醇类低温保护剂水溶液过冷和水合性质研究

利用差示扫描量热仪研究了乙二醇、丙三醇、1,3丙二醇、1,3丁二醇和2,3丁二醇水溶液的过冷行为和水合性质,得出了这些性质与线性多元醇溶液浓度的关系.研究发现,在低浓度过冷度与浓度之间没有明显关系;而在中高浓度则具有相似的变化规律,即随着溶液浓度增大而增大.各低温保护剂在水合性质上所表现出的差异性,体现了保护剂的官能团(羟基、甲基)所起到的重要作用.     

生物材料玻璃化保存液的热分析

在玻璃化超低温保存生物材料的研究中,低温保护剂的热分析对玻璃化溶液的优化和保存方案的选择具有重要的指导意义.本文以渗透性低温保护剂二甲基亚砜和丙二醇以及非渗透性保护剂聚乙烯醇作为研究对象,利用差式扫描量热法对聚乙烯醇/二甲基亚砜/丙二醇体系进行升温和降温实验,考察了体系的结晶特性、玻璃化转变特性、聚乙烯醇的浓度等因素对体系热性能参数的影响.     

纳米微粒对低温保护剂溶液玻璃化性质的影响

利用差示扫描量热仪(DSC)研究了加入羟基磷灰石(HA)纳米微粒对低温保护剂溶液玻璃化的影响,实验得到了不同粒径和不同质量浓度的HA纳米微粒加入PVP溶液的玻璃化转变温度与反玻璃化温度.实验结果表明加入纳米微粒能显著的影响低温保护剂溶液的玻璃化性质.且随着纳米微粒质量分数的增加,溶液的玻璃化转变温度与反玻璃化温度均显著...     

二甲亚砜对关节软骨渗透性研究

玻璃化被认为是低温保存关节软骨的一种有效方法,但需要考虑低温保护剂渗入软骨的速率以及低温保护剂毒性的制约。本文选用二甲亚砜(DMSO)作为低温保护剂,对其在1℃,22℃和37℃时对绵羊关节软骨的渗透特性进行了研究,得到相应的扩散系数为1.9×10~(-6) cm~2/s,3.3×10~(-6) cm~2/s和5.7×10~(-6)cm~2/s,活化能为22.84 kJ/mol。认识低温保护剂对关节软骨的渗透特性有助于建立低温保护剂加入/取出过程的数学模型,从而优化关节软骨的玻璃化保存方案。     

HA纳米微粒对PEG-600低温保护剂反玻璃化结晶的影响

为了研究羟基磷灰石HA纳米微粒对低温保护剂反玻璃化结晶的影响,本文利用DSC和低温显微镜研究了含有不同粒径(20nm、40nm、60nm)和不同质量浓度(0.1%、0.2%、0.4%、0.8%)HA纳米微粒的PEG-600(50%,w/w)溶液反玻璃化过程中的结晶现象.试验结果表明:与未添加纳米微粒的PEG-600溶液相比,加入40nm、0.4%纳米微粒的HA-PEG600溶液的反玻璃化温度升高了7℃;加入20nm、0.4%和40nm、0.8%纳米微粒的HA-PEG600溶液的冰晶生长速率分别降低了35%和提高了50%;纳米低温保护剂溶液的冰晶形貌从大圆形变成了小圆形、枝晶或小圆形中夹带枝晶.     

纳米微粒对低温保护剂溶液结晶性质的影响

为了研究纳米微粒对低温保护剂溶液结晶性质的影响,实验利用差示扫描量热仪(DSC)测量了加入不同粒径、不同质量分数的HA纳米微粒的乙二醇(EG)低温保护剂溶液的成核温度和结晶焓。实验结果表明:纳米微粒加入EG溶液后,成核温度明显升高,并且随着纳米微粒粒径的和质量浓度的增大而升高显著;加入一定质量浓度(>0.2%)的纳米微粒后,同浓度的低温保护剂溶液的结晶焓稳定地升高。成核温度与结晶焓的升高说明,纳米微粒能够促进低温保护剂溶液的结晶。     

