C–X(X = Cl, Br, I) bond dissociation energy as a descriptor for the redispersion of sintered Au/AC catalysts

负载型Au基催化剂在工业过程中具有非常广泛的潜在应用,如催化加氢/脱氢过程、精细化学品合成、能源催化转化及环境保护等过程,表现出很高的催化活性和选择性.Au基催化剂活性物种或活性中心基本由纳米粒子或化合物构成,但在应用过程中因Ostwald熟化效应或粒子迁移作用,尤其是高温高压等苛刻反应条件下,均随应用时间延长从小尺寸粒子逐渐长为大粒子,造成活性降低或完全失活,这也是负载型催化剂失活的最主要原因之一.其中因成本、稀缺等特性,负载型Au催化剂的烧结问题是影响和制约其应用的主要因素.除可通过载体改性、助剂和官能团配位稳定等方法来延缓其失活过程外,对已烧结催化剂的高效、快捷和绿色的再分散/再生过程也具有基础和应用研究的重要意义.活性炭载Au催化剂(Au/AC)广泛应用于乙炔氢氯化反应中,以期替代高毒性的汞基催化剂,但在反应过程中因高活性的Au~(3+)物种易被还原而形成Au~0物种进而烧结导致失活;如新鲜Au/AC催化剂表面的Au粒子尺寸为1-2 nm,经乙炔氢氯化反应后变为33 nm左右;随之在453 K、0.1 MPa、乙炔体积空速(GHSV)为600 h~(-1)、氯化氢与乙炔摩尔比为1.1的反应条件下,乙炔转化率从81.8%降至11.2%.如何有效对大粒子Au再分散/再生可为其应用提供有力支撑.有研究表明,气相CHI_3在甲醇羰基化反应过程中明显改变Au/AC表面的Au粒子尺寸;或采用浓盐酸或王水也可将烧结的Au/AC催化剂进行再分散/再生.但已有的Au基催化剂再分散/再生过程均伴随着强酸、强氧化或高毒性在分散剂的应用,对环境的影响及后续处理有明显的局限性,且再分散机理尚不明确.在前期工作基础上,本文采用系列卤代烃(碘代烃、溴代烃和氯代烃)对烧结的Au/AC进行再分散/再生研究.结果表明,在室温常压条件下CHI_3可以快捷高效地对烧结Au/AC催化剂进行再分散/再生,具有最优的再分散性能;通过对系列碘代烃C-I键的解离能分析,发现C-I解离能越低越有利于大粒子Au的再分散.同时,溴代烃和氯代烃对烧结的Au/AC催化剂也具有再分散能力,但比碘代烃的再分散效率低.C-X键的解离能与再分散效率有高相关性,即C-X键的解离能越低越有利于Au的再分散.总体上,三类卤代烃再分散效率高低顺序为C-I>C-Br>C-Cl.进而,通过不同分散过程中Au粒子分散状态推测了卤代烃对Au粒子的再分散机理,即卤代烃先在Au粒子表面化学吸附,然后C-X键解离,形成Au-X物种,小粒子Au在AC表面聚集并稳定,最后形成高分散Au粒子(粒径<1 nm)催化剂.以乙炔氢氯化反应考察了再生Au/AC催化剂性能,结果表明,该催化剂上乙炔转化率可达79.4%,基本恢复至初始水平,且该方法可对失活催化剂进行多次高效再生.Disintegration or redispersion of supported sintered gold nanoparticles(Au NPs) in the presence of alkyl halide can give catalyst regeneration or redispersion of sintered Au catalysts. The selectivity of alkyl halides, temperature and size distributions were investigated to elucidate the redispersion of Au NPs during halide-induced decomposition. This study proved that the alkyl halide induced the redispersion of sintered Au NPs which depended on the R–X(X = I, Br, Cl) bond dissociation energy(BDE) and thus provided a simple descriptor for the regeneration of inactive supported Au cata-lysts. A correlation between the BDE of R–X and dispersion efficiency was established. The tendency for disintegration and redispersion followed the R–X BDE of the alkyl halide. Compared to alkyl chlorides and bromides, iodides were more efficient for redispersing sintered Au NPs. As a descriptor, the BDE of R–I played a crucial role in particle redispersion. These findings provided insights into the mechanism of organic halide-induced Au NP disintegration and the effect of the halide type on the redispersion of sintered catalysts.国家自然科学基金(21403178,21473145,21503173,91545115);; 教育部创新团队发展计划(IRT_14R31);; 福建省青年教师教学科研基金(JA15003

厦门市86例吸毒人员的心理状况调查

目的采用抑郁自评量表(SDS)、焦虑自评量表(SAS)和90项症状清单(SCL-90)综合分析吸毒人员的心理状况。材料与方法使用SDS、SAS和SCL-90对厦门市86名吸毒人员进行心理健康分析,并与常模比较;进一步分析、比较吸毒人员性别、职业、婚姻状况、文化程度及吸毒方式之间的心理健康的差别。结果所有吸毒人员的SDS,SAS,SCL-90各因子评分均比常模高(P<0.001);男性SAS及SCL-90中的偏执因子分比女性高(P<0.05);高中以上文化程度的吸毒人员在SCL-90中的抑郁和焦虑因子分比初中文化的高(P<0.05),但与小学文化的无显著性差别。有职业的吸毒人员的人际关系因子分比无职业的高(P<0.1)。结论吸毒人员有明显的心理障碍,尤其是抑郁及焦虑广泛存在,在强制性戒毒时,可给予适当的药物,同时加强心理干预

