RESUMO
Reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of methyl methacrylate (MMA) is successfully performed in water in the presence of a poly(methacrylic acid) (PMAA) macromolecular chain transfer agent (macroCTA) leading to the formation of self-stabilized PMAA-b-PMMA amphiphilic block copolymer particles. At pH 3.7, the reactions are well-controlled with narrow molar mass distributions. Increasing the initial pH, particularly above 5.6, results in a partial loss of reactivity of the PMAA macroCTA. The effect of the degree of polymerization (DPn) of the PMMA block, the solids content, the nature of the hydrophobic segment, and the pH on the morphology of the obtained diblock copolymer particles is then investigated. Worm-like micelles are formed for a DPn of PMMA of 20 (PMMA20), while "onion-like" particles and spherical vesicles are obtained for PMMA30 and PMMA50, respectively. In contrast, spherical particles are obtained for the DPns higher than 150. This unusual evolution of particle morphologies upon increasing the DPn of the PMMA block seems to be related to hydrogen bonds between hydrophilic MAA and hydrophobic MMA units.
Assuntos
Emulsões , Metilmetacrilato , Polimerização , Ácidos Polimetacrílicos , Emulsões/química , Ácidos Polimetacrílicos/química , Ácidos Polimetacrílicos/síntese química , Metilmetacrilato/química , Substâncias Macromoleculares/química , Substâncias Macromoleculares/síntese química , Interações Hidrofóbicas e Hidrofílicas , Polimetil Metacrilato/química , Concentração de Íons de Hidrogênio , Tamanho da Partícula , Estrutura Molecular , MicelasRESUMO
STATEMENT OF PROBLEM: Denture base materials are highly susceptible to microbial colonization, which can lead to denture stomatitis. In addition, patients who sleep with their dentures have an increased chance of contracting pneumonia. Commercially available antimicrobial denture base materials to prevent or combat microbial colonization are lacking. PURPOSE: The purpose of this in vitro study was to determine the effects of K18 quaternary ammonium methacryloxy silane-functionalized filler (K18-Filler) and methyl methacrylate (K18-MMA) on the polymerization of 3D printed denture base material and its esthetic, mechanical, and antimicrobial properties. MATERIAL AND METHODS: K18-Filler (0%, 10%, 20% w/w) and K18-MMA (0%, 5%, 12.5% w/w) were added to a 3D printable denture base resin (Denture Base Resin, Original Pink; Formlabs Inc) and 3D printed. Specimens were tested by using the Rockwell15T hardness, near infrared FTIR monomer-to-polymer degree of conversion (DoC), transparency parameter (TP), color shift, and 3-point bend and by counting colony forming units against Streptococcus aureus, Streptococcus sanguinis and Candida albicans tests. Data were analyzed using analysis of variance with the Tukey-Kramer HSD post hoc test. RESULTS: Control resins had significantly higher Rockwell15T hardness than most of the K18 groups (P<.05) but had comparable DoC with all K18 groups except one, showing that all groups were well polymerized. Controls had significantly higher TP than most K18 groups, but most K18 groups had ΔE<3.3, so the color shift was not noticeable. However, the 12.5% K18-MMA with 10% and 20% K18-Filler groups, which were also the groups used to test for antimicrobial activity, had ΔE>8. All K18 groups had comparable or greater moduli than the controls, but the controls had significantly higher ultimate transverse strengths than most K18 groups (P<.05). All 12.5% K18-MMA with K18-Filler groups had significant antimicrobial activity against S. aureus, S. sanguinis, and C. albicans. CONCLUSIONS: 12.5% K18-MMA and K18-Filler produced 3D printable denture materials with comparable polymerization properties and significant antimicrobial properties against S. mutans, S. sanguinis, and C. albicans. High K18-MMA and K18-Filler concentrations caused significant color shifts and reductions in ultimate strengths.
