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Production of unsaturated polyesters by Pseudomonas oleovorans.

Pseudomonas oleovorans was grown separately on 3-hydroxy-6-octenoic acid and 3-hydroxy-7-octenoic acid as the only carbon source and under ammonium nutrient-limiting conditions to produce storage polyesters. The polyesters produced contained mainly unsaturated C8 units. Small amounts of both the saturated and the unsaturated C6 units were also present, but only about 1% of the saturated 3-hydroxyoctanoate units was detected. The polyester obtained from 3-hydroxy-6-octenoic acid, which was a mixture of the cis and trans isomers, also contained units with cis and trans double bonds. The weight average molecular weights of the polymers produced were in the range of 339,000-383,000 as determined by g.p.c. relative to polystyrene, with Mw/Mn ratios of 1.8-2.1. The mechanism of PHA formation from n-octene previously reported is discussed in relation to the present results, and the two were found to be in good agreement.

Culture Media↗

Extraction of lipid membrane incorporated vitamin E by sucrose polyesters.

2H and 31P solid state NMR have been used to probe, at the molecular level, the interaction between structurally different sucrose polyesters and a phospholipid membrane into which alpha-tocopherol and specifically deuterated alpha-[5,7-(2)H(6)] tocopherol has been incorporated. Our results show that at high concentration (>or=10 mol%) sucrose octapalmitate (SOP) and sucrose hexapalmitate (SHxP) deplete bilayer-associated alpha-tocopherol in dipalmitoyl phosphatidalcholine (DPPC) multilamellar dispersions and preferentially sequester the alpha-tocopherol into a fluid sucrose polyesters (SPE) phase located proximal to the membrane surface. It is demonstrated that the ability of SPEs to function as a 'lipophilic sink' depends strongly on sucrose polyester concentration and degree of esterification.

1,2-Dipalmitoylphosphatidylcholine↗

Clinical experience of patellar fracture fixation using metal wire or non-absorbable polyester--a study of 37 cases.

The results of patellar fracture fixation using metal wire and non-absorbable polyester (5 Ethibond) are presented. In group 1 (21 cases), the standard "AO" technique using stainless steel wire was used, and in group 2 (16 cases) we used 5 Ethibond. Patients were assigned to the two groups on surgeon preference. Post-operative management in the two groups was similar, with patients being allowed to mobilise as comfort allowed, under the supervision of the physiotherapists. All patients were followed-up until union of the fractures or until further surgical intervention was carried out. At a mean of 2 years and 6 months (range 1-4 years), we reviewed the notes and X-rays of all 37 cases. In group 2 there were no cases of infection but there were three cases of post-operative infections in group 1. Re-operation rate was 6/21 (38%) in group 1 and 1/6 (6%) in group 2. Therefore, the relative risk of re-operation in the metal group is six times that in the non-absorbable polyester group. The risk of infection in the metal group is also higher. These have implication on patient morbidity associated with the operative treatment of patellar fractures. Non-absorbable polyester appears to compare favourably with the use of metallic wire to fix patellar fractures.

Adult↗

Necrotizing scleritis after intraocular surgery associated with the use of polyester nonabsorbable sutures.

We present 2 elderly patients who developed necrotizing scleritis after cataract extraction in which the wound was sutured with polyester. In the first case, a 73-year-old woman who had right phacoemulsification via a limbal incision developed necrotizing scleritis 8 months after surgery. The eye became progressively painful and phthisical, necessitating enucleation. Microscopic examination of the enucleated globe showed a predominantly lymphocytic infiltration of the ocular tissues with no evidence of an infectious agent. In the second case, a 78-year-old woman had bilateral extracapsular cataract extraction through a limbal incision closed with a polyester suture. The patient presented 3 years later with bilateral necrotizing sclerokeratitis. No underlying systemic vasculitis or autoimmune condition was identified in either patient. To our knowledge, the association of necrotizing scleritis after intraocular surgery and polyester fiber suture material (Mersilene) has not been described.

