Effect of electron-electron interaction on polarization process of exciton and biexciton in conjugated polymer

By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene.The dynamical simulation is performed by adopting the non-adiabatic evolution approach.The results show that under the effect of moderate electric field,when the strength of electron-electron interaction is weak,the singlet exciton is stable but its polarization presents obvious oscillation.With the enhancement of interaction,it is dissociated into polaron pairs,the spin-flip of which can be observed through modulating the interaction strength.For the triplet exciton,the strong electron-electron interaction restrains its normal polarization,but it is still stable.In the case of biexciton,the strong electron-electron interaction not only dissociate it,but also flip its charge distribution.The yield of the possible states formed after the dissociation of exciton and biexciton is also calculated.

Reversed charge transfer induced by nickel in Fe-Ni/Mo_(2)C@nitrogen-doped carbon nanobox for promoted reversible oxygen electrocatalysis

The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption energies of reaction intermediates,and ultimately impacts the catalytic performance.In this study,we discovered a unique charge transfer reversal phenomenon in a metal/carbon nanohybrid system.Specifically,electrons were transferred from the metal-based species to N-doped carbon,while the carbon support reciprocally donated electrons to the metal domain upon the introduction of nickel.This led to the exceptional electrocatalytic performances of the resulting Ni-Fe/Mo_(2)C@nitrogen-doped carbon catalyst,with a half-wave potential of 0.91 V towards oxygen reduction reaction(ORR)and a low overpotential of 290 m V at 10 mA cm^(-2)towards oxygen evolution reaction(OER)under alkaline conditions.Additionally,the Fe-Ni/Mo_(2)C@carbon heterojunction catalyst demonstrated high specific capacity(794 mA h g_(Zn)~(-1))and excellent cycling stability(200 h)in a Zn-air battery.Theoretical calculations revealed that Mo_(2)C effectively inhibited charge transfer from Fe to the support,while secondary doping of Ni induced a charge transfer reversal,resulting in electron accumulation in the Fe-Ni alloy region.This local electronic structure modulation significantly reduced energy barriers in the oxygen catalysis process,enhancing the catalytic efficiency of both ORR and OER.Consequently,our findings underscore the potential of manipulating charge transfer reversal between the metal and support as a promising strategy for developing highly-active and durable bi-functional oxygen electrodes.

A New Three-dimensional Supramolecular Polymer Built from Non-covalent Bonding Interactions

A new complex, [Ni2（L）4（H2O）8]（1, L1 = 4-（1H-imidazol-4-yl）benzoic acid）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with α = 22.281（2）, b = 7.3959（7）, c = 24.978（3） ？, β = 90.876（10）, V = 4115.6（7） ？3, Z = 8, C20H22N4O8Ni, Mr = 505.13, Dc = 1.630 g/cm3, μ = 1.001 mm-1, S = 1.080, F（000） = 2096, the final R = 0.452 and wR = 0.1152 for 9380 observed reflections （I 〉 2σ（I））. The result of X-ray diffraction analysis revealed three different kinds of Ni（II） centre mononuclear molecules in the asymmetric unit. The independent mononuclear units are bridged to form a three-dimensional supramolecular polymer by extensive hydrogen bonds and C–H… non-covalent bonding interactions.

Interactions between gas flow and reversible chemical reaction in porous media

Taking into consideration the gas compressibility and chemical reaction reversibility, a model was developed to study the interactions between gas flow and chemical reaction in porous media and resolved by the finite volume method on the basis of the gas-solid reaction aA(g)+bB(s)cC(g)+dD(s).The numerical analysis shows that the equilibrium constant is an important factor influencing the process of gas-solid reaction. The stoichiometric coefficients, molar masses of reactant gas, product gas and inert gas are the main factors influencing the density of gas mixture. The equilibrium constant influences the gas flow in porous media obviously when the stoichiometric coefficients satisfy a/c≠1.

