Absorption of Iodine on the Surface of Silica Modified by Polyvinylpyrrolidone and Albumin

The influence of modification of a fumed silica by polyvinylpyrrolidone (PVP) and bovine serum albumin (BSA) on its ability to adsorb iodine has been investigated by UV spectroscopy. It has been established that the adsorption of iodine molecules on the silica surface is increased several times after its modification by high-molecular compounds. The role of structural factors in complexing of iodine with macromolecules has been estimated. Using PVP and BSA as an example, it is shown that the structure of a modifying layer on the silica surface depends on the nature and structure of the polymer.     

AT1受体拮抗剂V8、V12和BZI8结构的量子化学研究

基于Mavromoustakos等人的分子动力学和蒙特卡罗方法结果,本文利用量子化学计算的方法研究了SARTANS(沙坦)类的3种AT1受体拮抗剂(V8、V12和BZI8).在B3LYP/6-31G(d)方法下计算得到了3种药物分子的平衡几何结构,并且采用B3LYP-GIAO/6-311G(d,p)方法计算了这些药物分子中的质子化学位移.通过研究结果可以看出,本文采用量子化学方法计算得到的3种分子的结构与Mavromoustakos等人通过分子动力学和蒙特卡罗方法得到的结果比较接近,计算结果与核磁共振实验的ROE数据和1H谱相比吻合得较好,说明所获得的结构较为合理.另外通过对所获得分子结构进行叠合分析发现,同属SARTANS类的3种分子在联苯咪唑环区域具有很大的相似性.     

AT1受体拮抗剂V8、V12和BZI8结构的量子化学研究

基于Mavromoustakos等人的分子动力学和蒙特卡罗方法结果，本文利用量子化学计算的方法研究了SARTANS（沙坦）类的3种AT1受体拮抗剂（V8、V12和BZI8）. 在B3LYP/6-31G(d)方法下计算得到了3种药物分子的平衡几何结构，并且采用B3LYP-GIAO/6-311G(d，p)方法计算了这些药物分子中的质子化学位移. 通过研究结果可以看出，本文采用量子化学方法计算得到的3种分子的结构与Mavromoustakos等人通过分子动力学和蒙特卡罗方法得到的结果比较接近，计算结果与核磁共振实验的ROE数据和¹H谱相比吻合得较好，说明所获得的结构较为合理. 另外通过对所获得分子结构进行叠合分析发现，同属SARTANS类的3种分子在联苯咪唑环区域具有很大的相似性.     

Liposome encapsulation of fluorescent nanoparticles: Quantum dots and silica nanoparticles

Quantum dots (QDs) and silica nanoparticles (SNs) are relatively new classes of fluorescent probes that overcome the limitations encountered by organic fluorophores in bioassay and biological imaging applications. We encapsulated QDs and SNs in liposomes and separated nanoparticle-loaded liposomes from unencapsulated nanoparticles by size exclusion chromatography. Fluorescence correlation spectroscopy was used to measure the average number of nanoparticles inside each liposome. Results indicated that nanoparticle-loaded liposomes were formed and separated from unencapsulated nanoparticles by using a Sepharose gel. As expected, fluorescence self-quenching of nanoparticles inside liposomes was not observed. Each liposome encapsulated an average of three QDs. These studies demonstrated that nanoparticles could be successfully encapsulated into liposomes and provided a methodology to quantify the number of nanoparticles inside each liposome by fluorescence correlation spectroscopy.     

High-resolution rotational spectroscopy of iminosilylene,HNSi

By means of Fourier transform microwave spectroscopy of a supersonic beam, the fundamental rotational transition of isotopic and vibrationally excited iminosilylene, HNSi, has been detected. In addition to seven isotopic species, vibrational satellite transitions from more than 30 vibrationally excited states, including the three fundamental modes, have been detected. Those from ν₂ are particularly intense, enabling detection of transitions from as high as (0,22⁰,0) (i.e. ～10,000 cm^?1 above ground). At high spectral resolution, well-resolved nitrogen quadrupole structure has been observed in nearly every transition. Excitation of ν₁ or ν₃ changes eQq(N) little, but eQq(N) systematically decreases with increasing excitation of the ν₂ bend, from a value of 0.376(5) MHz for (0,0⁰,0) to ?2.257(5) MHz for (0,20⁰,0). With the large amount of new data in hand, it has also been possible to determine the leading vibration–rotation constants (α_i and γ_i) for ν₂ or ν₃ to high precision, and derive a revised semi-empirical equilibrium structure for this fundamental triatomic molecule. Various electronic and molecular properties of iminosilylene have been calculated at the coupled cluster level of theory, and these generally agree well with experiment and previous calculations. An unsuccessful search for HSiN, a highly polar isomer calculated to lie nearly 3 eV above HNSi, is also reported.     

