Low-molecular weight protein profiling of genetically modified maize using fast liquid chromatography electrospray ionization and time-of-flight mass spectrometry

In this work, the use of liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC-TOFMS) has been evaluated for the profiling of relatively low-molecular weight protein species in both genetically modified (GM) and non-GM maize. The proposed approach consisted of a straightforward sample fractionation with different water and ethanol-based buffer solutions followed by separation and detection of the protein species using liquid chromatography with a small particle size (1.8 μm) C(18) column and electrospray-time-of-flight mass spectrometry detection in the positive ionization mode. The fractionation of maize reference material containing different content of transgenic material (from 0 to 5% GM) led to five different fractions (albumins, globulins, zeins, zein-like glutelins, and glutelins), all of them containing different protein species (from 2 to 52 different species in each fraction). Some relevant differences in the quantity and types of protein species were observed in the different fractions of the reference material (with different GM contents) tested, thus revealing the potential use of the proposed approach for fast protein profiling and to detect tentative GMO markers in maize.     

Supramolecular staircase via self-assembly of disklike molecules at the solid-liquid interface.

A series of soluble hexabenzocoronene (HBC) derivatives with pendant optically active (S)-3,7-dimethyloctanyl and (R,S)-3,7-dimethyloctanyl (mixture of stereoisomers) hydrocarbon side chains with and without a phenylene spacer were assembled into differently ordered arrays at the interface between a solution and the basal plane of highly oriented pyrolytic graphite (HOPG). Molecularly resolved scanning tunneling microscopy (STM) images revealed that all derivatives self-assemble into oriented crystals in quasi-two dimensions. However, while for the alkyl-substituted HBCs (1,4) all of the single aromatic cores within a monolayer exhibit the same contrast in the STM, the single aromatic cores with a phenylene group between the alkyl side chains and the aromatic core (2a,2b,3) exhibit different contrasts within a monolayer. For the disks carrying racemic branched or n-alkyl side chains (2b,3) a random distribution of the two different contrasts within the 2D-crystal is observed, while the optically active phenylene-alkyl-substituted HBC (2a) exhibits a periodical distribution of three contrasts within the monolayer. We attribute the different contrasts of the aromatic cores in the presence of the phenylene groups to a loss of the planarity of the whole molecule and different conformations, which allow the conjugated disks to attain different equilibrium positions above the surface of HOPG. In the case of the optically active side chains a regular superstructure with three distinctly different positions such as in a staircase is attained. The self-assembly processes are governed by the interplay of intramolecular as well as intermolecular and interfacial interactions. In the present case, the interactions may induce both the molecules to acquire well distinct positions along the z axis and to adopt different conformations. The reported results open new avenues of exploration. For instance, the different couplings of conjugated molecules with the substrate at different separations can be investigated by means of scanning tunneling spectroscopy (STS). Furthermore, experiments on the STM tip-induced switching of single molecules embedded in a monolayer appear feasible.     

Novel techniques of PDLC film preparation furnishing manifold properties in a single device

Three novel techniques of polymer dispersed liquid crystal (PDLC) film preparation have been proposed to obtain/induce systematically varying manifold properties in a single device. These three techniques were used to prepare ‘wedge-shaped’, ‘multi-channelled’ and ‘grating type’ PDLC films. Arrangement and configuration of liquid crystal (LC) microstructures inside these PDLC films, which were conveniently divided into different zones, have been investigated using a polarising optical microscope (POM) and scanning electron microscope (SEM). POM images indicate a predominant bipolar structure in all zones of different types of PDLC films but with varying size and density. Further, the electro-optical (EO) properties of PDLC films for different zones have different morphological characteristics as indicated (observed) in POM and SEM images and were dependent on LC droplet shape, size and distribution. Also different zones show different absorbance/transmittance characteristics in the visible range. Thus, our study proposes a single device with manifold properties. Also, the desired properties can be obtained by selecting the suitable zone from the PDLC composite film.     

