Natural and edible biopolymer poly-gamma-glutamic acid: synthesis, production, and applications

Poly-gamma-glutamic acid (gamma-PGA) is a very promising biodegradable polymer that is produced by Bacillus subtilis. Gamma-PGA is water-soluble, anionic, biodegradable, and edible. This paper reviews the production of a strain of gamma-PGA and recent developments with respect to applications in terms of Ca absorption, moisturizing properties, gamma-PGA conjugation, super absorbent polymer, and so on. Our recent research shows that gamma-PGA can be used as an immune-stimulating and anti-tumor agent, especially at high molecular weight.     

In vitro enzymatic degradation of nanoparticles prepared from hydrophobically-modified poly(gamma-glutamic acid)

Amphiphilic poly(gamma-glutamic acid) (gamma-PGA) was prepared by the introduction of L-phenylalanine ethylester (L-PAE) as a side chain. This gamma-PGA-graft-L-PAE formed monodispersed nanoparticles in water. The particle size of the gamma-PGA nanoparticles could be controlled by the degree of L-PAE grafting. The hydrolytic degradation and enzymatic degradation by gamma-glutamyl transpeptidase (gamma-GTP) of these gamma-PGA nanoparticles was studied by gel permeation chromatography (GPC) and scanning electron microscopy (SEM). The hydrolysis ratio of gamma-PGA was found to decrease upon increasing the hydrophilicity of the gamma-PGA. The degradation of the gamma-PGA backbone by gamma-GTP resulted in a dramatic change in nanoparticle morphology. With increasing time, the gamma-PGA nanoparticles reduced in size and finally disappeared completely.Time-course of the changes in the morphology of the gamma-PGA nanoparticles following incubation with gamma-glutamyl transpeptidase.     

Efficient production of poly-gamma-glutamic acid by Bacillus subtilis ZJU-7

A strain with high poly-gamma-glutamic acid (gamma-PGA) production was isolated from fermented bean curd, a traditional Chinese food. The strain was named Bacillus subtilis ZJU-7 according to 16s rDNA sequencing and its taxonomic characters. The culture conditions for gamma-PGA production were evaluated. The most suitable carbon and nitrogen sources were sucrose and tryptone, respectively. Exogenous L-glutamic acid was necessary for gamma-PGA production, and the production of gamma-PGA increased on the addition of L-glutamic acid to the medium. In the medium containing 60 g/L of sucrose, 60 g/L of tryptone, 80 g/L of L-glutamic acid, and 10 g/L of NaCl, the yield of gamma-PGA reached 54.4 g/L after cultivation at 37 degrees C for 24 h, which was the highest gamma-PGA production compared with values reported in the literature. The average molecular mass of gamma-PGA produced was about 1.24 x 106 Daltons. B. subtilis ZJU-7 is genetically stable and can synthesize levan instead of gamma-PGA without the addition of L-glutamic acid to the medium.     

Formation of Pickering emulsions stabilized via interaction between nanoparticles dispersed in aqueous phase and polymer end groups dissolved in oil phase

The influence of end groups of a polymer dissolved in an oil phase on the formation of a Pickering-type hydroxyapatite (HAp) nanoparticle-stabilized emulsion and on the morphology of HAp nanoparticle-coated microspheres prepared by evaporating solvent from the emulsion was investigated. Polystyrene (PS) molecules with varying end groups and molecular weights were used as model polymers. Although HAp nanoparticles alone could not function as a particulate emulsifier for stabilizing dichloromethane (oil) droplets, oil droplets could be stabilized with the aid of carboxyl end groups of the polymers dissolved in the oil phase. Lower-molecular-weight PS molecules containing carboxyl end groups formed small droplets and deflated microspheres, due to the higher concentration of carboxyl groups on the droplet/microsphere surface and hence stronger adsorption of the nanoparticles at the water/oil interface. In addition, Pickering-type suspension polymerization of styrene droplets stabilized by PS molecules containing carboxyl end groups successfully led to the formation of spherical HAp-coated microspheres.     

