碳纳米胶囊中水分子的分子动力学研究

采用分子动力学方法研究了不同温度下碳纳米胶囊中水分子及其氢键的聚集密度分布,讨论了水分子内部键角及其取向规律.计算结果表明,由于碳纳米胶囊的束缚作用,水分子主要聚集在与胶囊形状相似的三个薄层中,随着温度的升高,聚集密度峰均会展宽并向管壁移动.氢键的分布规律与水分子聚集密度类似并对其取向角分布有明显影响.与通常情况不同,在1000K高温时仍存在相当数量的氢键.在3100 K附近,碳纳米胶囊发生破裂,溢出少量水分子后自动愈合.     

褐煤O2/CO2燃烧时可吸入颗粒物中碱性金属分布特性

通过沉降炉燃烧实验,研究了褐煤O2/CO2燃烧时可吸入颗粒物的生成和碱性金属元素在颗粒物中的分布特性.结果表明,燃烧气氛由O2/N2燃烧转变为O2/CO2燃烧时,亚微米颗粒物的生成量减少,但超细颗粒量增加.气氛对碱性金属元素分布的影响主要体现在亚微米颗粒范围内.与O2/N2燃烧相比,相同氧浓度下O2/CO2燃烧时所生成亚微米颗粒物中碱性金属向小粒径颗粒中富集.O2/CO2气氛下,低氧浓度燃烧时碱性金属元素对亚微米颗粒物的生成贡献大,而增加氧浓度其在亚微米颗粒物中质量份额则减小.     

用于亚微米颗粒测量的后向散射光谱法

针对后向散射光谱粒径测量法对亚微米颗粒测量准确度较差的问题,提出了一种采用紫外光作为光源的测量方法.通过快速傅里叶变换计算了粒径为0.25~1 μm的聚苯乙烯亚微米颗粒的后向散射频谱,将频谱峰值对应的频率值与相应的颗粒粒径进行线性回归,各粒径值相对于回归直线的平均误差为±0.02 μm. 结果表明,本文提出的300~400 nm的紫外光适用于测量0.25~1 μm的亚微米颗粒,相比目前国外最新的采用可见光谱或红外光谱的方法准确度提高了一个数量级,同时该方法也适用于测量双峰分布亚微米颗粒系.     

用于亚微米颗粒测量的后向散射光谱法

针对后向散射光谱粒径测量法对亚微米颗粒测量准确度较差的问题,提出了一种采用紫外光作为光源的测量方法.通过快速傅里叶变换计算了粒径为0.25～1 μm的聚苯乙烯亚微米颗粒的后向散射频谱,将频谱峰值对应的频率值与相应的颗粒粒径进行线性回归,各粒径值相对于回归直线的平均误差为±0.02 μm.结果表明,本文提出的300～40...     

跨微米尺度混合颗粒粒径的同步测量方法

基于多波长消光法和图像法颗粒测量原理,提出了跨微米尺度混合颗粒粒径同步测量方法,建立了亚微米-十微米尺度颗粒粒径消光光谱反演算法及十微米以上尺度颗粒粒径图像处理算法;采用分光棱镜,搭建了消光光谱与背光图像同步测量装置,利用500 nm～76.9μm粒径范围内的10种标准颗粒配成跨微米尺度混合颗粒样品并开展实验研究。结果表明:利用所提方法开展跨微米尺度混合颗粒粒径同步测量时,亚微米-十微米尺度颗粒消光光谱与十微米以上尺度颗粒背光图像的相互影响可忽略,可同步测量得到跨微米尺度混合颗粒粒径;利用消光法和图像法分别开展亚微米-十微米、十微米以上尺度颗粒粒径测量,与标准颗粒粒径相比,相对误差均小于8%,且测量重复性较好,这为跨微米尺度混合颗粒提供了一种有效的粒径测量手段。     

电子显微镜散斑照相技术

提出了一种新颖的人工亚微米/纳米散斑制作技术.采用超声波分散亚微米/纳米颗粒,然后利用范德华力、静电力和毛细力将其吸附在试件表面.在特定分辨率的扫描电镜下,物体表面的亚微米/纳米颗粒可以看作是亚微米/纳米散斑.此外,发展了一种测量面内亚微米/纳米级变形的电子显微镜散斑照相技术.详细介绍了人工制作亚微米/纳米散斑和电子显微镜散斑照相技术,实验验证了技术的可行性     

