Effect of lattice distortion on spin admixture and quantum transport in organic devices with spin–orbit coupling

With an extended Su–Schrieffer–Heeger model and Green's function method, the spin–orbit coupling(SOC) effects on spin admixture of electronic states and quantum transport in organic devices are investigated. The role of lattice distortion induced by the strong electron–lattice interaction in organics is clarified in contrast with a uniform chain. The results demonstrate an enhanced SOC effect on the spin admixture of frontier eigenstates by the lattice distortion at a larger SOC,which is explained by the perturbation theory. The quantum transport under the SOC is calculated for both nonmagnetic and ferromagnetic electrodes. A more notable SOC effect on total transmission and current is observed for ferromagnetic electrodes, where spin filtering induced by spin-flipped transmission and suppression of magnetoresistance are obtained.Unlike the spin admixture, a stronger SOC effect on transmission exists for the uniform chain rather than the organic lattices with distortion. The reason is attributed to the modified spin-polarized conducting states in the electrodes by lattice configuration, and hence the spin-flip transmission, instead of the spin admixture of eigenstates. This work is helpful to understand the SOC effect in organic spin valves in the presence of lattice distortion.

In-situ coupling construction of interface bridge to enhance electrochemical stability of all solid-state lithium metal batteries

Polymer-based composite electrolytes composed of three-dimensional Li_(6.4)La_(3)Zr_(2)Al_(0.2)O_(12)(3D-LLZAO)have attracted increasing attention due to their continuous ion conduction and satisfactory mechanical properties.However,the organic/inorganic interface is incompatible,resulting in slow lithium-ion transport at the interface.Therefore,the compatibility of organic/inorganic interface is an urgent problem to be solved.Inspired by the concept of“gecko eaves”,polymer-based composite solid electrolytes with dense interface structures were designed.The bridging of organic/inorganic interfaces was established by introducing silane coupling agent(3-chloropropyl)trimethoxysilane(CTMS)into the PEO-3D-LLZAO(PL)electrolyte.The in-situ coupling reaction improves the interface affinity,strengthens the organic/inorganic interaction,reduces the interface resistance,and thus achieves an efficient interface ion transport network.The prepared PEO-3D-LLZAO-CTMS(PLC)electrolyte exhibits enhanced ionic conductivity of 6.04×10^(-4)S cm^(-1)and high ion migration number(0.61)at 60℃and broadens the electrochemical window(5.1 V).At the same time,the PLC electrolyte has good thermal stability and high mechanical properties.Moreover,the Li Fe PO_(4)|PLC|Li battery has excellent rate performance and cycling stability with a capacity decay rate of 2.2%after 100 cycles at 60℃and 0.1 C.These advantages of PLC membranes indicate that this design approach is indeed practical,and the in-situ coupling method provides a new approach to address interface compatibility issues.

Impact of transparent exopolymer particles on the dynamics of dissolved organic carbon in the Amundsen Sea,Antarctica

The Southern Ocean is an important carbon sink pool and plays a critical role in the global carbon cycling.The Amundsen Sea was reported to be highly productive in inshore area in the Southern Ocean.In order to investigate the influence of transparent exopolymer particles(TEP)on the behavior of dissolved organic carbon(DOC)in this region,a comprehensive study was conducted,encompassing both open water areas and highly productive polynyas.It was found that microbial heterotrophic metabolism is the primary process responsible for the production of humic-like fluorescent components in the open ocean.The relationship between apparent oxygen utilization and the two humic-like components can be accurately described by a power-law function,with a conversion rate consistent with that observed globally.The presence of TEP was found to have little impact on this process.Additionally,the study revealed the accumulation of DOC at the sea surface in the Amundsen Sea Polynya,suggesting that TEP may play a critical role in this phenomenon.These findings contribute to a deeper understanding of the dynamics and surface accumulation of DOC in the Amundsen Sea Polynya,and provide valuable insights into the carbon cycle in this region.

A Pd-metalated porous organic polymer as a highly efficient heterogeneous catalyst for C–C couplings

An efficient catalyst system based on a Pd-metalated porous organic polymer bearing phenanthroline ligands was designed and synthesized.This catalyst was applied to various C–C bond-forming reactions,including the Suzuki,Heck and Sonogashira couplings,and afforded the corresponding products while exhibiting excellent activities and selectivities.More importantly,this catalyst can be readily recycled.These features show that such catalysts have significant potential applications in the future.

