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Biodegradable network elastomeric polyesters from multifunctional aliphatic carboxylic acids and poly(epsilon-caprolactone) diols.

Biodegradable elastomeric network polyesters were prepared from multifunctional aliphatic carboxylic acids such as tricarballylic acid (Yt) or meso-1,2,3,4-butanetetracarboxylic acid (Xb) and poly(epsilon-caprolactone) (PCL) diols with molecular weights of 530, 1,250 and 2,000 g.mol-1. Prepolymers prepared by a melt polycondensation were cast from DMF solution and postpolymerized at 280 degrees C for various periods of times to form a network. The resultant films were transparent, flexible and insoluble in organic solvents. The network polyesters obtained were characterized by IR absorption spectra, WAXS, density measurement, DSC, and tensile test. YtPCL1250, and XbPCL1250 network polyester films showed good elastomeric properties with high ultimate elongation (540-590%), and low Young's modulus (2.5-3.3 MPa). The enzymatic degradation was estimated by the weight loss of network films in a buffer solution with Rhizopus delemar lipase at 37 degrees C. The degree and rate of degradation were significantly affected by the molecular weight of PCL diol, chemical structures of multifunctional aliphatic carboxylic acids and the morphology of network films. The changes in the solid states of network films during the degradation were also estimated by the results of DSC and WAXS. [see text]

Biocompatible Materials↗

Gelatin-sealed polyester resists Staphylococcus epidermidis biofilm infection.

BACKGROUND: The purpose of this study was to show that gelatin-impregnated polyester grafts inhibit Staphylococcus epidermidis biofilm infection in a canine model of aortic graft interposition. A clinically native species and two engineered strains, which differed in slime and adhesin antigen components, were compared to determine differential gelatin and slime interactions. METHODS: In vitro bacterial graft colonization was validated by immersion of graft segments in inoculating solutions (10(6) colony forming units/ml) of a clinically native species RP62A and two genetically engineered S. epidermidis species, M187sn3 (SN3: slime and adhesin negative) or M187sp11 (SP11: slime and adhesin positive), for 18 h at 23 degrees C. The grafts were washed, sonicated, and cultured to assess in vitro bacterial graft adherence. Grafts similarly inoculated were placed as aortic interposition grafts in dogs. Three sterile grafts were implanted as controls. Grafts were excised after 6 weeks and cultured for bacterial growth as in the in vitro study. Infection was defined by a positive culture in the excised grafts. Data were analyzed with nonparametric statistical methods. RESULTS: In vitro bacterial graft adherence in colony forming units per milliliter was similar at 18 h postsonication for RP62A (8 x 10(4) +/- 1 x 10(4)), SN3 (7 x 10(4) +/- 2 x 10(4)), and SP11 (6 x 10(4) +/- 2 x 10(4)) (P = NS). Only one of five grafts inoculated with RP62A was culture positive after 6 weeks. No grafts inoculated with the engineered strains SN3 or SP11 were culture positive after explanation. CONCLUSION: In vitro bacterial inoculation of gelatin-impregnated polyester was similar among the species and not dependent upon the presence of slime and adhesin components. Gelatin-impregnated polyester grafts demonstrated in vivo resistance to coagulase-negative staphylococcal biofilm infection.

Animals↗

Clinical evaluation of the polypropylene-polyester knit used as a cranioplasty material.

UNLABELLED: The paper presents clinical evaluation of the polypropylene-polyester knit used as a cranioplasty material. MATERIAL: Between year 1980 and 2002 275 cranioplastic procedures using the polypropylene-polyester plates Codubix were carried out in the Department of Neurosurgery of the Medical University of Łódź. There were 146 patients who primarily sustained head injuries and 129 non-traumatic patients with craniectomies carried out for various other reasons. In the majority of cases, i.e. in 158 patients, cranioplasty was performed later than 6 months after the primary surgery. The largest implant measured 430 cm2. RESULTS: Excellent and good outcome was achieved in 92% of the patients whereas the rate of local infection was 8%. CONCLUSIONS: Codubix knitted polypropylene-polyester implant proved to be useful and a safe cranioplastic material.

Adolescent↗

Experimental treatment of vascular graft infection due to Staphylococcus epidermidis by in situ replacement with a rifampin-bonded polyester graft.

