《生物质材料现代分析技术》

(ISBN 978-7-122-09316-5)该书系统地介绍了现代分析技术在生物质材料结构分析中的应用,主要内容包括傅里叶变换红外光谱、核磁共振谱、X射线光电子能谱、凝胶渗透色谱、电子自旋共振谱、气相色谱-傅里叶红外光谱联用、X射线衍射、激光小角散射、扫     

ATR-FTIR在研究环境固液微界面吸附过程中的应用

微界面吸附过程是许多环境微界面反应的初始步骤或关键步骤。通过原位分析方法实时研究环境微界面吸附过程,可以获得更直接的界面反应信息和更可靠的反应机制证据,对于认识污染物在环境中分配转化和迁移传输规律有着重要意义。衰减全反射红外光谱技术由于其独特的采样原理、简便的制样方法和广泛的适应性,正逐渐成为研究微界面反应的一个有力工具。本文在简要介绍原位衰减全反射红外光谱的技术原理的基础上,综述其在环境微界面吸附过程,尤其是矿物-水界面吸附过程中的应用,并探讨其在环境微界面过程研究中的发展前景。     

X射线吸收谱学在锕系环境放射化学中的应用

锕系环境放射化学对于核废料尤其是高放废物的安全处理和处置至关重要,同步辐射技术尤其是X射线吸收谱学在解析锕系元素在不同介质表面的配位结构方面可以发挥关键作用,对于理解锕系元素在环境介质中的迁移转化行为意义重大.本文综述了近年来国内外利用X射线吸收谱学研究锕系元素环境化学方面的最新进展,主要包括锕系核素在不同地质条件下的迁移和转化以及微生物对核素迁移的影响等方面.     

原位同步辐射红外关联谱学技术研究界面电化学反应过程

电化学界面动力学决定了所有电化学反应性质.从原子和分子水平上多维度原位观察电极的表界面电化学反应动态过程对于典型的电化学储能技术(电解槽、燃料电池)中催化剂的结构设计、合成和筛选具有重要意义,但是复杂的电化学界面以及微量、快速的反应中间态信号给界面电化学反应动态过程研究带来了极大的挑战.同步辐射傅里叶变换红外光谱(SR-FTIR)具有独特的分子指纹识别功能,可以用来确定电化学界面的活性物质,结合对纳米材料的局部原子结构高度敏感的同步辐射X射线吸收精细结构(SR-XAFS)光谱可以开展界面电化学反应过程的实时动态研究,有助于指导设计用于高效高能量密度能源系统的先进电催化剂.本文基于近年来本课题组的研究工作,系统地介绍了获得高质量的电化学反应过程中同步辐射红外关联谱学实验结果的策略,及其应用于电催化反应动态过程研究成果,其中主要选用当前热门的金属有机框架(MOF)纳米材料以及金属单原子催化剂(SACs)作为研究对象.最后,对原位同步辐射实验方法发展及其针对电化学反应动态过程的研究进行了展望,旨在通过揭示电化学反应的动态机理来指导和合成高效稳定的催化材料.     

功能化介孔二氧化硅的制备及其吸附分离水中铀的研究进展

铀是一种高效、清洁的核能燃料,但在核工业中不可避免地会产生含铀废水。如果不及时处理,泄漏到环境中,将对动植物和人类的健康构成威胁。因此,从能源回收和环境保护的角度来说,研究水溶液中U(Ⅵ)的分离工艺迫在眉睫。吸附技术因其可行性、效率高和操作简单等优点备受关注。功能化介孔二氧化硅材料具有比表面积大、孔容量大和吸附能力强等优点,是一种理想的吸附剂,在铀的吸附分离领域有着广泛的应用。本文在功能化介孔二氧化硅制备方法的基础上,结合X射线光电子能谱、傅里叶变换红外光谱、X射线吸收精细结构谱、X射线能谱分析和拉曼光谱等分析方法,对国内外目前水溶液中U(Ⅵ)吸附的表征及吸附机理进行了综述。虽然功能化介孔硅吸附铀已经取得了令人鼓舞和潜在的发展,但新型多功能吸附剂的设计和批量生产在实际环境的应用方面仍具有挑战性。     