液相线跟踪低温保存方法的研究

液相线跟踪法是生物材料玻璃化保存的一种手段。降温时通过边降温边提高低温保护剂浓度、复温时边升温边降低低温保护剂浓度的方式,该方法能够有效减轻降温/复温过程中高浓度保护剂对细胞的毒性损伤,从而提高生物材料低温保存的成活率。文中介绍可实现液相线跟踪的低温保存装置,该装置以液氮为冷源、采用计算机控制。以二甲亚砜-氯化钠-水溶液为例进行的实验表明,该装置能够实现温度和保护剂浓度的良好匹配,二甲亚砜的最终浓度达到了玻璃化所需浓度。     

基于薄液膜蒸发的超高速冷冻方法初探

玻璃化冷冻方法是细胞超低温保存的有效冷冻方法之一.在细胞的玻璃化冷冻过程中,降温速率的提高有利于细胞内外溶液玻璃化程度的增加,同时可以降低低温保护剂的浓度,进而减少低温保护剂对细胞的毒性损伤和渗透性损伤.本文尝试将薄液膜蒸发这种高效相变传热方式与液氮的低温冷却过程相结合,发展了一种超高速、超低温冷冻降温方法.初步的实验结果表明:冷冻载体从10℃降到-180℃,其平均冷却速率达到了148052℃/min。     

冻干溶液的低温显微研究与热分析

利用低温显微系统研究了叔丁醇水溶液降温时的晶体形态,并利用差示扫描量热法(DSC)研究了溶液的反玻璃化结晶。低温显微实验表明:叔丁醇／水溶液结晶形状、大小与叔丁醇的浓度有关,浓度为10％时形成粗大的针状结晶, 有利于升华速率的提高。DSC实验表明:10％叔丁醇／10％蔗糖／水三元溶液的临界复温速率为250℃／min左右。     

铂表面甘油脱除羟基的从头算分子动力学研究

随着生物质能源的开发,从生物柴油制备中大量获取的甘油成为热门的工业原材料. 甘油可以通过氢解生成1,2-丙二醇和1,3-丙二醇两种丙二醇,这两种丙二醇都具有十分广泛的用途. 实验上报道的众多相关金属催化剂中,铂具有性质稳定、不易失活、可活化氢分子提供氢原子等优点. 此外甘油在铂上氢解生成1,2-丙二醇的选择性高于1,3-丙二醇. 本文主要利用从头算分子动力学对甘油在Pt(111)和Pt(211)表面上发生的羟基解离过程进行了模拟计算,并对比分析了其自由能的变化和表面物种结构参数的变化,得出了以下结论：(i)密度泛函理论优化气相甘油分子结构的结果显示,氢键对于气相中分子的结构与能量有较大贡献,三个羟基形成三个分子内氢键结构时甘油分子能量最低;(ii)通过比较从头算分子动力学模拟得到的自由能能垒和反应自由能,可以得出,在Pt(111)和Pt(211)表面,末端碳上的羟基比中间碳上的羟基更容易发生解离. 这表明在类似的条件下,铂作为催化剂可以为1,2-丙二醇的生产提供更高的选择性,这与文献中报道的实验结果一致;(iii)通过对从头算分子动力学模拟得到的初始吸附态和过渡态结构参数的分析,发现在羟基解离的过程中,C-C键的键长没有明显变化,而氧原子的相对位置以及氢键的长度有明显变化,且氢键长度的变化更加剧烈;(iv)通过比较从头算分子动力学研究所得的自由能能垒和结构参数的相关趋势发现,自由能能垒与初始吸附态和过渡态的氧原子间位置的变化量之间存在线性关系,而分子内氢键对自由能能垒的贡献可以忽略不计. 氧原子间位置的变化越大,自由能能垒越高.     

