Desenvolvimento e avaliação de eletrodos de difusão gasosa (EDG) para geração de H2O2 in situ e sua aplicação na degradação do corante reativo azul 19

This work reports the development of GDE for electrogeneration of H2O2 and their application in the degradation process of Reactive Blue 19 dye. GDE produced by carbon black with 20% polytetrafluoroethylene generated up to 500 mg L-1 of H2O2 through the electrolysis of acidic medium at -0.8 V vs Ag/AgCl. Reactive Blue 19 dye was degraded most efficiently with H2O2 electrogenerated in the presence of Fe(II) ions, leading to removal of 95% of the original color and 39% of TOC at -0.8 V vs Ag/AgCl.

Synthesis of 15N-enriched urea (CO(15NH2)2) from 15NH3, CO, and S in a discontinuous process

CO(15NH2)2 enriched with the stable isotope 15N was synthesized based on a reaction involving CO, 15NH3, and S in the presence of CH3OH. The method differs from the industrial method; a stainless steel reactor internally lined with polytetrafluoroethylene (PTFE) was used in a discontinuous process under low pressure and temperature. The yield of the synthesis was evaluated as a function of the parameters: the amount of reagents, reaction time, addition of H2S, liquid solution and reaction temperature. The results showed that under optimum conditions (1.36, 4.01, and 4.48 g of 15NH3, CO, and S, respectively, 40 ml CH3OH, 40 mg H2S, 100 ºC and 120 min of reaction) 1.82 g (yield 76.5%) of the compound was obtained per batch. The synthesized CO(15NH2)2 contained 46.2% N, 0.55% biuret, melting point of 132.55 ºC and did not exhibit isotopic fractionation. The production cost of CO(15NH2)2 with 90.0 at. % 15N was US$ 238.60 per gram.

Inorganic-organic hybrid polymers: Solution-processible coating materials for defined surface functionalization

A new class of inorganic-organic hybrid polymers could successfully been prepared by the combination of different polymerization techniques. The access to a broad range of organic polymers incorporated into the hybrid polymer was realized using two independent approaches.rnIn the first approach a functional poly(silsesquioxane) (PSSQ) network was pre-formed, which was capable to initiate a controlled radical polymerization to graft organic vinyl-type monomers from the PSSQ precursor. As controlled radical polymerization techniques atom transfer radical polymerization (ATRP), as well as reversible addition fragmentation chain transfer (RAFT) polymerization could be used after defined tuning of the PSSQ precursor either toward a PSSQ macro-initiator or to a PSSQ macro-chain-transfer-agent. The polymerization pathway, consisting of polycondensation of trialkoxy-silanes followed by grafting-from polymerization of different monomers, allowed synthesis of various functional hybrid polymers. A controlled synthesis of the PSSQ precursors could successfully be performed using a microreactor setup; the molecular weight could be adjusted easily while the polydispersity index could be decreased well below 2.rnThe second approach aimed to incorporate differently derived organic polymers. As examples, polycarbonate and poly(ethylene glycol) were end-group-modified using trialkoxysilanes. After end-group-functionalization these organic polymers could be incorporated into a PSSQ network.rnThese different hybrid polymers showed extraordinary coating abilities. All polymers could be processed from solution by spin-coating or dip-coating. The high amount of reactive silanol moieties in the PSSQ part could be cross-linked after application by annealing at 130° for 1h. Not only cross-linking of the whole film was achieved, which resulted in mechanical interlocking with the substrate, also chemical bonds to metal or metal oxide surfaces were formed. All coating materials showed high stability and adhesion onto various underlying materials, reaching from metals (like steel or gold) and metal oxides (like glass) to plastics (like polycarbonate or polytetrafluoroethylene).rnAs the material and the synthetic pathway were very tolerant toward different functionalities, various functional monomers could be incorporated in the final coating material. The incorporation of N-isopropylacrylamide yielded in temperature-responsive surface coatings, whereas the incorporation of redox-active monomers allowed the preparation of semi-conductive coatings, capable to produce smooth hole-injection layers on transparent conductive electrodes used in optoelectronic devices.rnThe range of possible applications could be increased tremendously by incorporation of reactive monomers, capable to undergo fast and quantitative conversions by polymer-analogous reactions. For example, grafting active esters from a PSSQ precursor yielded a reactive surface coating after application onto numerous substrates. Just by dipping the coated substrate into a solution of a functionalized amine, the desired function could be immobilized at the interface as well as throughout the whole film. The obtained reactive surface coatings could be used as basis for different functional coatings for various applications. The conversion with specifically tuned amines yielded in surfaces with adjustable wetting behaviors, switchable wetting behaviors or as recognition element for surface-oriented bio-analytical devices. The combination of hybrid materials with orthogonal reactivities allowed for the first time the preparation of multi-reactive surfaces which could be functionalized sequentially with defined fractions of different groups at the interface. rnThe introduced concept to synthesis functional hybrid polymers unifies the main requirements on an ideal coating material. Strong adhesion on a wide range of underlying materials was achieved by secondary condensation of the PSSQ part, whereas the organic part allowed incorporation of various functionalities. Thus, a flexible platform to create functional and reactive surface coatings was achieved, which could be applied to different substrates. rn

