn, grapeseed, soybean, and sunflower oils; and mixtures of virgin olive oils from different geographical origins. Oils were divided into two sets of samples. The training set (98 samples) was employed to select the variables that resulted in significant discrimination among the different oil classes. By using stepwise discriminant analysis, more than 98% of correct validated assignments were obtained; these results were confirmed when applied to the test set (11 blind samples). Results suggest that the use of oil fractions considerably increases the discriminating power of NMR in the analysis of vegetable oils.