Structure and growth of self-assembling monolayers

The structural phases and the growth of self-assembled monolayers (SAMs) are reviewed from a surface science perspective, with emphasis on simple model systems. The concept of self-assembly is explained, and different self-assembling materials are briefly discussed. A summary of the techniques used for the study of SAMs is given. Different general scenarios for structures obtained by self-assembly are described. Thiols on Au(1 1 1) surfaces are used as an archetypal system to investigate in detail the structural phase diagram as a function of temperature and coverage, the specific structural features on a molecular level, and the effect of changes of the molecular backbone and the end group on the structure of the SAM. Temperature effects including phase transitions are discussed. Concepts for the preparation of more complex structures such as multi-component SAMs, laterally structured SAMs, and heterostructures, also with inorganic materials, are outlined. The growth and ways to control it are discussed in detail. Solution and gas phase deposition and the impact of various parameters such as temperature, concentration (in solution) or partial pressure (in the gas phase) are described. The kinetics and the energetics of self-assembly are analyzed. Several more complex issues of the film formation process including non-equilibrium issues are discussed. Some general conclusions are drawn concerning the impact of various molecular features on the growth behavior and concerning the relationship between growth and structural phase diagram. Finally, the potential of self-assembly as a route for the preparation of monolayers with pre-designed properties and SAMs as building blocks in heterostructures as well as application strategies are discussed.     

The use of solid sorbents for direct accumulation of organic compounds from water matrices–a review of solid-phase extraction techniques

The main principles of solid-phase extraction techniques are reviewed in this paper. Various solid sorbents can be used as a suitable trap for direct accumulation of organic compounds from aqueous solutions. The trapped analytes can be desorbed by elution with suitably chosen liquid phases. These preconcentration procedures can be considered as low performance liquid chromatography and the efficiency of the procedure can thus be related to the retention characteristics of the preconcentration column. The main sorbents used for trace enrichment purposes are also reviewed. Besides, the concise methodology, sample storage, and automation are discussed. The advantages of solid phase extraction as compared to liquid-liquid extraction are given as well as some drawbacks of this method.     

环糊精衍生物气相色谱手性固定相研究进展

评述近年环糊精衍生物气相色谱手性固定相的研究进展,对环糊精衍生物进行分类并总结了近年来其在GC手性分离上的应用,介绍环糊精衍生物的手性分离机制及纯度问题进展,展望环糊精衍生物作GC手性固定相的应用前景。     

几种方酸菁染料的NMR及光谱特性研究

研究了几种方酸菁染料的核磁、可见、荧光光谱。通过二维核磁共振谱和¹³CNMR确定了分子的结构和构型。测定了其在不同溶剂中吸收光谱和荧光发射光谱及其发射的荧光量子产率。发现它具有微弱的正向溶致变色特性,通过光谱特征分析得出整个分子处于平面结构并形成一个长的共轭体系,其激发态和基态的结构相近的结论。同时,讨论了结构对分子电荷分布及相应荧光光谱特征的影响。     

Molecular modeling and photovoltaic applications of porphyrin-based dyes: A review

In this review, the introduction of solar cells is presented. Old and new generation solar cells are briefly described. Quantum dot solar cells (QDSCs), perovskite solar cells, and dye-sensitized solar cells (DSSCs) are concisely introduced. The sensitization mechanism in DSSCs is discussed in detail concerning the spectral and electron injection properties of different dyes. An analysis of the intramolecular charge transfer process in the excited dye molecule is also provided. The use of porphyrin-based dyes as sensitizers in DSSCs is then reviewed. The design, synthesis, and photovoltaic application of a wide variety of porphyrin-based dyes as well as porphyrin dyads are presented and discussed. Theoretical studies of the spectral and electronic properties of different porphyrin-based dyes using DFT and TD-DFT methods are described. The different possibilities for improving the light-to-electrical energy conversion performance are discussed, such as structural modifications through introducing push-pull moieties, which in turn tunes the HOMO-LUMO energy gap of the sensitizing dye used in the DSSC. Experimental, as well as theoretical calculations of adsorption energies of the sensitizing dyes, are crucial for predicting the relative performance and efficiency of the dyes.     

纤维素的均相化学反应

本文回顾了近10多年来的纤维素均相反应发展过程,研究了PF/DMSO、LiCl/DMAc、N₂O₄/DMF、苯/DMSO、LiCl/DMI和水等溶剂体系的纤维素均相反应条件(如酯化反应、交联反应、醚化反应、接枝共聚等),并总结了纤维素均相衍生化的分析方法,讨论了各种方法的优缺点以及发展前景.     

