Fabrication and characteristics of self‐aggregation nanoparticles used for conformance control treatment

In order to alleviate the contradiction between injectability of the profile control agent and its profile control performance, a novel core‐shell heterogeneous structure colloidal particles (CSA) were synthesized, and the mechanism of self‐aggregation plugging was proposed. Cross‐linking inside the nanoparticles and chain‐growth polymerization via capturing acrylamide in the aqueous phase result in the formation of core‐shell heterogeneous structures as proved by TEM observation and XPS analysis. Moreover, CSA nanoparticles exhibit good hydrophilic properties, outstanding thermal stability and limited expansion capacity. Effects of different metal cations and surface group on the self‐aggregation time of CSA nanoparticles were systematically studied. Results showed that divalent cations contributed to more significant aggregation of CSA nanoparticles in comparison to monovalent cations. The increasing cations concentration and valency decreased the thickness of electric double layer, which lead to a decrease in the zeta potential. Core flooding test shows that the injection of nanoparticles which diameter is much smaller that of pore‐throats into the target reservoir can not only successfully enter the depth of porous media, but also effectively block the high permeability areas by the formation of self‐aggregation particle clusters. This study provides a new method for the equilibrium between nanoparticles injectivity and in‐depth profile control of nanoparticles.     

基于配位键和次级作用力协同效应构建的两个Co (Ⅱ)/Cd (Ⅱ)配位超分子网络的结构及荧光性质

以3-羧基-1-（4-羧基苄基）吡啶溴酸盐（（H₂L） Br）分别与Co （Ⅱ）和Cd （Ⅱ）金属盐反应,制备了2个配合物[Co （L）₂（H₂O）₄]·2H₂O （1）和[Cd （L）2（H₂O）]·3H₂O （2）。晶体结构分析揭示配合物1是一个中性的单核配合物,其拥有丰富的并可作为超分子合成子的氢键和π-π作用力组分。对于1,单核的[Co （L）₂（H₂O）₄]实体首先通过氢键形成具有孔道结构的二维层,该二维层进一步通过π-π堆积作用形成三维的多孔配位超分子。配合物2具有一维的“之”字形链状结构,该链通过悬挂的L配体之间的π-π作用力形成一维梯形结构。该一维梯形链进一步通过梯形边之间存在的2种π-π堆积作用形成波浪状的二维层。二维层进一步通过8种类型的O—H…O氢键连接形成三维的超分子结构。根据拓扑的观点,配合物2中的一维链采取胶合板排列。此外,配合物2显示了强的紫外荧光发射,平均寿命为2.54 ns。     

柔性双咪唑配体导向的Co(Ⅱ)⁃戊二酸金属有机骨架材料的合成、结构和性能

在水热条件下合成并表征了2例基于柔性配体构筑的Co(Ⅱ)-MOFs:{[Co(glu)(bimb)]·4H2O}n (1),[Co(glu)(bix)0.5]n (2)(H2glu=戊二酸;bimb=1,4-双(咪唑-1-基)-丁烷;bix=1,4-双(咪唑-1-基-亚甲基)-苯)。配合物1显示非穿插的(4,4)-菱形网格,通过层间氢键和π…π作用拓展为三维超分子结构。加热失水后1的结构不可逆地降解。配合物2呈现典型的柱-层状三维结构,其拓扑符号为41263,中心Co(Ⅱ)离子采用四方锥构型。此外,性质研究表明:配合物1在水溶液中对染料甲基橙具有显著的吸附活性,配合物2表现出弱的反铁磁行为。     

CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest

In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO₂ responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO₂,1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO₂ and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.     

碳点的性质及其在生物传感器领域的应用

碳点(carbon dots,CDs)作为一种具有优良生物相容性、低毒性和表面功能可调的新型碳基纳米材料,在生物传感领域具有极大的应用潜力.本文对碳点的生物效应、发光性质及其发光机理进行了简述,并根据传感机制的不同,将CDs在生物传感领域的应用分为荧光(fluorescence,FL)传感器、电致发光(electrochemiluminescence,ECL)传感器以及化学发光(chemiluminescence,CL)传感器三类进行综述.最后分析了CDs目前在生物传感器领域应用中存在的问题,并对其发展进行了展望.     

