Residue‐centric modeling and design of saccharide and glycoconjugate structures

The RosettaCarbohydrate framework is a new tool for modeling a wide variety of saccharide and glycoconjugate structures. This report describes the development of the framework and highlights its applications. The framework integrates with established protocols within the Rosetta modeling and design suite, and it handles the vast complexity and variety of carbohydrate molecules, including branching and sugar modifications. To address challenges of sampling and scoring, RosettaCarbohydrate can sample glycosidic bonds, side‐chain conformations, and ring forms, and it utilizes a glycan‐specific term within its scoring function. Rosetta can work with standard PDB, GLYCAM, and GlycoWorkbench (.gws ) file formats. Saccharide residue‐specific chemical information is stored internally, permitting glycoengineering and design. Carbohydrate‐specific applications described herein include virtual glycosylation, loop‐modeling of carbohydrates, and docking of glyco‐ligands to antibodies. Benchmarking data are presented and compared to other studies, demonstrating Rosetta's ability to predict glyco‐ligand binding. The framework expands the tools available to glycoscientists and engineers. © 2016 Wiley Periodicals, Inc.     

THE EFFECT OF CLAY DISPERSION ON THE CRYSTALLIZATION AND MORPHOLOGY OF POLYPROPYLENE／CLAY COMPOSITES

PP/clay composites with different dispersions, namely, exfoliated dispersion, intercalated dispersion and agglomerates and particle-like dispersion, were prepared by direct melt intercalation or compounding. The effect of clay dispersion on the crystallization and morphology of PP was investigated via PLM, SAXS and DSC. Experimental results show that exfoliated clay layers are much more efficient than intercalated clay and agglomerates of clay in serving as nucleation agent due to the nano-scale dispersion of clay, resulting in a dramatic decrease in crystal size (lamellar thickness and spherulites) and an increase of crystallization temperature and crystallization rate. On the other hand, a decrease of melting temperature and crystallinity was also observed in PP/clay composites with exfoliated dispersion, due to the strong interaction between PP and clay. Compared with exfoliated clay layers, the intercalated clay layers have a less important effect on the crystallization and crystal morphology. No effect is seen for samples with agglomerates and particle-like dispersion, in regard to melting temperature, crystallization temperature, crystal thickness and crystallinity.     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

Tautomeric and conformational isomerism of natural hydroxyanthraquinones

Natural 1,5-di-, 1,4,5-tri-, and 1,4,5,8-tetrahydroxyanthraquinones and their anions and metal complexes were shown to be equilibrium mixtures of tautomers and conformers using quantum-chemical and correlation analysis of elecronic absorption spectra. Solvent effects, ionization, complexation, and the introduction and substitution of substituents were accompanied by shifts of tautomeric and conformational equilibria that determine the color of the compounds. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 224–229, May–June, 2006.     

Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry

Carbenes and nitrenes can exist in both singlet and triplet states, sometimes equally stable and interconverting either thermally or photochemically. Many carbene and nitrene reactions proceed via tunneling at low temperatures. Numerous singlet and triplet states have been characterized spectroscopically, and a detailed understanding of the chemical and physical properties of carbenes and nitrenes is emerging. There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years through the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered and numerous rearrangements and fragmentations have been documented. The correlation of the zero‐field splitting parameter D with calculated spin densities on nitrenes and carbenes is discussed. This Minireview gives an overview of some of these developments.     

线状铜电极在磷酸溶液中电流混沌振荡的同步行为

研究了恒电位下两个铜线电极在磷酸溶液中的电流混沌振荡行为,通过恒定不同的电位数值,改变单个电极的电流振荡混沌行为,研究了不同混沌间的相互作用.调整线电极间的距离,研究了电极间距对电流振荡行为的影响.实验中两电极的振荡间呈现了复杂的耦合作用,耦合后的频率与耦合前电极原有的频率不同.两电极的混沌电流振荡中呈现出同步、准周期同步和反相同步等现象.电极距离一定时,振荡波形差别很大的两电极的电流容易呈现反相同步和准周期同步,波形差别不大时容易产生同步.强的耦合导致电极间电流振荡的同步,电极距离的加大,电极间电流振荡难以产生同步.对耦合作用机制也进行了探讨.     

