固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布

具有AEI结构的SSZ-39分子筛的骨架外阳离子落位和铝分布对其催化性能影响显著.AEI笼中有三个结晶学不等价位，且铝取代T位具有一定的倾向性.本文结合固体核磁共振（NMR）技术（²⁷Al/²³Na MQ MAS NMR），以及密度泛函理论（DFT）计算，研究了不同硅铝比Na-SSZ-39分子筛中的Na⁺落位和铝分布.在孤立铝分布的情况下，铝原子优先占据于T3位，Na⁺主要落位于AEI笼中的SIIa0和SIII'a0位点上，其中SIII'a0位点的优先度较高，此外少部分Na⁺还落位于六棱柱内部的SIa0.当铝对存在时，AlSiSiAl分布的铝对占据六元环的对位（T3-T3），对应的Na⁺分别落位于SIIa1和SⅢ'a1位点.随着分子筛结构的部分破坏，游离的Na⁺可能形成明显的SIII'b位点.本文可加深对SSZ-39分子筛构效关系的理解，为更好地调控催化性能奠定基础.     

InSb芯片碎裂与迸溅金点的关系

批量生产中经常发生的锑化铟(InSb)芯片碎裂问题制约着InSb红外焦平面探测器(IRFPAs)成品率的提升.经分析认为:低周期液氮冲击下发生在器件边沿区域的InSb芯片破碎与该区域中迸溅金点的存在有关.为从理论上明晰迸溅金点对InSb芯片局部碎裂的影响,本文建立了包含迸溅金点的InSb IRFPAs结构模型,分析了迸溅金点的存在对应力分布的影响.在此基础上,在应力集中处预置不同长度的初始裂纹用以描述InSb晶片中的位错,以能量释放率为判据,探究InSb芯片碎裂与迸溅金点和位错线长短的关系.结论如下:1)迸溅金点的存在对InSb芯片碎裂的影响是局部的,在迸溅金点与InSb芯片接触区域的两侧会形成两个应力集中点; 2)环绕预置裂纹的能量释放率会随着预置裂纹长度的增加而加速增大,当预置裂纹长度接近InSb芯片上表面时,能量释放率近乎指数增加,并在预置裂纹贯穿InSb芯片时达到最大值; 3)迸溅金点引起的InSb芯片破碎属于Ⅰ型断裂失效模式,在多周期液氮冲击中,位错线在应力集中效应的驱使下逐步扩展,直至贯穿InSb芯片,最终形成宏观碎裂失效现象.     

Triterpenes and limonoids of Cedrela: Distribution,biosynthesis, and 1H and 13C NMR data

Cedrela genus, a member of the Meliaceae family, presents both chemical characteristics associated with and those that distinguish it from the rest of its members. The presence of triterpenes and limonoids is the characteristic of the Meliaceae family, but the class and type of these chemical constituents are distinctive for each genus. Cedrela includes cycloartane, ursane, oleanane, tirucallane, butyrospermane, and apotirucallane triterpenes, and its limonoids belongs to six class and nine types, known as class Ia-type havanensines, class Ib-type delevoyin, class II-type gedunin, class IIIb-type andirobin, class IIIg-type mexicanolide, class IVa-type evoludone, class Va-type obacunol, class V-type limonin, and class VIII. Each of these structural arrangements includes specific traits, defined by their biosynthetic origin, which can be established by means of structural elucidation techniques, particularly ¹H and ¹³C NMR, which assisted by 2D NMR techniques, allowing to deduce their structures unequivocally. The constant presence of these skeletal arrangements in Cedrela ensures that they are its chemophenetic markers and their recurrence is an important criterion for their identity. This review is a compilation of the occurrence of triterpenes and limonoids in Cedrela genus, detailing their biosynthetic association and collecting and organizing their NMR data, with the purpose of facilitating its location, analysis, and use in the phytochemical study of species from this genus.     

Effects of Charged Surfactants on Interfacial Water Structure and Macroscopic Properties of the Air-Water Interface

Surfactants are used to control the macroscopic properties of the air-water interface. However, the link between the surfactant molecular structure and the macroscopic properties remains unclear. Using sum-frequency generation spectroscopy and molecular dynamics simulations, two ionic surfactants (dodecyl trimethylammonium bromide, DTAB, and sodium dodecyl sulphate, SDS) with the same carbon chain lengths and charge magnitude (but different signs) of head groups interact and reorient interfacial water molecules differently. DTAB forms a thicker but sparser interfacial layer than SDS. It is due to the deep penetration into the adsorption zone of Br⁻ counterions compared to smaller Na⁺ ones, and also due to the flip-flop orientation of water molecules. SDS alters two distinctive interfacial water layers into a layer where H⁺ points to the air, forming strong hydrogen bonding with the sulphate headgroup. In contrast, only weaker dipole-dipole interactions with the DTAB headgroup are formed as they reorient water molecules with H⁺ point down to the aqueous phase. Hence, with more molecules adsorbed at the interface, SDS builds up a higher interfacial pressure than DTAB, producing lower surface tension and higher foam stability at a similar bulk concentration. Our findings offer improved knowledge for understanding various processes in the industry and nature.     

