Role of oxygen in the polymerization and de‐polymerization of alginate produced by Azotobacter vinelandii

Microbial polymers have diverse chemical structures, which determine their functional properties. Many microbial sources produce either intracellular or extracellular biopolymers. For example, Azotobacter vinelandii is a non‐pathogenic soil bacterium that produces alginate, an extracellular polysaccharide. Alginates are used mainly in the food and pharmaceutical industries as stabilizing, thickening, gel‐ or film‐forming agents. Due to its characteristics of biocompatibility, biodegradability and non‐antigenicity, new applications for alginate are being discovered, such as biomaterial in the biomedical field and tissue engineering. It is well established that alginate is first synthesized as a polymannuronate from its cytosolic precursor. However, the mechanisms involved in the polymerization, modification (acetylation, epimerization and depolymerization) and translocation of alginate have been poorly elucidated. Two of the most important parameters in alginate production by A. vinelandii are dissolved oxygen tension (DOT) and the oxygen supply conditions, as these impact both the polymer concentration and its composition, particularly its molecular weight (MW). Several studies have revealed that increased alginate molecular weight occurs in oxygen limited conditions, specifically at oxygen concentrations near zero. This article reviews recent studies examining the influence of oxygen, under limitation (microaerophilic) and non‐limitation conditions (measured as DOT and oxygen transfer rate, OTR), on the polymerization and degradation of alginate produced by A. vinelandii. This review also provides evidence for understanding these processes at the cellular level and the effect of oxygen on alginate biosynthesis. © 2014 Society of Chemical Industry     

Mechanism and kinetics of ultra‐high molecular weight polytetrafluoroethylene sintering

The effect of sintering time on the melt evolution of Ultra‐High Molecular Weight Polytetrafluoroethylene was studied in situ by high temperature Wide Angle X‐ray Scattering, and by cyclic thermal loading profiles within a Differential Scanning Calorimeter (DSC) and Thermo‐Mechanical Analyzer (TMA). Results obtained from these techniques support the concept of molecular ordering in the melt state as a function of sintering time well above the melting temperature. TMA, which is not a conventional technique for monitoring thermal transitions, is shown to be sensitive enough for such purposes. Both DSC and TMA exhibit nonequilibrium melt behavior even 30°C above its equilibrium melting temperature for long time periods. A correlation between the DSC and TMA results is established. The cyclic thermal profile leads to a dramatic growth in enthalpy of crystallization/melting. The mechanism for this growth is associated with two independent processes; isothermal annealing at the sintering temperature and lamellar thickening in the solid state. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40967.     

Lipolytic enzyme production in batch and fed‐batch cultures of Ophiostoma piceae and Fusarium oxysporum

Lipase and esterase production by Ophiostoma piceae and Fusarium oxysporum were enhanced and extended by developing a fed‐batch process in stirred tank reactors. Fed‐batch strategy improved lipolytic enzyme production from Ophiostoma piceae in both 2 and 20 dm³ stirred tank reactors. However, fed‐batch fermentation of Fusarium oxysporum in the 2 dm³ reactor was more effective than both batch and fed‐batch fermentations in the 20 dm³ reactor. When a medium composed of only carbon and nitrogen source was intermittently fed to the cultures, the maximum specific lipase activity was improved by more than 80% and 35% in Ophiostoma piceae and Fusarium oxysporum cultures respectively. The maximum specific esterase activity was improved by 20% and 15% in Ophiostoma piceae and Fusarium oxysporum cultures respectively. The duration of production for both fungi extended from 144 to 216 h compared with a batch culture under the same condition. © 2000 Society of Chemical Industry     

Study on gel‐spinning process of ultra‐high molecular weight polyethylene

An ultra‐high molecular weight polyethylene (UHMW‐PE) fiber was prepared by gel spinning using general kerosene as the solvent and gasoline as the extraction solvent. The process of the phase separation of gel as‐spun, spun under various spinning conditions, was investigated. Its extracting and drying process were also studied. The results reveal that the gel as‐spun, spun under a lower spin draft and a lower spin quenching temperature, extracted in times and dried under free‐shrinkage, exhibits a good afterdrawability that eventually endows the fiber with excellent mechanical behaviors. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 670–675, 1999     

