铜(II)-5-取代邻菲啰啉-二氧四胺大环三元体系的稳定性研究

The stability of copper (Ⅱ)-13-(2'-Hydroxy-3',5'-substituted benzyl)-1,4,8,11-tetraazacyclotetradecane-12, 14-dione(RTADO-14) binary complex compounds and of copper (Ⅱ)-5-substituted-1,10-phenanthrolines(R'TADO)-RTADO-14 ternary complex compounds was studied by means of pH titration method at 25.0±0.1 ℃ and I=0.1mol?dm-3KNO3. The formation constants of binary and ternary complexes were obtained. The structures of the binary and ternary complxes and the effects fo substituents on macrocyclic ligands and on R'Phen were also discussed.     

铜-洛美沙星-曙红三元络合物分光光度法测定洛美沙星

pH 4.1的条件下,铜与洛美沙星、曙红反应生成三元络合物,使曙红溶液褪色并产生新的吸收峰,最大褪色峰谷波长位于508 nm,三元络合物吸收峰波长位于546 nm.利用吸收峰、谷的高度差,进行洛美沙星的测定,洛美沙星的质量浓度在0.7～3.8 mg/L范围内符合比耳定律.方法的表观摩尔吸光系数为5.47×104 L·mol-1·cm-1,检出限为0.46 mg/L.该方法用于HCl洛美沙星片剂样品中洛美沙星的测定,准确、灵敏、选择性好.对样品平行6次测定,相对标准偏差为0.42%～3.1%,回收率为92.6%～106.9%.     

铜离子对烟草多酚氧化酶变性和复性影响的热力学研究(英)

在有无5 mmol·L^-1 CuSO₄存在的两种情况下，运用荧光光谱研究了烟草多酚氧化酶在盐酸胍诱导下的变性和复性平衡。烟草多酚氧化酶在6.0 mol·L^-1盐酸胍变性30 min(25 ℃)即完全失活。荧光光谱结果表明：铜离子能够提高烟草多酚氧化酶的结构稳定性和抗盐酸胍变性的能力，进而影响烟草多酚氧化酶在盐酸胍诱导下的变性和复性过程。没有外源铜存在的情况下，盐酸胍诱导的烟草多酚氧化酶变性和复性是一个可逆的二态过程；在5 mmol·L^-1 CuSO₄存在的条件下，由于结合了Cu²⁺的酶的中间态稳定性增加，显示特征荧光，结果显示，外源铜存在时，盐酸胍诱导的烟草多酚氧化酶变性和复性是一个可逆的三态过程。根据相应模型，进行了热力学计算。上述实验结果得到酶活性测定的进一步证实，在6 mol·L^-1盐酸胍中放置5，10，15，20，25，30 min，烟草多酚氧化酶的剩余活性分别为18.7%，11.7%，8.9%，6.6%，3.6%，0.06%，但在5 mmol·L^-1 CuSO₄存在的条件下，剩余活性则分别为60.3%，44.6%，42.5%，40.2%，25.6%，25.3%。     

铜基催化剂的制备方法对草酸二乙酯加氢反应的影响

草酸二乙酯加氢性成乙二醇的反应过程中，所用的铜基催化剂是由Ｃｕ（ＮＯ３）２与硅溶胶凝法制得的。本文考察了该催化剂的ＴＰＲ特性，结果表明，随着催化剂中Ｃｕ／ＳｉＯ２值的增大，其ＴＰＲ主峰ＴＭ峰温有所升高，这意味着催化剂的还原温度随Ｃｕ／ＳｉＯ２值的增大而提高。用ＸＲＤ和ＸＰＳ等手段对该催化剂还原后铜的含量及价态进行了考察，表明用胶凝法制备的铜基催化剂，还原后存在Ｃｕ＾ｏ和Ｃｕ＾＋两种价态。结合活性评     

Phen-铜(II)-氨基酸配合物的合成、表征及其SOD活性

合成了3个新的SOD模拟配合物：[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O (1)、[Cu(Phen)(L-Ala)(H₂O)]Cl·4H₂O (2)、[Cu(Phen)(L-Thr)(H₂O)]Cl·2H₂O (3) [Phen(1，10-邻菲咯啉)、L-Gln(谷氨酰胺)、L-Ala(丙氨酸)、L-Thr(苏氨酸)]。用元素分析、摩尔电导、红外光谱、紫外-可见光谱对配合物进行了表征。用X-射线衍射对配合物[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O的晶体结构进行了测定。用氯化硝基四氮唑蓝(NBT)光还原法对这3个配合物催化歧化超氧阴离子自由基(O₂^{- ·})的能力进行了测定。结果表明：这些配合物具有较高的SOD活性， 催化速率常数K_Q分别为1.58 × 10⁷ mol^-1·L·s^-1、5.65 × 10⁷ mol^-1·L·s^-1、0.83 × 10⁷ mol^-1·L·s^-1。     

