德国小蠊性信息素类似物的设计与合成

德国小蠊是世界上最难治理的卫生害虫之一.昆虫性信息素可作为一种安全有效的引诱剂用于害虫的综合治理.德国小蠊性信息素(blattellaquinone)因其结构不稳定而妨碍了它的实际应用.为了发现结构新颖且稳定的性信息素类似物,对blattellaquinone的结构中苯醌(A)、酯基(B)和脂肪链(C)部分进行了改造,设计并合成了一系列类似物,结构均通过1H NMR,IR和HRMS分析确证.     

吗啉核苷类似物及其磺胺衍生物的合成及初步抗牛病毒性腹泻病毒(BVDV)活性研究

以核糖核苷为原料,通过糖环的结构转化合成了系列吗啉核苷类似物,再与磺胺类药物的母核偶联得到吗啉核苷磺胺衍生物.所得化合物均经HRMS、~(1)H NMR和~(13)C NMR谱分析确证.以牛病毒性腹泻病毒(BVDV)感染的牛肾细胞为模型对目标化合物抗病毒活性进行筛选,结果显示此类化合物无明显抗病毒活性.     

基于天然产物Mevalocidin手性中心的结构类似物的设计与合成（英文）

Mevalocidin是从Rosellinia DA092917和Fusarium DA056446菌株中分离到的一种天然产物,在4 kg/ha的高剂量下具有苗后除草活性.希望对其手性中心进行改造以提高除草活性,通过设计不同合成路线,合成了2个类似物,通过~1H NMR、~(13)C NMR及HRMS对所合成化合物的结构进行了确认.活性筛选结果表明,所合成的目标化合物不具有除草活性,说明天然产物手性中心上的甲基和羟基对其活性保持至关重要,为进一步结构修饰提供了指导.     

N,N′-二苄基乙二胺类番荔枝内酯简化类似物的合成

运用生物电子等排原理及简化策略,设计含乙二胺结构片段的番荔枝内酯简化类似物.通过N,N′-二苄基乙二胺与两个手性环氧片段依次拼接,合成了手性简化类似物.其结构经1H NMR,13C NMR和MS表征.     

质体醌类似物的合成研究——Ⅰ.不同侧链的质体醌类似物

本文通过对2,3-二甲基-1,4-苯醌与脂肪酸在过硫酸铵及硝酸银作用下发生的自由基烷基化反应,合成了九种新的具有不同长短侧链的质体醌类似物。其结构已经IR,UV,~1H NMR和MS证实。     

1,2,3—二氮磷杂环戊二烯类化合物的合成及性质

合成了2-乙酰基-1,2,3-二氮磷杂环戊二烯类系列化合物,用~1H、~(13)C、~(31)P NMR和MS确定了其结构,讨论了结构和NMR谱间的关系。     

几种有机硫逐磷酰胺酯类杀虫剂的~1H、~(21)P、~(13)C多核NMR研究

本文记录了通式为的10个有机硫逐磷酰胺酯类杀虫剂的~1H、~(31)P、~(13)C的NMR谱,确定了其化学位移,~(31)P与~1H、~(31)P与~(13)C、~1H与~1H的偶合常数,并讨论了核磁参数与结构的关系。     

7-氨基-6-芳基偶氮-5-羟基吡唑[1,5-a]并嘧啶-3-甲酸乙酯的合成

以氰乙酸乙酯和原甲酸三乙酯为原料,经过缩合、肼解、关环、重氮化及偶合等反应合成了13个新型的嘌呤类似物7-氨基-6-芳基偶氮-5-羟基吡唑[1,5-a]并嘧啶-3-甲酸乙酯(5a-5m)。通过IR、~1H NMR、MS和元素分析确定了所得化合物的结构。     

南海柳珊瑚Menella Spinifera Kukenthal化学成分的研究(一)

从中国南海针小月柳珊瑚(Menella Spinifera Kukenthal)中分离到一种长链甘油醚,其结构经UV、IR、MS、~1H NMR、~(13)C NMR、~1H-~1H COSY以及元素分析确定为3—十八烷氧基—1,2—丙二醇鲨肝醇(Ⅰ)。本文是第一次报导它存在于该种属柳珊瑚之中。 (Ⅰ)的化学结构     

