A New Tetranuclear Cobalt Cluster with （1H-Benzimidazol-2-yl）-methanol Synthesis and Crystal Structure

A new tetranuclear cluster [Co4(bm)6Cl2]·(H2O)2·(CH3OH)(1, Hbm is(1H-benzimidazol-2-yl)-methanol) has been synthesized by solvothermal method and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. Complex 1 belongs to monoclinic space group P21/n with a = 21.1713(5), b = 12.7948(3), c = 24.0195(9) , β = 95.309(3)°, V = 6478.6(3) 3, Z = 4, F(000) = 2568, Dc = 1.289 g·cm–3, Mr = 1257.63, μ = 9.096 mm–1, S = 1.000, the final R = 0.0861 and wR = 0.2552 for 4956 observed reflections with I 2σ(I). Two connected face-sharing cubes are observed in the framework of 1, each with one vertex missing. Complex 1 forms a 2-D network through N–H···O hydrogen bonds. The apparent holes can be observed.     

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc(II) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(II) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.     

Synthesis of binuclear palladium complexes with a rigid phenylene bridge linker

The complexes [PdX₂Py]₂(di-NHC) (X = Br or Cl) in which di-NHC represents a di-N-heterocyclic carbene, featuring a rigid phenylene spacer between the carbene units, have been prepared from reactions of the corresponding diimidazolium halide salts with PdCl₂ in pyridine. The molecular structures of three of the complexes were determined by X-ray diffraction studies. The influences of different substitutions and of the halide ligand (Br or Cl) on the structure and reactivity of the complexes have been studied. The catalytic activity of the binuclear palladium complexes was tested in the Mizoroki–Heck reaction of styrene with bromobenzene.     

羟甲基化木质素磺酸盐添加剂对钻井液性能的影响

为了进一步优化木质素磺酸盐作为钻井液处理剂的效能,利用其与甲醛的羟甲基化反应制备了羟甲基化木质素磺酸盐;采用红外光谱仪、X射线粉末衍射仪、扫描电镜等分析了其结构;测定了改性前后的木质素磺酸盐对钻井液流变性、降滤失性、黏土水化膨胀抑制性等性能的影响.结果显示,改性后的羟甲基化木质素磺酸盐的整体结构变化不大,但羟基数量增加,与水的相溶性增强.与木质素磺酸盐相比,羟甲基化木质素磺酸盐在室温下对基浆有较强的提黏作用,经180℃高温老化后降黏、降滤失作用有所增强,形成的泥饼厚度降低,对黏土水化膨胀的抑制作用增强.     

共振散射法测定安乃近含量

在pH=5.0的B-R缓冲溶液中,Fe(Ⅲ)与邻菲啰啉反应生成无色配合物,从而使得体系在374nm波长处产生1个较强的共振散射峰。加入安乃近(或4-甲氨基安替比林)后,其将Fe(Ⅲ)还原成Fe(Ⅱ),而生成一种橙红色配合物,使得体系在374nm(或373nm)波长处的共振散射信号减弱。在最佳实验条件下,当安乃近浓度在0.634~15.2μg/mL范围内,体系的共振散射信号△I与安乃近的浓度之间有较好的线性关系,检出限为5.75ng/mL。该方法可直接用于测定安乃近含量,回收率为100.4%~103.4%。     

新型双荧光二氧化硅纳米颗粒的制备

本文采用改良的反相微乳液法制备得到双染料掺杂的二氧化硅荧光纳米颗粒。扫描电镜结果显示,荧光纳米颗粒呈球形,平均粒径约为90nm。利用荧光光谱及共聚焦荧光显微镜对该纳米颗粒的光学性能进行表征,结果发现其可同时发出红、绿双色荧光,这为进一步制备具有更多种荧光信号的硅纳米颗粒提供基础。同时,由于硅纳米颗粒生物相容性好,易功能化的特点,使得该新型硅纳米荧光颗粒在生物标记及生物成像的多组分分析中具有潜在的应用。     

