Noncovalent interactions on the electrocatalytic oxidation of ethanol on a Pt/C electrocatalyst

Due to their environmentally friendly nature and high energy density,direct ethanol fuel cells have attracted extensive research attention in recent decades.However,the actual Faraday efficiency of the ethanol oxidation reaction(EOR)is much lower than its theoretical value and the reaction kinetics of the EOR is sluggish due to insufficient active sites on the electrocatalyst surface.Pt/C is recognized as one of the most promising electrocatalysts for the EOR.Thus,the microscopic interfacial reaction mechanisms of the EOR on Pt/C were systematically studied in this work.In metal hydroxide solutions,hydrated alkali cations were found to bind with OH_(ad)through noncovalent interactions to form clusters and occupy the active sites on the Pt/C electrocatalyst surface,thus resulting in low Faraday efficiency and sluggish kinetics of the EOR.To reduce the negative effect of the noncovalent interactions on the EOR,a shield was made on the electrocatalyst surface using 4-trifluoromethylphenyl,resulting in twice the EOR catalytic reactivity of Pt/C.

Dinuclear Silver(Ⅰ) Complex Based on 1-Picolyl-3-propylbenzimidazolium Salt: Crystal Structure and Weak Interactions

1-Picolyl-3-propylbenzimidazolium bromide （LBr） was prepared from benzimida- zole by alkylation with 2-chloromethyl-pyridine in the presence of NaH, followed by quaternization with 1-bromopropane. Ligand LBr was treated with AgBr in CH2Cl2 to afford a dinuclear silver（I） complex L2Ag2Br4 （1）. In complex 1, a 2-D supramolecular layer is formed through two types of π-π stacking interactions. Fluorescent emission spectra of ligand LBr and complex 1 are described.

A Silver Complex of 6,7-Dicyanodipyridoquinoxaline:π-Stacking Interactions and Luminescence

The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the space group Ibca of orthorhombic system with eight formula units in a cell. Crystal data for 1： a = 15.7055（17）, b = 18.411（2）, c = 20.680（2）A, V = 5979.7（11）A3, Z = 8, C32Hl2AgN13O3, Mr = 734.42, Dc = 1.632 g/cm3, μ= 0.734 mm-1, F（000） = 2928, S = 1.023 and T= 293（2） K. The final R = 0.0659 and wR = 0.1927 for 2118 observed reflections with I 〉 2σ（I）, and R = 0.0801 and wR = 0.2196 for all data. The complex builds up a packing structure by π-π stacking interactions and shows a luminescent feature.

A New Cadmium(Ⅱ) Coordination Polymer Extended through Hydrogen Bonds and π-π Stacking Interactions: Synthesis and Photoluminescence Property

A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.

Construct Protein-Protein Interaction Network by Mining Domain-Domain Interactions

Domain-domain interactions are important clues to inferring protein-protein interactions. Although about 8 000 domain-domain interactions are discovered so far,they are just the tip of the iceberg. Because domains are conservative and commonplace in proteins,domain-domain interactions are discovered based on pairs of domains which significantly co-exist in proteins. Meanwhile,it is realized that:( 1) domain-domain interactions may exist within the same proteins or across different proteins;( 2) only the domain-domain interactions across different proteins can mediate interactions between proteins;( 3) domains have biases to interact with other domains. And then,a novel method is put forward to construct protein-protein interaction network by using domain-domain interactions. The method is validated by experiments and compared with the state- of-art methods in the field. The experimental results suggest that the method is reasonable and effectiveness on constructing Protein-protein interactions network.

A New Cobalt(Ⅱ)Polymer Based on 1-Butylben-zimidazole and Terephthalate Mixed-ligands:Crystal Structure and Weak Interactions

A new cobalt（Ⅱ） polymer with quasi-rectangular cavities, [Co（L）2（TP）·H2O]n 1 （L=1-butylbenzimidazole, TP = terephthalate ion） has been prepared by means of self-assembly of 1-butylbenzimidazole, terephthalic acid and Co（NO3）2·6H2O. The structure of 1 was characterized by X-ray diffraction analysis. In the crystal packing, 2-D supramolecular layers are formed via π-π stacking interactions. The fluorescence emission spectra of L and 1 are described.

