Molecular mechanism of temporal physico/chemical changes that take place during imidization of polyamic acid: Coupled real-time rheo-optical and IR dichroism measurements

Multiple overlapping physical and chemical changes often take place during casting/drying and imidization from PMDA-ODA polyamic acid precursors from cast solutions. To shed light into details of these complex phenomena, we designed a unique real time measurement system that combines true stress, true strain, in-plane birefringence and temperature with polarized ultra-rapid scan FT-IR spectrometry (URS-FT-IR). At the early stages of heating (21°C–130 °C), initially isotropic solution cast film was observed to develop stress and birefringence as the solvent decomplexed and evaporated without showing any imidization as it was held in uniaxially constrained state. At a temperature around 130 °C, the onset of imidization reaction was detected while the stress went through a maximum. Beyond this stage, the evaporation of bound solvent and chemical conversion was observed to take place simultaneously and this is accompanied by a steady increase in birefringence. As the majority of the bound solvent evaporated, the stress and birefringence values started leveling off at long times.     

Processing characteristics and structure development in solid-state extrusion of bacterial copolyesters: Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The bacterial copolyesters poly(3-hydroxybutyrate-co-3-hydroxyvalerate) have been successfully commercialized by ICI and are currently being distributed worldwide. Because of their bacterial origin, they are completely biodegradable. This has opened up numerous opportunities to develop new environmentally friendly products. The solid-state extrusion of a series of biodegradable copolyesters (P(3HB-3HV)) was performed in our laboratory with the aim of gaining fundamental understanding about their processability below their melting temperatures. The extrudability windows were found to span the temperature range from 135 to 150°C, depending on the composition of the samples under our experimental setup. The solid-state extrudates were found to exhibit an extra melting endotherm about 15–20°C above their normal melting temperature. This high temperature melting peak increasingly became dominant at lower extrusion temperatures. Wide angle X-ray diffraction studies did not indicate any phase change that might be responsible for this increase in the melting point. Contrary to the expectations, the solid-state extruded samples did not show significant chain orientation along the extrusion direction. This might be a result of fracture of the mass in the barrel into smaller pieces and their randomization during the course of their passage through the die. When the extrusion temperature was raised closer to the melting temperature, the quality of the extrudates was improved, and this was reflected in improvement of their mechanical properties. © 1996 John Wiley & Sons, Inc.     

Free radical crosslinking of unsaturated bacterial polyesters obtained from soybean oily acids

Summary Poly(-3-hydroxy alkanoate) containing unsaturated side chains, PHA-soybean, were produced by feeding Pseudomonas oleovorans with soybean oily acids obtained from soybean oil. Unsaturation of PHA-soybean were found to be 10 mol-% of unsaturated side chains. Main saturated part of the biopolymer was Poly(3-hydroxy octanoate) with minor hexanoate and decanoate units. PHA films were crosslinked via free radical mechanism by means of thermally or under UV irradiation in the presence of benzoyl peroxide, benzophenon, and /or ethylene glycol dimethacrylate (EGDM). Crosslinking yield of the PHA films were found to be from 81 to 93 wt.-% from the sol-gel analysis. Swelling properties of the crosslinked PHA films in chloroform and toluene were also studied. Mc values of crosslinked PHAs were also calculated using Flory-Rehner equation. The crosslinked biopolyester obtained by thermally at 60 °C with benzoyl peroxide indicated the highest crosslinking density. Glass transition temperatures (Tg) of crosslinked biopolyester samples were changed from −33 to −45 °C while that of PHA-soybean was −60 °C. Received: 16 June 2000/Revised version: 22 January 2001/Accepted: 20 May 2001     

Aromatic liquid crystalline copolyesters with low Tm and high Tg: Synthesis,characterization, and properties

