Characterization of β‐cyclodextrin modified SiO2

Silica particles containing a layer of β‐cyclodextrins were synthesized using a modified method of Armstrong (1985). The modified silica particles were extensively characterized to both the presence and amount of β‐cyclodextrin introduced onto the surface. Raman confirmed that β‐cyclodextrin was introduced onto the particle. The combination of thermogravmetric analysis (TGA) and direct pyrolysis mass spectroscopy were used to determine the amount and the chemical composition of organic material present on the silica, respectively. The two methods confirmed that β‐cyclodextrin was successfully introduced in amounts comparable to earlier literature values. The values obtained by TGA were compared to amounts found by elemental analysis and XPS. The elemental analysis and TGA found the same amount of β‐cyclodextrin, while the XPS values were in the region of 1.5 times higher. This suggests a heterogeneous distribution of the β‐cyclodextrin on the silica particles. Copyright © 2010 John Wiley & Sons, Ltd.     

SET–LRP of N‐isopropylacrylamide in the presence of chain transfer agent

In this study, single electron transfer‐living radical polymerization (SET–LRP) of N‐isopropylacrylamide (NIPAM) in the presence of 2‐mercaptoethylamine chain transfer agent (CTA) was carried out by Cu(0) generated in situ from the disproportionation of CuBr/2,2′‐bipyridine (2,2′‐bpy) in N,N‐dimethylformamide (DMF) at 90 °C. Analysis of polymerization kinetics in the presence of CTA showed that the premature termination of growing polymer chains leads to retardation. The apparent rate constant of polymerization (k) decreased from 4.49 × 10^?4 to 2.59 × 10^?4 min^?1 with increasing CTA concentration. The initiator efficiency (I_eff) and the chain transfer constant (C_s) were found to be 0.524 and 0.286, respectively. The molecular weights of poly(N‐isopropylacrylamide) [poly(NIPAM)] produced were significantly higher than the predicted values, and the polydispersities were less than 1.22. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and Identification of Epoxy Derivatives of 5-Methylhexahydroisoindole-1,3-dione and Biological Evaluation

Cyclic imides belong to a well-known class of organic compounds with various biological activities, promoting a great interest in compounds with this functional group. Due to the structural complexity of some molecules and their spectra, it is necessary to use several spectrometric methods associated with auxiliary tools, such as the theoretical calculation for the structural elucidation of complex structures. In this work, the synthesis of epoxy derivatives of 5-methylhexahydroisoindole-1,3-diones was carried out in five steps. Diels–Alder reaction of isoprene and maleic anhydride followed by reaction with m-anisidine afforded the amide (2). Esterification of amide (2) with methanol in the presence of sulfuric acid provided the ester (3) that cyclized in situ to give imides 4 and 4-ent. Epoxidation of 4 and 4-ent with meta-chloroperbenzoic acid (MCPBA) afforded 5a and 5b. The diastereomers were separated by silica gel flash column chromatography, and their structures were determined by analyses of the spectrometric methods. Their structures were confirmed by matching the calculated ¹H and ¹³C NMR chemical shifts of (5a and 5b) with the experimental data of the diastereomers using MAE, CP3, and DP4 statistical analyses. Biological assays were carried out to evaluate the potential herbicide activity of the imides. Compounds 5a and 5b inhibited root growth of the weed Bidens pilosa by more than 70% at all the concentrations evaluated.     

三次DP曲线定义区间的扩展及其形状优化

为构造一种带形状参数的三次DP曲线，解决DP曲线在给定控制顶点时不具有形状修改功能的缺陷。将传统的三次DP基函数的定义区间由[0,1]推广为[0,α]，重新参数化后得到一组新的含参扩展基，分析扩展基的性质并将其与固定的控制顶点进行线性组合，构造了三次α-DP曲线。讨论了曲线的性质与形状，分析了形状参数的几何意义，并给出了曲线光滑拼接的条件：当满足一定条件时，曲线可达到G¹或G²连续。同时，运用张量积方法将三次α-DP曲线推广到曲面。实例表明，三次α-DP曲线曲面不仅继承了传统DP曲线曲面的优良性质，而且具有形状可调性。最后给出了3种形状参数的选取方案以及相应实例。     

Dendronized Polymers via Macromonomer Route in Supercritical Carbon Dioxide

Radical polymerizations from third to fifth generation macromonomers were conducted in supercritical carbon dioxide (scCO₂). It was found that all monomers were not soluble in such a medium, and reactions occurred in the CO₂‐swollen monomer matrices. Despite the expected severe diffusion limitations, very high conversions and molecular weights were obtained. It is believed that the plasticization effect induced by the CO₂ plays a key role in these surprising findings. Scanning force microscopical analyses confirmed that mainly linear dendronized polymers were obtained and therefore chain transfer to polymer is virtually irrelevant.

