交联羧甲基魔芋葡甘聚糖空心微球制备及应用

以魔芋葡甘聚糖(KGM)为壁材,通过羧甲基化并经乳状液化学交联制备球体较为完好的羧甲基魔芋葡甘聚糖(CMKGM)空心微球.通过扫描电镜(SEM)和透射电镜(TEM)对CMKGM空心微球的形貌和粒径进行了表征.结果表明,KGM溶胶浓度为0.5%-1%、乳化剪切速率为8000r/min、环氧氯丙烷(ECH)为5ml时,可以得到粒径均匀、形貌规整、溶胀性能良好的CMKGM空心微球.增大溶液的pH和羧甲基试剂的用量均有利于CMKGM空心微球对水中Cu2+的吸附.     

Non-Newtonian flow behaviour of gellan gum aqueous solutions

Rheological properties of gellan gum solutions with and without salt have been monitored using oscillatory measurements and steady-shear viscosity measurements. The steady-shear viscosity measurements indicated that gellan gum solutions showed a wide Newtonian plateau when gellan gum molecules took a coil conformation, and that the shear-thinning behaviour became more conspicuous with conformational change of gellan gum molecules from coiled to helical, and the range of the Newtonian plateau became limited only to very low shear rates. When gellan gum solutions showed rheological behaviour as a dilute or concentrated polymer solution, these systems obeyed the Cox–Merz superposition of steady-state viscosity and dynamic viscosity. As gellan gum solutions formed a weak gel, the Cox–Merz rule was not valid; however, the deviation from this superposition was less significant than that of xanthan gum solutions which also show weak-gel behaviour. Received: 8 December 1998 Accepted in revised form: 5 March 1999     

Effect of environmental factors and carbohydrate on gellan gum production

Submerged culture fermentation studies were carried out in batch mode for optimizing the environmental parameters and carbon source requirement by Pseudomonas elodea for the production of gellan gum. The maximum production of gellan gum was obtained with 16-h-old culture and 8% inoculum at 30°C and pH 7.0 after 52 h of incubation (6.0 g/L). Of the various carbon sources tested, 2% sucrose, glucose, and soluble starch yielded considerably high amounts of gellan. Studies on the concentration of various carbohydrates on gellan gum production indicated that the optimum concentration of glucose and starch was 3%, whereas for sucrose it was 4%. The addition of glucose in the medium above 3% had a detrimental effect on gellan yield. The investigation of intermediate two-step addition of glucose under identical conditions of fermentation showed an enhanced production of gellan (8.12 g/L) as compared with the control (6.0 g/L). To optimize the recovery of gellan from fermented broth, different solvents were tested for precipitation of gellan gum. Among the various solvents tested, tetrahydrofuran gave better recovery of gellan (82%) as compared with the conventional solvent isopropanol (49%).     

Structural characteristics of crosslinking domain in gellan gum gel

Gellan gum samples having different counterions of TMA⁺ (tetramethyl-ammonium ion), Na⁺, K⁺ and Cs⁺ were prepared, and the small-angle X-ray scattering was observed from the aqueous solutions of those samples. A sharp peak appears in the SAXS profile at low temperature, indicating the electrostatic interaction between the domains composed of multiple gellan gum chains. The SAXS profile revealed a rigid rod-like characteristics of gellan gum chain. The cross-sectional radius of gyration was evaluated from the scattering profiles, and the gelation mechanism was discussed from the change of the cross-sectional radius of gyration upon gel-sol transition. Taking the difference of the scattering power of counter ions into account, the ion condensation due to gelation was evaluated from the excess scattering of Cs⁺ gellan gum with respect to K⁺ gellan gum in respective aqueous solutions.     

Viscoelastic properties of konjac glucomannan in the presence of salts

Journal of Thermal Analysis and Calorimetry - Viscoelastic properties of konjac glucomannan (KGM) were studied in the entanglement region using steady and small-amplitude oscillatory rheological...     

Molecular origin for rheological characteristics of native gellan gum

The ¹H-nuclear magnetic resonance spectrum showed that the l-rhamnosyl residues of native gellan gum were coinvolved in both a small number of ⁴C₁-pyranose conformations and a large number of ¹C₄-pyranose conformations, whereas for deacylated polymer, almost of the residues were involved in ⁴C₁-pyranose conformation. The flow curves of native gellan gum showed plastic behavior above 0.2%. The elastic modulus stayed at a constant value with increase in temperature up to 40 °C, then decreased rapidly. The elastic modulus increased with addition of CaCl₂ (6.8 mM) and stayed constant value with increase in temperature up to 65 °C, then decreased rapidly. The stronger elastic modulus was observed in deacylated gellan gum with addition of CaCl₂. The elastic modulus of native gellan gum showed larger value than that in aqueous solution in the presence of urea (4.0 M). Intra- and intermolecular associations of native gellan gum molecules in the presence of Ca⁺² were proposed.     

