Energy transfer as a function of collision energy. I Collision partners: Hydrogen halides + inert gases,hydrogen halides,H2S and propane

Infrared emission has been recorded from a heated seeded supersonic primary beam of HCl or HF (1) prior to collision with a target beam, and (2) subsequent to that collision. Mean collision energy and collision partner were varied systematically. After correction for elastic scattering, the net population change due to inelastic scattering in a translation—rotation (T ? R) energy-transfer encounter was obtained for specific J states ranging from J = 0–16 of vibrational level υ = 1 of the primary-beam molecule. The broad picture is that a net transfer into low-J states out of higher-J states takes place at low collision energies, and the converse at high collision energies. These observations are interpreted in terms of the “exponential model” for the relative cross sections of T ? R inelastic collisions, S^R (J_i → J_f), proposed earlier [J.C. Polanyi and K.B. Woodall, J. Chem. Phys. 56 (1972) 1563], modified here to satisfy microscopic reversibility. The constant C in the model, which governs the exponential decrease in S^R with increasing energy difference ΔE_J between J_f and J_i, can be derived, as a function of collision energy T, from the present experimental data; C decreases as T increases, i.e. larger ΔJ become more probable. In order to check the validity of the model, it was compared with 3D trajectory results; according to this criterion it was found to give a very good representation of S^R(J_i → J_f) with a single value for C, within a limited range of J_i. The collision partners HCl + HF exhibit anomalously efficient rotational deactivation; evidence is presented which indicates that at low collision energies this is due to resonant R → R transfer. Very efficient deactivation of HCl by HCl, at low collision energy, is likely to be due to V — V transfer.     

A small molecule with osteogenesis-inducing activity in multipotent mesenchymal progenitor cells

Purmorphamine, which is a 2,6,9-trisubstituted purine compound, was discovered through cell-based high-throughput screening from a heterocycle combinatorial library. It differentiates multipotent mesenchymal progenitor cells into an osteoblast lineage. It will serve as a unique chemical tool to study the molecular mechanisms of osteogenesis of stem cells and bone development.     

Application of Liquid Crystalline NMR Solvents to a Mixture of Ketones

A series of dilute liquid crystalline solvents are used to study the effect of slight anisotropy caused by partial alignment on chemical shift and residual dipolar coupling (RDC) in small molecules. The residual dipolar couplings between protons in solutes are found to be almost independent of the local environment. It is also found that the chemical shift does not change over the concentration range observed. A linear relationship between residual dipolar coupling and liquid crystal concentration is observed at relatively low concentrations, but is severely violated at high concentrations.     

Investigation of the hydrogen bonds between formaldehyde and hydrogen halides by pseudopotential Ab Initio method

The weak hydrogen bonded systems H₂CO ?HX (X = F, Cl, Br, and I) have been studied by means of ab initio MO method with pseudopotential approximation. The stabilization energies of these hydrogen bonds are 8.96, 4.12, 3.00, and 2.21 kcal/mol, respectively. The interaction eneraction energies are farther decomposed according to Morokuma's energy decomposing scheme. It is found that the title complexes are mainly electrostatic, although the contribution of charge transfer is also significant.     

化学镀钴基合金镀液中钴的快速测定

研究了采用显色剂 苦胺酸偶氮变色酸对化学镀钴基合金镀液中钴含量进行测定的试验条件,在pH11的氨 氯化铵缓冲溶液中,钴与显色剂配合物的最大吸收峰在650nm波长处,钴(Ⅱ)在0～60μg/25ml范围内服从比耳定律,表观摩尔吸光系数为3.1×104L·mol-1·cm-1。该法测定钴的选择性好,在大量镍存在下,也能准确测定,对镀液样品进行了测定,相对标准偏差小于1%,结果满意。     