Molecular weight and the Mark‐Houwink relation for ultra‐high molecular weight charged polyacrylamide determined using automatic batch mode multi‐angle light scattering

This study presents an automatic batch mode (i.e., off‐line) multi‐angle light scattering (MALS) method for the molecular weight (MW) determination of ultra‐high MW (UHMW) polyacrylamide (PAM) homopolymer and acrylamide copolymers. This method combines a MALS detector with a sample dilution and injection device that automatically delivers a concentration gradient from a stock solution. The automation makes it practical to use the batch MALS method for routine MW analysis of UHMW polymers. The automatic batch MALS analyses of a series of poly(sodium acrylate‐co‐acrylamide) (30:70 mol %) in 1.0M NaCl show a non‐linear Mark‐Houwink relation in the MW range of 1.2 × 10⁶ to 12.6 × 10⁶ g mol^?1. The entire molecular weight range can be fit with a quadratic relation or two linear equations, one for molecular weight up to 5.3 × 10⁶ g mol^?1 and the other from 5.3 × 10⁶ to 12.6 × 10⁶ g mol^?1. The non‐linear Mark‐Houwink relation suggests that the extrapolation of the Mark‐Houwink equation beyond the measured MW range into the UHMW regions can significantly overestimate the MW of the UHMW polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43748.     

Preparation and characterization of a foam regulator with ultra‐high molecular weight

Multistage emulsion polymerization was used to prepare ultra‐high molecular weight foam regulator of low cost, with methyl methacrylate (MMA), butyl acrylate (BA), styrene (St) as main raw materials. Ubbelohde viscometer, dynamic light scattering, infrared and raman spectra, TEM, DSC, TGA, and GPC were all used to characterize constituent and structure, morphology, and molecular weight. As a result, when the ratio of soft monomer (BA) and hard monomer (St + MMA) is 1:3, MMA:St = 4:1, potassium persulfate (KPS): 0.15%, sodium hydrogen sulfite (SHS): 0.05%, azodiisobutyronitrile (AIBN): 0.15%, divinyl benzene (DVB): 0.3%, the final product terpolymer has obvious core‐shell structure and ultra‐high molecular weight (M_w = 1,400,000). This kind of foam regulator showed improvements in the melt strength, prevention of bubble coalescence and reduction on cost when compared with the traditional. Finally, the coefficients of poly (methyl methacrylate‐butyl acrylate‐styrene) terpolymer's Mark‐Houwink equation were calculated with tetrahydrofuran (THF) solvent at 25 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44479.     

Properties of compression molded ultra‐high molecular weight polyethylene products pretreated by eccentric rotor extrusion

Low processing efficiency and fusion defects limit the application of ultra‐high molecular weight polyethylene (UHMWPE) in artificial joint implants. These problems result from the high melt viscosity of UHMWPE. Here, we use an eccentric rotor extruder (ERE) based on elongational flow to pretreat UHMWPE. Compression molded UHMWPE is obtained without and with ERE pretreatment (EP‐UHMWPE). The processing efficiency of EP‐UHMWPE is improved compared with direct compression molded UHMWPE. This is because the preheating time can be omitted during the molding process, and the residence time of UHMWPE in the extruder is less than 90 s. The mechanical properties and friction resistance of EP‐UHMWPE are significantly improved compared with those of direct compression molded UHMWPE. The yield strength increases from 21 MPa to 23 MPa, the tensile strength increases from 36 MPa to 46 MPa, the elongation at break increases from 610% to 700%, and the abrasion loss decreases from 1.73 mg/1000 r to 0.93 mg/1000 r when UHMWPE is subjected to ERE pretreatment. We attribute these improvements to the elongational flow enhancing the orientation and disentanglement of UHMWPE molecular chains, which in turn improves particle fusion. The molecular weight is well maintained when subjected to ERE pretreatment. UHMWPE components pretreated by ERE have good prospects in artificial joint implants. © 2019 Society of Chemical Industry     

