pH值敏感型食品新鲜度指示标签及其应用的研究进展

近年来,智能包装的研究受到巨大关注,pH值指示标签是新鲜度指示器中的一种,可以简单、高效、实时、直观地通过标签颜色变化反映食品的新鲜度,在食品供应链中有巨大的发展潜力。为了改善pH值指示标签的效果,研究者们开发了多种类型的pH值敏感色素和基体材料,以强化指示标签的显色强度,优化阻隔性、机械强度、稳定性及生物活性。本文从pH值敏感色素来源和基膜类型两方面分析pH值新鲜度指示膜的研究进展,并对当前研究面对的困难、挑战与未来研究趋势进行讨论,以期为pH值敏感型指示标签的研究和应用提供参考。     

Radiation Synthesis of pH-Sensitive Hydrogels From Carboxymethyl Cellulose/Poly(ethylene Oxide) Blends as Drug Delivery Systems

Gamma irradiation was used to prepare hydrogels from carboxymethyl cellulose (CMC) and poly(ethylene oxide) (PEO) blends in the form of films. The hydrogels were characterized by IR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, mechanical testing, and scanning electron microscopy. The swelling in different buffers of different pH values was also studied. The results indicated the formation of network structure and that the swelling of hydrogels is thermo- and pH-sensitive. The CMC/PEO hydrogels were evaluated for the possible use in drug delivery field, in which the release profile of ketoprofen, as a drug model was investigated.     

Heteroarm Star-Shaped Poly (N-isopropylacryamide-co-itaconic acid) Copolymer Prepared by Glucose Core as ATRP Initiator

Star-shaped temperature- and pH-sensitive poly (N-isopropylacryamide-co-itaconic acid) copolymer is synthesized by atom transfer radical polymerization (ATRP) using 1,2,3,4,6-penta-O-Isobutyrylbromide-α-D-glucose as 5-Arm ATRP Initiator. For ATRP of itaconic acid (IA), carboxylic groups of IA are protected via silylation by hexamethyldisilazane (HMDS) using Fe₃O₄ as a magnetic catalyst. The polymerization is carried out in 2-propanol/toluene 50:50 (v/v) mixed solvent at 90°C. Structure of copolymers is studied with FT-IR, ¹H NMR, glass transition temperature (Tg), and scanning electron microscopy (SEM). Results of temperature, pH, and percentage variation on polymer structure and the effects on lower critical solution temperature (LCST), which is investigated with potentiometery and conductometry, show that LCST of copolymer is around body temperature and demonstrate the ability of this polymer in the design of controlled drug delivery systems. According to the obtained results from naltrexone release, the investigated star-shaped copolymer may have potential applications in the controlled release of drugs.     

基于pH敏感型葡聚糖水凝胶微球的药物载体

以葡聚糖为原料,采用反相微乳液技术制备了一种含有席夫碱结构的葡聚糖基水凝胶纳米微球作为载体,通过交联剂聚乙烯亚胺(PEI)的静电吸附作用对药物模型8-羟基芘-1,3,6-三磺酸三钠盐(HPTS)进行了包埋,利用FTIR、SEM和DLS等对微球的结构和形貌进行了表征。结果表明,这种葡聚糖纳米水凝胶载药前后均具有良好的球形结构,平均粒径分别在459和648 nm左右。载药效果及药物释放行为研究发现,该葡聚糖纳米水凝胶可对HPTS进行有效负载,且其释放行为具有明显的酸性环境敏感性,酸性越强,释放越快。含有席夫碱结构的葡聚糖纳米凝胶微球可作为pH敏感型载体应用于药物递送领域。     

环境敏感型纤维素水凝胶及其在药物控释方面的应用

综述了纯纤维素、纤维素衍生物、纤维素与有机无机物共混制备纤维素水凝胶的方法,并且综述了温敏性、pH敏感性、磁响应性纤维素水凝胶在药物控释领域的应用。在此基础上展望了纤维素水凝胶的研究方向。     

Reactive and stimuli-responsive maleic anhydride containing macromers – multi-functional cross-linkers and building blocks for hydrogel fabrication

