Advanced 1H Solid‐State NMR Spectroscopy on Hydrogels, 1

Summary: The nature of the pH dependent collapse of poly(methacrylic acid) (PMAA) hydrogels is investigated using recent ¹H solid‐state NMR methods. In aqueous solution, PMAA changes from an expanded conformation at high pHs to a compact contracted form at low pHs, where hydrogen bonds play a central role. In solid‐state ¹H NMR spectra, recorded under fast magic angle spinning (MAS), dried PMAA samples previously collapsed at low pHs show characteristic signals in the spectral region of the carboxylic acid protons. With the aid of 2D ¹H‐¹H double‐quantum (DQ) MAS NMR spectra, three signals can be distinguished at 8, 10.5 and 12.5 ppm, which are attributed to free carboxylic groups and two different types of hydrogen bonded forms, respectively. The 12.5 ppm signal arises from the hydrogen bond with the shortest H? H distance, corresponding to the form that is most stable with respect to increasing temperature and pH. The weaker hydrogen‐bonded form (with a signal at 10.5 ppm) requires a slightly lower pH, while the free acid signal (at 8 ppm) emerges under the most acidic medium. Moreover, the stabilities of the hydrogen‐bonded carboxylic acid dimers can be inferred from the proton‐proton distances within the dimers, i.e. (275 ± 5) pm and (295 ± 15) pm for the protons at 12.5 and 10.5 ppm, respectively, which are determined by means of DQ MAS sideband patterns. Both the stability of the hydrogen bonds and the acidity of the protons may be related to the stereochemistry and the conformation of the PMAA chains.

     

Flame Retardant Mechanisms of Red Phosphorus and Magnesium Hydroxide in High Impact Polystyrene

Summary: The flame retardant mechanisms of red phosphorus, magnesium hydroxide and red phosphorus combined with magnesium hydroxide were studied in high impact polystyrene by means of comprehensive decomposition studies and combustion tests. The study is intended to illuminate prerequisites and the potential of red phosphorus as a fire retardant for hydrocarbon polymers in the condensed phase and in the gas phase. Thermal and thermo‐oxidative decomposition, decomposition kinetics and the product gases evolved were characterized using thermogravimetry coupled with Fourier transform infrared spectroscopy and mass spectroscopy, respectively. Fire behaviour was investigated with a cone calorimeter using different external heat fluxes, whereas the flammability was determined by limited oxygen indices. The combustion residues were analysed using XPS. Red phosphorus reduced the heat release in HIPS due to radical trapping in the gas phase. Magnesium hydroxide influenced fire behaviour by heat sink mechanisms, release of water and the formation of a magnesia layer acting as a barrier. The combination of both flame retardants in HIPS nearly resulted in a superposition. A slight synergy in barrier characteristics was due to the formation of magnesium phosphate, whereas a slight anti‐synergism occurred in flammability and in the gas phase action. The latter effect is controlled by a decreased fuel rate due to the barrier layer rather than by an initiation of red phosphorus oxidation in the condensed phase.

Heat release rate and total heat release at various external heat fluxes for HIPS (dotted = 70 kW · m^?2, dashed = 50 kW · m^?2, solid = 30 kW · m^?2).     

基因表达系列分析及其应用前景

基因表达系列分析(Serial analysis of gene expression，SAGE)是一种研究真核细胞表达基因信息的高通量检测技术，它能对细胞内所有表达基因进行定性与定量分析。近年来此技术广泛应用于获得表达基因谱的研究，并且可以发现新基因信息，还可发现基因的靶向定位以及对其它基因的影响，明确表达基因的功能。本文就SAGE的原理、实验方案、技术发展与演变及其应用前景进行详细介绍。     

Blood supply to the retina and the lens in the gerbil (<Emphasis Type="Italic">Meriones unguiculatus</Emphasis>)