STUDY ON THE NON-COVALENT INTERACTION OF APIGENIN MOLECULARLY IMPRINTED POLYMERS BY SPECTROMETRY

The non-covalent interaction between apigenin (API) and different functional monomers (α-methylacrylic acid (MAA), acrylamide (AM), 2-vinylpyridine (2-Vpy) and combined functional monomers (AM/2-Vpy)) was determined by UV spectrometry, and a series of apigenin molecularly imprinted polymers (API-MIPs) was synthesized with different functional monomers through molecular imprinting technology. The relationship between the non-covalent interaction of template/functional monomer and absorption of MIPs also was studied. The results showed that the order of the strength of the non-covalent interaction between API and different functional monomers in tetrahydrofuran (THF) is as follows: 2-Vpy> AM/2-Vpy>AM>MAA, which is positive correlation to the absorption capability of corresponding MIPs, and 2-Vpy is the optimum functional monomer among the used monomer for preparing API- MIPs.

Weaker Interactions in Zn^(2+)and Organic Ion-pre-intercalated Vanadium Oxide toward Highly Reversible Zinc-ion Batteries

Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.

Non-covalent interaction between almond protein and sinapic acid: impact on protein structure and antioxidant activity

Plant phenolic acids are good sources of antioxidants and sinapic acid(SA)is one of them that can be applied in protein-based food system.However,little research is available regarding interactions between almond protein(AP)and SA.In this study,structure-affinity interaction between SA and AP,structure and antioxidant activity of proteins were investigated.Different mathematical models showed that Ka of binding SA and AP were 3.27×10^4 L/mol and 3.08×10^4 L/mol.CD(Circular dichroism)spectroscopy and FT-IR(Fourier transform infrared)spectroscopy showed that the amount of random coil andα-helix decreased whileβ-sheet increased in AP-SA complex.In combination,the interaction model of AP-SA complex was static quenching and attributed to hydrophobic interaction.Further,AP-SA complex exerted better DPPH radical scavenging ability(36.97±0.78%),ABTS+radical scavenging ability(47.26±0.45%),and higher ORAC value(2.41±0.23 M trolox/g)compared to AP.In the further,SA can be applied in protein matrix to improve film stability,gel strength and restraining fat oxidation degradation.

Modulating vectored non-covalent interactions for layered assembly with engineerable properties

Vectored non-covalent interactions—mainly hydrogen bonding and aromatic interactions—extensively contribute to(bio)-organic self-assembling processes and significantly impact the physicochemical properties of the associated superstructures.However,vectored non-covalent interaction-driven assembly occursmainly along one-dimensional(1D)or three-dimensional(3D)directions,and a two-dimensional(2D)orientation,especially that of multilayered,graphene-like assembly,has been reported less.In this present research,by introducing amino,hydroxyl,and phenyl moieties to the triazine skeleton,supramolecular layered assembly is achieved by vectored non-covalent interactions.The planar hydrogen bonding network results in high stability,with a thermal sustainability of up to about 330°C and a Young’s modulus of up to about 40 GPa.Upon introducing wrinkles by biased hydrogen bonding or aromatic interactions to disturb the planar organization,the stability attenuates.However,the intertwined aromatic interactions prompt a red edge excitation shift effect inside the assemblies,inducing broad-spectrum fluorescence covering nearly the entire visible light region(400–650 nm).We show that bionic,superhydrophobic,pillar-like arrays with contact angles of up to about 170°can be engineered by aromatic interactions using a physical vapor deposition approach,which cannot be realized through hydrogen bonding.Our findings show the feasibility of 2D assembly with engineerable properties by modulating vectored non-covalent interactions.

Switching Optimally Balanced Fe-N Interaction Enables Extremely Stable Energy Storage

The interaction between electrode materials and charge carriers is one of the central issues dominating underlying energy storage mechanisms.To address the notoriously significant volume changes accompanying intercalation or formation of alloy/compounds,we aim to introduce and utilize a weak,reversible Fe-N interaction during the(de)intercalation of ammonium ions(NH_(4)^(+))within iron(Ⅲ)hexacyanoferrate(FeHCF),inspired by manipulating the electrostatic adsorption between N and Fe in the early stages of ammonia synthesis(Bosch-Harber Process,Chemical Engineering)and steel nitriding processes(Metal Industry).Such strategy of switching well-balanced Fe-N interaction is confirmed in between the nitrogen of ammonium ions and highspin Fe in FeHCF,as observed by using X-ray absorption spectroscopy.The resulting material provided an extremely stable energy storage(58 mAh g^(-1) after 10000 cycles at current density of 1 A g^(-1))as well as high-rate performance(23.6 mAh g^(-1) at current density of 10 A g^(-1)).