Coupling effect of evaporation and condensation processes of organic Rankine cycle for geothermal power generation improvement

Organic Rankine cycle(ORC)is widely used for the low grade geothermal power generation.However,a large amount of irreversible loss results in poor technical and economic performance due to its poor matching between the heat source/sink and the working medium in the condenser and the evaporator.The condensing temperature,cooling water temperature difference and pinch point temperature difference are often fixed according to engineering experience.In order to optimize the ORC system comprehensively,the coupling effect of evaporation and condensation process was proposed in this paper.Based on the laws of thermodynamics,the energy analysis,exergy analysis and entropy analysis were adopted to investigate the ORC performance including net output power,thermal efficiency,exergy efficiency,thermal conductivity,irreversible loss,etc.,using geothermal water at a temperature of 120℃as the heat source and isobutane as the working fluid.The results show that there exists a pair of optimal evaporating temperature and condensing temperatures to maximize the system performance.The net power output and the system comprehensive performance achieve their highest values at the same evaporating temperature,but the system comprehensive performance corresponds to a lower condensing temperature than the net power output.

Surface organic modification of Fe_3O_4 nanoparticles by silane-coupling agents

Fe3O4 nanoparticles were prepared by chemistry co-precipitation and the mean crystal size was 17.9 nm measured by XRD. After it had been treated by silane-coupling agents KH570, magnetic micro-spheres dispersed in organic medium glycol were gained and the mean size of Fe3O4 nanopowders was 33.7 nm. So it can be concluded that magnetic micro-sphere is made of a few Fe3O4 crystals. Many factors of modification were researched, such as the time of ball milling, the content of Fe3O4 and the content of KH570. The modification of Fe3O4 is relative to the time of ball milling, but the dominant function is affected by the content of Fe3O4 and KH570. When the content of Fe3O4 is known, there is a suitable content of KH570. Different content of Fe3O4 will make the different suitable content of KH570, but the range of latter is less than former, which is relative to the distribution of KH570 on Fe3O4 surface or in the solution.

Effect of interfacial coupling on rectification in organic spin rectifiers

The effect of interfacial coupling on rectification in an organic co-oligomer spin diode is investigated theoretically by considering spin-independent and spin-resolved couplings respectively. In the case of spin-independent coupling, an optimal interfacial coupling strength with a significant enhanced rectification ratio is found, whose value depends on the structural asymmetry of the molecule. In the case of spin-resolved coupling, we found that only the variation of the interfacial coupling with specific spin is effective to modulate the rectification, which is due to the spin-filtering property of the central asymmetric magnetic molecule. A transition of the spin-current rectification between parallel spin-current rectification and antiparallel spin-current rectification may be observed with the variation of the spin-resolved interfacial coupling. The interfacial effect on rectification is further analyzed from the spin-dependent transmission spectrum at different biases.

The effect of spin-orbit coupling on magnetoresistance in nonmagnetic organic semiconductors

We investigated the effect of spin-orbit coupling on magnetoresistance in nonmagnetic organic semiconductors.A Lorentz-type magnetoresistance is obtained from spin-orbit coupling-dependent spin precession under the condition of a space-charge-limited current.The magnetoresistance depends on the initial spin orientation of the electron with respect to the hole in electron-hole pairs,and the increasing spin-orbit coupling slows down the change in magnetoresistance with magnetic field.The field dependence,the sign and the saturation value of the magnetoresistance are composite effects of recombination and dissociation rate constants of singlet and triplet electron-hole pairs.The simulated magnetoresistance shows good consistency with the experimental results.

Organic Polyvalent Iodinc Reagents-Promoted Coupling Reaction of 1-Alkynes

Teminal alkynes couple smoothly in the presence of PhI(OAc)2 or PhI(OH)OTs.catalytie Cul and base. affording conjugated diynes.