Aged↗

Characterization of polyether and polyester polyurethane soft blocks using MALDI mass spectrometry

Selective degradation reactions combined with MALDI analysis have been applied for molecular weight (MW) determination of polyether and polyester polyurethane (PUR) soft blocks. Selective degradation allows recovery of the polyols, and direct observation of the soft block oligomer distribution is possible for the first time by using MALDI. Ethanolamine is applied for polyether PUR degradation. MALDI analysis indicates that the recovered polytetrahydrofuran (pTHF) MW distribution is nearly identical to the unreacted pTHF material. Reduction in the ethanolamine reaction time allows observation of oligomer ions containing the diisocyanate linkage, which provide identification of the diisocyanate. Ethanolamine is not used for polyester PUR's degradation because the ester bonds will be cleaved. Therefore, phenylisocyanate is applied for polyester PUR degradation. Polybutylene adipate (pBA) oligomers were directly observed in the MALDI spectra of the degraded pBA-PUR samples. Comparison of the degraded pBA-PUR oligomer distribution with the unreacted pBA material indicates that low-mass oligomers are less abundant in the degraded pBA-PURs. Oligomer ions containing the diisocyanate linkage are also observed in the spectrum, providing a means for identifying the diisocyanate used for PUR syntheses. Size-exclusion chromatography (SEC) was combined with MALDI to provide accurate MW determination. Narrow MW fractions of the degraded and unreacted polyols were collected and analyzed by MALDI. This method allows precise calibration of the SEC chromatogram. The SEC-MALDI results provide significantly larger Mw and PD values than MALDI alone. Using SEC-MALDI, it was determined that the PD indexes of the pTHF and pBA samples are larger than the assumed values, which are based on the polyol synthesis reactions. The combination of selective degradation with SEC-MALDI, using either ethanolamine or phenylisocyanate, is a viable method for polyurethane polyol characterization.

Journal Article↗

Adhesion between graphite and modified polyester surfaces: a theoretical study.

This study examines the adhesion of graphite to functionalized polyester surfaces using a range of qualitative and quantitative measures of theoretical adhesion. Modifications to the polyester surfaces include the addition of hydroxyl, carboxyl, or fluorine substituents with coverages of 0.4 and 0.9 groups per nm(2). In each case, the introduction of substituents to the surface of the polyester was calculated to lead to reduced adhesion to graphite. Effects of surface relaxation on adhesion are studied by employing different simulation protocols. The theoretical results suggest one mechanism to reduce adhesion to carbonaceous solids is to increase atomic roughness using strongly hydrophilic or alternatively strongly hydrophobic substituents.

Journal Article↗

Invertible architectures from amphiphilic polyesters.

We synthesized and characterized novel amphiphilic polyesters with both hydrophilic and hydrophobic functionalities. The polyesters are soluble in organic and aqueous media and reveal the formation of inverse architectures whose behavior could be correlated to their chemical structure. We foresee that the amphiphilic properties of the polyesters reported here are obviously the basis of new architectures both in solution and on the solid surfaces, which could be used in a broad range of applications. The described synthesis of the copolymers is very simple and is based on commercially available products. That makes this approach attractive in various uses.

Journal Article↗

Synthesis of amphiphilic silver nanoparticles in nanoreactors from invertible polyester.

A silver complex is transformed into amphiphilic nanoparticles at room temperature using nanoreactors formed from an amphiphilic polyester. It takes a few minutes to form silver nanocolloids with a narrow particle size distribution. Developed silver forms a stable dispersion in both polar and nonpolar media. The amphiphilic polyester acts as a reducing and stabilizing agent simultaneously. The size of the synthesized amphiphilic silver nanoparticles depends on the concentration of the invertible polyester and solvent polarity.

Journal Article↗

Release of peptide YY and inhibition of gastric acid secretion by long-chain and medium-chain triglycerides but not by sucrose polyester in men.

METHODS: In the present study, we have investigated the effects of intraduodenal perfusion of long-chain and medium-chain triglycerides and of sucrose polyester on the release of peptide YY in healthy men. RESULTS: Perfusion of medium-chain triglycerides (180 mmol fatty acids) increased the plasma concentration of peptide YY from 7.9 pmol L(-1) (SEM 0.2, n=8) to 10.7 pmol L(-1) (SEM 0.5, n=8), whereas perfusion of long-chain triglycerides (180 mmol fatty acids) had a significantly greater effect, increasing peptide YY concentration from 8 6 pmol L(-1) (SEM 0.2, n=8) to 18.9 pmol L(-1) (SEM 2.4, n=8, P < 0.008). A smaller quantity of long-chain triglycerides (90 mmol fatty acids) increased plasma concentration of peptide YY from 7.4 pmol L(-1) (SEM 0.4, n=8) to 13.3 pmol L(-1) (SEM 1.5, n=8), whereas sucrose polyester (90 mmol fatty acids) did not change peptide YY concentration. In a previous study, we investigated gastrin-stimulated gastric acid output in response to these treatments. The correlation between increases in peptide YY in response to all treatments and the decrease in acid output was r=0.72 (n=48, P < 0.0001). These results show that both long-chain and medium-chain triglycerides, but not sucrose polyester, stimulate the release of peptide YY. CONCLUSION: We speculate that peptide YY may play an important role in the inhibition of gastrin-stimulated gastric acid secretion by long-chain and medium-chain triglycerides.