In situ prosthetic graft replacement (ISPGR) of an infected prosthesis raises the risk of recurrent infection in the new graft, especially in cases involving drug-resistant microorganisms. The purpose of this animal study was to evaluate in situ replacement of a vascular graft infected by a highly rifampin-resistant strain of Staphylococcus epidermidis with the use of a rifampin-bonded polyester graft. Antibiotic bonding was obtained by soaking grafts in a high dose of rifampin solution (60 mg/mL). The infrarenal abdominal aorta of 20 dogs was replaced using a polyester prosthesis infected with a highly rifampin-resistant strain of Staphylococcus epidermidis. One week later, the 18 surviving animals were randomized into three groups. Group I (n = 6) did not undergo reoperation. Group II (n = 6) underwent ISPGR using a rifampin-bonded prosthesis. Group III (n = 6) underwent ISPGR using an untreated prosthesis. All surviving animals were killed 28 days after the first procedure. Infectious signs were noted and bacteriological study was carried out on explanted prostheses and various tissue samples. The findings of this experimental study show that soaking a polyester prosthesis in a high-dose rifampin solution can prevent reinfection after in situ replacement of a prosthesis infected by a highly rifampin-resistant Staphylococcus epidermidis.

Anastomosis, Surgical↗

Cathepsin D activity of venous and polyester vascular grafts implanted in the abdominal aorta of the dog.

Autogenous veins and polyester prostheses were implanted in the abdominal aorta of dogs. The venous or polyester grafts were removed together with sections of the normal arteries and veins 1 month, 4 months, and 3 years after the operation. This material was then dissected into the intimal, medial, and adventitial layers, and homogenized after which their cathepsin D activity was determined. It was found that the cathepsin D activity was far higher in all the layers of the venous grafts, particularly in the polyester grafts, than in the corresponding layers of the normal arteries and veins.

Animals↗

Ability of the phototrophic bacterium Rhodospirillum rubrum to produce various poly (beta-hydroxyalkanoates): potential sources for biodegradable polyesters.

Studies have been carried out in order to optimize growth and culture conditions for the intracellular formation of poly(beta-hydroxyalkanoates) (PHA) in the phototrophic, purple, non-sulphur bacterium Rhodospirilum rubrum. Its potential to produce novel copolymers was investigated. Recently, it has become of industrial interest to evaluate these polyesters as potentially biodegradable plastics for a wide range of possible applications. On an industrial scale, the use of photosynthetic bacteria could harness sunlight as an energy source for the production of these materials. R. rubrum was grown anaerobically in the light on different linear and branched beta-hydroxycarboxylic acids and various n-alkanoic acids. Under nitrogen-limiting conditions a PHA content of up to 45% of cellular dry weight was detected. When R. rubrum was grown on different concentrations of various n-alkanoic acids, intracellular PHA production was detected on all acids used. In most of the cases, the storage polymer contained beta-hydroxybutyrate (HB) and beta-hydroxyvalerate (HV) monomer units. Grown on n-alkanoic acids with a chain length of four carbon atoms and more, R. rubrum produced a copolymer containing the beta-hydroxyhexanoate (HC) repeating unit in addition to the HB and HV monomer. Using beta-hydroxyheptanoic acid as the carbon source, a polyester which contained HB, HV, HC, and beta-hydroxyheptanoate was formed. These copolyesters represent a novel class of biodegradable thermoplastics. The results demonstrate the metabolic flexibility of R. rubrum to form many different types of polyesters which might substitute plastics synthesized from petrochemicals.

Ammonia↗

Resorbable polyesters: composition, properties, applications.

Synthetic polymers, in particular polyesters based on lactic acid, glycolic acid and other raw materials are described for medical and technical applications. Their main advantages are compatibility and safety. As they are degradable in the human body they are particularly suitable for implants needed only temporarily for the healing process. Resorbable polyesters are produced by direct polycondensation or ring opening polymerization resulting in a broad range of polymers with different features. The main properties such as degradation (hydrolytic and thermal), crystallinity and mechanical strengths are discussed. These polyesters, which can be processed like other thermo-plastic polymers by extrusion and injection moulding, are used mainly for wound closure products (sutures, staples, clips), fracture fixation devices (nails, screws, plates) and parenteral depot systems for the sustained release of drugs. Possibilities for polymer and process improvement to develop better implants and additional applications are presented.

Biocompatible Materials↗

Expression of fibrinolysis activators and their inhibitor in neointima of polyester vascular grafts.