傅里叶变换红外光谱及其联用技术在反应研究中的新进展

综述了傅里叶变换红外光谱（ＦＴＩＲ）及其联用技术在界面与电化学反应、生物反应、催化反应和动力学研究中的最新进展，参考文献５７篇。     

一种水溶性涂料的化学成分分析

采用傅里叶变换红外光谱、电镜/X射线能谱和原子吸收光谱等现代仪器测试方法对一种水溶性涂料的化学成分进行检测分析,对材料的红外光谱特征进行解析,综合定性和定量分析结果,确定出该涂料的各种组份及其配比.     

X射线荧光光谱分析

本文评述了我国在2002年7月～2004年6月间X射线荧光光谱, 包括粒子激发的X射线光谱的发展和应用, 内容包括仪器的研制、维护和维修、样品制备技术、 X射线荧光光谱基础研究、谱处理、分析方法研究和应用.     

电化学谱学表征方法的应用与发展

经历两个多世纪的发展,电化学表征方法的理论和实验研究不断完善,在表界面精细结构表征、电化学反应机理研究等方面起到重要作用。电化学谱学表征技术的出现,填补了传统电化学表征方法在分子水平上鉴定电化学反应活性位点及中间物种的空白。本文总结了近年来红外光谱(IR)、表面增强拉曼光谱(SERS)及和频振动光谱(SFG)三种经典分子振动光谱电化学表征技术的研究进展。首先介绍了三种光谱的基本原理和电化学联用电解池的设计,然后从基础电化学理论出发,介绍其在模型单晶体系及界面水机理研究中的应用,进一步重点介绍了其在锂离子电池和燃料电池领域的相关研究进展,最后展望了电化学谱学表征技术的未来发展方向。     

近边X射线吸收精细结构光谱法研究土壤腐殖质组分含碳官能团组成及磷酸根影响

应用同步辐射近边X射线吸收精细结构(NEXAFS)光谱技术研究了土壤腐殖质各组分(富里酸、胡敏酸及胡敏素等)的含碳官能团组成信息,并通过分析PO43-存在条件下胡敏酸、胡敏素的官能团组成变化特征,探讨了PO43-与土壤腐殖质之间的微观作用机制。结果表明,土壤腐殖质不同组分的官能团分布具有类似的光谱特征,但组成比例存在明显差异。随着腐殖质组分的酸不溶性增加,胡敏酸、胡敏素疏水性脂肪基官能团比例显著高于富里酸,芳构化程度也明显增加,而亲水性羧基官能团比例趋于降低;PO43-通过静电作用、取代反应可以选择性释放胡敏酸中部分小分子羧基官能团,从而改变胡敏酸官能团的组成特征。此研究结果对于应用NEXAFS研究有机碳官能团形态、结构及理解PO43-在土壤微界面上的反应机制具有重要意义。     

蛋白质膜界面流变行为研究进展

随着界面流变测量技术以及相关的光学辅助仪器的发展,近10年来界面流变学在食品、化妆品、医药等领域发挥了重要作用。本文介绍了近年来蛋白质膜界面流变行为的研究进展,着重介绍了蛋白质界面流变学在泡沫和乳液方面的研究。本文主要分为3个部分,内容包括:蛋白质膜界面流变学行为与泡沫、乳液稳定性的相互关系,蛋白质-多聚糖的界面流变行为研究,蛋白质-表面活性物质的界面流变行为研究。界面流变学在泡沫和乳液方面取得的较快研究进展不仅促进了人们对蛋白质膜界面流变行为更为深刻的理解,而且为更好地开发和应用蛋白质及其混合物作为表面活性物质和胶体稳定剂而提供重要的理论依据和指导。     