CeO2担载Cu纳米粒子电催化CO2还原产乙烯：CeO2不同暴露晶面对催化性能的影响

Fossil fuels are expected to be the major source of energy for the next few decades. However, combustion of nonrenewable resources leads to the release of large quantities of CO₂, the primary greenhouse gas. Notably, the concentration of CO₂ in the atmosphere is increasing annually at an astounding rate. Electrochemical CO₂ reduction (ECR) to value-added fuels and chemicals using electricity from intermittent renewable energy sources is a carbon-neutral method to alleviate anthropogenic CO₂ emissions. Despite the steady progress in the selective generation of C₁ products (CO and formic acid), the production of multi-carbon species still suffers from low selectivity and efficiency. As an ECR product, ethylene (C₂H₄) has a higher energy density than do C₁ species and is an important industrial feedstock in high demand. However, the conversion of CO₂ to C₂H₄ is plagued by low productivity and large overpotential, in addition to the severe competing hydrogen evolution reaction (HER) during the ECR. To address these issues, the design and development of advanced electrocatalysts are critical. Here, we demonstrate fine-tuning of ECR to C₂H₄ by taking advantage of the prominent interaction of Cu with shape-controlled CeO₂ nanocrystals, that is, cubes, rods, and octahedra predominantly covered with (100), (110), and (111) surfaces, respectively. We found that the selectivity and activity of the ECR depended strongly on the exposed crystal facets of CeO₂. The overall ECR Faradaic efficiency (FE) over Cu/CeO₂(110) (FE ≈ 56.7%) surpassed that of both Cu/CeO₂(100) (FE ≈ 51.5%) and Cu/CeO₂(111) (FE ≈ 48.4%) in 0.1 mol·L^-1 KHCO₃ solutions with an H-type cell. This was in stark contrast to the exclusive occurrence of the HER over pure carbon paper, CeO₂(100), CeO₂(110), and CeO₂(111). In particular, the FE toward C₂H₄ formation and the partial current density increased in the sequence Cu/CeO₂(111) < Cu/CeO₂(100) < Cu/CeO₂(110) within applied bias potentials from -1.00 to -1.15 V (vs. the reversible hydrogen electrode), reaching 39.1% over Cu/CeO₂(110) at a mild overpotential (1.13 V). The corresponding values for Cu/CeO₂(100) and Cu/CeO₂(111) were FE_C2H4 ≈ 31.8% and FE_C2H4 ≈ 29.6%, respectively. The C₂H₄ selectivity was comparable to that of many reported Cu-based electrocatalysts at similar overpotentials. Furthermore, the FE for C₂H₄ remained stable even after 6 h of continuous electrolysis. The superior ECR activity of Cu/CeO₂(110) to yield C₂H₄ was attributed to the metastable (110) surface, which not only promoted the effective adsorption of CO₂ but also remarkably stabilized Cu⁺, thereby boosting the ECR to produce C₂H₄. This work offers an alternative strategy to enhance the ECR efficiency by crystal facet engineering.     

2—（6—硝基—2—苯并噻唑偶氮）—5—二甲氨基苯甲酸与铜显色反应的研…

本研究了２－（６－硝基－２－苯并噻唑偶氮）－５－二甲氨基苯甲酸（６－ＮＯ２－ＢＴＡＭＢ）与铜的显色反应。结果表明，在ｐＨ２．０￣４．５的乙醇水溶液中６－ＮＯ２－ＢＴＡＭＢ与铜形成一种稳定的蓝绿色络合物，其最大吸收波长位于６５０ｎｍ处，表观摩尔吸收系数为７．７５×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，络合物的组成为６－ＮＯ２－ＢＴＡＭＢ∶Ｃｕ＝１∶１，铜浓度在０￣１０μｇ／１０ｍｌ范围内服从比尔定     

Preparation and Properties of Doped Lanthanum Gallate Film on a Ni/SDC Porous Anode Support

IntroductionIn intermediate-temperature solid oxide fuel cells(SOFCs),doped ceria with a fluorite structure anddoped lanthanum gallate(LSGM)with a perovskitestructure are commonly used as electrolyte materials.However,the former easily exhibits an electro…     

利用钐掺杂氧化铈提高燃料电池阳极活性

用浸渍法制备并采用交流阻抗、极化等技术考察了不同组成的Ni-Sm3＋掺杂的CeO2(SDC) 复合镍阳极的电化学性能及相应电池的功率输出性能.结果表明，SDC掺入镍阳极后,阳极极化过电位及电池的欧姆电阻显著减小.其中阳极过电位的减小与SDC掺入镍电极引起的三相界扩展有关，但SDC的掺入同时引起了电极反应活化能的增加,造成低温下Ni-SDC的极化过电位大于纯Ni电极.高温下,Ni-SDC阳极的阻抗谱由两个半圆组成，其中高频半圆随着SDC掺入量的增加而减小,而低频环与SDC的掺入量基本无关.低温下只观察到一个高频环.高频环可能对应三相界反应,而低频环可能对应氢的解离吸附及扩散.75％（w）Ni-25％（w）SDC/La0.9Sr0.1Ga0.8Mg0.2O3(LSGM)/Sm0.5Sr0.5CoO3(SSC)在所研究的电池中具有最大功率输出密度，其值在1073、973、873 K下分别达到1.1、0.43、0.14 W•cm－2.     

Catalytic Preparation of Optically Active 1,1′—Binaphthalene—2,2′—Diol by Chiral Benzoimidazole—Cu（Ⅱ）Complex

Inthepastseveraldecades ,muchattentionhasbeenpaidtoopticallyactive ,C2 asymmetric1,1′ bi naphthalene 2 ,2′ diolanditsderivativesbecauseoftheirapplicationininducingchiralityinasymmetricsynthesis[1,2 ] .Enantiomericallypure1,1′ binaphtha lene 2 ,2′ diolhasbeen preparedbymanymethodsrangingfromtheclassicalresolutionviacrystalliza tionofthediastereoisomericsalts[3] toasymmetricox idativecoupling[4～ 6 ] .However ,theuseofexpensivechiralreagentsandthetediousnessoftheprocessessetalimitontheuseof…