液体核磁共振 HSQC 实验的量子化学计算与模拟

核磁共振（NMR）异核单量子相干（HSQC）实验因具有较高的灵敏度和分辨率而被广泛用于液体大分子化合物的结构鉴定和研究．然而由于HSQC脉冲的复杂性,需要严格控制实验参数和实验条件才能得到高质量的谱图．本文基于量子力学原理对HSQC实验进行数学建模,通过理论推导、数值计算求解自旋1/2的IS双核体系在每个脉冲节点作用后的密度矩阵,然后结合二维NMR信号采样方法,使用计算机程序完成了该体系HSQC谱图的模拟,同时,还实现了乙醇分子的HSQC谱图模拟． HSQC实验的成功模拟基于对复杂演化过程的精确计算,可用于预测谱图以及实验参数改变对NMR谱图的影响,指导高质量HSQC实验谱图的采集．     

Quantum computation and simulation with vibrational modes of trapped ions

Vibrational degrees of freedom in trapped-ion systems have recently been gaining attention as a quantum resource,beyond the role as a mediator for entangling quantum operations on internal degrees of freedom, because of the large available Hilbert space. The vibrational modes can be represented as quantum harmonic oscillators and thus offer a Hilbert space with infinite dimensions. Here we review recent theoretical and experimental progress in the coherent manipulation of the vibrational modes, including bosonic encoding schemes in quantum information, reliable and efficient measurement techniques, and quantum operations that allow various quantum simulations and quantum computation algorithms. We describe experiments using the vibrational modes, including the preparation of non-classical states, molecular vibronic sampling, and applications in quantum thermodynamics. We finally discuss the potential prospects and challenges of trapped-ion vibrational-mode quantum information processing.     

A Raman Spectroscopic Investigation of Sulphadiazine and of Its Dirhodium Tetracarboxylate Adducts

A tentative assignment of the vibrational modes of sulphadiazine is made, based on the infrared and Raman data. In addition, dirhodium tetracarboxylates and their adducts with sulphadiazine are investigated by Raman spectroscopy, with emphasis in the identify the metal-metal and metalligand stretching modes.     

Ultrafast proton transfer dynamics of 2-(2'-hydroxyphenyl)benzoxazole dye in different solvents

The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.     

药物小分子化学位移的量子化学计算研究

核磁共振的谱峰归属对分子结构的确定至关重要,用理论计算方法预测化学位移对谱峰的正确归属是极其有帮助的. 我们用量子化学的方法预测了乙酰水杨酸及其衍生物分子上碳原子的化学位移,并通过比较计算值和实验值得到不同理论计算方法的误差范围. 用HF和DFT理论计算芳环碳的化学位移时,CSGT方法比GIAO方法更为准确. 与其它方法相比,B3PW91//CSGT 在6-311G(d,p)基组下得到的芳环碳的化学位移最接近实验值. 采用B3LYP//GIAO计算时, 使用不同的基组 6-31G(d,p)和6-311++G(3df,3pd)得到的化学位移计算值只有δ 0.01~2.04的差异. MP2方法非常耗时,且对于计算精度的改善并不显著; 并且,由于电子相关性的影响,碳原子周围的电子环境对化学位移计算的准确性影响很大. 与实验值比较,HF方法由于忽略电子相关效应所以表现较差. 另外,碳链的增长对计算准确性也存在一定影响.      

量子相干态的二维电子光谱测量的原理、应用和发展

二维电子光谱是一种同时具有高的时间分辨率和光谱分辨率的非线性光谱学方法.它不仅可以对凝聚相分子复杂动力学过程进行直接测量,还可以测量不同电子态、电子态-振动态之间的量子相干过程.2007年,Flemming课题组利用二维电子光谱于低温77 K的条件下在捕光天线蛋白Fenna-Matthews-Olson中发现了能量传递过程存在量子相干现象.尽管后续的实验研究表明,该体系中实验观测到的量子相干现象不可能是由单纯的电子态相干引起的,然而这一实验现象的报道极大地激发了人们对天然或人工模拟光合系统中存在量子相干传能途径的探索,目前还是一个相当活跃的研究领域.本文旨在通过介绍二维电子光谱学原理、装置及其在光合作用体系能量传递中量子相干现象的应用,使二维电子光谱这种实验方法能够在更多的研究领域得以普及与推广.     

