Modification of polybutadiene with caprolacton during polymerization

Polybutadiene has been modified with ?-caprolacton during butadiene polymerization carried out in the presence of catalytic systems based on neodymium and organoaluminum compounds at a butadiene conversion of 90–96%. The structure, phase state, and temperature behavior of polybutadienes modified with ?-caprolacton have been studied by IR and ¹³C NMR spectroscopy, DSC, and X-ray diffraction analysis. The above approach shows promise for the synthesis of new-generation elastomers which do not rank below conventional rubbers in terms of their characteristics but possess biodegradability.     

金属有机骨架化合物催化合成不对称有机碳酸酯

金属有机骨架化合物(MOFs)是通过过渡金属和有机配体的自组装形成的一类新型材料, 具有高表面积、多孔性、孔尺寸可调等优点, 在催化、分离和气体储存等方面得到广泛应用. 用三种不同方法制备了金属有机骨架化合物, 并用扫描电镜(SEM)、X射线衍射(XRD)和红外(IR)光谱等方法进行了表征. 结果表明, 用不同方法制备的MOFs表现出不同的结构和形貌, 用直接混合法制备的MOFs是有效的催化碳酸二乙酯与醇酯交换制备有机碳酸酯的多相催化剂. 系统地考察了反应时间、反应温度、催化剂用量和底物摩尔比对反应的影响, 结果表明, 碳酸二乙酯与芳香醇、脂环醇、脂肪醇和杂环醇均能以100%选择性高产率地合成有机碳酸酯, 固体催化剂经简单离心分离可重复使用至少2次.     

The catalytic mechanism of an aspartic proteinase explored with neutron and X-ray diffraction

Hydrogen atoms play key roles in enzyme mechanism, but as this study shows, even high-quality X-ray data to a resolution of 1 A cannot directly visualize them. Neutron diffraction, however, can locate deuterium atoms even at resolutions around 2 A. Both neutron and X-ray diffraction data have been used to investigate the transition state of the aspartic proteinase endothiapepsin. The different techniques reveal a different part of the story, revealing the clearest picture yet of the catalytic mechanism by which the enzyme operates. Room temperature neutron and X-ray diffraction data were used in a newly developed joint refinement software package to visualize deuterium atoms within the active site of the enzyme when a gem-diol transition state analogue inhibitor is bound at the active site. These data were also used to estimate their individual occupancy, while analysis of the differences between the bond lengths of the catalytic aspartates was performed using atomic resolution X-ray data. The two methods are in agreement on the protonation state of the active site with a transition state analogue inhibitor bound confirming the catalytic mechanism at which the enzyme operates.     

Liquid-crystalline octopus dendrimers: block molecules with unusual mesophase morphologies

The synthesis and the mesomorphic properties of several new main-chain liquid-crystalline dendrimers, thereafter designated as octopus dendrimers in accordance with their eight sidearms, are reported. In these dendritic systems, the arborescence is ensured by anisotropic segments, acting as branching cells with a double multiplicity, which are incorporated at every node of the dendritic architecture. In such a way, these compounds radically differ from the classical end-functionalized liquid-crystalline dendrimers, the most commonly reported systems. Following our previous report on purely homolithic systems, that is, the building blocks constituting the dendritic matrix are all identical, several heterolithic systems made of different anisotropic blocks have been prepared. The dendritic branches and corresponding dendrimers were synthesized using a modular construction. Polarized optical microscopy and X-ray diffraction studies showed that all of these new octopus dendrimers exhibit either smectic-like or columnar phases with novel morphologies, the nature of the mesophases depending on the number of terminal chains attached to the peripheral groups. The mesomorphism of these heterolithic dendrimers is discussed in terms of their intrinsic architecture and compared to the analogous homolithic octopus systems. Models for the molecular organizations within both the smectic and the columnar phases are proposed on the basis of small Bragg angle X-ray diffraction studies and are supported by molecular modelizations. Moreover, this study showed that the mesophase stability is very sensitive to the nature and to the mutual arrangement (the spatial location) of the mesogenic segments within the dendritic matrix, illustrating the intimate relationships existing between the mesomorphic properties and the molecular architecture of these dendrimers.     

Isothermal sections at 1473 K through the Pb-Au-FeS and Pb-Ag-FeS phase diagrams

The interactions in the Pb-Au-FeS and Pb-Ag-FeS systems have been studied using X-ray powder diffraction, electron probe microanalysis, and optical microscopy. Isothermal sections of the phase diagrams at 1473 K have been designed. The systems are ternary systems with two immiscibility regions. The equilibrium phases are an iron monosulfide-based alloy and a gold-lead or lead-silver metal alloy, respectively.     

