丙三醇对水溶液中血红蛋白构象的影响——荧光猝灭和动态光散射研究

利用荧光猝灭法和动态光散射法测定丙三醇-水混合溶剂中血红蛋白(Hb)与联苯胺的结合距离和Hb的流体动力学半径, 并通过分析Hb荧光光谱和吸收光谱的变化, 探讨丙三醇与蛋白质分子在水溶液中相互作用的机理及其对蛋白质构象的影响. 结果表明, 丙三醇-水混合溶剂中Hb通过优先水化作用形成更紧密的构象, 溶剂体系的氢键形成能力下降对稳定蛋白质的构象有重要的影响, 丙三醇浓度较高的混合溶剂中氢键网络发生崩塌, 导致蛋白质构象产生进一步的折叠. 实验显示, 尽管Hb在丙三醇-水混合溶剂中保持较完整的血红素疏水空穴结构, 但是血红素疏水空穴以外肽段的构象发生显著变化, 并对血红蛋白的聚集状态造成一定的影响.     

用动态光散射跟踪钙-海藻酸水溶液凝胶化

海藻酸(alginate)是一种天然多糖,是直链键合的β-D-甘露糖醛酸(M)和α-L-古洛糖醛酸(G)的无规嵌段共聚物[1].在海藻酸水溶液中加入钙、铜、锌、铅等二价正离子,能够形成凝胶;其中钙-海藻酸凝胶在细胞输送、组织工程等领域受到人们的关注[2,3].影响海藻酸凝胶化的因素包括海藻酸的分子量和分子量分布、M/G值和序列分布、溶液浓度、正离子种类与浓度等[4,5].     

基于与铁氰化钾和Zn~(2+)作用共振光散射法测定异烟肼

在酸性介质中,异烟肼能将铁氰酸根离子还原成亚铁氰酸根离子,后者与硫酸锌反应生成K2Zn3[Fe(CN)6]2粒子引起体系的共振光散射信号显著增强.在345nm处增强的散射信号强度ΔIRLS与异烟肼的浓度在0.01~1.0μg/mL范围内呈线性关系,据此建立了一种检测异烟肼含量的共振光散射(RLS)分析方法.线性回归方程为ΔIRLS=136.1+4239c(c,μg/mL),相关系数(r)为0.9984,检测限(3σ)为3.8ng/mL.该方法已成功用于异烟肼片剂及血清样品的测定.此外,文中还结合吸收光谱,动态光散射,扫描电子显微镜等表征手段对反应机理和RLS信号强度增强的原因进行了探讨.     

Pressure-induced variation of cellulose tablet studied by two-dimensional (2D) near-infrared (NIR) correlation spectroscopy in conjunction with projection pretreatment

Projection two-dimensional (2D) correlation analysis, achieved by selectively eliminating specific portion of dynamic spectra synchronized with the projecting vector, was used to study compression-induced variation of cellulose tablet monitored by near-infrared (NIR) spectroscopy and water sorption test. The increased density of the tablet by compression provided apparent variation of spectral intensity much larger than those caused by the change in the cellulosic structure. The direct calculation of 2D NIR correlation spectra from the raw spectra generated a relatively uninformative synchronous correlation spectrum and a very noisy asynchronous correlation spectrum due to the predominant intensity variation arising from the light scattering. In contrast, significant correlation features were elucidated without being hampered by the baseline fluctuation when the projection-corrected NIR spectra were constructed by the projection onto the space spanned orthogonal to the baseline change. Fine features of the compression-induced variation of the system were also elucidated by 2D hetero-correlation analysis based on the NIR spectra and water sorption profiles. The 2D correlation analysis revealed that the compression produces a disordered amorphous component of cellulose. The development of mobile amorphous phase results in a more tightly packed matrix with less porosity, which in turn prevents the penetration of water into the tablet and delays the water sorption.     