COUPLING MODEL OF EXTENDED MANUFACTURING ORGANIZATION AND ITS APPLICATION

For the feature of complex weapon manufacturing on internet,a coupling model is proposed.By using the model,the correlation between manufacturing cells in an extended manufacturing organization can be evaluated quantitatively,so an appropriate control plan is determined.A strategy to improve and reduce the coupling relationship of the organization is studied.A correlation matrix of extended tasks is built to analyze the relationship between sub-tasks and manufacturing resources.An optimization method for manufacturing resource configuration is presented based on the coupling model.Finally,a software system for analyzing coupling model about manufacturing organization on internet is developed,and the result shows that the coupling model is effective.

Ultrathin organic polymer with p-πconjugated structure for simultaneous photocatalytic disulfide bond generation and CO_(2)reduction

Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.

Application study of coupled model between reservoir organic pollutant BOD5-DO and temperature

The BOD5-DO (Biochemical Oxygen Demand in five days and Dissolved Oxygen) are important indexes that reflect the organic pollution extent of water,but the variation of the indexes is closely related with water temperature. The study on the coupled mathematical model reflecting the BOD5-DO with temperature is the key to reveal the mechanism of the migration and distribution of BOD5-DO in the water. The authors presented 1-D mathematical model for the three variables in vertical direction,and gave accurate solution for the equations under steady state,the relation among the variables and the method for solving BOD5-DO concentrations at different depth and temperature.

Simulating the Impacts of Marine Organic Emissions on Global Atmospheric Chemistry and Aerosols Using an Online-Coupled Meteorology and Chemistry Model

To realistically simulate the impacts of marine isoprene and primary organic aerosols (POA) on atmospheric chemistry, a unified model framework with online emissions, comprehensive treatment of gas-phase chemistry, and advanced aerosol microphysics is required. In this work, the global-through-urban WRF/Chem model (GU-WRF/Chem) implemented with the online emissions of marine isoprene and size-resolved marine POA is applied to examine such impacts. The net effect of these emissions was increased surface concentrations of isoprene and organic aerosols and decreased surfaced concentrations of hydroxyl radical and ozone over most marine regions. With the inclusion of these emissions, GU-WRF/Chem better predicted the surface concentrations of isoprene and organic aerosols and the aerosol number size distribution when compared to measurements in clean marine conditions.

Astrocyte-Synapse Receptor Coupling in Tripartite Synapses: A Mechanism for Self-Observing Robots

A model of an intentional self-observing system is proposed based on the structure and functions of astrocyte-synapse interactions in tripartite synapses. Astrocyte-synapse interactions are cyclically organized and operate via feedforward and feedback mechanisms, formally described by proemial counting. Synaptic, extrasynaptic and astrocyte receptors are interpreted as places with the same or different quality of information processing described by the combinatorics of tritograms. It is hypothesized that receptors on the astrocytic membrane may embody intentional programs that select corresponding synaptic and extrasynaptic receptors for the formation of receptor-receptor complexes. Basically, the act of self-observation is generated if the actual environmental information is appropriate to the intended observation processed by receptor-receptor complexes. This mechanism is implemented for a robot brain enabling the robot to experience environmental information as “its own”. It is suggested that this mechanism enables the robot to generate matches and mismatches between intended observations and the observations in the environment, based on the cyclic organization of the mechanism. In exploring an unknown environment the robot may stepwise construct an observation space, stored in memory, commanded and controlled by the intentional self-observing system. Finally, the role of self-observation in machine consciousness is shortly discussed.

Factors controlling deep-profile soil organic carbon and water storage following Robinia pseudoacacia afforestation of the Loess Plateau in China

