用于单分子动力学实验的微流控混合器

设计制作了用于单分子动力学实验的微流控混合器, 该混合器用聚二甲基硅氧烷(PDMS)芯片和石英载玻片密封而成, 具有低的荧光背景, 广泛的生物相容性, 结合激光共聚焦显微镜能够在非平衡态下进行单分子荧光探测. 我们设计的压力控制系统和进样流路方便而稳定, 保证了微流路中流形的长时间稳定, 从而实现了样品流速和流量的精准控制. 这些技术特点保证了单分子探测得到准确和高信噪比的结果. 利用蛋白质的塌缩过程远快于混合过程的特点,采用荧光标记的金黄色葡萄球菌核酸酶作为指示物,分辨出蛋白质变性态的特征峰,并利用变性态的荧光共振能量传递效率随时间的变化表征出混合器在适合于单分子探测条件下的混合时间为150 ms.     

1H NMR研究溶质浓度对三碳多元醇水溶液氢键作用以及玻璃化的影响

为考察溶质浓度对三碳多元醇水溶液氢键作用以及不同物质玻璃态形成能力的影响,采用¹H NMR外标法研究不同浓度的1-丙醇（NPA）,2-丙醇（IPA）,1,2-丙二醇（PG）,1,3-丙二醇（PD）和丙三醇（glycerol）的水溶液在室温常压下质子化学位移.结果表明:具有CH₃CH（OH）一基团的PG烷基质子的化学位移变化趋势与其他几种醇相比有较大差异.醇羟基质子与水分子的氧形成较强O-H…O氢键.相同摩尔分数下,羟基数的增加导致水质子和羟基质子的化学位移降低,而且羟基位置不同也会导致水质子和羟基质子化学位移差异.这几种三碳多元醇碱性强弱的顺序和降低冰的均相成核温度能力的顺序一致,即glycerol>PG>PD>IPA>NPA,¹H NMR技术表明glycerol和PG更适合用作低温保护剂.     

Kinetic Analysis of the Interaction between Nonsteroidal Anti-inflammatory Drugs and Cyclooxygenase-2Using Wavelength Modulation Surface Plasmon Resonance

A surface plasmon resonance (SPR) biosensor based on wavelength modulation technology was developed and validated for the kinetic analysis of the interactions between two nonsteroidal anti‐inflammatory drugs (NSAIDs) and cyclooxygenase‐2 (COX‐2). After the effect of different concentration COX‐2 on the binding capacity of the SPR biosensor surface was studied, the COX‐2 was immobilized covalently onto the biosensor surface using a standard amine coupling method. The affinity constants for indomethacin, ketoprofen binding to COX‐2 are 7.5×10³ L/mol and 9.25×10³ L/mol, respectively. The biosensor surface can be regenerated after being rinsed with 0.01 mol/L NaOH, and the biosensor can be used repeatedly. These indicated that the wavelength modulation SPR biosensor has the potential application in the fields of pharmacokinetics, pharmacodynamics and drug discovery.     

Photonic Bandgap Properties of Atom-lattice Photonic Crystals in Polymer

The present paper covers the various photonic crystals(PhCs) structures mimicking real atom-lattice structures in electronic crystals by using the femtosecond laser-induced two-photon photopolymerization of SU-8 resin. The bandgap properties were investigated by varying the crystal orientations in <111>, <110> and <100> of diamond-lattice PhCs. The photonic stop gaps were present at λ=3.88 μm in <111> direction, λ=4.01 μm in <110> direction and λ=5.30 μm in <100> direction, respectively. In addition, defect...     

共振条件下p-Laplace型方程多点边值问题的可解性

本文研究了共振条件下一类p-Laplace 型方程边值问题的可解性. 利用度理论, 得到至少存在一个解的充分条件, 并举例说明所得的结果是有效的.     

Localized surface plasmon resonance: nanostructures, bioassays and biosensing--a review

Localized surface plasmon resonance (LSPR) is an optical phenomena generated by light when it interacts with conductive nanoparticles (NPs) that are smaller than the incident wavelength. As in surface plasmon resonance, the electric field of incident light can be deposited to collectively excite electrons of a conduction band, with the result being coherent localized plasmon oscillations with a resonant frequency that strongly depends on the composition, size, geometry, dielectric environment and separation distance of NPs. This review serves to describe the physical theory of LSPR formation at the surface of nanostructures, and the potential for this optical technology to serve as a basis for the development bioassays and biosensing of high sensitivity. The benefits and challenges associated with various experimental designs of nanoparticles and detection systems, as well as creative approaches that have been developed to improve sensitivity and limits of detection are highlighted using examples from the literature.     

