Pb^2+对核糖核酸酶活性及其结构的影响

通过各种光谱学手段研究了Pb^2+对核糖核酸酶活性的影响及其作用机制。结 果表明低浓度的Pb^2+可提高酶活性，高浓度则严重抑制酶活性，这是因为在高浓 度下Pb^2+能完全竞争出核糖核酸酶中的Ca^2+，荧光滴定显示核糖核酸酶可结合3 个Pb^2+。利用EXAFS表征出Pb^2+已结合到核糖核酸酶方链氨基酸残基上，与N或O 发生了配位，Pb-N(或O)键长分别为0.242nm和0.312nm，配位数均为2。圆二色谱测 试进一步表明高 浓度的Pb^2+结合使核糖核酸酶的二级结构遭到严重破坏，α－螺 旋含量、β－折叠及β－转角大量下降，无规则卷曲则明显增加。     

Ce3+对细胞内游离Ca2+的影响

研究了Ce^3 对肝细胞和V79细胞中游离Ca^2 的影响。低浓度的Ce^3 能使肝细胞内游离Ca^2 浓度增高，高浓度的Ce^3 能使肝细胞内游离Ca^2 浓度显著升高。Ce^3 可促进细胞外Ca^2 的内流，高浓度的Ce^3 对细胞是有毒性的。     

铈对猪胰α-淀粉酶活性影响的研究

在α 淀粉酶介质中加入Ce3+ ,研究了对α 淀粉酶活性影响及其对酶中Ca2 + 的竞争结合作用。低浓度下 (0 .5～ 10mmol·L- 1 ) ,Ce3+ 对α 淀粉酶具有激活现象 ,而高浓度则抑制酶活力。在高浓度下 ,Ce3+ 能完全竞争出α 淀粉酶中的Ca2 + 。荧光滴定表明Ce3+ 能够完全占据Ca2 +的结合位点     

黄孢展齿革菌菌丝球同时吸附铅镉离子的动力学

采用间歇法，利用黄孢展齿革菌菌丝球吸附溶液中的Pb^2 和Cd^2 ，研究Pb^2 和Cd^2 共存体系中吸附初速率随初始浓度的变化规律。实验结果表明，少量Cd^2 的存在促进其对Pb^2 的吸附，并提高吸附初速率，但随着Cd^2 初始浓度的增加，促进作用逐渐减弱并转为抑制作用；Cd^2 的吸附初速率随着Pb^2 初始浓度增大而减小；Pb^2 和Cd^2 的吸附初速率都随自身初始浓度的增加而增大。     

CMC-Na/DETA-B62型蛇笼树脂对金属离子的吸附性能

本文研究了自合成的蛇笼型螯合树脂-二乙烯三胺交联甘油环氧树脂/羰甲基纤维素体系对Cd^2 ,Pb^2 ,Fe^2 的吸附量，吸附动力学，等温吸附过程等静态吸附性能，同时研究了pH值等因素对吸附性能的影响。实验结果表明，该树脂对Cd^2 具有较强的吸附选择性，能在Cd^2 ,Pb^2 ,Fe^2 3种离子共存时选择吸附Cd^2 ，其选择性系数分别为Kcd^2 /pb^2 =3.77,Kcd^2 /Fe^2 =9.61。该树脂对上述3种离子的吸附量可分别达4.00,1.06,0.42mmol/g。该类树脂可用于含重金属离子污水的处理和金属离子的分离等方面。     

巯基壳聚糖富集火焰原子吸收光谱法测定天然水体中Pb2+和Cd2+ 的研究

利用自己研制的巯基壳聚糖对Pb^2 和Cd^2 具有良好的吸附效果这一特性，建立了巯基壳聚糖分离富集原子吸收光谱法测定天然水体中Pb^2 和Cd^2 的新方法，研究了最佳吸附和脱附条件，该法对Pb^2 和Cd^2 的准确检测下限可达到1.00μg/L和0.050μg/L。回收率分别达到96.5%和97.6%。该法灵敏度高，选择性好，用于实际水样的测定取得了满意的。     

含硫氮杂套索冠醚的合成及应用研究

合成了一系列分别带有香豆素基和α—萘胺基套索冠醚，用紫外光谱法测定了 这些套索冠醚与Cu^2+，Pb^2+，Cd^2+，Hg^2+，Cr^3+，Ni^2+，Mg^2+，Zn^2+金属 离子的络合作用，及所形成络合物的λmax及摩尔消光系数ε，发现其中一些化合 物对Pb^2+，Hg^2+，Cr^3+金属离子具有较高的灵敏度和选择性．     

植物钙调素与Ce3+离子结合反应的荧光光谱法研究

水合Ce^3＋离子发射强荧光,而用Ce^3＋滴定植物钙调素（CaM）时,Ce^3＋离子荧光被完全淬灭,据此建立了测定Ce^3＋离子与植物钙调素结合位点数及逐级结合常数的方法。实验表明,Ce^3＋离子与植物钙调素的荧光激发光谱及发射光谱形状与光谱强度都有显著差别,前者的荧光强度远大于后者,故CaM存在时可以测定游离Ce^3＋的浓度。Ce^3＋离子荧光淬灭法测定结果说明,在0.5 mol·L^-1KCl溶液中,CaM有4个Ce^3＋离子结合位点。进一步通过Ce^3＋滴定植物钙调素的实验,并结合Excel规划求解法,计算出Ce^3＋与CaM的结合常数,K1=4.17×10^7,K2=1.26×10^7,K3=1.89×10^6,K4=2.04×10^6。     

