Investigation of neuroprotective action of drug “Semax” at ischemic insult by Raman spectroscopy method by estimation of damage of low density lipoprotein of rat blood

With the help of Raman spectroscopy method the protective action of Semax on free radical lipoperoxide oxidation of non-saturated fatty acids of external amphipatic phospholipid layer of low density lipoprotein (LDL) of blood serum of rats at ischemic insult is investigated, that allow one to make the conclusions about degree of oxidative stress in brain tissues at action of Semax at this pathological condition. By estimation of damage of LDL it is shown that Semax decreases the oxidative stress in brain tissues at ischemia. Lipoperoxide oxidation of LDL of blood serum can be used as marker, determinating the level of oxidative stress in brain tissues at ischemic insult that can be used in clinical practice.     

基于光谱学技术对丁香油与乙酸乙酯相抑LDL非酶糖基化、氧化修饰能力的比较

低密度脂蛋白(LDL)非酶糖基化和氧化修饰均是导致动脉粥样硬化(AS)的关键因素。前人发现,丁香可有效抑制牛血清白蛋白(BSA)、高密度脂蛋白(HDL)糖基化修饰,丁香乙酸乙酯相(EAEC)和丁香油(CBO)均具有很强的抗氧化活性。为了确定丁香抑制LDL糖基化及氧化所对应的最有效成分,在前人研究基础上采用光谱学技术对EAEC和CBO抑制LDL糖基化及氧化功能进行了比较。首先建立LDL-葡萄糖糖基化孵育体系,通过测定糖基化早期、中期和末期产物及三维荧光光谱的变化比较CBO和EAEC抑制LDL糖基化修饰的效果。其次,建立LDL-CuSO₄氧化孵育体系,通过测定荧光指标和三维荧光光谱、紫外可见波长扫描来比较两者抑制LDL氧化修饰效果。结果发现,EAEC和CBO对LDL糖基化修饰过程中产生的早期产物(Amadori产物)、中期产物(二羰基化合物)及终末期产物(戊糖素和AGEs)均具有很强的抑制效果,且EAEC的抑制效果均强于CBO;三维荧光光谱表征得到相同的结果。在LDL氧化修饰比较中,CBO对色氨酸(Trp)荧光猝灭、总荧光产物及脂褐素的生成、赖氨酸(Lys)修饰的抑制效果均显著强于非油成分的EAEC;三维荧光光谱表征也得到相同的结果;紫外、可见全波长扫描反映CBO比EAEC对共轭二烯(CD)生成及光谱红移的抑制效果更强。研究结果为后续锁定重点成分分离、纯化及研发丁香抗LDL糖基化及氧化功能食品提供参考。     

A Method for In Vitro Measurement of Oxidized Low-Density Lipoprotein in Blood,Using Its Antibody,Fluorescence-Labeled Heptapeptide and Polyethylene Glycol

Two oxidized forms of low-density lipoprotein (LDL), oxidized (Ox-LDL) and minimally modified (MM-LDL), and the immune complexes (LDL-ICs) that they form with their corresponding antibodies, play a major role in the pathogenesis of atherosclerosis. Recently, we reported that the heptapeptide KP6 (Lys-Trp-Tyr-Lys-Asp-Gly-Asp) coupled through its ε-amino group present on the N-terminal Lys to fluorescein isothiocyanate (FITC)— (FITC)KP6— binds specifically to Ox-LDL and MM-LDL, but not to native LDL. Here, to develop a novel method for measuring the levels of oxidatively modified LDL in blood, using (FITC)KP6, we analyzed the latter’s binding with MM-LDL-IC and Ox-LDL-IC. Polyacrylamide gel electrophoresis analysis revealed that (FITC)KP6 could efficiently and specifically bind to polyethylene glycol (PEG)-precipitated MM-LDL-IC and Ox-LDL-IC in a dose-dependent manner with high sensitivity in plasma and serum. Our results indicate that the above method for measuring the levels of PEG-precipitated, oxidatively modified LDL-ICs, formed by the addition of anti-Ox-LDL antibody to blood, using (FITC)KP6, can aid the diagnosis of atherosclerosis.     

