Novel Branched Template for the Use in Construction of [CuNCS]<Subscript>n</Subscript> Polypseudorotaxane: Synthesis,Structures, and Photocatalytic Properties

Three novel extended supramolecular structures based on pseudohalides (SCN) and the flexible cationic template 1, n-bis(4-aminopyridine)alkane cations(n?=?2–4), namely {(bape)_0.5[Cu(SCN)₂]}_n (bape?=?1, 2-bis(4-aminopyridine)ethane) (1), {(bapp) [Cu₂(SCN)₄]}_n (bapp?=?1, 3-bis(4-aminopyridine)propane) (2),{(bapb)_0.5[Cu(SCN)₂]}_n (bapb?=?1, 4-bis(4-aminopyridine)butane) (3) have been synthesized and characterized by IR spectroscopy, thermal gravimetric analysis, X-ray Powder Diffraction (PXRD), UV–Visdiffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compounds 1 and 3 exhibit infinite two-dimensional polypseudorotaxane architecture. In compound 2, the cationic template bapp²⁺ induced [Cu₂(SCN)₄]^2? cluster unit to generate a 3D coordination framework. The structural diversities show that the branched cationic template should very likely be excellent candidates to construct higher dimensional threading supramolecular architectures. In addition, the optical band gap, photocatalytic and the structure–property relationship of compounds 1–3 were also investigated.     

Preparation of 4-sulfonylcalix[6]arene modified Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> as adsorbent for adsorption of U(VI) from aqueous solution

The 4-sulfonylcalix[6]arene modified Fe₃O₄ (MFS) was characterized by FT-IR, SEM, VSM, TGA, etc., which showed that its saturation magnetization was 64.99 emu g^?1 with the particle size 10–40 nm. The maximum adsorption efficiency by MFS for 2.5 mg L^?1 U(VI) solution amounted to 94.39%, which was higher than that by Fe₃O₄ (65.22%) under its optimum adsorption conditions. The adsorption of MFS and Fe₃O₄ were both followed the pseudo-second order model and the Langmuir isotherm model. The Gibbs free energy change and enthalpy change revealed that the adsorption of U(VI) by MFS was a spontaneous and endothermic process.     

Pollution characteristics and risk assessment of uranium and heavy metals of agricultural soil around the uranium tailing reservoir in Southern China

For the first time the pollution of the paddy soil within 2 km around the uranium tailing reservoir was investigated. The concentrations of U, Cd, Cr, Pb, Cu, Zn, Hg and As were determined by ICP-MS. The study showed that there was severe pollution in the first area (within 0–1 km of the tailing reservoir), which was caused by Cd, As, U and Hg. The pollution level of the second area (within 1–2 km) was relatively low. Hg and As were the main pollutants. In the first area, the contamination degree and risk of elements were positively correlated with the distance from the tailing reservoir. The second area was less polluted and influenced by mining and human activities because of mountain barriers.     

{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms

A protein‐sized (ca. 4.2×4.2×3.6 nm³) non‐biologically derived molecule {Nb₂₈₈O₇₆₈(OH)₄₈(CO₃)₁₂} ( Nb₂₈₈ ) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb₂₈₈ is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb₂₈₈ can be described as a giant windmill‐like cluster aggregate of six nanoscale high‐nuclearity PONb units {Nb₄₇O₁₂₈(OH)₆(CO₃)₂} ( Nb₄₇ ) joined together by six additional Nb ions. Interestingly, the 47‐nuclearity Nb₄₇ units generated in situ can be isolated and bridged by copper complexes to form an inorganic–organic hybrid three‐dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb₄₇ cluster also provides a new type of topology to very limited family of Nb‐O clusters.     

Ambient Electrosynthesis of Ammonia: Electrode Porosity and Composition Engineering

Ammonia, a key precursor for fertilizer production, convenient hydrogen carrier, and emerging clean fuel, plays a pivotal role in sustaining life on Earth. Currently, the main route for NH₃ synthesis is by the heterogeneous catalytic Haber–Bosch process (N₂+3 H₂→2 NH₃), which proceeds under extreme conditions of temperature and pressure with a very large carbon footprint. Herein we report that a pristine nitrogen‐doped nanoporous graphitic carbon membrane (NCM) can electrochemically convert N₂ into NH₃ in an acidic aqueous solution under ambient conditions. The Faradaic efficiency and rate of production of NH₃ on the NCM electrode reach 5.2 % and 0.08 g m^?2 h^?1, respectively. Functionalization of the NCM with Au nanoparticles dramatically enhances these performance metrics to 22 % and 0.36 g m^?2 h^?1, respectively. As this system offers the potential to be scaled to industrial levels it is highly likely that it might displace the century‐old Haber–Bosch process.     

One-step synthesis of Fe-Ni hydroxide nanosheets derived from bimetallic foam for efficient electrocatalytic oxygen evolution and overall water splitting

For the first time, the Fe-Ni LDH nanosheets were prepared through simple one-step hydrothermal treatment of Fe-Ni bimetallic foam both as the substrate and Fe/Ni sources. The ratio of Ni/Fe elements played the important role in realizing the optimal catalytic activities for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). An alkaline water electrolyzer was constructed with the Fe-Ni hydroxide nanosheets/Fe-Ni alloy foam-60% Fe as anode and Ni(OH)₂/Fe-Ni alloy foam-25% Fe as cathode, which displays superior electrolytic performance (affording 10 mA/cm² at 1.62 V) and lasting durability.     