Chemical reaction and Soret effects on MHD convective flow of second grade fluid through an absorbent medium with ramped wall temperature as well as ramped surface concentration

In the present paper, the heat generating and/or absorption as well as thermo-diffusion on the unsteady free convection MHD gyrating flow of radiation and chemical reactive second grade fluid past an unbounded perpendicular plate during absorbent medium have been discussed. Here, it is assumed that, the confining plate has the ramped wall temperature with ramped surface concentration and isothermal temperature with ramped surface concentration. The analytical solutions for the governing equations are found by utilization of Laplace transformation methodology. The velocity, temperature and concentration profiles are analyzed with quite few figures. It is determined that, velocity, temperature and concentration distribution sketches in case of ramped temperature as well as ramped surface concentration are not as much of as those of isothermal temperature as well as ramped surface concentration. In addition to the idioms of skin friction, Nusselt number as well as Sherwood number are achieved and characterized numerically with tabular format.     

Chromatographic determination of fungicides in biological and environmental matrices. New achievements

The newest results in the chromatographic analysis of synthetic and natural fungicides present in biological and environmental matrices are collected and critically evaluated. Examples of the employment of gas chromatography, liquid chromatographic technologies, such as thin-layer chromatography and high-performance liquid chromatographic methods as well as electrically driven systems are presented. The advantages and disasdvantages of the various chromatographic technologies are briefly discussed and the efficacies of the methodologies are compared.     

Hydrotalcite catalysis for the synthesis of new chiral building blocks

The use of hydrotalcites for the synthesis of two chiral building blocks in a simple way is described as a new and green methodology. The synthesis of these compounds implies a regioselective Baeyer–Villiger reaction in a very selective way with ulterior opening and lactonisation. This methodology should be considered green for the use of hydrogen peroxide as the only oxidant and hydrotalcites as the catalyst, and because no residues are produced apart from water. The procedure is very adequate for using in gram scale, in order to increase the value of the obtained compounds. The conditions are excellent and can be applied for nonstable compounds, as they are very mild. The synthesised compounds are magnific starting materials for the synthesis of biologically active or natural compounds. The use of a cheap, commercial and chiral compound as carvone disposable in both enantiomeric forms adds an extra value to this methodology.     

Effect of phosphate activating group on oligonucleotide formation on montmorillonite: the regioselective formation of 3',5'-linked oligoadenylates

The effects of amine structure on the montmorillonite-catalyzed oligomerization of the 5'-phosphoramidates of adenosine are investigated. 4-Aminopyridine derivatives yielded oligoadenylates as long as dodecamers with a regioselectivity for 3',5'-phosphodiester bond formation averaging 88%. Linear and cyclic oligomers are obtained and no A5'ppA-containing products are detected. Oligomers as long as the hexanucleotide are obtained using 2-aminobenzimidazole as the activating group. A predominance of pA2'pA is detected in the dimer fraction along with cyclic 3',5'-trimer; no A5'ppA-containing oligomers were detected. Little or no oligomer formation was observed when morpholine, piperidine, pyrazole, 1,2,4-triazole, and 2-pyridone are used as phosphate-activating groups. The effects of the structure of the phosphate activating group on the oligomer structure and chain lengths are discussed.     

人工智能味觉系统：概念、结构与方法

本文将传统的味觉传感器、人工味觉、电子舌等研究统一纳入人工智能味觉的框架中，提出了人工智能味觉的概念、结构及方法学问题。在传统分析科学中，非特异性感应是一个极力避免的现象，而交互感应传感器阵列则是将其作为基本出发点，设计构建成一个优化的组合，使得人工智能化学感受在技术上得以实现，交互感应理论和技术也因此成为其核心概念。作为一种仿生感觉技术，人工智能味觉系统是由交互感应电极及阵列、自学习专家数据库和智能模式识别三部分构成；电位法和伏安法是两类主要的传感方法；传感器材料包括贵金属及稀土金属、类脂/聚合物、硫属玻璃、导电聚合物以及其它如碳糊、酞菁、普鲁士蓝等；主成分分析和人工神经网络是智能识别过程中主要的模式识别工具。导电聚合物修饰电化学传感器和多技术联用分析方法目前已成为人工智能味觉系统研究的两个重要发展方向。     

Optimal group symmetric localized molecular orbitals

Summary The concept and generating method of optimum group symmetric localized molecular orbitals (OSLMOs) are proposed. The OSLMOs have strong points of orthogonality, equivalence and symmetry, and they are simultaneously as close to the classical VB structure as possible. By using the OSLMOs as one-electron orbitals the multiconfigurational correlation calculations are reduced. The scheme is also a valuable popularization and development to hybridization theory.     