丁香有效部位对LDL中脂类、蛋白氧化修饰及光谱学变化的抑制

LDL氧化修饰是致动脉粥样硬化的关键性因素。其中,在氧化修饰过程中LDL所含脂类、蛋白及其光谱学性质均会受到影响。前期研究结果发现丁香对LDL氧化修饰具有很强的抑制作用。但是,丁香是否是通过抑制脂类及蛋白氧化来实现,以及丁香是否能抑制LDL氧化修饰后光谱学性质的改变,这些问题目前均不清楚。据此,运用紫外吸收光谱、荧光光谱等方法研究了丁香有效部位(effective fraction from clove,EFC)对LDL氧化修饰的抑制效果。研究结果表明,EFC能有效延缓脂质氧化过程中共轭二烯(CD)增殖及推后其达到最大值,并抑制胆固醇降解;也可抑制蛋白组分apoB100中Trp荧光猝灭及Lys氧化修饰和荧光光谱变化;同时也能抑制LDL中脂质与蛋白过氧化产物-脂褐素的生成;此外,该部位对LDL 氧化修饰过程中紫外-可见光谱学特征的改变也有影响。论文将为丁香抗AS功能食品研发提供参考。     

Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm² for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.     

Effect of stearic acid, zinc stearate coating on the properties of synthetic hydromagnesite

Synthetic hydromagnesite (SHM), used as flame retardant for polymers, may have similar or better flame retardancy effectiveness than aluminum tri-hydroxide (ATH) and magnesium di-hydroxide (MDH). Suitable surface modifiers are often employed to improve its dispersion and compatibility with polymer matrix. In this study, we chose stearic acid (SA) and zinc stearate (ZS) as the surface modifier, and investigated the properties of SHM modified with various surface modifier content using dry blending coating process. Scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TG), particle size distribution, contact angle, oil absorption, bulk density, tapped density and Carr's index were employed to characterize the effect of surface modification. The results showed that the surface of SHM powders was changed from hydrophilic to lipophilic. The flowability of the surface modified powder was also improved. TG graphs showed that the surface modifier had no obvious influence on the degradation pathway of the SHM.     

光谱法研究Cu~(2+)诱导的不同时间的LDL体外氧化

氧化低密度脂蛋白(oxidized low density lipoprotein,oxLDI)被认为是动脉硬化的关键致病因素.文章综合运用紫外吸收光谱、荧光光谱、同步荧光光谱及圆二色(circular diclaro‘lsm.CD)光谱研究了(好'诱导不同时间的U)IJ体外氧化过程.随着氧化时间的增加.生成的丙二醛(malonaldehyde,MDA)的量逐渐增加,其相对应的430 nm 处的荧光强度也随之加强,氧化过程中生成了新的氧化产物.氧化低密度脂蛋白紫外吸收增强;表征氨基酸残基信息的特征荧光强度和同步荧光强度降低;载脂蛋白B-100(apolipoproteinB-100,apoB-100)α-螺旋含量减少.实验结果表明,LDL氧化过程中Cu2+不仅诱导了氧化产物的生成,而且改变了apoB-100的构象进而导致了生色基团的微环境的变化.     

Surface grafting density analysis of high anti-clotting PU-Si-g-P(MPC) films

Well-defined zwitterionic polymer brushes with good blood compatibility were studied, grafted from polyurethane (PU) substrate (PU-Si-g-P(MPC)) by surface-initiated reverse atom transfer radical polymerization (SI-RATRP). We found that the structure of polymer brushes and hence their properties greatly depend on the grafting density. To solve the problems of the normal method for grafting density measurement, i.e., more requirements for qualified and proficient instrument operator, we established an effective and feasible way instead of the conventional method of spectroscopic ellipsometer combined with gel permeation chromatograph (ELM/GPC) to calculate the grafting density of PU-Si-g-P(MPC) films by using a software named ImageJ 1.44e in combination with scanning electronic microscope (SEM) or atomic microscope (AFM). X-ray photoelectron spectroscopy (XPS), SEM and AFM were employed to analyze the surface topography and changes of elements before and after graft modification of the synthetic PU-Si-g-P(MPC) biofilms.     