     

Review of validation and reporting of non-targeted fingerprinting approaches for food authentication

Food fingerprinting approaches are expected to become a very potent tool in authentication processes aiming at a comprehensive characterization of complex food matrices. By non-targeted spectrometric or spectroscopic chemical analysis with a subsequent (multivariate) statistical evaluation of acquired data, food matrices can be investigated in terms of their geographical origin, species variety or possible adulterations. Although many successful research projects have already demonstrated the feasibility of non-targeted fingerprinting approaches, their uptake and implementation into routine analysis and food surveillance is still limited. In many proof-of-principle studies, the prediction ability of only one data set was explored, measured within a limited period of time using one instrument within one laboratory. Thorough validation strategies that guarantee reliability of the respective data basis and that allow conclusion on the applicability of the respective approaches for its fit-for-purpose have not yet been proposed. Within this review, critical steps of the fingerprinting workflow were explored to develop a generic scheme for multivariate model validation. As a result, a proposed scheme for “good practice” shall guide users through validation and reporting of non-targeted fingerprinting results. Furthermore, food fingerprinting studies were selected by a systematic search approach and reviewed with regard to (a) transparency of data processing and (b) validity of study results. Subsequently, the studies were inspected for measures of statistical model validation, analytical method validation and quality assurance measures. In this context, issues and recommendations were found that might be considered as an actual starting point for developing validation standards of non-targeted metabolomics approaches for food authentication in the future. Hence, this review intends to contribute to the harmonization and standardization of food fingerprinting, both required as a prior condition for the authentication of food in routine analysis and official control.     

Presence of virgin olive oil phenolic metabolites in human low density lipoprotein fraction: determination by high-performance liquid chromatography-electrospray ionization tandem mass spectrometry

The biological benefits of olive oil in preventing the oxidation of low density lipoprotein (LDL) would seem to be linked to its high monounsaturated fatty acid contents, but also to its respective phenolic compounds contents. One prerequisite to assess the in vivo physiological significance of phenolic compounds is to determine their presence in human LDL following the ingestion of virgin olive oil.In this work, olive oil phenolic metabolites were identified using high-performance liquid chromatography in tandem with electrospray mass spectrometry (HPLC-ESI-MS/MS) detection, after solid phase extraction (SPE). Quantitative methods were developed in carrying out linearity, precision, sensitivity and recovery tests. The results from two methods of LDL separation were compared and shorter LDL isolation procedure showed a better recovery for antioxidants compounds in LDL. The metabolites identified in LDL were: hydroxytyrosol monoglucuronide, hydroxytyrosol monosulfate, tyrosol glucuronide, tyrosol sulfate and homovanillic acid sulfate. The fact that olive oil phenolic metabolites are able to bind LDL strengthens claims that these compounds act as in vivo antioxidants.     

A Study of Large Plastic Deformations in Dual Phase Steel Using Digital Image Correlation and FE Analysis

Large plastic deformation in sheets made of dual phase steel DP800 is studied experimentally and numerically. Shear testing is applied to obtain large plastic strains in sheet metals without strain localisation. In the experiments, full-field displacement measurements are carried out by means of digital image correlation, and based on these measurements the strain field of the deformed specimen is calculated. In the numerical analyses, an elastoplastic constitutive model with isotropic hardening and the Cockcroft–Latham fracture criterion is adopted to predict the observed behaviour. The strain hardening parameters are obtained from a standard uniaxial tensile test for small and moderate strains, while the shear test is used to determine the strain hardening for large strains and to calibrate the fracture criterion. Finite Element (FE) calculations with shell and brick elements are performed using the non-linear FE code LS–DYNA. The local strains in the shear zone and the nominal shear stress-elongation characteristics obtained by experiments and FE simulations are compared, and, in general, good agreement is obtained. It is demonstrated how the strain hardening at large strains and the Cockcroft–Latham fracture criterion can be calibrated from the in-plane shear test with the aid of non-linear FE analyses. An erratum to this article can be found at     

Isolation of indole alkaloid and anthranilic acid derivatives from Indigo Pulverata Levis

A new indole alkaloid, pulveratinol (1), and two new anthranilic acid derivatives (2 and 3) were isolated from Indigo Pulverata Levis, together with 12 known compounds (4–15). The structures of the new compounds (1–3) were determined through spectroscopic methods. The absolute configuration of 1 was confirmed further by electronic circular dichroism (ECD) data analysis and computational method with advanced statistics (DP4). All isolated compounds (1–15) were evaluated for their potential neuroprotective effects through induction of nerve growth factor (NGF) in C6 glioma cells.     

量子化学计算核磁共振参数在天然产物结构鉴定中的应用

在过去的十多年中，伴随着量子化学理论与计算机硬件、软件的不断发展，量子化学计算核磁共振参数（quantum chemical calculation of nuclear magnetic resonance parameters，qcc-NMR）的方法也日趋成熟，这些方法往往在较小的计算成本下就可以获得比较理想的计算精度，且对于NMR参数计算结果的分析也从最初的简单统计学方法逐渐发展为基于更为复杂的统计学原理或人工神经网络的方法，这些进展都促使qcc-NMR这一工具在天然产物研究中得到了越来越广泛的应用，从而对传统的NMR技术、质谱，以及各种光谱技术做出了重要补充.本文对qcc-NMR在天然产物结构鉴定中的应用进行了综述，并对近年来的一些应用实例进行了较为详细的分析.