不同形式壳聚糖基水凝胶的微观结构与控释性能对比

本文采用离子交联和巯基化两种不同方式改性壳聚糖,制备载有活性蛋白的壳聚糖水凝胶。通过红外光谱、粒径/zeta电位分析、透射电镜、扫描电镜、模拟消化实验等手段,探讨了其微观结构和控释性能。实验结果发现,由于分子间氢键作用,p H值、CS:TPP质量比以及BSA浓度等对交联壳聚糖水凝胶的蛋白包载率影响明显,而由于巯基的引入,使得巯基化壳聚糖水凝胶在酸性环境下具有较小的粒径(平均409.61 nm)和较低的表面电势(平均-0.67 mV)。壳聚糖基材料微观结构的变化进而影响其水凝胶的控释性能。模拟消化实验显示,交联壳聚糖水凝胶在模拟胃液中出现突释现象,在运送至结肠前,已有44.76%的活性蛋白释放,而巯基化壳聚糖水凝胶在模拟上消化道环境中释放缓慢,仅有8.42%的活性蛋白释放,运转至模拟结肠,活性蛋白释放速度逐渐增加,呈现持续释放的效果,约有34.53%的BSA逐渐释放在结肠中。因此,巯基化壳聚糖基水凝胶具有更好的控释性能,这对活性蛋白的生物利用改善具有重要作用。     

交联壳聚糖水凝胶的分子结构差异与其控释性能关系

为了提高活性物质的生物利用度,该研究以三聚磷酸钠(TPP)或六偏磷酸钠(SHMP)为交联剂,制备具有不同微观结构的壳聚糖基水凝胶,探讨其控释性能,并通过红外光谱、X-射线衍射和热重分析对水凝胶结构进行分析。热重分析结果表明,壳聚糖上的氨基与交联剂磷酸基团之间通过氢键进行交联,提高了壳聚糖水凝胶的热稳定性。同时,与TPP相比,SHMP为壳聚糖链段与阴离子基团间的结合提供更多静电作用位点,使得SHMP交联壳聚糖水凝胶在1530 cm^-1附近表现出强的特征峰。此外,TPP交联水凝胶的溶胀性能优于SHMP交联水凝胶,但在体外模拟消化实验中,由于胃肠道的生理环境以及交联壳聚糖水凝胶的微观结构随p H的改变,SHMP交联水凝胶的活性蛋白累积释放率(30.47%~50.27%之间)小于TPP交联水凝胶(59.90%~76.57%之间)。通过控制交联过程中壳聚糖与交联剂的质量比,可改变交联壳聚糖水凝胶分子结构,调控壳聚糖分子链段的溶解/溶胀行为,从而影响水凝胶的控释性能。该研究结果可为壳聚糖载体材料的选用、缓释及改善活性蛋白类功能因子的生物利用情况提供一定的参考。     

具有不同微结构的壳聚糖/淀粉复合材料的性能及其应用

本文选择4种具有不同微结构的壳聚糖,与淀粉形成复合材料,并对复合溶液的流变、粘弹性能以及复合薄膜的机械性能进行探讨,利用复合材料对含药片剂进行薄膜包衣,考察其控释性能。实验结果发现,壳聚糖/淀粉复合溶液具有假塑性流体特征,壳聚糖粘均分子量越大,剪切稀化现象越明显。同时,在复合薄膜制备过程中,壳聚糖可促进淀粉分子链的排布,提升复合薄膜的抗拉强度、断裂伸长率,调控壳聚糖微观结构可改善复合薄膜的机械性能。当包衣片剂运转至模拟肠液,借助壳聚糖上的-NH_3~+与淀粉的-OH间的氢键作用,片剂外可形成凝胶层,阻碍药物的释放,壳聚糖分子量越大,药物从复合薄膜包衣片剂中释放的累积量越小。以粘均分子量2.543×10~5 g/mol的壳聚糖CTS60与玉米淀粉制备的复合薄膜包衣片剂,约有70.59%药物可递送至肠道,其中有21.83%释放于模拟小肠,48.77%释放于模拟结肠,表现出一定的控释性能。     

食品风味物质在水凝胶中的控释研究进展

食品中的风味物质往往具有一定的挥发性和不稳定性,易在加工及贮藏过程中损失,需要一定的传递体系对其进行保护,控制其扩散,在食用过程中释放被相应的受体感知。水凝胶是一种以水为分散介质的凝胶,可通过物理或化学方法形成交联及网状结构,控制风味化合物的转运,从而达到对风味物质的控释效果。文章主要介绍了水凝胶对风味物质的包埋和释放的控释机理及应用,着重描述了水凝胶控释风味物质的影响因素,最后对风味物质在水凝胶中的控释发展趋势及应用前景进行了展望。     