Structural and Nonlinear Optical Characteristics of In Vitro Glycation of Human Low-Density Lipoprotein,as a Function of Time

Modified low-density lipoprotein (LDL) is a well-known risk marker for diabetes and cardiovascular disease. In vitro and in vivo studies have shown that native LDL particles, when modified by oxidation and/or glycation processes, become proatherogenic. Other studies have shown that high LDL concentrations also contribute to atherogenic diseases. In the present in vitro study, we investigate structural characteristics, linear and nonlinear optical properties of LDL particles modified by glycation, compared to modified-control and non-modified LDL (LDL_nat). LDL particles were isolated from normolipidemic individuals and aliquots were incubated in PBS (LDL_control) and glycated (LDL_glyc) with glycolaldehyde (GAD) from 2 to 6 days. The nonlinear optical Z-Scan experiments indicate that GAD modifies the optical properties of the LDL. These results indicate the application of a nonlinear optical technique as a tool to investigate the characteristics of LDL particles, in particular when modifications are induced in the particles by glycation.     

Surface modification of polymethyl methacrylate intraocular lenses by plasma for improvement of antithrombogenicity and transmittance

To improve antithrombogenicity and reduce ultraviolet transmittance, polymethyl methacrylate intraocular lenses (PMMA IOLs) were pretreated with Ar plasma and combined with heparin (Hp), with polyglycol (PEG) and with both Hp and PEG in a plasma atmosphere. The resulting modified PMMA IOLs denoted as PEG-PMMA, Hp-PMMA and Hp-PEG-PMMA were characterized by attenuated total reflectance Fourier transfer infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), ultraviolet-visible spectroscopy (UV-vis), contact angle (CA) and platelet adhesion experiments. The results indicated that Hp and PEG had been successfully immobilized onto the surfaces of PMMA IOLs. Antithrombogenicity was improved remarkably and ultraviolet transmittance was reduced as well.     

异性官能团修饰石墨烯吸附GIS 特征气体能力的DFT研究

为研制高灵敏度气体绝缘组合开关(GIS)特征气体检测传感器,利用密度泛函理论方法,采用分子模拟软件对GIS特征气体(SO_2,SOF_2,SO_2F_2,CF_4)在异性官能团(羟基、羧基与氨基)修饰石墨烯表面的吸附过程进行模拟计算,从微观角度研究了GIS特征气体在异性官能团修饰石墨烯表面的吸附机理.首先计算了各吸附体系的吸附能、净电荷转移量以及态密度,比较了羟基与羧基修饰石墨烯对GIS特征气体的吸附能力;再通过分子前线轨道与能隙对吸附能力强弱的机理进行了研究,得出强吸附修饰官能团的规律性特征,并通过氨基石墨烯进行验证.结果表明:羧基与羟基修饰石墨烯能够有效提高对SO_2,SOF_2,SO_2F_2的吸附能力,但羧基石墨烯对GIS特征气体的整体吸附能力更强;异性官能团修饰石墨烯后的能隙及其与气体分子前线轨道能量差越小,对GIS特征气体吸附能力就越强,异性官能团修饰石墨烯的能隙与前线轨道能量差可以作为选择特征气体敏感材料的依据.     

Fabrication and characterizations of a polymer hybrid OA/MA/St-TiO2

A nano-hybrid composite of octadecyl acrylate/maleic anhydride/styrene (OA/MA/St) encapsulating nano-TiO₂ with an average particle size of 30-60 nm was fabricated based on chemical modification of nanotitania. The polymer hybrid OA/MA/St-TiO₂ and nano-TiO₂ were characterized by infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), static contact angle (CA) as well as transmission electron microscopy (TEM). FT-IR spectra and TGA results suggest that the copolymer OA/MA/St adheres on the surface of nano-TiO₂ through physical adsorption and chemical bonding. The calculated reacted OH surface density is about 0.6 OH/nm², and the modification efficiency is approximately 27.28%. In addition, when the molar ratio of OA/MA/St is 7:2:1, the hybrid shows the strongest hydrophobicity, and its static contact angle reaches as high as 146°. TEM image of the hybrid OA/MA/St-TiO₂ reveals that the modified particles have good dispersibility and compatibility with n-hexane.     