Background:Afforestation is a common and effective approach used for the restoration of degraded ecosystems worldwide.In China,Robinia pseudoacacia(RP)is among the main non-native tree species and has been widely planted in revegetation of the Loess Plateau.However,owing to uncertainties regarding soil water consumption and carbon sequestration,it is necessary to assess the suitability and sustainability of R.pseudoacacia in restoration.In this study,we aimed to analyse the dynamic effects of R.pseudoacacia forest on soil carbon storage(SCS)and soil water storage(SWS).Specifically,we investigated the association between soil water content(SWC)and soil organic carbon(SOC)and underlying factors in the 0-500-cm profile of a 10-to 50-year-old chronosequence.Results:The results obtained indicated that the dynamics of SWS and SCS on this time scale could be divided into an initial reduction phase(the initial 20 years after afforestation)and subsequent recovery(20-50 years after afforestation).Compared with in the abandoned land(AL),the net accumulation of SCS in R.pseudoacacia forest was 2.51 Mg·ha^(-1)at 50 years after afforestation,whereas there was a 398.76-mm deficit in SWS.Additionally,the natural succession of R.pseudoacacia forest has contributed to the continuous change in stand structure(e.g.vegetation cover(VC),understory vegetation coverage(UVC),and litter biomass(LB)).Conclusions:These findings indicate that vegetation restoration increases carbon sequestration while causing soil water deficit.Furthermore,stand density(SD)was established to make a predominant contribution to the dynamics of SWS and SCS via its effects in altering vegetation,soil,and litter characteristics.Therefore,high-density plantation forests in the Loess Plateau area should be appropriately thinned to reduce the density of forest stands on the basis of soil erosion control and wind and sand fixation,so as to increase carbon sink with lower water consumption,thus realizing the synergistic development of soil carbon sequestration and water connotation.

微波消解-电感耦合等离子体质谱法同时测定有机肥料中9种有毒有害元素的含量

提出了微波消解-电感耦合等离子体质谱法(ICP-MS)同时测定有机肥料中As、Cd、Co、Cr、Ni、Pb、Sb、Tl、V等9种有毒有害元素含量的方法。取0.10 g有机肥料样品于聚四氟乙烯微波消解罐中,以2.5 mL盐酸、7.5 mL硝酸和2.0 mL氢氟酸为混合酸进行微波消解。消解结束后,于140℃赶酸,然后加入1.0 mL 50%(体积分数)硝酸溶液,再用水定容至50 mL,摇匀,过滤,取滤液待测,在线加入混合内标溶液。结果表明:9种元素标准曲线的线性范围均为2~100μg·L^(-1),方法检出限(3s)为0.59~66.75μg·kg^(-1);按照标准加入法对典型有机肥料样品进行回收试验,9种元素测定值的相对标准偏差(n=7)为2.0%~3.5%,回收率为81.5%~112%。

胺功能化的铜催化剂:氢键介导的电化学CO_(2)还原为C_(2)产物以及优越的可充电Zn-CO_(2)电池性能

有机分子功能化是一种有前景的策略,用于调控电化学CO_(2)还原反应(eCO_(2)RR)的C_(2+)产物选择性和活性。然而,我们对于电化学CO_(2)还原调控机制的分子水平理解仍然不够清晰。在本文中,我们成功制备了铜纳米颗粒,并使用一系列胺类衍生物(如十六胺(HAD)、N-甲基十六胺(N-MHDA)、十六烷基二甲胺(HDDMA)和十六酰胺(PMM))对其进行功能化,以系统地研究胺表面活性剂分子结构对eCO_(2)RR选择性和活性的影响。结果表明,HDA的功能化可以将C_(2)产物和C_(2)H_(4)的法拉第效率(FE)提高至73.5%和46.4%,并且在−0.9 V vs.RHE(可逆氢电极)电位下,C_(2)产物的分电流密度为131.4 mA·cm^(−2)。理论研究发现,HDA通过与CO_(2)和eCO_(2)RR中间体之间的氢键相互作用,富集了^(*)CO_(2)、^(*)CO和其他反应中间体,降低了CO―CHO耦合反应的动力学能垒,从而促进了eCO_(2)RR向C_(2)产物的转化。当胺基的H原子被甲基取代后,氢键相互作用减弱,竞争的析氢反应加剧。PMM通过Cu―O键与Cu表面发生键合,而不是通过Cu―N键,导致Cu-PMM更倾向于产乙醇。原位拉曼光谱显示,在Cu-HDA表面,CO主要吸附在Cu的顶位吸附位点上,与在Cu表面上的桥式吸附不同,这可能是因为前者表面对CO的富集引发了CO的吸附构型变化。HDA功能化还提高了Cu催化剂的表面pH。基于Cu-HDA组装的可充电Zn-CO_(2)电池在放电电流密度为16 mA∙cm^(−2)时,最大功率密度为6.48 mW∙cm^(−2),并具有长达60 h的良好充放电稳定性。本研究的重点在于通过在分子水平上调节Cu基材料的CO_(2)RR活性和选择性,促进CO_(2)-C_(2)的转化,这可能为提高C_(2)产物的产率提供新的见解。