In vivo quantification of propylene glycol,glucose and glycerol diffusion in human skin with optical coherence tomography

The purpose of study is to quantify and compare diffusion of propylene glycol, glucose, glycerol in the human skin in vivo noninvasively. Optical coherence tomography (OCT) was utilized in the functional imaging of optical cleaning agents for monitoring and quantifying the permeability coefficients (PCs) of them. Our experiments showed that the permeability coefficient of 40% propylene glycol from different subjects was averaged and found to be (2.52 ± 0.02) × 10⁻⁶ cm/s, the permeability coefficient of 40% glucose was (1.94 ± 0.05) × 10⁻⁶ cm/s, and the permeability coefficient of 40% glycerol was (1.82 ± 0.04) × 10⁻⁶ cm/s. The results indicated that the diffusion of propylene glycol solutions was faster than that of glucose solution, and the diffusion of glucose solutions was faster than that of glycerol solutions. The dependence of the permeability on the different hyperosmotic analytes could potentially be used in various basic science and clinical fields, such as optical clearing of tissues and cells as well as in clinical pharmacology.     

Sonoluminescence quenching in aqueous solutions of aliphatic diols and glycerol

The multibubble sonoluminescence (MBSL) signals that were generated using 358kHz ultrasound in aqueous solutions of ethylene glycol, 1,3-propanediol, 1,4-butanediol and glycerol, over a range of concentrations, have been studied. It was found that the intensity of the MBSL was either reduced or enhanced, relative to the signal in water, depending on the concentration of the solute. It was concluded that the reduction in the MBSL intensity was dependent on the strength of the intermolecular forces, in particular hydrogen bonding, between the solute molecules and water. The enhancement in the MBSL signal was ascribed to presence of the solute molecules at the bubble/solution interface that hinder the coalescence of the bubbles in the multibubble clouds produced at the antinodes in the system.     

Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit^® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.     

玉米秸秆常压催化液化及产物分析

以玉米秸秆粉末为原料,浓磷酸为反应催化剂,选取多种有机溶剂为液化剂,170 ℃的条件下,在高压反应釜中制备秸秆生物质油。考察了三乙酸甘油酯复配碳酸乙烯酯、甘油复配碳酸乙烯酯以及聚乙二醇复配碳酸乙烯酯(均为6∶1ω/ω)三种不同的混合液化剂对液化得率和生物质油产品性能的影响。采用气质联用仪(GC-MS)分析秸秆生物质油的化学组成;傅里叶红外光谱仪(FTIR)分析原料和液化残渣的主要官能团。实验结果表明聚乙二醇与碳酸乙烯酯混合溶剂液化时,秸秆生物质油得率为97.84%,三乙酸甘油酯与碳酸乙烯酯混合液化时得率为80.20%,甘油与碳酸乙烯酯混合液化时得率为36.97%。FTIR分析结果表明,以聚乙二醇与碳酸乙烯酯混合溶剂为液化剂,秸秆中纤维素、半纤维素和木素的特征官能团几乎全部消失,液化效果最好。GC-MS分析结果表明,生物质油的成分复杂,主要包括有机酸和酮类、醇和醚类、芳香类、糖类和酯类等化合物。     

Effect of polymer adsorption on the water structure at the quartz/water interface studied by optical sum frequency generation

The effect of polymers weakly adsorbed on a quartz surface on the structure of the interfacial water molecules was investigated by optical sum frequency (SF) spectroscopy. As polymers, poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and two types of tri-block copolymer of Pluronic L64 and 17R-4 were used. SF intensity spectra of OH stretching mode of water molecules at the interface between a quartz substrate and aqueous solutions of the polymers were measured. The total SF intensity of the interfacial water of the L64 aqueous solution was smaller than those of other solutions. This result indicates that the L64 aqueous solution has smaller number of oriented interfacial water molecules. It is suggested that the rapid motion of hydrophilic parts of the adsorbed L64 disturbs the average orientation of the interfacial water molecules. On the other hand, the SF intensity from the interfacial water molecules of aqueous solutions with high ion strength did not depend on the species of the polymers in the solutions. The latter result suggests that the hydration of ions determines the structure of the interfacial water molecules.     

Anti-stokes Raman scattering from DODCI solutions

A clearly resolved anti-Stokes peak was observed in the Raman scattering of He-Ne laser radiation from room temperature solutions of DODCI in ethanol and ethylene glycol, but not from solutions of DODCI in glycerol. A slight red-shift and broadening of the Raman-active vibrational mode was noted in ethylene glycol compared to ethanol. Evidence is presented that solutions of DODCI in glycerol have photochemical instabilities.     

