Transport Polymerization of Gaseous Intermediates and Polymer Crystals Growth

Man is always enchanted with discoveries of new and better ways of making things. Even after more than a hundred years of synthetic chemistry, scientists are today still as enthusiastic as ever looking for “novel” reactions and “novel” syntheses. One of the great achievements of the last decade was the development and usage of “intermediates” for syntheses. Knowing the extensive applications [1-4] of these intermediates in modern synthetic chemistry, it is, however, surprising to find that only few groups of these intermediates have been used in polymer syntheses. For instance [5], even though there are radical polymerizations and polymerizations involving carbanions and carbonium ions, there are practically no polymer syntheses using benzynes [2], carbenes [3], or nitrenes [4].     

High-efficiency polymer light-emitting diodes using neutral surfactant modified aluminum cathode

High-efficiency polymer light-emitting diodes were fabricated by inserting a layer of nonionic neutral surfactant between the electroluminescent (EL) layer and the high-work-function aluminum cathode via spin coating. It was found that both the poly(ethylene glycol)- and poly(propylene glycol)-based surfactants as well as their copolymers can all demonstrate similar performance enhancement. Device performances comparable to or even better than those of the control devices using calcium as the cathode have been achieved for both poly(p-phenylene)-based and polyfluorene-based conjugated polymers with orange-red, green, and blue emission colors. It is possible that when both surfactant and aluminum are used as the cathode, the abundant hole injection through a hole-transporting layer and hole pile-up at the inner side of the EL/surfactant interface might cause an effective electric field to induce the realignment of the dipole moment of those polar surfactant molecules, thus lowering the barrier for electron injection. In addition, the coordination between the aluminum and oxygen atoms on the surfactant might cause n-type doping in the areas near surfactant in the EL polymer layer that causes the enhancement of electron injection.     

Direct Synthesis of Chiral 3‐Arylsuccinimides by Rhodium‐Catalyzed Enantioselective Conjugate Addition of Arylboronic Acids to Maleimides

Chiral rhodium catalysts comprising 2,5‐diaryl‐ substituted bicyclo[2.2.1]diene ligands L1 – L10 were utilized in the enantioselective 1,4‐addition reaction of arylboronic acids to N‐substituted maleimides. In the presence of 2.5 mol % of Rh^I/ L2 , enantioenriched conjugate addition adducts were isolated in 72–99 % yields with 86–98 % ee. This protocol offers a convenient method to access a variety of 3‐arylsuccinimides in a highly enantioselective manner. Maleimides with readily cleavable N‐protecting groups were tolerated enabling the synthesis of useful synthetic intermediates. Pyrrolidine 4 , a biologically active compound, and pyrrolidine 5 , an ent‐precursor to an HSD‐1 inhibitor, were synthesized to demonstrate the utility of this method.     

The conceptual analysis (CA) method in theories of microchannels: Application to quantum theory. Part I. Fundamental concepts

A method is proposed that should facilitate the construction of theories of submicroscopic particles (denoted as theories of microchannels) in a way similar to the use of group-theoretical methods. The conceptual analysis (CA) method is based on the analysis of the basic concepts of a theory; it permits a determination of necessary conditions imposed on the mathematical apparatus (of the theory) which then appear as a mathematical representation of the structures obtained in a formal scheme of a theory. A pertinent conceptual analysis leads to a new definition (relativization) of the concept empirical implication. The approach may be characterized as realistic and operational. The application of the CA method is illustrated on the example of quantum theory. In Part I the algebraic structure of a partially ordered, up-ward directed, bounded set is deduced from the rudimentary concepts. In Parts II and III, we shall deduce the Hilbert-space structure (well established in quantum mechanics) from postulates on some essential idealizations accepted in the theory. Whereas Part II is concerned with the idealizations of existing quantum theories based on the Hilbert-space formalism, Part I may be considered as a general basis for a wider class of theories.Dedicated to Prof. G. Ludwig on the occasion of his 60th birthday.     

Differential pulse polarographic determination of cyanuric chloride

Cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) can be determined by fastscan differential pulse polarography in methanolic acetate buffer solution at pH 5.6 at a hanging mercury drop electrode. At positive potentials, the insoluble salt formed between cyanuric chloride and mercury(I) is adsorbed on the mercury surface and the d.p.p. current is enhanced. The detection limit is 0.2gmg ml^?1. Cyanuric chloride in air can be determined after absorption in methanol.     

The detection of formaldehyde in textiles using interdigitated microelectrode array diffusion layer titration with electrogenerated hypobromite

An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher (78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a detection limit of 4×10⁻⁶ mol dm⁻³.     

Embedded units in conjugated polymers

The problem of embedding of several monomeric units (benzene, thiophene, isothianaphthene) into linear oligoenes or into a polymer built up by the same units is discussed. Using a simple model Hamiltonian, we evaluate the geometry (bond lengths) and electronic structure (energy gaps) of conjugated oligomers containing up to 200 atoms. Special attention is paid to end effects. The quinoid-aromatic transition and the conjugation interruption due to embedded defects is studied in some detail.     

Autoignition of methanol: Experiments and computations

An experimental and computational investigation into the autoignition of methanol under high‐pressure and low‐to‐intermediate temperature conditions is conducted. The ignition delay results have been obtained using a heated rapid compression machine, over a pressure range of 7–30 bar, a temperature range of 850–1100 K, and an equivalence ratio range of 0.25–2.0. Using kinetic schemes recently reported in the literature for the combustion of methanol, the experimental results are compared to computationally obtained values. The kinetic schemes studied are found to significantly underpredict ignition delays for the conditions investigated. A sensitivity analysis of the computed results to reaction rate constants is also conducted. It is shown that the reaction of methanol with HO₂ radical is critical to the predicted values of ignition delays under the current experimental conditions. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 175–184, 2011     

Synthesis and applications of cyano‐vinylene‐based polymers containing cyclopentadithiophene and dithienosilole units for photovoltaic cells

Two β‐cyano‐thiophenevinylene‐based polymers containing cyclopentadithiophene ( CPDT‐CN ) and dithienosilole ( DTS‐CN ) units were synthesized via Stille coupling reaction with Pd(PPh₃)₄ as a catalyst. The effects of the bridged atoms (C and Si) and cyano‐vinylene groups on their thermal, optical, electrochemical, charge transporting, and photovoltaic properties were investigated. Both polymers possessed the highest occupied molecular orbital (HOMO) levels of about ?5.30 eV and the lowest unoccupied molecular orbital (LUMO) levels of about ?3.60 eV, and covered broad absorption ranges with narrow optical band gaps (ca. 1.6 eV). The bulk heterojunction polymer solar cell (PSC) devices containing an active layer of electron‐donor polymers ( CPDT‐CN and DTS‐CN ) blended with an electron‐acceptor, that is, [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM), in different weight ratios were explored under 100 mW/cm² of AM 1.5 white‐light illumination. The PSC device based on DTS‐CN: PC₇₁BM (1:2 w/w) exhibited a best power conversion efficiency (PCE) value of 2.25% with V_oc = 0.74 V, J_sc = 8.39 mA/cm², and FF = 0.36. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.