Investigation of finite system-size effects in molecular dynamics simulations of lipid bilayers

In the absence of external stress, the surface tension of a lipid membrane vanishes at equilibrium, and the membrane exhibits long wavelength undulations that can be described as elastic (as opposed to tension-dominated) deformations. These long wavelength fluctuations are generally suppressed in molecular dynamics simulations of membranes, which have typically been carried out on membrane patches with areas <100 nm2 that are replicated by periodic boundary conditions. As a result, finite system-size effects in molecular dynamics simulations of lipid bilayers have been subject to much discussion in the membrane simulation community for several years, and it has been argued that it is necessary to simulate small membrane patches under tension to properly model the tension-free state of macroscopic membranes. Recent hardware and software advances have made it possible to simulate larger, all-atom systems allowing us to directly address the question of whether the relatively small size of current membrane simulations affects their physical characteristics compared to real macroscopic bilayer systems. In this work, system-size effects on the structure of a DOPC bilayer at 5.4 H2O/lipid are investigated by performing molecular dynamics simulations at constant temperature and isotropic pressure (i.e., vanishing surface tension) of small and large single bilayer patches (72 and 288 lipids, respectively), as well as an explicitly multilamellar system consisting of a stack of five 72-lipid bilayers, all replicated in three dimensions by using periodic boundary conditions. The simulation results are compared to X-ray and neutron diffraction data by using a model-free, reciprocal space approach developed recently in our laboratories. Our analysis demonstrates that finite-size effects are negligible in simulations of DOPC bilayers at low hydration, and suggests that refinements are needed in the simulation force fields.     

Energy dispersive X-ray diffraction potentiality in the field of cultural heritage: simultaneous structural and elemental analysis of various artefacts

The applicability of an Energy Dispersive X-ray Diffractometer to some technical questions in the field of Cultural Heritage is presented. This diffractometer, equipped with a white source, has been utilized for the structural and elemental analysis of some items having different nature. Given its design, the instrument allows to collect data from samples as big as a book or a little more. Samples, without collection of any portion and without any preliminary preparation, have been placed in the instrument and spectra have been collected in a wide energy range that contains X-ray fluorescence and diffraction features. In all cases, data acquired in air and in a non destructive way were reliable and their collection was fast. Fluorescence and X-ray diffraction information, when possible, have been compared with those obtained by XRF micro-analysis and by an Angle Dispersive X-ray Diffractometer equipped with a Cu X-ray source. By using the last two techniques, data have been collected from small areas of the samples.     

A highly pi-stacked organic semiconductor for field-effect transistors based on linearly condensed pentathienoacene

We present the synthesis and characterization of a fused-ring compound, dithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dithiophene (pentathienoacene, PTA). In contrast to pentacene, PTA has a larger band gap than most semiconductors used in organic field-effect transistors (OFETs) and therefore is expected to be stable in air. The large pi-conjugated and planar molecular structure of PTA would also form higher molecular orders that are conductive for carrier transport. X-ray diffraction and atomic force microscopy experiments on its films show that the molecules stack in layers with their long axis upright from the surface. X-ray photoelectron spectroscopy suggests that there are no chemical bonds at the PTA/Au interface. OFETs based on the PTA have been constructed, and their performances as p-type semiconductors are also presented. A high mobility of 0.045 cm(2)/V s and an on/off ratio of 10(3) for a PTA OFET have been achieved, demonstrating the potential of PTA for application in future organic electronics.     

Optical chemical biosensors for high-throughput screening of drugs

Optical biosensors have been commercially available since the early 1990s, and have been used extensively in many areas of research in the life sciences. Optical biosensors developed for drug analysis generally exploit the high selectivity of the antigen-antibody and drug-protein interaction. Optical biosensors can be made based on optical diffraction or electro-chemiluminescence. High-throughput screening, (HTS) which includes automated preparation of a large number of samples and then screening of their properties in multi-well plates, improves the efficiency of research in many scientific areas, e.g., catalyst screening, food processing, chemical synthesis, drug discovery, absorption, distribution, metabolism, and excretion and toxicological and cell based screening. The three most common detection techniques used in HTS are UV-VIS absorbance, fluorescence and luminescence. In this review, we summarize some recent trends and developments in the construction of optical chemical biosensors used in high-throughput screening of drugs. Also, we have included environmental, biological and other medical applications of biosensors.     