应力为SGBVE分布强度为指数分布下结构可靠度的估计

考虑了应力服从SGBVE分布,强度服从指数分布的应力—强度模型,分别在应力参数未知和部分强度参数未知的情形下给出了该模型可靠度的估计,并讨论了其性质.     

Direct analysis in real time mass spectrometry (DART‐MS) of highly non‐polar low molecular weight polyisobutylenes

Low molecular weight polyisobutylenes (PIB) with chlorine, olefin and succinic acid end‐groups were studied using direct analysis in real time mass spectrometry (DART‐MS). To facilitate the adduct ion formation under DART conditions, NH₄Cl as an auxiliary reagent was deposited onto the PIB surface. It was found that chlorinated adduct ions of olefin and chlorine telechelic PIBs, i.e. [M + Cl]^? up to m/z 1100, and the deprotonated polyisobutylene succinic acid [M? H]^? were formed as observed in the negative ion mode. In the positive ion mode formation of [M + NH₄]⁺, adduct ions were detected. In the tandem mass (MS/MS) spectra of [M + Cl]^?, product ions were absent, suggesting a simple dissociation of the precursor [M + Cl]^? into a Cl^? ion and a neutral M without fragmentation of the PIB backbones. However, structurally important product ions were produced from the corresponding [M + NH₄]⁺ ions, allowing us to obtain valuable information on the arm‐length distributions of the PIBs containing aromatic initiator moiety. In addition, a model was developed to interpret the oligomer distributions and the number average molecular weights observed in DART‐MS for PIBs and other polymers of low molecular weight. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of Diamond Nanoparticles by High-Speed Micro-Thermal Field-Flow Fractionation

Micro-thermal field-flow fractionation was used to characterize the particle size distribution of nanometer-sized diamond nanoparticles. Although the experimental conditions were chosen to perform high-speed separation, and, consequently, the resolution achieved experimentally was not very high, the application of the original correction method for the zone spreading allowed for obtaining of very good calculated particle size distribution or, explicitly, a true polydispersity index of the diamond nanoparticle sample. The future use of several samples of diamond nanoparticles of different average sizes and different surface chemistries should allow deeper insight into the effect of these particulate characteristics on the retention in micro-thermal field-flow fractionation.     

A statistical approach to characterize the viscoelastic creep compliances of a vinyl ester polymer

The objective of this study was to develop a model to predict the viscoelastic material functions of a vinyl ester (VE) polymer with variations in its experimentally obtained material properties under combined isothermal and mechanical loading. Short-term tensile creep experiments were conducted at three temperatures below the glass transition temperature of the VE polymer, with 10 replicates for each test configuration. The measured creep strain versus time responses were used to determine the creep compliances using the generalized viscoelastic constitutive equation with a Prony series representation. The variation in the creep compliances of a VE polymer was described by formulating the probability density functions (PDFs) and the corresponding cumulative distribution functions (CDFs) of the creep compliances using a two-parameter Weibull distribution. Both Weibull scale and shape parameters of the creep compliance distributions were shown to be time and temperature dependent. Two-dimensional quadratic Lagrange interpolation functions were used to characterize the Weibull parameters to obtain the PDFs and, subsequently, the CDFs of the creep compliances for the complete design temperature range during steady state creep. At each test temperature, creep compliance curves were obtained for constant CDF values and compared with the experimental data. The predicted creep compliances of the selected VE polymer in the design space are in good agreement with the experimental data for all three test temperatures.     

Computational Insights into the Charge Relaying Properties of β‐Turn Peptides in Protein Charge Transfers

Density functional theory calculations suggest that β‐turn peptide segments can act as a novel dual‐relay elements to facilitate long‐range charge hopping transport in proteins, with the N terminus relaying electron hopping transfer and the C terminus relaying hole hopping migration. The electron‐ or hole‐binding ability of such a β‐turn is subject to the conformations of oligopeptides and lengths of its linking strands. On the one hand, strand extension at the C‐terminal end of a β‐turn considerably enhances the electron‐binding of the β‐turn N terminus, due to its unique electropositivity in the macro‐dipole, but does not enhance hole‐forming of the β‐turn C terminus because of competition from other sites within the β‐strand. On the other hand, strand extension at the N terminal end of the β‐turn greatly enhances hole‐binding of the β‐turn C terminus, due to its distinct electronegativity in the macro‐dipole, but does not considerably enhance electron‐binding ability of the N terminus because of the shared responsibility of other sites in the β‐strand. Thus, in the β‐hairpin structures, electron‐ or hole‐binding abilities of both termini of the β‐turn motif degenerate compared with those of the two hook structures, due to the decreased macro‐dipole polarity caused by the extending the two terminal strands. In general, the high polarity of a macro‐dipole always plays a principal role in determining charge‐relay properties through modifying the components and energies of the highest occupied and lowest unoccupied molecular orbitals of the β‐turn motif, whereas local dipoles with low polarity only play a cooperative assisting role. Further exploration is needed to identify other factors that influence relay properties in these protein motifs.