Effect of deacetylation rate on gelation kinetics of konjac glucomannan

Effect of deacetylation rate on the gelation behaviors on addition of sodium carbonate for native and acetylated konjac glucomannan (KGM) samples with a degree of acetylation (DA) range of 1.38-10.1 wt.% synthesized using acetic anhydride in the presence of pyridine as catalyst was studied by dynamic viscoelastic measurements. At a fixed alkaline concentration (C(Na)), both the critical gelation times (t(cr)) 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 (C(Na)/DA), the similar t(cr) and (G'(sat)) 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 C(Na)/DA on the gelation kinetics of the KGM samples were discussed.     

Swelling characteristics of konjac glucomannan superabsobent synthesized by radiation-induced graft copolymerization

Graft copolymerization of konjac glucomannan (KGM) and acrylic acid was induced by ⁶⁰Co-γ irradiation at room temperature. The effects of radiation dose and monomer-to-KGM ratio on grafting yield and equilibrium water absorbency were investigated. The KGM-based superabsorbent polymer (KSAP) could absorb water 625 times of its dry weight when the radiation dose was 5.0 kGy and monomer-to-KGM ratio was 5. The structure of KSAP was characterized by FTIR, XRD, and SEM. KSAP showed a lower crystallinity than KGM. The porous microstructure of KSAP was revealed by SEM. The diffusion mechanism of water in the hydrogel is consistent with the anomalous diffusion model. Cations, especially multivalent cations, greatly reduced water absorbency of KSAP. Rising temperature, acidic or basic solutions are not favorable for the swelling of KSAP.     

Preparation and characterization of cellulose and konjac glucomannan blend film from ionic liquid

Blend films from cellulose and konjac glucomannan (KGM) in room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride were satisfactorily prepared by coagulating with water. The composition of the blend films was gravimetrically analyzed, and the compatibility of the two natural polymers was characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction. The results indicate good compatibility and strong interactions between cellulose and KGM, resulting in almost no loss of the water‐soluble KGM from the blend films even after the water coagulating and washing. However, microstructure analyses portrayed phase separations in the blend films, namely, egg‐like new phase particles were embedded in a continuous matrix base (MB). Phase diagram analysis and differential scanning calorimetry of the phase inversion coagulation process suggest that relative low molecular mass part of both cellulose and KGM formed the continuous MB, whereas the egg‐like new phase particles were super patterns of relative high molecular mass of both polymers, which played an important role in strengthening the blend material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1686–1694, 2009     

Preparation and physicochemical properties of konjac glucomannan ibuprofen ester as a polysaccharide-drug conjugate

Abstract

A novel drug-polysaccharide conjugate with konjac glucomannan (KGM) as a drug carrier was fabricated through the esterification of ibuprofen (IBU), an anti-inflammatory drug, with KGM. The influences of the reaction conditions, such as the amount of ibuprofen acryl chloride, reaction time, reaction temperature, and the amount of catalyst, on the degree of substitution were investigated. KGM ibuprofen ester (KGM-IBU) was characterized by Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD), solid-state ¹³C NMR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The hydrophobic structure of IBU in KGM-IBU was proven by the fluorescence emission spectra of pyrene. In addition, by using commercially available ibuprofen sustained-release capsules (IBU-SRC) as a control, the in vitro controlled release performance of KGM-IBU was evaluated. The cumulative release of IBU-SRC within 36?h was 94%, while that of KGM-IBU within 36?h was 77%. The results showed that KGM-IBU had better sustained-release performance without a burst release effect. The obtained products could be used as a potential biocompatible sustained-release drug delivery system.     

Rheological properties of water-soluble cross-linked xanthan gum

Water-soluble crossslinked xanthan gum (CXG) was prepared from xanthan gum (XG) and epichlorohydrin under alkaline condition by ethanol solvent method. Rheological properties and heat resistance performance of different concentrations of aqueous XG and CXG solutions were investigated. The results showed that the apparent viscosity of 4 g · L^?1 CXG solution was 2.57 times that of 4 g · L^?1 XG solution. The storage modulus G′ and the loss modulus G″ of CXG solutions were greater than those of XG solutions, and viscoelastic and thixotropic properties were more significant in CXG solutions. At 80°C, these two solutions were sheared at 170 s^?1 for 90 minutes, the reserved viscosity was 32.30 and 62.15 mPa · s for XG and CXG solutions, respectively. The heat resistance performance of CXG solution was better than that of XG solution. Nonlinear co-rotational Jeffreys model could be applied to describe the flow curves of XG and CXG solutions correctly, and the calculated values were in good agreement with the experimental data.     