Two-dimensional Metal-Organic Frameworks and Derivatives for Electrocatalysis

The most important topics in the world today are environmental and resource issues. The development of green and clean energy is still one of the great challenges of social sustainable development. Two-dimensional(2D) metal-organic frameworks(MOFs) and derivatives have exceptional potential as high-efficiency electrocatalysts for clean energy technologies. This review summarizes various synthesis strategies and applications of 2D MOFs and derivatives in electrocatalysis. Firstly, we will outline the advantages and uniqueness of 2D MOFs and derivatives, as well as their applicable areas. Secondly, the synthetic strategies of 2D MOFs and derivatives are briefly classified. Each category is summarized and we list classic representative fabrication methods, including specific fabrication methods and mechanisms, corresponding structural characteristics, and insights into the advantages and limitations of the synthesis method. Thirdly, we separately classify and summarize the application of 2D MOFs and derivatives in electrocatalysis, including electrocatalytic water splitting, oxygen reduction reaction(ORR), CO₂ reduction reaction(CO₂RR), and other electrocatalytic applications. Finally, the development prospects and existing challenges to 2D MOFs and derivatives are discussed.     

Selecting polymers for medical devices based on thermal analytical methods

This biomaterials overview for selecting polymers for medical devices focuses on polymer materials, properties and performance. An improved understanding of thermoplastics and thermoset properties is accomplished by thermal analysis for device applications. The medical applications and requirements as well as the oxidative and mechanical stability of currently used polymers in devices are discussed. The tools used to aid the ranking of the thermoplastics and thermosets are differential scanning calorimetry (DSC), thermogravimetry (TG), thermal mechanical analysis (TMA) and dynamic mechanical analysis (DMA) as well as a number of key ASTM polymer tests. This paper will spotlight the thermal and mechanical characterization of the bio-compatible polymers e.g., olefins, nylon, polyacetals, polyvinyl chloride and polyesters.     

Nature spermidine and spermine alkaloids: Occurrence and pharmacological effects

Spermidine and spermine are special polyamines in organisms, and produced in vivo by putrescine and S-adenosylmethionine catalyzed by a variety of enzymes. Spermidine and spermine possess multiple amino groups, and are closely related to cell division, growth and survival. Spermidine and spermine alkaloids are widely distributed in plants, bacteria and marine organisms, and can be divided into macrocyclic and open chain according to the skeletons. Spermidine and spermine alkaloids exhibited numerous pharmacological effects such as anti-inflammatory, antibiotics, anti-tumor, anti-Alzheimer and anti-virus. However, up to now, there are few systematic reviews on spermidine and spermine alkaloids. In this review, based on the number of atoms in the ring, we summarized the distributions and pharmacological effects of spermidine and spermine alkaloids. Spermidine and spermine alkaloids have special chemophenetic significances in the plant kingdom, especially the macrocyclic spermidine and spermine alkaloids. Spermidine alkaloids are much more abundant in nature than spermine alkaloids. The pharmacological activities of the open chain spermidine and spermine alkaloids are studied in depth. Polycyclic guanidine spermidine alkaloids, isolated from marine sponge, exhibit great potential in various cancer cells. However, pharmacological studies of macrocyclic spermidine and spermine alkaloids are scarce. Synthesis is an effective way to get more spermidine and spermine alkaloids and their analogues for further study.     

聚硅氧烷侧链甲基化β-环糊精键合交联手性毛细管柱分离对映体

合成了聚硅氧烷侧链的甲基化β-环糊精衍生物手性固定相,成功地进行了固载化,固载化程度高于90%。经测试,柱性能稳定,可在200℃下长期使用。暴露于空气中存放两年,柱效及选择性未见明显改变。对卤代烃及一些醇对映体的直接分离表现出良好的立体选择性,并应用于毛细管电色谱拆分手性化合物。     

Recent progress in MXene and graphene based nanocomposites for microwave absorption and electromagnetic interference shielding

There is widespread use of telecommunication and microwave technology in modern society, and raised the electromagnetic interference (EMI) issue to alarming situation due to apprehensive demand and growth of 5G technology undesirably disturbing the human health. The two dimensional (2D) materials including graphene and MXenes are already been used for variety of electronic devices due to their exceptional electrical, mechanical, optical, chemical, and thermal properties. MXene is composed of metal carbides, in which mainly metals are the building blocks for dielectrics, semiconductors, or semimetals. However, the strong interfaces with electromagnetic waves (EM) are variable from terahertz (THz) to gigahertz (GHz) frequency levels and are widely used in EMI and Microwave absorption (MA) for mobile networks and communication technologies. The use of different organic materials with metal, organic, inorganic fillers, polymers nanocomposite and MXene as a novel material has been studied to address the recent advancement and challenges in the microwave absorption mechanism of 2D materials and their nanocomposites. In this concern, various techniques and materials has been reported for the improvement of shielding effectiveness (SE), and theoretical aspects of EMI shielding performance, as well stability of 2D materials particularly MXene, graphene and its nanocomposites. Consequently, various materials including polymers, conducting polymers, and metal–organic frameworks (MOF) have also been discussed by introducing various strategies for improved MA and control of EMI shieling. Here in this comprehensive review, we summarized the recent developments on material synthesis and fabrication of MXene based nanocomposites for EMI shielding and MA. This research work is a comprehensive review majorly focuses on the fundamentals of EMI/MA.  The recent developments and challenges of the MXene and graphene based various structures with different polymeric composites are described in a broader perspective.     

