Dissipation functions and conservation laws of molecular liquids and solids

Thermodynamics of molecular liquids (anisotropic liquids, liquid crystals, etc.) and molecular solids (e.g. dielectrics, pyroelectrics, molecular crystals) are treated in a unified way, using an internal energy potentialU and a dissipation functionD. Assuming that the motion of the mass points making up the molecule is essential in determiningU we write down the appropriate field equations of motion and the entropy equation. With the assumed invariance ofU under a group of space-time transformations and the invariance ofD under rigid body uniform motions, we derive the conservation laws of mass, momentum, energy and angular momentum. In particular, we show that the total stress tensor is asymmetric.Furthermore, a symmetric stress tensor does not guarantee angular momentum conservation. The complete specification ofD leads to symmetry relations between the dissipative coefficients in an unambiguous way, without invoking the concept of so called forces and fluxes, in contrast to the conventional Onsager approach. Our formalism allows for a class of different dissipation functions, and is applicable to linear or nonlinear molecular media of arbitrary symmetry. It covers simple materials as special cases.     

Solid-phase synthesis of imidazo[1,2-a]pyridine using sodium benzenesulfinate as a traceless linker

[formula: see text] The preparation of the first library of imidazo[1,2-a]pyridine derivatives on a solid support is described. A sulfone linker strategy was applied in the synthesis. Key steps involved in the solid-phase synthetic procedure include (i) alpha-haloketone resin formation by sulfinate-->sulfone alkylation, (ii) imidazo[1,2-a]pyridine ring formation by treatment with 2-aminopyridine, (iii) sulfone anion alkylation, and (iv) traceless product release by oxidation-elimination. A library of 12 imidazo[1,2-a]pyridines was synthesized.     

Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-g-poly(vinylpyrrolidone): association behavior in aqueous solution and interaction with anionic surfactants

In this work, we aimed to study the association and interaction behavior of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) block copolymers grafted with poly(vinylpyrrolidone). Critical micellization concentrations were determined using fluorescent probes (pyrene) and critical micellization temperatures characterizing temperature-dependent transitions from monomers to multimolecular micelles were measured. The thermal responsiveness of the copolymer is not affected by the grafting. The hydrodynamic radius of the graft copolymer micelles is found to be greater than that of the original copolymer micelles. The graft copolymer is found to form anisotropic aggregates. The structure of the graft copolymer micelles is less disrupted by the anionic surfactant sodium dodecyl sulfate, compared to the ungraft copolymer.     

Low-valent chemistry of cobalt amide. Synthesis and structural characterization of cobalt(II) amido, aryloxide, and thiolate compounds

The binuclear cobalt(II) amide complex [(CoL2)2-(TMEDA)] (1) [L = N(Si(t)BuMe2)(2-C5H3N-6-Me); TMEDA = Me2NCH2CH2NMe2] has been synthesized by the reaction of anhydrous CoCl2 with 2 equiv of [Li(L)(TMEDA)]. X-ray crystallography revealed that complex 1 consists of two [CoL2] units linked by one TMEDA ligand molecule, which binds in an unusual N,N'-bridging mode. Protolysis of 1 with the bulky phenol Ar(Me)OH (Ar(Me) = 2,6-(t)Bu2-4-MeC6H2) and thiophenol ArSH (Ar = 2,4,6-(t)Bu3C6H2) gives the neutral monomeric cobalt(II) bis(aryloxide) [Co(OAr(Me))2(TMEDA)] (2) and dithiolate [Co(SAr)2(TMEDA)] (3), respectively. Complexes 1-3 have been characterized by mass spectrometry, microanalysis, magnetic moment, and melting-point measurements, in addition to X-ray crystallography.     

Channel activity of a viral transmembrane peptide in micro-BLMs: Vpu(1-32) from HIV-1

We report for the first time on pore-suspending lipid bilayers, which we call micro-black lipid membranes (micro-BLMs), based on a highly ordered macroporous silicon array. Micro-BLMs were established by first functionalizing the backside porous silicon surface with gold and then chemisorbing 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol followed by spreading 1,2-diphytanoyl-sn-glycero-3-phosphocholine dissolved in n-decane. Impedance spectroscopy revealed the formation of single lipid bilayers confirmed by a mean specific capacitance of 0.6 +/- 0.2 microF/cm2. Membrane resistances were in the G omega-regime and beyond. The potential of the system for single channel recordings was demonstrated by inserting the transmembrane domain of the HIV-1 accessory peptide Vpu(1-32), which forms helix bundles with characteristic opening states. We elucidated different amilorides as potential drugs to inhibit channel activity of Vpu.     

