离子诱导气溶胶成核过程的研究

离子诱导成核是大气气溶胶形成的重要路径之一。大气中团簇离子的形成,主要由宇宙射线电离空气产生的初级离子与H2O、H2SO4、HNO3、NH3、有机物等物质发生的离子-分子反应而产生。成核是团簇离子生长和蒸发相互竞争的一个过程,团簇离子生长到临界核尺寸时,便可自发生长。研究表明临界核大小约1.6 nm,对应的粒子的质量数在5000 amu以上。离子诱导生成的气溶胶粒子对气候的影响以及离子诱导成核在大气成核事件中是否占主要作用还存在很大争议,这需要进行进一步的外场观察、理论模拟、实验室研究来充分弄清离子诱导成核机理。     

有机酸促进大气气溶胶成核机理研究进展

大气中有机成分种类繁多，结构复杂，有机酸作为大气环境各相中含量最丰富的有机物种之一备受关注，最近的实验研究表明，部分芳香族有机酸能够促进硫酸-水团簇的成核及生长。理论计算也表明在有机酸的存在下，一些小分子有机酸与硫酸通过氢键的相互作用形成非均相的团簇降低了成核壁垒，从而促进团簇的形成，对新粒子的成核产生具有重要促进作用。鉴于有机酸对大气气溶胶成核机理研究具有重要的意义，文中对其近些年在实验和理论上的进展进行了回顾，并对未来前景作了展望。     

2-甲基甘油酸-硫酸/甲磺酸团簇的大气物化特性研究

气溶胶通过散射或吸收长波和短波辐射影响着地球的气候系统。 2-甲基甘油酸是一种气溶胶示踪剂, 在 大气观测和成核实验中被多次观测到。而硫酸和甲磺酸作为非常重要的气溶胶前体物, 也受到广泛的关注。基于 DF-MP2-F12/VDZ-F12 结合 M06-2X/6-311++G(3df,3pd) 理论方法对 2-甲基甘油酸-硫酸/甲磺酸团簇进行了计算模拟, 分析了其在大气中的物理化学性质。结果表明 2-甲基甘油酸-硫酸团簇和 2-甲基甘油酸-甲磺酸团簇的吉布斯自由能 具有相同的温度依赖性。 2-甲基甘油酸-硫酸/甲磺酸团簇会优先蒸发 2-甲基甘油酸分子而不是硫酸/甲磺酸分子, 且随 着尺寸增加, 2-甲基甘油酸分子的蒸发速率迅速增加。此外, 还计算了 2-甲基甘油酸-硫酸/甲磺酸团簇的瑞利散射强 度和极化率, 有助于理解此类团簇对大气光辐射的影响。     

乙醇/水混合团簇的多光子电离质谱研究

利用激光器(输出波长355nm)激发乙醇和水二元混合团簇中的离子-分子反应,运用飞行时间质谱技术检测反应后生成的团簇离子.实验观测到多个序列的质子化团簇离子:(C2H5OH)nH 和(C2H5OH)n(H2O)mH (n=1-12,m=1-4),其产生是通过团簇内的质子转移反应.通过对团簇离子的峰强度同乙醇数目n和水分子数目m的关系的研究发现,团簇离子(C2H5OH)8(H2O)H 是幻数结构.     

飞秒强激光脉冲与氢团簇相互作用产生的最大质子能量与团簇尺寸的相关性

报道了飞秒强激光脉冲(60 fs,790 nm,2×1016W/cm2)与纳米尺寸的氢团簇(半径rc约为1~3 nm)相互作用,产生的最大质子能量Emax对于团簇半径rc相关性的实验研究结果。从激光-氢团簇相互作用产生的质子的飞行时间谱测量以及团簇尺寸的瑞利散射诊断结果,得到Emax与r2c成线性正比关系,比例系数为0.75,与报道的理论模拟结果一致,表明氢团簇发生纯库仑爆炸。实验结果同时提示,进一步的理论模拟应考虑气体喷流中团簇的尺寸分布。     

随机分布烟幕凝聚粒子对激光的消光特性研究

基于团簇-团簇凝聚(CCA)模型采用蒙特卡罗方法对随机分布的碳黑烟幕凝聚粒子进行了模拟,用离散偶极子近似(DDA)方法研究了该模型对激光的消光特性.研究表明:碳黑烟幕凝聚粒子对激光的消光特性受原始微粒数量及粒径的影响,粒子的凝聚将削弱烟幕的红外消光性能;当凝聚结构中原始微粒的数量一定时,存在使烟幕红外消光性能达到最大的原始微粒粒径.     