Two Cd(Ⅱ) and Cu(Ⅱ) Complexes Based on 1-Butylbenzimidazole: Crystal Structures and Weak Interactions

1-Butylbenzimidazole L reacted with Cd（NO3）2·4H2O to afford complex [CdL（NO3）3H2O]·[HL] 1. The heptacoordinated Cd（Ⅱ） center adopts a distorted pentagongal bipyramidal geometry, and complex [CdL（NO3）3H2O]-entity and the protonated benzimidazium salt [HL]＋ are connected via N–H···O hydrogen bond to form a dimeric unit [CdL（NO3）3H2O]·[HL]. A 3-D supramolecular network of 1 is formed through N–H···O and O–H···O hydrogen bonds together with π-π stacking interactions. Reaction of L with CuCl2 afforded a mononuclear complex, [CuL2Cl2] 2, in which the tetracoordinated Cu（II） center adopts a distorted tetrahedral geometry. In contrast, 2-D supramolecular layers of 2 are formed by C–H···Cl hydrogen bonds. The fluorescent emission spectra of L, 1 and 2 are described.

A 3D Supramolecular Pd(Ⅱ) Complex via Hydrogen-bonding and Weak M…M Interactions

The reaction of 2,4,6-tris（2-pyridyl）-1,3,5-triazine （tptz） and K2PdCl4 in THF/H2O （10：1） results in the hydrolysis of tptz to bis（2-pyridylcarbonyl）amide anion （bpca）, and affords complex Pd（bpca）Cl 1, which is the first example of Pd（Ⅱ）-promoted hydrolysis of ligands. Crystal data for 1： orthorhombic, space group Pbcn, a = 12.0136（17）, b = 14.180（2）, c = 6.9747（11）A, V= 1188.2（3） A3, Z = 4, Mr = 368.06, Dc = 2.058 g/cm3, F（000） = 720,μ = 1.786 mm^-1, λ（MoKα） = 0.71073 A, T= 293（2） K, 2θmax = 54.9°, GOOF = 1.085, the final R= 0.0647 and wR = 0.1051 for 1234 observed reflections with I 〉 2σ（I） （refinement on F2）. Complex 1 is connected through hydrogen bonding to give a 2D network. And weak Pd...Pd interactions are also found between adjacent molecules with the distance of 3.6074（5） A, so the complex is further extended into a 3D supramolecular structure. Thermal gravity analysis （TGA） shows that 1 exhibits high thermal stability below 310℃. X-ray powder diffraction （XRD） and UV/Vis spectrum of 1 are also discussed.

Elastic responses of underground circular arches considering dynamic soil-structure interaction:A theoretical analysis

Due to the wide applications of arches in underground protective structures, dynamic analysis of circular arches including soil-structure interactions is important. In this paper, an exact solution of the forced vibration of circular arches subjected to subsurface denotation forces is obtained. The dynamic soil-structure interaction is considered with the introduction of an interfacial damping between the structure element and the surrounding soil into the equa- tion of motion. By neglecting the influences of shear, rotary inertia and tangential forces and assuming the arch incompressible, the equations of motion of the buried arches were set up. Analytical solutions of the dynamic responses of the protective arches were deduced by means of modal super- position. Arches with different opening angles, acoustic impedances and rise-span ratios were analyzed to discuss their influences on an arch. The theoretical analysis suggests blast loads for elastic designs and predicts the potential failure modes for buried protective arches.