P2-type Na0.6[Mg(II)0.3Mn(IV)0.7]O2 as a new model material for anionic redox reaction

In this work, P2-Na_0.6[Mg(II)_0.3Mn(IV)_0.7] O₂ with inoxidizable elements (Na⁺, Mg²⁺ and Mn⁴⁺) except O^2- was synthesized and investigated, which exhibited high reversible capacity (~210 mAh/g) with highly reversible ARR characteristic.     

Voltammetric determination of DNA based on regulation of DNA strand displacement using an allosteric DNA toehold

An electrochemical biosensor for determination of DNA is described that is based on the reaction of regulated DNA (reg-DNA) first with substrated DNA (subs-DNA) to form a reaction intermediate. The intermediate binds target DNA (T) by hybridization and initiates a branch migration leading to the production of complex of substrated DNA and target DNA (TC). Once TC is produced, it reacts with assisted DNA (ass-DNA) through a toehold exchange mechanism, yielding the product complex of substrated DNA and assisted DNA (CS). The target is then released back into the solution and and catalyzes the next cycle of toehold-exchange with the reaction intermediate of substrated DNA and regulated DNA (CPR). Unlike in a conventional DNA toehold that is hardwired with the branch migration domain, the allosteric DNA toehold is designed into a reg-DNA which is independent of the branch migration domain. Under the optimal experimental conditions and at a working potential as low as 0.18 V, response to DNA is linear in the 1 fM to 1000 pM concentration range, and the detection limit is 0.83 fM. The assay is highly specific and can discriminate target DNA even from a single-base mismatch. It was applied to the analysis of DNA spiked plasma samples.

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Graphical abstract Schematic illustration of the electrochemical strategy for target DNA detection based on regulation of DNA strand displacement using an allosteric DNA toehold strategy. It can be used to analyze DNA-spiked plasma samples and has a low detection limit of 0.83 fM.

     

单核锇配合物的合成、晶体结构及其与DNA的作用

使用溶剂热合成法,以p-bitmb配体(1,4-二(1-咪唑基-亚甲基)-2,3,5,6-四甲基苯)与[(η6-cymene)Os(μ-Cl)Cl]2或[(η6-bip)Os(μ-Cl)Cl]2为原料,合成了2种单核芳基锇配合物,并利用核磁、质谱、元素分析和X射线单晶衍射等手段对配合物进行了表征。配合物1属于单斜晶系,P21/c空间群,为一个单核锇的结构。中心锇原子与2个配体p-bitmb上的氮原子以及氯原子进行配位,2个配体的另一个咪唑基团通过一个亚甲基碳原子进行连接形成咪唑嗡离子,形成一个类似"碗"状的结构。一个氯离子通过氢键装载在结构的空腔内。利用核磁共振氢谱研究了结构中亚甲基的来源,并研究了配合物在缓冲溶液中的稳定性。用紫外吸收光谱、圆二色谱以及粘度法研究了配合物与DNA的相互作用,结果表明,配合物中的亚甲基来自于溶剂二氯甲烷。配合物以嵌入的方式与CT-DNA相互作用,结合常数分别为3.222×10~4 L·mol-1 (1)和1.53×10~4 L·mol-1 (2),同时配合物会减弱DNA的碱基堆积作用并可以使DNA发生解旋。     

用恒温热重法测定1-己基-3-甲基咪唑苏氨酸离子液体[C6mim][Thr]蒸汽压和蒸发焓

用中和法合成了氨基酸离子液体(AAIL)1-己基-3-甲基苏氨酸盐[C₆mim][Thr],并用核磁共振氢谱(¹H NMR)和核磁共振碳谱(¹³C NMR)进行了表征。以苯甲酸为参考物质,用恒温热重法确定了AAIL[C₆mim][Thr]的蒸汽压和在平均温度下(T_av= 438.15 K)的蒸发焓(Δ^g_lH_m^? (T_av) =128.5 ± 6.0 kJ·mol^-1)。利用Verevkin等人提出的方法计算得到AAIL[C₆mim][Thr]气态和液态的恒压热容差(Δ^g_lC_pm^? = -70.8 J·K^-1·mol^-1),进而计算了不同温度的蒸发焓,其中参考温度(298.15 K)下的蒸发焓Δ^g_lH_m^? (298.15 K) = 138.4 kJ·mol^-1,只比应用我们提出的蒸发焓理论模型估算值大1.6 kJ·mol^-1,小于恒温热重法的实验误差3.0 kJ·mol^-1,说明这个蒸发焓的理论模型有一定的合理性。借助Clausius-Clapeyron方程估算了AAIL[C₆mim][Thr]的假想的正常沸点T_b= 522.07 K,以及沸点的蒸发熵Δ^g_lS_m^? (T_b) = 228.5 J·K^-1·mol^-1,进一步得到了不同温度的蒸发熵和蒸发自由能Δ^g_lG_m^? (T),其结果表明蒸发自由能随着温度的上升而减小,达到沸点温度T_b时变为零,而蒸发熵则随着温度上升而增大,是AAIL[C₆mim][Thr]蒸发过程的驱动力。