Sas_analyzer software for small-angle X-ray scattering data treatment

New approaches to the analysis of small-angle X-ray scattering data from nanoscale systems based on the optimization and direct multiple shooting methods are presented. A program is developed, which bears on these new approaches and allows a user to model small-angle X-ray diffraction data, introduce collimation corrections, and analyze dispersions in the samples. The program results for a number of typical nanosized systems (sols, catalysts) are reported and the comparison with currently available programs for small-angle data processing is presented.     

Applications of synchrotron radiation micro-focus techniques to the study of polymer and biopolymer fibers

Micro-X-ray diffraction using synchrotron radiation has been developed in recent years as a tool for the local analysis of bulk polymer and biopolymer samples. Developments in X-ray optics associated with the introduction of third generation synchrotron radiation sources now allow routine experiments at the 1 μm scale. Several experiments at the 100 nm scale have also been reported with future developments aiming for the 50 nm scale and smaller. In this review, the current state of experimental possibilities have been summarised with an emphasis on in-situ fiber scanning and deformation studies. Examples of unconventional in-situ studies such as microhardness testing or hydration by inkjet printing systems demonstrate the largely unexplored potential of micro-X-ray diffraction techniques.     

A colloid "digesting" route to novel, thermally stable high surface area ZrO2 and Pd/ZrO2 catalytic materials

Zirconia having high thermal stability and high surface area (up to 160 m(2)/g at 700 degrees C) has been prepared by a colloidal "digesting" process. This material having demonstrated high surface areas at elevated temperatures was then applied as a catalyst support. A Pd colloid with diameter of approximately 12 nm has been successfully deposited on the high surface area zirconia material. All systems have been well characterized by TEM, X-ray diffraction, N2 adsorption isotherms, FTIR, elemental analysis and dynamic light scattering techniques. The colloidal Pd particles have been found homogeneously well dispersed in the hydrous zirconia matrix without aggregation. The Pd/ZrO2 catalysts have been screened for cyclohexene and 1-hexene hydrogenation activity and it was found that the catalyst is extremely active.     

熔铁催化剂还原过程的原位XRD研究及活性相的形成机理

选择Fe1-xO基和Fe3O4基氨合成熔铁催化剂ZA-5和A110, 采用XRD原位反应器模拟真实的还原条件进行原位XRD实验. 通过对还原过程的物相跟踪分析和对前驱体、活性相的XRD微结构动态演化分析表明, ZA-5和A110的还原温度区间分别为300~362 ℃和343~450 ℃, 前者比后者具有更快的还原速度及更低的还原温度; ZA-5和A110在(211)和(110)方向的晶粒度比值(D₍₂₁₁₎/D₍₁₁₀₎)分别为0.7014和0.8631, ZA-5催化剂具有更好的高活性(211)晶面, 其活性相微观应力明显比A110大, 且随着温度升高逐渐减小; 采用Rietveld全谱拟合结构分析和Popa模拟技术对活性相晶形进行模拟, 得到A110活性相晶形为凹陷立方体, ZA-5为立方体和球形的混合晶形, ZA-5的高活性晶面(111)和(211)晶面比A110生长更好; ZA-5催化剂活性相晶形从低温的类八面体向高温球形演化, 在355 ℃时有比较完善的八面体晶形, 此温度下(111)晶面生长得最好; ZA-5催化剂活性相与前驱体的八面体晶形结构匹配性好, 比A110更容易还原.     

Synchrotron X-ray diffraction characterization of healthy and fluorotic human dental enamel

With the introduction of fluoride as the main anticaries agent used in preventive dentistry, and perhaps an increase in fluoride in our food chain, dental fluorosis has become an increasing world-wide problem. Visible signs of fluorosis begin to become obvious on the enamel surface as opacities, implying some porosity in the tissue. The mechanisms that conduct the formation of fluorotic enamel are unknown, but should involve modifications in the basic physical-chemistry reactions of demineralization and remineralisation of the enamel of the teeth, which is the same reaction of formation of the enamel's hydroxyapatite (HAp) in the maturation phase. The increase of the amount of fluoride inside of the apatite will result in gradual increase of the lattice parameters. The aim of this work is to characterize the healthy and fluorotic enamel in human tooth using Synchrotron X-ray diffraction. All the scattering profile measurements were carried out at the X-ray diffraction beamline (XRD1) at the Brazilian Synchrotron Light Laboratory—LNLS, Campinas, Brazil. X-ray diffraction experiments were performed both in powder samples and polished surfaces. The powder samples were analyzed to obtain the characterization of a typical healthy enamel pattern. The polished surfaces were analyzed in specific areas that have been identified as fluorotic ones. X-ray diffraction data were obtained for all samples and these data were compared with the control samples and also with the literature data.     