Pb2+对胰蛋白酶活性影响的作用机理研究

在胰蛋白酶介质中加入Pb²⁺， 研究其对胰蛋白酶活性影响的作用机理。结果表明低浓度的Pb²⁺对酶有激活作用，高浓度则严重抑制酶活性。在高浓度下，Pb²⁺能完全竞争出胰蛋白酶中的Ca²⁺而结合到了胰蛋白酶上，其EXAFS的测试表明Pb²⁺与多肽链氨基酸残基上的氨基或羧基发生了配位，配位数为2，Pb-N或Pb-O键长为0.241nm。圆二色谱测试表明高浓度的Pb²⁺结合使胰蛋白酶的二级结构被破坏，α-螺旋含量、β-转角及无规则卷曲下降，β-折叠增加，因而使酶失去活性。     

石墨烯纳米筛负载钴铁双金属层状氢氧化物的制备及其在重金属离子电化学传感中的应用北大核心CSCD

本文采用自组装-碳热造孔-刻蚀的方法将钴铁双金属层状氢氧化物(Co_(3)FeLDH)与石墨烯纳米筛(HG)复合,进而制备了基于Co_(3)FeLDH/HG复合材料的电化学传感器,用于同时检测水中Pb^(2+)、Cd^(2+)和Zn^(2+)。由于HG的高比表面积、多孔性和良好的导电性,以及Co_(3)FeLDH阵列结构对重金属离子的强亲和性,所制备传感器表现出良好的分析性能。实验结果显示,Pb^(2+)与Cd^(2+)的峰电流与浓度在1~1500μg·L^(-1)、Zn^(2+)峰电流与浓度在5~1800μg·L^(-1)范围线性关系良好,方法对Pb^(2+)、Cd^(2+)和Zn^(2+)的检测限分别达2.41 nmol·L^(-1)、4.45 nmol·L^(-1)和15.38 nmol·L^(-1),大大低于世界卫生组织(WHO)允许的生活水中3μg·L^(-1)(27 nmol·L^(-1))、10μg·L^(-1)(48 nmol·L^(-1))和1 mg·L^(-1)(33 mmol·L^(-1))的阈值。所制备的电化学传感器具有良好的稳定性和重现性,在环境分析检测方面具有良好的应用前景。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Catalyst free,visible-light promoted photoaddition reactions between C60 and N-trimethylsilylmethyl-substituted tertiary amines for synthesis of aminomethyl-1,2-dihydrofullerenes

An efficient and benign method for the preparation of aminomethyl-substituted fullerenes has been developed. The process, involving catalyst free, visible-light irradiation of 10% EtOH-toluene solutions containing fullerene C₆₀ and N-trimethylsilylmethyl-substituted amines by using a 20 W compact fluorescent lamp, leads to formation of aminomethyl-substituted fullerene adducts in a highly efficient manner. The photoaddition reaction takes place via a pathway initiated by visible light absorption by C₆₀, followed by SET from the amine to the triplet excited state of C₆₀. Ethanol-promoted desilylation of the resulting a minimum radical then generates the corresponding α-amino radical which couples with the C₆₀ radical anion to form the anion precursor of the fullerene adducts. The new approach using visible-light takes place under mild conditions and it does not require the use of photocatalysts. Thus, the method developed in this effort could broadens the range of functionalized fullerene derivatives that can be readily prepared.     

Highly efficient and stereoselective cycloaddition of nitrones to indolyl- and pyrrolylacrylates

The reactions of various nitrones with indolyl- and pyrrolylacrylates proceeds regioselectively with high diastereoselectivity in the case of aldonitrones, and represents an effective method for obtaining new indolyl- and pyrrolyl-substituted isoxazolidine carboxylates stabilized by weak (CH?O) and moderate (NH?N) strength intramolecular hydrogen bonding. The resulting cycloadducts exhibit promising in vitro anti-influenza activities.     

Transition metal-free direct amination of benzoxazoles using formamides as nitrogen sources

A transition metal-free method for the direct amination of benzoxazoles using formamides as nitrogen sources is reported, which was mediated by an inexpensive and environmentally friendly tetrabutylammonium iodide/tert-butyl hydroperoxide system and gave the 2-aminobenzoxazole derivatives with moderate to good yields.     

l-Proline-catalyzed five-component domino reaction leading to multifunctionalized 1,2,3,4-tetrahydropyridines

Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl₃-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction.     

Exploring the scope of the Gewald reaction: Expansion to a four-component process

An efficient four-component reaction was developed to take advantage of the reactivity of the 2-aminothiophene-3-carbonitrile functionality, which is obtained during the classical three-component Gewald reaction. Various α-methylene bearing ketones were reacted with malononitrile, elemental sulfur, and aryl/heteroarylnitrile derivatives in t-BuOH/NaOH to afford 2-arylthieno[2,3-d]pyrimidin-4-amines in high yields. Preliminary studies revealed the photophysical properties of the products and their potential for use as metal sensors.