Detection of electronic and vibrational coherences in molecular systems by 2D electronic photon echo spectroscopy

Two-dimensional optical photon echo spectra are simulated for model systems which exhibit vibrational, electronic and a combination of electronic and vibrational coherent dynamics. The coherent motion manifests itself as periodic beatings of the spectrum cross-peak intensity with the population time. The intensity modulations are compared to evolution of the excited-state population and coordinate expectation value. The advantageous capabilities of the technique as well as possible difficulties in spectra interpretations are outlined. Possibilities for distinguishing electronic and vibrational coherences are discussed.     

Catalytic hydrogen production at cobalt centres

The catalytic properties of a wide range of cobalt complexes with respect to proton reduction are discussed. Electrocatalytic as well as photocatalytic systems are addressed and to allow comparison between the different systems reported considerable attention is paid to the reaction conditions used. For the photocatalytic proton reduction a range of ruthenium, iridium and rhenium complexes are discussed as potential photosensitizers. The photocatalytic systems are discussed in detail and issues such as the nature of the sacrificial agent and the solvents used. Both intermolecular and intramolecular photocatalysis are considered. The results obtained are considered with respect to the need to the development of sustainable energy sources.     

Simultaneous determination of carbohydrates and organic acids in beer and wine by ion chromatography

The simultaneous determination of mono-organic acids and carbohydrates by ion chromatography with both conductometric and pulsed amperometric detection is described. The carbohydrates, such as mannitol, arabinose, glucose, fructose, lactose, sucrose, raffinose, and maltose, as well as monoorganic acids including acetate, glycolate, formate, pyruvate, and fluoride are separated as anions by ion-exchange chromatography with 0.080 mol/L sodium hydroxide eluent at 1 mL/min within 12 min. Carbohydrates are determined by pulsed amperometric detection and mono-organic acids are determined by suppressed conductivity detection. The species in beverages are determined.     

氮掺杂改性二氧化钛光催化剂的研究进展

综述了近年来国内外利用氮掺杂改性二氧化钛的光催化剂性能、提高可见光的利用效率的最新研究进展;分析和讨论了氮掺杂二氧化钛的制备方法、理论计算和结构模型、掺杂机理等;总结了氮掺杂改性二氧化钛存在的问题,同时讨论了今后的研究方向.     

Lewis碱改性氧化锆基质色谱固定相的研究进展

综述了Lewis碱改性氧化锆(或其复合氧化物)基质高效液相色谱填料的研究进展,涉及的改性剂包括氟离子、磷酸盐、有机膦酸、羧酸、酚类化合物、蛋白质和环糊精衍生物等。简要介绍了Lewis碱改性氧化锆固定相在毛细管电色谱中的应用。 引用文献51篇。     

Square‐Wave Voltammetry of Cathodic Stripping Reactions. Diagnostic Criteria,Redox Kinetic Measurements,and Analytical Applications

A comparative study of different types of cathodic stripping reactions under conditions of square‐wave voltammetry is presented. Cathodic stripping processes involving reactions of second order as well as reactions coupled by adsorption of the reacting ligand are analyzed The inherent parameters, controlling the overall voltammetric behavior of each cathodic stripping electrode reaction are derived. The criteria for qualitative distinguishing of each mechanism are established as well as a methodology for redox kinetic measurements is proposed. The influence of the parameters of the excitation signal on the properties of the voltammetric response is analyzed in order to find optimal conditions for analytical application. The theoretical results are illustrated by the experiments with a series of uracil derivatives.     

Homogeneous catalysis by ruthenium carbonyl clusters

The historical background of and the incentive for using ruthenium carbonyl clusters as homogeneous catalysts are outlined. Keeping in view the possible solutions the uncertainties arising from declusterification and metal colloid formation are discussed. All ruthenium cluster-catalysed reactions are broadly classified as reactions with or without carbon monoxide as one of the reactants and the basic differences between such reactions are highlighted. Some of the factors of special relevance to cluster-catalysed reaction systems are mentioned. The reactions involving carbon monoxide are then discussed. These include water-gas-shift reaction, carbon monoxide hydrogenation, hydroformylation, reductive carbonylation of nitrobenzene and other carbonylation reactions. Hydrogenation, transfer hydrogenation, isomerisation and a few other reactions are then discussed. For all these reactions, special emphasis is laid on well-characterised cluster complexes that have been proposed as catalytic intermediates. Finally an attempt has been made to identify the path that future research in cluster catalysis is likely to follow.