乙烷部分氧化制C2氧化物用Fe－Al－P－O催化剂的研究Ⅰ．超细Fe－Al－P－O催化剂的制备与表征

 用溶胶－凝胶法制备了超细Fe－Al－P－O催化剂，并用DTA－TG，BET，TEM，XRD，TPR和IR等技术研究了催化剂的微观组成和结构及其晶格氧活性，探讨了催化剂的制备工艺，考察了溶胶－凝胶的形成机理、凝胶干燥及焙烧条件对催化剂微观组成和结构的影响规律．结果表明，Fe－Al－P－O催化剂呈非晶态，是具有均匀分布的超细粒子（10nm），其比表面积大（238m2／g），晶格氧活性高．FePO4和AlPO4间隔分布在催化剂表面，形成Lewis碱位（P＝O，P－O－Fe）和Lewis酸位（Fe3＋，Al3＋）．     

Anticancer IrIII–Aspirin Conjugates for Enhanced Metabolic Immuno-Modulation and Mitochondrial Lifetime Imaging

The chemo-anti-inflammatory strategy is attracting ever more attention for the treatment of cancer. Here, two cyclometalated Ir^III complexes Ir2 and Ir3 formed by conjugation of Ir1 with two antiphlogistics (aspirin and salicylic acid) have been designed. Ir2 and Ir3 exhibit higher antitumor and anti-inflammatory potencies than a mixture of Ir1 and aspirin/salicylic acid. We show that they can be hydrolyzed, accumulate in mitochondria, and induce mitochondrial dysfunction. Due to their intense long-lived phosphorescence, Ir2 and Ir3 can track mitochondrial morphological changes. Phosphorescence lifetime imaging shows that Ir2 and Ir3 can aggregate during mitochondrial dysfunction. As expected, Ir2 and Ir3 exhibit immunomodulatory properties by regulating the activity of immune factors. Both Ir2 and Ir3 can induce caspase-dependent apoptosis and caspase-independent paraptosis and inhibit several events related to metastasis. Moreover, Ir2 and Ir3 show potent tumor growth inhibition in vivo. Our study demonstrates that the combination of mitochondrial-targeting and immunomodulatory activities is feasible to develop multifunctional metal-based anticancer agents.     

Corrosion resistance of cement mortars containing spent catalyst of fluidized bed cracking (FBCC) as an additive

Compatibility is an important property for energetic materials and their additives such as a casing material or a binder. If these substances are incompatible an extra risk is introduced in handling and storage of ammunition and explosives. As part of a co-operation program between the Dutch TNO-PML and the Polish MIAT several compatibility tests are performed and compared with each other. All tests are performed according to a NATO Standard in which several tests are described which can be used to determine the compatibility of an energetic material and an additive. These tests were performed on a huge set of energetic materials e.g. propellants (single and double base), explosives (RDX, PETN, HMX and TNT) and several additives like Teflon, polypropylene, self-burning case, inhibitors etc. The results of pressure vacuum stability tests, dynamic thermogravimetry measurements and differential scanning calorimetry tests with several combinations of energetic materials and additives used during the co-operation program are presented and discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simultaneous determination and method validation of difenoconazole,propiconazole and pyraclostrobin in pepper and soil by LC–MS/MS in field trial samples from three provinces,China