益母草碱类似物设计、合成及其Na+/H+交换器-1抑制活性

以中药益母草中有效成分益母草碱为先导化合物,按生物电子等排原理,设计合成了18个益母草碱类似物.通过MS,1H NMR,13C NMR对化合物结构进行表征.初步的药效研究结果表明部分化合物具有Na+/H+交换器-1 (NHE-1)抑制活性,其中化合物1a和1e的活性显著强于阳性对照药Cariporide.     

苹果酸酶结合域定点突变对烟酰胺腺嘌呤二核苷酸类似物催化性能的影响

通过对苹果酸酶(ME)辅酶结合域L310、Q401、L404饱和位点突变库与辅酶烟酰胺腺嘌呤二核苷酸(NAD⁺)类似物库的高通量筛选,研究了苹果酸酶结合域位点对NAD⁺及其类似物(B1~B7)催化活性的影响。 结果表明,突变后酶ME-Q401H/L404T对类似物B4的k_cat/K_m是野生型酶的50倍;突变后酶ME-L310M/Q401N对类似物B4的k_cat/K_m是野生型酶的16倍,对类似物B3的k_cat/K_m是野生型酶的5倍,因此通过对结合域定点突变,NAD⁺类似物的催化活性得到提高。     

Capillary electrophoresis of nicotinamide—adenine dinucleotide and nicotinamide—adenine dinucleotide phosphate derivatives in coated tubular columns

HPCE was shown to be an effective and convenient method for the determination of nicotinamide—adenine dinucleotide (oxidized, NAD⁺; reduced, NADH), nicotinamide—adenine dinucleotide phosphate (oxidized, NADP; reduced, NADPH) and their synthetic derivatives. The coenzymes were easily separated among themselves and from their degradation products, which are inhibitors of dehydrogenases, in 15 min in a coated capillary. Several coenzyme derivatives such as N⁶-(2-aminoethyl)-NAD(P)⁺ and N(1)-(2-aminoethyl)-NAD(P)⁺ were separated by zone electrophoresis in uncoated or coated capillaries using 50 mM 3-(N-morpholino)propanesulphonic acid (pH 7.0) or Tris—HCl (pH 8.0) as buffer systems. Capillary zone electrophoresis and micellar electrokinetic capillary chromatography can also be used to monitor continuously coenzyme chemical modifications.     

Reactivity of tri- and tetra-nuclear ethylidyne cyclopentadienylcobalt clusters towards protonic acids

The bis(μ₃-ethylidyne) tricobalt cluster [(CpCo)₃(μ₃-CCH₃)₂] (1b) is protonated by trifluoroacetic acid to give the dicobalt edge-protonated cation [H(CpCo)₃(μ₃-CCH₃)₂]⁺ [lb + H]⁺. Protonation of the μ₃-ethylidyne tetracobalt cluster hydride [H(CpCo)₄(μ₃-CCH₃)] (3) takes place in two consecutive steps. At low temperature [H₂(CpCo)₄(μ₃-CCH₃)]⁺ [3 + H]⁺ is formed first, and is then slowly converted into [H₃(CpCo)₄(μ₃-CCH₃)]²⁺ [3 + 2H]²⁺ by an excess of acid. As judged by the ¹H NMR data and the crystal structure of [3 + X]⁺[(CF₃COO)₂X]⁻ (X = H or D) the endo hydrogens in [3 + H]⁺ and [3 + 2H]²⁺ occupy μ₃-(Co₃) face capping hydridic positions. The cations [1b + H]⁺ and [3 + H]⁺ show hydride fluxionality in solution, which in the case of [3 + H]⁺ can be frozen out on the NMR timescale at low temperature (ΔG ^≠ (203 K) = 40.8 kJ/mol). The structure of [3 + X]⁺ [(CF₃COO)₂X]⁻ (X = H or D) was determined by X-ray crystallography. One of the hydrides/deuterides is located on the crystallographic mirror plane, capping a tricobalt face of the cluster cation. The other endo hydrogen atom is believed to be disordered between the other two μ₃-(Co₃) sites, which are related by space group symmetry. Deuteronation of 3 shows a strong normal kinetic deuterium isotope effect. From the temperature independence of the ¹H NMR spectrum of [3 + 2D]²⁺ a non-fluxional solution structure can be inferred. In all the systems studied, hydridic (μ₂- or μ₃-) sites are thermodynamically preferred to possible isomeric agostic CoHC or Co₂HC sites for the endo hydrogens. Agostic interactions cannot, however, be ruled out in transient intermediates during the course of the protonations.     