应用动态光散射和透射电镜研究热力学不相容条件下果胶与乳清蛋白混合体系的微观结构

应用动态光散射、透射电镜和粘度-剪切模型3种方法互相配合,研究了果胶与乳清分离蛋白的混合体系在热力学不相容条件下的微观结构。在90℃及pH7.4条件下,向5%蛋白浓度的乳清蛋白溶液中加入带有负电的果胶分子,可导致热变性乳清蛋白分子之间发生损耗聚集,并引发混合体系内的相分离现象。确切地说,当果胶与乳清蛋白的混合重量比小于0.08时,溶液内可观察到粒径小于300nm的聚集颗粒,体系呈现牛顿流体特征;而当混合重量比大于0.08时,体系粘度上升,切稀特征逐渐明显,聚集集团粒径接近700nm。     

煤燃烧亚微米颗粒数浓度特性实验研究和理论分析

煤粉燃烧过程中亚微米颗粒数浓度的准确采样和测量是一个颇具挑战性的问题,本文基于清华大学高温-维炉实验系统产生的亚微米颗粒物,发展了适用于气溶胶扫描电迁移率颗粒粒径谱仪(SMPS)的两级氮气稀释水冷等速取样技术.为得到炉膛内亚微米颗粒的真实数浓度粒径分布,本文探索了不同稀释比对测量结果的影响,最后发展了基于成核、团聚和表...     

纳米多晶铜的超塑性变形机理的分子动力学探讨

在聚能装药爆炸压缩形成射流的过程中, 伴随着金属药型罩的晶粒细化, 从原始晶粒30-80 μm细化到亚微米甚至纳米量级, 从微观层面研究其细化机理和动态超塑性变形机理具有很重要的科学意义. 采用分子动力学方法模拟了不同晶粒尺寸下纳米多晶铜的单轴拉伸变形行为, 得到了不同晶粒尺寸下的应力-应变曲线, 同时计算了各应力-应变曲线所对应的平均流变应力. 研究发现平均流变应力最大值出现在晶粒尺寸为14.85 nm时. 通过原子构型显示, 给出了典型的位错运动过程和晶界运动过程, 并分析了在不同晶粒尺寸下纳米多晶铜的塑性变形机理. 研究表明: 当晶粒尺寸大于14.85 nm时, 纳米多晶铜的变形机理以位错运动为主; 当晶粒尺寸小于14.85 nm时, 变形机理以晶界运动为主, 变形机理的改变是纳米多晶铜出现软化现象即反常Hall-Petch关系的根本原因. 通过计算结果分析, 建立了晶粒合并和晶界转动相结合的理想变形机理模型, 为研究射流大变形现象提供微观变形机理参考.     

ZnO@SiO_2核壳量子点的制备及其荧光性能的研究

用一种操作简单、反应条件温和的方法制备了分散性好的超微小Zn O@Si O2核壳量子点透明溶液,利用透射电子显微镜(TEM)、紫外吸收光谱(UV)、荧光光谱(FL)、纳米粒度和ZETA电位分析仪等技术对所制备纳米粒子的粒径大小、吸收光谱、发光性质进行表征。结果表明,Zn O@Si O2核壳量子点平均粒径在3~5 nm,在紫外灯下发出黄绿色荧光,紫外最大吸收在330 nm左右,可以发射出510 nm的荧光。同时,系统地考察了p H值、温度、不同金属阳离子以及不同阴离子对量子点荧光强度的影响。实验结果表明:当p H≤7时,量子点荧光完全猝灭;当p H7时,量子点荧光强度随着p H值的增加而增强,当p H为9.0时,荧光强度达到最大,然后随着p H值的升高荧光略有降低。量子点随着温度的升高荧光强度逐渐降低,当温度达到50℃以上荧光完全猝灭。一价金属离子对量子点荧光强度基本没有影响,二价金属离子对量子点荧光削弱程度的大小顺序为Fe2+Mn2+Cu2+Pb2+Co2+Ba2+Mg2+,三价金属离子对量子点荧光削弱程度的大小顺序为Fe3+Cr3+Bi3+Al3+。其中,Fe3+、Fe2+、Bi3+、Cr3+、Mn2+等金属离子对量子点的荧光有猝灭作用,PO43-、HPO42-、H2PO4-等离子对量子点荧光稍有增加作用,HCO3-、CO32-、CH3COO-、SO32-等阴离子对量子点的荧光有削弱甚至猝灭的作用,Cl-、SO42-、NO3-等离子对量子点荧光几乎没有影响。     

Characterization of sonochemically prepared human serum albumin nanocapsules using different plant oils as core component for targeted drug delivery

The focus of this study is the preparation of proteinaceous human serum albumin (HSA) nanocapsules with biocompatible plant oil cores avoiding toxic cross-linker and noxious non-aqueous liquids. The sonochemical preparation of HSA capsules with different plant oils yields particles with narrow size distribution forming suspensions stable for at least 14 days and enabling long-term storage by freezing. Furthermore, wheat germ agglutinin (WGA) as a targeting molecule was successfully embedded into the proteinaceous particle shell at a molar ratio of 7:1 (HSA/WGA). As urothelial cell binding studies revealed up to 55% higher cell binding potential of WGA-grafted particles than those without a targeter, targeted protein nanocapsules represent the first step towards new and innovative formulations.     