Near-infrared spectroscopy of autunites

NIR spectroscopy has been applied to the study water in the interlayer of the autunite minerals. The spectra of autunites and metaautunites in the first HOH fundamental overtone are different and the spectra of autunites of different origins in the 6000-7500 cm(-1) region are considerably different. A number of conclusions are made based upon the NIR spectra: (a) The spectra of different autunites are different in the NIR spectral region; (b) the spectra of metaautunites show similarity; (c) the spectra of metaautunites are different from that of autunites. NIR spectroscopy provides a method of determination of the structure of water in the interlayer of natural autunites. The implication from the variation in the NIR spectra is that the structural arrangement of water for different autunites is different and is sample dependent. NIR spectroscopy has a wide potential for the study of the autunite minerals.     

Impedance measurements of self-assembled lipid bilayer membranes on the tip of an electrode

Supported lipid membranes were self-assembled on the tip of a freshly cleaved silver wire, in the presence of an appropriate polarization voltage, to facilitate, during the membrane formation, the organization of the lipids into an ordered structure. Radiowave impedance spectroscopy measurements have been carried out to provide information on the relaxation properties of the system. We have measured the conductometric and dielectric properties of bilayers built up of different lipids [dipalmitoylphosphatidic acid (DPPA), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), linoleic acid (LIN)] in a wide frequency range (from 10(3) to 10(6) Hz) and in electrolyte solutions of different ionic strengths, in the presence of uni-univalent (KCl) and di-univalent (CaCl(2), MgCl(2), ZnCl(2)) electrolytes. This made it possible to measure the influence of different cations and different lipid compositions on the membrane properties. In particular, we have found a different capacitive behaviour of the supported lipid bilayer membrane (s-BLM) structure in the presence of different counterions in the electrolyte solution. This peculiarity offers the opportunity for the preparation of a variety of biosensors with diverse applications in membrane biophysics, biochemistry and biotechnology.     

Ion-Exchange Reaction of Silver(I) and Copper(II) in Optical Sensors Based on Thiaglutaric Diamide

Bulk optode membranes based on a recently reported thiaglutaric diamide ionophore were developed for measurements of silver(I) and copper(II) ions in aqueous solutions. The response properties of optical films containing ionophore and chromoionophores with different pK(a) values were investigated at different sample pH. At certain pH the measuring range of the optode can be shifted when choosing different chromoionophores. Optode with ionophore and chromoionophore V exhibited good responses to silver ions from 10(-6) - 10(-1) M at pH 5.5. The proposed sensor showed high selectivity, good reproducibility and stability. With a different chromoionophore ETH 5418 the optode could response to copper(II) ions from 10(-6) - 10(-2) M.     

疏水高分子单链在疏水表面上吸附和扩散过程的分子动力学模拟

采用分子动力学模拟方法研究不同聚合度(N)的聚乙烯(PE)单链在Si(111)表面上的吸附和扩散行为. 分别设置相对介电常数为1和78模拟无溶剂和不良溶剂环境. PE单链的平衡吸附构象均呈现为二维吸附构象, 但在这两种截然不同的环境中呈现不同的构象和动力学特征, 说明溶剂环境对于疏水高分子单链在疏水表面上的吸附和扩散起到了很大的作用. 吸附能与聚合度呈线性关系, 单位链长的平均吸附能是-0.38 kJ·mol^-1. 另外, 扩散系数(D)与聚合度之间的标度关系是D~N^-3/2.     

Examination of Selectivities of Thermally Stable Geminal Dicationic Ionic Liquids by Structural Modification

Dicationic ionic liquids (ILs) are widely used as gas chromatography (GC) stationary phases as they show higher thermal stabilities, variety of polarities, and unique selectivities towards certain compounds. An important aspect contributing to them is that they show multiple solvation interactions compared to the traditional GC stationary phases. Dicationic ILs are considered as combination of three structural moieties: (1) cationic head groups; (2) a linkage chain; and (3) the counter anions. Modifications in these structural moieties can alter the chromatographic properties of IL stationary phases. In this study, a series of nine thermally stable IL stationary phases were synthesized by the combination of five different cations, two different linkage chains, and two different anions. Different test mixtures composed of a variety of compounds having different functional groups and polarities were analyzed on these columns. A comparison of the separation patterns of these different compounds on nine different IL columns provided some insights about the effects of structural modifications on the selectivities and polarities of dicationic ILs.     