Leakage of the arterial prosthesis of an Impella RVAD

Seromas occurring around a vascular graft are a rare complication. We report a life-threatening plasma leakage that occurred through the polytetrafluoroethylene vascular prosthesis of an Impella right ventricular assist device (Impella RD [Impella Cardiosystems GmbH, Aachen, Germany]) implanted in a 62-year-old patient with acute right ventricular failure after cardiac transplantation. The leakage became progressively massive. Weaning the patient from the right ventricular assist device was not possible. The prosthesis was thus wrapped within a pericardial patch to contain the leakage. Three days later the patient could be successfully weaned and the pump was removed. The clinical evolution was favorable.

The effect of rhBMP-2 around endosseous implants with and without membranes in the canine model

BACKGROUND: Bone morphogenetic protein (BMP) is a potent differentiating agent for cells of the osteoblastic lineage. It has been used in the oral cavity under a variety of indications and with different carriers. However, the optimal carrier for each indication is not known. This study examined a synthetic bioabsorbable carrier for BMP used in osseous defects around dental implants in the canine mandible. METHODS: Twelve canines had their mandibular four premolars and first molar teeth extracted bilaterally. After 5 months, four implants were placed with standardized circumferential defects around the coronal 4 mm of each implant. One-half of the defects received a polylactide/glycolide (PLGA) polymer carrier with or without recombinant human BMP-2 (rhBMP-2), and the other half received a collagen carrier with or without rhBMP-2. Additionally, one-half of the implants were covered with a non-resorbable (expanded polytetrafluoroethylene [ePTFE]) membrane to exclude soft tissues. Animals were sacrificed either 4 or 12 weeks later. Histomorphometric analysis included the percentage of new bone contact with the implant, the area of new bone, and the percentage of defect fill. This article describes results with the PLGA carrier. RESULTS: All implants demonstrated clinical and radiographic success with the amount of new bone formed dependent on the time and presence/absence of rhBMP-2 and presence/absence of a membrane. The percentage of bone-to-implant contact was greater with rhBMP-2, and after 12 weeks of healing, there was approximately one-third of the implant contacting bone in the defect site. After 4 weeks, the presence of a membrane appeared to slow new bone area formation. The percentage of fill in membrane-treated sites with rhBMP-2 rose from 24% fill to 42% after 4 and 12 weeks, respectively. Without rhBMP-2, the percentage of fill was 14% rising to 36% fill, respectively. CONCLUSIONS: After 4 weeks, the rhBMP-2-treated sites had a significantly higher percentage of contact, more new bone area, and higher percentage of defect fill than the sites without rhBMP-2. After 12 weeks, there was no significant difference in sites with or without rhBMP-2 regarding percentage of contact, new bone area, or percentage of defect fill. In regard to these three outcomes, comparing the results with this carrier to the results reported earlier with a collagen carrier in this study, only the area of new bone was significantly different with the collagen carrier resulting in greater bone than the PLGA carrier. Thus, the PLGA carrier for rhBMP-2 significantly stimulated bone formation around dental implants in this model after 1 month but not after 3 months of healing. The use of this growth factor and carrier combination appears to stimulate early bone healing events around the implants but not quite to the same degree as a collagen carrier.