A Novel Lead- bis (4-Chloro-2-Methylphenoxy)- Acetate Polymeric Complex

The bis (4-chloro-2-methylphenoxy)acetato lead (II) monohydrate infinite polymer was synthesized and characterized by elemental analysis and infrared spectroscopy. The crystal and molecular structure has been determined and the bond valences were computed. Molecules of the monomer, each occupying an asymmetric unit, are connected by the inversion center and a polymer chain is created by Pb(2O)Pb rings in spiro arrangement. The lead atom is seven coordinate by four oxygen atoms from two chelating carboxyl groups, one water molecule, and two oxygen atoms provided by symmetry generated carboxyl groups. Each carboxyl group acts as a bidentate ligand toward one metal atom and as a monodentate ligand with respect to a second. The lead-oxygen distances are spread over a wide range of values. One molecule of (4-chloro-2-methylphenoxy)acetate in the monomer is close to planarity, and the second is bent. All 4-chloro-2-methylphenoxy groups are almost parallel. The polymer infinite chains are assembled by weak hydrogen bonds to a layered structure.     

Synthesis of highly monodisperse quantum dot‐loaded polymer beads by impregnation and precipitation techniques

A novel approach to the synthesis of highly monodisperse quantum dot‐loaded polymer beads by combining impregnation and precipitation techniques was reported. The monodisperse poly(glycidyl methacrylate) (PGMA) beads were first synthesized by dispersion polymerization. Then, the PGMA beads were chemically modified to generate carboxyl groups, and impregnation of cadmium ions (Cd²⁺) inside the beads. Subsequently, the cadmium ions were reacted with thioacetamide to form cadmium sulfide (CdS) quantum dots within the polymer beads. The morphology, structure, and properties of CdS quantum dot‐loaded polymer beads were studied by field emission scanning electron microscope (SEM), transmission electron microscope, fluorescence spectrophotometer, fluorescence microscope, Fourier transform infrared spectroscopy, powder X‐ray diffraction, and thermogravimetric analysis. The results indicated that the CdS quantum dot‐loaded polymer beads had an average size of 1.4 μm, and were highly monodisperse. More interestingly, the CdS quantum dots distributed evenly within the polymer beads, which provide very strong fluorescence intensity. The existence of carboxyl groups on the quantum dot‐loaded polymer beads was measured quantitatively, and was found to be 0.2 mmol/g. These CdS quantum dot‐loaded polymer beads involving functional carboxyl groups would have potential applications in biological immunoassay and photoelectronic fields. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

羧化聚丙烯载体的链结构对丙烯腈聚合的影响

研究了羧化聚丙烯载体(不饱和羧酸接枝聚丙烯)接枝链的结构对丙烯腈聚合速度的影响。在引发活性方面对聚羧酸氧钒(聚合物负载催化剂)、异丁酸氧钒(小分子同系物)和硫酸氧钒(小分子非同系物)作了对比。实验结果表明:(1)(P-COO)_2VO两羧基之间存在着协同作用;(2)大分子链效应加强了羧基的协同作用;(3)聚羧酸链的d-、1-构型、羧基间距和载体的传质效应对聚合速度均有影响;(4)在本实验条件下,引发机理与高分子载体的链结构无关。     

Mechanism of activation of hydroxyl-containing polymers with N-hydroxysuccinimide and carbodiimides: Reason for leakage