The aim of the study was to evaluate dynamic changes in the expression of fibrinolytic system components in neointima forming in polyester vascular grafts. The study was carried out on 18 mongrel dogs divided into three groups, that underwent replacement of abdominal aorta with a polyester double velour prosthesis. Grafts were removed at 1, 4 and 12 months. The specimens were fixed according to AMeX method. Immunohistochemical labeling for von Willebrand factor (vWf), tissue plasminogen activator (t-PA), urokinase (u-PA), its receptor (u-PAR), plasminogen activator inhibitor type 1 (PAI-1) and D-dimer (DD) was performed. Increasing intensity of vWf expression on the graft luminal surface was found in successive periods of the study. A light positive t-PA and u-PA staining was shown in neointima at 1 month and its intensity was significantly increased at 4 and 12 months. Expression of u-PAR appeared at 4 months. A light positive PAI-1 and DD staining was demonstrated in neointima in all periods of the study. The results demonstrated increasing expression of fibrinolysis activators in neointima of polyester vascular grafts. Intensive expression of plasminogen activators, when compared to their inhibitor may reduce thrombotic properties of graft neointima particularly in the late period after prosthesis implantation.

Blood Vessel Prosthesis↗

Efficacy and complications in the surgical treatment of stress urinary incontinence by insertion of a silicone-coated polyester tape (Lift).

OBJECTIVES: To evaluate the efficacy and safety of a surgical treatment for stress urinary incontinence by implantation of a silicone-coated polyester tape (Lift). MATERIALS AND METHODS: This retrospective study included 72 female patients having had a suburethral silicone-coated polyester tape inserted as treatment for stress urinary incontinence, combined or not with pelvic surgery. We recorded the patient's characteristics, the surgical procedure, the short and long-term results and complications. RESULTS: Seventy-two patients were operated, 60 of whom were fully evaluated. The average follow-up was 17 months. On 48 patients (80%) the treatment was successful, 3 (5%) were improved, and 9 (15%) were regarded as a failure. Dysuria occurred in six (10%) patients, five were de novo, and one was persistent. Ten patients (16.6%) presented de novo urge incontinence. The main complication was a higher rate of severe infections, accompanied by defective healing (4, i.e. 6.7%). CONCLUSION: The procedure using a silicone-coated polyester tape seems to be efficient, but insufficiently secure. This higher rejection rate leads us to prefer other synthetic materials proved to be better tolerated.

Coated Materials, Biocompatible↗

Transport behavior of n-alkane penetrants into castor oil based polyurethane-polyester nonwoven fabric composites.

Castor oil based polyurethane (PU)-polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a composition containing castor oil and diisocyanate. Composites were fabricated with two different isocyanates such as toluene-2,4-diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). Transport behavior of n-alkane penetrants (pentane, hexane and heptane) into both PUs and PU-polyester nonwoven fabric composites were studied. Sorption studies were carried out at different temperatures. From the sorption results, the diffusion (D) and permeation (P) coefficients of penetrants have been calculated. Significant increase in the diffusion and permeation coefficients was observed with increase in the temperature of sorption experiments. Drastical reduction in diffusion and permeation coefficients was noticed in the composites compared to neat PUs. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport and K is a constant depends on the structural characteristics of the composite in addition to its interaction with penetrants. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameter for diffusion (E(D)) and permeation (E(P)) processes from Arrhenius plots. Furthermore, the sorption results have been interpreted in terms of the thermodynamic parameters such as enthalpy (DeltaH) and entropy (DeltaS).

Adsorption↗

Temporary placement of an expandable polyester silicone-covered stent for treatment of refractory benign esophageal strictures.

BACKGROUND: Benign, refractory esophageal strictures are an important therapeutic challenge. Metal stents occasionally have been used, but results have been disappointing. The present study assessed the safety and the efficacy of temporary placement of the new expandable polyester silicone-covered stent for management of problematic esophageal strictures. METHODS: Fifteen patients with benign esophageal strictures were treated by temporary (6 weeks) placement of an expandable polyester silicone-covered stent. All patients had previously been treated, unsuccessfully, by repetitive endoscopic dilation. RESULTS: Stent placement was successful in all patients. There was no procedure-related complication. Dilation with over-the-guidewire polyvinyl dilators was required before stent placement. With the stent in situ, dysphagia completely resolved in all patients. Six weeks after placement, one stent was found to have migrated into the stomach. In the remaining patients, the stent was easily removed with a foreign body forceps. The pretreatment dysphagia score was 3 (range 2-4); the post-treatment score was 1 (range 0-1) (p < 0.0005). Long-term resolution (mean follow-up 22.7 [2.6] months) of the stricture was achieved in 12 patients (80%). The treatment failed in 3 patients, all of whom continue to require periodic dilation. CONCLUSIONS: In patients with benign esophageal strictures refractory to conventional dilation, temporary placement of a removable expandable polyester silicone-covered stent may lead to long-term relief of dysphagia with minimal morbidity.