Assuntos
Materiais Dentários , Bases de Dentadura , Metilmetacrilato , Impressão Tridimensional , Compostos de Amônio Quaternário , Silanos , Bases de Dentadura/microbiologia , Metilmetacrilato/química , Silanos/química , Silanos/farmacologia , Compostos de Amônio Quaternário/farmacologia , Compostos de Amônio Quaternário/química , Materiais Dentários/química , Anti-Infecciosos/farmacologia , Teste de Materiais , Polimerização , Técnicas In Vitro , Humanos , Candida albicans/efeitos dos fármacosRESUMO
To fabricate nanoscale proteinosomes, thermoresponsive miktoarm polymer protein bioconjugates were prepared through highly efficient molecular recognition between the ß-cyclodextrin modified BSA (CD-BSA) and the adamantyl group anchored at the junction point of the thermoresponsive block copolymer poly(ethylene glycol)-b-poly(di(ethylene glycol) methyl ether methacrylate) (PEG-b-PDEGMA). PEG-b-PDEGMA was synthesized by the Passerini reaction of benzaldehyde-modified PEG, 2-bromo-2-methylpropionic acid, and 1-isocyanoadamantane, followed by the atom transfer radical polymerization of DEGMA. Two block copolymers with different chain lengths of PDEGMA were prepared, and both self-assembled into polymersomes at a temperature above their lower critical solution temperatures (LCST). The two copolymers can undergo molecular recognition with the CD-BSA and form miktoarm star-like bioconjugates. The bioconjugates self-assembled into â¼160 nm proteinosomes at a temperature above their LCSTs, and the miktoarm star-like structure has a great effect on the formation of the proteinosomes. Most of the secondary structure and esterase activity of BSA in the proteinosomes were maintained. The proteinosomes exhibited low toxicity to the 4T1 cells and could deliver model drug doxorubicin into the 4T1 cells.
Assuntos
Polietilenoglicóis , Polímeros , Polímeros/química , Polietilenoglicóis/química , Micelas , Metacrilatos/química , Doxorrubicina/farmacologia , MetilmetacrilatoRESUMO
Modulating on-demand polymerization is a challenge in synthetic macromolecules. Herein, tailoring polymerization controllability and dispersity during single-electron transfer mediated living radical polymerization (SET-LRP) of methyl methacrylate (MMA) is achieved. Hexaarylbiimidazole (HABI) is employed as a photoswitchable catalyst, allowing reversible control of catalytic activity between an active and inactive state. In the presence of HABI and with the light on (active state), control SET-LRP of MMA follows first-order kinetics, resulting in polymers with a narrow molecular weight distribution. In contrast, polymerization responds to light and reverts to their original uncontrolled state with light off (inactive state). Therefore, repeatable resetting polymerization can be easily performed. The key to photomodulating dispersity is to use an efficient molecular switch to tailor the breadths of dispersity. Besides, the mechanism of HABI-mediated SET-LRP with switchable ability is proposed.
Assuntos
Polímeros , Polimerização , Substâncias Macromoleculares , MetilmetacrilatoRESUMO
Reversible deactivation radical polymerization (RDRP) is a facile and highly efficient technique for the synthesis of well-defined polymer with precise structure. dl-Methionine (Met) as a RDRP control agent is described and assessed for RDRP of styrene (St) and methyl methacrylate (MMA) with AIBN as radical initiator at 75 °C, which enables excellent control of this polymerization. The addition of dl-Methionine significantly decreased the dispersity (D) of the polymers for both monomers and first-order linear kinetic plots of polymethyl methacrylate (PMMA) are observed in DMSO. Considering the heat resistance of dl-Methionine, kinetic studies indicate that polymerization develops at a faster rate at higher reaction temperature (100 °C) with the same dl-Methionine content. Well-defined polymethyl methacrylate-block-polystyrene (PMMA-block-PSt) is successfully achieved by the chain extension reaction that demonstrates the high end fidelities of this polymerization approach. The system allows the use of dl-Methionine, a rich source and easily synthesized agent, to mediate RDRP strategy.