不同淀粉的壳聚糖/淀粉复合薄膜结构性能比较

为改善功能因子的生物利用率,本文采用流延法,分别将壳聚糖(分子量150000g/mol)与玉米淀粉、马铃薯淀粉和木薯淀粉制备复合薄膜及其包衣片剂,并通过红外光谱、扫描电镜、拉伸仪、模拟消化实验等手段对壳聚糖/淀粉复合薄膜结构性能进行分析。借助壳聚糖上的-NH3+与淀粉的-OH间的氢键作用,可形成壳聚糖/淀粉复合结构,受淀粉结构差异的影响,复合薄膜中壳聚糖/淀粉复合结构的有序性存在差异,进而影响复合薄膜的机械力学性能、耐酸性及其薄膜包衣片剂的控释性能。其中,复合薄膜CTS/Potato、CTS/Tapioca中壳聚糖/淀粉复合结构的有序性优于复合薄膜CTS/Corn,其耐酸性能良好,在模拟胃液中运转2h,薄膜的损失率分别在18.71%～26.15%、16.14%～19.64%之间。同时,这两种复合薄膜包衣片剂的控释性能亦表现良好,约有60%的模型功能因子可顺利递送至小肠、结肠部位,具有作为药物、活性功能因子小肠、结肠定向释放载体材料的可能。     

大豆蛋白基复合水凝胶的制备及其体外释放

利用天然无毒的京尼平交联大豆蛋白(SB)和壳聚糖(CS)制备复合水凝胶(HD)控释载体,以茶碱(TP)作为药物模型,结合扫描电镜和核磁共振研究了复合凝胶的表观形态和结构,并对其在模拟胃肠液中的控释特性进行研究。结果表明:复合水凝胶中大豆蛋白和壳聚糖通过京尼平发生了明显的交联作用,并呈现紧密的网络结构。在pH1.2模拟胃液中,复合水凝胶的溶胀度和茶碱释放率较低,但在pH6.8模拟肠液中,却呈现较高的溶胀度和释放率。复合水凝胶在模拟胃肠液中120h内可实现对茶碱的可控释放。复合凝胶的释放特性不仅与SB/CS比例相关,而且还取决于添加的京尼平的含量。本实验结果说明了这种京尼平交联的复合凝胶较为适合用作药物在胃肠道中的定向运送载体。     

不同芯材的海藻酸-壳聚糖微球的体外模拟释放

以酪氨酸、维生素B1或牛血清白蛋白为芯材,在芯材/壁材比为1:10、pH 5.0的条件下,采用锐孔法制备Ca2+单一交联和双重交联海藻酸-壳聚糖凝胶微球,测定芯材的包埋率,并考察芯材在模拟胃肠液中的释放.结果表明,牛血清白蛋白包埋率最大,超过83%;模拟胃液中芯材的释放速率低于其在模拟肠液中的释放速率,释放速度与分子质量有关;模拟胃液中双重交联微球比Ca2+单一交联微球的芯材释放速率更慢,释放速度也与分子质量有关,30min时芯材释放率低于50%.结果表明,双重交联海藻酸-壳聚糖微球在酸性条件下可限制性释放芯材,在中性条件下较快地释放芯材.     

两种海藻酸钠基凝胶的溶胀和质构性能

壳聚糖、果胶和海藻酸钠是天然多糖,具有良好的生物相容性和生物可降解性等优点。以CaCl_2为交联剂制备壳聚糖-海藻酸钠水凝胶和果胶-海藻酸钠水凝胶,研究Ca Cl2浓度、多糖质量比(壳聚糖与海藻酸钠、果胶与海藻酸钠)和交联温度对水凝胶在模拟人体胃肠道环境(pH 1.2胃、pH 6.8小肠、pH 7.4结肠缓冲溶液)中溶胀性能的影响。当壳聚糖或果胶和海藻酸钠质量比为1.25∶1、CaCl_2浓度为0.09 mol/L、温度为60℃时,制备的水凝胶在pH 1.2溶液中溶胀率最小,在pH 6.8和pH 7.4溶液中溶胀率较大;结果表明所制备水凝胶具有pH值敏感性。此外,在优化条件下水凝胶具有较好的质构性能。     

