A 3-D noninterpenetrating diamondoid network of a decanuclear copper(I) complex

The solvothermal reaction of CuCl(2).2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and mu(4)-Cl ligands. The in situ generation of CuSO(4).5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.     

α''-取代磺酰基-α,β-不饱和酮的不对称催化环加成反应的研究

在手性金属钛配合物催化剂存在下，研究了α′－取代磺酰基－α，β－不饱和酮的不对称催化环加成反应；讨论了α，β－不饱和酮各种取代磺酰基对反应活性和对映选择性的影响；高收率地合成了高光学纯度的环加成产物，并对环加成产物的构型进行了鉴定。     

镓改性ZSM-5沸石中镓活性中心的形成与表征

采用脉冲微反体系研究了经不同程度还原和不同镓含量的GaZSM-5沸石的芳构化性能与吡啶吸附红外光谱特征谱带吸收度的关联，证实了1458 cm~(-1)吸收带的用于表征与Ga物种有关的活性中心，并研究了沸石的硅铝比对Ga中心形成和Ga的价态对芳构化性能的影响。结果表明，对Ga含量相同的样品来说，硅铝比愈低，起始Ga中心生成量愈多，高价态与低价态的Ga中心对丙烷芳构化反应都有促进作用。     

BonDNet: a graph neural network for the prediction of bond dissociation energies for charged molecules

A broad collection of technologies, including e.g. drug metabolism, biofuel combustion, photochemical decontamination of water, and interfacial passivation in energy production/storage systems rely on chemical processes that involve bond-breaking molecular reactions. In this context, a fundamental thermodynamic property of interest is the bond dissociation energy (BDE) which measures the strength of a chemical bond. Fast and accurate prediction of BDEs for arbitrary molecules would lay the groundwork for data-driven projections of complex reaction cascades and hence a deeper understanding of these critical chemical processes and, ultimately, how to reverse design them. In this paper, we propose a chemically inspired graph neural network machine learning model, BonDNet, for the rapid and accurate prediction of BDEs. BonDNet maps the difference between the molecular representations of the reactants and products to the reaction BDE. Because of the use of this difference representation and the introduction of global features, including molecular charge, it is the first machine learning model capable of predicting both homolytic and heterolytic BDEs for molecules of any charge. To test the model, we have constructed a dataset of both homolytic and heterolytic BDEs for neutral and charged (−1 and +1) molecules. BonDNet achieves a mean absolute error (MAE) of 0.022 eV for unseen test data, significantly below chemical accuracy (0.043 eV). Besides the ability to handle complex bond dissociation reactions that no previous model could consider, BonDNet distinguishes itself even in only predicting homolytic BDEs for neutral molecules; it achieves an MAE of 0.020 eV on the PubChem BDE dataset, a 20% improvement over the previous best performing model. We gain additional insight into the model''s predictions by analyzing the patterns in the features representing the molecules and the bond dissociation reactions, which are qualitatively consistent with chemical rules and intuition. BonDNet is just one application of our general approach to representing and learning chemical reactivity, and it could be easily extended to the prediction of other reaction properties in the future.

Prediction of bond dissociation energies for charged molecules with a graph neural network enabled by global molecular features and reaction difference features between products and reactants.     

Synthesis and Mesogenic Properties of Liquid Crystals Containing Terminal Cyclohexylmethanol,Cyclopentylmethanol, Cyclobutylmethanol and Cyclopropylmethanol Moiety

Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 .     

Decontamination of radioactive cesium from natural NaCl by amide-type open-chain crown ethers

An attempt has been made to develop a radiochemical methodology for the decontamination of a trace amount of radioactive cesium from a bulk amount of natural NaCl by liquid-liquid extraction (LLX). Open chain crown ethers, of amide type, namely, N,N,N",N"-tetraphenyl-3,6-dioxaoctanediamide (TDD), N,N,N",N"-tetraphenyl-3,6,9-trioxaundecanediamide and N,N"-dinaphthyl-N,N"-diphenyl-3,6-dioxaoctanediamide (DDD) have been chosen for this purpose. The separation factor between Cs and Na is the highest when 10^-4M TDD dissolved in nitrobenzene is used as extractant and 0.4M picric acid at pH 5.0 is used as aqueous phase. About 60% Cs is extracted in this condition in a single run.     

Synthesis of 2'-O-methoxyethylguanosine using a novel silicon-based protecting group

A short and efficient synthesis of 2'-O-methoxyethylguanosine (8) is described. Central to this strategy is the development of a novel silicon-based protecting group (MDPSCl(2), 2) used to protect the 3',5'-hydroxyl groups of the ribose. Silylation of guanosine with 2 proceeded with excellent regioselectivity and in 79% yield. Alkylation of the 2'-hydroxyl group of 6 proceeded with methoxyethyl bromide and NaHMDS and afforded compound 7 in 85% yield, without any noticeable cleavage of the silyl protecting group and without the need to protect the guanine base moiety. Finally, deprotection of 7 was achieved using TBAF and produced 8 in 97% yield.     

Tetra‐n‐butylammonium bis(2‐thioxo‐1,3‐dithiole‐4,5‐dithiolato‐κ2S4,S5)nickelate(III)

The crystal structure of the title compound, (C₁₆H₃₆N)[Ni(C₃S₅)₂], is isomorphous with that of the corresponding Pt complex but different from the structures reported for compounds of the same chemical composition, and so provides a new crystalline phase of this complex. The nickel complex anion has good planarity and lies on a crystallographic inversion centre. There is disorder in the two terminal C atoms of two of the butyl chains of the tetra‐n‐butyl­ammonium cation, the N atom of which is located on a twofold axis.     

Effect of nucleating agent on the structure and properties of polypropylene/poly(ethylene-octene) blends

The effect of the sorbital nucleating agent on properties of the ethylene-octene copolymer (POE) toughened polypropylene (PP) was studied. The results show that the addition of POE increases notched Izod and Charpy impact strength significantly but impair the tensile strength and flexural modulus. As a nucleating agent (1,3,2,4-di(p-methylbenzylidene) sorbitol, DM) was added, the toughness and stiffness of toughed PP increased simultaneously at the same content of POE. This result shows that the toughness and stiffness of toughed PP are in balance. Polarized light microscopy analysis shows that with the addition of POE and nucleating agent, only a low level of PP spherulites were observed.     

Calculation of Gurney parameters for aqueous tetraalkylammonium halides based on Friedman's cosphere-overlap model

Recalculations of the Gurney free-energy parameters A_ij based on the cosphereoverlap model of Friedman and co-workers have been made using more recent experimental data. Our procedure for calculation seems to be more systematic than those previously reported. The excess energy, entropy, and volume parameters (E_ij, TS_ij, and V_ij) were also recalculated for some aqueous tetraalkylammonium halides. In addition, the excess-heat-capacity parameters C_ij are also reported here for the first time. These data are discussed briefly in terms of the structural implications.