Extra contribution to the crystal stability of insensitive explosive TATB: The cooperativity of intermolecular interactions

An in-depth analysis on the cooperativity of intermolecular interactions including hydrogen bonding andπ-π stacking in 1,3,5-triamino-2,4,6-trinitrobenzene(TATB) crystal was studied. Two quantities, cooperativity rate and energy, were defined to evaluate the nature and strength of cooperativity in a series of clusters diverging from 1D to 3D prototypes. The origin and mechanism of the cooperative effect were settled to demonstrate that the nature of cooperativity is determined by whether the non-covalent interactions compete or promote with each other, which is manifested by the changing trend of electron transfer. There exists obvious cooperative effect in intra-layer and inter-layer structures as they own the equivalent non-covalent interactions, while anti-cooperative effect is also observed if two interactions correlate with each other. On the whole, in the process of crystal formation, the apparent cooperativity is the check and balance of the two effects, which is capable to support a global interaction among all of molecules and contribute to the stabilization of system. Based on the results, one may get a new insight to understand the relationship between non-covalent interactions and low impact sensitivity.

Simultaneous Determination of Amlodipine with H₁-Receptor Antagonists by Reversed Phase High Performance Liquid Chromatography and Application to Interaction Studies

A rapid, fast and precise method has been developed and validated for the simultaneous determination of amlodipine with H1-receptor antagonists (cetirizine, fexofenadine, and buclizine) from dosage forms. The chromatography was performed on a Purospher? Star, C18 (5 mm, 250 × 4.6 mm) column using acetonitrile: buffer (0.01 mM) (40:60, v/v, pH adjusted to 3.0), as a mobile phase. The mobile phase was pumped at a flow rate of 1.0 mL·min-1 and UV detection was performed at 240 nm. The method was validated for linearity, accuracy, precision and specificity. The method was applied to study the interaction between amlodipine and H1-receptor antagonists. These interactions were carried out in simulated gastric juice (pH 1), simulated full stomach (pH 4), blood pH (pH 7.4) and simulating GI (pH 9). The interacting drugs were heated at 37℃ with intermit-tent shaking and the samples were withdrawn every thirty minutes for three hours and drug contents were analyzed by RP-HPLC techniques. In most cases the in vitro availability of amlodipine was decreased. It was observed that the change in in vitro availability was pH dependent.

Effect of annealing time on the exchange coupling interactions and microstruc-ture of nanocomposite Pr_(7.5)Dy_1Fe_(71)Co_(15)Nb_1B_(4.5) ribbons

The influence of annealing time on the magnetic properties and microstructure of nanocomposite Pr7.5Dy1Fe71Co15Nb1B4.5 ribbons was systematically investigated by the methods of vibrating sample magnetometer （VSM）, X-ray diffraction （XRD） and high resolution transmission electron microscopy （HRTEM）. Interaction domains derived from strong exchange coupling interactions between hard and soft magnetic grains were imaged using magnetic force microscopy （MFM）. Maximum remanence, intrinsic coercivity, and maximum energy product values were obtained in the ribbons annealed at 700℃ for 15 min, which were composed of Pr2（Fe, Co）14B, α-（Fe, Co）, and slight Pr2（Fe, CO）17 phases. Although Jr, Hci, and （Bn）max decreased gradually with further increase of annealing time, it is emphasized that comparatively high Jr and Hci and （BH）max were obtained in a wide annealing time period of 15 to 360 min. The shape of initial magnetization curves and hysteresis loops change as a function of annealing time, indicating different magnetization reversal routes, which can be fully explained by the corresponding microstructure.