Evanescent Wave Light Scattering A Fusion of the Evanescent Wave and Light Scattering Techniques to the Study of Colloids and Polymers Near the Interface

The evanescent wave light scattering technique, which is produced by a fusion of the evanescent wave technique and light scattering technique, is a very powerful and useful tool for investigation of colloidal particles and polymers near the surface and interfaces. We have developed two kinds of evanescent wave light scattering apparatuses. One is the evanescent wave dynamic light scattering (EVDLS) technique and the other is the evanescent wave light scattering microscope (EVLSM). By EVDLS, the diffusion behavior of a colloidal particle near the interface can be extracted quantitatively as a function of the distance from the interface. The diffusion coefficient was smaller than those for particles in bulk, reflecting electrostatic and hydrodynamic interactions. By EVLSM, the interaction potential profile between a colloidal particle and the surface in dispersion can be evaluated directly. EVLSM will play an important role in colloidal interaction studies, especially at a low ionic strength. It is also pointed out that a particle dynamics study is also possible by the EVLSM technique. A new field will be developed in colloid science and polymer science by application of the evanescent wave light scattering technique, i. e. a fusion of the evanescent light and a light scattering techniques.     

Application of dynamic 2D FTIR to cellulose

Cellulose, the dominant polymer in the biosphere, is a homopolysaccharide composed of (1,4)-β-d-glucopyranose. Interactions between and within the cellulose polymer chains are mainly determined by inter- and intramolecular hydrogen bonds, which are therefore mainly responsible for mechanical properties of cellulosic materials. The coupling of dynamic mechanical analysis (DMA) and 2D step-scan Fourier transform infrared (FTIR) spectroscopy, is shown to be a very promising way of investigating these submolecular interactions in cellulosic materials. The broad and unstructured band in the OH-stretching vibration region (3100 and 3700 cm⁻¹) of the cellulose vibrational spectra, which contains information about the intra- and intermolecular hydrogen bonds, can be unraveled by this new technique. In the experiments reported here, cellulose sheets have been stretched sinusoidally at low strains while being irradiated with polarized infrared light. For the obtained dynamic IR signals (the in-phase and the out-of-phase responses of the sample), the dynamic IR cross-correlation was defined. It consists of two terms which are referred to as the synchronous and the asynchronous 2D infrared correlation intensities. In the 2D spectra, obtained by DMA–FTIR, several distinct peaks are observed in the OH-range between 3700 and 3100 cm⁻¹ which may be related to specific interactions.     

Dynamic scaling of the critical binary mixture methanol-hexane

Acoustical attenuation spectrometry, dynamic light scattering, shear viscosity, density, and heat capacity measurements of the methanol/n-hexane mixture of critical composition have been performed. The critical part in the sonic attenuation coefficients nicely fits to the empirical scaling function of the Bhattacharjee-Ferrell [Phys. Rev. A 24, 1643 (1981)] dynamic scaling model if the theoretically predicted scaled half-attenuation frequency Omega(12) (BF)=2.1 is used. The relaxation rates of order parameter fluctuations, as resulting from the acoustical spectra, within the limits of experimental error agree with those from a combined evaluation of the light scattering and shear viscosity measurements. Both series of data display power law with amplitude Gamma(0)=44x10(9) s(-1). The amplitude of the fluctuation correlation length follows as xi(0)=0.33 nm from the light scattering data and as xi(0)=0.32 nm from the amplitude of the singular part of the heat capacity if the two-scale factor universality relation is used. The adiabatic coupling constant g=0.11 results from the amplitude of the critical contribution to the acoustical spectrum near the critical point, in conformity with g=0.12 as following from the variation of the critical temperature with pressure along the critical line and the thermal expansion coefficient.     