手性配体在钯催化不对称碳氢键活化反应中的应用

目前,手性配体辅助钯催化的区域和对映选择性碳氢键活化是过渡金属催化的前沿领域.在过去的十年中,它作为一种越来越重要的合成工具,用于合成含有各种不对称元素(中心手性、轴手性和平面手性)的手性分子,也是快速构建各种碳碳键和碳杂原子键的最有效方法之一.本文介绍了一些典型手性配体在钯催化不对称sp²和sp³碳氢键活化/官能团化反应中的应用,如单齿配体亚磷酰胺、手性磷酸(CPAs)和双功能氮端单保护的氨基酸(MPAAs)配体;探讨了这些手性配体辅助催化反应的创新性和特点,在理清这一研究领域发展脉络的同时,展望了未来研究工作的方向.此外,本文还介绍了这一不对称合成策略在天然产物、药物分子全合成中的应用.     

A Novel Fluorescence Probe for the Reversible Detection of Bisulfite and Hydrogen Peroxide Pair in Vitro and in Vivo

The detection of changes in the reactive oxygen species (ROS)/reactive sulfur species (RSS) couple is important for studying the cellular redox state. Herein, we developed a 1,8-naphthalimide-based fluorescence probe ( NI ) for the reversible detection of bisulfite (HSO₃⁻) and hydrogen peroxide (H₂O₂) in vitro and in vivo. NI has been designed with a reactive ethylene unit which specifically reacts with HSO₃⁻ by a Michael addition reaction mechanism, resulting in the quenching of yellow fluorescence at 580 nm and the appearing of green fluorescence at 510 nm upon excitation at 500 nm and 430 nm, respectively. The addition product ( NI−HSO₃ ) could be specifically oxidized to form the original C=C bond of NI , recovering the fluorescence emission and color. The detection limits of NI for HSO₃⁻ and NI−HSO₃ for H₂O₂ were calculated to be 2.05 μM and 4.23 μM, respectively. The reversible fluorescence response of NI towards HSO₃⁻/H₂O₂ couple can be repeated for at least five times. NI is reliable at a broad pH range (pH 3.0–11.5) and features outstanding selectivity, which enabled its practical applications in biological and food samples. Monitoring the reversible and dynamic inter-conversion between HSO₃⁻ and H₂O₂ in vitro and in vivo has been verified by fluorescence imaging in live HeLa cells, adult zebrafish and nude mice. Moreover, NI has been successfully applied to detect of HSO₃⁻ levels in food samples.     

BODIPY-based Fluorescent Probe for Fast Detection of Hydrogen Sulfide and Lysosome-targeting Applications in Living Cells

Hydrogen sulfide (H₂S) is recognized as an endogenous gaseous signaling agent in many biological activities. Lysosomes are the main metabolic site and play a pivotal role in cells. Herein, we designed and synthesized two new fluorescent probes BDP-DNBS and BDP-DNP with a BODIPY core to distinguish H₂S. The sensing mechanism is based on the inhibition-recovery of the photo-induced electron transfer (PET) process. Through comparing the responsive behaviors of the two probes toward H₂S, BDP-DNBS showed a fast response time (60 s), low limit of detection (LOD, 51 nM), high sensitivity and selectivity. Moreover, the reaction mechanism was demonstrated by mass spectrometry and fluorescence off-on mechanism was proved by density functional theory (DFT). Significantly, confocal fluorescence imaging indicated that BDP-DNBS was successfully used to visualize H₂S in lysosomes in living HeLa cells.     

Polymer Electrolytes – New Opportunities for the Development of Multivalent Ion Batteries

Batteries, as highly concerned energy conversion system, have a great development prospect in various fields, especially in the field of energy powered vehicles. Multivalent ion batteries are getting more attention due to their low cost, high abundance in earth crust, high capacity and safety compared with Lithium batteries. Despite above advantages, several problems still need to be solved before multivalent ion batteries achieve large-scale application, such as interfacial parasitic reaction, anode passivation, and dendrites. The replacement of liquid electrolytes with gel polymer electrolytes (GPEs) which pose high safety, high mechanical strength and simplified battery system, is an effective strategy to inhibit dendrite growth and improve electrochemical performance. This review mainly discusses the advantages and challenges of multivalent ion batteries including zinc, magnesium, calcium and aluminum batteries. Meanwhile, the major targets of this review are introducing the recent developments and making a summary of the future trends of GPEs in the multivalent ion batteries.     

高频燃烧红外吸收法测定铅精矿中的硫

利用高频燃烧红外吸收碳硫仪测定铅精矿中的硫含量。低硫含量(S<5%)铅精矿样品直接称样测定;高硫含量(S>5%)铅精矿样品添加稀释剂后称样测定。对样品称样量、助熔剂类型及用量等条件进行了研究,获得最佳分析条件。通过空白实验测得方法检出限为0.0010%,利用铅精矿有证标准物质进行精密度和准确度验证,方法的标准偏差在0.295%~1.3%之间,结果表明该方法精密度高、准确度好,能够满足铅精矿中硫含量的快速准确测定。