Differential Gene and Protein Expression in Soybean at Early Stages of Incompatible Interaction with Phytophthora sojae

Soybean root and stem rot caused by Phytophthora sojae is a destructive disease worldwide. Using genetic resistance is an important and major component in the integrated pest management of this disease. To understand molecular mechanisms of root and stem rot resistance in soybeans, the gene and protein expression in hypocotyls and stems of variety Suinong 10 carrying resistance genes Rps1a and Rps2 was investigated by using mRNA differential display reverse transcription PCR and two-dimensional electrophoresis at 0, 0.5, 1, 2, and 4 h after inoculation with P. sojae race 1. The results of the comparison of gene and protein expression showed that at least eight differential fragments at the transcriptional level were related to metabolic pathway, phytoalexin, and signal transduction in defense responses. Sequence analyses indicated that these fragments represented cinnamic acid 4-hydroxylase gene, ATP b gene coding ATP synthase b subunit and ubiquitin-conjugating enzyme gene which upregulated at 0.5 h post inoculation, blue copper protein gene and UDP-N-acetyl-a-D-galactosamine gene which upregulated at 2 h post inoculation, TGA-type basic leucine zipper protein TGA1.1 gene, cyclophilin gene, and 14-3-3 protein gene which upregulated at 4 h post inoculation. Three resistance-related proteins, a-subunit and b-subunit of ATP synthase, and cytochrome P450-like protein, were upregulated at 2 h post inoculation. The results suggested that resistance-related multiple proteins and genes were expressed in the recognition between soybean and P. sojae during zoospore germination, penetration and mycelium growth of P. sojae in soybean.

Non-covalent interaction-based molecular electronics with graphene electrodes

Recent years have witnessed the fabrication of various non-covalent interaction-based molecular electronic devices.In the noncovalent interaction-based molecular devices,the strength of the interfacial coupling between molecule and electrode is weakened compared to that of the covalent interaction-based molecular devices,which provides wide applications in fabricating versatile molecular devices.In this review,we start with the methods capable of fabricating graphene-based nanogaps,and the following routes to construct non-covalent interaction-based molecular junctions with graphene electrodes.Then we give an introduction to the reported non-covalent interaction-based molecular devices with graphene electrodes equipped with different electrical functions.Moreover,we summarize the recent progress in the design and fabrication of new-type molecular devices based on graphene and graphene-like two-dimensional(2D)materials.The review ends with a prospect on the challenges and opportunities of non-covalent interaction-based molecular electronics in the near future.

Regulating the melting point by non-covalent interaction toward a promising insensitive melt-castable energetic material:1,2-Difluoro-4,5-dinitrobenzene

Searching for insensitive melt-castable energetic materials is still facing great challenges.In this work,we developed a promising strategy that is regulating the ratio of non-covalent interaction by fluorine atoms to regulate the melting point to develop new melt-castable energetic materials.Using this method,a highly sym-metric 1,2-difluoro-4,5-dinitrobenzene(DFDNB)was synthesized in one step and fully characterized.DFDNB has a desirable melting point(83.2℃),high decomposition temperature(>400℃),acceptable detonation properties(6786 m s^(-1),21.5 GPa)but superior safety performance(>40 J,>360 N),and excellent chemical compatibility with 1,3,5-trinitro-1,3,5-triazine(RDX)that make it a promising insensitive melt-castable energetic material.A detailed study based on crystal stacking,electrostatic potential,and intermolecular weak interactions in DFDNB and its isomers or analogs demonstrates that non-covalent interactions including the C-F…H,N-O…H hydrogen bonding,and C-F…O halogen-like bonding play an important role in regulating the melting point.

服务业进出口、OFDI和全要素生产率的动态关系研究——基于VAR模型的实证分析

研究服务业贸易、投资与服务业之间的影响关系,对提升我国服务行业国际竞争力、促进其高质量发展具有重要意义。论文使用我国2000—2021年数据,构建VAR模型对服务业进出口、服务业对外直接投资(OFDI)和全要素生产率的动态交互关系进行实证分析。研究结果显示,服务业进出口对服务业对外直接投资具有正相关关系,且长期支持效果明显;服务业进出口对OFDI、全要素生产率提升具有促进作用;在短期内,全要素生产率与OFDI之间存在双向促进作用,从长期来看则存在一定负向影响。基于实证研究结论,文中提出制定政策鼓励服务企业参与国际化竞争、发挥服务业进出口对OFDI的促进效应、提升服务企业自主创新能力等相关对策建议。

