Experimental Boosting of the Oxygen Reduction Activity of an Fe/N/C Catalyst by Sulfur Doping and Density Functional Theory Calculations

向Fe/N/C非贵金属催化剂中再引入S掺杂是进一步提高其氧还原催化活性的有效方法。为了探究活性提高的原因,本文以三聚氰胺-甲醛树脂为前驱体,氯化; 钙为模板,氯化铁为铁源,通过添加硫氰化钾(KSCN)来控制热解催化剂的S掺杂量。通过对比分析催化剂的物化性质,结合密度泛函理论(DFT)计算,分; 析S掺杂促进Fe/N/C催化剂氧还原活性的原因。透射电子显微镜(TEM)和N_2吸脱附等温线测试结果表明,S元素可抑制含铁纳米粒子的形成,促使形; 成多孔碳结构,提高比表面积。X射线光电子能谱(XPS)结果表明,适量S前驱体可实现较高的S掺杂含量,得到最优的活性,过量的S反而会导致Fe和S的; 掺杂量同时降低,影响活性。DFT计算结果表明在Fe-N_4大环中引入S掺杂,可增强O_2分子和中间体OOH与Fe-N_4结构中的Fe的相互作用,; 促进形成Fe―O键,从而导致O―O键的键能显著降低,为后续反应O―O键的断裂提供可能,促进ORR反应的进行。S doping in Fe/N/C non-precious metal catalysts is an effective approach to further improve their catalytic activity for the oxygen reduction reaction (ORR). However, the enhancement mechanism is not yet clear. Here, we synthesized an Fe/N/C catalyst using melamine-formaldehyde resin as the N and C precursors, CaCl2 as the template, and FeCl3 as the Fe precursor. The effects of S doping on the morphology, textural property, composition, and ORR catalytic activity were investigated by adding various amounts of KSCN as a precursor. Transmission electron microscopy (TEM) and N-2 adsorption-desorption isotherm results revealed that S prevented the growth of Fe-containing nanoparticles, and facilitated the formation of a porous structure, which increased both the catalyst surface area and mass transfer rate. X-ray photoelectron spectroscopy (XPS) results indicated that a suitable amount of S precursor led to a high doping level of S and provided the highest ORR activity. However, too much S in the precursor decreased the doping levels of both Fe and S, due to the formation of FeS, which could be completely removed by acid leaching. Density functional theory (DFT) calculations showed that the addition of S in an Fe-N-4 macrocycle could enhance the interaction strength of the Fe-O bond between the O-2 molecule or the intermediate OOHspecies and Fe in the Fe-N-4 structure, resulting in a significant decrease in the O-O bond energy, and may help in bond breaking in subsequent reactions, facilitating the ORR process.National Natural Science Foundation of China [21373175, 21621091

Experimental Study on the Effect of Sanchong Banxia Baizhu Tianma Decoction on the Expression of 5-HT1B/1D Receptor in the Brain of Rats with Migraine

目的探索三虫半夏白术天麻汤治疗偏头痛的作用机制。方法建立硝酸甘油致大鼠偏头痛模型,给予半夏白术天麻汤高、中、低剂量灌胃干预7 d,以苯甲酸利扎曲普坦为西药阳性对照药物,并予空白组、模型组进行对照。运用RT-PCR检测5羟色胺1B、1D(5-HT1B/1D)受体的基因表达。结果 1)对5-HT1B受体表达的影响:与空白组相比,模型组显著低于空白组(P0.05),中药中剂量组、中药高剂量组、西药组及联合用药组显著低于空白组(P0.05)。2)对5-HT1D受体表达的影响:与空白组相比,中药中剂量组显著降低(P0.05);与模型组相比,各组无显著差异(P>0.05);与中药中剂量组相比,空白组、中药低剂量组、西药组、联合用药组较中药中剂量组显著升高(P0.05)。结论 5-HT1B/1D受体调节异常为偏头痛的发病环节之一。三虫半夏白术天麻汤可以提高偏头痛大鼠脑组织5-HT1B受体的基因表达,对5-HT1D受体的基因表达具有双向调节作用,临床运用,剂量不宜过大。Objective: To explore the mechanism of Sanchong Banxia Baizhu Tianma Decoction in the treatment of migraine. Methods: Migraine model of SD rats were set up with nitroglycerin,given Banxiabaizhutianma decoction of high,medium and low-dose intervention respectively for 7 days,taking Rizatriptan Monobenzoate as a positive control drug medicine,compared with the blank control group and the model group. RT-PCR was used to test the genetic expression of the 5-HT1 B receptor and the 5-HT1 D receptor. Results: The influence on the expression of the 5-HT1 B receptor: compared with the blank control group,the model group was significantly lower than the control group(P 0.05);traditional Chinese medicine medium dose group,high dose group,western medicine group and the combination group were significantly lower than the blank control group(P 0.05). The influence on the expression of 5-HT1 D receptor:compared with the blank control group,traditional Chinese medicine medium dose group decreased significantly(P 0.05);compared with the model group,there was no significant differ ence among them(P > 0.05);compared with the traditional Chinese medicine medium dose group,the blank control group,traditional Chinese medicine low dose group,western medicine group and combination group were significantly higher(P 0.05). Conclusion: 5-HT1B/1D receptor dysregulation is one cause of the pathogenesis of migraine. Sanchong banxia baizhu tianma decoction can improve the genetic expression of 5-HT1 B receptors in migraine rats′ brains,and has a dual-direction regulation on genetic expression of the 5-HT1 D receptors. In the field of clinical application,the dose should not be too large.2012福建省中医药科研课题(wst201211