Analysis of nucleotides binding to chromatography supports provided by nuclear magnetic resonance spectroscopy

The epitope mapping of nucleotides bound to three chromatography supports is accomplished using saturation transfer difference (STD)-NMR spectroscopy. This experiment involves subtracting a spectrum in which the support was selectively saturated from one recorded without support saturation. In the difference spectrum only the signals of the ligands that bind to the support and received saturation transfer remain. The nucleotide protons in closer contact with the support have more intense signals due to a more efficient transfer of saturation. We investigate the effects on the binding to the nucleotides by the introduction of a spacer arm between l-histidine and Sepharose. Our NMR experiments evidence a clear contribution of the spacer to the interaction with all the nucleotides, increasing the mobility of the amino acid and giving different STD responses. This enhanced mobility originates the reinforcement of the interactions with the sugar moiety and phosphate group of 5'-CMP and 5'-TMP or the base of 5'-GMP and 5'-UMP. Hence, with this study we show that by using STD NMR technique on chromatographic systems it is possible to provide a fast, robust and efficient way of screening the atoms involved in the binding to the supports.     

A study of aromatic three membered rings

The resonance energies (REs) of neutral three membered ring analogs of the cyclopropenyl cation, computed using block localized wave function (BLW) methods, reveal considerable variations. The RE's of cyclopropenes substituted with exocyclic double bonded groups C?X, (X = O, NH, CH₂, S, PH, SiH₂) increase with the electronegativity of X in the same row (SiH₂ < PH < S and CH₂ < NH < O). The extra cyclic resonance energies (ECREs) (an energetic measure of aromaticity based on comparisons with the RE's of acyclic models) of these derivatives range from +10.5 kcal/mol for cyclopropenone (X = O) (somewhat aromatic; the benzene ECRE is 29.3 kcal/mol) to ?2.4 kcal/mol (slightly antiaromatic) for X = SiH₂. Additional disubstitution of the C?C double bond by X′ groups (X′ = CH₃, NH₂, OH, SiH₃, PH₂, SH) increases the REs considerably, but has only small effects on the ECREs. Even the ECRE of deltic acid (X = O, X′ = OH) is only increased to +13.3 kcal/mol. The conclusion based on ECRE's, that all 12 of the three membered rings are only marginally aromatic/antiaromatic, is supported by the satisfactorily plot (R² = 0.92) of ECRE against values of NICS(0)_πzz (a superior nucleus chemical independent shift magnetic index of aromaticity), which range only from ?6.1 ppm (diatropic) for deltic acid (cf., ?35.5 ppm for benzene and ?14.2 ppm for the parent cyclopropenium ion) to +8.9 ppm (paratropic) for the silicon derivative, X = SiH₂, X′ = SiH₃. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

N?H···S and S?H···N intramolecular hydrogen bond in β‐thioaminoacrolein: A quantum chemical study

The conformational study of β‐thioaminoacrolein was performed at various theoretical levels, HF, B3LYP, and MP2 with 6‐311++G(d,p) basis set, and the equilibrium conformations were determined. To have more reliable energies, the total energies of all conformers were recomputed at high‐level ab initio methods, G2MP2, G3, and CBS‐QB3. According to these calculations, the intramolecular hydrogen bond is accepted as the origin of conformational preference in thialamine (TAA) and thiolimine groups. The hydrogen bond strength in various resonance‐assisted hydrogen bond systems was evaluated by HB energy, geometrical parameters, topological parameters, and charge transfers corresponding to orbital interactions. Furthermore, our results reveal that the TAA tautomer has extra stability with respect to the other tautomers. The population analyses of the possible conformations by NBO predict that the origin of this preference is mainly due to the π‐electron delocalization in framework of TAA forms, especially usual π_C?C → π*_C?S and Lp (N) → π*_C?C charge transfers. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011