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.     

Semiconductor quantum dots and metal nanoparticles: syntheses,optical properties,and biological applications

We review the syntheses, optical properties, and biological applications of cadmium selenide (CdSe) and cadmium selenide–zinc sulfide (CdSe–ZnS) quantum dots (QDs) and gold (Au) and silver (Ag) nanoparticles (NPs). Specifically, we selected the syntheses of QDs and Au and Ag NPs in aqueous and organic phases, size- and shape-dependent photoluminescence (PL) of QDs and plasmon of metal NPs, and their bioimaging applications. The PL properties of QDs are discussed with reference to their band gap structure and various electronic transitions, relations of PL and photoactivated PL with surface defects, and blinking of single QDs. Optical properties of Ag and Au NPs are discussed with reference to their size- and shape-dependent surface plasmon bands, electron dynamics and relaxation, and surface-enhanced Raman scattering (SERS). The bioimaging applications are discussed with reference to in vitro and in vivo imaging of live cells, and in vivo imaging of cancers, tumor vasculature, and lymph nodes. Other aspects of the review are in vivo deep tissue imaging, multiphoton excitation, NIR fluorescence and SERS imaging, and toxic effects of NPs and their clearance from the body. Figure Semiconductor quantum dots and metal nanoparticles have extensive applications, e.g., in vitro and in vivo bioimaging Tamitake Itoh and Abdulaziz Anas contributed equally to this article.     

Simultaneous analysis of serotonin, melatonin, piceid and resveratrol in fruits using liquid chromatography tandem mass spectrometry

An analytical method was developed for the simultaneous quantification of serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol using reversed-phase high performance liquid chromatography coupled to mass spectrometry (HPLC-MS) with electrospray ionization (ESI) in both positive and negative ionization modes. HPLC optimal analytical separation was achieved using a mixture of acetonitrile and water with 0.1% formic acid as the mobile phase in linear gradient elution. The mass spectrometry parameters were optimized for reliable quantification and the enhanced selectivity and sensitivity selected reaction monitoring mode (SRM) was applied. For extraction, the direct analysis of initial methanol extracts was compared with further ethyl acetate extraction. In order to demonstrate the applicability of this analytical method, serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol from 24 kinds of commonly consumed fruits were quantified. The highest serotonin content was found in plantain, while orange bell peppers had the highest melatonin content. Grape samples possessed higher trans- and cis-piceid, and trans- and cis-resveratrol contents than the other fruits. The results indicate that the combination of HPLC-MS detection and simple sample preparation allows the rapid and accurate quantification of serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol in fruits.     

Photo‐hardenable and patternable PDMS/SU‐8 hybrid functional material: A smart substrate for flexible systems

The fabrication of flexible electronics and systems, using rigid and brittle materials directly produced on stretchable substrate, leads to some issues and incompatibilities. These include rigidity for processing and modular flexibility for applications, macroscopic flexibility, and local rigidity to shield components from strain, compatibility with technological steps, and at the same time allowing patterning and machining. The development of smart substrate materials which meet such needs is therefore a promising route for flexible systems. Here, we demonstrate that by mixing polydimethylsiloxane (PDMS) and SU‐8 photoresist, we obtain both a photo‐hardenable and patternable stretchable hybrid material. A set of PDMS/SU‐8 and baking process combinations have been tested to determine an effective photo‐sensitive mixture. A standard photolithographic approach has been used on tensile test samples demonstrating a local hardening of millimeter‐sized ultraviolet exposed features and a local strain reduction reaching 35%. In addition, surface topography analysis and wet‐etching techniques have been used to demonstrate a light‐induced molding process and a selective etching of micrometer‐sized ultraviolet exposed patterns. The combined functional properties of the following material, its simplicity of implementation, and the well‐known assets of PDMS and SU‐8 make the PDMS/SU‐8 material very interesting and promising for various applications, especially stretchable systems. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1281–1291     