Theoretical study on structures and stability of C4P isomers

The structures, energetics, spectroscopies, and stabilities of doublet C(4)P isomeric species are explored at the DFT/B3LYP, QCISD, and CCSD(T) (singlet-point) levels. A total of 12 minimum isomers and 27 interconversion transition states are located. At the CCSD(T)/6-311G(2df)//QCISD/6-311G(d)+ZPVE level, the lowest-lying isomer is a floppy CCCCP 1 (0.0 kcal/mol) mainly featuring a cumulenic structure |C=C=C=C=P*|, which differs much from the analogous C4N radical (|*C-C[triple bond]C-C[triple bond]N|). The quasi-linearity and the low bending mode of 1 are in contrast to the previous prediction. The second energetically followed isomer PC-cCCC 3 (14.9 kcal/mol) possesses a CCC ring-bonded to CP. The two low-lying isomers are separated by a high-energy ring-closure/open transition state (26.5 kcal/mol) and thus are very promising candidates for future laboratory and astrophysical detection. Furthermore, four high-energy isomers, that is, two bent isomers CCPCC 2 (68.4 kcal/mol) and CCPCC 2' (68.5 kcal/mol) and two cagelike species 10 (56.0 kcal/mol) and 11 (67.9 kcal/mol), are also stabilized by considerable barriers. The present work is the first detailed potential energy survey of CnP clusters and can provide useful information for the investigation of larger CnP radicals and for understanding the isomerism of P-doped C vaporization processes.     

Advanced Current Collectors for Alkali Metal Anodes

High-energy-density batteries are in urgent need to solve the ever-increasing energy storage demand for portable electronic devices, electric vehicles, and renewable solar and wind energy systems. Alkali metals, typically lithium(Li), sodium(Na) and potassium(K), are considered as the promising anode materials owing to their low electrochemical potential, low density, and high theoretical gravimetric capacities. However, the problem of dendrite growth of alkali metals during their plating/stripping process will lead to low Coulombic efficiencies, a short lifespan and huge volume expansion, eventually hindering their practical commercialization. To resolve this issue, a very effective approach is engineering the anodes on structured current collectors. This review summarizes the development of the alkali metal batteries and discusses the recent advances in rational design of anode current collectors. First, the challenges and strategies of suppressing alkali-metal dendrite growth are presented. Then the special attention is paid to the novel current collector design for dendrite-free alkali metal anodes. Finally, we give conclusions and perspective on the current challenges and future research directions toward advanced anode current collectors for alkali metal batteries.     

Zeolite NaY-mediated oxidation of dyes with H2O2: unique heterogeneous non-transition metal center cleavage of H2O2 under visible light irradiation

This study investigated the visible-light catalysis mediated by zeolite NaY on the oxidation of dyes with H₂O₂. The results demonstrated that zeolite NaY acts as a sink for the electron from the photo-excited dye in the heterogeneous catalysis. Furthermore, the electron can effectively activate H₂O₂ to produce ^·OH radical that is a powerful oxidant for the oxidation of dye at room temperature. The effects of the framework topology, Si/Al ratio, and exchangeable cation of the zeolite on the oxidation of various dyes were also shown.     

Ni的掺入对复合氧化物LaFeO3的结构及性质的影响

合成子Ｎｉ替代铁酸稀土复合氧化物ＬａＦ３１－ｘＮｉｘＯ３（ｘ＝０．１－０．６），对样品进行了ＸＲＤ、ＩＲ及Ｍｏｓｓｂａｕｅｒ谱测试，结果表明：ｘ＝０＼１，０＼２，０＼３的样品为正交相，ｘ＝０．５，０．６的样品为菱方相；伴随相结构从正交向菱方结构的转变，ＩＲ谱上Ｆｅ（Ｎｉ）－Ｏ键伸振动谱带向高频移动近２０ｃｍ＾－１，Ｍｏｓｓｂａｕｅｒ谱测试表明Ｆｅ均处于＋３自旋态，Ｎｉ离子以＋３价进入晶格。