POLY (β-HYDROXYALKANOATES): NATURAL BIOCOMPATIBLE AND BIODEGRADABLE POLYESTERS PRODUCED BY BACTERIA

A wide variety of different types of microorganisms are known to produce intracellular energy and carbon storage products, which have been generally described as being poly (β-hydroxybutyrate), PHB, but which are, more often than not, copolymers containing different alkyl groups at the β-position. Hence, PHB belongs to the family ofpoly (β-hydroxyalkanoastes), PHA, all of which are usually formed as intracellular inclusions in bacteria under unbalanced growth conditions. Recently, it became of industrial interest to evaluate these PHA polyesters as natural biodegradable and biocompatible plastics for a wide range of possible applications, such as surgical sutures or packaging containers. For industrial applications, the controlled incorporation of repeating units with different chain lengths into a series of copolymers is desirable in order to produce polyesters with a range of material properties because physical and chemical characteristics depend strongly on the polymer composition. Such 'tailor-made' copolymers can be produced under controlled growth conditions in that, if a defined mixture of substrates for a certain type of microorganisms is supplied, a well defined and reproducible copolymer is formed.

SYNTHESIS OF NOVEL HYDROPHILIC BIODEGRADABLE POLYESTER WITH FUNCTIONALIZED SIDE CHAIN GROUPS

A substituted glycolide, 3-benzyloxymethyl-1,4-dioxane-2,5-dione, was synthesized. It is a suitable precursor for the preparation of a new hydrophilic biodegradable poly(a-hydroxy acid). The polymerizations were carried out in bulk in the presence of Sn(Oct)(2) at 120-140 degreesC. The resulting polymers were subjected to hydrogenolysis with a Pd/C catalyst in a mixed solvent to remove the protecting benzyl groups. A novel poly(a-hydroxy acid) with pendant hydroxy groups was obtained. The hydrophilicity of the resulting polymer was evaluated preliminarily.

The effect of mechanical loads on the degradation of aliphatic biodegradable polyesters

Aliphatic biodegradable polyesters have been the most widely used synthetic polymers for developing biodegradable devices as alternatives for the currently used permanent medical devices.The performances during biodegradation process play crucial roles for final realization of their functions.Because physiological and biochemical environment in vivo significantly affects biodegradation process,large numbers of studies on effects of mechanical loads on the degradation of aliphatic biodegradable polyesters have been launched during last decades.In this review article,we discussed the mechanism of biodegradation and several different mechanical loads that have been reported to affect the biodegradation process.Other physiological and biochemical factors related to mechanical loads were also discussed.The mechanical load could change the conformational strain energy and morphology to weaken the stability of the polymer.Besides,the load and pattern could accelerate the loss of intrinsic mechanical properties of polymers.This indicated that investigations into effects of mechanical loads on the degradation should be indispensable.More combination condition of mechanical loads and multiple factors should be considered in order to keep the degradation rate controllable and evaluate the degradation process in vivo accurately.Only then can the degradable devise achieve the desired effects and further expand the special applications of aliphatic biodegradable polyesters.

Study on Structure and Crystallinity of A New Biodegradable Aliphatic-Aromatic Copolyester

A series of biodegradable aliphatic-aromatic copolyesters, poly(butylene terephthalate-co-butylene adipate-co- ethylene terephthalate-co-ethylene adipate) (PBATE), were synthesized from terephthalic acid (PTA), adipic acid (AA), 1,4-butanediol (BG) and ethylene glycol (EG) through direct esterification and polycondensation. The sequence structure and crystallinity of the copolyester were investigated by 1H NMR spectroscopy and the wide-angle X-ray diffractometry (WAXD). The analytical results showed that the PBATE copolyester was a random copolymer and the composition of PBATE copolyester was almost consistent with the feed molar ratios. The crystal structure of PBATE copolyester belonged to the triclinic crystalline system; The variation in melting point of the synthesized PBATE copolyester agreed well with the estimation obtained by the Flory equation and was applicable to the random copolymer.

Increased Elongation at Breaking Point with Improved Mechanical Characteristics in PLA

The main goal of this research was to increase the strength of Polylactic acid (PLA), an entirely biodegradable thermoplastic polyester, and an increase in elongation at the breaking point compared to neat PLA. To this end, S1, S2, and S3 were melt blended with various percentages of Zeolite, Glycerol, White vinegar, green camphor, Eucalyptus, and Carom seed oils. Here, the addition of glycerol, eucalyptus, and carom seed oils demonstrated an average improvement in impact and tensile strength of 13.44% and 14.55% respectively. Zeolite and glycerol work together as binding agents to improve stress transfer in the matrix, which increases tensile and flexural modulus as well as toughness elongation (>10%). The addition of the aforementioned materials led to an increase in the glass transition temperature and melting temperature, according to further DSC investigation. The thermal stability increased gradually, according to TGA data.

