NMR Studies on Interactions between Diperoxovanadate and Imidazole-like Ligands

为探讨咪唑环上取代基团对反应平衡的影响,在模拟生理条件(0.15 mol·L~(-1)NaCl溶液)下,应用多核(~1H、~(13)C和~(51)V)、扩散排序谱(DOSY)以及变温NMR等谱学技术研究双过氧钒配合物NH_4[OV(O_2)_2{2-(2'-Pyri-dine)- [midazole}]·4H_2O(简写为bpV(Imi-Py))和咪唑类配体(咪唑、2-甲基-咪唑、4-甲基-咪唑和组氨酸)的相互作用,其从强到弱的顺序为咪唑≈4-甲基-咪唑>2-甲基-咪唑>组氨酸.研究结果表明,咪唑环上取代基团空间位阻对反应平衡产生较大影响,同时竞争配位的结果导致新的6配位过氧物种[OV(O_2)_2L]~-(L为咪唑类配体)的生成,当配体为4-甲基-咪唑和组氨酸时,生成的则是一对异构体.To understand the substituting effects of imidazole ring on the reaction equilibrium,the interactions between diperoxovanadate complex NH_4[OV(O_2)_2{2-(2'-Pyridine)-Imidazole}]·4H_2O (abbr.bpV(Imi-Py)) and a series of imidazole-like ligands (imidazole,2-methyl-imidazole,4-methyl-imidazole,and histidine) in solution were explored using multinuclear (~1H,~(13)C,and ~(51)V) magnetic resonance,diffusion ordered spectroscopy (DOSY),and variable temperature NMR in 0.15 mol·L~(-1) NaCl ionic medium for mimicking the physiological conditions.The experimental results indicated that the activities of bpV(Imi-Py) and organic ligands were as follows:imidazole≈4-methyl-imidazole>2-methyl- imidazole>histidine.The stedc effect of the organic ligands affects the reaction equilibrium.At the same time,new six- coordinated peroxovanadate species [OV(O_2)_2L]-(L=imidazole-like ligands) were formed due to the competitive coordination between 2-(2'-pyridyl)-imidazole and the imidazole-like ligands.When the ligand was 4-methyl- imidazole or histidine,a pair of isomers was formed.国家自然科学基金(20772027);; 973子课题(2003CB716005);; 湖南省自然科学基金(06JJ30004);; 中国博士后科学基金(20070410805);; 湖南省教育厅青年项目(068028);; 卫生部(福建省)卫生教育联合攻关计划(3502220051027);; 厦门市重大疾病攻关研究基金(Wkj2005-2-019);; 固体表面物理化学国家重点实验室开放基金和湖南科技大学博士基金(E55107)资

NMR studies on interactions between diperoxovanadate complexes and 1-methylimidazole

To understand the effects of organic ligands of the diperoxovanadate complexes on the reaction equilibrium, the interactions between a series of diperoxovanadate complexes [OV(O-2)(2)LL '](n-) [n=1 similar to 3; LL '=oxalate, abbr. oxa; picolinate, abbr. pic; 2,2 '-bipyridine, abbr. bipy; and 1,10-phenanthroline, abbr. phen. The corresponding peroxovanadate species abbreviate bpV(oxa), bpV(pic), bpV(bipy), and bpV(phen)] and I-methylimidazole (abbr. N-Me-Im) in solution were explored using multinuclear (H-1, C-13, and V-51) magnetic resonance, COSY, and variable temperature NMR in 0.15 mol/L NaCl ionic medium for mimicking the physiological conditions. The experimental results indicated the activity order of these four complexes with I-methylimidazole as follows: bpV(oxa)> bpV(pic)> bpV(bipy)> bpV(phen). Both the coordinating capability and the steric effect of the organic ligands affect the reaction equilibrium. At the same time, a new six-coordinated peroxovanadate species [OV(O-2)(2)(N-Me-Im)](-) is formed due to the competitive coordination

design and implementation of trusted network system based on traffic characteristic