Key role of receptor density in colloid/cell specific interaction: a quantitative biomimetic study on giant vesicles

This paper presents an experimental study of the adsorption of colloids on model membranes mediated by specific ligand-receptor interactions. The colloids consist of lipid multilamellar liposomes (spherulites) functionalized with the B-subunit of Shiga Toxin (STxB), while the membranes are lipid Giant Unilamellar Vesicles (GUV) containing STxB lipid receptor, Globotriaosylceramide (Gb3). Through confocal microscopy and flow cytometry, we show the specificity of the adsorption. Moreover, we show that flow cytometry can be used to efficiently quantify the kinetics of colloid adsorption on GUVs with very good statistics. By varying the bulk colloid concentration and receptor density in the membrane, we point out the existence of an optimum Gb3 density for adsorption. We propose that this optimum corresponds to a transition between reversible colloid adsorption at low Gb3 density and irreversible adsorption, and likely spherulite fusion, at high density. We compare our results both to STxB-colloids adhering on living cells and to free STxB proteins interacting with GUVs containing Gb3. This biomimetic system could be used for a quantitative evaluation of the early stage of virus infection or drug delivery.     

分光光度法测定半交联壳聚糖珠对肝素的吸附

本文采用分光光度法测定水目的物肝素浓度来计算吸附量,结果表明,半交联壳聚糖珠对肝素有较好的吸附效果。     

Modification of nano-fibriform silica by dimethyldichlorosilane

The modification of nano-fibriform silica by dimethyldichlorosilane was studied by transmission electron microscopy, X-ray powder diffraction, infrared spectroscopy, Raman spectroscopy, physical N₂ adsorption techniques, differential thermal and thermogravimetric analysis, scanning electron microscopy, and elemental analyzer.The results show that dimethyl silane derivatives have been successfully covalently grafted on nano-fibriform silica. The polarity of the modified product decreases with the substitution of -OH groups by siloxyl groups. Therefore, the modified product can be easily dispersed in organic solvent and its compatibility with organic molecules is improved. After modification the pore volume decreases and the ductility greatly increases, indicating that the modified product is of a higher strength than before. The study demonstrates that the modified product can be used as an ideal additive to reinforce the strength of organic materials.     

High Hydrostatic Pressure Induces a Lipid Phase Transition and Molecular Rearrangements in Low‐Density Lipoprotein Nanoparticles

Low‐density lipoproteins (LDL) are natural lipid transporter in human plasma whose chemically modified forms contribute to the progression of atherosclerosis and cardiovascular diseases accounting for a vast majority of deaths in westernized civilizations. For the development of new treatment strategies, it is important to have a detailed picture of LDL nanoparticles on a molecular basis. Through the combination of X‐ray and neutron small‐angle scattering (SAS) techniques with high hydrostatic pressure (HHP) this study describes structural features of normolipidemic, triglyceride‐rich and oxidized forms of LDL. Due to the different scattering contrasts for X‐rays and neutrons, information on the effects of HHP on the internal structure determined by lipid rearrangements and changes in particle shape becomes accessible. Independent pressure and temperature variations provoke a phase transition in the lipid core domain. With increasing pressure an interrelated anisotropic deformation and flattening of the particle are induced. All LDL nanoparticles maintain their structural integrity even at 3000 bar and show a reversible response toward pressure variations. The present work depicts the complementarity of pressure and temperature as independent thermodynamic parameters and introduces HHP as a tool to study molecular assembling and interaction processes in distinct lipoprotein particles in a nondestructive manner.     