Interaction of 14-3-3σ with KCMF1 suppresses the proliferation and colony formation of human colon cancer stem cells

AIM: To investigate the biological function of 14-3-3σ protein and to look for proteins that interact with 14-3-3σ protein in colon cancer stem cells. METHODS: Reverse transcription polymerase chain reaction was performed to amplify the 14-3-3σ gene from the mRNA of colon cancer stem cells. The gene was then cloned into the pGEM-T vector. After being sequenced, the target gene 14-3-3σ was cut from the pGEM-T vector and cloned into the pGBKT7 yeast expression plasmid. Then, the bait plasmid pGBKT7-14-3-3σ was transformed into the yeast strain AH109. After the expression of the pGBKT7-14-3-3σ fusion protein in the AH109 yeast strain was accomplished, a yeast two-hybrid screening assay was performed by mating AH109 with Y187 that contained a HeLa cDNA library plasmid. The interaction between the 14-3-3σ protein and the proteins obtained from positive colonies was further confirmed by repeating the yeast two-hybridscreen. After extracting and sequencing the plasmids from the positive colonies, we performed a bioinformatics analysis. A coimmunoprecipitation assay was performed to confirm the interaction between 14-3-3σ and the proteins obtained from the positive colonies. Finally, we constructed 14-3-3σ and potassium channel modulatory factor 1 (KCMF1) siRNA expression plasmids and transfected them into colon cancer stem cells. RESULTS: The bait plasmid pGBKT7-14-3-3σ was constructed successfully, and the 14-3-3σ protein had no toxic or autonomous activation effect on the yeast. Nineteen true-positive colonies were selected and sequenced, and their full-length sequences were obtained. We searched for homologous DNA sequences for these sequences from GenBank. Among the positive colonies, four coding genes with known functions were obtained, including KCMF1 , quinone oxidore-ductase (NQO2 ), hydroxyisobutyrate dehydrogenase (HIBADH ) and 14-3-3σ . For the subsequent coimmu-noprecipitation assay, the plasmids PCDEF-Flag-14-3-3σ, PCDEF-Myc-KCMF1, PCDEF-Myc-NQO2 and PCDEF-Myc-HIBADH were successfully constructed, and the sequences were further confirmed by DNA sequencing. The Fugene 6 reagent was used to transfect the plasmids, and fluorescence-activated cell sorting analysis showed the transfection efficiency was 97.8% after 48 h. The HEK 293FT cells showed the stable expression of the PCDEF-Flag-14-3-3σ, PCDEF-Myc-KCMF1, PCDEF-Myc-NQO2 and PCDEF-Myc-HIBADH plasmids. After anti-Myc antibody immunoprecipitation with Myc-KCMF1, Myc-NQO2 and Myc-HIBADH from cell lysates, the presence of Flag-14-3-3σ protein in the immuno-precipitated complex was determined by western blot analysis. The knock-down expression of the 14-3-3σ and KCMF1 proteins significantly inhibited cell proliferation and colony formation of SW1116csc. CONCLUSION: Genes of the proteins that interactedwith 14-3-3σ were successfully screened from a HeLa cDNA library. KCMF1 and 14-3-3σ protein may affect the proliferation and colony formation of human colon cancer stem cells.

Jet formation in shock-heavy gas bubble interaction

The influences of the acoustic impedance and shock strength on the jet formation in shock-heavy gas bubble interaction are numerically studied in this work. The process of a shock interacting with a krypton or a SF6 bubble is studied by the numerical method VAS2D. As a validation, the experiments of a SF6 bubble accelerated by a planar shock were performed. The results indicate that, due to the mismatch of acoustic impedance, the way of jet formation in heavy gas bubble with different species is diversified under the same initial condition. With respect to the same bubble, the manner of jet formation is also distinctly different under different shock strengths. The disparities of the acoustic impedance result in different effects of shock focusing in the bubble, and different behaviors of shock wave inside and outside the bubble. The analyses of the wave pattern and the pressure variation indicate that the jet formation is closely associated with the pressure perturbation. Moreover, the analy- sis of the vorticity deposition, and comparisons of circulation and baroclinic torque show that the baroclinic vorticity also contributes to the jet formation. It is concluded that the pres- sure perturbation and baroclinic vorticity deposition are the two dominant factors for the jet formation in shock-heavy gas bubble interaction.