铜纳米粒子在有机合成中的应用

随着纳米技术的飞速发展,铜纳米粒子因其独特的物理化学性质,如高活性、大比表面积和良好的选择性,在有机合成中展现了广泛的应用前景。讨论了新型铜纳米材料在各种类型有机反应中的应用,包括多组分“一锅法”反应合成药物活性分子、炔-叠氮化合物环加成反应合成三唑和四唑衍生物、醇的选择性氧化反应、硝基的还原反应、C—X(C,N,O)偶联反应(其中C—C偶联包括Mizoroki-Heck、Suzuki-Miyaura、Glaser-Hay等偶联反应;C—N及C—O偶联包括Chan-Lam、Buchwald-Hartwig、Ullmann、Goldberg等偶联反应)。大多数铜纳米粒子催化反应具有反应操作简单、反应条件温和、催化效率高、官能团耐受性好、成本低、反应体系干净且铜催化剂可重复使用等优点。铜纳米粒子在有机合成中的应用将对有机合成方法学产生重要影响,并促进有机铜化学的进一步发展。

电解水制氢耦合有机物氧化研究进展

利用可再生能源(太阳能、风能)驱动的电解水制氢技术是获取“绿氢”的必经之路,是实现碳中和的重要战略措施。然而,目前电解水制氢技术仍面临电解效率低和能耗高等问题。其原因之一在于阳极析氧反应(OER)动力学过程缓慢,制约了阴极产氢,并且阳极产物氧气的附加值较低。利用电解水过程中阳极产生的“活性氧”物种催化有机物选择性氧化(替代OER),被证明是能够降低电解水反应电压、提高产氢效率的有效策略,并且利用阳极得到高附加值化学品可以进一步分摊并降低制氢成本,最近受到科研界和产业界的广泛关注。基于此,总结了近年来电解水制氢耦合有机物氧化方面的研究进展,包括:阳极表面水活化产生活性氧的种类及其催化有机氧化反应机理、反应物吸附过程强化提升反应速率相关策略、电解水制氢耦合氧化反应器设计和产物分离等技术。最后,对该领域的未来发展前景和面临的挑战进行了总结和展望。

塔里木盆地西北缘埃迪卡拉纪—寒武纪转折期黑色岩系中硅质岩成因及其环境指示意义

埃迪卡拉纪—寒武纪转折期是地质历史上的关键期,全球范围内普遍发育一套黑色岩系,包括硅质岩、泥岩和白云岩。在这套黑色岩系中下部,发育了不同厚度的硅质岩,尤其是在塔里木盆地西北缘,黑白燧石条带韵律性互层且硅质岩分布变化大,其成因对寒武系玉尔吐斯组优质烃源岩形成环境具有重要指示意义。本文以塔西北地区新柯地1井这套黑色岩系中硅质岩为研究对象,运用岩芯观察、镜下薄片鉴定、主微量元素和稀土元素分析,研究硅质岩与有机质的成因及其二者之间的共生机理,硅质岩较高的Ti、V、Y、Ba等元素含量、较低的δ^(30)Si值(1.2‰~0.7‰)、明显的Ce负异常说明其硅质流体为热液来源,但是硅质岩不是热液脉体侵入形成,而是富含硅质的流体与冰冷的海水混合沉积而成,硅质岩沉积受温度、pH值、有机质等因素共同控制,有机质的存在可以促进硅质沉淀。同时系统地研究了黑白燧石条带韵律性互层的成因,白色层由纯的微晶石英组成,而黑色层由碎屑碳质颗粒、石英颗粒和碳质纹层组成,认为是微生物席活动的结果,硅质岩中黑白燧石层受冰期和间冰期控制。硅质岩中较高的Al_(2)O_(3)/(Al_(2)O_(3)+Fe_(2)O_(3))比值和较低的Lan/Cen比值代表受陆源影响的大陆边缘沉积环境,结合古气候、海平面变化等信息,认为塔西北地区寒武系玉尔吐斯组硅质岩以及硅质页岩沉积于局限海湾或潟湖环境,为正确认识硅质页岩的形成环境和烃源岩的评价预测提供理论指导。