A liquid chromatography–electrospray ionization tandem mass spectrometry method was developed for simple and accurate detection of the fungicides difenoconazole, propiconazole and pyraclostrobin in peppers and soil. Three fungicides residues were extracted from samples by acetonitrile and cleaned up by dispersive solid‐phase extraction before instrumental analysis. The accuracy and precision of the method were evaluated by conducting an intra‐ and inter‐day recovery experiment. The limits of quantification and detection of difenoconazole, propiconazole and pyraclostrobin in pepper and soil were 0.005 and 0.0015 mg/kg, respectively. The recoveries were investigated by spiking pepper and soil at three levels, and were found to be in the ranges 79.62–103.15% for difenoconazole, 85.94–103.35% for propiconazole and 80.14–97.69% for pyraclostrobin, with relative standard deviations <6.5%. Field experiments were conducted in three locations in China. The half‐lives of difenoconazole, propiconazole and pyraclostrobin were 5.3–11.5 days in peppers and 6.1–32.5 days in soil. At harvest, pepper samples were found to contain difenoconazole, propiconazole and pyraclostrobin well below the maximum residue limits of European Union at the interval of 21 days after last application following the recommended dosage.     

超声波-微波法制备NiW/Al2O3加氢脱硫催化剂

 采用一次浸渍技术制备了NiW/Al2O3加氢脱硫(HDS)催化剂,在制备过程中采用超声波处理浸渍液,采用微波进行样品干燥. 以噻吩为模型化合物,在微反装置上评价了该催化剂的加氢脱硫活性. 使用X射线光电子能谱和透射电镜等表征手段研究了催化剂的表面状态和物化性. 结果表明,使用超声波及微波技术制备的NiW/Al2O3催化剂具有较高的加氢脱硫活性,催化剂的活性组分较易硫化,可生成更多的硫化物种参与反应. 催化剂中硫化态钨的表面原子浓度较高,从而使硫化态钨物种保持较高的表面分散度,有利于增加活性中心的数目. 该催化剂的活性中心结构具有较多配位不饱和的边缘位和棱边位,因而具有较高的加氢脱硫活性.     

Determination of neutral and cationic herbicides in water by micellar electrokinetic capillary chromatography

The separation and determination of two s-triazines and two quats in water samples by MEKC was described. The influence of pH, type and concentration of buffer, concentration and type of surfactant, organic modifier and the added salt on the separation of the two neutral and the two cationic herbicides was studied. Simazine and atrazine (neutral compounds at the working pH) were little influenced by the chemical variables, while the cationic paraquat and diquat were more influenced. In the optimisation on the separation voltage, the total concentration of salt in the run buffer and the repeatability of the separation were taken into consideration. The composition of dissolution, in which the analytes were dissolved, was also studied.A solid-phase extraction method to retain and to elute the four analytes in a single step was also developed. Recoveries between 80 and 95% and R.S.D. between 6 and 10% was obtained in the analysis of a well-water sample spiked with 2 and 5 ppb of triazines and quats, respectively. Detection limits were between 0.6 and 1.9 ppb.     

In vivo metabolism study of rhubarb decoction in rat using high-performance liquid chromatography with UV photodiode-array and mass-spectrometric detection: a strategy for systematic analysis of metabolites from traditional Chinese medicines in biological samples

High-performance liquid chromatography with diode-array detection (HPLC-DAD) and tandem mass spectrometry (HPLC-MS/MS) was used for separation and identification of metabolites in rat urine, bile and plasma after oral administration of rhubarb decoction. Based on the proposed strategy, 91 of the 113 potential metabolites were tentatively identified or characterized. Besides anthraquinones metabolites, gallic acid, (-)-epicatechin and (+)-catechin metabolites were also detected and characterized in these biological samples. Our results indicated that glucuronidation and sulfation were the main metabolic pathways of anthraquinones, while methylation, glucuronidation and sulfation were the main metabolic pathways of gallic acid, (-)-epicatechin and (+)-catechin. Phase I reactions (e.g., hydroxylation and reduction) played a relatively minor role compared to phase II reactions in metabolism of phenolic compounds of rhubarb decoction. The identification and structure elucidation of these metabolites provided essential data for further pharmacological and clinical studies of rhubarb and related preparations. Moreover, the results of the present investigations clearly indicated the relevance and usefulness of the combination of chromatographic, spectrophotometric, and mass-spectrometric analysis to detect and identify metabolites.     

Intellectual property—The Foundation of Innovation: A scientist's guide to intellectual property

Increasingly, the activities of the practicing scientist inextricably intersect with the business world. Science is central to the development and delivery of many goods or services, and scientific discovery can directly, or indirectly, lead to substantial revenue generation. Scientists, however, have little training in the complex issues of intellectual property (IP), and often little understanding of their rights and obligations. Here, we define IP and disuss what it means to be an inventor or creator of IP. We define and differentiate between the primary forms of IP—trade secrets, copyright, trademarks, and patents—and discuss their implementation and implications for the practicing scientist.     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).