中性或弱酸性体系下锌基水系电池负极材料研究进展

锌具有原料丰富、质量轻便、金属导电性与延展性好以及理论比容量高等优势,可以作为绿色可充电电池的理想电极材料。其中,以中性或弱酸性水溶液为电解质、锌为负极的锌基水系电池具有安全性高、电池材料廉价无毒、制备工艺简单、环境友好等特点,在储能和动力电池领域具有极高的应用价值和发展前景。但电池充放电过程中伴随的锌枝晶、析氢、腐蚀、钝化等问题限制了其实际应用。本文综述了锌基水系电池负极存在的问题及当前的解决策略,并对其负极研究发展方向进行了展望。     

Self-assembled lamellar nanochannels in polyoxometalate-polymer nanocomposites for proton conduction

The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials,as it can enhance ion conductivity by offering short ion-transport pathways.In this work,we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels,by the electrostatic self-assembly of a polyoxometalate H_3 PW_(12)O_(4 O)(PW) and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone).PW can effectively regulate the self-assembling order of polymer moieties to form a large-ra nge lamellar structure,meanwhile,introducing protons into the nanoscale lamellar domains to build proton transport channels.Moreover,the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites.The lamellar nanocomposite exhibits a conductivity of 4.3 × 10~(-4) S/cm and a storage modulus of 1.1 × 10~7 Pa at room temperature.This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials.     

Booting the electrochemical properties of Fe-based anode by the formation multiphasic nanocomposite for lithium-ion batteries

Fe-based compounds with good environmental friendliness and high reversible capacity have attracted considerable attention as anode for lithium-ion batteries.But,similar to other transition metal oxides(TMOs),it is also affected by large volume changes and inferior kinetics during redox reactions,resulting in the destruction of the crystal structure and poor electrochemical performance.Here,Fe_3O_4/C nanospheres anchored on the two-dimensional graphene oxide as precursors are phosphated and sintered to build the multiphasic nanocomposite.XRD results confirmed the multiphasic nanocomposite composed of Fe_2O_3,Fe_3O_4 and Fe_3PO_7,which will facilitate the Li~+ diffusion.And the carbonaceous matrix will buffer the volume changes and enhance electron conduction.Consequently,the multiphasic Febased anode delivers a large specific capacity of 1086 mAh/g with a high initial Coulombic efficiency of 87% at 0.1 C.It also has excellent cycling stability and rate property,maintaining a capacity retention of～87% after 300 cycles and a high reversible capacity of 632 mAh/g at 10 C.The proposed multiphasic structure offers a new insight into improving the electrochemical properties of TMO-based anodes for advanced alkali-ion batteries.     

肿瘤乏氧靶向响应的罗丹明荧光探针及其成像介导手术治疗

基于罗丹明的良好荧光性能, 经化学偶联反应制备并表征了一个偶氮乏氧特异响应的“Off-On”型荧光成像探针(FY-4). 从分子层面证实了其荧光“Off-On”性能和响应机制; 在L02正常细胞及4T1, HeLa和A549肿瘤细胞层面考察了其对受试细胞株的毒性和不同乏氧时间的荧光成像性能; 再利用4T1肿瘤模型, 分别以肿瘤原位注射和尾静脉注射的方式考察了其荧光成像性能, 并探究了其荧光成像介导切除肿瘤性能, 最后还考察了FY-4的生物安全性. 结果表明, FY-4有高的肿瘤乏氧靶向特异“关-开”响应的荧光成像差异显影及荧光成像介导切除肿瘤的潜能, 结合其良好的光物理性能、 生物安全性和明晰的给药时间等特性, 有望为生物医学荧光成像介导肿瘤切除提供新的研究工具.     

碳掺杂六方氮化硼/二硫化钼吸附还原六价铬和助催化降解有机污染物

针对二硫化钼(MoS₂)因易团聚导致去除六价铬[Cr(Ⅵ)]容量低的问题, 利用六方氮化硼(BN)良好的吸附性和化学稳定性, 以多巴胺作为BN改性剂, 通过煅烧法和水热法制得碳掺杂六方氮化硼(c-BN)负载MoS₂纳米复合材料(c-BN@MoS₂). 研究了室温条件下c-BN@MoS₂对Cr(Ⅵ)的吸附还原和助催化降解有机污染物的性能. 实验结果表明, c-BN@MoS₂在40 min内对50 mg/L的Cr(Ⅵ)吸附还原去除率高达95%以上, 且以将 Cr(Ⅵ)还原至Cr(Ⅲ)为主, 在pH值为2、 温度为25 ℃条件下去除Cr(Ⅵ)最大容量可达401 mg/g, 显著高于 MoS₂(98 mg/g). 分析显示, c-BN不仅提高了MoS₂的平均孔径, 还可促进MoS₂生成金属特性的1T相, 有利于吸附Cr(Ⅵ)和加快氧化还原过程中的电子转移. 在Fe²⁺/PMS(过一硫酸氢盐)催化体系加入c-BN@MoS₂, 该体系对磺胺甲恶唑的降解性能明显增强, 其反应速率常数提高3倍, 这主要归因于c-BN@MoS₂明显加快了Fe³⁺到Fe²⁺的转变, 导致更多?OH产生, 达到增强降解污染物的目标.     