Assuntos
Polímeros , Polimetil Metacrilato , Polimetil Metacrilato/química , Metilmetacrilato , Polimerização , Cinética , Polímeros/química , Poliestirenos/química , Metacrilatos , Metionina , RNA Polimerase Dependente de RNARESUMO
This review addresses the need for a framework to increase the consistency, objectivity and transparency in the regulatory assessment of respiratory sensitisers and associated uncertainties. Principal issues are considered and illustrated through a case study (with methyl methacrylate). In the absence of test methods validated for regulatory use, formal documentation of the weight-of-evidence for hazard classification both at the level of integration of individual studies within lines of evidence and across a broad range of data streams was agreed to be critical for such a framework. An integrated approach is proposed to include not only occupational studies and clinical evidence for the regulatory assessment of respiratory sensitisers, but also information on structure and physical and chemical factors, predictive approaches such as structure activity analysis and in vitro and in vivo mechanistic and toxicokinetic findings. A weight-of-evidence protocol, incorporating integration of these sources of data based on predefined considerations, would contribute to transparency and consistency in the outcome of the assessment. In those cases where a decision may need to be taken on the basis of occupational findings alone, conclusions should be based on transparent weighting of relevant data on the observed prevalence of occupational asthma in various studies taking into account all relevant information including the range and nature of workplace exposures to the substance of interest, co-exposure to other chemicals and study quality.
Assuntos
Metacrilatos , Metilmetacrilato/toxicidade , Medição de Risco/métodos , Incerteza , Metacrilatos/toxicidadeRESUMO
Measuring quality of life (QOL) after cranioplasty is increasingly evident as a necessary component of patient-centered care. For data to be useful in clinical decision-making and approval of new therapies, studies must utilize valid and reliable instruments. Our objective was to critically appraise studies evaluating QOL in adult cranioplasty patients and determine validity and relevance of the patient-reported outcome measures (PROMs) used. Electronic databases of PubMed, Embase, CINAHL, and PsychINFO were used to identify PROMs measuring QOL in adult patients with cranioplasty. The methodological approach, cranioplasty outcomes, and domains measured by the PROMs were extracted and summarized descriptively. A content analysis of the identified PROMs was completed to identify the concepts measured. From 2236 articles identified, 17 articles containing eight QOL PROMs met the inclusion criteria. None of the PROMs was specifically validated or developed for adults undergoing cranioplasty. The QOL domains included physical health, psychological health, social health, and general QOL. These four domains encompassed 216 total items among the PROMs. Appearance was only assessed in two PROMs. To our knowledge, there are currently no validated PROMs that comprehensively measure appearance, facial function, and adverse effects in adults undergoing cranioplasty. There is an urgent need to develop PROMs to measure QOL outcomes rigorously and comprehensively in this patient population to inform clinical care, research, and quality improvement initiatives. Findings from this systematic review will be used to derive an outcome instrument containing important concepts related to QOL in patients who undergo cranioplasty.