Theoretical picture of positive electrode–solid electrolyte interface in all-solid-state battery from electrochemistry and semiconductor physics viewpoints

All-solid-state battery has attracted significant attention as a promising next-generation energy storage. However, interfacial resistance of ion transport between the positive electrode and solid electrolyte is still a crucial issue for the all-solid-state battery commercialization. Although some mechanisms such as space charge layer and reaction layer effects have been suggested, the ionic and electronic behaviors at the solid–solid interfaces have not yet been fully elucidated. Here, we address theoretical microscopic understanding of the interfacial ionics and electronics from the viewpoints of electrochemistry and semiconductor physics, in conjunction with the results of recent density functional theory calculations.     

Molecular level studies of polymer behaviors at the water interface using sum frequency generation vibrational spectroscopy

Industrial plastics, biomedical polymers and numerous other polymeric systems are contacted with water for everyday functions and after disposal. Probing the interfacial molecular interactions between widely used polymers and water yields valuable information that can be extrapolated to macroscopic polymer/water interfacial behaviors so scientists can better understand polymer bio-compatibility, hygroscopic tendencies and improve upon beneficial polymer behavior in water. There is an ongoing concerted effort to elucidate the molecular level behaviors of polymers in water by using sum frequency generation vibrational spectroscopy (SFG). SFG stands out for its utility in probing buried interfaces in situ and in real time without disrupting interfacial chemistry. Included in this review are SFG water interfacial studies performed on poly(methacrylate) and (acrylate)s, poly(dimethyl siloxane)s, poly(ethylene glycol)s, poly(electrolyte)s and other polymer types. The driving forces behind common water/polymer interfacial molecular features will be discussed as well as unique molecular reorientation phenomena and resulting macroscopic behaviors from microscopic polymer rearrangement. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

有机污染物分子的STM研究

本文结合本研究室的部分工作,简要介绍了近年来运用扫描隧道显微镜(STM)对吸附在金属及非金属表面的有机污染物分子的结构、界面行为及反应动力学过程研究中所取得的代表性结果,展示了该技术在污染物降解研究中的重要作用及发展前景。     

TODGA/HNO_3萃取La~(3+)的界面性质

利用滴体积法研究了La~(3+)/HNO_3/N,N,N',N'-四辛基-3-氧戊二酰胺(TODGA)/稀释剂体系的界面性质,考察了TODGA浓度、液滴形成时间、稀释剂种类、La~(3+)浓度、体系温度、离子强度和溶液酸度等因素对体系界面性质的影响.实验结果表明,体系达到界面饱和吸附时间约为120 s,可认为体系达到萃取平衡;TODGA浓度不同时,界面张力也不同,进而判定界面饱和吸附物种亦不相同;极性较小的稀释剂体系的界面张力降低较大,按照正辛烷环己烷苯甲苯次序降低;HNO_3对TODGA的质子化作用使其表面活性显著增强,故硝酸浓度增大导致界面张力降低;Na NO_3的存在降低了界面上游离萃取剂分子的浓度,致使界面张力增大.     

Potential effects of climate change on the chemical quality of aquatic biota

Climate changes can alter and modify the distribution and the partitioning of contaminants in water bodies through several factors (e.g., rise in temperature, decrease in oxygen through water scarcity, acidification and remobilization of pollutants in sediments due to flooding). Other indirect effects can be linked to climate changes (e.g., increased use of pesticides due to the rise of plant diseases caused by new vectors and erosion of coastal areas due to rise in sea level). All these factors have the potential to enhance the bioavailability of dangerous pollutants with bioaccumulative properties with an increasing risk of transfer in the food chain.The data available on aquatic species for compounds such as, polychlorinated biphenyls, dioxins and mercury show that the legislative standards for food are exceeded in some areas. These data also show that levels in aquatic biota of other emerging compounds with bioaccumulative properties (such as, perfluorinated octane sulfonate, polybrominated diphenyl ethers and hexabromocyclododecane can be relevant in some areas and at some trophic levels. In particular, the effect of climate changes can be relevant in vulnerable water bodies (e.g., estuaries of rivers or coastal lagoons), where fishing, extensive and intensive aquaculture activities and sites of high biodiversity value are often present.For these reasons, there is a need to change the water-monitoring strategies with a focus on analytical methods for biota determination and to have monitoring programs that include detection of long-term trends and share procedures for the setting of quality criteria for biota.     