A multi-shear perfusion bioreactor for investigating shear stress effects in endothelial cell constructs

Tissue engineering research is increasingly relying on the use of advanced cultivation technologies that provide rigorously-controlled cell microenvironments. Herein, we describe the features of a micro-fabricated Multi-Shear Perfusion Bioreactor (MSPB) designed to deliver up to six different levels of physiologically-relevant shear stresses (1-13 dyne cm(-2)) to six cell constructs simultaneously, during a single run. To attain a homogeneous fluid flow within each construct, flow-distributing nets photo-etched with a set of openings for fluid flow were placed up- and down-stream from each construct. Human umbilical vein endothelial cells (HUVECs) seeded in alginate scaffolds within the MSPB and subjected to three different levels of shear stress for 24 h, responded accordingly by expressing three different levels of the membranal marker Intercellular Adhesion Molecule 1 (ICAM-1) and the phosphorylated endothelial nitric oxide synthetase (eNOS). A longer period of cultivation, 17 d, under two different levels of shear stress resulted in different lengths of cell sprouts within the constructs. Collectively, the HUVEC behaviour within the different constructs confirms the feasibility of using the MSPB system for simultaneously imposing different shear stress levels, and for validating the flow regime in the bioreactor vessel as assessed by the computational fluid dynamic (CFD) model.     

超支化聚合物的光物理行为及其压力效应

在溶液中观察到超支化聚合物2-甲氧基-5-（2’-乙基已氧基）-对-苯乙烯/3 ，5-二乙烯基苯共聚体（MEH-PPV-HS_1）具有很强的荧光发射，并且在紫外区有两 个明显的相邻吸收带。分别激发这两个吸收带得到相同的荧光发射。在压力作用下 ，这两个吸收带表现出不同的压力效应，并且在不同的压力下分别激发这两个吸收 带时，所得到的荧光发射效率随压力的变化趋势表现出明显的不同。结果表明，这 两个相邻的吸收带分别来自于超支化聚合物分子中具有不同长短的有效共轭结构。 不同的共轭结构受光激发后到达不同的激发态。然后经过不同的松弛途径到达相同 的发光激发态而发出荧光。     

The effect of different impact modifiers in halogen-free flame retarded polycarbonate blends - II. Fire behaviour

In this second of a series of two papers, the fire behaviour of halogen-free flame retarded polycarbonate (PC) blends with different impact modifiers was studied. The impact modifiers were acrylonitrile-butadiene-styrene (ABS), a poly(n-butyl acrylate) rubber (PBA) with a poly(methyl methacrylate) (PMMA) shell and two silicone-acrylate rubbers consisting of PBA with different amounts of polydimethylsiloxane (PDMS) and different shell materials (PMMA and styrene-acrylonitrile, SAN). The flame retardant was bisphenol A bis(diphenyl phosphate) (BDP). Flammability was determined by LOI and UL 94. The burning behaviour under forced flaming conditions was studied by cone calorimeter under different external irradiations and by pyrolysis combustion flow calorimeter measurements. The exchange of ABS with the pure acrylate rubber worsened flammability, while similar results were obtained in cone calorimeter measurements. The exchange of ABS with the silicone-acrylate rubbers is promising, particularly with higher amounts of PDMS. In flammability tests strongly enhanced LOI values were obtained and therefore silicone-acrylate rubbers look like promising alternatives for ABS.     

Blue emitting 3π-2spiro terfluorene-indenofluorene isomers: a structure-properties relationship study

Two novel terfluorenyl derivatives, 2,2',7,7'-tetrakis(9,9-dioctyl-9H-fluoren-2-yl)dispiro[fluorene-9,11'-indeno-(2,1-a)-fluorene-12',9'-fluorene] ((2,1-a)-DST-IF) and 2,2',7,7'-tetrakis(9,9-dioctyl-9H-fluoren-2-yl)dispiro- [fluorene-9,6'-indeno-(1,2-b)-fluorene-12',9'-fluorene] ((1,2-b)-DST-IF) have been synthesized by two different synthetic approaches. These terfluorenyl derivatives possess a different central indenofluorene core, namely (2,1-a)-indenofluorene or (1,2-b)-indenofluorene, which imposes two distinct geometry profiles, and different structural environments for the terfluorenyl fluorophores that translates into drastically different optical and electrochemical properties for (2,1-a)-DST-IF and (1,2-b)-DST-IF. These properties have been carefully studied through a combined experimental and theoretical approach. The (2,1-a)-DST-IF isomer has been successfully used as emitting layer in a blue single-layer small-molecule organic light-emitting diode (SMOLED) and appears as the first example of a blue emission arising from intramolecular terfluorenyl excimers. Regarding the importance of terfluorenyl derivatives in organic electronics, the present structure-properties relationship study, may open new avenues in the design of efficient blue fluorophores.     