Assuntos
Medidas de Resultados Relatados pelo Paciente , Procedimentos de Cirurgia Plástica , Adulto , Humanos , Tomada de Decisão Clínica , Bases de Dados Factuais , Saúde Mental , Qualidade de Vida/psicologia , MetilmetacrilatoRESUMO
The high cost of CAD/CAM systems and materials is a severe economic burden. Therefore, repair of CAD/CAM PMMA, selecting appropriate repair materials, and surface modifications are clinically important. This study aims to evaluate the shear bond strength of PMMA repair materials after various surface treatments on CAD/CAM PMMA denture base material. For this purpose, a total of 480 CAD/CAM PMMA denture base test specimens were manufactured. Then all test specimens were divided into 6 groups, and different surface treatments were applied. Group A: sandblasting, Group B: 4% hydro fluoric acid, Group C: tungsten carbide bur, Group D: dichloromethane + methyl methacrylate mixture, Group E: dichloromethane and methyl methacrylate, Group F: no surface treatment. Each group is then divided into 4 different subcategories; repair processes were performed using; heat-cured acrylic resin (n:20), auto-polymerized acrylic resin (n:20), gingiva composite (n:20), and CAD/CAM PMMA tooth material (n:20). After repairs, thermal aging was applied to half of the test specimens in each subcategory. The shear bond strength value was measured with a universal test device. Sandblasting group showed the highest surface roughness value in all test specimens (p < 0.001). Heat-cured acrylic resin with sandblasting exhibited the highest bond strength, while the untreated gingiva composite resin exhibited the lowest value. Thermal aging decreased bond strength in all repair materials (p < 0.001). Among the surface treatment groups, sandblasting with Al2O3 particles exhibited the highest surface roughness value and repair bond strength. The application of organic solvents to the surface increased the surface roughness and repair bond strength. Applying dichloromethane and methyl methacrylate monomer separately is more effective than applying it as a mixture. The ideal bonding among repair materials was obtained with heat-cured acrylic resin.
Assuntos
Colagem Dentária , Polimetil Metacrilato , Humanos , Polimetil Metacrilato/química , Bases de Dentadura , Cloreto de Metileno , Teste de Materiais , Resinas Acrílicas/química , Metilmetacrilato , Metacrilatos/química , Propriedades de Superfície , Resistência ao Cisalhamento , Reparação em DentaduraRESUMO
In this work, two compounds belonging to the BODIPY family, and previously investigated for their photosensitizing properties, have been bound to the amino-pendant groups of three random copolymers, with different amounts of methyl methacrylate (MMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) in the backbone. The P(MMA-ran-DMAEMA) copolymers have inherently bactericidal activity, due to the amino groups of DMAEMA and to the quaternized nitrogens bounded to BODIPY. Systems consisting of filter paper discs coated with copolymers conjugated to BODIPY were tested on two model microorganisms, Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). On solid medium, irradiation with green light induced an antimicrobial effect, visible as a clear inhibition area around the coated disks. The system based on the copolymer with 43% DMAEMA and circa 0.70 wt/wt% of BODIPY was the most efficient in both bacterial species, and a selectivity for the Gram-positive model was observed, independently of the conjugated BODIPY. A residual antimicrobial activity was also observed after dark incubation, attributed to the inherently bactericidal properties of copolymers.
Assuntos
Anti-Infecciosos , Fotoquimioterapia , Escherichia coli , Metilmetacrilato , Staphylococcus aureus , Anti-Infecciosos/farmacologia , Metacrilatos/farmacologia , Polímeros/farmacologia , Antibacterianos/farmacologia , Fármacos Fotossensibilizantes/farmacologiaRESUMO