The carbodiimide-mediated reaction of N-hydroxysuccinimide with carboxyl groups immobilized to hydroxyl-containing polymers (such as Sepharose or Trisacryl) leads to N-hydroxysuccinimide ester and N-hydroxysuccinimide derivatives of β-alanine which react subsequently with the hydroxyl group of the polymer via ester and carbamate bonds. These derivatives are formed upon interaction of dicyclohexyl carbodiimide with three equivalents of N-hydroxysuccinimide followed by a Lossen rearrangement. The amount of β-alanine thus coupled is very high compared to the number of carboxyl groups present on the resin. The β-alanine bound through the ester bond comprises about 90% of the β-alanine bound. Alkaline treatment of the ester bonded β-alanine containing polymers (prior to coupling of amino-containing ligands) causes a rearrangement yielding β-alanine with a free carboxyl group coupled through a stable carbamate linkage. After coupling of amino-containing ligands, the above-described rearrangement cannot occur, and the β-alanine-linked ligand leaks from the polymer via hydrolysis of the ester bond. The newly formed carboxyl groups (derived from the rearrangement) can be used to prepare active esters (e.g. nitrophenyl). Upon coupling with amino-containing ligands, these esters yield resins bearing chemically stable bonds.     

Interpenetrating polymer networks from polyurethanes and methacrylate polymers. II. Interpenetrating polymer networks with opposite charge groups

Interpenetrating polymer networks (IPNs) with opposite charge groups (tertiary amine and carboxyl groups) made from polyurethanes and methacrylate polymers have been synthesized and their properties and morphology, studied. With increasing carboxyl group concentration the mechanical properties and compatibility between the component networks were significantly improved, possibly because of the negative (or zero) free energy produced by the interaction contribution between the tertiary amine groups in the polyurethanes and the carboxyl groups in the methacrylate polymers determined by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The improved molecular mixing in these IPNs was thought to be due to the influence of the opposite charge groups in these systems.     

Synthesis of end‐functionalized AB copolymers. II. Synthesis and characterization of carboxyl‐terminated poly(ethylene glycol)–poly(amino acid) block copolymers

AB block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(amino acid) with a carboxyl group at the end of PEG were synthesized with α‐carboxylic sodium‐ω‐amino‐PEG as a macroinitiator for the ring‐opening polymerization of N‐carboxy anhydride. Characterizations by ¹H NMR, IR, and gel permeation chromatography were carried out to confirm that the diblock copolymers were formed. In aqueous media this copolymer formed self‐associated polymer micelles that have a carboxyl group on the surface. The carboxyl groups located at the outer shell of the polymeric micelle were expected to combine with ligands to target specific cell populations. The diameter of the polymer micelles was in the range of 30–80 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3527–3536, 2004     

Adsorption of polyacrylic acid and its copolymers with acrylonitrile on zinc oxide particles

Adsorption of polyacrylic acid and its copolymers with acrylonitrile, containing different quantities of carboxyl groups, on the dispersion of zinc oxide was investigated. The kinetics of polymer desorption was investigated based on data concerning the change in concentration of free carboxylic groups of polymer and zinc ions in solution. The concentration of free carboxyl groups decreases and the concentration of zinc ions in the liquid phase above the residue after separation of zinc oxide particles increases with time, reaching a constant value. The dependence of the concentration of free carboxyl groups and zinc ions in the liquid phase on the initial concentration of polymer in the plateau section of the kinetic curve was investigated. Adsorption isotherms of copolymers depend on their solubility in water and can be described by different mathematical models.     

Complexation of sequence-ordered methacrylic acid copolymers with poly(4-vinylpyridine)

The complexation of three kinds of sequence-ordered acid (co)polymers with a base homopolymer was studied. The acid polymers used are poly(methacrylic acid) 1 , alternating (1:1) ethylene-methacrylic acid copolymer 2 , and periodic (2:1) ethylene-methacrylic acid copolymer 3 , and the base polymer is poly(4-vinylpyridine) 4. When mixing a methanol solution of 1, 2 , or 3 with that of 4 (0.1 M of each functional group), precipitate was formed immediately for all polymer pairs. All the precipitates contained carboxyl and pyridyl groups in ca. 1:1 molar ratio and showed IR spectra indicating the hydrogen bonding between carboxyl and pyridyl groups. When mixing dilute methanol solutions (10⁻⁴M) of the above polymer pairs, no precipitation was observed, but the extinction coefficient (ϵ_B) at 255 nm of pyridyl groups in 4 was found to increase with an increasing acid polymer concentration. This is ascribed to hydrogen bonding between carboxyl and pyridyl groups in methanol. Based on the ϵ_B variation, the order of complexation constants for acid/base polymer pairs was estimated as follows: 1/4 pair ∼ 2/4 pair ≫ 3/4 pair. © 1996 John Wiley & Sons, Inc.     