壳多糖抑制细菌生长的构效关系

运用化学结构已清楚, 分属4大系列的29种壳多糖, 以4种不同类型的细菌(革兰氏阳性菌Ecoli K1、革兰氏阴性菌Bacillus cereus、Bacillus megaterium和Staphlylococcu aureus)为研究对象, 进行了壳多糖抑菌能力构效关系的研究. 在实验中采用96孔平板, 用计算机\|吸光值读数仪直接测定每个孔的吸光值, 获得了各个细菌在不同壳多糖浓度中的生长曲线和壳多糖抑制细菌生长的最低抑制浓度(MIC, Minimum inhibit concentration). 通过比较同一(各个)系列的壳多糖在这些相同(不同)细菌的MIC变化规律与壳多糖的化学结构的关系, 发现同一壳多糖对不同的细菌的MIC值是不相同的, 因而壳多糖抑制细菌生长的能力首先与细菌本身特点有关, 但与是否为革兰氏阳性菌或阴性菌无直接的相关性; 同一细菌对不同化学结构的壳多糖有一定的相关性, 在壳多糖的聚合程度(DP)相同的条件下, 壳多糖中氨基被乙酰化(DA)的程度越低, 壳多糖抑制细菌生长的MIC值越低, 壳多糖抑制细菌生长的能力就越强; 同样,在DA相同的情况下, 分子越小, 壳多糖抑制细菌生长的MIC值越低, 抑制细菌生长的能力越强. 根据上述实验结果, 初步推测壳多糖抑制细菌生长的机制可能与其在溶液中所带的正电荷多少有关.     

Studies on the Anionic Species of Sodium Aluminate Solutions

Raman, UV, IR and NMR spectra, activity measurement and quantum chemical calculation methods are used concurrently to study the anionic species of sodium aluminate solutions. It has been found that sodium aluminate solutions with the same composition but different preparative histories may exhibit quite different optical andNMg spectra.Sodium aluminate solutions contain a series of aluminium-containing anions including Al(OH)_4~-,Al(OH)_6~(3-) and [(HO)_3Al-O-Al(OH)_3]~(2-).They may convert into each other but the reactions may be rather slow,so that solutions with the same composition but different preparative histories may have different ratios between various anions, and exhibit different spectroscopic properties.     

Acetylcholinesterase liquid crystal biosensor for identification of AChE inhibitors by a reactivator

An improved acetylcholinesterase liquid crystal(LC) biosensor has been developed for the identification of organophosphates(OPs) by using a reactivator. When the acetylcholinesterases(AChEs) inhibited by different kinds of OPs are reactived by a reactivator, the catalytic activity of AChEs can be recovered with different activation efficiency because of the different phosphorylation structures formed in the inhibited AChEs. Accordingly, the reactived AChEs can catalyze the hydrolysis of acetylthiocholine to generate thiocholine product in different degrees, which will result in different catalytic growth of AuNPs and further form distinct orientational response of LCs. Based on such a reactivation mechanism, the AChE LC biosensor with a simple, rapid and visual procedure achieves an obvious identification of three OPs pesticides, methamidophos, trichlorfon and paraoxon, by using a pralidoxime reactivator.     