PURPOSE: The aim of this study was to evaluate the bond strength between two types of artificial teeth with a 3D-printed denture base resin using different bonding agents. MATERIALS AND METHODS: Two types of artificial teeth were evaluated: 3D-printed (Cosmos TEMP) and prefabricated polymethylmethacrylate (Biotone) bonded to cylinders (2.5 mm in height and 5 mm in diameter) of 3D-printed denture bases (Cosmos Denture designing by Meshmixer and printed by Flashforge Hunter DLP Resin 3D Printer). Two combinations between denture base and artificial teeth were eveluated: Cosmos Denture - Biotone, n = 30, and Cosmos Denture - Cosmos TEMP, n = 30. For each combination, the specimens were randomly distributed according to the bonding agent: (1) autopolymerized acrylic resin-Duralay, n = 10; (2) 3D-printed resin Cosmos TEMP, n = 10; and (3) methylmethacrylate monomer (MMA) + 3D-printed resin Cosmos TEMP, n = 10, totaling 60 specimens. The application of MMA was done conditioning the tooth surface for 180 seconds; the other agents were applied on the same surface. The virtual design of the 3D-printed resin teeth was obtained by scanning the first maxillary molar of the prefabricated teeth as the same protocol of cylinders. The control group (n = 10) was a conventional heat-polymerized denture base resin (Lucitone 550) bonded to the prefabricated resin teeth (Biotone). The shear bond tests were performed by applying a perpendicular force to the artificial tooth - denture base resin, through a chisel at 1 mm/min until failure. Two-way ANOVA and Bonferroni post hoc tests (α = 0.05) were used for multiple comparisons. RESULTS: For the Biotone tooth, the bond strength was significantly higher using MMA + Cosmos TEMP (10.04 MPa), and similar to the control (11.84 MPa, p = 0.484). For the 3D-printed tooth (Cosmos TEMP), the bond strength using the agents Cosmos TEMP (9.57 MPa) and MMA + Cosmos TEMP (12.72 MPa) were similar to the control (11.84 MPa, p = 0.169 and p = 1, respectively), but different from each other (p = 0.016). CONCLUSIONS: From the results, it is recommended to use: MMA + Cosmos TEMP bonding agent for the Biotone tooth; and Cosmos TEMP or MMA + Cosmos TEMP bonding agents for the Cosmos TEMP tooth, both attached to the 3D-printed denture resin Cosmos Denture.
Assuntos
Colagem Dentária , Bases de Dentadura , Colagem Dentária/métodos , Dente Artificial , Polimetil Metacrilato/química , Metilmetacrilato , Impressão Tridimensional , Teste de Materiais , Propriedades de Superfície , Resistência ao CisalhamentoRESUMO
Reconstruction of bone loss in the cranial vault may be necessary for functional or aesthetic reasons following trauma, decompression craniectomy, or craniofacial malformations. Many techniques have been described in the literature, using various materials, each with its own advantages and drawbacks. Reconstruction with polymethylmetacrylate cement has the advantage of a durable result and relative ease of use. In this article we present our cement cranioplasty technique through 4 clinical cases of cranial vault reconstruction, by direct intraoperative modeling on the bone defect. This accessible, effective method, applicable to all sizes of defect, remains an attractive option in the arsenal of techniques available today.
Assuntos
Procedimentos de Cirurgia Plástica , Polimetil Metacrilato , Humanos , Metilmetacrilato , Craniotomia/métodos , Resultado do Tratamento , Estudos RetrospectivosRESUMO
Background: In childhood supracondylar fractures of the humerus, fixation with percutaneous Kirschner wire is the standard treatment. In the case of irreducible-unstable fractures, these can be defined as fractures in which reduction is not well-achieved or in which fixation cannot be achieved with the K-wire. Intraoperative management of these types of fractures may be difficult. Treatment with a methyl methacrylate fixator consisting of K-wire and methyl methacrylate cement, as defined by the senior author of the article, may be a good option for Gartland type IV supracondylar humeral fractures where the fracture is unstable in flexion and extension due to complete periosteal tearing. Materials and Methods: The short-term and mid-term results of 27 patients between the ages of 4-12 with Gartland type IV supracondylar fracture of the humerus treated with methyl methacrylate fixation were reviewed. The patients were scored in terms of function and cosmetic satisfaction. Results: A total of 19 of the 27 patients treated with the methyl methacrylate fixator had full elbow motion function and rated the outcome of the treatment as excellent, which was judged by orthopedic surgeons on the basis of Flynn's criteria. Six patients had nearly full elbow motion and evaluated their recovery outcome as good. Two patients reported nearly full range of motion (ROM) and evaluated the method as moderate in terms of treatment. Discussion: Treatment with the methyl methacrylate fixation method is an inexpensive method that allows early joint mobilization, provides strong biomechanical stability, ensures good outcomes, and should be considered in the treatment of irreducible and unstable supracondylar fractures of the humerus.