Stent-grafts in the treatment of emergent or urgent carotid artery disease: review of 25 cases

PURPOSE: To report the authors' initial experience with carotid artery stent-grafts in a comparatively large patient series for the treatment of acute bleeding and impending rupture or the prevention of distal embolization. MATERIALS AND METHODS: This retrospective study was approved by the institutional review boards and performed according to HIPPA standards. Twenty-five patients were treated with 27 carotid artery stent-grafts (Gore Viabahn, n = 10; Bard Fluency, n = 9; polytetrafluoroethylene-covered Palmaz, n = 5; and Wallgraft, n = 3). Thirteen stent-grafts were placed in patients with carotid blow-out syndrome (including three patients with carotid-airway fistula), 12 in patients with either pseudoaneurysm (n = 9) or true aneurysm (n = 3), and two in patients with intractable high-grade bare stent restenosis. RESULTS: The technical success rate was 100% (27 of 27 cases). No acute procedural transient ischemic attacks or strokes occurred. Procedural dissections occurred in two of the 27 cases (7.4%). Short-term complications occurred in three of the 27 cases (11%) (repeat hemorrhage, n = 2; common carotid artery occlusion, n = 1). The overall patient mortality rate was 36% (nine of 25 patients, all with carotid blow-out syndrome). Six-month follow-up in 15 of the 16 living patients demonstrated widely patent stent-grafts. Two patients with pseudoaneurysm also demonstrated patent stents at 18- and 33-month follow-up. CONCLUSIONS: Stent-grafts may be useful in the treatment of carotid artery bleeding syndrome, aneurysm, and stenosis, with a high procedural success rate in selected cases. The results of mid-term follow-up are encouraging, but results of long-term follow-up must be evaluated in future studies.

Comparative study of biphasic calcium phosphates with different HA/TCP ratios in mandibular bone defects. A long-term histomorphometric study in minipigs

Three biphasic calcium phosphate (BCP) bone substitute materials with hydroxyapatite (HA)/tricalcium phosphate (TCP) ratios of 20/80, 60/40, and 80/20 were compared to coagulum, particulated autogenous bone, and deproteinized bovine bone mineral (DBBM) in membrane-protected bone defects. The defects were prepared in the mandibles of 24 minipigs that were divided into four groups of six with healing times of 4, 13, 26, and 52 weeks, respectively. The histologic and histomorphometric evaluation focused on differences in amount and pattern of bone formation, filler degradation, and the interface between bone and filler. Collapse of the expanded polytetrafluoroethylene barrier membrane into the coagulum defects underlined the necessity of a filler material to maintain the augmented volume. Quantitatively, BCP 20/80 showed bone formation and degradation of the filler material similar to autografts, whereas BCP 60/40 and BCP 80/20 rather equaled DBBM. Among the three BCP's, the amount of bone formation and degradation of filler material seemed to be inversely proportional to the HA/TCP ratio. The fraction of filler surface covered with bone was highest for autografts at all time points and was higher for DBBM than BCP 80/20 and 60/40 at the early healing phase. TRAP-positive multinucleated cells were identified on BCP and DBBM surfaces without showing typical signs of resorption lacunae.

