Use of a fluorosurfactant in micellar electrokinetic capillary chromatography

Beads prepared from a thermosensitive polymer, hydroxypropylcellulose, exhibit temperature-dependent porosity. At temperatures below 40°C the beads are swollen having large pores, while at temperatures above 45°C the beads are in a shrunken state having smaller pores. In the presence of 1 M NaCl the transition temperature decreased to about 30°C. In a swollen state the size of pore is large enough to accommodate lysozyme (mol. mass 14 400) and -chymotrypsin (mol. mass 21 600) but not bovine serum albumin (mol. mass 67 000). When the beads are shrunken, all the proteins are eluted from the column packed with hydroxypropylcellulose beads in the volume close to the void volume of the column.     

Sol–gel preparation and properties of hydroxypropylcellulose–titania hybrid thin films

Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC₃H₇ ⁱ )₄ was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO₂/(HPC + TiO₂) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC₃H₇ ⁱ )₄ is converted into TiO₂. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where cracking did not occur at higher HPC contents even when the substrate was bent.     

Design,characterization and enhanced bioavailability of hydroxypropylcellulose-naproxen conjugates

Polysaccharides are beneficially used as drug carriers via prodrug formation and offer a mechanism for better effectiveness and delivery of the drug. The unique geometry of hydroxypropylcellulose (HPC), a polysaccharide, allows the attachment of drug molecules with a higher degree of substitution because the hydroxyls groups are projected outside the HPC chains. Therefore HPC-Naproxen conjugates, i.e., macromolecular prodrugs, were synthesized using a powerful acylation reagent carbonyldiimadazole (CDI) in N,N' dimethylacetamide (DMAc) solvent. The reactions were carried out at 80 °C under stirring for 24 h and inert environment. This reaction strategy appeared efficient to obtain a high degree of drug substitution (DS = 0.88–1.40) on the polymer parent chain as calculated by UV–visible spectrophotometry after hydrolysis of the samples. The method provides high efficacy as product yields were high (77–81%). Macromolecular prodrugs (MPDs) with different DS of naproxen designed were found soluble in organic solvents.     

Shape and structure recovery of an LCP droplet under a large step strain: observation and stress calculation

Shape recovery of a droplet of liquid crystalline polymer (LCP) hydroxypropylcellulose in a matrix of poly(dimethyl siloxane) subjected to a step shear strain has been studied via optical microscopy. Just after application of a large strain, the LCP droplet shape is flat ellipsoid, and then the droplet takes cylindrical shape and band texture perpendicular to the flow direction appears. The band texture fades away before emergence of poly-domain structure. In the final process with the shape of spheroid, poly-domain structure recovers very slowly. Except for the final process, the shape change is identical with that of isotropic droplet at strains smaller than 3, when the LCP viscosity in Region II is taken as an equivalent viscosity for normalization. For a 20:80 blend, the excess relaxation modulus is calculated based on the Doi-Ohta theory, taking account of the distribution of droplet size and compared with experimental modulus data.     

Zwitterionically modified hydroxypropylcellulose for biomedical applications

Novel polyelectrolytes have been synthesized by grafting sulfobetaine side chains onto hydroxypropylcellulose backbone. Polymers with various degrees of grafting have been obtained. The polymers do not interact with model anionic, cationic and zwitterionic surfactants as found in fluorescence studies using pyrene as a molecular probe. Dynamic light scattering (DLS) studies indicated that in the graft polymer solution two types of polymers are present. The films were formed from the grafted polymers. Using atomic force microscopy (AFM) technique it was found that they are resistant to the adhesion of proteins and can be used for the preparation of antiadhesive surfaces which may find biomedical applications.     

Body temperature-responsive gels derived from hydroxypropylcellulose bearing lignin II: adsorption and release behavior

The lower critical solution temperature (LCST) of hydroxypropylcellulose bearing lignin (HPC-L) prepared from unbleached pulp depends on the amount of residual lignin. An HPC-L gel having thermal properties reflective of original HPC-L was prepared using ethyleneglycol diglycidylether as a crosslinker, as previously reported [Uraki et al. (2004) Carbohydr. Polym. 58:123–130], and the volume transition temperature was detected as an endothermic peak by differential scanning calorimetry (DSC). The adsorption and release behavior of the guest molecules to/from this gel was then examined. When the adsorption of cationic and anionic guests was compared, cationic methylene blue (MB) was adsorbed in larger amounts than anionic methyl orange (MO). In addition, MB adsorption into the HPC-L gel was greater than MB adsorption into the HPC gel prepared from commercially available HPC. This suggests that residual lignin affects the adsorption of organic dyes. Significant differences were not observed with respect to the release of MB from HPC-L at 38 °C and lower temperatures. In the adsorption of surfactants, marked adsorption at around the critical micelle concentration of the ionic surfactants and gel swelling were observed. Such swelling did not occur in the aqueous nonionic surfactant solution, although the nonionic surfactant was adsorbed into the gel. Gel swelling may have been caused by the electrostatic repulsion of the ionic surfactants adsorbed onto the polymer chains within the gel structure.     