Structure and properties of ultra‐high molecular weight bisphenol a polycarbonate synthesized by solid‐state polymerization in amorphous microlayers

The structure and properties of ultrahigh molecular weight polycarbonate synthesized by solid‐state polymerization in micro‐layers (SSP_m) are reported. A low molecular weight prepolymer derived from the melt transesterification of bisphenol A and diphenyl carbonate as a starting material was polymerized to highly amorphous and transparent polycarbonate of molecular weight larger than 300,000 g mol^?1 in the micro‐layers of thickness from 50 nm to 20 µm. It was observed that when the polymerization time in micro‐layers was extended beyond conventional reaction time, insoluble polymer fraction increased up to 95%. Through the analysis of both soluble and insoluble polymer fractions of the high molecular weight polycarbonate by ¹H NMR spectroscopy and pyrolysis‐gas chromatography mass spectrometry (Py‐GC/MS), branches and partially crosslinked structures have been identified. The thermal, mechanical and rheological properties of the ultra‐high molecular weight nonlinear polycarbonates synthesized in this study have been measured by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and rheometry. The nonlinear chain structures of the polymer have been found to affect the polymer's thermal stability, mechanical strength, shear thinning effect, and elastic properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41609.     

Preparation and characterization of ultra‐low molecular weight poly(vinyl alcohol) graft copolymer

Graft reaction of acrylamide (AM) and 4‐vinyl pyridine (4‐VP) onto ultra‐low molecular weight poly(vinyl alcohol) by ceric (IV) ion initiation had been systematically investigated; and the graft conditions were optimized by studying the effect of monomer/initiator concentration, solvents composition, reaction time and temperature. At optimized conditions, the maximum grafting efficiency and grafting ratio was ～ 50% and 51%, respectively with the presence of AM, whereas they decreased to 19% and 23%, respectively, without the presence of AM. Thermogravimetric analysis showed that as‐resulted graft copolymer had a lower thermal stability than homopolymer PVA. FTIR and ¹H‐NMR confirmed chemical structure of as‐synthesized graft copolymer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of sucrose on nisin production in batch and fed‐batch culture by Lactococcus lactis

The effects of sucrose on cell growth and nisin production by Lactococcus lactis were investigated in batch and pH feed‐back controlled fed‐batch cultures. In batch cultures, nisin titer reached its maximum, 2658 IU cm^?3, at the initial sucrose concentration of 30 g dm^?3. With sucrose concentrations higher than 30 g dm^?3, nisin production decreased while the biomass was not influenced significantly. By using the pH feed‐back controlled method, residual sucrose concentration could be controlled well in fed‐batch cultures and three conditions (sucrose maintained at 2, 16, 20 g dm^?3, respectively) were evaluated. Maintaining a low sucrose concentration at 2 g dm^?3 during feeding favored nisin biosynthesis, and the maximum nisin titer obtained was 4961 IU cm^?3 compared with 3370 IU cm^?3 (16 g sucrose dm^?3)and 3498 IU cm^?3 (20 g sucrose dm^?3), respectively. Copyright © 2005 Society of Chemical Industry     

Surface modification of ultra‐high molecular weight polyethylene fiber by different kinds of SiO2 nanoparticles

We successfully improved the interfacial adhesion strength between ultra‐high molecular weight polyethylene (UHMWPE) fiber and resin by the surface modification of UHMWPE fiber with two kinds of SiO₂ nanoparticles through gel spinning process. Modified effect of treated SiO₂ nanoparticles by coupling agent was superior to original SiO₂ nanoparticles. Compared with unmodified fibers, pull‐out tests of modified UHMWPE/treated SiO₂ fibers revealed that interfacial adhesion strength increased by the maximum of 10.95%, but corresponding breaking strength decreased by 8.51%. In addition, the interfacial adhesion strength and breaking strength could continue to enhance with increasing the additive amount of treated SiO₂ nanoparticles. The results of Differential Scanning Calorimetry (DSC), X‐ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM) indicated that the crystallinity of all modified fibers decreased while crystallite dimension increased, and the surface of modified fibers by treated SiO₂ nanoparticles exhibited polar functional group (C=O). The superiority of this modified technology was that it realized the bulk industrial production and maneuverability, low cost, and no pollution. POLYM. COMPOS., 38:1928–1936, 2017. © 2015 Society of Plastics Engineers     