Adult↗

Endoscopic treatment of thoracic esophageal anastomotic leaks by using silicone-covered, self-expanding polyester stents.

BACKGROUND: Surgery, as well as conservative treatment, in patients with clinically apparent intrathoracic esophageal anastomotic leaks often is associated with poor results and carries a high morbidity and mortality. The successful treatment of esophageal anastomotic insufficiencies and perforations when using covered, self-expanding metallic stents is described. METHODS: The feasibility and the outcome of endoscopic treatment of intrathoracic anastomotic leakages when using silicone-covered self-expanding polyester stents were investigated. Twelve consecutive patients presented with clinically apparent intrathoracic esophageal anastomotic leak caused by resection of an epiphrenic diverticulum (n = 1), esophagectomy for esophageal cancer (n = 9), or gastrectomy for gastric cancer (n = 2), were endoscopically treated in our department. The extent of the dehiscences ranged from about 20% to 70% of the anastomotic circumference. After endoscopic lavage and debridement of the leakage at 2-day intervals (mean duration, 8.6 days), a large-diameter polyester stent (Polyflex; proximal/distal diameters 25/21 mm) was placed to seal the leakage. Simultaneously, the periesophageal mediastinum was drained by chest drains. OBSERVATIONS: All 12 patients were successfully treated endoscopically without the need for reoperation. A complete closure of the leakage was obtained in 11 of 12 patients after stent removal (median time to stent retrieval, 4 weeks, range 2-8 weeks). In one patient, a persistent leak was sealed endoscopically after stent removal by using 3 clips. Distal stent migration was obtained in two patients. CONCLUSIONS: The placement of silicone-covered self-expanding polyester stents seems to be a successful minimally invasive treatment option for clinically apparent intrathoracic esophageal anastomotic leaks.

Aged↗

Erosion of woven polyester pubovaginal sling.

PURPOSE: Various materials have been used for pubovaginal slings to correct female stress urinary incontinence. Use of synthetic materials provides a theoretical advantage in that no graft harvesting is necessary. Major risks of synthetic material use are erosion and infection of the sling. We report on erosion of woven polyester slings treated with pressure injected bovine collagen (ProteGen) which required removal. MATERIALS AND METHODS: Office records of patients who had ProteGen slings removed at 5 centers during the last 24 months were retrospectively reviewed. Presenting symptoms, interval between sling placement and removal, subsequent procedures and continence status following sling removal were evaluated. RESULTS: A total of 34 women required removal of the polyester sling secondary to erosion, infection or pain. The most common presenting complaints were delayed vaginal discharge in 21 patients (62%), vaginal pain or pressure in 21 (62%), suprapubic pain in 11 (32%) and recurrent urinary tract infection in 5 (15%) at a mean of 7.95 months (range 1 to 22) after sling placement. Of the patients 17 (50%) had vaginal erosion only, 7 (20%) isolated urethral erosion and 6 (17%) urethrovaginal fistulas. In 4 patients no erosion was obvious but slings were removed secondary to vaginal pain. Before sling removal 16 patients (47%) were totally dry, 13 (38%) had some degree of urinary incontinence and 3 (8%) had retention. Following sling removal 7 patients (20%) remained dry, 25 (74%) had mild to severe stress urinary incontinence with or without urgency and urge incontinence, and 2 (6%) are pending followup. CONCLUSIONS: Woven polyester slings treated with pressure injected bovine collagen are prone to erosion. Although the ProteGen sling was recalled in January 1999, patients who have had the sling placed must be followed closely.

Female↗

Biodegradable semi-crystalline comb polyesters influence the microsphere production by means of a supercritical fluid extraction technique (ASES).

The aerosol solvent extraction system (ASES) is a method based on solvent extraction using supercritical carbon dioxide for the preparation of microspheres. The ASES technology seems to be strongly affected by physico-chemical properties of biodegradable polymers, leading to incomplete or unsuccessful microsphere formation. The number of suitable polymers for ASES, such as poly(L-lactide) (L-PLA) and poly(beta-hydroxy-butyric acid) (PHB) is rather limited for unknown reasons. Therefore linear and novel branched polyesters were synthesized and subjected to the ASES process to explore the function property relationship. The properties of these polymers as well as of the ASES products were characterized by NMR spectroscopy, differential scanning calorimetry, light scattering, wide-angle X-ray scattering and scanning electron microscopy. It appears that high degrees of polymer crystallinity are the key factor for successful microsphere formation using the ASES process. Under the conditions investigated two types of polymers were especially suitable: semi-crystalline comb polyesters as well as comb polyesters in which crystallinity could be induced. These novel polymers are of particular interest for the ASES encapsulation technology since they combine beneficial properties both controlling drug release due to their three-dimensional architecture and faster biodegradability with sufficient mechanical stability to allow particle formation using supercritical carbon dioxide.