An Observational Study of the 30-50 Day Atmospheric Oscillations Part II: Temporal Evolution and Hemispheric Interaction across the Equator

In this part, the temporal evolution and interaction across the equator of 30-50 day oscillation in the atmosphere are investigated further. The annual variation of 30-50 day oscillation is quite obvious in the mid-high latitudes. In the tropical atmosphere, the obvious interannual variation is an important property for temporal evolution of 30-50 day oscillation. The low-frequency wavetrain across the equator over the central Pacific and central Atlantic area, the movement of the long-lived low-frequency system across the equator and the meridional wind component across the equator will obviously show the interaction of 30-50 day oscillation in the atmosphere across the equator.

Characteristics of lateral vehicular interactions in heterogeneous traffic with weak lane discipline

Heterogeneous traffic conditions prevail in developing countries. Vehicles maintain weak lane discipline which increases lateral interactions of vehicles significantly. It is necessary to study these interactions in the form of maintained lateral gaps for modeling this traffic scenario. This paper aims at determining lateral clearances maintained by different vehicle types while moving in a heterogeneous traffic stream during overtaking. These data were collected using an instrumented vehicle which runs as a part of the stream. Variation of obtained clearance with average speed of interacting vehicles is studied and modeled. Different instrumented vehicles of various types are developed using （1） ultrasonic sensors fixed on both sides of vehicle, which provide inter-vehicular lateral distance and relative speed; and （2） GPS device with cameras, which provides vehicle type and speed of interacting vehicles. They are driven on different roads in six cities of India, to measure lateral gaps maintained with different interacting vehicles at different speeds. Relationships between lateral gaps and speed are modeled as regression lines with positive slopes and beta-distributed residuals. Nature of these graphs （i.e., slopes, intercepts, residuals） are also evaluated and compared for different interacting vehicle-type pairs. It is observed that similar vehicle pairs maintain less lateral clearance than dissimilar vehicle pairs. If a vehicle interacts with two vehicles （one on each side） simultaneously, lateral clearance is reduced and safety of the vehicles is compromised. The obtained relationships can be used for simulating lateral clearance maintaining behavior of vehicles in heterogeneous traffic.

Dicobalt Complex with Metal-metal Interaction of a Naphthyridine and Pyrazine Amine Ligand

Molecular structure of a naphthyridine and pyrazine amine ligand, N2,N7-di（pyrazin-2-yl）-1,8-naphthyri-dine-2,7-diamine（H2dpznda 1） was studied, and a three-dimensional supramolecular network with a double helix chain structure through intermolecular hydrogen bonds and π-π interactions between the naphthyridine and pyrazine rings was depicted. Through ligand 1, [Co2（μ2-dpznda）2（μ2-CH3OH）2]（2） was obtained and two ligands coordinate to two Co2＋）as tetradentate bridging ligands. Single crystal and magnetism study on 2 revealed that the complex exhibited weak yet significant metal-metal interaction.

Thermal Stability Improved by π–π Stacking Interactions: Synthesis, Crystal Structure and Thermal Decomposition of Sodium Nitroformate

An energetic salt, sodium nitroformate （NaNF）, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was first determined by single crystal X-ray diffraction. The structure exhibits two types of π-π stacking interactions between the nitroformate anions, i e, the parallel-displaced and T-shaped confgurafions. Furthermore, the thermal decomposition mechanism was investigated by DSC, TG-DTG and FTIR techniques. The kinetic parameters of the thermal decomposition were also calculated by using Kissinger＇s and Ozawa-Doyle＇s methods. The results show that NaNF has a good thermal stability, which is attributed to the π-π stacking interactions.