Improvement of a fed‐batch process for high level xylanase production by a Bacillus strain

In this paper, the improvement of a fed‐batch fermentation from the point of view of an industrial xylanase production process is described. The Bacillus strain chosen for this study is able to produce high quantities of a xylanase that is suitable to be used as bleach boost agent in chlorine‐free bleaching sequences of paper pulp. It was found that xylo‐oligosaccharides (hydrolysis products from xylan by xylanase action) were indispensable for induction of the enzyme synthesis, but that their presence in quantities of only 0.1 g dm^?3 xylose equivalents led to catabolite repression. A substrate‐limited fed‐batch process, that is the most adapted, was furthermore improved with regard to nutrient requirement of the microorganism, especially the nitrogen source. A process with constant supply of a culture medium containing xylan, peptone and mineral nitrogen was able to produce 20 240 nkat cm^?3 with a productivity of 910 nkat cm^?3 h^?1, which places the process among the best ever reported. © 2001 Society of Chemical Industry     

Thermal and dynamic mechanical properties of vitamin E infused and blended ultra‐high molecular weight polyethylenes

Vitamin E (or α‐tocopherol) is an alternative via to thermal treatments to achieve oxidative stability of gamma or electron beam irradiated ultra‐high molecular weight polyethylenes (UHMWPE) used in total joint replacements. Our aim was to study the effects of vitamin E on the molecular dynamics and microstructural properties of UHMWPE. We hypothesized that the antioxidant would plasticize UHMWPE. Vitamin E was incorporated into UHMWPE at different concentrations by diffusion and blending and detected by ultraviolet and infrared spectroscopies from 500 ppm and 4000 ppm, respectively. Dynamic mechanical thermal analysis was used to characterize the influence of this antioxidant in the relaxations of the raw material. Differential scanning calorimetry and transmission electron microscopy served to characterize thermal and microstructure properties, respectively. Vitamin E concentrations above 3% by weight significantly reduced the degree of crystallinity and increased the melting transition temperature of raw UHMWPE. The presence of increasing concentrations of α‐tocopherol introduced and/or strengthened the beta relaxation, which was also shifted toward gradually lower temperatures and had rising activation energies up to 188 kJ/mol. In addition, the gamma relaxation remained unaltered on vitamin E addition. Therefore, no plasticizing effects of vitamin E on the molecular dynamics of UHMWPE could be confirmed from mechanical spectroscopy data. However, the α relaxation was modified in intensity and location due to the changes in the degree of crystallinity introduced by the incorporation of vitamin E. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Elevated production of the aromatic fragrance molecule, 2‐phenylethanol,using Metschnikowia pulcherrima through both de novo and ex novo conversion in batch and continuous modes

BACKGROUND

2‐phenylethanol (2PE) is a fragrance molecule predominantly used in perfumes and the food industry. It can be made from petrochemicals inexpensively, however, this is unsuitable for most food applications. Currently, the main method of production for the bio‐derived compound is to extract the trace amounts found in rose petals, which is extremely costly. Potentially fermentation could provide an inexpensive, naturally sourced, alternative.

RESULTS

In this investigation, 2PE was produced from the yeast Metschnikowia pulcherrima, optimised in flasks before scaling to 2 L batch and continuous operation. 2PE can be produced in high titres under de novo process conditions with up to 1500 mg L^?1 achieved in a 2 L stirred bioreactor. This is the highest reported de novo titre to date, and achieved through high sugar loadings coupled with low nitrogen conditions. The process successfully ran in continuous mode also, with a concentration of 650 mg L^?1 of 2PE being maintained. The 2PE production was further increased by the ex novo conversion of phenylalanine and semi‐continuous solid phase extraction from the supernatant. Under optimal conditions 14 000 mg L^?1 of 2PE was produced.