Collaborative studies of zeta-potential measurements and electrophoretic measurements using reference sample

Simultaneous measurements of zeta-potential for two standard latex suspensions were carried out so as to assess the reliability of each of these measurement techniques and find means for their improvement. Furthermore, syntheses of a reference particle dispersion stabilized sterically in an aqueous medium without any electrostatic effects and measurements of zeta-potential using the reference dispersion as a standard were performed under various experimental conditions. It became apparent that the dense adsorption layer of hydroxypropylcellulose (HPC), with a lower critical solution temperature (LCST), formed on latex particles with a low surface charge density at temperatures higher than the LCST, plays a role in completely shielding the electrostatic effect arising from the surface charge on the bare particles. Such reference particles with zero zeta-potential allow us to determine the electrophoretic mobility of unknown samples at the one-half depth in the electrophoretic cell by subtracting the mobility of the reference sample at the same level. Furthermore, the zeta-potential of the cell wall can be easily determined from the mobility of the reference sample, because the apparent velocity profile of the reference sample indicates the liquid flow velocity in the cell.     

Reinforcement of hydroxypropylcellulose films by cellulose nanocrystals in the presence of surfactants

Hydroxypropylcellulose (HPC) films were prepared by casting with cellulose nanocrystals in the presence of anionic surfactant sodium dodecylsulphate (SDS) and cationic surfactant hexadecyltrimethyl ammonium bromide (CTAB). The cellulose nanocrystals were isolated from maize straw, a biomass source produced in huge quantities as an agrowaste in Brazil. These bionanocomposite films had good transparency and their surface hydrophilic character was evidenced by static contact angle measurements. Thermogravimetry (TGA) measurement revealed that nanocrystals and surfactants changed the thermal stability of the HPC films. Dynamic mechanical analysis (DMA) showed that the tensile storage and loss moduli of the HPC films increased by increasing the contents of cellulose nanocrystals and surfactants, especially in the case of CTAB. This good reinforcing effect of HPC matrix can be explained as due to electrostatic attractive interactions brought about by the presence of CTAB and the nanocrystals.     

新型温敏羟丙基纤维素微凝胶的合成

天然高分子具有良好的生物相容性和生物可降解性,因此用天然高分子制备的微凝胶更适合于生物医学领域的应用。羟丙基纤维素(HPC)是一种具有温度敏感性的纤维素衍生物,可通过不同的方法制备为微凝胶,然而现有方法制备的HPC微凝胶都不能完全降解。我们采用一种新方法制备HPC微凝胶。首先通过NaIO4处理将醛基引入HPC。红外光谱检测证明了醛基的生成。氧化后的HPC仍具温敏性,其最低临界溶解温度(LCST)保持不变;当加热到LCST以上时,HPC分子通过疏水相互作用聚集成纳米小球;再加入交联剂己二酸二酰肼,通过醛基与胺基之间的反应,使纳米小球共价交联得到HPC微凝胶。电镜研究表明HPC微凝胶呈球形,粒径在100～300nm之间。浊度和光散射研究表明HPC微凝胶仍具温敏性。细胞毒性实验表明我们制备的微凝胶几乎没有细胞毒性。由于HPC及交联剂己二酸二酰肼均可生物降解,预期我们制备的微凝胶也能很好地降解,并有望应用于生物医学领域。     

Sol/gel transition and liquid crystal transition of HPC in ionic liquid

This work uses an ionic liquid (IL), 1-butyl-3-methylimidazolium acetate, as a solvent to study the sol/gel transition (SGT) and liquid crystal transition (LCT) of hydroxypropylcellulose (HPC) solution. The LCT concentration of HPC at room temperature is 7 wt%, which is slightly higher than its SGT concentration of 6 wt%. For HPC concentrations of over 7 wt%, three rheological approaches were utilized, and the parameters relaxation time, hysteresis ratio and loss modulus (G″) are measured to determine the LCT temperature. The relaxation study concludes that the LC-critical concentration of HPC is 7 wt%. When HPC exceeds 7 wt%, the LC transition temperatures, ranging from 45 to 51 °C, can be measured and are proportional to the HPC concentration. The rheological results are then confirmed by making observations under a polarized optical microscope. All results are highly mutually consistent. Most significantly, the rheological parameters adopted herein can be used as good indicators of the LC transition. Of those indicators, G″ changes distinctly at the LCT point, and can thus be suggested to be the most helpful indicator in determining the LCT temperature.