Optimization of Propionic Acid Feeding for Production of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in Fed-Batch Culture of Ralstonia eutropha

The feeding method of propionic acid for production ofpoly(3-hydroxybutyrate-co-3-hydro xyvalerate) [P(3HB-co-3HV)] by fed-batch culture of Ralstoniaeutropha was optimized to achieve high cell density and high 3HV yield. Effects of different feedingstrategies of propionic acid on the production of P(3HB-co-3HV) were investigated. A decline ofspecific synthesis rate of copolymer and the yield of 3HV unit from propionic acid were observed dueto the propionic acid accumulation in culture broth when the feeding solution with highP/G(propionic acid to glucose) ratio was employed. It was further confirmed by controlling propionicacid concentration at a low level in the separate feeding of propionic acid. An optimal feedingstrategy was demonstrated to reduce the propionic acid accumulation. The cell concentration,P(3HB-co-3HV) productivity and 3HV unit fraction reached to 163.9kg·m^(-3), 1.8kg·m^(-3)·h^(-1),and 10.6%(by mass), respectively, resulting in a yield of 0.33g HV per g propionic acid.

Effect of TiO2 on the Photodegradation Mechanism of Poly(butylene succinate)

The photodegradation behaviors of poly（butylene succinate）（PBS） and TiO2/PBS nanocomposite were monitored over a period of six months. Material properties and aging mechanisms were studied and explored by various characterizations including 1HNMR, FTIR, XRD, mass spectrum, and TGA. The TiO2/PBS nanocomposite was found to be more thermally stable and mechanically robust than the PBS. During aging, crystal formation and the final crystal structure changed notably. Based on the characterization results, it is proposed that the polymer chains have cleaved at the ester linkage by the dissociation of O–H groups and the conversion of C=O to C–O bonds. It was also believed that polymer chain transfer took place, which resulted in the formation of C=C bonds and O–H groups, and the polyester changed to enol or polyether.

Comparative evaluation of physico-chemical characteristics of biopolyesters P（3HB） and P（3HB-co-3HV） produced by endophytic Bacillus cereus RCL 02

BACKGROUND： Bacteria endogenously residing within the plant tissues have attracted significant attention for production of biopolyester, polyhydroxyalkanoates （PHAs）. Bacillus cereus RCL 02 （MCC 3436）, a leaf endophyte of oleaginous plant Ricinus communis L. accumulates 81% poly（3-hydroxybutyrate） [P（3HB）] of its cell dry biomass when grown in mineral salts （MS） medium. METHODS： The copolymer production efficiency of B. cereus RCL 02 was evaluated in valeric acid supplemented MS medium under biphasic cultivation condition. The copolymer so produced has been compared with the P（3HB） isolated from RCL 02 in terms of thermal, mechanical and chemical properties. RESULTS： Valeric acid supplementation as co-substrate in the medium has led to the production of copolymer of 3- hydroxybutyrate （3HB） and 3-hydroxyvalerate （3HV） [P（3HB-co-3HV）] with 14.6 mol% 3HV. The identity of the polymers has been confirmed by X-ray diffraction （XRD） analysis, Fourier transform infrared （FTIR） and nuclear magnetic resonance （NMR） spectroscopic studies. Thermogravimetric analysis （TGA） revealed that P（3HB） and P（3HB-co-3HV） films degraded at 278.66℃ and 273.49℃, respectively. The P（3HB-co-3HV） showed lower melting temperature （165.03℃） compared to P （3HB） （170.74℃） according to differential scanning calorimetry （DSC）. Incorporation of 3HV monomers decreased the tensile strength （21.52 MPa）, tensile modulus （0.93 GPa）, storage modulus （E＇） （0.99 GPa） and increased % elongation at break （12.2%） of the copolyester. However, P（3HB） showed better barrier properties with lower water vapor transmission rate （WVTR） of 0.55 g-mil/100 in2/24 h. CONCLUSION： These findings emphasized exploration of endophytic bacterial strain （RCL 02） to produce biodegradable polyesters which might have significant potential for industrial application.