表面能与晶体生长/溶解动力学研究的新动向

界面现象使物质在结晶过程中出现了临界现象.但最近的研究指出在物质溶解过程中,在表面能量的控制下也存在着临界现象以及尺寸效应.实验发现,当晶体自身小到一 定的程度时(通常在纳米尺度上并和临界蚀坑的大小相近),在溶解过程中其速度会自发降 低,反应被抑制乃至停止.尽管在热力学上表面能的因素可以赋予小颗粒晶体较大的溶解度 ,但表面能却也能通过对临界条件的控制而使这些微粒在动力学上不被溶解.这个发现不仅 解决了纳米颗粒在水溶液中稳定性的问题,而且还从动力学的角度解释了生物矿物选择纳米 尺度作为其基本构成单元的原因.由于表面能和晶体生长/溶解的动力学有着密切的关系, 我们可以通过对表面能的调节来修改它们的动力学速度和晶体的形貌.反过来,也可以用动力学的方法来测定表面能及表面吸附/脱附常数等.相对于常规的界面研究手段,通过生 长和溶解动力学途径所得的数据有着很好的可靠性及重复性.我们认为,晶体生长和溶解的 动力学和表面能的研究相结合,不仅为界面研究提供了新的思路和方法,而且也会推动晶体生长和材料科学的发展.     

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration) affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field-theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.     

受限空间内油水界面动态特性及粘附行为的荧光原位观测

水污染作为润滑油污染的常见形式,对润滑油本身以及机械系统都有巨大的危害。为了模拟实际非均匀多相系统中的界面行为,本文搭建了高精度点接触实验台来研究传统的不溶相替换问题。将目前静态平行受限空间内油水界面行为的研究推广到动态点接触楔形受限空间内,探究了游离水滴穿过点接触狭缝间毛细油池过程中的界面特性。重点关注固壁润湿性以及固壁的分离运动对整个侵入过程中液滴动态行为的影响。实验发现了铺展系数是决定油水界面融合和分离特性的关键因素,揭示了固壁润湿性和球盘间的相对分离运动会影响游离水滴穿过毛细油池之后的粘附行为。表面张力和液体与壁面之间的粘附功能够解释观测的实验现象。     

Dynamic behaviors of molecular assemblies at liquid/liquid interfaces studied by time-resolved quasi-elastic laser scattering spectroscopy.

The dynamic behaviors of molecular assemblies at two immiscible liquid interfaces are intriguing topics in many fields of science and technology. However, it is generally difficult to investigate the dynamic behaviors of such molecular assemblies because of the buried nature of liquid/liquid interfaces. In the present paper, our recent investigations on dynamic behaviors of various molecular self-assemblies at liquid/liquid interfaces are reviewed. We monitored dynamic behaviors of the molecular assemblies by time-resolved quasi-elastic laser scattering (TR-QELS) and fluorescent spectroscopy. The former method allows us to monitor the change in interfacial tension with millisecond time-resolution. As molecular assemblies, bis(2-ethylhexyl)sulfosuccinate (AOT) microemulsion, phospholipid biomembrane models, and liposome-DNA complexes have all been studied, since they are relevant in material sciences and biological technologies. At liquid/liquid interfaces, these molecular assemblies showed characteristic behaviors. We review the finding of rebound response of the interfacial tension at the liquid/liquid interface induced by the adsorption of the AOT microemulsion. We monitored the hydrolysis reaction of phospholipid biomembrane models formed at oil/water interfaces, observing the different types of behavior of liposome-DNA complexes at biomembrane models with different kinds of phospholipids.