The blood supply to the retina and the lens in 32 gerbils (Meriones unguiculatus) of both sexes from infancy to maturity was studied under light and stereoscopic microscopes, and a scanning electron microscope. Mercox (CL-2R; Dai Nippon Ink, Tokyo, Japan) was injected into the left ventricle of 30 animals in order to visualize the blood supply to the retina and the lens from the ophthalmic artery. The central retinal artery arises from the ophthalmic artery, passes through the papilla of the optic nerve together with the central retinal vein and penetrates the vitreous space (cavity of the eye) between the lens and the internal limiting membrane of the retina, where it divides into the central branches covering the lens and the parietal branches to supply the retina. The former passes through the hyaloid space after branching several arterioles and then covers the lens like a network from its medial and marginal sides. Different from small experimental animals, the parietal branches, just after separating from the central one, divides into the nasal, dorsal and temporal branches in the vitreous space, each of which then subdivides to distribute across the retina on the inner limiting membrane, then delineates the membrana vasculosa retinae. This basal pattern of vasculization 1 day after birth continues to death. Both the central and parietal branches of the central retinal artery correspond to the branches of the hyaloid artery in embryo and the latter is preserved in adult gerbils.     

Kinetic Studies of the Copolymerization of Ethylene with Norbornene by ansa‐Zirconocene/Methylaluminoxane Catalysts: Evidence of a Long‐Lasting “Quasi‐Living” Initial Period

Copolymers of ethylene (E) with norbornene (N) were synthesized using the catalysts rac‐Et(Ind)₂ZrCl₂/MAO ( 1 ), 90%rac/10%meso‐Et(4,7‐Me₂Ind)₂ZrCl₂/MAO ( 2 ), and rac‐H₂C(3‐t‐BuInd)₂ZrCl₂/MAO ( 3 ). Catalyst activity, molar mass (MM), and copolymer composition were studied as a function of time. The polymers showed an unusually narrow molar mass distribution (MMD) and a significant increase of their MM with time for up to one hour, suggesting a “quasi‐living” polymerization at 30 °C. The experimental data were fitted to kinetic equations and the propagation and transfer reactions were described in quantitative terms. Norbornene greatly depressed the propagation rate, along with the chain transfer rate. The more sterically hindered catalysts of the series showed lower propagation and chain transfer turnover frequency than 1 and yielded polymers with a low ( 2 ) to very low ( 3 ) norbornene content. The presence of norbornene in solution seemed to be one of the main factors responsible for the observed “quasi‐living” character of the copolymerization, probably due to coordination of norbornene to the active site. Time‐resolved kinetic studies also allowed for the calculation of the fraction of active metal centers, ranging from 56% ( 3 ) and 66–68% ( 1 ) to 94% ( 2 ) of the total zirconium present, depending on catalyst structure.

Left: molar mass (top) and polydispersity (bottom) as a function of the normalized polymer yield. The dashed line is the theoretical curve for ideal living polymerization. Catalysts 1 (□), 2 (?), and 3 (○) at N/E ratio 12.5 and catalyst 1 (?) at N/E ratio 28.4. Right: enlargement of the low yield section.     

Preparation of chromosomes from plant leaf meristems for karyotype analysis and in situ hybridization

A reliable method for preparing metaphase chromosomes from plant leaf tissues is described. The chromosomes are suitable for karyotype analysis and gene mapping by fluorescence in situ hybridisation (FISH). The method is based on enzymatic digestion of young leaf tissues (shoot-tips) after which the resulting protoplasts are treated hypotonically before being dropped onto microscopic slides. Compared to root-tip chromosomes, leaf chromosomes tend to be longer, or less condensed, and hence more karyotypically differentiated. Metaphase index in young leaf tissues is also very high. Metaphase spread consists of evenly and well-distributed chromosomes and this allows accurate counting. The plant used to demonstrate this method is birch (Betula L.), a group of tree species that has extremely small chromosomes. Root-tip chromosomes of these plants are difficult to obtain, as cutting does not produce roots readily. Seedling chromosomes do not represent the same genomic constitution as their mother trees due to introgressive hybridisation. Furthermore, sample collection in the field is convenient and actively growing leaf buds are available throughout the growing season. FISH experiments with these leaf chromosomes also give good results comparable to those obtained with root-tip chromosomes or even better as mapping on long or extended chromosomes has high resolution in general. Mapping of the 16S–28S ribosomal genes on birch leaf chromosomes has been shown to differentiate between birch species and therefore can accurately confirm their interspecific hybrids.     

