à 3E态CH3N自由基的稳定性

观察到了CH_3N自由基Ã ~3E←X~3A_2体系317-272 nm的荧光激发谱, 特别讨论了振动激发的Ã 态的稳定性. 报导了v_3~′=6态的色散荧光和荧光时间谱, 该态在240 Pa下的寿命大约是80 ns. 实验表明Ã ~3E 态CH_3N自由基是稳定的, 势能面至少距振动基态4800 cm~(-1)内是束缚的, 异构化或预离解作用并不重要.     

结合三维静电势参数研究二取代苯的定量结构－疏水性关系

对含有常见取代基的92个二取代苯化合物进行了结构优化和静电势及其导出参数的计算,运用多元线性回归方法对化合物的疏水常数与分子的结构参数进行了关联.结果表明,分子表面负静电势的加和ΣV－S、分子空间内最负的静电势Vmin、表面最大静电势Vs,max以及分子体积V、极性表面积APS和分子的偶极密度μ/V这六个参数,可以很好地用于表达这些化合物疏水性与分子结构间的定量关系,而不用具体考虑分子中极性基团间的相互作用.用建立起来的QSPR(quantitative structure-property relationship)关系式对111个类似化合物的疏水性进行了预测,获得了满意的结果.     

Synthesis and Second‐Order Nonlinearities of Chiral Prolinol‐Substituted Chromophores

A new series of thiophene‐ and furan‐containing chromophores with a chiral prolinol donor and a sulfone acceptor has been synthesized. The UV‐vis absorptions, second‐order nonlinear optical properties, and X‐ray crystal structures are described.     

巡游电子系化合物La0.8Ce0.2(Fe1-xCox)11.4Si1.6的磁热效应

对制备的化合物La0.8Ce0.2(Fe1-xCox)11.4Si1.6(x=0.02,0.04,0.06)的相组成、巡游电子变磁转变(IEMT)特性和磁热效应(MCE)进行了研究。粉末X射线衍射结果表明,经1373 K真空退火处理7 d后,化合物La0.8Ce0.2(Fe1-xCox)11.4Si1.6(x=0.02,0.04,0.06)均为单相立方NaZn13型晶体结构。随着Co含量由x=0.02增加到x=0.06,样品的居里温度TC由207 K上升到277 K。在0~1.5 T磁场变化下,x=0.02,0.04,0.06时样品的最大磁熵变|ΔSM(T)|分别为40.17,12.60和7.65 J.kg-1.K-1,可见该化合物有巨大的磁熵变,而且随Co含量的增加最大磁熵变迅速减小。该化合物的巨大磁熵变来源于TC处的一级相变,以及在TC以上由磁场诱导IEMT,但由于Co原子对Fe原子的替代能够抑制变磁转变的发生,因此该系化合物最大磁熵变随Co含量的增加迅速减小。     

Diagnosis of OH Radical by Optical Emission Spectroscopy in Atmospheric Pressure Unsaturated Humid Air Corona Discharge and its Implication to Desulphurization of Flue Gas

OH radical in the corona discharge with pipe–nozzle–plate electrode has been diagnosed by optical emission spectroscopy. Spatial variations of OH radical emission in discharge gap have been measured. Relative intensity of OH radical emission spectroscopy increases with increasing water vapor flux injected into the reactor or intensity of electric field supported. In positive pulsed corona discharge, relative intensity is higher than that in positive DC corona discharge and lower than that in negative DC corona discharge. Strongest intensity of OH radical spectrum appears within the range of 5 mm near the discharge nozzle- electrode. In addition, it is proved that the efficiency of desulphurization from flue gas by pulsed corona discharge plasma processes can be improved when OH radical is produced in the reactor.     

Sequosempervirin A, a novel spirocyclic compound from Sequoia sempervirens

A novel spirocyclic compound (4R)-4-(4-hydroxy-benzyl) spiro [4,5] dec-1-en-8-ol (sequosempervirin A) was isolated from the branches and leaves of Sequoia sempervirens. Its structure and relative stereochemistry were mainly determined by MS, 2D NMR and X-ray means, which is the first naturally occurring norlignan containing one spirocycle with C6 (cyclohexane)-C2-C3-C6 skeleton.     

Mixed Cationic‐nonionic Surfactants and pH Adjustment Route to Synthesize High‐quality MCM‐48

Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N₂ adsorption/desorption isotherm, TEM, TG‐DSC and ²⁹Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail.     

Carbohydrate-binding module O-mannosylation alters binding selectivity to cellulose and lignin

Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies. In this study, we examine the impact of O-glycosylation on the binding selectivity of a model Family 1 carbohydrate-binding module (CBM), which has been shown to be one of the primary sub-domains responsible for non-productive lignin binding in multi-modular cellulases. Specifically, we examine the relationship between glycan structure and the binding specificity of the CBM to cellulose and lignin substrates. We find that the glycosylation pattern of the CBM exhibits a strong influence on the binding affinity and the selectivity between both cellulose and lignin. In addition, the large set of binding data collected allows us to examine the relationship between binding affinity and the correlation in motion between pairs of glycosylation sites. Our results suggest that glycoforms displaying highly correlated motion in their glycosylation sites tend to bind cellulose with high affinity and lignin with low affinity. Taken together, this work helps lay the groundwork for future exploitation of glycoengineering as a tool to improve the performance of industrial enzymes.

Improved understanding of the effect of protein glycosylation is expected to provide the foundation for the design of protein glycoengineering strategies.