Adult↗

Removal of anaphylatoxins C3a and C5a and chemokines interleukin 8 and RANTES by polyester white cell-reduction and plasma filters.

BACKGROUND: A few bedside polyester white cell (WBC)-reduction filters have been shown to scavenge C3a anaphylatoxin from stored blood components. One has been shown to remove the chemokines interleukin (IL)-8 and RANTES, but not the proinflammatory cytokines IL-1, IL-6, and tumor necrosis factor alpha. Removal by any filter of the anaphylatoxin C5a or the soluble membrane attack complex (SC5b-9) has not been studied. Further, the ability of other filters to scavenge these biologic response modifiers (BRM) is not known. Four WBC-reduction filters and one plasma filter were studied for their ability to remove IL-8, RANTES, IL-1 beta, C3a, C5a, and SC5b-9. STUDY DESIGN AND METHODS: Plasma was obtained either as freshly thawed fresh-frozen plasma, fresh-frozen plasma thawed and stored for 5 days, or platelet-poor supernatant. Cell-poor plasma was obtained and samples were taken before and after filtration through the various filters Levels of IL-1 beta, IL-8, RANTES, C3a, and SC5b9 were quantitated by enzyme immunoassay. To evaluate filter scavenging of C5a, an in vitro model was developed to generate high levels of C5a in plasma by activating plasma with zymosan. RESULTS: Levels of C3a, C5a, IL-8, and RANTES were reduced by filtration through two bedside platelet WBC-reduction filters, a plasma filter, and a prestorage red cell WBC-reduction filter, but not following filtration through a prestorage platelet WBC-reduction filter. For some BRMs and filters, however, evidence of filter saturation was seen. IL-1 beta was not removed by any of the filters tested. CONCLUSION: Some, but not all, bedside polyester filters and prestorage polyester filters can remove IL-8, RANTES, C3a, and C5a from units of plasma or platelets. Improved biomaterial engineering of these and other filters could maximize scavenging of BRMs and potentially diminish the adverse reactions associated with their infusion during transfusion.

Blood Component Removal↗

The effect of autoclave resterilisation on polyester vascular grafts.

OBJECTIVES: polyester grafts are expensive, single-use items. Some manufacturers of uncoated, woven grafts include instructions for autoclave resterilisation to be performed at the surgeon's own request. Others warn against such manipulation. Theoretically, the glass transition point of polyester at 70-80 degrees C and the possible acceleration of hydrolysis suggest that autoclave resterilisation at 135 degrees C might be a problem. MATERIALS AND METHODS: a DeBakey Soft Woven Dacron Vascular Prosthesis (Bard) and a Woven Double Velour Dacron Graft (Meadox) were autoclave-resterilised 0 to 20 times, having been weighed before and after sterilisation. Tactile testing was performed. Mechanical properties were examined by probe puncture and single-filament testing, the surface was examined by scanning electron microscopy and the degree of hydrolysis by infra-red spectroscopy. RESULTS: tactile testing revealed a change of feeling with increasing cycles of resterilisation. Investigation of weight, textile strength, single-filament strength, electron microscopy of the surface and infra-red spectroscopy showed no change of the material. CONCLUSIONS: changes felt are presumably a surface phenomenon, not measurably affecting strength or chemistry of material after autoclave resterilisation. We therefore feel that it is safe to use once-autoclave-resterilised surplus uncoated polyester grafts, provided that sterility is guaranteed.

Blood Vessel Prosthesis↗

Occupational allergic contact dermatitis to cobalt octoate included as an accelerator in a polyester resin.

A 46-year-old woman, who worked as a laminator of spa baths, presented with hand dermatitis, which was suspected to be related to her occupation. Patch testing revealed strong reactions to both cobalt chloride and a polyester resin that the patient had been using at her workplace. She also reacted to latex and had been wearing cotton gloves underneath rubber gloves at work. It was later discovered that cobalt octoate (synonym: cobalt-2-ethylhexanoate), a compound not listed on the manufacturer's material safety data sheet, was included as an accelerator in the polyester resin. She was then tested to cobalt octoate, which was also strongly positive. Her successful treatment included protection of her hands at work with cotton lined PVC gloves. This case highlights the role of cobalt salts as sensitizers and their presence as accelerators used in polyester resins, and the importance of recognizing concomitant latex allergy that may complicate occupational dermatitis. It also illustrates the difficulties in relying on material safety data sheets to identify all possible allergens.