常温常压下吡咯及其衍生物的镍催化加氢反应考察

为进一步研究常温常压下吡咯及其衍生物的镍催化加氢反应,我们对试剂吡咯、吡咯烷和吡咯烷酮做了相应的催化加氢实验。并采用电镜（TEM-HREM）、X射线衍射（XRD）对Ni基催化剂的形貌、结构、加氢活性和超声波对其影响进行了检测,同时还用紫外吸收光谱、气相色谱等对加氢产物进行了分析考察。结果表明超声波能促进镍基催化剂活性,使镍微晶(111)晶面间距增大1.5%、并保持高分散态。常温常压下纳米镍基催化剂对吡咯、吡咯烷和吡咯烷酮的加氢反应显示一定的催化活性;吡咯加氢首先生成吡咯烷,进而使环打开生成低碳烃、氨等产物,总反应为零级,符合表面接触反应特征。     

智能响应材料在磷酸化肽和糖肽富集中的应用

蛋白质的磷酸化和糖基化作为研究最广泛的两种翻译后修饰(PTMs),在疾病的早期无创诊断、预后和治疗评估中表现出越来越大的潜力。蛋白质的异常磷酸化和糖基化经常被用于临床蛋白质组学研究和疾病相关生物标志物的发现。目前已有多种材料被开发用于磷酸化肽和糖肽的富集研究,其中,智能响应材料由于具有独特的响应特性,已被陆续报道用于磷酸化肽和糖肽的富集。智能响应材料可对外界刺激做出响应,发生结构和性质上的变化,将光、电、热、机械等信号转化为生物化学信号。响应分子是决定智能响应材料响应特性的先决条件,它们在不同刺激条件下(如温度、pH、光、机械应力、电磁场等)的可逆异构化将导致材料的宏观物理和化学性质的动态变化。与传统材料相比,智能响应材料可以可逆地“打开”和“关闭”,具有更好的可调控性。由于引起智能材料响应的刺激信号对其性能具有重要的影响,综述根据施加的刺激种类对智能响应材料进行分类,具体分为外源性响应材料和内源性响应材料,且分别总结了外源性响应材料、内源性响应材料以及内外源共同响应材料在磷酸化肽和糖肽富集方面的工作。此外,综述对智能响应材料在磷酸化肽和糖肽富集方面的发展前景进行了展望,并且提出了智能响应材料在其他蛋白质翻译后修饰方面的应用中存在的挑战。     

蛋白质、凝胶电泳及其分析应用

蛋白质是重要的生物高分子，具有催化、传输、运动、防御和调节等重要生理功能，其分离、纯化和表征对理解和利用它们在生命过程中的作用具有重大理论意义和实际价值。凝胶电泳是蛋白质测定中应用最广泛和最强有力的工具。本文讨论凝胶电泳方法及其在蛋白质分析方面的新进展。首先介绍蛋白质的性质和功能，然后讨论蛋白质试样制备方法，最后评述各种凝胶电泳分离技术及其在蛋白质分离、纯化和表征等方面的应用。     

Surface chemistry and diffusion of trace and alloying elements during in vacuum thermal deoxidation of stainless steel

Removal of the native surface oxide from steel is an important initial step during vacuum brazing. Trace and alloying elements in steel, such as Mn, Si, and Ni, can diffuse to the surface and influence the deoxidation process. The detailed surface chemical composition and grain morphology of the common stainless-steel grade 316L is imaged and spectroscopically analyzed at several stages of in-vacuum annealing from room temperature up to 850°C. Measurements are performed using synchrotron-based X-ray photoemission and low-energy electron microscopy (XPEEM/LEEM). The initial native Cr surface oxide is amorphous and unaffected by the underlying Fe grain morphology. After annealing to ~700°C, the grain morphology is seen at the surface, persisting also after the complete oxygen removal at 850°C. The surface concentration of first Mn and then Si increases significantly when annealing to 500°C and 700°C, respectively, while Ni and Cr concentrations do not change. Mn and Si are not located only in grain boundaries or clusters but are distributed across over the surface. Both Mn and Si appear as oxides, while Cr oxide becomes metallic Cr. Annealing from 500°C up to 850°C leads to the removal of first the Mn and then Si oxides from the surface, while Cr and Fe are completely reduced to metals. Deoxidation of Cr occurs faster at the grain boundaries, and the final Cr metal surface content varies between the grains. The findings are summarized in a general qualitative model, relevant for austenite steels.     