Reactions of transition-metal carbonyls with anhydrous HF

The reactions of a wide range of transition-metal carbonyls with anhydrous HF are described. In particular, Ru₃(CO)₁₂, Os₃(CO)₁₂ and Ir₄(CO)₁₂ give the solution stable [Ru₃(CO)₁₂H]⁺, [Ru(CO)₅H]⁺, [Os₃(CO)₁₂H]⁺, [Os(CO)₅H]⁺ and [Ir₄(CO)₁₂H₂]²⁺ respectively, which have been characterised by a combination of ¹H and ¹³C NMR spectroscopy.     

Selective enzyme amplification of NAD/NADH using coimmobilized glycerol dehydrogenase and diaphorase with amperometric detection

A flow system for substrate recycling of NAD⁺/NADH was set up with an enzyme reactor containing coimmobilized glycerol dehydrogenase (GDH) and diaphorase. The product from the diaphorase catalysis, hexacyanoferrate(II), aws detected amperometrically at a glassy carbon electrode. The amplification factor was 150 for a reactor volume of 100 μ l at a flow-rate of 0.5 ml/min. With a stopped flow of four minutes, the signal increased another 88 times, resulting in a signal amplification of 13 300 times. Equations are derived for the amplification factor and used for a discussion of the optimization of amplification systems. The K_m for GDH with glycerol as a substrate was found to be 5 × 10⁻³ M at pH 8.0. GDH from Cellulomonas sp. was purified on a gel filtration column and the purified enzyme showed a specificity toward NAD⁺, compared to NADP⁺, that was higher than 99.9%. Due to the NAD⁺ specificity of the purified GDH, the enzyme amplification system reported here could be used in detection systems for enzyme immunoassays when using alkaline phosphatase as a label and NADP⁺ as a substrate. The stability of immobilized GDH and diaphorase is several orders of magnitude better than that of alcohol dehydrogenase, which is the enzyme commonly used for NAD⁺-specific detection in these applications.     

Cr3+比色荧光探针的合成及细胞成像应用

以2,3,3-三甲基-3H-苯并[e]吲哚和对二甲氨基苯甲醛为原料, 乙醇作溶剂, 在酸性催化条件下, 通过一步反应合成了比色荧光探针B. 在EtOH/HEPES(pH=7.4)体积比为9∶1的混合体系中, 向探针B溶液中加入Cr ³⁺后, 溶液颜色由淡黄色变为紫红色, 说明探针B可以对Cr ³⁺进行裸眼识别. 紫外-可见吸收光谱和荧光发射光谱分析表明, 探针B对Cr ³⁺的选择性好、 灵敏度高且对EDTA有良好的接力识别. 探针B对Cr ³⁺的结合常数K_a=0.28×10 ² mol/L, 检出限为1.90×10 ^-8 mol/L, 该检出限低于世界卫生组织(WHO)规定的饮用水中Cr ³⁺的最大含量(9.60×10 ^-8 mol/L). 利用荧光发射光谱对实际水样中Cr ³⁺的浓度进行了定量检测. 探针B也可应用于对活细胞中Cr ³⁺的检测, 具有较好的应用前景和实用价值.     