Allergens↗

Purification and Properties of a Polyester Polyurethane-Degrading Enzyme from Comamonas acidovorans TB-35.

A polyester polyurethane (PUR)-degrading enzyme, PUR esterase, derived from Comamonas acidovorans TB-35, a bacterium that utilizes polyester PUR as the sole carbon source, was purified until it showed a single band in sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). This enzyme was bound to the cell surface and was extracted by addition of 0.2% N,N-bis(3-d-gluconamidopropyl)deoxycholamide (deoxy-BIGCHAP). The results of gel filtration and SDS-PAGE showed that the PUR esterase was a monomer with a molecular mass of about 62,000 Da. This enzyme, which is a kind of esterase, degraded solid polyester PUR, with diethylene glycol and adipic acid released as the degradation products. The optimum pH for this enzyme was 6.5, and the optimum temperature was 45 degrees C. PUR degradation by the PUR esterase was strongly inhibited by the addition of 0.04% deoxy-BIGCHAP. On the other hand, deoxy-BIGCHAP did not inhibit the activity when p-nitrophenyl acetate, a water-soluble compound, was used as a substrate. These observations indicated that this enzyme degrades PUR in a two-step reaction: hydrophobic adsorption to the PUR surface and hydrolysis of the ester bond of PUR.

Journal Article↗

Photoinduced anisotropy in a family of amorphous azobenzene polyesters for optical storage.

We investigate parameters associated with optical data storage in a variety of amorphous side-chain azobenzene-containing polyesters denoted as E1aX. The polyesters possess a common cyano-substituted azobenzene chromophore as a side chain, but differ in their main-chain polyester composition. Seventeen different polymers from the E1aX family divided into four classes, depending on the type of the main-chain substituent (one-, two-, and three-ring aromatic or alicyclic) have been thoroughly investigated. Various parameters characterizing the photoinduced birefringence in these materials, such as the response time, thermal and light stability, and long-term stability under ambient light at room temperature have been measured. Each of these parameters is quantitatively represented and therefore it is possible to make a clear comparison between the properties of the polymers. The results indicate that the long-term stability at ambient temperature is closely related to the thermal stability of the photoinduced birefringence. A strong correlation has also been found between the response time and the stability of the induced anisotropy toward illumination with unpolarized white light. One of the classes of E1aX polymers characterized by two-ring aromatic substituent in the main chain is a good candidate for optical data storage media. A recording energy of approximately 2 J/cm2 is sufficient to induce high refractive-index modulations of deltan = 0.13 in these materials, which is retained even at elevated temperatures (>130 degrees C). Long-term stability of greater than one year for the induced anisotropy has also been achieved.

Journal Article↗

Quantitative analysis of cotton-polyester textile blends from near-infrared spectra.

Quantitative analysis of textile blends and textile fabrics is currently of particular interest in the industrial context. In this frame, this work investigates whether the use of Fourier transform (FT) near-infrared (NIR) spectroscopy and chemometrics is powerful for rapid and accurate quantitative analysis of cotton-polyester content in blend products. As samples of the same composition have many sources of variability that affect NIR spectra, indirect prediction is particularly challenging and a large sample population is required to design robust calibration models. Thus, a total of more than three-hundred cotton-polyester samples were selected covering the range from the 0% to 100% cotton and the corresponding NIR reflectance spectra were measured on raw fabrics. The data set obtained was used to develop multivariate models for quantitative prediction from reference measurements. A successful approach was found to rely on partial least squares (PLS) regression combined with genetic algorithms (GAs) for wavelength selection. It involved evaluating a set of calibration models considering different spectral regions. The results obtained considering 27.5% of the original variables yielded a prediction error (RMSEP) of 2.3 in percent cotton content. It demonstrates that FT-NIR spectroscopy has the potential to be used in the textile industry for the prediction of the composition of cotton-polyester blends. As a further consequence, it was observed that the spectral preprocessing and the complexity of the model are simplified compared to the full-spectrum approach. Also, the relevancy of the spectral intervals retained after variable selection can be discussed.

Journal Article↗

Broad-spectrum biodegradation of aliphatic and aliphatic-aromatic polyesters by Papiliotrema laurentii isolated from locust frass.