Nanocomposite of polypyrrole and alumina nanoparticles as a coating filler for the corrosion protection of aluminium alloy 2024-T3

Aluminium (Al) alloys such as 2024-T3 are widely used in industry as low weight construction materials with excellent mechanical properties. Until recently corrosion protection of Al alloys was carried out with coatings containing hexavalent chromium (Cr⁶⁺). However, Cr⁶⁺ is a health and environmental hazard and has to be replaced. Intrinsically conducting polymer (ICP) technology is the promising alternative to chromate coating technology because of good corrosion protection properties of ICPs, their moderate cost and good environmental compatibility. In this paper we report successful attempt of making nanocomposite comprised of alumina nanoparticles modified by polypyrrole for the purpose of corrosion protection of Al alloy. Modified nanoparticles were used as coating filler. Coating was designated to perform as an active barrier to electrolyte diffusion. Properties of the coating were examined by adhesion test, electrochemical impedance spectroscopy, X-rays elemental analysis, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy.     

壳聚糖包裹AgInS_2的物理表征及生物毒性研究

选用天然多糖中唯一的碱性多糖——壳聚糖作为稳定剂和包裹剂,成功合成了水溶性的Ag In S2量子点/低分子量壳聚糖纳米复合材料(Ag In S2/LCSMS)。利用透射电子显微镜(TEM)、FT-IR傅里叶红外光谱仪、紫外吸收光谱、荧光分光光度计等表征手段对纳米复合材料的形貌、化学组成及光学性质进行了研究。结果表明,Ag In S2/LCSMS纳米复合材料的粒径约为5~6 nm,在水相中仍具有较稳定的发光。之后,对Ag In S2/LCSMS纳米复合材料的生物相容性进行了研究,对比Ag In S2/LCSMS纳米复合材料与Ag In S2量子点的细胞活性测试结果发现,Ag In S2/LCSMS纳米复合材料的细胞活性比Ag In S2量子点有了明显的提高,说明通过低分子量壳聚糖的包裹可以明显提高纳米材料的生物相容性。因此,这类具有较好水溶性和生物相容性的荧光Ag In S2/LCSMS纳米复合材料可作为优良的生物荧光标记材料在生物医学检验、细胞以及活体成像研究中有广泛的应用前景。     

Investigation on surface properties of TiO2 films modified by DC glow discharge plasma

In the present work, TiO₂ films deposited on polyethylene terephthalate substrates by dip coating technique were subsequently treated by DC glow discharge plasma as a function of discharge potential. Hydrophilicity of these TiO₂ film surfaces was analyzed by contact angle measurements. Atomic force microscopy (AFM) revealed changes in surface morphology of the plasma treated TiO₂ films. Modifications in structural and chemical composition of the TiO₂ films were detected by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The blood compatibility of TiO₂ films was studied by in vitro investigation which includes thrombus formation and whole blood clotting time analysis (WBCT). It was found that the plasma treatment results in blood compatibility enhancement attributed to the structural, chemical and morphological properties of the modified film surfaces.     

Mechanical properties and platelet adhesion behavior of diamond-like carbon films synthesized by pulsed vacuum arc plasma deposition

Diamond-like carbon (DLC) is an attractive biomedical material due to its high inertness and excellent mechanical properties. In this study, DLC films were fabricated on Ti6Al4V and Si(1 0 0) substrates at room temperature by pulsed vacuum arc plasma deposition. By changing the argon flow from 0 to 13 sccm during deposition, the effects of argon flow on the characteristics of the DLC films were systematically examined to correlate to the blood compatibility. The microstructure and mechanical properties of the films were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) surface analysis, a nano-indenter and pin-on-disk tribometer. The blood compatibility of the films was evaluated using in vitro platelet adhesion investigation, and the quantity and morphology of the adherent platelets was investigated employing optical microscopy and scanning electron microscopy.The Raman spectroscopy results showed a decreasing sp³ fraction (an increasing trend in I_D/I_G ratio) with increasing argon flow from 0 to 13 sccm. The sp³:sp² ratio of the films was evaluated from the deconvoluted XPS spectra. We found that the sp³ fraction decreased as the argon flow was increased from 0 to 13 sccm, which is consistent with the results of the Raman spectra. The mechanical properties results confirmed the decreasing sp³ content with increasing argon flow. The Raman D-band to G-band intensity ratio increased and the platelet adhesion behavior became better with higher flow. This implies that the blood compatibility of the DLC films is influenced by the sp³:sp² ratio. DLC films deposited on titanium alloys have high wear resistance, low friction and good adhesion.