A novel cellulose solvent, 1.5 M NaOH/0.65 M thiourea aqueous solution, was used to dissolve cotton linters having a molecular weight of 10.1 × 104 to prepare cellulose solution. Regenerated cellulose (RC) films were obtained from the cellulose solution by coagulating with sulfuric acid (H2SO4) aqueous solution with a concentration from 2 to 30 wt %. Solubility of cellulose, structure, and mechanical properties of the RC films were examined by infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, 13C NMR, and tensile tests. 13C NMR analysis indicated that the novel solvent of cellulose is a nonderivative aqueous solution system. The presence of thiourea enhanced significantly the solubility of cellulose in NaOH aqueous solution and reduced the formation of cellulose gel; as a result, thiourea prevented the association between cellulose molecules, leading to the solvation of cellulose. The RC film obtained by coagulating with 5 wt % H2SO4 aqueous solution for 5 min exhibited higher mechanical properties than that with other H2SO4 concentrations and a homogenous porous structure with a mean pore size of 186 nm for free surface in the wet state. The RC film plasticized with 10% glycerin for 5 min had a tensile strength of 107 MPa and breaking elongation of 10%, and about 1% glycerin in the RC film plays an important role in the enhancement of the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1521–1529, 2002
BackgroundOur previous study suggested that SEB exposure in pregnant rats could lead to the change of T cells subpopulation in both peripheral blood and thymus of the offspring rats. However, rarely is known about the influence of SEB exposure in pregnant rats on T cell subpopulation in the spleens of offspring rats.ResultsSEB was intravenously administered to the pregnant rats at gestational day 16 in this study. The percentages, in vivo and in vitro responses of CD4 and CD8 T cells were investigated with flow cytometry. The prenatal SEB exposure obviously increased splenic CD4 T cell percentages of both neonates and adult offspring rats, and obviously reduced splenic CD8 T cell percentages of both the fifth day neonates and adult offspring rats. After spleens in the adult offspring rats were re-stimulated with SEB in vivo or in vitro, in vivo SEB stimulation could lead to the marked decrease of splenic CD4 T cell percentage and the marked increase of splenic CD8 T cell percentage. While in vitro SEB stimulation to the cultured splenocytes markedly decreased the proliferation of the splenic lymphocytes and the CD4 T cell percentage, and had no influence on CD8 T cell percentage.ConclusionThe prenatal SEB exposure could alter the percentages of CD4/CD8 T cell subpopulation and the response of CD4 and CD8 T cells to the in vivo and in vitro secondary SEB stimulation in the splenocytes of adult offspring rats.
Poly(ε‐caprolactone) (PCL) was grafted to the surface of starch nanocrystals (StN) via microwave‐assisted ROP. The resultant nanoparticles were then incorporated into a poly(lactic acid) matrix to produce fully‐biodegradable nanocomposites with good mechanical properties. A loading level of 5 wt.‐% StN‐g‐PCL resulted in simultaneous enhancements of strength and elongation. The StN‐g‐PCL self‐aggregated as rubbery microparticles to enhance the elongation by ca. 10‐fold over that of neat PLA. Meanwhile, the grafted PCL chains were miscible with PLA and formed a stress‐transferring interface to the StN, providing a reinforcing function.magnified image
Semiinterpenetrating polymer networks (semi-IPNs) were synthesized from castor oil-based polyurethane (PU) and 20 wt % nitrokonjac glucomannan (NKGM) with weight-average molecular weights (M w) from 2.86 × 104 to 14.1 × 104. Results from the dynamic mechanical analysis, differential scanning calorimetry, wide-angle X-ray diffraction, and ultraviolet spectrometer showed that the semi-IPNs have a single broad α-relaxation peak, one glass transition, and higher optical transmittance (Tr) in the wavelength range of 400−800 nm than PU, suggesting good miscibility in the range of NKGM M w used. Noted that tensile strength (σb) of the semi-IPNs films was much higher than that of films PU and NKGM, and the Tr, σb, and breaking elongation (εb) obviously increased with decrease of NKGM M w from 8.44 × 104 to 4.75 × 104 (Tr = 88% at 800 nm, σb = 34 MPa, εb = 110%). This indicated that the NKGM with relatively lower M w plays an important role in plasticizing, accelerating cure, and enhancement of intermolecular interaction between two polymers in the semi-IPNs films. The semi-IPNs system provided a novel way for modification and exploitation of natural polymers such as polysaccharides.
Blend films were prepared by blending 7 wt % konjac glucomannan (KGM) aqueous solution with 2 wt % chitosan (CH) in acetate solution and dried at 40°C for 4 h to obtain the transparent films. Their structure and properties were studied by infrared (IR), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential thermal analysis (DTA). Crystallinities of the blend films decreased with the increase of konjac glucomannan. The thermostability, tensile strength, and breaking elongation of the blend films in dry state were obviously higher than those of both konjac glucomannan and chitosan films. Tensile strength of the dry blend film achieved 73.0MPa when the weight ratio of chitosan to konjac glucomannan was 7:3. The structure analysis indicated that there is a strong interaction between konjac glucomannan and chitosan resulted from intermolecular hydrogen bonds. The water solubility of the blend films was improved by blending with konjac glucomannan, so they have promising applications to soluble antiseptic coating of pills.
Effect of the degree of acetylation (DA) on the gelation behaviors on addition of sodium carbonate for native and acetylated konjac glucomannan (KGM) samples with a DA range from 1.38 to 10.1 wt % synthesized using acetic anhydride in the presence of pyridine as catalyst was studied by dynamic viscoelastic measurements. At a fixed alkaline concentration (CNa), both the critical gelation times (tcr) and the plateau values of storage moduli (G'sat) of the KGM gels increased with increasing DA, while at a fixed ratio of alkaline concentrations to values of DA (CNa/DA), similar tcr and values independent of DA were observed. On the whole, increasing KGM concentration or temperature shortened the gelation time and enhanced the elastic modulus for KGM gel. The effect of deacetylation rate related to the CNa/DA on the gelation kinetics of the KGM samples was discussed.
Abstract. Understanding the projection performance of hydrological models under contrasting climatic conditions supports robust decision making, which highlights the need to adopt time-varying parameters in hydrological modeling to reduce performance degradation. Many existing studies model the time-varying parameters as functions of physically based covariates; however, a major challenge remains in finding effective information to control the large uncertainties that are linked to the additional parameters within the functions. This paper formulated the time-varying parameters for a lumped hydrological model as explicit functions of temporal covariates and used a hierarchical Bayesian (HB) framework to incorporate the spatial coherence of adjacent catchments to improve the robustness of the projection performance. Four modeling scenarios with different spatial coherence schemes and one scenario with a stationary scheme for model parameters were used to explore the transferability of hydrological models under contrasting climatic conditions. Three spatially adjacent catchments in southeast Australia were selected as case studies to examine the validity of the proposed method. Results showed that (1) the time-varying function improved the model performance but also amplified the projection uncertainty compared with the stationary setting of model parameters, (2) the proposed HB method successfully reduced the projection uncertainty and improved the robustness of model performance, and (3) model parameters calibrated over dry years were not suitable for predicting runoff over wet years because of a large degradation in projection performance. This study improves our understanding of the spatial coherence of time-varying parameters, which will help improve the projection performance under differing climatic conditions.
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