In this study, a series of aromatic copolyesters P‐BPAx with lower melting temperature and higher glass transition temperature derived from hydroxybenzoic acid (HBA), 6‐hydroxy‐2‐naphthoic acid (HNA), bisphenol A (BPA) and terephthalic acid (TA) were synthesized via melt polymerization. The copolyesters were characterized by FTIR, solid state ¹³C NMR, DSC, TGA, polarized optical microscopy, X‐ray diffraction, and rheometry measurements. With addition of BPA, the resulting copolyester's melting temperature decreased from 260 to 221°C and its glass transition temperature increased from 70 to 135°C, compared with the parent copolyester P‐HBA70 (HBA/HNA copolymer). With exception of copolyester P‐BPA5.0 (225–280°C), the copolyesters could maintain liquid crystalline behavior in a broad temperature range from 230°C to higher than 410°C. The ability to form nematic liquid crystalline phase disappeared when BPA concentration became higher than 15 mol %. X‐ray diffraction analysis showed crystallinity decreased as the BPA content increased. A slightly distorted O" and a substantially distorted O′ orthorhombic phase was observed for P‐BPA2.5. Upon annealing at 220°C, the O" phase disappeared and the O′ phase became stronger gradually. Rheology study data showed the ability to process the copolyesters improved in those compositions containing <2.5 mol % BPA. Continuing to increase concentrations of BPA, they became intractable. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40487.     

Effect of reuterin produced by Lactobacillus reuteri on the surface of sausages to inhibit the growth of Listeria monocytogenes and Salmonella spp

Reuterin is a bacteriocin produced by some strains of Lactobacillus reuteri. The strain used in this study was isolated from raw milk from a dairy farm nearby Ankara. Beef sausage is a long years produced bratwurst style meat product in Turkey, as well as in some other countries in the Mediterranean region. Sausages are produced by raw meat; sometimes lactic starter cultures are added or spontaneous fermentation is employed. The production and storage conditions of the product promotes the growth of Listeria monocytogenes and Salmonella spp. Although nitrate is added as an antimicrobial substance against many pathogens, sometimes however nitrate application is not preventive enough on the surface because of the natural film around the sausages. Since most of the contaminations take place at post production steps, pathogenic growth is more effective on the surface of the sausages in refrigerated conditions. In this study, reuterin was applied to the surface of the sausages in order to prevent the growth of these two pathogens along with nitrate used as an additive in the product. Reuterin has inhibited the growth of L. monocytogenes considerably but not of Salmonella spp. on the surface of the sausages.     

Preparation of multiphase block copolymers by redox polymerization process, 4. Polymerization of methyl methacrylate by the redox system Mn(III)-poly(ethylene glycol) containing azo groups

Redox polymerization of methyl methacrylate using Mn(III) with poly(ethylene glycol) having azo and hydroxy functions was carried out to yield ethylene glycolmethyl methacrylate block copolymers with labile azo linkages in the main chain. These prepolymers were used to initiate free-radical polymerization of styrene through thermal decomposition of the azo groups, resulting in the formation of multiblock copolymers. Successful blocking has been confirmed by fractional precipitation, a strong change in the molecular weight, and spectral measurements.     

Pressure control system for electrospinning process

Electrospinning is used to produce micro‐ and nano‐sized synthetic fibers through the use of electrostatic forces. Commercially, viable production of fibers requires high throughput of uniform fibers that are free of defects. To achieve greater control over the process variables that affect the fiber formation, a scalable closed loop control system that can maintain a constant pressure at the capillary tip was designed and tested. Two sensing technologies, infrared and ultrasonic, were used and compared for their ability to detect the height of polymer solution in the electrospinning fluid container. The air pressure above the solution was measured with a pressure transducer and adjusted through a controllable syringe pump. The closed loop electrospinning system was successful at controlling and maintaining a constant pressure at the capillary tip to within 2% of the specified pressure continuously. The controlled pressure at the capillary tip showed a strong correlation to fiber diameter and uniformity for polydimethylsiloxane‐based polyurethane/DMF‐based fibers. However the control system was less effective to control fiber diameter for polyethylene oxide/Water‐based fibers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Fabrication of highly reflective gratings in 1.5 μm semiconductor lasers using focused ion beam-based etching