石子级配对混凝土工作性的影响

基于研究石子级配对混凝土工作性的影响,对混料设计方法设计了10组三级配石子混凝土配合比,测试了不同石子级配的混凝土的坍落度和扩展度,并对测试结果进行优化。结果表明:石子级配对混凝土工作性有重要影响,良好的石子级配可有效改善混凝土的工作性。采用混料设计的方法设计的混凝土配合比,可在尽量少实验量的基础上快速有效得到满足工作性要求的石子比例

厦门市86例吸毒人员的16项人格因素量表分析

目的:采用卡特尔16项人格因素量表(16PF)分析吸毒人员的人格特征。方法:使用16PF对厦门市86名吸毒人员进行人格分析,并与常模比较;进一步分析吸毒人员不同性别之间的人格特征。结果:男、女吸毒人员与正常成年人对照存在明显的人格偏差:除男性O因子分,女性M及Q1因子分无显著性差异(P>0.05)外,其它各因子分之间均有统计学差异(P<0.05);不同性别吸毒人员的人格之间也有差异,在M因子分方面,女性高于男性,除此以外,A、C、E、F、G、I、L、N、Q、Q1、Q2、Q3因子分均是男性吸毒者较女性高(P<0.05);在B、Q因子分之间无统计学差异,其它各因子之间均有显著性差异(P<0.05);结论:吸毒人员有明显的人格偏离,不同性别的人格特征表现不同,在强制性戒毒及心理疏导的同时,要注意人格特点的影响

Nuclear Gluon Distributiom in the Extended x-Rescaling Model

利用推广X重新标度模型，并结合考虑核内邻近核子的海夸克和胶子发生空间重叠而在小X区域引起的核遮蔽效应，计算了Sn和C核胶子分布函数之比值，所得结果与nMC组最新实验数据符合甚好。Using the extended x-rescaling model and taking account of the nuclear shadowingeFFect by the spatial overlap of sea quarks and gluons From neighbouring nucleons in thenucleus in small x region, we calculate the ratios Gsn(x)/Gc(x).The calculated results arein good agreement with recent NMC experimental data国家及河北省自然科学基金和省教委资

Influence of Inimicusjaponicasliver extract on mice's immune function

目的研究鬼鲉肝脏提取物对免疫低下小鼠免疫功能的影响。方法采用环磷酰胺诱导建立免疫低下动物模型,免疫器官重量法测定胸腺指数和脾脏指数,碳粒廓清法测定小鼠单核巨噬细胞的功能,绵羊红细胞免疫法测定小鼠体液免疫功能,采用血细胞计数仪检测小鼠外周血常规,采用ElISA方法测定小鼠血清中Tnf-α、Il-1β、Il-2、Il-6的水平,采用流式细胞仪测定脾细胞周期。结果鬼鲉肝脏提取物可以减缓免疫低下小鼠体重的下降趋势以及脾脏和胸腺的损伤、促进其脾细胞的分裂和增殖、增加其单核巨噬细胞吞噬功能和血清溶血素含量以及白细胞数、中性粒细胞数、淋巴细胞数和单核细胞数和血清中Tnf-α、Il-1β、Il-2、Il-6的含量。结论鬼鲉肝脏提取物可以增强免疫低下小鼠的免疫功能。Objective To investigate the influence of Inimicus japonicas liver extract on the immune function of immunosuppressed mice.Methods Immunosuppression animal model was established by cyclophosphamide induction.The immunity organs were weighed to measure the thymus index and spleen index;the clearance of charcoal particles method was used to measure mice's mononuclear macrophages functions,and sheep red blood cells immunizations was used to measure mice's humoral immune functions;mice's blood counts were measured by blood-counter system,and Enzyme-linked Immuno Sorbent Assay(ELISA)was used to measured the TNF-α,IL-1β,IL-2and IL-6level in blood serum;the spleen cell cycle was measured by flow cytometry.Results Inimicus japonicas liver extract significantly improved the thymus index and spleen index,promoted the division and proliferation of spleen cells,improved the mononuclear macrophages functions,increased the hemolysin level of blood serum and the levels of leukocytes,neutrophils,lymphocytes and monocytes,and also increased the levels of TNF-α,IL-1β,IL-2and IL-6in blood serum.Conclusion Inimicus japonicas liver extract enhanced immunosuppressed mice's immune function.海洋公益性行业科研专项(201205024-1)资

Resource chemistry evaluation of fatty acids on Sipunculus nudus collected from different habitats