Dielectric Dispersion Study of Poly(vinyl Pyrrolidone)–Polar Solvent Solutions in the Frequency Range 20 Hz–1 MHz

Influence of polar solvents environment and polymer concentrations on the electrical properties (complex dielectric constant, ac electrical conductivity, complex electric modulus and complex impedance) of the solutions of poly(vinyl pyrrolidone) (PVP) in polar solvents, namely water, ethyl alcohol, ethylene glycol, diethylene glycol, poly(ethylene glycol), glycerol, dimethyl sulfoxide and dimethyl formamide, have been investigated in the frequency range 20 Hz–1 MHz at 25°C. Comparative analysis of the dielectric dispersion curves confirms that the solvent molecular size and number of its hydroxyl groups, and the solutions viscosity, are the major factors which governs the PVP chain segmental motion. The ionic conduction and electrode polarization phenomena has a dominant influence on the large increase of complex dielectric constant values of the solutions of PVP‐polar solvent in the lower frequency region. The values of relaxation times corresponding to these phenomena are also reported.     

Laser Diagnostics of the Mesoscale Heterogeneity of Aqueous Solutions of Polar Organic Compounds

A mesoscale droplet phase, which is spontaneously formed in aqueous solutions of some polar organic compounds, has been experimentally investigated by methods of dynamic light scattering and laser phase microscopy. It is shown that tetrahydrofuran and tert-butanol aqueous solutions demonstrate a strong peak of light scattering intensity in the range of molecular concentrations of about 0.02 to 0.08, which corresponds to inhomogeneities with a characteristic size of about 100 nm. These liquid droplets are enriched with molecules of dissolved substance. A similar light scattering peak for aqueous solutions of glycerol and ethylene glycol is less pronounced. A theoretical model of the phase separation of binary solutions with twinkling (i.e., existing for a finite time) intermolecular hydrogen bonds is developed. The model predicts the existence of an additional low-concentration light scattering peak near the spinodal of the solution free of hydrogen bonds. A characterization of solutions according to the numerical values of twinkling hydrogen bond parameters is outlined.     

Cryopreservation of human ovarian tissue by direct plunging into liquid nitrogen: negative effect of disaccharides in vitrification solution

Given that it has been possible to successfully cryopreserve human ovarian tissue by direct plunging into liquid nitrogen, this study was designed to establish the future direction to be taken in this line of research. Bovine oviductal epithelial fragments (as a tissue model) and large biopsy fragments (approximately 2.0 cubic mm) of human ovarian tissue were used for cryopreservation. Two protocols were tested: with permeable cryoprotectants (dimethyl sulphoxide, propylene glycol, glycerol) + egg yolk + sucrose or trehalose + a synthetic blocker of ice nucleation, Supercool X-1000; and using only permeable cryoprotectants (glycerol and ethylene glycol) + egg yolk + Supercool X-1000. The cryopreserved tissue specimens were subsequently thawed and the cryoprotectants removed by dilution in graded sucrose solutions. Both the dynamic growth and hormonal activity of the ovarian tissue pieces, vitrified using only permeable cryoprotectants, were greater than after vitrification in a mixture of permeable cryoprotectants and sucrose. Unlike the case for other reproductive tissue (spermatozoa, oocytes, embryos), these findings suggest that the cryopreservation of ovarian tissue by direct plunging into liquid nitrogen must be achieved by vitrification using only permeable cryoprotectants and agents that prevention ice formation.     

荧光光谱法辨别丙二醇和二甘醇

以齐药二厂的假药事件为背景,对1,2-丙二醇、1,3-丙二醇和二甘醇的吸收光谱和荧光光谱进行了测量,实验结果证明光谱法不失为一种快捷有效的区分手段.在紫外吸收光谱中,可以通过最大吸光度的差异区分二甘醇和丙二醇;在一定紫外波长激励下,三种醇的荧光光谱特性均存在差异,以此可以对三种醇作出有效区分;在230nm激发下,将二甘醇和两种丙二醇分别混合,混合溶液的相对荧光强度均与两种丙二醇体积比呈线性反比关系,这在一定程度上证明了二甘醇的荧光量子效率大于两种丙二醇.