广州亚运会及残运会期间大气细粒子谱特征分析

2010年广州亚运会及残运会期间利用大气细粒子谱分析仪, 对广州城区和周边地区进行了大气细粒子谱的连续在线监测。研究了测量获得的粒子数浓度谱,分析了粒子数浓度的日变化特征,并对各个模态的粒子数浓度变化分别进行了研究。结果表明大气中气溶胶粒子主要集中在较小粒径。核模态粒子的数浓度主要受交通排放和气相成核影响,其中大学城站点呈单峰值分布,鹤山站点呈三峰值分布。爱根核模态粒子的数浓度受人类活动和核模态粒子涨大成爱根核模态粒子的影响,大学城站点呈三峰值分布,鹤山站点呈两峰值分布。积聚模态粒子和粗粒子模态粒子的数浓度的显著特点是白天低晚上高。鹤山监测站的粗粒子模态粒子的数浓度谱线受海盐溅沫的影响,在夜间有一峰值。最后分析了降雨对大气细粒子的清除作用。     

α-乳糖一水合物太赫兹动力学研究

乳糖一水合物是一种重要的水合物,其结合水对乳糖分子结构的影响一直是相关领域的研究热点之一。利用太赫兹时域光谱技术通过设置温度梯度对α-乳糖一水合物进行低温下的太赫兹动力学研究,发现α-乳糖一水合物在1.2 THz、1.3 THz的2个吸收峰随温度变化而红移。为进一步探究其吸收峰的产生机理,基于密度泛函理论对α-乳糖一水合物分别进行了单分子和晶胞理论计算并分析了α-乳糖一水合物的吸收峰振动模式。结果表明, α-乳糖一水合物的吸收峰来源于水分子和乳糖分子间的相互作用以及乳糖分子骨架振动,晶胞计算比单分子计算对于太赫兹波段内振动模式的预测更加准确。     

激光光谱学的应用:Ⅰ 分子团簇研究

1引言材料的结构、电子和化学特性主要决定于凝聚物所处的状态和它本身的尺寸。团簇是包含2～104个粒子（原子、分子或离子）的有限的凝聚物。它靠物理的或化学的结合力组合在一起，已显示出奇特的物理和化学现象。团簇研究为探索物质从分子到凝聚态物质的逐渐过渡或演变提供了方法和手段，并且由于团簇具有大的表面体积比，因而有利于人们研究微观表面现象。团簇在分子、表面和凝聚态化学物理之间架起了一座桥梁。团簇科学是一门新型的交叉学科，是当代科学基础研究的前沿课题之一。团簇研究除涉及到许多未知的过程和新奇的现象之外，也是…     

利用低温生长法制备水纳米团簇和二维冰

利用低温扫描隧道显微镜(LT?STM)研究了水分子在高定向裂解石墨(HOPG)表面的低温吸附和薄膜生长.在低覆盖度下,水分子在HOPG表面会形成二聚体,三聚体,甚至更大的自组装纳米团簇.在高覆盖度下,水分子形成单分子层厚的二维水膜,其面内结构是非共边的六边形蜂窝状结构,类似于体材料的Ice?Ⅱ相.通过傅里叶变换和莫尔条纹分析,本文发现水膜和HOPG衬底之间存在不同的夹角,表明分子-衬底之间的相互作用很弱.     