Chronic critical leg ischemia: revascularization of the isolated popliteal segment in comparison with femoro-distal bypass

Several patients with chronic critical limb ischemia show angiographically an isolated popliteal segment (IPS) and a single calf vessel (SCV) with no direct communication to the former. In this situation a bypass can be inserted from the common femoral artery to the IPS or to the SCV. The results of 73 bypass procedures--40 to an isolated popliteal segment and 33 to a single calf vessel for limb salvage--were prospectively evaluated. Eighty percent of the grafts were performed with an autogenous saphenous vein (ASV), the rest with a thin wall polytetrafluoroethylene (PTFE) prosthesis. The mean age of our patients was 75 years and many suffered from cardiovascular disease. The operative mortality rate was 3% and the mean postoperative survival 32 months. Three year patency and limb salvage rates for ASV grafts was 83% and 87% (IPS) respectively 77% and 76% (MCV); for PTFE grafts 58% and 88% (IPS) respectively 17% and 50% (MCV). There was no significant difference found in patency and limb salvage rates of the two procedures if the graft was an autogenous saphenous vein (p > 0.05). The PTFE prosthesis was only suitable for grafts inserted to the isolated popliteal segment.

Randomized controlled trial: lip piercing: the impact of material on microbiological findings

PURPOSE The purpose of this study was to investigate whether there are microbiological differences in bacterial samples collected from labial piercings made of different materials. METHODS Sterile piercings of 4 materials were randomly allocated to 80 pierced subjects. After 2 weeks, microbiologic samples were collected and processed by checkerboard DNA-DNA hybridization methods. Wilcoxon signed ranks and Mann-Whitney tests were used for statistical analysis (adjustment for multiple comparisons). RESULTS There were no statistically significant differences between material groups in relation to baseline data. In samples from stainless steel piercings, the total microbial load was significantly higher than the other materials (P<.05). Ten (mainly periopathogenic) species were found at significantly higher levels (P<.001) on steel than on polypropylene and/or polytetrafluoroethylene piercings. CONCLUSIONS Labial piercings made of stainless steel could promote the development of a pathogenic biofilm.

Influence of carbon enrichment on electrical conductivity and processing of polycarbosilane derived ceramic for MEMS applications

An analysis about the effect of carbon enrichment of allylhydridopolycarbosilane SMP10® with divinylbenzene (DVB) as a promising material for electrical conductive micro-electrical mechanical systems (MEMS) is presented. The liquid precursors can be micropipetted and cured in polytetrafluoroethylene (PTFE) molds to produce 14 mm diameter disc shaped samples. The effect of pyrolysis temperature and carbon content on the electrical conductivity is discussed. The addition of 28.7 wt.% of DVB was found to be the optimum amount. Carbon was preserved in the microstructure during pyrolysis and the ceramic yield increased from 77.5 to 80.5 wt.%. The electrical conductivity increased from 10−6 to 1 S/cm depending on the annealing temperature. Furthermore, the ceramic samples obtained with this composition were found to be in many cases crack free or with minimal cracks in contrast with the behavior of pure SMP10. Using the same process we demonstrate that also microsized ceramic samples can be produced.

Only Neochordoplasty Achieves Physiological Trans-valvular Pressure Gradients After Repair Of Acute Posterior Leaflet Prolapse In Porcine Mitral Valves