多弧离子镀TiN与不同金属基材间的接触界面与表面特性

用多弧离子镀技术在不同金属基材上进行TiN镀膜实验,制备了TiN/Fe、 TiN/Cu和TiN/Cr/Cu复合膜.借助扫描电子显微镜(SEM)、 X射线衍射仪(XRD)和光电子能谱(XPS),研究了TiN与Fe、 Cu和Cr/Cu三种不同衬底接触界面的形貌、结构及其表面特性.SEM观察发现,在一定离子镀膜条件下, TiN涂层可与Fe、 Cu和Cr/Cu金属基材形成均匀平整的接触界面,在铜基上TiN界面清晰,在Fe与Cr/Cu界面有明显的层状晶界微结晶分布.XRD分析显示, Fe、 Cu和Cr/Cu表面生成的薄膜都包含TiN、 Ti2N等多晶相,在Cr/Cu界面还包含Ti-Cr的金属间化合物.XPS结果表明,表面除了TiN膜外,还生成TiO2和TiOxNy等氧化膜.Ar+刻蚀5 min后, TiO2消失, TiOxNy减少, TiN则呈增加趋势.TiN与Cr/Cu界面形成明显的Ti-Cr和Cr-Ni互扩散层,这有助于增强薄膜附着力,形成较牢固的TiN涂层.     

GC-MS analysis of penta- and tetra-cyclic triterpenes from resins of Pistacia species. Part II. Pistacia terebinthus var. Chia

Pistacia species contain oleoresins with bioactive triterpenes. In this study triterpenes, including minor components, were identified and quantified in both neutral and acidic fractions of Pistacia terebinthus var. Chia resin, grown exclusively in Chios island (Greece), collected traditionally, as well as using stimulating agents (liquid collection). It was proved that these two resin samples were composed of several different minor triterpenes, while major constituents were similar but in different proportions. Compounds that differentiated two resin samples of P. lentiscus and P. terebinthus var. Chia, both traditionally collected, were detected, in order to identify the nature of resins present in archaeological materials. In the traditionally collected resin, 37 triterpenes were identified, 12 in the acidic and 25 in the neutral fraction. In the liquid collection resin 10 compounds were identified in the acidic and 23 in the neutral fraction, while 16 compounds were not contained in the traditionally collected resin. The main triterpenes in both resin samples collected traditionally and using stimulating agents were: isomasticadienonic acid (23.6 and 26.3% w[sol ]w of the triterpenic fraction, respectively), 28-norolean-17-en-3-one (16.3 and 17.5% w[sol ]w of the triterpenic fraction, respectively) and masticadienonic acid (5.8 and 6.0% w[sol ]w of the triterpenic fraction). In this study the qualitative and quantitative composition of triterpenes was compared in the Pistacia lentiscus and P. terebinthus var. Chia resin samples collected with the traditional and new liquid techniques, and also triterpenes in resins of P. terebinthus obtained by the traditional technique and using stimulating agents. The aim of the study was also to examine whether the collection technique influenced the triterpenes contained in P. terebinthus var. Chia resin samples.     