Macromers with functional groups that allow for chemical derivatization, polymerization reactions or impart specific physico-chemical properties are functional building blocks for polymeric systems used in different biomedical applications. With this motivation, a series of oligomeric macromers was synthesized by free radical polymerization of maleic anhydride (MA) with N-isopropylacrylamide (NiPAAm) and pentaerythritol diacrylate monostearate (PEDAS). This chemical design provides anhydride groups for effective reactivity of the macromers with amines and other nucleophiles, copolymerized NiPAAm for temperature responsiveness and lipophilic stearate domains for increased hydrogel stability. Macromers were synthesized with different MA co-monomer feeds and oligomeric molecules (Mn below 5000 Da) were obtained with MA contents between 7% and 27% as determined by titration. The fraction of chemically intact anhydrides was calculated to range from 75% to 80%. The ability of the macromers to cross-link di- or oligovalent amines as a function of MA content was investigated rheologically. It was also demonstrated that monovalent amines, e.g. aminofluorescein, could be grafted to the macromer chain utilizing only a fraction of the anhydride functionalities. The derivatized macromers could still participate in cross-linking reactions due to the remaining anhydrides. Temperature sensitivity was shown for aqueous solutions of macromers with fully dissociated anhydride groups. The solutions were additionally responsive to changes in calcium ion concentration and pH. Extracts from macromer cross-linked polyether hydrogels showed no toxicity on L929 fibroblasts.The macromers have perspective as biocompatible cross-linkers for hydrogel fabrication from various biomacromolecules with the opportunity to decorate the gels with monoamine molecules that alter the biological or physico-chemical properties.     

Temperature- and pH-sensitive membrane formed from blends of poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide) and poly(acrylic acid) microgels

Temperature- and pH-responsive membranes prepared from blends of poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide)(PVDF-g-PNIPAM) copolymer and poly(acrylic acid) (PAA) microgels in N,N-dimethylformamide (DMF) solution by phase inversion method. PAA microgels help PNIPAM chains largely enrich onto membrane surface. Furthermore, adding PAA microgels increases the porous size, porosity and hydrophilic property of the blend membrane. The membranes show temperature-sensitivity between 30 and 35 °C, and pH-sensitivity between pH 3 and 5 on permeating aqueous solutions. Meanwhile, the blend membranes keep good antifouling property even if one of the hydrophilic components becoming hydrophobic in response to temperature or pH stimuli, which is superior to single-sensitive PVDF membrane.     

pH-sensitive self-assembling property of poly(ethyleneimine)/cinnamic acid mixture and its effect on pH-dependent release of monoolein cubic phase

Poly(ethyleneimine) (PEI)/cinnamic acid (CA) mixture was self-assembled into microsphere in aqueous phase. As the pH value increased, the self-assembly became hardly formed. As the molar ratio of the amino group of PEI to the carboxyl group of CA increased, the pH window for the formation of self-assembly became broader. The phase transition temperature of cubic phase was 58.5–67.5°C, depending on the PEI/CA content. The release of dye loaded in cubic phase containing PEI/CA increased in a first-order fashion. The release degree was higher at a lower pH value.     

Acetals moiety contained pH-sensitive amphiphilic copolymer self-assembly used for drug carrier

pH-sensitive nanoparticles were prepared from a novel amphiphilic copolymer poly(2-phenyl-1, 3-dioxan-5-yl methacrylate-co-2-hydroxyethyl acrylate), poly(PDM-co-HEA), which was synthesized from the pH-sensitive hydrophobic monomer 2-phenyl-1, 3-dioxan-5-yl methacrylate (PDM) and the hydrophilic monomer 2-hydroxyethyl acrylate (HEA) with unit ratio (4:6) via radical polymerization. The random amphiphilic polymer could form nanoparticles in aqueous media with sizes of about 167 nm (PDI = 0.03). The morphology of the nanoparticles was determined by dynamic light scattering (DLS) and transmission electron microscopy (TEM). When the nanoparticles solution was adjusted to pH = 5.5, sizes of the nanoparticles increased from 167 nm to about 800 nm within 24 h, characterized by DLS. The critical aggregation concentration (CAC) of the copolymer was determined to be 5.3 mg/L (1.7 × 10⁻⁷ M). The insoluble Nile Red could be delivered into the Hep3B cells by the nanoparticles and released in cytoplasm determined by fluorescence microscopy.     

壳聚糖/聚丙烯酸共聚物微球的制备及性能

以环己烷为油相,壳聚糖溶液为水相,运用反相乳液聚合法制得了具有pH敏感性的壳聚糖/聚丙烯酸共聚物微球。讨论了微球在pH=1～10缓冲溶液中的溶胀率变化,研究表明,微球在强酸性(pH≈1)和碱性(pH>7)条件下,溶胀率均在10倍以上;而在pH=2～6时溶胀较差,当pH=4时出现最低值,溶胀率低于1倍。光学显微镜所观察到的微球粒径均在40μm以内,且大小均匀。采用傅里叶红外光谱仪分析了不同配比样品特征峰的峰值和峰面积的变化。用722光栅分光光度计研究了共聚物微球包埋考马斯亮蓝的溶胀释放过程。