Stochastic/Controlled Symmetry Breaking of the T8‐POSS Cages toward Multifunctional Regioisomeric Nanobuilding Blocks

Precise synthesis of nanobuilding blocks with accurately positioned functional groups presents a daunting challenge. Herein, a practical synthesis and thorough characterization of a series of T₈‐polyhedral oligomeric silsesquioxane (POSS) di‐ and triadducts is reported. Upon addition of triflic acid across the double bonds in octavinylPOSS (V₈T₈) followed by hydrolysis, the cubic symmetry of the T₈‐POSS cage (O_h) is broken into C_2v (ortho‐), C_2v (meta‐), and D_3d (para‐) for diadducts and further to C_s (oom‐), C_s (omp‐), and C_3v (mmm‐) for triadducts in a stochastic fashion. Their structures and regioconfigurations have been unambiguously demonstrated by ¹H, ¹³C, and ²⁹Si NMR spectroscopy, as well as MALDI‐TOF mass spectrometry. The assignment of the diadducts was further corroborated by converting each individual diadduct into triadduct(s), the structure of which is controlled by the symmetry of the precursor. Except for the C_3v triadduct, they can all be prepared in synthetically useful quantities. The presence of two types of highly reactive and mutually orthogonal functional groups facilitates further modification into complex nanostructures and composite materials. These unique regioisomers provide a versatile platform for constructing giant molecules and Janus silsesquioxanes.     

2-氰基-3-甲硫基-3-苄氨基丙烯酸取代苯氧乙酯的合成及其除草活性

基于D1蛋白结构模型,设计并合成了一系列2-氰基-3-甲硫基-3-苄氨基丙烯酸取代苯氧乙酯,结构经¹HNMR、元素分析和IR确证.生物活性结果表明,化合物显示出较好的Hill反应抑制活性;而酯基部分的乙氧乙氧基被苯氧乙氧基取代后,活性有所下降,其原因可能是苯环分散了β-氧原子上的电荷密度,使之与Ser268的结合力降低,这进一步证实了Ser268位点的重要性.同时实验结果证明,苯环上的取代基对化合物活性有一定影响.     

Gelation behavior of thermoplastic-modified epoxy systems during polymerization-induced phase separation

The rheological behavior and gelation characteristics of epoxy blends are of critical importance to property study and industrial application. In this work, we studied the rheological behavior and structural transition of different thermoplastics, including polyetherimide, polymethylmethacrylate, and polyethersulfone (PES), modified epoxy systems by using rheometry instrument, differential scanning calorimetry, time-resolved light scattering, and scanning electronic microscopes. At the same molecular weight level of thermoplastics, different epoxy blends show profound diversities on the rheological and gelation behavior due to the large differences in phase separation and curing process. For early phase-separation systems of PES-modified epoxy blends, two gel points are identified, which correspond to physical gelation and chemical gelation, respectively. With the variation of the PES molecular weight and curing rate, dramatic changes in gel time and critical exponent were observed. As the molecular weight of thermoplastics is increased, the gelation time becomes shorter and the gel strength gets lower, while the faster curing rate would increase the physical gel strength significantly.     

Investigation on the thermal stability of nitroguanidine by TG/DSC-MS-FTIR and multivariate non-linear regression

Thermal behavior of nitroguanidine (NQ) has been investigated by TG/DSC-MS-FTIR simultaneous analysis performed under both isothermal and nonisothermal conditions. The isothermal test at 230 °C indicated that the release of gas products can be divided into several stages. The processing of the non-isothermal data, namely 5, 10, 15, and 20 K/min, was performed by using Netzsch Thermokinetics. The dependence of the activation energy evaluated by Friedman’s isoconversional method on the conversion degree shows that the investigated process is complex one, and can be divided into three parts. The mechanism of the process and the corresponding kinetic parameters were determined by Multivariate Non-linear Regression Program. The kinetic results was used to simulate the thermal decomposition of NQ under isothermal condition at 210 °C. The simulated curve is in agreement with the tested curve. The obtained results were also used for prediction of the thermal lifetime of NQ corresponding to a certain temperature.     

Tuning the band-gap energy of TiO2-xCx nanoparticle for high performance photo-catalyst

We describe a method tuning the band-gap energy (E_g) of visible light sensitive TiO_2-xC_x nanoparticle. E_g tends to become smaller with the increase in the amount of carbon dopant in TiO_2-xC_x nanoparticle due to the increase in excess electrons. Photo-catalytic oxidative activity, however, did not depend on only the value of E_g, but also the energy level of valence band. TiO_1.96C_0.04 nanoparticle having E_g of 2.6 eV showed outstanding performance in oxidative decomposition of phenol under the irradiation of visible light.     

Accurate free energy calculation along optimized paths

The path‐based methods of free energy calculation, such as thermodynamic integration and free energy perturbation, are simple in theory, but difficult in practice because in most cases smooth paths do not exist, especially for large molecules. In this article, we present a novel method to build the transition path of a peptide. We use harmonic potentials to restrain its nonhydrogen atom dihedrals in the initial state and set the equilibrium angles of the potentials as those in the final state. Through a series of steps of geometrical optimization, we can construct a smooth and short path from the initial state to the final state. This path can be used to calculate free energy difference. To validate this method, we apply it to a small 10‐ALA peptide and find that the calculated free energy changes in helix‐helix and helix‐hairpin transitions are both self‐convergent and cross‐convergent. We also calculate the free energy differences between different stable states of β‐hairpin trpzip2, and the results show that this method is more efficient than the conventional molecular dynamics method in accurate free energy calculation. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

组合改性Y型分子筛的加氢裂化性能

采用水热、草酸脱铝及表面活性剂存在下的水热晶化相结合的组合法对Y型分子筛进行了改性, 考察了表面活性剂十六烷基三甲基溴化铵（CTAB）存在下的CTAB加入量对Y型分子筛相对结晶度（Xc）、晶胞常数（a₀）、硅铝比、比表面积、孔结构及加氢裂化性能的影响, 并利用NH₃-TPD对改性Y型分子筛进行了酸性表征。结果表明, 少量的CTAB就可以使Y型分子筛的相对结晶度从37.9%提高到68.3%, 硅铝比从7.72增大到9.32, a0从2.4534nm减小到2.4485nm, 介孔的孔体积从0.157mL/g提高到0.180mL/g以上,且总酸酸量降低。VGO的加氢裂化反应结果表明,CTAB存在下改性Y型分子筛的加氢裂化活性和中间馏分油收率比工业催化剂分别高2.42%和4.20%。     

Metallic Co4N Porous Nanowire Arrays Activated by Surface Oxidation as Electrocatalysts for the Oxygen Evolution Reaction

Designing highly efficient electrocatalysts for oxygen evolution reaction (OER) plays a key role in the development of various renewable energy storage and conversion devices. In this work, we developed metallic Co₄N porous nanowire arrays directly grown on flexible substrates as highly active OER electrocatalysts for the first time. Benefiting from the collaborative advantages of metallic character, 1D porous nanowire arrays, and unique 3D electrode configuration, surface oxidation activated Co₄N porous nanowire arrays/carbon cloth achieved an extremely small overpotential of 257 mV at a current density of 10 mA cm⁻², and a low Tafel slope of 44 mV dec⁻¹ in an alkaline medium, which is the best OER performance among reported Co‐based electrocatalysts to date. Moreover, in‐depth mechanistic investigations demonstrate the active phases are the metallic Co₄N core inside with a thin cobalt oxides/hydroxides shell during the OER process. Our finding introduces a new concept to explore the design of high‐efficiency OER electrocatalysts.