Objective: Minimizing resection and preserving leaflet tissue has been previously shown to be beneficial for mitral valve function and leaflet kinematics after repair of acute posterior leaflet prolapse in porcine valves. We examined the effects of different additional methods of mitral valve repair (neochordoplasty, ring annuloplasty, edge-to-edge repair and triangular resection) on hemodynamics at different heart rates in an experimental model. Methods: Severe acute P2 prolapse was created in eight porcine mitral valves by resecting the posterior marginal chordae. Valve hemodynamics was quantified under pulsatile conditions in an in vitro heart simulator before and after surgical manipulation. Mitral regurgitation was corrected using four different methods of repair on the same valve: neochordoplasty with expanded polytetrafluoroethylene sutures alone and together with ring annuloplasty, edge-to-edge repair and triangular resection, both with non-restrictive annuloplasty. Residual mitral valve leak, trans-valvular pressure gradients, flow and cardiac output were measured at 60 and 80 beats/min. A validated statistical linear mixed model was used to analyze the effect of treatment. The p values were calculated using a two-sided Wald test. Results: Only neochordoplasty with expanded polytetrafluoroethylene sutures but without ring annuloplasty achieved similar hemodynamics compared to those of the native mitral valve (p range 0.071-0.901). Trans-valvular diastolic pressure gradients were within a physiologic range but significantly higher than those of the native valve following neochordoplasty with ring annuloplasty (p=0.000), triangular resection (p=0.000) and edge-to-edge repair (p=0.000). Neochordoplasty alone was significantly better in terms of hemodynamic than neochordoplasty with a ring annuloplasty (p=0.000). These values were stable regardless of heart rate or ring size. Conclusions: Neochordoplasty without ring annuloplasty is the only repair technique able to achieve almost native physiological hemodynamics after correction of leaflet prolapse in a porcine experimental model of acute chordal rupture.

Microwave Spectroscopy and Structures of Several Substituted Acetylenes and Fluorocarbons

The structures of two substituted acetylene compounds have been characterized from their microwave rotational spectra. In the first study, two structures of 6-methyl-3-heptyne have been determined. This compound can be thought of as an ethyl group separated from an isobutyl group by a C≡C spacer. Both structures have the ethyl and isobutyl groups eclipsed, consistent with the dominant interaction determining the orientation about the acetylene axis being the weak dispersion attraction between the end groups. One structure is with the isobutyl group in a symmetric conformation and the other with the isobutyl group asymmetric. In addition, the microwave spectrum of the butane analogue 3,5-octadiyne has been observed. This compound consists of two ethyl groups separated by two C≡C spacers. The study is still in progress, but it appears that the ethyl end groups are freely rotating. Therefore, it seems that the dispersion attractions between the end groups are too weak at this longer distance of about 7 Å. The structures of several fluorocarbons have also been studied by microwave spectroscopy. The structures of perfluoropentane and perfluorohexane have been shown to be helical, like the polymer polytetrafluoroethylene (Teflon©). The structure of perfluoropropane and two conformers of 1H-heptafluoropropane have been determined to be non-helical. It is apparent that the steric and dipole repulsions between fluorine atoms that have been attributed to the helical structure of longer fluorocarbon chains are not sufficient in a three carbon chain to cause a twist in the structures.

Chain scission and branching in irradiated poly(tetrafluoroethylene-co-hexafluoropropylene)

The radiation chemistry of poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) with a TFE mole fraction of 0.90 has been studied under vacuum using Co-60 gamma-radiation over a range of temperatures and absorbed doses. The radiolysis temperatures were 300, 363, 423, 523 and 543 K. New structure formation in the copolymers was analysed by solid-state F-19 NMR spectroscopy. The new structures formed in the copolymers have been identified and the G-values for the formation of new chemical structures have been investigated at 363 and 523 K. These two temperatures are just above and just below the polymer T-g and T-m, respectively. At the lower temperature, there was no evidence for any chain branching and an estimate of G(S) of 1.0 was obtained. A value of G(S) of 1.3 and a minimum value of G(X)(Y) of 1.3 were obtained at 523 K. (C) 2003 Society of Chemical Industry.