pH敏感性壳聚糖/果胶复合物对牛血清蛋白的负载及缓释

以壳聚糖和果胶复合物(CTS/PE)为对象,研究其对pH的敏感特性及其对牛血清蛋白(BSA)的负载与缓释,结果表明:在pH处于6～8之间时,CTS/PE溶胀速率急剧增大;壳聚糖分量小、脱乙酰度高,CTS/PE溶胀度大。壳聚糖的分子量、脱乙酰度影响CTS/PE胶复合物对BSA的负载有明显影响。在模拟胃液和模拟肠液中的释放研究表明,随着壳聚糖分子量减小,载药凝胶的体外控释效果越来越好;随着壳聚糖脱乙酰度的增大,载药凝胶的体外控释效果越来越好。     

单宁酸交联处理对明胶性质的影响

采用单宁酸作交联剂对明胶进行交联改性处理,对其凝胶性、降解性进行分析,制备VB1 微胶囊并确定芯材的释放性能。结果表明,与原料明胶相比,交联明胶形成凝胶的最低浓度基本未发生改变,仍为0.6 % 左右,但是在相同浓度下交联明胶的凝胶强度明显降低。体外降解实验表明,原料明胶和交联明胶在模拟胃液中几乎不发生降解,但在模拟肠液中都发生降解,且交联明胶的降解速度更慢。交联明胶为壁材制备的微胶囊,其芯材在模拟胃液和模拟肠液中有一定的缓释效果。     

Chitosan Polymer as Bioactive Coating and Film against Aspergillus niger Contamination

ABSTRACT: The inhibitory activity of chitosan-based edible coatings and films was assessed against the Aspergillus niger food pathogen and deterioration microorganism. Spore-counting assays showed an almost total inhibition of A. niger growth when either film-forming solution or film were used at a low concentration of chitosan (0.1% w/v). Epifluorescence microscopic results showed the action of chitosan on the relative proportion of RNA compared with DNA. The water vapor permeability (WVP) of chitosan film was relatively low compared with the poor moisture barrier of some polysaccharide films. Moreover, a coating with chitosan film on an agar gel, used as a food model, induced a 30% reduction in water loss. These results showed potential applications of chitosan-based films as bioactive packaging with properties to limit the food dehydration phenomenon.     

Chitosan-coated pectin beads: Characterization and in vitro release of mangiferin

Microspheres of low degree of esterification (DE) pectin with calcium and the same sphere coated with chitosan (PCaC) were prepared. The spheres have diameters in the range 650–680 μm. The layer of chitosan is about of 5–15 μm thick. To obtain firm and stable PCaC beads, chitosan was reacetylated. Two different degrees of acetylation, giving PCaC50 and PCaC80 were adopted. The beads were characterized by FTIR, SEM and swelling measurements. Mangiferin was loaded in PCaC reacetylated in two different ways: by addition in pectin solution (M_p) and by addition in CaCl₂ solution (M_c). The yield in producing the beads, the efficiency in encapsulation and the content of mangiferin in beads were determined. A swelling kinetics study was done in simulated gastric fluid (SGF, pH 1.2) and in simulated intestine fluid (SIF, pH 7.4). The release of mangiferin from the beads was performed in SGF followed by the release in SIF. Based on the yield and efficiency in encapsulation the best bead was found to be PCaC50-M_p. The highest release (7.8 mg of mangiferin/g of bead) was achieved by the PCaC50-M_c. For all beads more bioactive was released in SGF than in SIF.     

Effect of complexation conditions on xanthan–chitosan polyelectrolyte complex gels

Polyelectrolyte hydrogels formed by xanthan gum and chitosan can be used for encapsulation and controlled release of food ingredients, cells, enzymes, and therapeutic agents. In this study, xanthan–chitosan microcapsules were formed by complex coacervation. The effects of initial polymer concentration and chitosan solution pH on the crosslinking density of xanthan–chitosan network were investigated by swelling studies and modulated differential scanning calorimetry (MDSC) analysis. The crosslinking density was found to be less dependent on chitosan solution concentration than xanthan solution concentration and chitosan pH. The capsules were completely crosslinked at all conditions studied when initial xanthan solution concentration was 1.5% (w/v). The changes in the conformation of chitosan chains as chitosan pH approaches 6.2 were found to be important in achieving capsule network structures with different crosslinking densities. These findings indicate that the parameters studied cannot be viewed as independent parameters, as their effects on the degree of swelling are interdependent.     

