Evidence for a dipolar-coupled AM system in carnosine in human calf muscle from in vivo 1H NMR spectroscopy

Spin systems with residual dipolar couplings such as creatine, taurine, and lactate in skeletal muscle tissue exhibit first-order spectra in in vivo 1H NMR spectroscopy at 1.5 T because the coupled protons are represented by (nearly) symmetrized eigenfunctions. The imidazole ring protons (H2, H4) of carnosine are suspected to form also a coupled system. The ring's stiffness could enable a connectivity between these anisochronous protons with the consequence of second-order spectra at low field strength. Our purpose was to study whether this deviation from the Paschen-Back condition can be used to detect the H2-H4 coupling in localized 1D 1H NMR spectra obtained at 1.5 T (64 MHz) from the human calf in a conventional whole-body scanner. As for the hydrogen hyperfine interaction, a Breit-Rabi equation was derived to describe the transition from Zeeman to Paschen-Back regime for two dipolar-coupled protons. The ratio of the measurable coupling strength (Sk) and the difference in resonance frequencies of the coupled spins (Deltaomega) induces quantum-state mixing of various degree upon definition of an appropriate eigenbase of the coupled spin system. The corresponding Clebsch-Gordan coefficients manifest in characteristic energy corrections in the Breit-Rabi formula. These additional terms were used to define an asymmetry parameter of the line positions as a function of Sk and Deltaomega. The observed frequency shifts of the resonances were found to be consistent with this parameter within the accuracy achievable in in vivo NMR spectroscopy. Thus it was possible to identify the origin of satellite peaks of H2, H4 and to describe this so far not investigated type of residual dipolar coupling in vivo.     

含硫氨基葡萄糖金属配合物的合成及与DNA和蛋白作用研究

合成了四种含硫氨基葡萄糖金属配合物(M-GLUS,M=Co, Cu, Ni和Zn),利用元素分析,摩尔电导,核磁共振氢谱进行了结构表征。结果表明含硫配体与这四种二价金属离子均形成了2∶1型非电解质配合物。在pH 7.08 Tris缓冲液中,采用紫外吸收光谱和荧光光谱研究了金属配合物与小牛胸腺DNA的作用机制,发现随着金属配合物量的逐渐增加,DNA电子吸收光谱的最大吸收峰呈增色效应,对配合物DNA-EB体系也能产生荧光猝灭作用,说明四种金属配合物均可与DNA发生相互作用,结合方式为部分插入;在近似生理酸度条件下,利用荧光光谱对金属配合物与HSA/BSA的结合特性进行了初步分析,发现配合物均能猝灭HSA/BSA的荧光强度,利用Scatchard方程计算了四种金属配合物与HSA/BSA的结合常数和结合位点数,表明金属配合物与血清白蛋白有较强的结合且只有1类键合位,其中Co-GLUS与蛋白的结合力最强。     

低剂量连续辐射引起的小鼠免疫系统的变化

为了评估低剂量X射线连续辐射对BALB/c小鼠健康机体免疫系统的影响, 实验采用X射线全身连续照射BALB/c小鼠, 照射第一天剂量为0.07 Gy, 剂量率0.2 Gy/min, 之后每天照射0.08 Gy, 共照射12 d, 累积剂量1.03 Gy, 照射后24和48 h取血、胸腺和脾脏。 流式细胞仪检测免疫细胞周期和凋亡的变化, 胸腺和脾脏指数用重量法获取。 实验结果表明, 小鼠胸腺细胞的周期在照射后24 h被阻滞在G2/M期; 外周血淋巴和胸腺细胞周期48 h被阻滞在 G0/G1期, 细胞凋亡比例在照射后两个时间点都显著增加; 脾脏淋巴细胞周期24 h被阻滞在 G0/G1期, 48 h被阻滞在 S期, 细胞凋亡比例在24和48 h显著减少; 脾脏指数在照射后48 h显著减少。 故低剂量X射线连续全身照射BALB/c小鼠可激活免疫细胞不同的周期监测点, 引起免疫细胞凋亡比例发生变化, 造成一定的辐射损伤, 且这种影响随着免疫器官的不同而不同。 For estimating the effect of low doses X ray continual irradiation to immunity system of mouse, BALB/c mice were continually irradiated to 1.03 Gy by X rays at a dose rate of 0.2 Gy/min in 13 d. At 24 or 48 h after irradiation, the immunocyte cycle and apoptosis were determined by flow cytometry, and the thymus and spleen weights were measured too. The results showed that the cycle of thymocyte were arrested in G2/M at 24 h, the number of peripheral blood lymphocytes and thymocytes in G0/G1 phase at 48 h was up and the percentage of apoptosis had a significance increase in both of time points; the cycle of spleen lymphocytes was delayed in G0/G1 at 24 h, in S phase at 48 h, the apoptosis had a significance decrase at 24 and 48 h; spleen index declined significantly at 48 h. The results suggested that low doses continual X ray whole body irradiation could activate different cell cycle checkpoints, and result in some changes of apoptosis and some damages to immunocytes. The continual X ray irradiation affects the organs differently, it might provide experiment basis for radioprotection.     