Nonlinear Three-Wave Interaction among Barotropic Rossby Waves in a Large-scale Forced Barotropic Flow

In this paper. the coupling equations describing nonlinear three-wave interaction amongRossby waves including the forcing of an external vorticity source are obtained. Under certainconditions, the coupling equations with a constant amplitude forcing, the stability analysis indicates that when the amplitude of the external forcing increases to a certain extent, a pitchforkbifurcation occurs. Also. it is shown fi-o m numerical results that the bifurcation can lead to chaoticbehavior of' strange' attractor. For the obtained three-variable equation, when the amplitude ofmodulated external forcing gradually increases, a Period-doubling bifurcation is found to lead tochaotic behavior. Thus, in a nonlinear three-wave coupling model in the large-scale forcedbarotropic atmospheric flow, chaotic behavior can be observed. This chaotic behavior can explainin part 30-60-day low-flequency oscillations observed in mid-high latitudes.

MD simulation on the interactions between CH＿2 groups and the(001) surface of tungsten

This work studies the angle dependence of the interactions between impinging CH2 particles of 150 eV with the tungsten surface. The simulations show that the carbon atoms are much more easily bonded to the tungsten atoms than hydrogen atoms, though a few of the latter can also penetrate into the tungsten material. When the incidence angle is greater than 75%, the incident CH2 particles are reflected without break-ups. Below this angle, a W-C layer of about 0.5 nm is formed with another C, H-rich layer depositing on top of it. The molecular dynamics （MD） approach has proved to be a powerful tool to solve the structural problems at atomic length scale of various materials. Some of its possible applications to the railway track materials have also been discussed.

Theoretical Studies on the Intermonomer Interaction of F^(-)·(H_(2)O)_(n)(n=1,2)

Five optimized geometries of F-?(H2O)n (n = 1, 2) were obtained with ab initio calculation at the B3LYP/6-311++G** level. The accurate intermonomer interaction energy was calculated using the MP2 electron correlation correction as well as the basis set superposition error correction by the Boys-Bernardi “counterpoise” protocol. Natural bond orbital (NBO) theory was applied to quantify the relative strength of these interactions and account for their effects on the stability, structural and vibrational parameters of Fˉ?(H2O)n (n = 1, 2). It is shown that the charge transferring from the lone pair of F-1 to the σ?OH(…F) antibonding orbital is important. The results indicate the occupancy of σ?OH(…F) is increased (denoted ?σ?OH(…F)) and the σOH(…F) bond is leng- thened (denoted ?ROH(…F)), leading to the red-shift and the red-shift values have linear correlation with both ?σ?OH(…F) and ?ROH(…F).

Luminescent properties of thermally activated delayed fluorescence molecule with intramolecular π-π interaction between donor and acceptor

Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence（TADF） molecule（3, 5-bis（3,6-di-tert-butyl-9 H-carbazol-9-yl）-phenyl）（pyridin-4-yl） methanone（DTCBPY） is theoretically studied by using the density functional theory（DFT） and time-dependent density functional theory（TD-DFT）.Four conformations（named as A, B, C, and D） of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios（44% and 52%） can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.

Conjugated polymerized bimetallic phthalocyanine based electrocatalyst with Fe-N_(4)/Co-N_(4) dual-sites synergistic effect for zinc-air battery

The bifunctional oxygen catalyst is essential for zinc-air batteries(ZABs).Here,an efficient bifunctional oxygen catalyst,PPcFeCo/3D-G,is obtained throughπ-πinteraction between the conjugated polymerized iron-cobalt phthalocyanine(PPcFeCo)with excellent thermal stability and three-dimensional graphene(3D-G).The bimetallic synergistic effect of PPcFeCo,verified by DFT(Density functional theory)calculation,andπ-πinteractions enhances the catalytic activity and durability of the PPcFeCo/3D-G.Regarding electrochemical performance,the PPcFeCo/3D-G with a high electron transfer number(3.98,@0.768 V vs.RHE)has excellent half-wave potential(E_(1/2)=0.890 V vs.RHE)and exhibits outstanding reversibility(ΔE=0.700 V,ΔE=Ej=10-E_(1/2)).The liquid ZAB(LZAB)employed PPcFeCo/3D-G displays a high power density(222 m W cm^(-2)),a specific capacity(792 m A h g-1),and excellent durability(120 h).This work has guiding significance for the preparation of high-efficiency bifunctional catalysts.