N,N-二甲基吡啶苯甲醛缩对二甲氨基苯甲酰腙的合成及对Cu2+的选择性识别

设计合成了可用于识别铜离子的化合物N,N-二甲基吡啶苯甲醛缩对二甲氨基苯甲酰腙(1), 通过¹H NMR, ¹³C NMR和MS等对其结构进行了表征; 采用荧光光谱和吸收光谱法研究了化合物1与金属离子间的相互作用. 结果表明, 化合物1对Cu²⁺ 呈现良好的选择性, Cu²⁺ 的加入使化合物1的荧光强度增强12.5倍, 加入其它金属离子如Fe³⁺, Zn²⁺, Pb²⁺, Hg²⁺, Cd²⁺, Co²⁺, Ni²⁺, Li⁺, K⁺, Ca²⁺, Mg²⁺ 和 Ag⁺, 仅引起化合物1荧光强度的微降. 采用双倒数线性回归拟合法计算可知, 化合物1与Cu²⁺ 形成了1: 1型强发光配合物, 结合常数为2.0×10⁷ L/mol.     

含蒽双三联吡啶化合物的合成及其对金属离子的荧光识别性能

以蒽,醋酸,溴化氢,1,3,5-三聚甲醛,N,N,N-三甲基-1-十四烷基溴化铵,双(2-吡啶基甲基)胺,三乙胺等为原料,合成了含蒽的双三联吡啶化合物,其结构经¹H NMR、 ¹³C NMR和HR-MS表征。目标产物中含有双三联吡啶结构,可以与金属离子之间具有较强的螯合作用,从而改变原来目标化合物的光学性质,尤其是其荧光性能。实验结果表明：体系中随着Zn²⁺、Ag⁺和Mn²⁺浓度不断增大,含蒽双三联化合物荧光强度不断增强;Cu²⁺、Co²⁺、Hg²⁺、Pb²⁺、Na⁺、Fe³⁺、Ni²⁺均随着浓度的增大,含蒽双三联化合物荧光强度不断减弱。在此基础上,运用荧光光谱法能高灵敏度的检测痕量金属离子。      

Symmetrization of methylmercury(II) and phenylmercury(II) salts induced by the tripodal ligand N(CH2CH2PPh2)3

Both ionic [HgR(DMSO)][CF₃SO₃] (R = Me or Ph) and covalent HgMeI organomercury(II) compounds react with the tripodal ligand N(CH₂CH₂PPh₂)₃ (np₃) to yield as ultimate products Hg(II) complexes, the new five-coordinated [Hg(OSO₂CF₃)(np₃)]⁺ or the known tetrahedral [HgI(np₃)]⁺ and symmetric diorganomercurials respectively. Monitoring of the reactions by ¹H, ³¹P and ¹³C NMR spectroscopy has shown that the mechanistic pathways depend on the nature of the reagents.     

[NHN] and [OHO] hydrogen bonding in the adduct of 1,8-bis(dimethylamino)naphthalene (DMAN) with 1,8-dihydroxy-2,4-dinitronaphthalene (DHDNN)

X-Ray diffraction, IR and ¹H NMR studies were performed on the 1:1 adduct of 1,8-bis(dimethylamino)naphthalene (DMAN) with 1,8-dihydroxy-2,4-dinitronaphthalene (DHDNN). The adduct crystallizes in the triclinic system, space group , a = 9.911(2) Å, b = 11.212(2) Å, c = 11.194(2) Å, = 68.95(2)°, β = 79.72(2)°, γ = 73.78(2)°, Z = 2. Both [NHN]⁺ and [OHO]⁻ hydrogen bonds formed in the ion pairs are asymmetrical with lengths equal to 2.574(2) Å and 2.466(4) Å respectively. The [NHN]⁺ bridge shows a typical behaviour in the IR spectrum, i.e. a low-frequency absorption between 300 and 700 cm⁻¹. The coupling of [OHO]⁻ hydrogen bonds with the naphthalene π-electron system is so strong that no absorption related to the proton stretching vibrations can be detected in the high- and low-frequency regions. The ¹H NMR chemical shifts for the [NHN]⁺ and [OHO]⁻ bridge protons of 18.63 and 15.81 ppm respectively confirm the strong hydrogen bonds.