Assuntos
Fixação Interna de Fraturas , Fraturas do Úmero , Humanos , Pré-Escolar , Criança , Fixação Interna de Fraturas/métodos , Metilmetacrilato , Resultado do Tratamento , Fraturas do Úmero/cirurgia , Metacrilatos , Estudos RetrospectivosRESUMO
Methyl methacrylate (MMA) is classified under GHS as a weak skin sensitiser and a skin and respiratory irritant. It has recently been proposed that MMA be classified as a respiratory sensitiser (a designation that in a regulatory context embraces both true respiratory allergens, as well as chemicals that cause asthma through non-immunological mechanisms). This proposal was based primarily upon the interpretation of human data. This review, and a detailed weight of evidence analysis, has led to another interpretation of these data. The conclusion drawn is that persuasive evidence consistent with the designation of MMA as a respiratory sensitiser is lacking. It is suggested that one reason for different interpretations of these data is that occupational asthma poses several challenges with respect to establishing causation. Among these is that it is difficult to distinguish between allergic asthma, non-allergic asthma, and work-related exacerbation of pre-existing asthma. Moreover, there is a lack of methods for the identification of true chemical respiratory allergens. The characterisation and causation of occupational asthma is consequently largely dependent upon interpretation of human data of various types. Recommendations are made that are designed to improve the utility and interpretation of human data for establishing causation in occupational asthma.
Assuntos
Asma Ocupacional , Alérgenos/toxicidade , Asma Ocupacional/induzido quimicamente , Humanos , Metacrilatos , Metilmetacrilato/toxicidade , Sistema RespiratórioRESUMO
The effect of the addition of the methyl methacrylate acrylonitrile butadiene styrene (MABS) copolymer on the miscibility, thermal degradation and rheological properties of epoxy systems is described. Epoxy resin/MABS blends containing 5, 10, 15 and 20 phr MABS were prepared using the solution mixing technique. Homogenous blends obtained using this technique have undergone a polymerization reaction induced phase separation process by the introduction of the curing agent 4,4'-diaminodiphenyl sulfone (DDS). The isothermal rheology at four different temperatures, 150, 160, 170 and 180 °C, was used to examine the effect of MABS on the gelation and vitrification time. The evolution of storage modulus, loss modulus and tan delta was found to be closely related to the evolution of complex phase separation. The increase in the complex viscosity during curing was determined by in situ rheometry and theoretically analysed by fitting with the Williams-Landell-Ferry equation. An exponential increase in complex viscosity was observed, which was induced by cross-linking. The variation of Tg before and after curing was studied using DSC analysis and dynamic kinetic modeling of the curing process was carried out by utilizing dynamic DSC scans. Thermal stability studies of completely cured epoxy/MABS blends using thermogravimetric analysis revealed that all the blends and neat epoxy exhibited single step degradation. Thermal degradation kinetics was calculated using the Coats Redfern equation.
Assuntos
Acrilonitrila , Metilmetacrilato , Butadienos , Resinas Epóxi , Poliestirenos , ReologiaRESUMO
An air-tolerant reversible complexation mediated polymerization (RCMP) technique, which can be carried out without prior deoxygenation, is developed. The system contains a monomer, an alkyl iodide initiating dormant species, air (oxygen), an aldehyde, N-hydroxyphthalimide (NHPI), and a base. Oxygen is consumed via the NHPI-catalyzed conversion of the aldehyde (RCHO) to a carboxylic acid (RCOOH). The generated RCOOH is further converted to a carboxylate anion (RCOO- ) by the base. The RCOO- generated in situ works as an RCMP catalyst; the polymerization proceeds with the monomer, alkyl iodide dormant species, and RCOO- catalyst. Thus, the system is not only air-tolerant but also does not require additional RCMP catalysts, which is a notable feature of this system. (NHPI is used as an oxidation catalyst for converting RCHO to RCOOH.) This technique is amenable to methyl methacrylate, butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, and styrene, yielding polymers with relatively low-dispersity (Mw /Mn = 1.20-1.49), where Mw and Mn are the weight- and number-average molecular weights, respectively.
