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.     

Lorentz-Minkowski空间中旋转W超曲面

1841年,D elaunay获得如下定理:如果在一平面上沿定直线滚动一条二次圆锥直线,然后将其焦点的轨迹绕定直线旋转,则所得到的曲面具有常数平均曲率,反之,所有旋转常数平均曲率曲面(除球面外)都有如此构造.本文将以上的D elaunay定理推广到Lorentz-M inkow sk i空间Rn1 1中类空的Sm型旋转W超曲面.     

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.     

The Cage Structure of IndanCHF3 is Based on the Cooperative Effects of CH⋅⋅⋅π and CH⋅⋅⋅F Weak Hydrogen Bonds

The structural and energetic features of the C?H???π interaction and the internal dynamics of the CHF₃ group change drastically in going from benzene?CHF₃ to indan?CHF₃, according to the analysis of the rotational spectrum of the latter complex generated in a supersonic expansion.     

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.     

Symmetry calculation for molecules and transition states

The symmetry of molecules and transition states of elementary reactions is an essential property with important implications for computational chemistry. The automated identification of symmetry by computers is a very useful tool for many applications, but often relies on the availability of three‐dimensional coordinates of the atoms in the molecule and hence becomes less useful when these coordinates are a priori unavailable. This article presents a new algorithm that identifies symmetry of molecules and transition states based on an augmented graph representation of the corresponding structures, in which both topology and the presence of stereocenters are accounted for. The automorphism group order of the graph associated with the molecule or transition state is used as a starting point. A novel concept of label‐stereoisomers, that is, stereoisomers that arise after labeling homomorph substituents in the original molecule so that they become distinguishable, is introduced and used to obtain the symmetry number. The algorithm is characterized by its generic nature and avoids the use of heuristic rules that would limit the applicability. The calculated symmetry numbers are in agreement with expected values for a large and diverse set of structures, ranging from asymmetric, small molecules such as fluorochlorobromomethane to highly symmetric structures found in drug discovery assays. The new algorithm opens up new possibilities for the fast screening of the degree of symmetry of large sets of molecules. © 2014 Wiley Periodicals, Inc.     

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.     

Experimental Charge Density Evidence for Pnicogen Bonding in a Crystal of Ammonium Chloride

Chemical binding in crystalline ammonium chloride, a simple inorganic salt with an unexpectedly complex bonding pattern, was studied by using a topological analysis of electron density function derived from high‐resolution X‐ray diffraction. Supported by periodic quantum chemical calculations, it provided experimental evidence for weak σ‐hole bonds (1.5 kcal mol^?1) that involve ammonium cations in a crystal. Our results show this type of supramolecular interaction to be more numerous than has been found to date by using gas‐phase calculations or statistical analysis of CSD.