Biodegradable aliphatic and aliphatic-aromatic polyesters, such as poly(butylene adipate-co-terephthalate) (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), and polyhydroxyalkanoates (PHA), are increasingly used as sustainable alternatives to petrochemical plastics. However, their depolymerization outside industrial composting facilities is often incomplete. This study characterized Papiliotrema laurentii strain 62UF-13, isolated from migratory locust frass, for broad-spectrum polyester hydrolysis. Emulsion assays demonstrated hydrolytic activity across all five polymers, with PCL and PBS showing the highest clearance rates. Solid-film assays revealed substantial gravimetric mass loss of PCL, PLA, and PHA cast films, whereas a commercial PBAT-PLA mulch film in minimal medium, underwent progressive fragmentation/disintegration, as assessed by the remaining film area. Incubation with the PBAT-PLA film was accompanied by the release of adipic acid (49.60 mg/L, week 1) and terephthalic acid (maximum 21.62 mg/L, week 4), followed by a decrease to 0.26 mg/L by week 8, coinciding with the emergence of putative 3,4-dihydroxymandelic acid and a putative acetylated derivative. Scanning electron microscopy (SEM) revealed pronounced pitting and erosion, while Fourier-transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) indicated ester-bond scission and changes in crystallinity/melting behavior. Whole-genome sequencing identified eight candidate polyesterases, including cutinases and esterases, with &#x2265; 60% amino acid identity to known hydrolases active on PCL, PBS, PHA, and PLA. This study is the first report of P. laurentii degrading a broad range of aliphatic and aliphatic-aromatic polyesters, including partial biotransformation of terephthalate moieties from PBAT. Integration of phenotypic assays and genomic evidence positions P. laurentii 62UF-13 as a viable biocatalyst for decentralized management of biodegradable plastic waste under mild environmental conditions.

Papiliotrema laurentii↗

Effect on peripheral blood natural killer cytotoxic cell activity in rats after intraperitoneal implantation of double veloured polyester (Dacron) prosthesis.

INTRODUCTION: The aim of this study was to assess the changes affecting natural killer cytotoxic cell (NKCC) activity following intraperitoneal implantation of a double veloured polyester prosthesis in a rat model. MATERIAL/METHODS: Blood samples were taken by cardiac puncture 1 h before (base line) and 14, 28, 100 and 180 days post-implantation. Peripheral blood mononuclear cells were separated from heparinized blood by density centrifugation. A standard, 4 h (51)Cr-release assay against YAC-1 target cells at effector to target ratios of 12:1; 25:1 and 50:1 was performed and the number of total leukocytes, lymphocytes, granulocytes, monocytes, and large granular lymphocytes (LGLs), as well as serum corticosterone levels (radioimmunoassay method) were determined. RESULTS: Comparative analysis of the results obtained from animals with implants, baseline samples, and a control group (laparotomy only) revealed lower NKCC, LGL, leukocyte and lymphocyte counts and elevated plasma corticosterone levels in animals receiving the implant on the 14th day post-implantation. CONCLUSIONS: Our findings indicate that the polyester implant can transiently modulate immune system activities. Since NK cells are important in the control of viral infection and carcinogenesis in humans, it is possible that the stress generated by polyester prostheses can exacerbate the surgical stress and put patients at a higher risk for viral infection and/or metastases.

Animals↗

A polyester intravascular stent for maintaining luminal patency: a gross and microscopic study of the device's incorporation, early maturation, and thrombogenicity.

Over the past 3 years, we have developed a polyester mesh stent designed to preserve luminal patency in cases of dissecting aortic aneurysm and to maintain arterial patency after angioplasty. To study the stent's incorporation into the aortic wall and to test its thrombogenicity, we implanted the device in the abdominal aortas of ten dogs. The device was compressed and inserted into a 10-Fr sheath, which was introduced through the femoral artery into the aorta. Once liberated from the sheath and fully expanded within the aorta, the stent measured 10 cm in length and 8 mm in outer diameter. Each animal was followed up clinically until it was killed at intervals ranging from 1 week to 6 months after implantation. The aorta was excised, and tissue incorporation was evaluated grossly, as well as with light and scanning electron microscopy. In all cases, the arteries and side branches were found to be widely patent. At 3 weeks, the stent already had become firmly adherent to the vessel, owing to the ingrowth of fibrous tissue and endothelium through the mesh. The thrombus-free surface area, assessed planimetrically, was minimal during the early part of the study but rose to a plateau of 80% by the second month. Each specimen was subjected to indium-111 platelet scanning. The polyester mesh initially stimulated much platelet deposition, but this phenomenon decreased markedly over a 2-month period. In summary, our experience showed that an intraluminal polyester mesh stent could be inserted into the aorta via the retrograde arterial route and could effectively line the inner surface of the vessel. Within 2 months, healing was nearly complete and thrombogenicity was minimal.

Journal Article↗