Chelation of vanadium(IV) by a natural and edible biopolymer poly(gamma-glutamic acid) in aqueous solution: structure and binding constant of complex

The naturally occurring edible biopolymer poly(gamma-glutamic acid) (gamma-PGA) is shown to be an efficient chelating agent of vanadium(IV). The structure of poly(gamma-glutamic acid)oxovanadium(IV) (VO-gamma-PGA) complex in solution has been analyzed by electron spin resonance and UV-visible absorption spectra. The equatorial coordination sphere of vanadium(IV) is proposed to be [2 x carboxylate (2O)-VO-(OH2)2]. The binding isotherm is determined for suspensions of gamma-PGA in vanadium(IV) oxide sulfate (VS) solutions of different concentrations, and the data have been adjusted to fit the modified Langmuir equation. The maximum amount of vanadium bound per gram of gamma-PGA is estimated to be 141 mmol . g(-1) with a binding constant of 22 L . g(-1) at pH 3.     

含悬挂羧基手臂聚乳酸材料的合成与血小板粘附性研究

制备了乳酸-β-苹果酸共聚物,并在此基础上进一步修饰合成了含悬挂羟基(PLMAHE)以及悬挂羧基(PCA-PLA)的聚乳酸共聚物,利用原子力显微镜及环境扫描电镜,观察了聚合物膜的表面形貌以及粘附在聚合物膜上的血小板数量与形态.结果表明含悬挂羟基材料表面粘附血小板时发生聚集并有伪足生成,含悬挂羧基材料表面血小板粘附数量较少且形态正常,有望成为优良的抗凝血材料.     

Surface-modulated and thermoresponsive polyphosphoesternanoparticles for enhanced intracellular drug delivery

The chemical structure of end groups influenced the phase transition temperature of thermoresponsive polymers. We demonstrated a strategy for the preparation of the pH/thermo-responsive polymeric nanoparticles via subtle modification of end groups of thermoresponsive polymer segments with a carboxyl group and revealed its potential application for enhanced intracellular drug delivery. By developing a polymeric nanoparticle composed of poly(aliphatic ester) as the inner core and thermoresponsive polyphosphoester as the outer shell, we showed that end groups of thermoresponsive polyphosphoester segments modified by carboxyl groups exhibited a pH/thermo-responsive behavior due to the hydrophilic to hydrophobic transitions of the end groups in response to the pH. Moreover, by encapsulating doxorubicin into the hydrophobic core of such pH/thermo-responsive polymer nanoparticles, their intracellular delivery and cytotoxicity to wild-type and drug-resistant tumor cells were significantly enhanced through the phase-transition-dependent drug release that was triggered by endosomal/lysosomal pH. This novel strategy and the multi-responsive polymer nanoparticles achieved by the subtle chain-terminal modification of thermoresponsive polymers provide a smart platform for biomedical applications.     

Grafting of Polymers onto a Crosslinked Polymer Carrying Carboxyl Groups as a Model Compound for Carbon Black

Abstract

A cation-exchange resin (a crosslinked polymer carrying carboxyl groups) was used as a model compound for carbon black, and the grafting of several polymers to the resin was investigated. Reaction of acyl chloride groups that had been placed on the ion-exchange resin with polymers having hydroxyl or amino groups, such as polypropylene glycol, polyethylene glycol, polybutadiene glycol, polyvinyl alcohol, silicone diol, silicone diamine, and polyethyleneimine, resulted in grafting to the ion-exchange resin. In further experiments, primary amino groups were placed on the cation-exchange resin by reaction of acyl chloride groups with ethylenediamine. It was found that ring-opening polymerization of γmethyl L-glutamate N-carboxyanhydride is initiated by the amino groups on the resin, and polypeptide was grafted from the cation-exchange resin. Therefore, the reactivity of carboxyl groups on the resin was found to be similar to that on carbon black. However, carboxyl groups on the resin failed to initiate the cationic polymerization of vinyl monomers, in contrast to those on carbon black. This suggested that the acidity of carboxyl groups on carbon black is greater than on the cation-exchange resin.     