高效液相色谱-质谱技术在蛋白质组学中的应用

蛋白质组学研究在生物医学领域发挥了重要作用,然而研究面临的主要难点在于其研究对象的复杂性和多样性。随着质谱技术的快速发展,高效液相色谱-质谱(HPLC-MS)分离分析复杂生物样品已经成为蛋白质组学研究的基础工具。蛋白质组学的研究从肽段分离,延伸到蛋白质和蛋白质复合物的分离,随着分析物的分子质量不断增大,其结构和组成复杂性也持续增加,分子特性也发生改变。面对不同的蛋白质组学研究对象,选择不同的分离模式、分离条件以及固定相参数是进行深度蛋白质组学研究的关键。本文综述了实验室常用的液相色谱分离模式,包括反相色谱(RPLC)、亲水相互作用色谱(HILIC)、疏水相互作用色谱(HIC)、离子交换色谱(IEC)和体积排阻色谱(SEC),以及其不同的组合模式与质谱联用在自下而上(bottom-up)分析、自上而下(top-down)分析、蛋白-蛋白相互作用分析中应用的研究。具体分析了色谱流动相与被分析对象之间的兼容性问题、色谱流动相与质谱兼容性问题,以及多维色谱中不同色谱模式之间流动相的兼容性问题。重点关注存在不兼容问题时研究者所提出的解决方案。此外,本文还评述了HPLC-MS结合样本前处理的方法在外泌体和单细胞蛋白质组学中的应用研究。总之,文章聚焦于近年来HPLC-MS技术在蛋白质组学中的研究进展,旨在为未来蛋白质组学领域的研究提供参考。

逆时偏移角道集速度分析方法研究与实现

与其它成像方法相比,逆时偏移能明显提高复杂介质的成像质量,但是它对速度模型的准确性要求也比其它方法高。作为一种重要的叠前偏移输出,共成像点道集除了能为深度偏移处理提供速度信息外,还可提供振幅和相位信息,同时还能为后续的属性解释提供依据。本文推导了角道集速度分析的公式,重点分析了该公式的特征、稳定性和速度敏感性等,为后续速度分析提供理论依据;给出了逆时偏移角道集人机交互速度分析的具体实现流程。模型数据和实际数据测试结果表明,本文给出的逆时偏移角道集人机交互速度分析方法具有实用性,能够得到较好的背景速度模型。

二维液相色谱分离鉴定桑葚中多酚类化合物

目的建立一套亲水作用色谱×反相色谱二维液相色谱系统对桑葚中多酚类化合物进行鉴定。方法首先采用单因素实验对色谱系统中一维色谱的流动相A的组成、二维色谱的色谱运行条件以及两维系统接口处的样品环的体积进行优化,然后利用优化系统对桑葚中多酚类化合物进行分离鉴定。结果当一维色谱流动相A中乙酸浓度为2.0%、二维色谱流动相流速为3.3 mL/min、二维色谱分析时间为1.3 min、接口处的样品环体积为150μL时,桑葚提取物中多酚类化合物分离效果最好;使用优化后的系统对桑葚提取物中多酚类化合物进行分离鉴定,成功分离鉴定了桑葚提取物中5种酚类化合物。结论本研究的优化方法可行,优化后的系统可以高效、准确分离桑葚提取物中多酚类化合物,为分离鉴定桑葚中多酚类化合物提供了一定的实践基础。

Lone pair-π interaction induced regioselective sulfonation of ethers under light irradiation

Non-covalent interactions are of significance in supramolecular chemistry and biochemistry,while synthetic procedures driven by these weak interactions remain challenging and rare.Inspired by the lone pair-π interaction presence in the Z-DNA structure,a light-induced regioselective sulfonation of ethers taking advantage of the lone pair-π interaction between the oxygen of ethers and sulfonyl chlorides has been disclosed.Moreover,this strategy is also applicable to the sulfonation of aniline derivatives.Features of the methods include readily accessible starting materials,high atom-economy,green and photocatalyst-free conditions and broad functional group tolerance.Mechanism studies suggest that the lone pair-πinteraction plays an important role to initiate the transformation.