In vitro bioactivity of MOEP grafted ePTFE membranes for craniofacial applications

The bioactivity of three methacryloyloxyethyl phosphate (MOEP) grafted expanded polytetrafluoroethylene (ePTFE) membranes with varying surface coverage as well as unmodified ePTFE was investigated through a series of in vitro tests: calcium phosphate (CaP) growth in simulated body fluid (SBF), serum protein adsorption, and a morphology and attachment study of human osteoblast-like SaOS-2 cells. The graft copolymers were prepared by means of gamma irradiation induced grafting and displayed various surface morphologies and wettabilities depending on the grafting conditions used. Unmodified ePTFE did not induce nucleation of Cal? minerals, whereas all the grafted membranes revealed the growth of Cal? minerals after 7 days immersion in SBF. The sample with lowest surface grafting yield (24% coverage), a smooth graft morphology and relatively high hydrophobicity (theta(adv) = 120 degrees, theta(rec) = 80 degrees) showed carbonated hydroxyapatite growth covering the surface. On the other hand, the samples with high surface grafting yield (76% and 100%), a globular graft morphology and hydrophilic surfaces (theta(adv) = 60 degrees and 80 degrees, theta(rec) = 25 degrees and 15 degrees, respectively) exhibited irregular growth of non-apatitic Cap minerals. Irreversibly adsorbed protein measured after a 1 h immersion in serum solution was quantified by the amount of nitrogen on the surface using XPS, as well as by weight increase. All grafted membranes adsorbed 3-6 times more protein than the unmodified membrane. The sample with the highest surface coverage adsorbed the most protein. Osteoblast-like SaOS-2 cells cultured for 3 h revealed significantly higher levels of cell attachment on all grafted membranes compared to unmodified ePTFE. Although the morphology of the cells was heterogeneous, in general, the higher grafted surfaces showed a much better cell morphology than both the low surface-grafted and the control unmodified sample. The suite of in vitro tests confirms that a judicious choice of grafted monomer such as the phosphate-containing methacrylate monomer (MOEP) significantly improves the bioactivity of ePTFE in vitro. (c) 2005 Elsevier Ltd. All rights reserved.

Evaluation of the sonically induced narrowing of nuclear magnetic resonance spectra of solids

The Nuclear Magnetic Resonance (NMR) spectra of liquids contain a wealth of quantitative information that may be derived, for instance, from chemical shifts and spin-spin couplings. The available information depends on the incoherent rapid molecular motion that causes complicating effects present in the solid state to average to zero. Whereas liquid state NMR spectra show narrow lines, the corresponding NMR spectra from the solid state are normally composed of exceedingly broad resonance lines due to highly restricted molecular motion. It is, therefore, difficult to obtain directly as detailed information from the spectra of solids as from those derived from the liquid state. Studies on a new technique (SINNMR, the sonically induced narrowing of the NMR spectra of solids) to remove line broadening effects in the NMR spectra of the solid state are reported within this thesis. SINNMR involves narrowing the NMR absorptions from solid particles by irradiating them with ultrasound when they are suspended in a support liquid. It is proposed that ultrasound induces incoherent motion of the suspended particles, producing motional characteristics of the particles similar to those of rather large molecules. The first report of apparently successful experiments involving SINNMR[1] emphasised both the irreproducibility of the technique and the uncertainty regarding its true origin. If SINNMR can be made reproducible and the effect definitively attributed to the sonically induced incoherent motional averaging of particles, the technique could offer a simple alternative to the now classical magic-angle spinning (MAS) NMR[2] and the recently reported dynamic angle spinning (DAS)[3] and double rotation (DOR)[4] techniques. Evidence is presented in this thesis to support the proposal that ultrasound may be used to narrow the NMR spectral resonances from solids by inducing incoherent motion of particles suspended in support liquids and, additionally, for some solids, by inducing rotational motion of molecular constituents in the lattices of solids. Successful SINNMR line narrowing using 20 kHz ultrasound is reported for a variety of samples: including trisodium orthophosphate, polytetrafluoroethylene and aluminium alloys. Investigations of SINNMR line narrowing in trisodium phosphate have revealed the relationship between ultrasonic power, particle size and support liquid density for the production of optimum SINNMR conditions. It is also proposed that the incoherent motion of particles induced by 20 kHz ultrasound can originate from interactions between acoustically induced cavitation microjets and particles.