Experimental Study on the Basic Effect of Huatan Anshen Decoction and on Orexin Expression in Hypothalamus of Insomnia Rats

目的：研究化痰安神方治疗失眠症的药效学基础及其对失眠大鼠下丘脑食欲素表达的影响,揭示本方部分药效学机制。方法：通过小鼠自发活动实验、戊巴比妥钠阈下及阈上睡眠协同实验探索化痰安神方治疗失眠症的药效学基础;通过对氯苯丙氨酸（PCPA）制造失眠大鼠模型,分为中药组、西药组、空白组、模型组,每组干预7天,使用免疫组化检测实验大鼠下丘脑食欲素（Orexin）。结果：（1）化痰安神方可抑制小鼠自发活动,与空白组比较,具有显著差异（P〈0.01）;（2）对戊巴比妥钠阈下入睡率的影响：中药组、对照组、西药组实验小鼠入睡率分别为：65%、72%和100%,西药组入睡率明显高于中药组、对照组（P〈0.01）;睡眠持续时间,中药组长于西药组（P〉0.05）,西药组长于对照组（P〈0.05）;（3）对戊巴比妥钠阈上睡眠情况的影响：中药组睡眠持续时间明显长于西药组（P〈0.01）,西药组长于对照组（P〈0.01）;（4）对氯苯丙氨酸（PCPA）致失眠大鼠各组下丘脑食欲素表达水平无差异（P〉0.05）。结论：化痰安神方具有一定的镇静催眠作用,可明显延长失眠患者的持续睡眠时间,其作用机理可能不是通过调节食欲素水平这一途径。Objective： To study the basic effect of Huatan Anshen decoction and the effect on orexin expressions in Hypothalamus of insomnia rats and reveal the partial pharmacodynamics mechanism. Methods： Spontaneous activity in mice and synergistic action test of pentobarbital sodium were observed to study the basic effect of Huatan Anshen decoction. The second part, through para chlorophenylalanine （PCPA） making rat model of insomnia, divided into Chinese medicine group and Western medicine group, blank group, model group, each group of rats were intervened for 7 days, Hypothalamus Orexin was detected by immunohistochemisty. Results： （1） Huatan Anshen Decoction can inhibit the spontaneous activity of mice, compared with the control group, with significant difference （P〈0.01）. （2） Effect on the rate of sleep pentobarbital sodium： Chinese medicine group and control group, western medicine group mice sleep rates were： 65%, 72% and 100%. The rate of western medicine group was significantly higher than that of traditional Chinese medicine group and control group （P〈0.01）. Sleep duration： Chinese medicine group was longer than the western medicine group （P〈0.05）, the western medicine group was longer than the control group （P〈0.05）. （3）Sleep duration of Chinese medicine group was significantly longer than the western medicine group （P〈0.01）, and the western medicine group was significantly longer than the control group（P〈0.01）. （4） There was no difference in the expression level of orexin （P〈0.05） in the hypothalamus of insomnia rats induced by phenylalanine （PCPA）. Conclusion： Huatan Anshen decoction has sedative and hypnotic effects, can prolong the duration of sleep in patients withinsomnia. The mechanism of Huatan Anshen decoction to prolong the duration of sleep in patients with insomnia may not be regulated by the level of orexin pathways.2013福建省中医药科研课题（批准号：wzln201311