大多数可信网络系统使用的完整性度量技术仅能度量可执行文件而忽略了脚本文件,造成安全隐患。针对该问题,设计实现一种基于流量特征的可信网络系统,不仅对终端进行完整性度量,还利用终端网络流量的周期统计信息判断终端的完整性状态,由此保证脚本文件的可信性。在Linux上实现该系统,结果证明其能够快速检测出特定的脚本病毒。Most integrity measurement technologies of trusted network systems make use of focuses on executable files.In order to solve the problem that integrity measurement can not guarantee the credibility of the script files,this paper designs a trusted network system based on network traffic characteristics.Besides executing the integrity measurement,the system also computes the network traffic statistic information to judge the integrity state of the endpoint,which can be used to detect security threats when executing scripts.The system is implemented on Linux,and application results show that the system can detect some script viruses quickly

混合输入五杆机构的实际轨迹研究

混合输入五杆机构在实际运转时,恒速电机的速度会出现波动,给末端输出的轨迹造成误差。为了可以精准地生成其轨迹,提出了一种实际轨迹综合方法将混合输入五杆机构的动力学考虑在内。通过五次样条函数插值法使得伺服电机的理想运动轨迹二阶连续,给出了考虑机构动力学的混合输入机构动力学模型,描述了动力学模型的求解方法,以伺服电机的输入为设计变量,来改善末端执行器的轨迹误差。实例仿真证实提出的方法可以使得生成的轨迹更为精准

晚期喉癌全喉切除术后复发的相关因素及预后分析

【目的】探讨接受全喉切除术晚期喉癌的复发、预后情况，以及影响复发的因素。【方法】回顾性研究1992—1999年行全喉切除术的晚期喉癌111例，对其生存、复发情况及影响复发的临床病理因素进行分析。【结果】接受全喉切除术的晚期喉癌总的3、5年生存率61．3％、53．8％。总复发率35．0％（39/111），其中原发灶复发率9．0％（10／111），颈部复发率26．1％（29／111）。原发灶出现复发影响预后（P=0．0000）；颈部出现复发亦影响预后（P=0．0113）。原发灶1年内复发占90％（9／10）；颈部复发1年内占75．9％（22／29），2年内复发占93．1％（27／29）。全喉切除术后有无放疗（P=0．032）、切缘状态（P=0．008）影响原发灶复发；N分期（P=0．027）、病变部位（P=0．028）影响颈部复发。【结论】接受全喉切除术的晚期喉癌有较高的复发率；原发灶、颈部复发均影响预后；复发多在术后1年内；全喉切除术后有无放疗、切缘状态影响原发灶复发；N分期、病变部位影响颈部复发

PSO-OCSVM based industrial control system communication behavior anomaly detection method

本发明基于OCSVM算法提出了一种基于PSO-OCSVM的工业控制系统通信行为异常检测方法。该发明利用改进的单类支持向量机算法，根据正常的Modbus功能码序列建立正常通信行为轮廓，设计了一种基于粒子群算法(PSO)进行参数优化的PSO-OCSVM方法，建立入侵检测模型，识别出异常的Modbus?TCP通信流量。该发明提高了异常检测的效率及其可靠性，更适用于实际应用

Wireless smart meter-oriented secure routing method

本发明公开了一种面向无线智能电表的安全路由方法，该方法为每块无线智能电表定义全球唯一的身份标识，代表其接入网络中的真实身份信息；在基于身份的公钥密码体制基础上，采用基于身份标识的加密、签名和认证机制保障无线智能电表数据传输的机密性、完整性和真实性；该方法提出控制逻辑与数据转发分离的无线智能电表安全路由架构，使用基于距离和链路质量相结合的路由算法，计算最优的路由路径，利用基于身份标识的加密、签名机制完成路由的安全发布与更新，并提供多条备选路径，设置路径优先级，增强路由的健壮性。该方法不仅实现了无线智能电表间的双向认证，还为电量收集、状态监测、控制交互等数据传输提供安全可扩展的路由与转发