Novel regular network polyester films from benezenetricarboxylic acids and glycols

Novel regular network polyester films were prepared from benzenetricarboxylic acids of trimesic (Y) and trimellitic (Z) acids, and glycols of ethylene (2G), tetramethylene (4G), and hexamethylene (6G) glycols. Prepolymers prepared by melt polycondensation for a short period within 1 h were cast from a DMF solution and successively post-polymerized at various temperatures and times to form a network. The resultant films were transparent, flexible, and insoluble in any solvents. Distortion temperature measured by a penetration mode of thermomechanical analysis (TMA) increased with increasing post polymerization time and temperature, and leveled out at 222, 168, 125 and 75°C, for the 2GY, 2GZ, 4GY, and 6GY films, respectively. Temperatures close to 400°C at which the probe had completely penetrated corresponded to the thermal decomposition temperature of these films. Two broad but strong peaks in the x-ray diffraction curves appears for the 2GY, 4GY, and 6GY, suggesting the formation of some ordered supramolecular structure owing to the regular network formed by symmetrical trimesic acid moiety, and the intensity of diffraction peaks became higher with increasing length of the methylene chain of the glycol monomer. Densities of the 2GY and 2GZ films decreased with increasing post-polymerization time and temperature. Tensile strength and Young's modulus increased and elongation decreased with increasing network formation. These tensile properties was affected by the chemical structure of the network films.     

In situ X-ray observation of phase transformation in Fe2O3 at high pressures and high temperatures

A laser-heated sample in a diamond anvil cell and synchrotron X-ray radiation was used to carry out structural characterization of the phase transformation of Fe₂O₃ at high pressures (30-96 GPa) and high temperature. The Rh₂O₃(II) (or orthorhombic perovskite) structure transforms to a new phase, which exhibits X-ray diffraction data that are indicative of a CaIrO₃-type structure. The CaIrO₃-type structure exhibited an orthorhombic symmetry (space group: Cmcm) that was stable at temperatures of 1200-2800 K and pressure of 96 GPa (the highest pressure used). Unambiguous assignment of such a structure requires experimental evidence for the presence of two Fe species. Based on the equation of state of gold, the phase boundary of the CaIrO₃-type phase transformation was P (GPa)=59+0.0022×(T−1200) (K).     

Enhancement of sonochemical reaction of terephthalate ion by superposition of ultrasonic fields of various frequencies

The ultrasonic reactor with dual frequency was used and the effect of frequency on the fluorescence intensity of terephthalate ion was experimentally investigated in the frequency range from 176 to 635 kHz. The sonochemical reaction fields were visualized by using sonochemical luminescence of luminol solution. Compared with the fluorescence intensity of terephthalate ion for single frequency, the fluorescence intensity for dual frequency increased. The fluorescence intensity ratio of dual frequency to single frequency had maximum value when the frequency of transducer attached at the bottom wall was comparable in magnitude to that at the side wall. In the case of dual frequency, the sonochemical reaction fields became more extensive in the reactor and more intensive around the center of the reactor.     

A Study of the Solvation Structure of l‐Leucine in Alcohol–Water Binary Solvents through Molecular Dynamics Simulations and FTIR and NMR Spectroscopy

The solvation structures of l ‐leucine (Leu) in aliphatic‐alcohol–water and fluorinated‐alcohol–water solvents are elucidated for various alcohol contents by using molecular dynamics (MD) simulations and IR, and ¹H and ¹³C NMR spectroscopy. The aliphatic alcohols included methanol, ethanol, and 2‐propanol, whereas the fluorinated alcohols were 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol. The MD results show that the hydrophobic alkyl moiety of Leu is surrounded by the alkyl or fluoroalkyl groups of the alcohol molecules. In particular, TFE and HFIP significantly solvate the alkyl group of Leu. IR spectra reveal that the Leu C?H stretching vibration blueshifts in fluorinated alcohol solutions with increasing alcohol content, whereas the vibration redshifts in aliphatic alcohol solutions. When the C?H stretching vibration blueshifts in the fluorinated alcohol solutions, the hydrogen and carbon atoms of the Leu alkyl group are magnetically shielded. Consequently, TFE and HFIP molecules may solvate the Leu alkyl group through the blue‐shifting hydrogen bonds.     

Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+: Experimental and Computational Studies of their Hydricities,Interaction with CO2, and Photochemistry

We prepared two geometric isomers of [Ir(tpy)(ppy)H]⁺, previously proposed as a key intermediate in the photochemical reduction of CO₂ to CO, and characterized their notably different ground‐ and excited‐state interactions with CO₂ and their hydricities using experimental and computational methods. Only one isomer, C‐trans‐[Ir(tpy)(ppy)H]⁺, reacts with CO₂ to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH₃CN/TEOA, a common reactive C‐trans‐[Ir(tpy)(ppy)]⁰ species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO₂ and produces CO with the same catalytic efficiency.     

Differential Effects of Cold Exposure on Gene Expression Profiles in White Versus Brown Adipose Tissue

The thermogenic function of brown adipose tissue (BAT) is known to be markedly elevated when animals are exposed to the cold, and intensive studies have been carried out to understand the molecular basis enabling effective thermogenesis in cold-exposed animals. In this study, we used microarray analysis to examine the effects of cold exposure of animals on their gene expression profiles in white adipose tissue (WAT), which seems to function as a counterpart tissue of BAT. The results indicate that the effects of cold exposure on the gene expression profiles of WAT were much more moderate than the effects on those of BAT. Possible reasons for the different responses of BAT and WAT to cold exposure are discussed.     

A recyclable, self-supported organocatalyst based on a poly(N-heterocyclic carbene)

We report the synthesis and catalytic activity of a polymeric imidazolium salt. In contrast to the well-known resin-supported N-heterocyclic carbenes (NHCs), the material described herein affords a polymer with NHCs orthogonally positioned along a main chain upon generation in situ. The unique structural characteristics of the corresponding poly(NHC)s enabled the materials to display catalytic activities that were similar or superior to those displayed by monomeric analogues. Moreover, the new catalyst was successfully recovered and reused with minimal loss of performance over several cycles.     

Numerical simulation of cyclic voltammetry for reversible systems with complex stoichiometry

Reversible waves of voltammetry with complex non-unity stoichiometry are studied here based on theory. Numerical simulations were performed for various stoichiometric systems in which coefficients m and q were independently varied from 1 to 4 in a general reaction scheme, mO + ne⁻ ai qR. The calculation results indicate that the peak current function at complex stoichiometry differs from that at simple unity stoichiometry. The relation between the half-wave potential and the formal potential has been partially corrected from that previously reported in the literature. Parameters in the relation between the peak potential and the half-wave potential are unique for each stoichiometric system. The parameter in the relation between the peak potential and the half-peak potential is also presented here.     

1,5]-H shift of aldehyde hydrogen in dienal compounds to produce ketenes

In 3-ethoxycarbonyl-2,4-dienal compounds, a thermal [1,5]-H shift of aldehyde hydrogen easily proceeded to produce the corresponding vinyl ketenes due to the remarkable substituent effect caused by the C3 ester group. The produced ketenes were captured by an alcohol and olefins to afford the corresponding esters and four-membered ring compounds, respectively.     

On distorted probabilities and m-separable fuzzy measures

Fuzzy measures are used in conjunction with fuzzy integrals for aggregation. Their role in the aggregation is to permit the user to express the importance of the information sources (either criteria or experts). Due to the fact that fuzzy measures are set functions, the definition of such measures requires the definition of 2ⁿ parameters, where n is the number of information sources. To make the definition easier, several families of fuzzy measures have been defined in the literature.In this paper m-separable fuzzy measures are introduced. We present some results on this type of measures and we relate them to some of the previous existing ones. We study generating functions for m-separable fuzzy measures and some properties related to these generating functions.