The Development of a New Type of Medical Rehabilitation Brace for Lower Limbs

本文阐述了一种新型医用下肢康复支具的研制过程。该装置主要由承重装置、负重装置、负重调节装置以及压力检测装置等结构组成,具有调节、设定以及控制负重载荷等功能,可使行内固定术后的下肢骨折患者早期进行负重、行走功能锻炼,促进其骨折愈合及肢体功能康复,减少术后并发症,具有一定的实用价值。The paper expounded the development of a new type of medical rehabilitation brace for lower limbs. The device was mainly composed of different structures including the hip weight-bearing device, the foot weight-bearing device, the weight-bearing adjustment device and the pressure detection device. The brace was designed to allow patients to carry out weight-bearing exercises and walking exercises in early postoperative period after receiving internal fixation of lower limb fracture. It could also promote fracture healing and functional recovery of lower limbs and reduce postoperative complications, which is of certain clinical value

盘状软骨的关节镜下治疗及临床特点

目的　总结盘状软骨的关节镜下治疗的方法和疗效及临床特点 ,为日后更好的诊治盘状半月板提供依据。方法　 31例(31膝 )盘状软骨患者分别采用关节镜下成形术 2 7例和全切术 3例、 1例边缘撕裂成形后缝合修补术。结果　按Ikeuchi氏膝关节评价等级评定疗效 :优 17例 (5 4 8%) ,良 11例 (35 5 %) ,可 3例 (9 7%)。 3例术后自述有弹响 ,查体见其中 2例有外侧半月残留部不稳的体征。结论　盘状软骨在膝关节屈伸运动中所产生的非生理性运动 ,易造成盘状软骨的破裂、关节软骨磨损以至关节软骨早期出现退行性改变等 ,症状性盘状软骨一旦发现 ,无论破裂与否均应早期手术。关节镜下盘状软骨成形术可获得优良疗效。盘状软骨引发的弹响交锁有其特征性临床特点 ;MRI对盘状软骨诊断有确诊意义

戊型肝炎病毒中和性单克隆抗体的鉴定

阻断实验发现,用戊型肝炎病毒(HEV)衣壳蛋白重组抗原制备的8株抗HEV单克隆抗体(mAb),分别识别3个构象表位和2个线性表位。用抗体捕获反转录PCR方法证实,其中识别2个构象表位的3个mAb可以直接捕获HEV颗粒,表明这2个表位位于HEV颗粒的外表面。识别这两个表位的mAb8C11和8H3均可中和HEV对恒河猴的致病性和感染性。mAb8C11缩短排毒时间的效应较明显,而mAb8H3延迟机体抗HEV抗体阳转时间的效应较明显。二者的中和效应具有较明显的协同作用。中和单抗8C11、8H3对戊肝不同感染时期的血清均有显著阻断作用,Fab片段的阻断作用与完整抗体类似,表明这两个mAb对应的中和表位是HEV体液免疫应答的优势表位

四氧化三钴催化燃烧形貌效应研究

通过水热法和微乳辅助水热法,合成了海胆状、片状以及球形3种不同形貌的四氧化三钴,并对其甲烷以及一氧化碳催化燃烧性能进行了测试,结合BET、SEM、XRD等微观结构表征,分析了催化性能和微观结构的构效关系。结果表明,四氧化三钴对甲烷和一氧化碳催化燃烧反应均具有明显的形貌效应,但四氧化三钴形貌对两种反应的影响表现出不同的规律。对于一氧化碳催化燃烧反应,海胆状四氧化三钴催化性能最佳,球形四氧化三钴优于片状四氧化三钴;对甲烷催化燃烧反应,海胆状四氧化三钴>片状四氧化三钴>球形四氧化三钴

四氧化三钴催化燃烧形貌效应研究

通过水热法和微乳辅助水热法,合成了海胆状、片状以及球形3种不同形貌的四氧化三钴,并对其甲烷以及一氧化碳催化燃烧性能进行了测试,结合BET、SEM、XRD等微观结构表征,分析了催化性能和微观结构的构效关系。结果表明,四氧化三钴对甲烷和一氧化碳催化燃烧反应均具有明显的形貌效应,但四氧化三钴形貌对两种反应的影响表现出不同的规律。对于一氧化碳催化燃烧反应,海胆状四氧化三钴催化性能最佳,球形四氧化三钴优于片状四氧化三钴;对甲烷催化燃烧反应,海胆状四氧化三钴>片状四氧化三钴>球形四氧化三钴