Stable carbon isotope analysis of different tissues of beef animals in relation to their diet

As part of a larger experiment, 31 young bulls, divided into three groups, were given different diets containing either C(3) plants or a combination of C(3) and C(4) plant-based feeds in three feeding periods before slaughter. Variation in the proportion of C(4) plant material in the diets was made by including or not maize or maize-derived ingredients, whereas the other dietary constituents were from C(3) plants. Analysis of stable carbon isotope ratios (delta(13)C value) was performed on different tissues taken at slaughter: blood, plasma, liver, kidney fat, hair, muscle and ruminal contents. Blood and plasma samples were also taken at the beginning of each period. A highly significant difference was found in the delta(13)C values of blood and plasma samples taken from animals that had received a diet of only C(3) plants or with 59% C(4) material for 70 days. The delta(13)C values of all different samples taken at slaughter were highly significantly different between the three feeding groups that had received diets with 0, 13.5 or 35% C(4) material for on average 137, 139 and 83 days, respectively. For the three groups, samples of hair, muscle, plasma, whole blood and liver were significantly enriched in (13)C compared with the diet (except for liver in one group), whereas kidney fat was significantly depleted. The proportion of C(4) plant material could be accurately estimated from the delta(13)C values of different tissue samples. Stable carbon analysis of different tissues from beef animals can be used to trace back diets containing variable proportions of C(3) and C(4) plant material.     

真实峰数及气相色谱的其它柱效参数

以半峰宽与保留数据的线性关系为基础,对真实峰数ＲＰＮ（ＲｅａｌＰｅａｋＮｕｍｂｅｒ）与其它柱效参数作了比较与讨论。指出用无限大容量比理论板数Ｎ＿（ｉｎｆ）不能真实反映有限容量比区间的柱效。由于柱温变化,用有效板数Ｎ＿（ｅｆｆ）评价柱效有不确切性。ＴＺ＿（１０）是一个较好的参数,但对峰宽线性关系作了较大地简化。而ＲＰＮ与ＴＺ＿（１０）具有同样的物理意义,对峰宽变化未作任何简化处理,是一个较完善的柱效参数。由不同极性同系物所得的ＲＰＮ与ＴＺ＿（１０）都没有显著差别。     

Light‐Switchable Janus [2]Rotaxanes Based on α‐Cyclodextrin Derivatives Bearing Two Recognition Sites Linked with Oligo(ethylene glycol)

Two Janus [2]rotaxanes, 5a and 5b , with α‐cyclodextrin (α‐CD) derivatives substituted on the 6‐position with two recognition sites (azobenzene and heptamethylene (C7)) that were linked with linkers of different lengths (oligo(ethylene glycol) with a degree of polymerization equal to 2 or approximately 21) were synthesized and characterized. 2D ROESY NMR spectroscopy and circular dichroism (cd) spectra demonstrated that the recognition site of the α‐CD moiety was switched by photoisomerization of the azobenzene moiety in 5a and 5b . The different size changes of 5a and 5b in hydrodynamic radius (R_H) owing to the different length of linker between two recognition sites were observed by pulse‐field‐gradient spin‐echo NMR spectroscopy. The kinetic results indicated that the different length of linker had no or a weak effect for the photoisomerization process of 5a and 5b .     

Size- and shape-selective isostructural microporous metal-organic frameworks with different effective aperture sizes

Two isostructural metal-organic frameworks (MOFs) having micropores of the same "static aperture size" but different "effective aperture size" have been prepared using 5-(pyridin-3-ylethynyl)isophthalic acid as a ligand having two different types of functional units, an isophthalate (iph) unit and a pyridyl unit, simultaneously in a single ligand. The combination of iph unit and Cu (or Zn) ion led to two-dimensional layers of Kagome? (kgm) net topology, the layers being further pillared by the internal auxiliary pyridyl unit to form a three-dimensional microporous framework having two different types of cage-like pores, cage A and cage B, with different aperture sizes and shapes. (1) The MOFs can distinguish the adsorbates (N(2)/Ar) not based on the widely used kinetic diameters of the adsorbates but based on the minimum diameters of the adsorbates, which are more shape dependent. While cage A with a sufficiently large aperture size compared with the size of the adsorbates does not show any size selectivity, cage B with an approximate size match between the adsorbates and the pore apertures shows shape selectivity for the adsorbates. The smaller but spherically shaped Ar atom is not allowed into the pore with the oval-shaped aperture; however, the larger linear N(2) molecule is allowed into the pore with the oval-shaped aperture. (2) Even though the two isostructural MOFs have the same static aperture size of cage B, they show different size selectivity for the adsorbates based on the effective aperture size, which reflects the different extents of the framework flexibility.