Poly(vinyl alcohol)‐Based Film Potentially Suitable for Antimicrobial Packaging Applications

This work aimed at developing a thin and water‐resistant food‐grade poly(vinyl alcohol) (PVOH)‐based matrix able to swell when in contact with high moisture content food products without rupturing to release antimicrobial agents onto the food surface. This film was prepared by blending PVOH and 7.20% (wt/wt of PVOH) of poly(ethylene glycol) (PEG) with citric acid as crosslinking agent. The film‐forming solution was then casted onto a flat surface and the obtained film was 60 μm in thickness and showed a good transparency (close to T = 100%) in the visible region (400 to 700 nm). After immersion in water for 72 h at room temperature, the crosslinked matrix loses only 19.2% of its original weight (the percentage includes the amount of unreacted crosslinking agent, antimicrobial in itself). Water content, degree of swelling, and crosslinking density of the film prove that the presence of PEG diminishes the hydrophilic behavior of the material. Also the mechanical properties of the wet and dry film were assessed. Alongside this, 2.5% (wt/wt of dry film) of grapefruit seed extract (GSE), an antimicrobial agent, was added to the film‐forming solution just before casting and the ability of the plastic matrix to release the additive was then evaluated in vitro against 2 GSE‐susceptible microorganisms, Salmonella enteritidis and Listeria innocua. The results indicate that the developed matrix may be a promising food‐grade material for the incorporation of active substances.     

壳聚糖对果蔬的抗菌保鲜效果及其应用研究进展

由于采后旺盛的生理代谢, 新鲜水果和蔬菜会出现品质劣变, 采取有效的抗菌保鲜策略是果蔬采后贮藏过程亟待解决的问题。天然大分子壳聚糖作为果蔬的活性包装材料具有来源广泛、安全和可生物降解等优点。本文综述了近年来壳聚糖基涂层/膜用于果蔬保鲜包装的抗菌保鲜效果及其对果蔬品质的影响, 首先介绍了壳聚糖的来源及应用特点以及制备壳聚糖薄膜材料的常用方法, 然后综述了壳聚糖及其与其他生物活性材料复合使用在果蔬保鲜中的应用, 并总结了使用壳聚糖基涂层/膜保鲜对果蔬外观品质、营养品质、挥发性香气物质等方面的影响; 最后, 对壳聚糖在果蔬抑菌保鲜机制方面的研究进行归纳介绍, 以期为其未来发展和应用提供新的思路。     

Antibacterial Activity and Physical Properties of Edible Chitosan Films Exposed to Low-pressure Plasma

The challenge for food industry is developing gentle processes concept, which will prevent food spoilage and leave a food natural, minimally processed, fresh-like and safe. A new technique of food preservation could be usage of combined methods of green process, such as cold gas plasma with bioactive substances, and protective coatings. The aim of this study was to determine the antibacterial activity of chitosan films incorporated with lysozyme exposed to helium plasma treatment as well as evaluate their physical properties. The edible films have been prepared basing on low molecular weight chitosan by casting from lactic acid solution with water solution of lysozyme in three various concentrations (0, 0.5 and 1 %). Dried films were then modified by exposition on cold helium plasma treatment for 0, 5 and 10 min. Obtained films were tested against growth of Listeria monocytogenes, Yersinia enterocolitica and Pseudomonas fluorescens. In order to characterize chitosan-based films, their mechanical properties, theromogravimetric analysis (TGA), dynamic mechanical thermal analysis (DMTA), contact angle measurement, water vapour permeability (WVP) and scanning electron microscopy (SEM) were evaluated. The films with 1 % lysozyme incorporation enhanced the inhibition efficiency of chitosan-based films against gram-positive (L. monocytogenes) and gram-negative (P. fluorescens) bacteria, where reduction zones were 42.5 and 69.8 mm, respectively. Besides that, hydrolytic changes of chitosan chain caused by lysozyme activity were confirmed by TGA and DMTA. Contact angles and WVP of tested films were not significantly affected by helium plasma exposition, nor lysozyme dosage. Hydrophilic natures of chitosan-based films were confirmed by both tests. Microscopy image of cross-section structure was smooth and continuous due to lysozyme addition in film composition. Application of chitosan films incorporated with lysozyme and low-pressure plasma treatment could be used as innovative preservation method in a wide range of food products.