Assuntos
Aldeídos , Iodetos , Metilmetacrilato , Oxigênio , PolimerizaçãoRESUMO
Sequential block copolymerization involving comonomers belonging to different classes, e.g., a vinyl-type monomer and a heterocycle, is a challenging task in macromolecular chemistry, as corresponding propagating species do not interconvert easily from one to the other by crossover reactions. Here, it is first evidenced that 1-methoxy 2-methyl 1-trimethylsilyloxypropene (MTS), i.e., a silyl ketene acetal (SKA)-containing initiator, can be used in presence of the P4 -t-Bu phosphazene organic base to control the ring-opening polymerization (ROP) of racemic lactide (rac-LA). The elementary reaction, which rapidly transforms SKA groups into propagating alkoxides, can be leveraged to directly synthesize well-defined poly(methyl methacrylate)-b-polylactide block copolymers. This is achieved using P4 -t-Bu as the single organic catalyst and MTS as the initiator for the group transfer polymerization of methyl methacrylate, followed by the ROP of rac-LA. Both polymerization methods are implemented under selective and controlled/living conditions at room temperature in THF. This sequential addition strategy further expands the scope of organic catalysis of polymerizations for macromolecular engineering of block copolymers involving propagating species of disparate reactivity.
Assuntos
Acetais , Polimetil Metacrilato , Polimerização , Metilmetacrilato , Polímeros/química , MetacrilatosRESUMO
OBJECTIVE: Antibiotic-loaded bone cement beads and spacers have been widely used for orthopaedic infection. Poor antibiotic elution is not capable of eradicating microbial pathogens and could lead to treatment failure. The elution profiles differ among different cement formulations. Although Simplex P cement has the least release amount, it is widely used due to its ready availability. Previous methods aiming to improve the elution profiles were not translated well to clinical practice. We sought to address this by using easily available materials to improve the elution profile of antibiotics from PMMA, which allows clinicians to implement the method intraoperatively. METHODS: Vancomycin was mixed with Simplex P cement. We used Vicryl Rapide sutures to fabricate sustained-release cement beads by repetitively passing the sutures through the beads and/or mixing suture segments into the cement formulation. Vancomycin elution was measured for 49 days. The mechanism of antibiotic release was observed with gross appearance and scanning electron microscopic images. The antimicrobial activities against MRSA were tested using an agar disk diffusion bioassay. RESULTS: Passing Vicryl Rapide sutures through cement beads significantly improved the elution profiles in the 7-week period. The increased ratios were 9.0% on the first day and 118.0% from the 2nd day to the 49th day. Addition of suture segments did not increase release amount. The Vicryl Rapide sutures completely degraded at the periphery and partially degraded at the center. The antibiotic particles were released around the suture, while antibiotic particles kept densely entrapped in the control group. The antimicrobial activities were stronger in passing suture groups. CONCLUSION: Passing fast absorbable sutures through PMMA cement is a feasible method to fabricate sustained-release antibiotic bone cement. Intra-cement tunnels can be formed, and the effect can last for at least 7 weeks. It is suitable for a temporary spacer between two stages of a revision surgery.
Assuntos
Cimentos Ósseos , Polimetil Metacrilato , Ágar , Antibacterianos , Preparações de Ação Retardada , Humanos , Metilmetacrilato , Poliglactina 910 , Suturas , VancomicinaRESUMO
Due to the environmental and production problems of emulsion, it is important to efficiently separate oil-water emulsion to meet the refinery requirement and clean up oil spills. Synthesis of a universal demulsifier is not an easy task because the physical properties of crude oil vary, which makes its characterization and demulsification procedure difficult. To overcome this problem, hydrophilic and magnetically recoverable poly (methyl methacrylate-acrylic acid)/iron oxide magnetic composite nanoparticles ((P(MMA-AA)/Fe3O4 NPs) were developed as an efficient and economical demulsifier via soap-free emulsion polymerization. To characterize the magnetic composite NPs for their appropriate surface morphology and magnetic domain, TEM, FTIR, VSM, and TGA analyses were carried out. The newly synthesized NPs displayed good hydrophilic properties as they migrated quickly to the aqueous emulsion phase, which was also reassured by their water contact angle of 75°. They exhibit strong magnetic characteristics (20 amu/g) in the oil-water emulsion, makings the hydrophilic wettability capable and attractive to the external magnet. Experimental results revealed that the prepared magnetic composite NPs separated 99% of the water from stable emulsion in 30 min and could be recycled 8 times through magnetic separation. The recycled magnetic composite NPs maintain their hydrophilic wettability and efficiency in separating oil-water emulsion, making them economical and commercially viable. The migration of magnetic composite NPs to the aqueous phase in the stable emulsion with a strong magnetic domain explains the coalescence of emulsified water droplets and their quick separation from the stable emulsions through the external magnet.