Allicin stimulates lymphocytes and elicits an antitumor effect: a possible role of p21ras

Allicin, the main organic allyl sulfur component in garlic, exhibits immune-stimulatory and antitumor properties. Allicin stimulated [(3)H]thymidine incorporation in mouse splenocytes and enhanced cell-mediated cytotoxicity in human peripheral mononuclear cells. Multiple administration (i.p.) of allicin elicited a marked antitumor effect in mice inoculated with B-16 melanoma and MCA-105 fibrosarcoma. The immune-stimulatory and antitumor effects of allicin are characterized by a bell-shaped curve, i.e. allicin at high, supra-optimal concentrations is less effective or inhibitory. Allicin induced activation of extracellular signal-regulated kinases 1 and 2 (ERK1/2) in human peripheral mononuclear cells, and also in wild-type Jurkat T-cells. Allicin failed to activate ERK1/2 in Jurkat T cells that express p21(ras), in which Cys118 was replaced by Ser. These cells are not susceptible to redox-stress modification and activation. We postulate that the immune stimulatory effect of allicin is mediated by redox-sensitive signaling such as activation of p21(ras). It is suggested that the antitumor effect of allicin is related to its immune-stimulatory properties.     

Central nervous system inflammatory response after cerebral infarction as detected by magnetic resonance imaging

Brain inflammation contributes to the tissue injury caused by ischemic stroke. Macrophages as the most abundant inflammatory cell population in stroke lesions can be visualized using ultrasmall superparamagnetic iron oxide (USPIO) as a cell-specific contrast agent for magnetic resonance imaging (MRI). The aim of our present study was to delineate the inflammatory response during experimental cerebral infarction by means of USPIO-enhanced MRI and to correlate the spatial distribution of USPIO-induced MR signal alterations with cellular infiltration and iron deposition. To this end USPIOs were administered to Wistar rats 5 days after photothrombotic cerebral infarction. MR imaging at 7 T performed 24 h later displayed a rim-like signal loss around the infarction in the USPIO treated animals. On histological brain sections obtained from the same animals after MRI the distribution of iron and ED1+ phagocytes was in full spatial agreement with the signal loss seen on T2*-weighted images. Our study validates USPIO-enhanced MRI as an important tool for the noninvasive visualization of brain inflammation in stroke and other CNS pathologies.     

Analysis of children with type 1 diabetes in Korea: high prevalence of specific anti-islet autoantibodies, immunogenetic similarities to Western populations with "unique" haplotypes, and lack of discrimination by aspartic acid at position 57 of DQB

This study analyzed the expression of anti-islet autoantibodies and HLA-DR and -DQ genotypes in Korean children with type 1 diabetes mellitus (T1DM). The positivity of the anti-ICA512, anti-GAD65, and anti-insulin autoantibodies in the newly onset T1DM patients (n = 15) was 66.7%, 86.7%, and 46.7%, respectively, and all of them had one or more of the autoantibodies. HLA analysis showed higher frequencies of HLA-DRB1*0301, *0405, *09012 and -DQB1*0201, *0401, *03032 alleles in T1DM patients compared to controls (P(c) < 0.05). Because HLA-DQB1*0401, *03032 alleles carry aspartic acid at position 57 of DQB, susceptibility to T1DM in Korean children was not related to the presence of aspartic acid at position 57 of DQB1 locus. We suggest this unique HLA-DR, -DQ allele distribution might be an important factor for the low incidence of T1DM in Korea, and the combined anti-islet autoantibody assays could be valuable screening markers for the early detection of T1DM in Korea.     

基于F-score特征选择和支持向量机的P300识别算法

如何从脑电信号中快速准确地识别出P300成分是脑-机接口研究中的一个热点问题.针对P300的识别问题,我们提出了一种将F-score特征选择与支持向量机相结合的判别方法,该方法采用F-score特征选择减少输入特征的维数,以克服支持向量机算法判别速度慢的缺点;然后借助支持向量机算法良好的分类性能实现P300的识别.本文在BCI Competition 2003的P300实验数据集上对该方法进行了验证,结果表明,在5次重复实验中该方法的识别准确率达到了100%,且判别速度与未经特征选择的传统支持向量机算法相比提高了近2倍.