六硝基六氮杂三环十二烷的结构和性能--HEDM分子设计

The compound Hexanitrohexaazatricyclododecane was designed and calculated by using the density functional theory method at the B3LYP/6-31G level. According to the calculated results, there are two optimized conformational structures, boat (α) and chair (β). It is found that the former is more stable based on the analysis of total energies, frontier molecular orbital energies and Mulliken populations. The IR spectra were obtained and assigned by means of normal-mode analyses. Thermodynamic properties at 200-800 K were provided using the statistical thermodynamics method. Finally, the detonation velocity and detonation pressure were predicted by Kamlet formula based on the calculated theory density and heat of formation. The predicted detonation velocity and detonation pressure of α conformer are 9.46 km/s and 41.74 GPa, while those of β are 9.34 km/s and 40.02 GPa, respectively.     

SYNTHESIS, CHARACTERIZATION, THERMAL DEGRADATION AND ELECTROCHEMICAL PROPERTIES OF OLIGO-4-m-TOLYLAZOMETHINEPHENOL

The oxidative polycondensation reaction conditions of 4-m-tolylazomethinephenol （4-TAMP） in the presence of air O2 and NaOCl as oxidants were studied in an aqueous alkaline medium between 50 and 90℃. The structures of the obtained monomer and oligomer were confirmed by FT-IR, UV-Vis, ^1H- and ^13C-NMR and elemental analysis techniques. The physical characterization was made by TG-DTA, size exclusion chromatography （SEC） and solubility tests. At the optimum reaction conditions, the yield of oligo-4-m-tolylazomethinephenol （O-4-TAMP） was found to be 62.50% （for air O2 oxidant） and 90.0% （for NaOCl oxidant）, respectively. According to the SEC analysis, the number-average molecular weight （Mn）, weight-average molecular weight （Mw） and polydispersity index （PDI） values of O-4-TAMP were found to be 2310, 2610 g tool 1 and 1. 13, respectively, using air O2, and 1390, 1710 g mol^-1 and 1.23, using NaOCl, respectively. According to TG-DTA analyses, O-4-TAMP was more stable than 4-TAMP against thermal decomposition. The weight losses of 4-TAMP and O-4-TAMP were found to be 68% and 58% at 1000℃. Electrical conductivity of the O-4-TAMP was measured, showing that the polymer is a typical semiconductor. Electrochemically, the highest occupied molecular orbital （HOMO）, the lowest unoccupied molecular orbital （LUMO） and electrochemical energy gaps （E＇g） for 4-TAMP are -5.96, -3.22 and 2.74 eV, respectively. The HOMO, LUMO and （E＇g） for O-4-TAMP are -5.78, -3.44 and 2.34 eV, respectively. According to UV-Vis measurements, optical band gaps （Eg） of 4-TAMP and O-4-TAMP were found to be 3.45 and 3. 1 0 eV, respectively.     

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANOMONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.     

Simultaneous Determination of Cadmium,Mercury, Lead,Arsenic, Copper,and Zinc in Human Breast Milk by ICP‐MS/Microwave Digestion

Abstract

An analytical method using microwave digestion and inductively coupled argon plasma-mass spectrometry (ICP‐MS) analysis was developed for the measurement of Cd, Hg, Pb, As, Cu, and Zn in human breast milk. We applied external calibration, internal calibration, and standard addition for reference material and pooled milk analysis. Method performances were defined in terms of detection limits, accuracy, and precision. Accuracy varied between 93% and 105% and precision between 3% and 8%. External calibration and background interferences were checked through a calibrator addition procedure. Our method has shown high accuracy, precision, and sensitivity, as well as linearity within a wide range of values. Our methodology, developed by treatment of reference material and pooled milk samples, was applied for determination of Cu, Zn, As, Cd, Hg, and Pb in 120 human breast milk samples.     

