Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study

We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.     

Microwave‐assisted polycondensation of 4‐octylaniline with dibromoarylene

The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

Thermal gradient induced sidebranching in directional solidification

The polycrystalline perovskitelike manganese oxides La_1-xA_xMnO (A = Na, and K, ) have been fabricated by sol-gel technique. For all the compositions explored in this work, the average manganese oxidation state is practically constant, at for A = Na, and for A = K, respectively. A close relationship is confirmed to hold between the Curie temperature (T_c) and the bond distance of Mn-O. Results of magnetic measurements show that these materials can be utilized as suitable candidates for magnetic refrigerants with wide applied temperature span, for their significant entropy change and the easily tuned Curie temperature. Received: 12 September 1997 / Revised: 18 December 1997 / Accepted: 21 January 1998     

Zeeman效应实验一定能推断出原子的g_J值吗?

本文以实例对Zeeman效应一定能推断原子的gJ值问题做了否定的回答。     

推广x重新标度模型的重标度参数经验公式

给出了推广x重新标度模型的重标度参数经验公式,其中建立了重标度参数与原子核的平均结合能之间的联系,由该公式可以得出A≥12的所有核的重标度参数值,利用这些参数值可以计算有关核过程并做出预言.     

Au-Au2S复合纳米球壳微粒的空腔谐振及参量讨论

Au-Au2S复合纳米球壳微粒（金纳米球壳），是一种新型复合结构的纳米微粒，其结构为纳米级的Au2S介质球外包裹了一层几个纳米厚的黄金球壳。这种复合纳米球壳微粒可以被抽象为球型谐振腔。报道了它的空腔谐振吸收的实验结果，并且运用经典理论结合介观结构特征，讨论了有关Au-Au2S复合纳米球壳微粒空腔谐振吸收的一些重要参量，其中包括谐振吸收波长、品质因数、谐振能量等。另外，还讨论了金球壳的厚度对这些重要参量的影响。     

Homohelicity induction of propylene-linked zinc bilinone dimers by complexation with chiral amine and α-amino esters. Preorganization of structurally coupled homohelical subunits

Homohelicity induction of a series of propylene-linked zinc bilinone (ZnBL; linear tetrapyrrople-zinc(II) complex) dimers upon complexation with chiral amine and α-amino esters was investigated. Introduction of substituents such as dimethyl and diisobutyl to the central carbon of the propylene spacer gave rise to stabilization of the homohelical (PP and MM) conformers rather than the heterohelical (PM) conformer. As bulkiness of the substituent increased, stability of the homohelical conformers was raised. The preorganization of the homohelical structures led to significantly amplified homohelicity induction upon complexation with chiral amine and α-amino esters.