染料木素及其葡萄糖苷与DNA相互作用的研究

在pH 7.2 Tris缓冲溶液中,采用紫外、荧光、粘度等方法研究了染料木素、染料木素葡萄糖苷、染料木素7,4’-二-O-β-D-葡萄糖苷与小牛胸腺ctDNA的作用。结果表明,在ctDNA存在下,染料木素及其葡萄糖苷的紫外吸收光谱的最大吸收峰均产生明显的减色效应。三种化合物的加入均能有效猝灭EB-DNA体系的荧光,而猝灭方式并不唯一。另外,ctDNA溶液的粘度也都随三种化合物的加入而增大。据此推断,染料木素及其葡萄糖苷与ctDNA之间具有较强的作用,可能以部分插入及氢键作用与ctDNA结合,其作用强弱顺序为染料木素葡萄糖苷>染料木素7,4’-二-O-β-D-葡萄糖苷>染料木素。结果提示染料木素的7位或4’位葡萄糖基化修饰有望作为抗癌活性候选物,值得进一步深入研究。     

吖啶橙共振光散射法测定痕量脱氧核糖核酸

研究了三环杂芳香类染料吖啶橙(AO)与DNA作用的共振光散射光谱,在pH11．5～12．5的范围内,加入DNA导致吖啶橙共振光散射增强,在339nm处,存在一共振光散射增强峰,其强度与DNA浓度呈线性关系,据此建立了一种测定DNA的共振光散射新方法?对于ctDNA,方法的线性范围为14．3～1000μg／L,检出限为2．86μg／L,RSD为3．6％;对于fsDNA,方法的线性范围为24．0～1250μg／L,检出限为4．78μg／L,RSD为6．0％。已用于合成样品中DNA的测定。     

DNA纳米网络修饰碳纤维盘电极及其分子传感应用

DNA immobilization on electrode surfaces has been widely used for fabricating sensors since DNA can interact with a wide variety of biomolecules. Recendy, DNA has been demonstrated as an electronic super conductor and become the most promising biomolecule for application of chemical sensing in biological system. Calf thymus DNA (ct-DNA) is a most popularly used native DNA in many applications. An electrochemical deposition on carbon fiber micro electrode can provide sensitive detection of dopamine in presence of large amount of ascorbic acid.     

季铵盐联吡啶-钌(Ⅱ)配合物的合成及其与小牛胸腺DNA的相互作用

利用紫外-可见吸收光谱、荧光光谱、圆二色谱等光谱手段,以及黏度测定等流体力学方法在三羟甲基氨基甲烷(tris)缓冲溶液和磷酸缓冲溶液中研究了含季铵盐联吡啶配体的钌(Ⅱ)配合物[Ru(L)(phen)2](PF6)4(L=5,5′-二(三甲铵基甲基)-2,2′-联吡啶离子,phen=邻菲咯啉)与小牛胸腺DNA(CT-DNA)的相互作用.结果表明,合成的配合物与CT-DNA之间存在一定的亲和作用,拟合得到的结合常数可达105;与此同时,该配合物能够稳定CT-DNA的结构,并对CT-DNA有较好的立体选择性(右旋异构体优先与DNA结合).     

DNA interaction,free radical scavenging and in‐vitro antibacterial activity of drug‐based copper(II) complexes

The Cu(II) complexes of type [Cu(cpf)(Aⁿ)Cl] (Aⁿ = terpyridines, cpf = ciprofloxacin) were synthesized and characterized using IR, mass and reflectance spectra. The free ligands and their complexes were evaluated for their in‐vitro antimicrobial activity against a panel of Gram‐positive and Gram‐negative bacteria. The complexes exhibit better or equal inhibition in comparison to free fluoroquinolones. Binding interactions of the complexes with calf thymus (CT DNA) were investigated by absorption titration, viscosity studies and DNA melting temperature experiment. The cleavage reaction on pUC19 DNA was monitored by agarose gel electrophoresis. The lower concentration of the complexes was catalysed the dismutation of superoxide radical at biological pH, which indicates that the complexes can act as a possible model for superoxide dismutase. Copyright © 2011 John Wiley & Sons, Ltd.     

1，10-邻菲咯啉-5，6-二酮铁(Ⅱ)配合物的合成、结构及与DNA相互作用的研究

在乙腈体系中合成了Fe(Ⅱ)的配合物[Fe(phon)3](ClO3)2.2CH3CN(phon=1,10-邻菲咯啉-5,6-二酮)。X-射线衍射单晶结构表明:配合物[Fe(phon)3](ClO3)2.2CH3CN属于正交晶系,P212121空间群,Fe(Ⅱ)与3个phon配体的6个氮原子配位,形成变形的八面体结构。配合物[Fe(phon)3](ClO3)2.2CH3CN中的氢键和C=O…π相互作用将配合物连接成二维网络结构。用红外光谱、紫外-可见光谱对配合物[Fe(phon)3](ClO3)2.2CH3CN进行了表征,并用紫外光谱法对配合物与ct-DNA的相互作用做了初步研究,结果表明配合物与ct-DNA的结合常数(Kb)为2.2×105L.mol-1。     

欧前胡素及同分异构体与DNA的作用机理及构效关系研究

在模拟人体生理条件下,采用紫外光谱法、荧光光谱法、DNA热变性及黏度法研究欧前胡素及同分异构体异欧前胡素与DNA的作用机制,并探讨其构效关系.紫外光谱表明,加入DNA后,欧前胡素和异欧前胡素的紫外光谱均呈现减色效应;荧光光谱显示,随着欧前胡素或异欧前胡素浓度的增大,DNA-BR的荧光被猝灭,表明欧前胡素和异欧前胡素对BR与DNA的结合存在竞争性抑制;盐效应、DNA热变性温度、黏度法等实验进一步证明欧前胡素和异欧前胡素与DNA的作用模式均为嵌插与静电混合作用模式.研究表明,欧前胡素和异欧前胡素均与DNA发生作用,且欧前胡素与DNA作用强于异欧前胡素.