Graphene Nanosheets and Quantum Dots: A Smart Material for Electrochemical Applications

A novel material for the electrochemical determination of endocrine disruptors using a composite based on graphene oxide modified with cadmium telluride quantum dots has been evaluated. The morphology, structure and electrochemical performance of the composite electrodes were characterised by transmission electron microscopy, dynamic light scattering, UV‐visible absorption spectra, fluorescence spectra, Raman spectra and cyclic voltammetry. The dynamic light scattering, transmission electronic microscopy and spectrophotometric measurements all showed good distribution of the quantum dots with a small particle size. The electrochemical measurements demonstrated the high performance of the composite response in the presence of a light source. Differential pulse voltammetry allowed the development of a method to determine 17β‐estradiol levels in the range from 0.2 to 4.0 μmol L ^?1 with a detection limit of 2.8 nmol L ^?1 (0.76 μg L ^?1).     

Static and dynamic scattering behavior of regularly branched chains: A model of soft-sphere microgels

The static structure factor and the first cumulant of the time correlation function in dynamic light scattering have been calculated for a regularly branched molecule with n shells of branching generations which are connected by chains of m repeating units per chain. Ideal flexibility for the chains is assumed. The dynamic scattering functions of these soft spheres show behavior significantly different from that of a hard sphere. The theory describes very satisfactorily the static and dynamic light scattering results obtained experimentally with polyvinyl acetate microgels. The possibility of determining the glass transition temperature of latex particles is briefly discussed.     

Particle sizing of colloidal suspensions by low-coherence fiber optic dynamic light scattering

A low-coherence fiber optic dynamic light scattering technique is used to measure the particle size distributions of colloidal suspensions with different volume fractions. We detect electric field autocorrelation function of the singly backscattered light from a sample and use the CONTIN algorithm to obtain the particle size distributions. As a result, in the range of volume fractions from 0.01 to 0.10 of monodispersive colloidal suspensions, the mean particle size with the deviation within 4% and the polydispersity approximate 5% can be determined for particles of different radii. The results demonstrate that the low-coherence fiber optic dynamic light scattering technique is effective in measuring particle size of colloidal suspensions.     

Synthesis of Pt, Pd, Pt/Ag and Pd/Ag nanoparticles by microwave-polyol method

Pt, Pd, Pt-Ag and Pd-Ag bimetallic nanoparticles were synthesized in ethylene glycol and glycerol using the microwave technique in the presence of a stabilizer poly(N-vinylpyrrolidone) (PVP). It has been observed that PVP is capable of complexing and stabilizing nanoparticles. Mixed clusters were formed by simultaneous reduction of the metal ions. The clusters were characterized using UV-Vis spectra, XRD and dynamic light scattering. To understand the mechanism of formation of mixed nanoparticles, several experimental parameters such asin situ irradiation of mixed metal salts and mixing of individual sols were attempted.     

Photon correlation spectroscopy of polystyrene near the glass–rubber relaxation

Polarized Rayleigh scattering is studied near the glass-rubber relaxation in atactic polystyrene using photon correlation spectroscopy. Average relaxation times determined from the data agree well with previous results obtained using depolarized Rayleigh scattering. The light scattering results follow the same trend observed by dielectric and mechanical relaxation studies, but the times for orientational relaxation are longer by approximately two orders of magnitude. Also, an extensive discussion of the experimental techniques necessary to use photon correlation spectroscopy of polymers near the glass-rubber relaxation is presented.     

光散射技术在蛋白质晶体生长研究中的应用和进展

光散射技术广泛应用于生物大分子的晶体生长研究中,它包括静态光散射和动态光散射两种。利用静态光散射可以测定蛋白质溶液渗透的第二维里系数;利用动态光散射可以测定蛋白质溶液的平动扩散系数,获得溶液中蛋白质粒子的流体力学半径及分布情况,分离蛋白质结晶的成核与生长过程,研究大分子的聚集行为和晶体生长的动力学。借助光散射技术可以实现蛋白质晶体生长过程的动态控制。近些年光散射仪器向着小型化、轻便化的方向发展,光散射技术不断得到改进,日益完善,不仅用于地面实验,也应用于空间领域蛋白质晶体生长的研究中。     

Determination of proteins with Fast Red VR by a corrected resonance light-scattering technique.

