Analysis of non-mucin protein in human gallstones by MALDI-Tof/Tof mass spectrometry

目的探讨胆固醇结石和胆色素结石中是否存在非黏性蛋白并鉴定蛋白质的组成。方法选取30例行保胆取石术患者的胆囊结石,男性11例,女性19例。采用肉眼观察并结合三酰甘油检测试剂盒(gPO-PAP)测定胆固醇含量的方法对胆结石进行分类,分为20例胆固醇型和10例胆色素型。应用组织裂解法(rIPA)提取胆囊结石蛋白,并用十二烷基硫酸钠聚丙烯酰胺凝胶电泳(SdS-PAgE)与基质辅助激光解析电离飞行时间串联质谱(MAldI-TOf-TOf)分析相结合的方法对该蛋白进行鉴定分析。通过dAVId工具对上述基因进行基因本体(gO)功能富集分析本图及京都基因、基因组百科全书(kEgg)信号转导通路富集分析。结果胆固醇结石和胆色素结石中出现特异性蛋白,经质谱鉴定为转铁蛋白前体蛋白(TrfE)、白蛋白(Alb)、抗胰蛋白酶1(SErPInA1)、免疫球蛋白γ-1(IgHg1)、α血红蛋白(HbA1)、β血红蛋白(Hbb),其中IgHg1不存在于胆色素结石中。结论 TrfE、Alb、SErPInA1、HbA1、Hbb等蛋白共同存在于胆固醇和胆色素结石中,而IgHg1只存在于胆固醇结石中,可见IgHg1蛋白或其对应基因是参与不同胆结石类型成因的重要元素及生物标志物。kEgg分析结果表明,SErPInA1参与补体和凝血级联反应。鉴定和分析胆囊结石中非黏性蛋白的成分及利用资料库的模拟对阐明胆囊结石的发病机制有重要的意义。【Objective】 To examine the presence of non-mucin proteins in the cholesterol calculi and pigment gallstones, and to further identify the type of proteins.【Methods】 Gallstones were obtained from 30 patients at endoscopic minimally invasive cholecystolithotomy, including 11 males and 19 females.The classification of gallstones was applied by visual observation and measurement of concentration of cholesterol through GPO-PAP method.There were 20 cases of cholesterol gallstones and 10 cases of pigment gallstones.The proteins in gallstones were extracted by RIPA, separated by SDS-PAGE and deciphered by matrix-assisted laser desorption/ ionization time of flight(MALDI-Tof-Tof) mass spectrometry.DAVID was used to analyze the GO(gene ontology) function annotation and the KEGG signal pathway of the targeted genes.【Results】Non-mucin proteins, transferrin(TRFE) precursor protein, ALB, SERPINA1, HBA1 and HBB were found and identified in cholesterol stones and pigment stones; while IGHG1 was only observed in cholesterol stones.【Conclusions】 The six proteins have been first figured out to exist in human gallstones.Interestingly, IGHG1 and its associated genes, solely present in cholesterol gallstones may play a novel role in the classification and/or development of gallstone as a biomarker.In KEGG pathway, SERPINA1 is involved in pathway of complement and coagulation cascades.It is important to further study the origin and the functions of these non-mucin proteins for understanding the pathogenesis of gallstones.贵州省省长基金临床应用课题专项研究项目[No:黔省专合字(2012)94号]; 国家国际科技合作项目(No:2014DFA31420

Surface Chemical Properties of Mo2C, W2C, Mo2N and W2N Probed with CO, CO2and O2 Adsorption: A DFT Analysis

作为具有吸引力的电极材料，过渡金属碳化物与氮化物被应用在许多电化学储能及能量转换领域. 本工作中，通过密度泛函理论计算，以及一氧化碳 （CO）, 二氧化碳（CO2）和 氧气（O2）分子的吸附来表征钼和钨的碳化物及氮化物，如碳化钼（Mo2C）、碳化钨（W2C）、氮化钼（Mo2N）和氮化钨（Mo2C）的表面化学性质. 这些探针分子可为研究钼和钨的碳化物及氮化物表面在酸性/碱性的氧化还原性质提供衡量方法. 计算结果表明，CO2分子的吸附发生在路易斯碱位，其碱性降低顺序为α-W2C(001) > α-W2N(001) > β-Mo2C(001) > γ-Mo2N(100). 此外，CO和O2分子吸附可用于评估上述碳化物及氮化物的还原能力，其还原性减小顺序为β-W2C(100) > α-Mo2C(100) > α-W2N(001) > α-W2C(001) > β-Mo2C(001) > γ-Mo2N(100). 由于还原本性，使得上述这些碳化物和氮化物成为在各种催化反应中有可能取代贵金属的良好候选材料.Transition metal carbides and nitrides are attractive materials for electrodes in many electrochemical energy storage and conversion applications. In the present study, we use density functional theory slab calculations to characterize the surface chemical properties of molybdenum (Mo) and tungsten (W) carbides and nitrides, namely, Mo2C, W2C, Mo2N and W2N with the adsorption of CO, CO2 and O2. These probing molecules provide measures of in both acidity/basicity and redox property of for the surfaces of these carbides and nitrides. Our results show that Lewis basic sites were responsible for CO2 adsorption and the basicity follows followed an order of α-W2C(001) > α-W2N(001) > β-Mo2C(001) > γ-Mo2N(100). Both CO and O2 adsorption provide measures of in the reducing ability of these carbides and nitrides. The results showed a reducing ability in the order of β-W2C(100) > α-Mo2C(100) > α-W2N(001) > α-W2C(001) > β-Mo2C(001) > γ-Mo2N(100). The reducing nature of these carbides and nitrides make them good candidates to substitute noble metals in various catalytic reactions.We acknowledge the support of NSF-CBET program (Award no. CBET-1438440).We acknowledge the support of NSF-CBET program (Award no. CBET-1438440).作者联系地址：美国南伊利诺伊大学化学与生物化学系, 卡本代尔, 伊利诺伊 62901Author's Address: Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL 62901, US

重离子周边碰撞和中心碰撞引起的不同裂变行为

本实验同时研究了 4 0 Ar+ 2 0 9Bi反应中周边碰撞和中心碰撞两者产生的关联裂变碎片 ,以及其与α粒子的再关联 .对裂变碎片质量分布和能量分布随热裂变核初始温度演化的系统分析 ,发现中心碰撞和周边碰撞所形成的热核存在着不同的裂变行为