Liquid crystal properties of some substituted pyrazines

A number of biphenyl, terphenyl analogues and ethynes which contain a pyrazine ring have been made and their liquid crystal transition temperatures, together with examples of birefringence measurements, are reported. All the 2,5-disubstituted pyrazine systems are liquid crystalline showing high birefringence values for the biphenyl and terphenyl analogues, whereas the 1,5-disubstituted systems are not liquid crystalline. The pyrazine ethyne systems exhibit very high birefringence values. X-ray diffraction has been used to identify the liquid crystal phases of 2-n-nonyloxy-5-(4'-propylbiphenyl-4-yl)pyrazine.     

ZnO-based hollow microspheres: biopolymer-assisted assemblies from ZnO nanorods

Many efforts have been made in fabricating three-dimensional (3D) ordered zinc oxide (ZnO) nanostructures due to their growing applications in separations, sensors, catalysis, bioscience, and photonics. Here, we developed a new synthetic route to 3D ZnO-based hollow microspheres by a facile solution-based method through a water-soluble biopolymer (sodium alginate) assisted assembly from ZnO nanorods. The products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectroscopy. Raman and photoluminescence spectra of the ZnO-based hollow microspheres were obtained at room temperature to investigate their optical properties. The hollow microspheres exhibit exciting emission features with a wide band covering nearly all the visible region. The calculated CIE (Commission Internationale d'Eclairage) coordinates are 0.24 and 0.31, which fall at the edge of the white region (the 1931 CIE diagram). A possible growth mechanism of the 3D ZnO superstructures based on typical biopolymer-crystal interactions in aqueous solution is tentatively proposed, which might be really interesting because of the participation of the biopolymer. The results show that this biopolymer-directed crystal growth and mediated self-assembly of nanocrystals may provide promising routes to rational synthesis of various ordered inorganic and inorganic-organic hybrid materials with complex form and structural specialization.     

Control growth of uniform platinum nanotubes and their catalytic properties for methanol electrooxidation

Uniform platinum nanotubes have been synthesized by directly mixing Ag nanowires and H₂PtCl₆ in saturated NaI solutions at room temperature. The crystal structure of the obtained Pt nanotube has been investigated in detail by field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Furthermore, their electrocatalytic behaviors for methanol oxidation in alkaline media have also been studied. Compared with conventional Pt/C catalysts, these hollow nanostructures possess high electrochemical active areas and demonstrate higher current densities.     

Locking the Conformation of a Paddlewheel Rhodium Complex: Design,Synthesis, and Applications in Catalytic Nitrene Transfers

The exponential proliferation of conformers makes it impossible to examine the entire population in most systems. Controlling conformational ensembles is thus pivotal in many areas of chemistry. Rh₂(esp)₂, a dicarboxylate-derived paddlewheel rhodium complex, is one of the most effective catalysts for nitrene chemistry. Its enormous success has led to preparing many analogous complexes. However, there has been little consideration for the conformational dynamics of the parent catalyst. Herein, we report a new ligand modification principle that prevents conformer interconversion. The resulting complex comprises two isolable conformers, whose structures have been determined by X-ray diffraction. Combined experimental and computational data has revealed similarities and dissimilarities between the conformationally confined and parent complexes. Three model cases have demonstrated the utility of conformational fixation in the development of stereoselective catalysts for nitrene transfer reactions. The design principle described in this study can be combined with other established modification strategies, serving as a springboard for further advancement of the chemistry of paddlewheel metal complexes.     

Spectroscopy and Structure of Sol-Gel Systems

Sol-gel derived glasses may differ from conventional melt-quenched glasses owing to the peculiar microstructures existing at the gel state, such that, even after gel densification, some differences may remain in their composition and molecular structure.This paper discusses structural characteristics of thin film oxide gels and glasses, with a special emphasis on SiO2-TiO2 based systems, which are of particular interest for sol-gel integrated optics applications. Short range structure aspects are discussed based on infrared, X-ray photoemission and X-ray photoabsorption spectroscopies. The chemical homogeneity of sol-gel materials is evaluated, based on X-ray photoemission and nuclear magnetic resonance spectroscopies, dealing in particular with the issue of homo- vs. heterocondensation. Finally, some microstructural features of sol-gel derived films are analyzed, namely the relationship between infrared absorption and porosity and the structure of nanocrystalline sol-gel films, based on grazing incidence X-ray diffraction and micro-Raman spectroscopy. The types of structural information obtainable by each different technique are compared in detail.