In Situ Liquid-Cell TEM Observation of Multiphase Classical and Nonclassical Nucleation of Calcium Oxalate

Calcium oxalate (CaOx) is the major phase in kidney stones and the primary calcium storage medium in plants. CaOx can form crystals with different lattice types, water contents, and crystal structures. However, the conditions and mechanisms leading to nucleation of particular CaOx crystals are unclear. Here, liquid-cell transmission electron microscopy and atomistic molecular dynamics simulations are used to study in situ CaOx nucleation at different conditions. The observations reveal that rhombohedral CaOx monohydrate (COM) can nucleate via a classical pathway, while square COM can nucleate via a non-classical multiphase pathway. Citrate, a kidney stone inhibitor, increases the solubility of calcium by forming calcium-citrate complexes and blocks oxalate ions from approaching calcium. The presence of multiple hydrated ionic species draws additional water molecules into nucleating CaOx dihydrate crystals. These findings reveal that by controlling the nucleation pathways one can determine the macroscale crystal structure, hydration state, and morphology of CaOx.     

光谱法在分子之间相互作用研究中的应用

本文综述了光谱法在生物大分子与小发子相互作用研究中的应用，重点介绍荧光光谱法、紫外－可见光谱法、拉曼光谱法、红外光谱法、圆二色谱法等几种方法的原理及应用，以及它们相对于其它相互作用仪器分析方法的优缺点。     

丙酮-水分子相互作用的傅里叶变换红外光谱研究

采用衰减全反射-傅里叶红外光谱法研究了丙酮和水分子间的相互作用.发现随着丙酮水溶液浓度的减小,丙酮CH<,3键的对称(3538cm-1)和不对称伸缩振动(3441cm-1)吸收峰位置波数减小方向迁徙,CO伸缩振动吸收(1713cm-1)向波数减小方向移动,丙酮浓度为20%时,迁徒至1691cm-1,减小了约19cm-1;同时1647cm-1处的吸收则迁徙至1626cm-1.由此说明丙酮与水分子间形成了氢键,而且氢键的强弱与丙酮水溶液的浓度有关.当磁场作用于丙酮水溶液时红外光谱发生了明显改变,在600-4000cm-1范围内,各吸收峰强度随磁场作用时间的增长由不同程度的增加;水分子OH伸缩振动吸收(3388cm-1)向波数减小的方向迁徒.这一结果则说明磁场作用能够增强丙酮与水分子间的氢键相互作用.     

乙醇在静磁场作用下的傅里叶红外光谱研究

采用衰减全反射-傅里叶红外光谱法研究了静磁场作用对乙醇和乙醇-水溶液的红外光谱的影响.发现磁场作用下乙醇的红外光谱发生了明显的改变,在400～4000cm-1范围内,吸收强度随磁场作用时间的增长而增加;在1031,1054,2052,2075,2842和2865cm-1处,由于磁场的作用出现了新的吸收峰,而且磁场作用时间越长,新的吸收峰越明显.乙醇-水溶液的光谱在磁场作用后也发生了改变.这些结果说明磁场作用不仅增强了乙醇溶液分子间氢键,同时还影响了O-H,-CH2和-CH3的振动.     

Effect of packing on the cluster nature of C nanotubes: An information entropy analysis

The possibility of the existence of single−wall carbon nanotubes (SWNTs) in organic solvents in the form of clusters is discussed. A theory is developed based on a bundlet model for clusters, which enables describing the distribution function of clusters by size. Comparison of the calculated values of solubility with experiments would permit obtaining energetic parameters characterizing the interaction of an SWNT with its surrounding, in a solid or solution. Fullerenes and SWNTs are unique objects, whose behaviour in many physical situations is characterized by remarkable peculiarities. Peculiarities in solutions show up first in that fullerenes and SWNTs represent the only soluble forms of carbon, what is related to the originality in the molecular structure of fullerenes and SWNTs. The fullerene molecule is a virtually uniform closed spherical or spheroidal surface, and an SWNT is a smooth cylindrical unit. Both structures give rise to the relatively weak interaction between the neighbouring molecules in a crystal and promote interaction of the molecules with those of a solvent. Another peculiarity in solutions is related to their trend to form clusters, consisting of a number of fullerene molecules or SWNTs. The energy of interaction of a fullerene molecule or SWNT with solvent molecules is proportional to the surface of the former molecule and roughly independent of the orientation of solvent molecules. All these phenomena have a unified explanation in the framework of the bundlet model of a cluster, in accordance with which the free energy of an SWNT involved in a cluster is combined from two components, viz. a volume one proportional to the number of molecules n in a cluster, and a surface one proportional to n^1/2. Algorithms for classification are proposed based on the criteria information entropy and its production. Many classification algorithms are based on information entropy. When applying these procedures to sets of moderate size, an excessive number of results appear compatible with data, and this number suffers a combinatorial explosion. However, after the equipartition conjecture, one has a selection criterion between different variants resulting from classification between hierarchical trees. According to this conjecture, for a given charge or duty, the best configuration of a flowsheet is the one in which the entropy production is most uniformly distributed. Information entropy, cluster and principal component analyses agree.     

