Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals

Whereas much of organic chemistry has classically dealt with the preparation and study of the properties of individual molecules, an increasingly significant portion of the activity in chemical research involves understanding and utilizing the nature of the interactions between molecules. Two representative areas of this evolution are supramolecular chemistry and molecular recognition. The interactions between molecules are governed by intermolecular forces whose energetic and geometric properties are much less well understood than those of classical chemical bonds between atoms. Among the strongest of these interactions, however, are hydrogen bonds, whose directional properties are better understood on the local level (that is, for a single hydrogen bond) than many other types of non-bonded interactions. Nevertheless, the means by which to characterize, understand, and predict the consequences of many hydrogen bonds among molecules, and the resulting formation of molecular aggregates (on the microscopic scale) or crystals (on the macroscopic scale) has remained largely enigmatic. One of the most promising systematic approaches to resolving this enigma was initially developed by the late M. C. Etter, who applied graph theory to recognize, and then utilize, patterns of hydrogen bonding for the understanding and design of molecular crystals. In working with Etter's original ideas the power and potential utility of this approach on one hand, and on the other, the need to develop and extend the initial Etter formalism was generally recognized. It with that latter purpose that we originally undertook the present review.     

ON SELF-ABSORPTION CORRECTION IN EXCIMER FLUORESCENCE MEASUREMENTS OF POLYMER SOLUTIONS

The effect of self absorption on the ratio of excimer to monochromophore emission intensities, I_e/I_m, has beenexplored by experimentally changing the solution layer thickness of the emission light path traversed in the solution in theright-angle geometry. The result shows that data obtained by front-face geometry are better than those obtained by right-angle geometry even after correction to zero solution thickness. The correction formula based on geometric optics given byTsai and Torkelson is not adequate.     

FIA Determination of Paracetamol in Pharmaceutical Drugs by Using Gold Electrodes Modified with a 3‐Mercaptopropionic Acid Monolayer

A flow injection analysis (FIA) method for the determination of paracetamol in pharmaceutical drugs using a gold electrode modified with a self‐assembled monolayer (SAM) of 3‐mercaptopropionic acid is described. At optimized experimental conditions the dynamic concentration range was 0.15 to 15.0 mg L^?1 with a detection limit of 0.2 μg mL^?1 (S/N=3). The repeatability of current responses for injections of 10 μmol L^?1 paracetamol was evaluated to be 3.2% (n=30) and the analytical frequency was 180 h^?1. The lifetime of the modified electrode was found to be 15 days. The results obtained by using the proposed amperometric method for paracetamol determination in four different drug samples compared well with those found by spectrophotometry.     

Electrochemical Characterization of the Self‐assembled Monolayer of 6‐Thioguanine on the Mercury Electrode

A self‐assembled monolayer (SAM) of 6‐thioguanine (6TG) was formed on the hanging mercury drop electrode, under open circuit potential, from 6TG solutions. The SAM has been characterized by cyclic voltammetry under both in situ and ex situ conditions and the experimental data reveal that the film is a densely packed structure of chemisorbed (mercury‐thiol) molecules. The presence of this SAM has no influence on the rate of outer‐sphere electrode reactions but strongly inhibits inner‐sphere processes. The electrode reaction involving the Fe(CN) couple appears reversible in a hanging mercury drop electrode coated by the 6TG‐SAM.     

Synthesis and Qualitative Analysis of BACy and Its Self‐polymer

Many synthetic strategies of a reversible cross‐linker N,N′‐bis(acryloyl)cystamine (BACy) involve the typical condensation between the amino group of cystamine and the acyl group of acryloyl chloride in the mixed‐phase solvent system. In this study, the synthesis of BACy was performed in pure organic phase during the whole process. The yield and purity of synthesized BACy were comparable to those from aqueous/organic phase procedures. In addition, polymerization of BACy was also carried out by free radical reaction to prepare the self‐polymer and hydrogel which were characterized with FT‐IR, DSC and UV/VIS spectrophotometer. Notably, the BACy and its self‐polymer were both cleavable when exposed to the reducing agents, i.e. 1,4‐dithiothreitol (DTT) and 2‐mercaptoethanol (β‐ME). Interestingly, the reduced product of BACy contains vinyl and thiol groups, which could be further applied to the co‐polymerization with other monomeric units. On the other hand, carefully controlled reduction of BACy self‐polymer may be used to create the modified polymers with available thiol‐end groups for further chemistry. Together, our study provides modified procedure for BACy synthesis and characteristics of BACy self‐polymer and hydrogel. Further application of BACy and its self‐polymer in developing polymers with additional functionality is anticipated.     