The cell walls of terrestrial plants primarily comprise the polysaccharides cellulose, hemicellulose, and pectin, as well as the heterogeneous aromatic polymer, lignin. In nature, carbohydrates derived from plant polysaccharides provide a massive carbon and energy source for biomass-degrading fungi, bacteria, and archaea, which together are the primary organisms that recycle plant matter and are a critical component of the global carbon cycle. Across the various environments in which these microbes break down lignocellulose, a few known enzymatic and chemical systems have evolved to deconstruct polysaccharides to soluble sugars.^1–6 These natural systems are, in several cases, being evaluated for industrial use to produce sugars for further conversion into renewable biofuels and chemicals.From an industrial perspective, overcoming biomass recalcitrance to cost-effectively produce soluble intermediates, including sugars for further upgrading remains the main challenge in biomass conversion. Lignin, the evolution of which in planta provided a significant advantage for terrestrial plants to mitigate microbial attack, is now widely recognized as a primary cause of biomass recalcitrance.⁷ Chemical and/or biological processing scenarios of lignocellulose have been evaluated⁸ and several approaches have been scaled to industrial biorefineries to date. Many biomass conversion technologies overcome recalcitrance by partially or wholly removing lignin from biomass using thermochemical pretreatment or fractionation. This approach enables easier polysaccharide access for carbohydrate-active enzymes and/or microbes. There are however, several biomass deconstruction approaches that employ enzymes or microbes with whole, unpretreated biomass.^9,10 In most realistic biomass conversion scenarios wherein enzymes or microbes are used to depolymerize polysaccharides, native or residual lignin remains.^11,12 It is important to note that lignin can bind and sequester carbohydrate-active enzymes, which in turn can affect conversion performance.¹³Therefore, efforts aimed at improving cellulose binding selectivity relative to lignin have emerged as major thrusts in cellulase studies.^14–25 Multiple reports in the past a few years have made exciting new contributions to our collective understanding of how fungal glycoside hydrolases, which are among the most well-characterized cellulolytic enzymes given their importance to cellulosic biofuels production, bind to lignin from various pretreatments.^15,17 Taken together, these studies have demonstrated that the Family 1 carbohydrate-binding modules (CBMs) often found in fungal cellulases are the most relevant sub-domains for non-productive binding to lignin,^15,17,20,26 likely due to the hydrophobic face of these CBMs that is known to be also responsible for cellulose binding (Fig. 1).²⁷Open in a separate windowFig. 1Model of glycosylated CBM binding the surface of a cellulose crystal. Glycans are shown in green with oxygen atoms in red, tyrosines known to be critical to binding shown in purple, and disulfide bonds Cys8–Cys25 and Cys19–Cys35 in yellow.Furthermore, several studies have been published recently using protein engineering of Family 1 CBMs to improve CBM binding selectivity to cellulose with respect to lignin. Of particular note, Strobel et al. screened a large library of point mutations in both the Family 1 CBM and the linker connecting the catalytic domain (CD) and CBM.^21,22 These studies demonstrated that several mutations in the CBM and one in the linker led to improved cellulose binding selectivity compared to lignin. The emerging picture is that the CBM-cellulose interaction, which occurs mainly as a result of stacking between the flat, hydrophobic CBM face (which is decorated with aromatic residues) and the hydrophobic crystal face of cellulose I, is also likely the main driving force in the CBM-lignin interaction given the strong potential for aromatic–aromatic and hydrophobic interactions.Alongside amino acid changes, modification of O-glycosylation has recently emerged as a potential tool in engineering fungal CBMs, which Harrison et al. demonstrated to be O-glycosylated.^28–31 In particular, we have revealed that the O-mannosylation of a Family 1 CBM of Trichoderma reesei cellobiohydrolase I (TrCel7A) can lead to significant enhancements in the binding affinity towards bacterial microcrystalline cellulose (BMCC).^30,32,33 This observation, together with the fact that glycans have the potential to form both hydrophilic and hydrophobic interactions with other molecules, led us to hypothesize that glycosylation may have a unique role in the binding selectivity of Family 1 CBMs to cellulose relative to lignin and as such, glycoengineering may be exploited to improve the industrial performance of these enzymes. To test this hypothesis, in the present study, we systematically probed the effects of glycosylation on CBM binding affinity for a variety of lignocellulose-derived cellulose and lignin substrates and investigated routes to computationally predict the binding properties of different glycosylated CBMs.     

与时俱进，不断开创物理化学课程建设新局面

As a necessary basic theory course for undergraduates majoring in chemistry, materials, pharmacy, chemical engineering, and biology, physical chemistry plays an important role in cultivating talents to meet the needs of social and economic development. Over the years, the teaching team of physical chemistry of East China University of Science and Technology has carried out the curriculum reform and innovation persistently based on "Team building as the foundation, resource building as the root, mode innovation as the soul, ability training as the origin". This paper will summarize our thinking and experience in striving for the first-class course from the aspects of first-class team construction, first-class resource construction, teaching connotation innovation, teaching mode exploration, and extract the experience that can be used as reference by teaching peers.     

The Regularity of Stochastic Convolution Driven by Tempered Fractional Brownian Motion and Its Application to Mean-field Stochastic Differential Equations

In this paper, some properties of a stochastic convolution driven by tempered fractional Brownian motion are obtained. Based on this result, we get the existence and uniqueness of stochastic mean-field equation driven by tempered fractional Brownian motion. Furthermore, combining with the Banach fixed point theorem and the properties of Mittag-Leffler functions, we study the existence and uniqueness of mild solution for a kind of time fractional mean-field stochastic differential equation driven by tempered fractional Brownian motion.