The effects of pH and ions on myelin figure formation in phospholipid-water system

Myelin figures were found to form at the main phase transition temperatures of several phospholipids for various ph values and Ca²⁺ concentrations. The optical observation of myelin figure formation provides a simple method of detecting the phase transition of phospholipids.     

Ce3+—高分子络合物发光的激发过程

本文研究了Ce3+-PMMA及Ce3+—PMA18·C·6两个高分子络合物发光材料的荧光激发过程以及激发过程与高分子结构的关系。通过荧光寿命、荧光光谱以及时间分辨光谱分析表明,在Ce3+—PMMA络合物体系中,Ce3+的荧光发射主要是来自高分子配体的能量传递,而对于Ce3+—PMA18·C·6粉末络合物体系,Ce3+发光的能量主要是来自入射光的直接激发。文章对上述两个稀土高分子络合物的激发机制的差异也做了较为详细地描述。     

Liquid-liquid critical point in heavy water

According to the liquid-liquid critical-point hypothesis about water, two liquid waters exist at low temperatures and are supposed to be merged at a critical point. The low-temperature metastable melting curves of D2O ices have been measured. It is found that the melting curve of D2O ice III is smoothly curved around 25 MPa and 238 K, whereas the melting curve of D2O ice IV undergoes an abrupt change of slope at 100 MPa and 220 K. This is consistent with the existence of a liquid-liquid critical point in the region between the melting curve of D2O ice III and the melting curve of D2O ice IV.     

Theoretical studies on tunneling ionizations from the doubly degenerate highest occupied molecular orbitals of benzene in intense laser fields

Combining our generalized Keldysh theory [Sov. Phys. JETP 20, 1307 (1965)] with the molecular orbital theory, the authors theoretically study tunneling ionizations of neutral benzene in intense linearly polarized Ti:sapphire laser fields (800 nm). They consider the ionizations from the highest occupied molecular orbitals (HOMOs) of the ground electronic state. The double degeneracy of the HOMOs is properly taken into account. In the theory, molecular ionizations consist of the individual ionizations from each atom and the quantum interferences between them. The theory reproduces the experimental data well. The authors also show that the polarization dependence of the ionization rates is strongly influenced by the quantum interferences.     

Isomeric solid enols on ring- and amide-carbonyls of substituted 2-carbanilido-1,3-indandiones

Both isomeric enols on ring carbonyl (5b) and on amide carbonyl (6b) derived from N-p-methoxyphenyl-2-carbamido-1,3-indandione (4b) were isolated, and their X-ray structures were determined. X-ray diffraction of the N-o,p-dimethoxy analogue indicated a disorder ascribed to the presence of a 6:4 mixture of 5c and 6c. Calculation (B3LYP/6-31+G*) gave good agreement with observed geometries. The calculated energies indicated that enols 6 are more stable by <1 kcal/mol than enols 5 and much more stable than amides 4.     

Structural effect on the stability of (pyridine)(2)Cu(+) complexes in the gas phase: nature of the bond between copper(I) ion and neutral molecules

Free energy changes (DeltaG degrees , copper cation basicity) for the reaction L(2)Cu(+) = Cu(+) + 2L were obtained in the gas phase for substituted pyridines based on the measurement of ligand-exchange equilibria in a Fourier transform ion cyclotron resonance (FT-ICR) spectrometer. For 3- and 4-substituted pyridines, the relative copper cation basicities (DeltaCCB[L(2)Cu(+)]) were linearly correlated with the corresponding gas-phase proton basicities (DeltaGB) with a slope of 1.01. On the basis of a linear relationship between the calculated copper cation basicities of dimeric and monomeric complexes at MP2/6-311+G(2p,2d)//B3LYP/6-311G*, DeltaCCB[L(2)Cu(+)](calcd) = 1.54DeltaCCB[LCu(+)](calcd), the substituent effect on the DeltaCCB for the first ligand was estimated to be 0.66 times smaller than the corresponding DeltaGB. A comparison with the corresponding results for other Lewis cation basicity of the pyridine system showed that the magnitude of the substituent effect decreases in the order H(+) (1.00) > Me(3)Si(+) (0.95) > Cl(+) (0.83) > Cu(+) (0.66) > Li(+) (0.47). This change was associated with the natural charges at the Lewis cation moiety and the natural atomic orbital (NAO) bond order of the M+-N bond of the complex ion, indicating the decrease in covalent character of the M(+)-N bond in this order. Furthermore, when a variety of neutral bases such as amines, carbonyl compounds, and ethers were included in a comparison between CCB[L(2)Cu(+)] and GB, it was found that there is a good linear relationship with significant deviations of small molecules and bulky tributylamine, which is attributed to their different steric environment at the binding sites from others, while there is no simple linear relationship with the lithium cation basicities (LCB). The similarity of the substituent effect between CCB[L(2)Cu(+)] and GB reflects the covalent character in the Cu(+) interaction. In conclusion, although the ionic (ion-dipole interaction) nature of the Cu(+) interaction results in a smaller substituent effect than that for the protonation, the covalent nature also plays an important role in the Cu(+) interaction with neutral molecules.     

Controlled random and alternating copolymerization of (meth)acrylates,acrylonitrile, and (meth)acrylamides with vinyl ethers by organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization reactions

Random and alternating copolymerizations of acrylates, methacrylates, acrylonitorile, and acrylamides with vinyl ethers under organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization (TERP, SBRP, and BIRP, respectively) have been studied. Structurally well‐controlled random and alternating copolymers with controlled molecular weights and polydispersities were synthesized. The highly alternating copolymerization occurred in a combination of acrylates and vinyl ethers and acrylonitorile and vinyl ethers by using excess amount of vinyl ethers over acrylates and acrylonitorile. On the contrary, alternating copolymerization did not occur in a combination of acrylamides and vinyl ethers even excess amount of vinyl ethers were used. The reactivity of polymer‐end radicals to a vinyl ether was estimated by the theoretical calculations, and it was suggested that the energy level of singly occupied molecular orbital (SOMO) of polymer‐end radical species determined the reactivity. By combining living random and alternating copolymerization with living radical or living cationic polymerization, new block copolymers, such as (PBA‐alt‐PIBVE)‐block‐(PtBA‐co‐PIBVE), PBA‐block‐(PBA‐alt‐PIBVE), and (PTFEA‐alt‐PIBVE)‐block‐PIBVE, with controlled macromolecular structures were successfully synthesized. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Electrochemical and structural study on LiMn0.8Fe0.2PO4 and Mn0.8Fe0.2PO4 battery cathodes: diffusion limited lithium transport

Journal of Solid State Electrochemistry - Electrochemical reactions in the particulate crystal of olivine cathodes topotactically proceed in the lithiated and delithiated phases....     

A cubic boron nitride P-N diode: Fabrication in a large-volume press

Abstract

A simple method to determine the temperature of synthesis was proposed. (Mishima et al., to be published) This method utilized the melting of NaCl as an indicator of heater temperature. Applying the method to the fabrication of cBN p-n diodes in a large volume belt-type apparatus, we obtained an UV LED of ～2 mm in size.