This paper reports on fabrication of semiconductor/air gratings in 1.5 μm double-section semiconductor lasers to achieve a high reflectivity in order to compensate low round-trip gain. Fabrication of the gratings with varying thicknesses and with thicknesses down to 160 nm is carried out at the gain section of the double-section diode laser using focused ion beam etching (FIBE) and inductively coupled plasma (ICP) techniques. Theoretical results of reflectivity are given for 1.5 μm AlGaInAs/InP semiconductor lasers by adding wavelength dependence of the refractive index into the calculations. We also compare our reflectivity results with that of a commercial simulation program and show a good agreement between them. Our results demonstrate that the gratings fabricated consist of only six air/semiconductor layer pairs and achieve theoretical reflectivity higher than 99%. Due to a high index contrast of the both layers, n_l = 1, n_h ∼ 3.5, a reflectivity bandwidth of >230 nm is obtained in 1.5 μm semiconductor lasers. Finally, lasing operation from AlGaInAs/InP semiconductor lasers with highly reflective grating section is achieved with a low threshold current of ∼8 mA, which is almost three times lower than devices without semiconductor/air gratings.     

Toward Sustainable Water Management in the Southeastern Anatolia Project (GAP)

Being the largest and the most comprehensive regional development effort ever undertaken in Turkey, the Southeastern Anatolia Project (GAP) will constitute the primary driving force for the socioeconomic development of the region and consequently of Turkey. Owing to its multipurpose nature, GAP necessitates, on the one hand, discreet conduct in meeting the demands on time so as to spur the rapid development of the region through prudent management of water, and on the other hand, careful consideration, for the sake of sustainable development, of imminent as well as long-term environmental impacts in order for the project to be viable. An integrated basin-wide approach leading to, among other things, quantity and quality management, prioritybased allocation, conservation, conjunctive use of various resources of water, maintenance of facilities as well as inter- and intra-institutional arrangements, has been adopted from the outset, and is being revised and improved in as profound a way as possible as the project progresses.     

Factors that may increase morbidity in a model of intra-abdominal contamination caused by gallstones lost in the peritoneal cavity

OBJECTIVE: To assess the effect of intraperitoneal gallstones with and without Escherichia coli and sterile bile on the incidence of intraperitoneal complications in mice. DESIGN: Prospective randomised study. SETTING: Teaching hospital, Turkey. MATERIAL: 180 Swiss albino mice in five groups, n = 20 in the control group, and n = 40 in each of the experimental groups. INTERVENTIONS: Group A laparotomy alone (controls); group B, laparotomy amd intraperitoneal instillation of E. coli 4 x 10(6) 0.1 ml; group C, laparotomy and insertion of sterilised gallstones; group D, laparotomy, insertion of gallstones and instillation of E. coli 4 x 10(6) 0.1 ml; and group E, laparotomy, insertion of gallstones, and instillation of E. coli 4 x 10(6) 0.1 ml and sterile bile 0.1 ml. A quarter of each group was killed after 1, 2, 4, and 8 weeks. MAIN OUTCOME MEASURES: Intra-peritoneal abscesses, adhesions, perforations, fistula, or obstruction. RESULTS: No mice died. Adhesions were found in 3(15%), 7(18%), 30(75%), 25(63%), and 24(60%) in the five groups, respectively. No mice in groups A, B, or C developed an abscess, but 8 did in each of groups D and E (20%). One mouse in group D developed obstruction. Logistic regression showed that abscess formation was significantly increased by the addition of gallstones and E. coli to the peritoneal cavity (p < 0.001) but the addition of bile had no effect. Gallstones increased the rate of adhesions more than nine fold (p < 0.001) but E. coli with or without bile had no effect (p = 0.75). CONCLUSIONS: Free gallstones within the peritoneal cavity with or without E. coli or sterile bile, or both, increased the rate of formation of both abscesses and adhesions in mice. These results suggest that efforts should be made retrieve gallstones that are dropped into the peritoneal cavity during laparoscopic cholecystectomy, particularly in patients with acute cholecystitis.