Quantum–Chemical Investigation of the Influence of Conformations and Extra–Ligation on Electronic Spectra of Chemical Dimers of Metalloporphyrins and Metallochlorins

We have made a theoretical analysis of the factors influencing the electronic absorption spectra of monomers of porphyrins and chlorins as well as of their chemically bound dimers in which the monomeric subunits are bound through the CH₂–CH₂ group. On the basis of quantum–chemical calculations by the semiempirical method CNDO/S it is shown that the addition of extra–ligands causes a change in the conformation of the dimers.     

Chemical Surface Coating: Synthesis and Characterization of a Silicon Oxynitride Coated Silica Sel

Mesoporous silica gel has been coated with a thin silicon oxynitridefilm via chemical surface coating. In the first part of the synthesis, achemically bound preceramic polysilazane coating is formed layer by layer onthe pore walls at low temperature, using SiCl₄ andNH₃ as reagents. In the second part of the synthesis, thepolysilazane coated silica gel is pyrolysed, yielding a chemically bound,thin oxynitride coating.During the synthesis, the evolution of the chemical and morphologicalcomposition has been investigated with several elemental and spectroscopicanalysis techniques as well as with nitrogen porosimetry.     

高分子化学位移的量化计算与固体NMR实验研究

该文以2种不同立构聚丙烯（iPP和sPP）为讨论对象,首先研究了量化计算方法在预测高分子¹³C 各向同性和各向异性化学位移（CSA）中的应用,然后讨论了近年来发展的测定¹³C CSA粉末线形的2种重要固体NMR实验技术（SUPER和RAI）的特点和实验优化问题. 最后,利用可获得接近无扭曲线形的SUPER技术测定了等规立构聚丙烯样品的¹³C CSA粉末线形,并与量化计算理论结果比较. 结果表明：¹³C 各向同性化学位移及CSA粉末线形的理论计算结果均与固体NMR实验结果有很好的符合,预示通过¹³C CSA量化计算结合固体NMR实验是阐明高分子微观结构的有力工具.     

季铵盐型纳米气相二氧化硅衍生物的合成、表征及生物学活性

以纳米气相SiO₂为载体,以γ- 氯丙基三甲氧基硅烷作偶联剂,用N,N-二甲基十四烷基叔胺进行了季铵化反应制备季铵盐型纳米气相二氧化硅衍生物。用红外光谱,DSC和激光粒度Zeta电位仪对纳米气相二氧化硅季铵盐衍生物进行了表征和测定,用悬菌定量实验(Suspension quantitative test)研究了其抗菌性能。结果表明：(1) γ- 氯丙基三甲氧基硅烷通过与纳米气相二氧化硅表面羟基的反应键合到二氧化硅表面,随着γ-氯丙基三甲氧基硅烷的用量增加,纳米气相二氧化硅表面羟基被取代程度也增加;(2)纳米气相二氧化硅的零电位在pH 4.8,纳米气相二氧化硅季铵盐衍生物的零电位在pH 10.5,季铵盐的引入使其零电位发生了较大的位移;(3)所制备的纳米气相二氧化硅季铵盐衍生物对大肠杆菌、金黄色葡萄球菌以及白色念珠菌在振荡作用15 min后,平均抑菌率分别为99.99%,99.99%和94.12%。     

Chemical ordering in As-Se glasses: X-ray absorption edge and XPES studies

X-ray absorption edge and X-ray photoelectron spectroscopic studies of As-Se glasses seem to support a chemical ordering model. Communication No. 94 from Solid State and Structural Chemistry Unit.     

Crystal and molecular structure of 2‐amino‐5‐chloropyridinium hydrogen selenate—its IR and Raman spectra,DFT calculations and physicochemical properties

The new organic‐inorganic salt, 2‐amino‐5‐chloropyridinium hydrogen selenate, has been synthesised and characterised by means of FT‐IR, FT‐Raman and single crystal X‐ray crystallography. Its vibrational spectra have been discussed on the basis of quantum chemical DFT calculations using the B3LYP/6‐31G(d,p) approach. The crystal and molecular structures have been compared and the role of the intermolecular interactions in this crystal has been analysed. The N HO interactions between the hydrogen atoms of the organic cation and oxygen atoms of hydrogen selenate anion determine the supramolecular arrangement in three‐dimensional space. The possible application of the studied composite material as a Raman laser has been discussed. Copyright © 2008 John Wiley & Sons, Ltd.