Biocompatible Materials↗

Long-term in vivo alterations of polyester vascular grafts in humans.

OBJECTIVES: To examine the influence of in vivo hydrolysis on the physical properties of polyester grafts and their correlation to the period of implantation in the human body. MATERIALS AND METHODS: Sixty-five explanted vascular grafts were obtained after 0-23 years of implantation due to suture aneurysms (18), occlusion (12), graft infection (12), failure of graft material (7) and post-mortem (16). The surface was examined by scanning electron microscopy, the molecular integrity by infra-red spectroscopy and physical strength by probe puncture. RESULTS: Scission of macromolecular chains and loss of strength were shown. It was demonstrated that hydrolytic degradation of polyester takes place with increasing time of implantation in humans. Analysis by linear regression showed that polyester grafts lose 31.4% of their bursting strength in 10 years and 100% in 25-39 years after implantation. CONCLUSIONS: Regular follow-ups of patients with aged vascular grafts and the precise documentation of implanted materials are necessary to estimate graft degradation.

Blood Vessel Prosthesis↗

Enzymatic synthesis of cross-linkable polyesters from renewable resources.

Enzymatic synthesis of a new class of cross-linkable polyesters has been achieved. Polymerization of divinyl sebacate and glycerol using Candida antarctica lipase as catalyst in the presence of unsaturated higher fatty acids produced the polyesters having an unsaturated group in the side chain. The polyester was subjected to hardening by cobalt naphthenate catalyst or thermal treatment, yielding cross-linked transparent film.

Candida↗

Enzymatic synthesis and curing of biodegradable epoxide-containing polyesters from renewable resources.

Epoxide-containing polyesters were enzymatically synthesized via two routes using unsaturated fatty acids as starting substrate. Lipase catalysis was used for both polycondensation and epoxidation of the unsaturated fatty acid group. One route was synthesis of aliphatic polyesters containing an unsaturated group in the side chain from divinyl sebacate, glycerol, and the unsaturated fatty acids, followed by an epoxidation of the unsaturated fatty acid moiety in the side chain of the resulting polymer. In another route, epoxidized fatty acids were prepared from the unsaturated fatty acids and hydrogen peroxide in the presence of lipase catalyst, and subsequently the epoxidized fatty acids were polymerized with divinyl sebacate and glycerol. The polymer structure was confirmed by NMR and IR, and for both routes, the high epoxidized ratio was achieved. Curing of the resulting polymers proceeded thermally, yielding transparent polymeric films with high gloss surface. Pencil scratch hardness of the present films improved, compared with that of the cured film obtained from the polyester having an unsaturated fatty acid in the side chain. The obtained film showed good biodegradability, evaluated by BOD measurement in an activated sludge.

Biodegradation, Environmental↗

Aliphatic polyesters: great degradable polymers that cannot do everything.

Nowadays the open and the patent literatures propose a large number of polymers whose main chains can be degraded usefully. Among these degradable polymers, aliphatic polyester-based polymeric structures are receiving special attention because they are all more or less sensitive to hydrolytic degradation, a feature of interest when compared with the fact that living systems function in aqueous media. Only some of these aliphatic polyesters are enzymatically degradable. A smaller number is biodegradable, and an even more limited number is biorecyclable. To be of practical interest, a degradable polymer must fulfill many requirements that depend very much on the targeted application, on the considered living system, and on living conditions. It is shown that aliphatic polyester structures made of repeating units that can generate metabolites upon degradation or biodegradation like poly(beta-hydroxy alkanoate)s and poly(alpha-hydroxy alkanoate)s are of special interest. Their main characteristics are confronted to the specifications required by various potential sectors of applications, namely, surgery, pharmacology, and the environment. It is shown that degradation, bioresorption, and biorecycling that are targets when one wants to respect living systems are also drastic limiting factors when one wants to achieve a device of practical interest. Finding a universal polymer that would be the source of all the polymeric biomaterials needed to work in contact with living organisms of the various life kingdoms and respect them remains a dream. On the other hand, finding one polymeric structure than can fulfill the requirements of one niche application remains a big issue.

Biocompatible Materials↗