Enantioselective Diels–Alder reactions with left-handed G-quadruplex DNA-based catalysts

Since the discovery of left-handed G-quadruplex(L-G4)structure formed by natural DNA,there has been a growing interest in its potential functions.This study uti...     

基于2，5-双(三氟甲基)对苯二甲酸配体的锌配合物的合成、晶体结构及性质

利用2,5-双（三氟甲基）对苯二甲酸（H₂L）为主配体,氯化锌为金属盐,分别与辅助配体4,4''-联吡啶（4,4''-bipy）和2,2''-联吡啶（2,2''-bipy）通过溶剂热法反应合成了配合物[Zn（L）₂（4,4''-bipy）（H₂O）]_n（1）和[Zn（L）（2,2''-bipy）]_n（2）。通过X射线单晶衍射、红外光谱、元素分析、荧光光谱、热重分析等测试手段对其结构和性质进行了表征与研究。结果表明,配合物1是以Zn²⁺为金属节点,L^2-和4,4''-bipy作为连接体相互连接,形成无限延伸的二维网状结构,层与层之间通过O5-H5B…O1氢键作用有序堆积形成三维结构。配合物2以Zn²⁺为金属节点,配体L^2-上的每个羧基都通过双齿螯合的方式桥联锌离子并无限连接形成三维网状结构。     

Syntheses,crystal structures and magnetic properties of two new cyano-bridged bimetallic complexes

Transition Metal Chemistry - Two complexes [Fe(1,10-phen)2Ni(CN)4]n (1), {[Fe2(1,10-phen)4(CN)4Co2(1,10-phen)2Fe(CN)6]·2H2O}n (2) were prepared in the reaction of K3[Fe(CN)6] as cyanometalate...     

DNAzyme- and light-induced dissipative and gated DNA networks

Nucleic acid-based dissipative, out-of-equilibrium systems are introduced as functional assemblies emulating transient dissipative biological transformations. One system involves a Pb²⁺-ion-dependent DNAzyme fuel strand-driven network leading to the transient cleavage of the fuel strand to “waste” products. Applying the Pb²⁺-ion-dependent DNAzyme to two competitive fuel strand-driven systems yields two parallel operating networks. Blocking the competitively operating networks with selective inhibitors leads, however, to gated transient operation of dictated networks, yielding gated catalytic operations. A second system introduces a “non-waste” generating out-of-equilibrium, dissipative network driven by light. The system consists of a trans-azobenzene-functionalized photoactive module that is reconfigured by light to an intermediary state consisting of cis-azobenzene units that are thermally recovered to the original trans-azobenzene-modified module. The cyclic transient photoinduced operation of the device is demonstrated. The kinetic simulation of the systems allows the prediction of the transient behavior of the networks under different auxiliary conditions.

Functional DNA modules are triggered in the presence of appropriate inhibitors to yield transient gated catalytic functions, and a photoresponsive DNA module leads to “waste-free” operation of transient, dissipative dynamic transitions.     

Preparation and Antibacterial Activity of Thermo-Responsive Nanohydrogels from Qiai Essential Oil and Pluronic F108

Essential oils (EOs) have been used in cosmetics and food due to their antimicrobial and antiviral effects. However, the applications of EOs are compromised because of their poor aqueous solubility and high volatility. Qiai (Artemisia argyi Levl. et Van. var. argyi cv. Qiai) is a traditional Chinese herb and possesses strong antibacterial activity. Herein, we report an innovative formulation of EO as nanohydrogels, which were prepared through co-assembly of Qiai EO (QEO) and Pluronic F108 (PEG-b-PPG-b-PEG, or PF108) in aqueous solution. QEO was efficiently loaded in the PF108 micelles and formed nanohydrogels by heating the QEO/PF108 mixture solution to 37 °C, by the innate thermo-responsive property of PF108. The encapsulation efficiency and loading capacity of QEO reached 80.2% and 6.8%, respectively. QEO nanohydrogels were more stable than the free QEO with respect to volatilization. Sustained QEO release was achieved at body temperature using the QEO nanohydrogels, with the cumulative release rate reaching 95% in 35 h. In vitro antibacterial test indicated that the QEO nanohydrogels showed stronger antimicrobial activity against S. aureus and E. coli than the free QEO due to the enhanced stability and sustained-release characteristics. It has been attested that thermo-responsive QEO nanohydrogels have good potential as antibacterial cosmetics.