Kinetic stability of hematite nanoparticles: the effect of particle sizes

Nanoparticles are ubiquitous in environment and are potentially important in many environmental processes such as sorption, coprecipitation, redox reactions, and dissolution. To investigate particle size effects on nanoparticle aggregation and stability, this study tested aggregation behavior of 12(±2), 32(±3), and 65(±3) nm (hydrated radius) hematite particles under environmental relevant pH and ionic strength conditions. The results showed that at the same ionic strength and pH conditions, different particle sizes show different tendency to aggregate. At the same ionic strength, aggregation rates are higher for smaller particles. The critical coagulation concentration also depends on particle size, and decreases as particle size decreases. As the particle size decreases, fast aggregation shifted to lower pH. This may be related to a dependence of PZC on particle size originating from change of structure and surface energy characteristics as particle size decreases. Under the same conditions, aggregation occurs faster as particle concentration increases. Even though the nanoparticles of different sizes show different response to the same pH and ionic strength, DLVO theory can be used to qualitatively understand hematite nanoparticle aggregation behavior.     

Optimization of Release Conditions of Alzheimer's Drug Donepezil Hydrochloride from Sodium Alginate/Sodium Carboxymethyl Cellulose Blend Microspheres

Microspheres of blends of sodium alginate (NaAlg) and sodium carboxymethyl cellulose (NaCMC) were prepared by a water-in-oil (w/o) emulsion crosslinking method and used for the release of donepezil hydrochloride (DP), which is an Alzheimer's drug. The microspheres were characterized with Fourier transform infrared spectroscopy (FTIR), differantial scanning calorimetry (DSC), and scanning electron microscopy (SEM). The microsphere characteristics, including DP entrapment efficiency, particle size, equilibrium swelling degree (ESD), and DP release kinetics, were determined. The effects of the preparation conditions, including the NaAlg/NaCMC (w/w) ratio, drug/polymer (w/w) ratio, cross-linker concentration and time of exposure to the cross-linker, on the release of DP were investigated for successive gastrointestinal tract pH values of 1.2, 6.8, and 7.4 at 37°C. The release of DP increased with the increase in NaAlg/NaCMC (w/w) ratio and drug/polymer (d/p) ratio, while it decreased with increasing extent of cross-linking. The optimum DP release was obtained as 99.13% for a NaAlg/NaCMC (w/w) ratio of 2/1, d/p ratio of 1/4, CaCl₂ concentration of 5% and crosslinking time of 30 min. It was also observed from release results that DP release from the microspheres through the external medium was higher at low pH (1.2) values than that at high pH (6.8 and 7.4) values. The DP release of the microspheres followed either Fickian transport below a value of n < 0.5 or anomalous transport (n = 0.5–1.0).     

Dependence of Nanofluid Viscosity on Particle Size and pH Value

We investigate the viscosity of silicon dioxide nanofluid at different particle sizes and pH values considering nanoparticle aggregation. The experimental and simulation results indicate that nanoparticle size is of crucial importance to the viscosity of the nanofluid due to aggregation. As the nanoparticle size decreases, the viscosity becomes much more dependent on the volume fraction. Moreover, when the nanoparticle diameter is smaller than 2Ohm, the viscosity is closely related to the pH of the nanofluid, and fluctuates with pH values from 5 and 7.     

Fabrication of micro–nanocapsules by a new electrospraying method using coaxial jets and examination of effective parameters on their production

This paper considers a new method related to the micro and nanocapsules production by using coaxial jets electrospray. The produced micro–nanocapsules were characterized on their structure, mean particles size and morphology by optical and scanning electron microscope. The effects of different operating parameters on the size of the particles were investigated. The obtained results showed the efficiency of the mentioned method in micro–nanocapsules fabrication. The average diameter of fabricated capsules was variable from 80 nm to 900 μm by adjusting different parameters of process.     

番茄红素与牛血清白蛋白的相互作用

采用荧光光谱法研究了番茄红素(Lycopene)与牛血清白蛋白(BSA)的相互作用关系。研究表明,番茄红素能使BSA在340nm(λem)处产生荧光猝灭,猝灭机理为静态猝灭。pH=7.4,温度为293K时,猝灭时表观结合常数KA为5.33×104L.mol-1,结合位点数n为0.6461,同时荧光猝灭最大速率常数Kq=2.76×1012L.mol-1.s-1。二者呈自发结合且主要作用力为氢键和范德华力,结合距离r与能量转移效率E分别为5.6nm和0.098,偏酸性或碱性的条件使番茄红素与BSA的结合常数增加。     

Freeze-fracture electron microscopy and light scattering studies on polyethylcyanoacrylate nanocapsule colloidal suspensions