CONCLUSIONS

The work presented here offers a novel route to naturally sourced 2PE through a scalable fermentation with a robust yeast highly suited to industrial biotechnology. © 2018 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

     

Crystallization behavior and foaming properties of polypropylene containing ultra‐high molecular weight polyethylene under supercritical carbondioxide

In this study, a systematic investigation on the nonisothermal crystallization kinetics of conversional polypropylene (PP) containing various amounts of ultra‐high molecular weight polyethylene (UHMWPE) was reported, and the effects of UHMWPE on crystallization behavior of these PP materials and their foaming properties were also presented. The kinetic studies revealed that the incorporation of UHMWPE into PP led to an increase in the crystallization temperature and temperature range during the crystallization process as well as the relative crystallinity. This behavior was attributed to a comprehensive effect of the nucleation and entanglement of the UHMWPE chains. The kinetic models based on Ozawa's and Mo's methods were used to analyze the nonisothermal crystallization behaviors. It was found that the latter succeeded in describing the nonisothermal crystallization behavior of the PP containing UHMWPE, while the former was not appropriate. The activation energy for the nonisothermal crystallization determined by Kissinger's method also indicated that the crystallization ability of PP was improved with the addition of UHMWPE. Owing to the modification of the crystallization kinetics of the PP materials by introduction of UHMWPE, the foaming properties (i.e., cell uniformity and expandability etc.) were improved significantly. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of novel ultra‐high molecular weight polyethylene composite fibers filled with nanosilica particles

Ultrahigh molecular weight polyethylene (UHMWPE)/nanosilica (F₂S_y) and UHMWPE/modified nanosilica (F₂S_mx‐y) as‐prepared fibers were prepared by spinning of F₂S_y and F₂S_mx‐y gel solutions, respectively. Modified nanosilica particles were prepared by grafting maleic anhydride grafted polyethylenes onto nanosilica particles. The achievable draw ratios (D_ra) of F₂S_y and F₂S_mx‐y as‐prepared fibers approached a maximal value as the original and modified nanosilica contents reached corresponding optimum values; the maximal D_ra value obtained for F₂S_mx‐y as‐prepared fiber specimens was significantly higher than that of the F₂S_y as‐prepared fiber specimens prepared at the optimum nanosilica content. The melting temperature and evaluated lamellar thickness values of F₂S_y and F₂S_mx‐y as‐prepared fiber series specimens decrease, but crystallinity values increase significantly, as their original and modified nanosilica contents respectively increase. Similar to the achievable drawing properties of the as‐prepared fibers, the orientation factor, tensile strength (σ_f) and initial modulus (E) values of both drawn F₂S_y and F₂S_mx‐y fiber series specimens with a fixed draw ratio reach a maximal value as the original and/or modified nanosilica contents approach the optimum values; the σ_f and E values of the drawn F₂S_mx‐y fiber specimens are significantly higher than those of the corresponding drawn F₂S_y fiber specimens prepared at the same draw ratios and nanosilica contents but without being modified. To understand the interesting ultradrawing, thermal, orientation and tensile properties of F₂S_y and F₂S_mx‐y fiber specimens, Fourier transform infrared, specific surface area and transmission electron microscopy analyses of the original and modified nanosilica were performed in this study. © 2012 Society of Chemical Industry     

Variation of periodic crazing based on polymer blends of an ultra‐high and a low molecular weight poly(methyl methacrylate)

Periodic crazes are caused in a polymer film by the unique mechanical method using bending. Generation of a craze depends on entanglements of the molecular chains of a polymer. Therefore, control of composite morphology of periodic crazes was attempted by varying the entanglements of molecular chains. An effective entanglement network became sparse by polymer blends of an ultra‐high molecular weight polymethylmethacrylate (PMMA) and a low molecular weight PMMA. Consequently, the composite morphology of periodic crazes caused in the blend film varied. In other words, the periodic craze can be used for the evaluation of the effective entanglements. In addition, it was figured out that PMMA of which the number‐average molecular weight (M_n) is less than twice of the effective entanglement molecular weight (M_e^*) works as a plasticizer in the blend film. And also, it was revealed that the mechanical properties of the blend film decreased dramatically at M_n ≒ 6M_e^*. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44332.