目的对裸体方格星虫样品中脂肪酸类成分进行比较研究。方法采用气相色谱-质谱联用技术(GCMS)对12个裸体方格星虫样品中的26种脂肪酸进行了含量测; 定,并进一步对各样品中的各成分的含量进行了主成分分析。结果对裸体方格星虫样品的测定结果显示各样品26种脂肪酸类成分总含量范围为198.20; ~578.05mug/g,总含量最高的样品是海南三亚的裸体方格星虫体腔液样品(S12);各产地样品中脂肪酸类成分总含量均呈现体腔液部位高于外壁+; 内脏部位。测定样品的26种脂肪酸中,不饱和脂肪酸总含量高于饱和脂肪酸总含量;多不饱和脂肪酸中,亚油酸和alpha-亚麻酸含量最高,分别占总含量的; 1.54%~5.65%和1.61%~4.94%;单不饱和脂肪酸中顺芥子酸含量最高,分别占各样品总含量的14.66%~46.41%;基于26种脂肪; 酸的含量测定结果对12个裸体方格星虫样品的PCA分析结果显示不同产地裸体方格星虫的外壁+内脏样品相互接近,体腔液样品差别较大。结论裸体方格星虫中; 脂肪酸不仅种类多样、含量丰富,而且具有多种重要活性作用的不饱和脂肪酸比例合理。本研究中对脂肪酸类成分的研究结果将对进一步开发利用裸体方格星虫提供; 一定的理论基础。Objective To compare and evaluate fatty acids in Sipunculus; nudus.Methods 26fatty acids in 12batches of S.nudus samples were; determined by GC-MS,and the data were further handled by a PCA scatter; plot to compare the content variation of the samples.Results The total; contents of 26fatty acids in the samples ranged from 198.20mug/g(S9)to; 578.05mug/g(S12),and the sample from Hainan had the highest total; contents of 26fatty acids.The total contents of 26fatty acids in; coelomic fluid were higher than those in body wall and intestine in; S.nudus collected from all the regions.The total contents of unsaturated; fatty acids were higher than saturated fatty acids.Among the; polyunsaturated fatty acids,the contents of linoleic acid were between; 1.54%and 5.65%and the contents ofalpha-linolenic acid were between; 1.61%and 4.94%.The contents of cis-sinapic acid were the highest in; monounsaturated fatty acids,which ranged from 14.66%to; 46.41%.Moreover,the results of PCA performed on the basis of the; contents of 26tested compounds showed the difference of the parts in; S.nudus samples. Conclusion S.nudus had an excellent source of fatty; acids with reasonable proportion of unsaturated fatty acids. The; research results provided a firm basis for further exploitation and; development of S.nudus.海洋公益性行业科研专

Effects of extracts of Sipunculus nudus Linnaeus on thrombosis

目的通过对家兔体外血浆血小板聚集和凝血功能的影响、对大鼠动-静脉血流旁路血栓形成的影响、对dPPH自由基的清除作用及对纤维蛋白的溶解作用,综合评价星虫提取物对血栓形成的影响。方法以二磷酸腺苷(AdP)诱导血小板聚集,采用比浊法观察星虫提取物对家兔体外血浆血小板6MIn聚集率和最大聚集率的影响;采用凝固法来评价星虫提取物对家兔体外血浆凝血酶原时间(PT)、活化部分凝血激酶时间(APTT)及凝血酶时间(TT)的影响;采用动静脉旁路模型,来研究星虫提取物对大鼠动静脉旁路血栓形成的影响;采用2,2-二苯基-1-苦肼基(dPPH)自由基清除率法,来评价星虫提取物清除OH自由基的作用;通过纤维蛋白平板实验研究星虫提取物的纤溶活性。结果星虫提取物能明显抑制AdP诱导的家兔体外血小板6MIn聚集率和最大聚集率,能明显延长家兔PT、APTT和TT,明显抑制大鼠动静脉旁路血栓形成,减轻血栓湿重和干重;具有清除OH自由基的作用以及不同程度地溶解纤维蛋白的作用。结论星虫提取物具有很好的抗血栓形成的作用。Objective To evaluate the thrombotic activity of Sipunculus nudus extracts by investigating their effects on rabbit plasma platelet aggregation and coagulation function in vitro,and the effect on the model of artery-vein bypass thrombosis in rats,as well as capacity of eliminating DPPH free radicals and dissolving fibrin.Methods Inhibition rates of platelet aggregation in vitro were determined in the model of platelet aggregation induced by adenosine diphosphate.Their anticoagulative effects were also evaluated with prothrombin time(PT),activated partial thromboplastin time(APTT) and thrombin time(TT).The model of artery-vein bypass thrombosis was established to observe their antithrombotic effect.The antioxidant effects were investigated by DPPH free radical scavenging capability test.The fibrinolytic activity was determined by fibrin plate.Results The results showed that the extracts had significant inhibition effect on platelet aggregation,and could obviously prolong PT,APTT and TT,inhibited the artery-vein bypass,reduced the thrombus weight significantly(wet or dry).And the extracts of S.nudus also could eliminate DPPH free radicals and dissolve fibrin at different degree.Conclusion Extracts of S.nudus had strong antithrombotic effect.海洋公益性行业科研专项(201205024)资