Summary Nanocapsule preparative procedures are able to change the availability of drugs from delivery devices. In particular, the influence of the organic solvent, used in the interfacial polymerisation process, on the shape, mean particle size, size distribution and type of colloidal suspension was investigated. The organic solvents employed in the preparation of PECA nanocapsules were ethanol, acetone or acetonitrile. A non-ionic surfactant (Pluronic F68) was used during the preparation process. The amount of monomer represented another variable, capable of influencing the final carrier properties of PECA nanocapsules. The presence of ethanol achieved the formation of both nanoparticles and nanocapsules. However, the presence of acetone or acetonitrile achieved not only a highly homogeneous size colloidal system, but also the formation of only one type of PECA nanosphere (nanocapsule). The different amount of monomer led to the formation of nanocapsules with a wall thickness proportional to the initial concentration of the polymerising agent. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Chitosan Nanocapsules for pH‐Triggered Dual Release Based on Corrosion Inhibitors as Model Study

Chitosan (CS) is known for its uniqueness in terms of containing reactive functional groups, i.e., amino and hydroxyl groups, along the chain which offer the noncovalent bonds and chemical modifications. At pH 3 in emulsion system, the CS chains are under charge‐charge repulsive force, leading the polysaccharide chains to align as the hollow nanospheres and at that time, the crosslink leads to the nanocapsules. The CS nanocapsules allow the model cargos, i.e., corrosion inhibitors, entrapment not only via the noncovalent bond based on the weak interaction in the core for 2‐mercaptobenzothiazole (MBT) cargo but also via the chemical bonds based on the amino group remaining on CS structure to result in either amide or Schiff base linkage in case of 3‐nitrosalicylic acid (3NiSA) cargo. The release studies indicate that CS nanocapsules can release two cargoes upon pH change due to the acidic/basic‐triggered cleavage of bonds between cargoes and nanocapsules. Once corrosion occurs, resulting in variation of the local pH value, the CS nanocapsules release MBT in fast and 3NiSA in a slow, sustained manner. The efficiency of the approach is demonstrated using the nanocapsules for hindering the corrosion of copper as measured by electrochemical quartz crystal microbalance.     

尼古丁与BSA相互作用的光谱研究

用紫外-可见光谱和荧光光谱研究了尼古丁与牛血清白蛋白(bovine serum albumin, BSA)的相互作用。荧光研究表明,尼古丁浓度的增加引起BSA 345 nm处荧光有规律地猝灭。Stern-Volmer 方程分析pH 5.0,pH 7.4和pH 11.0体系的荧光猝灭机理发现,pH 5.0体系属动态猝灭,而pH 7.4和pH 11.0体系为静态猝灭。Lineweaver-Burk双倒数方程计算pH 7.4和pH 11.0体系在温度为20和37 ℃条件下尼古丁和BSA的结合常数k分别为：k_{20 ℃}=140.15 L·mol-1 ,k_{37 ℃}=131.83 L·mol-1 (pH 7.4)和k_{20 ℃}=141.76 L·mol-1,k_{37 ℃}=27.79 L·mol-1(pH 11.0),表明结合常数在pH 7.4条件下受温度的影响要比pH 11.0条件下小,推测是由于不同pH下尼古丁存在的不同形态所致。紫外-可见光谱研究表明,pH 7.4条件下尼古丁浓度的增加引BSA在210 nm处吸收峰吸收强度减小且红移,说明BSA二级结构发生变化,即螺旋结构变松散;紫外二阶导数光谱和同步荧光光谱(Δλ=λ_em-λ_ex=15 nm和Δλ=λ_<i>em-λ_ex=60 nm)分析尼古丁对BSA芳香性氨基酸(Trp, Tyr和Phe)残基微环境的变化,结果表明高浓度的尼古丁使所有这些芳香性氨基酸残基微环境由疏水环境转变为亲水环境。     

pH Fluorescent Probes: Chlorinated Fluoresceins

A series of regiospecific chlorinated fluoresceins have been synthesized by the reaction of the regiospecific chlorinated resorcinols with chlorinated phthalic anhydride. The regioisomers were successfully separated by chromatography. The photophysical properties of the obtained chlorinated fluoresceins were examined and found their absorption and emission maxima at long wavelength with high fluorescence quantum yield. Especially, pH-dependent properties of chlorinated fluoresceins have been studied in detail. These compounds show strongly pH-sensitive range of 3.5-7.0, and have lower pK (a) values than fluorescein. Furthermore, their fluorescent intensity could reach the maximum in the physiological environment of pH range 6.8-7.4. Due to higher fluorescence quantum yield and lower pK (a) values, chlorinated fluoresceins will be expected to be used as excellent pH fluorescent probes for pH measurement of the acidic cell.