两种异马来二氰基二硫烯镍(II)-取代苄基喹啉鎓盐的制备及其光谱性质和晶体结构

以甲醇为溶剂,将异马来二氰基二硫烯酸钾[K2(i-mnt)]和六水氯化镍分别与溴化4-溴苄基喹啉盐([4-BrBzQl]Br)或溴化4-硝基苄基喹啉盐([4-NO2BzQl]Br)直接反应,得到两种新的离子对配合物[4-BrBzQl]2[Ni(i-mnt)2](1)和[4-NO2BzQl]2[Ni(i-mnt)2](2);测定了其红外光谱和紫外-可见光谱,并利用X射线衍射表征了配合物1的晶体结构.结果表明,配合物[4-BrBzQl]2[Ni(i-mnt)2]为三斜晶系,P-1空间群,其每个不对称单元含半个[Ni(i-mnt)2]2-阴离子和1个[4-BrBzQl]+阳离子,晶体中的阴、阳离子通过静电作用和C-H…S、C-H…N氢键作用形成网络结构.     

DNA Nanoribbon-Templated Self-Assembly of Ultrasmall Fluorescent Copper Nanoclusters with Enhanced Luminescence

Fluorescent copper nanoclusters (CuNCs) have been widely used in chemical sensors, biological imaging, and light-emitting devices. However, individual fluorescent CuNCs have limitations in their capabilities arising from poor photostability and weak emission intensities. As one kind of aggregation-induced emission luminogen (AIEgen), the formation of aggregates with high compactness and good order can efficiently improve the emission intensity, stability, and tunability of CuNCs. Here, DNA nanoribbons, containing multiple specific binding sites, serve as a template for in situ synthesis and assembly of ultrasmall CuNCs (0.6 nm). These CuNC self-assemblies exhibit enhanced luminescence and excellent fluorescence stability because of tight and ordered arrangement through DNA nanoribbons templating. Furthermore, the stable and bright CuNC assemblies are demonstrated in the high-sensitivity detection and intracellular fluorescence imaging of biothiols.     

The Stabilization Effect of CO2 in Lithium–Oxygen/CO2 Batteries

The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O₂), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O₂⁻, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li-air battery. Even worse, the water and/or CO₂ in air bring parasitic reactions and safety issues. Therefore, applying such systems in open-air environment is challenging. Herein, contrary to previous assertions, we have found that CO₂ can improve the stability of both anode and electrolyte, and a high-performance rechargeable Li–O₂/CO₂ battery is developed. The CO₂ not only facilitates the in situ formation of a passivated protective Li₂CO₃ film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O₂⁻. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li₂CO₃. The Li–O₂/CO₂ battery achieves a full discharge capacity of 6628 mAh g⁻¹ and a long life of 715 cycles, which is even better than those of pure Li–O₂ batteries.     

Single-Atom Electrocatalysts from Multivariate Metal–Organic Frameworks for Highly Selective Reduction of CO2 at Low Pressures

Single-atom catalysts (SACs) are of great interest because of their ultrahigh activity and selectivity. However, it is difficult to construct model SACs according to a general synthetic method, and therefore, discerning differences in activity of diverse single-atom catalysts is not straightforward. Herein, a general strategy for synthesis of single-atom metals implanted in N-doped carbon (M₁-N-C; M=Fe, Co, Ni and Cu) has been developed starting from multivariate metal–organic frameworks (MOFs). The M₁-N-C catalysts, featuring identical chemical environments and supports, provided an ideal platform for differentiating the activity of single-atom metal species. When employed in electrocatalytic CO₂ reduction, Ni₁-N-C exhibited a very high CO Faradaic efficiency (FE) up to 96.8 % that far surpassed Fe₁-, Co₁- and Cu₁-N-C. Remarkably, the best-performer, Ni₁-N-C, even demonstrated excellent CO FE at low CO₂ pressures, thereby representing a promising opportunity for the direct use of dilute CO₂ feedstock.