A simple corrected resonance light-scattering (CRLS) technique was established to correct for any distortion of the resonance light scattering (RLS) spectra resulting from molecular absorption. By using an absorption cell holder to change the propagation direction of the incident light beam of a common spectrofluorometer, the molecular absorption was directly measured through a spectrofluorometer. With measurements of the CRLS signals of the interaction of Fast Red VR (FRV) and proteins, we proved that the present correction for the RLS spectra in terms of the molecular absorption of excitation and scattering radiation can improve the detection sensitivity by about two fold.     

In situ approaches to establish colloidal growth kinetics

A technique based on the back scattering phenomenon of dynamic light scattering has been employed to monitor the kinetics of gold and platinum metal nanoparticle growth and silver nanoparticle oxidation as well as in the determination of particle sizes ranging from 1 to 200 nm in diameter. The systems were chosen to examine the applicability of dynamic light scattering to nanoresearch over a broad range of sizes as well as both metallic and nonmetallic systems. The advantages of this instrumentation over traditional instruments such as X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) have been highlighted.     

Nanometer-sized gelatin particles prepared by means of gamma-ray irradiation

Nanometer-sized gelatin particles have been prepared by means of gamma-ray irradiation and characterized by static and dynamic light scattering combined with circular dichroism (CD) measurements. The molecular weight of the nanoparticles was much larger than that of the original gelatin molecules, whereas the hydrodynamic radius was much smaller. Radius of gyration evaluated from the angular dependence of the static light scattering intensity decreased with increasing irradiation dose. CD spectra of the gelatin nanoparticles were independent of temperature, and it is suggested that the nanoparticles consist of highly and randomly packed gelatin and their conformation is stable against the temperature change.     

Giant vesicles of a single-tailed chiral cationic surfactant, (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide, in water

Self-assembly properties of a single-tailed chiral cationic surfactant, (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide (DMEB), have been studied in water. The molecular self-assemblies of the amphiphile have been characterized by surface tension, fluorescence probes, light scattering, and microscopic techniques. The results have been compared with those of dodecyltrimethylammonium bromide (DTAB) surfactant. The critical aggregation concentration of DMEB was found to be much less than that of DTAB. Surface tension and fluorescence probe studies have suggested formation of micellar structures at low temperature (<28 degrees C) and spontaneous formation of giant vesicles in water above 28 degrees C. The mean size of the aggregates has been measured by a dynamic light scattering method. The micropolarity and microviscosity of the self-assemblies were determined by fluorescence probe technique. The (1)H NMR and FTIR spectra were recorded to elucidate the role of the hydrophobic head group towards the formation of bilayer structures. The phase transition temperatures of the vesicular aggregates were determined by measurement of fluorescence anisotropy at various temperatures.     

Field correlation effects on the resonant light scattering

Effects of incident photon field coherence on resonant light scattering have been investigated. In order to obtain the scattering intensity and the photon counting rate, an expression for the reduced density matrix for the scattered field has been derived. The expression involves the first-order correlation function of the incident field. The relation between the line shape of the scattered light and the bandwidth of the incident field has been clarified. Model calculations of the photon counting rate have been performed in the case of an incident field without first-order coherence. In our treatment, the transverse and longitudinal relaxation constants have been taken into account by using the impact approximation.     

Hydrodynamic radius of polyethylene glycol in solution obtained by dynamic light scattering

In order to compare the size characterizations in poly(ethylene glycol) (PEG) obtained by dynamic light scattering (DLS) and small angle neutron scattering (SANS), DLS experiments were performed in various PEG solutions to ascertain the hydrodynamic radius. Data from the experiments were analyzed by using a method to eliminate effects of PEG aggregation on dynamic correlation functions. The results of the analysis were then compared to the radii of gyration reported from SANS experiments. The relation between the hydrodynamic radius, obtained by DLS, and the radius of gyration, obtained by SANS, in PEG in solution was found to be in agreement with a previously obtained relation for PEG, where the radius of gyration was found by static light scattering.