Assuntos
Nanoestruturas , Água , Acrilatos , Emulsões , Compostos Férricos , Fenômenos Magnéticos , Metacrilatos , Metilmetacrilato , Óleos , MolhabilidadeRESUMO
Use of iron-based catalysts in atom transfer radical polymerization (ATRP) is very interesting because of the abundance of the metal and its biocompatibility. Although the mechanism of action is not well understood yet, iron halide salts are usually used as catalysts, often in the presence of nitrogen or phosphorous ligands (L). In this study, electrochemically mediated ATRP (eATRP) of methyl methacrylate (MMA) catalyzed by FeCl3, both in the absence and presence of additional ligands, was investigated in dimethylformamide. The electrochemical behavior of FeCl3 and FeCl3/L was deeply investigated showing the speciation of Fe(III) and Fe(II) and the role played by added ligands. It is shown that amine ligands form stable iron complexes, whereas phosphines act as reducing agents. eATRP of MMA catalyzed by FeCl3 was investigated in different conditions. In particular, the effects of temperature, catalyst concentration, catalyst-to-initiator ratio, halide ion excess and added ligands were investigated. In general, polymerization was moderately fast but difficult to control. Surprisingly, the best results were obtained with FeCl3 without any other ligand. Electrogenerated Fe(II) effectively activates the dormant chains but deactivation of the propagating radicals by Fe(III) species is less efficient, resulting in dispersity > 1.5, unless a high concentration of FeCl3 is used.
Assuntos
Ferro , Substâncias Redutoras , Aminas , Catálise , Dimetilformamida , Compostos Ferrosos , Ferro/química , Ligantes , Metacrilatos/química , Metilmetacrilato/química , Nitrogênio , Polimerização , SaisRESUMO
To investigate the utility of acrylic monomers from various plant oils in adhesives manufacturing, 25-45 wt. % of high oleic soybean oil-based monomer (HOSBM) was copolymerized in a miniemulsion with commercially applied butyl acrylate (BA), methyl methacrylate (MMA), or styrene (St). The compositions of the resulting ternary latex copolymers were varied in terms of both "soft" (HOSBM, BA) and "rigid" (MMA or St) macromolecular fragments, while total monomer conversion and molecular weight of copolymers were determined after synthesis. For most latexes, results indicated the presence of lower and higher molecular weight fractions, which is beneficial for the material adhesive performance. To correlate surface properties and adhesive performance of HOSBM-based copolymer latexes, contact angle hysteresis (using water as a contact liquid) for each latex-substrate pair was first determined. The data showed that plant oil-based latexes exhibit a clear ability to spread and adhere once applied on the surface of materials differing by polarities, such as semicrystalline polyethylene terephthalate (PET), polypropylene (PP), bleached paperboard (uncoated), and tops coated with a clay mineral paperboard. The effectiveness of plant oil-based ternary latexes as adhesives was demonstrated on PET to PP and coated to uncoated paperboard substrates. As a result, the latexes with high biobased content developed in this study provide promising adhesive performance, causing substrate failure instead of cohesive/adhesive break in many experiments.