明胶/葡甘聚糖/聚乙烯醇缓释肥料包膜的表征

以甲醛作交联剂,甘油为增塑剂,用溶液共混法制备了明胶/葡甘聚糖/聚乙烯醇缓释尿素包膜。采用红外光谱(FT-IR)、X-射线衍射、扫描电镜、热重分析和差示量热扫描等表征了包膜的结构,结果表明该条件下包膜中原料之间产生了较强的相互作用,形成了一个较稳定的复合体。     

以数字处理对魔芋葡甘聚糖膜面特征的初步研究

以天然生物材料为原料的绿色环保型膜材料取代塑料薄膜将是今后膜材料的发展趋势[1 4 ] 。从魔芋 (ＡｍｏｒｐｈｏｐａｌｌｕｓＫｏｎｊａｃＫ .ＫｏＣｈ)中提取出的魔芋精粉 ,其主要成分为葡甘聚糖 ,其优良的成膜性已引起人们的重视[4 5] 。分形维数在材料研究中得到了广泛的应用[6 ] ,本文以魔芋葡甘聚糖为主要原料制成膜 ,对膜的扫描电镜图象进行数字化处理 ,探讨膜面的微观形貌特征及制膜条件对膜面的影响。1　实验部分1 1　膜的制备以魔芋精粉 (四川安县魔芋精粉厂 )为主要原料 ,并添加明胶增强剂、甘油 (食品级 )增塑剂 (质量比为 1…     

Phase behavior in mixtures of a homopolymer and a block copolymer 1. FTIR and DSC studies

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm^-1 region due to COCH₃ band of PVME and peak position of 698 cm^-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. ©1995 John Wiley & Sons, Inc.     

Rheological and microrheological characterization of a novel amphoteric xanthan gum

A novel amphoteric xanthan gum (AXG) containing anionic carboxyl groups and cationic quaternary ammonium substituents was prepared from xanthan gum (XG) and 3-chloro-2-hydroxypropyltriethanolammonium acetate. The rheological and microrheological properties of AXG and XG solutions were studied in this work. The rheological results showed that the apparent viscosity of the 0.4% AXG solution was 5.26 times that of the 0.4% XG solution, and the AXG solution exhibited more obvious thixotropy and much stronger viscoelasticity than the XG solution. Both experiment and numerical simulations were adopted to investigate the gel-breaking process of the AXG solution, and the rheokinetics equations can well describe the evolution of complex viscosity. Moreover, the optical microrheology method was also adopted to investigate the microrheological behavior of AXG and XG solutions. The microrheological results showed that the AXG solution exhibited higher viscosity index at zero shear and a more obvious solid-like behavior than the XG solution. Good agreement is found when comparing the results obtained from microrheology to classical rheology, which verifies the feasibility of the microrheology method for measuring the solution properties, especially some properties not well described by the current rheological approach.     

羧甲基羟丙基瓜尔胶的流变特性

考查了羧甲基羟丙基瓜尔胶溶液的流变特性,发现其水溶液呈典型的假塑性,不同浓度下溶液表观粘度随剪切速率的变化可以用Ostwald-Dewaele方程描述;零切粘度与温度的关系符合Andrade方程;溶液的粘度在酸性条件下随溶液pH的减小迅速降低,在碱性条件下则变化不大;溶液对NaCl很敏感,表现出典型的聚电解质的特征。     

Influence of Ca2+-ion upon viscoelastic properties of gellan gum aqueous solutions

Viscoelastic properties of gellan gum aqueous solutions [San-Eigen F.F. I. (Osaka), Lot No. 62058A] were observed in order to study the influence of Ca²⁺-ions upon the solution properties. The results were (i) the solution of Sample 1 (Ca²⁺ ~ 0.5%) showed narrowing of the oscillating amplitude of the ball after ~10 cycles (this is known as negative thixotropy); (ii) abrupt decreases in viscosity were observed for the solution of Sample 2 (Ca²⁺ ~ 0.1%) in the narrow temperature range of ± 0.5 °C; (iii) unstable behavior of oscillating ball was found for the solution of Sample 3 (Ca²⁺ ~ 0.00%), and this may be attributed to the inhomogeneity in the solution of the order of 10⁻⁴ m, which was removed after stirring for one week.     

Preparation and properties of novel hydrogels from oxidized konjac glucomannan cross-linked chitosan for in vitro drug delivery

In this paper, a novel composite hydrogel was prepared by the use of dialdehyde konjac glucomannan (DAK) as macromolecular cross-linking agent for chitosan (CS). This biocompatible material cross-links and gels in minutes. The structure and morphology were characterized by various analyses. The results indicate that the hydrogels formed through the Schiff-base reaction between the amino groups of CS chains and the aldehyde groups of DAK. The cross-link density (rho(x)) increases with the enhancement of DAK content in hydrogels, while equilibrium swelling ratio (SR) and the average molecular weight between cross-links (Mc) value decrease. Drug release was evaluated by varying the pH of the release medium, reversed dependence of release rate on the equilibrium SR of hydrogel indicated that drug release may be impeded by the association of drug with the polymer. Importantly, this process offers an entirely new window of materials preparation when compared with the traditional preparation of CS-based hydrogels with small molecules cross-linking agent.