PAN/CoFe_2O_4纳米复合物的制备及表征

以硝酸铁、硝酸钴和柠檬酸为原料,通过溶胶-凝胶微波加热自蔓延燃烧法制备出了纯的立方尖晶石型铁酸钴(CoFe2O4)纳米粒子,然后通过原位聚合将聚苯胺(PAN)对所得粒径约20～30nm铁酸钴纳米粒子进行了包覆,制得了PAN/CoFe2O4纳米复合物。通过傅里叶变换红外光谱(FTIR)、透射电子显微镜(TEM)、X射线衍射(XRD)等测试手段对所得产物的形貌和结构进行了表征。结果表明,PAN链段与CoFe2O4纳米粒子之间存在作用力,通过原位聚合制得的PAN包覆在CoFe2O4纳米粒子表面,X射线粉末衍射和红外光谱进一步证实了PAN/CoFe2O4纳米复合物的形成。荧光分析结果表明,引入CoFe2O4纳米粒子后PAN荧光强度增强。     

Novel synthesis of cerium oxide nano photocatalyst by a hydrothermal method

Crystalline cubic cerium oxide nano particles have been synthesized from cerium (Ⅲ) nitrate (Ce (NO3)3.6H2O) and sodi-um hydroxide by a hydrothermal method.The effect of three different molar ratios of the NaOH precipitating agent on structur-al,optical,and photo catalytic activity was investigated.The synthesized cerium oxide nano particles were characterized by X-ray diffraction (XRD),a UV-vis spectrometer,scanning electron microscope (SEM),energy-dispersive X-ray spectroscopy (EDAX),Raman spectroscopy and X-ray photo electron spectroscopy (XPS).According to the findings,hydrothermally synthesized ceri-um oxide NPs have a high efficiency for photocatalytic degradation of methylene blue when exposed to UV light.Environment-al water pollution is the major issue of the atmosphere.To get fresh water,humans could search the resources to purify the wa-ter in simple way and degradation is the one of the methods to purify salt water.     

On‐Chain Fluorenone Defect Emission from Single Polyfluorene Molecules in the Absence of Intermolecular Interactions

The emission of semiconducting polyfluorenes is often accompanied by an undesired feature in the green spectral region. Whereas a number of previous investigations have argued in favor of a monomolecular origin of the emission species based on ketonic defects, recent experimental results suggested the necessity of excimer formation between individual fluorenone units. We provide a range of new evidence supporting the monomolecular origin of green band emission in polyfluorenes. Most importantly, we succeed in performing single‐molecule spectroscopy on fluorenone‐containing polyfluorene model compounds. Whereas most fluorenone‐containing molecules exhibit both blue backbone and green fluorenone emission independent of fluorenone concentration, it is the relative intensities of the two species which correlate strongly with the fluorenone concentration on the single‐molecule level. Furthermore, we consider a novel model compound with a bifacial arrangement of two fluorenone units. This compound does not provide any signatures of enhanced intramolecular excimer formation but does strongly indicate that concentration quenching effects occur once fluorenone units can interact electronically. The ability to detect on‐chain defect emission in a single polymer molecule demonstrates that photochemical reactions in conjugated polymers can be monitored by fluorescence spectroscopy down to the level of a few atoms, constituting an unprecedented degree of materials characterization.