Reactions in aminosilane-epoxy prepolymer systems. II. Reactions of alkoxysilane groups with or without the presence of water

The hydrolysis and reactions of alkoxy silane groups have been studied on a model compound (TA) prepared from 2 mol of phenyl glycidyl ether and 1 mol of aminopropyl triethoxy silane. At low (40°C) and high (140°C) temperatures, the monomer conversion and the evolution of the molecular mass are followed by size exclusion chromatography (SEC). During the same reaction time, the evolution of the functional groups, hydroxyl CH? OH, ethoxy ? O? C₂H₅, and siloxane Si? O? Si, is observed by FTIR spectroscopy. Without the presence of water, reactions between hydroxyl and ethoxy silane lead to gelation at the end of the reaction. A by-product, probably a cyclic tetramer is also formed. After the hydrolysis, the reaction of the model compound is quite different. The product of reaction is always soluble, even after a treatment at high temperatures, and the evolution of the molecular mass versus the reaction time seems to correspond to the condensation giving a dead cyclic tetramer. From this study it is evident that the curing cycle has a great influence on the properties of the interface of a composite based on a epoxy matrix.     

Photoinitiated cationic polymerization with triarylsulfonium salts

Triarylsulfonium salts Ar₃S⁺MX with complex metal halide anions such as BF, AsF, PF, and SbF are a new class of highly efficient photoinitiators for cationic polymerization. In this article we describe several synthetic routes to the preparation of these compounds along with their physical and spectroscopic properties. Mechanistic studies have shown that when these compounds are irradiated at wavelengths of 190–365 nm carbon–sulfur bond cleavage occurs to form radical fragments. At the same time the strong Br??nsted acid HMX_n, which is the active initiator of cationic polymerization that takes place in subsequent “dark” steps, is also produced. A study of the parameters that affect the photolysis of triarylsulfonium salts is reported with a measurement of the absolute quantum yields. The cationic polymerizations of four typical monomers—styrene oxide, cyclohexene oxide, tetrahydrofuran, and 2-chloroethyl vinyl ether—with triarylsulfonium salt photoinitiators are described.     

Dipole moments of selenophene analogs of the chalcones

The dipole moments of 24 selenophene analogs of the chalcones have been measured and have been compared with the data calculated by a vectorial additive scheme and also with their chemical structures. Considerations are expressed on the conformational state of the molecules of the compounds investigated. The existence of a correlation between the dipole moments the intramolecular distances, and the Hammett's -parameters has been shown. The applicability of Higashi's equation to the calculation of for , -unsaturated ketones is pointed out.     

Carbolithiation of aromatic rings: cyclohexadienes from N-aroyl-2,2,6,6-tetramethylpiperidines

Benzamides whose nitrogen atom is part of a 2,2,6,6-tetramethylpiperidine ring are dearomatised by alkyllithiums, which attack them regioselectively to yield, after electrophilic quench, substituted cyclohexadienes.     

Synthesis of SBA-15/carbon composite with an ink-bottle-like pore structure by a novel pulse CVD technique

A novel and easy post modification method, pulse chemical vapor deposition (pulse CVD), was developed to tailor the pore-opening of SBA-15 while largely keeping its surface area and pore volume. By using acetylene as carbon precursor and nitrogen as carrier gas, the pore-mouth of SBA-15 was effectively reduced from 8.1 nm to 5.1 nm within 5 min while maintaining the pore body at 8.1 nm. This ink-bottle-structured SBA-15/carbon composite only losses 12% BET specific surface area and 16% total pore volume, respectively. The SBA-15/carbon composite is highly hexagonally ordered and has similar particle morphology as the original SBA-15. The effect of three pore modification factors—the number of cycles of pulse CVD, the ratio of acetylene/nitrogen and the feeding time of carbon precursor, on the final pore structure of the SBA-15/carbon composite is also studied.