Phenolics from Medicinal and Aromatic Plants: Characterisation and Potential as Biostimulants and Bioprotectants

Biostimulants and bioprotectants are derived from natural sources and can enhance crop growth and protect crops from pests and pathogens, respectively. They have attracted much attention in the past few decades and contribute to a more sustainable and eco-friendly agricultural system. Despite not having been explored extensively, plant extracts and their component secondary metabolites, including phenolic compounds have been shown to have biostimulant effects on plants, including enhancement of growth attributes and yield, as well as bioprotectant effects, including antimicrobial, insecticidal, herbicidal and nematicidal effects. Medicinal and aromatic plants are widely distributed all over the world and are abundant sources of phenolic compounds. This paper reviews the characterisation of phenolic compounds and extracts from medicinal and aromatic plants, including a brief overview of their extraction, phytochemical screening and methods of analysis. The second part of the review highlights the potential for use of phenolic compounds and extracts as biostimulants and bioprotectants in agriculture as well as some of the challenges related to their use.     

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS： EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.     

醛类标志物的化学衍生化色谱-质谱分析方法进展

人体接触环境中的化学污染物会导致多种疾病,包括癌症、糖尿病、心血管疾病、神经退行性疾病(阿尔茨海默症、帕金森病等)等.作为一类具有高反应活性的亲电化合物,醛类(包括外源性醛类或环境污染物暴露后产生的内源性醛类)可与人体中多种重要生物分子形成共价修饰产物而产生毒害作用.暴露组研究自2005年被首次提出以来一直是一个前沿热...     

Temperature effects on the structure and dynamics of liquid dimethyl sulfoxide: A molecular dynamics study

The molecular dynamics (MD) simulation technique has been employed to investigate the thermodynamic properties and transport coefficients of the neat liquid dimethyl sulfoxide (DMSO). The fluid has been studied at temperatures in the range 298–353 K and at a pressure equal to 1 atm. The simulations employed a nine-site potential model, which is presented for the first time here, and all the available non-polarizable models. The performance of each model is tested using the same statistical mechanical ensemble and simulation method under the same conditions, revealing its weaknesses and strengths. Thermodynamic properties, microscopic structure and dynamic properties, such as transport coefficients, rotational and single-dipole correlation times have been calculated and compared with available experimental results. Estimations of transport coefficients from various theoretical and empirical models are tested against experimental and MD results. Translational and rotational dynamics suggest the existence of the cage effect and agree with the Stokes–Einstein–Debye relation. The dipole relaxation times calculated are discussed in terms of simple and useful approximations, such as the Glarum–Powles and Fatuzzo–Mason models.     

Perfluorocarbons: Life sciences and biomedical uses Dedicated to the memory of Professor Guy Ourisson,a true RENAISSANCE man.

Perfluorocarbons are primarily characterized by outstanding chemical and biological inertness, and intense hydrophobic and lipophobic effects. The latter effects provide a powerful noncovalent, labile binding interaction that can promote selective self‐ assembly. Perfluoro compounds do not mimic nature, yet they can offer abiotic building blocks for the de novo design of functional biopolymers and alternative solutions to physiologically vital issues. They offer new tags useful for molecular recognition, selective sorting, and templated binding (e.g., selective peptide and nucleic acid pairing). They also stabilize membranes and provide micro‐ and nanocompartmented fluorous environments. Perfluorocarbons provide inert, apolar carrier fluids for lab‐on‐a‐chip experiments and assays using microfluidic technologies. Low water solubility, combined with high vapor pressure, allows stabilization of injectable microbubbles that serve as contrast agents for diagnostic ultrasound imaging. High gas solubilities are the basis for an abiotic means for intravascular oxygen delivery. Other biomedical applications of fluorocarbons include lung surfactant replacement and ophthalmologic aids. Diverse colloids with fluorocarbon phases and/or shells are being investigated for molecular imaging using ultrasound or magnetic resonance, and for targeted drug delivery. Highly fluorinated polymers provide a range of inert materials (e.g., fluorosilicons, expanded polytetrafluoroethylene) for contact lenses, reconstructive surgery (e.g., vascular grafts), and other devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1185–1198, 2007.