信息与生命

理解生命的本质的关键，在于信息科学与生物学的结合，以系统和综合的观点去理解生物，综合多种信息对生物体进行分析。生物信息学正是这样一个新兴的交叉学科。     

Studies of Adsorption Kinetics and Defects of Self‐Assembled Thiol Monolayers on Gold by Capacitance Plane Plot

The capacitive property of an electrode/electrolyte interface can be described by complex capacitance. The capacitance plane plots (CPPs) of ideal polarized and kinetic controlled electrodes are derived based on the concept of complex capacitance. By using CPPs, the capacitance of electrode/electrolyte interface can be conveniently determined. In this work, CPPs obtained in ac impedance experiments are employed for the first time in studying the kinetics of adsorption process of the thiol monolayer. The coverage of octadecanethiol (ODT) monolayer on gold is examined as a function of adsorption time. The adsorption process of ODT molecules on gold exhibits two distinct phases: an initial rapid step followed by a slow one. The simple Langmuir model best explains our experimental data in the initial adsorption stage. CPPs and cyclic voltammetry (CV) indicate that, in the initial adsorption step, the ODT monolayer contains defects whose number decreases with the increasing of adsorption time.     

Second Harmonic Generation of Self Focused Cosh‐Gaussian Laser Beam in Collisionless Plasma

This paper presents an investigation of self‐focusing of a Cosh‐Gaussian (ChG) laser beam and its effect on second harmonic generation in collisionless plasma. In the presence of ChG laser beam the carriers get redistributed from high field region to low field region on account of ponderomotive force as a result of which a transverse density gradient is produced in the plasma which in turn generates an electron‐plasma wave at pump frequency. Generated plasma wave interacts with the incident laser beam and hence generates its second harmonics. Moment theory has been used to derive differential equation governing the evolution of spot size of ChG laser beam propagating through collisionless plasma. The differential equation so obtained has been solved numerically. The effect of decentered parameter, intensity of ChG laser beam and density of plasma on self‐focusing of the laser beam and second harmonic yield has been investigated. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Generalized Monotone Operators on Dense Sets

In the present work we show that the local generalized monotonicity of a lower semicontinuous set-valued operator on some certain type of dense sets ensures the global generalized monotonicity of that operator. We achieve this goal gradually by showing at first that the lower semicontinuous set-valued functions of one real variable, which are locally generalized monotone on a dense subsets of their domain are globally generalized monotone. Then, these results are extended to the case of set-valued operators on arbitrary Banach spaces. We close this work with a section on the global generalized convexity of a real valued function, which is obtained out of its local counterpart on some dense sets.     

Effect of the Electron‐Beam Self‐Fields on Gain in an Optical Wiggler Pumped Free‐Electron Laser

The effects of self fields on gain for a free‐electron lasers (FELs) with electromagnetic‐wave wiggler and an axial guide magnetic field is presented. The relativistic equation of motion for a single electron for all relevant fields, including wiggler, self‐fields and axial guide magnetic field has been solved. Two classes of possible single‐particle trajectories in this configuration are found. Result of the numerical calculation shown that the relativistic part of group I (group II) orbits decreases (increases) monotonically with the axial field. The gain equations for the FEL configuration by adding the effect of self‐fields have been derived. The numerical calculation has been employed to analysis the gain induced by the effects of the self‐fields. It is shown that, for group I orbits the gain decreases in the presence of self‐fields and the gain decrement increases with increasing axial guide magnetic field, while for group II orbits the self‐fields enhances the gain. The gain decrement and enhancement are due to diamagnetic and paramagnetic effects of the self‐magnetic field, respectively. The comparison of the gain for electromagnetic‐wave wiggler with the gain in helical wiggler has been done (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)