The thermal degradation of poly(-(d)-β-hydroxybutyric acid): Part 2—Changes in molecular weight

Changes in molecular weight occur in poly(-(d)-β-hydroxybutyric acid) in the temperature range 170–200°C, at which latter temperature evolution of volatile products of degradation becomes significant. Two processes are involved in these changes in molecular weight. The more important is random chain scission at ester groups, which results in the formation of carboxyl and vinyl groups. Although this ultimately results in a drastic reduction in the molecular weight of the polymer, this is delayed in the early stages of the reaction by a condensation reaction between the terminal hydroxyl groups present in the original polymer and the terminal carboxyl groups, which were either originally present or formed in the chain scission process. This delay could have relevance to the industrial processing of this material.     

Copolyesters of glycols and bisphenols: Concurrent reactions of a new preparative process

A mechanism for the preparation of copolyesters from a preformed polyester, diacid, and bisphenol diacetate in the melt phase is described. Utilizing copoly(ethylene:4,4′-isopropylidenediphenylene 50:50 2-methylisophthalate) as a model system, the reaction is shown to proceed through simultaneous cleavage of the preformed polyester by diacid, polymerization by condensation of carboxyl and bisphenol acetate groups, and equilibration through polyester cleavage by carboxyl polymer ends. In this model system, the rates of cleavage and polymerization are competitive, which results in a random sequence distribution early in the reaction.     

In situ particle film ATR FTIR spectroscopy of carboxymethyl cellulose adsorption on talc: binding mechanism, pH effects, and adsorption kinetics

Carboxymethyl cellulose (CMC), in solution and adsorbed on the surface of talc, has been studied with ATR FTIR spectroscopy as a function of the solution pH. The solution spectra enable the calculation of the extent of ionization of the polymer (due to protonation and deprotonation of the carboxyl group) at various pH values, yielding a value of 3.50 for the pK(app)(1/2) (pH at which half of all carboxyl groups are ionized) in a simple electrolyte solution and a value of 3.37 for the pK(app)(1/2) in solutions containing magnesium ions (3.33 x 10(-4) M). The spectra of the adsorbed layer reveal that CMC interacts with the talc surface through a chemical complexation mechanism, via the carboxyl groups substituted on the polymer backbone. The binding mechanism is active at all pH values down to pH 2 and up to pH 11. The adsorbed layer spectra reveal that protonation and deprotonation of the polymer are affected by adsorption, with an increase in the pK(app)(1/2) to a value of 4.80. Spectra of the adsorbed polymer were also acquired as a function of the adsorption time. Adsorption kinetic data reveal that the polymer most likely has two different interactions with the talc surface, with a stronger interaction with the talc edge through chemical complexation and a weaker interaction with the talc basal plane presumably through the hydrophobic interaction.     

Chemical structure of polycaproamide obtained by anionic polymerization of caprolactam in solvent

Chemical structure of polycaproamide (nylon-6), obtained by low temperature anionic polymerization of caprolactam in the presence of the sodium salt of caprolactam and carbon dioxide in solvent has been investigated. The polymer formed in a heterogeneous system, depending upon its final treatment, is terminated with amino and cyclic lactam groups or, after hydrolysis, with amino and carboxyl group. i.r. Spectra and acid-base titrations have shown the presence of amino and carboxyl groups in macromolecules. The contents of basic and acidic groups in the final product and its fractions were determined by potentiometric titrations. Number-average molecular weights of samples based on the results of titrations were compared with the results of osmotic measurements. Equal numbers of basic and acid groups in the polymer suggests that macromolecules are terminated at one end by an amino group and at the other by a carboxyl group. The results indicate a linear and regular structure for the polycaproamide.