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1.
Macromol Rapid Commun ; : e2400282, 2024 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-38850266

RESUMO

Soft actuators are one of the most promising technological advancements with potential solutions to diverse fields' day-to-day challenges. Soft actuators derived from hydrogel materials possess unique features such as flexibility, responsiveness to stimuli, and intricate deformations, making them ideal for soft robotics, artificial muscles, and biomedical applications. This review provides an overview of material composition and design techniques for hydrogel actuators, exploring 3D printing, photopolymerization, cross-linking, and microfabrication methods for improved actuation. It examines applications of hydrogel actuators in biomedical, soft robotics, bioinspired systems, microfluidics, lab-on-a-chip devices, and environmental, and energy systems. Finally, it discusses challenges, opportunities, advancements, and regulatory aspects related to hydrogel actuators.

2.
Int J Mol Sci ; 25(10)2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38791537

RESUMO

Many years of foundry practice and much more accurate analytical methods have shown that sands with organic binders, in addition to their many technological advantages, pose risks associated with the emission of many compounds, including harmful ones (e.g., formaldehyde, phenol, benzene, polycyclic aromatic hydrocarbons, and sulfur), arising during the pouring of liquid casting alloys into molds, their cooling, and knock-out. The aim of this research is to demonstrate the potential benefits of adopting inorganic binders in European iron foundries. This will improve the environmental and working conditions by introducing cleaner and more ecological production methods, while also ranking the tested binders studied in terms of their harmful content. The article pays special attention to the analysis of seven innovative inorganic binders and one organic binder, acting as a reference for emissions of gases from the BTEX (benzene, toluene, ethylbenzene, and xylenes) and PAHs (polycyclic aromatic hydrocarbons) groups and other compounds such as phenol, formaldehyde, and isocyanates (MDI and TDI) generated during the mold pouring process with liquid metals. The knowledge gained will, for the first time, enrich the database needed to update the Reference Document on The Best Available Techniques for the Smitheries and Foundries Industry (SF BREF).


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Hidrocarbonetos Policíclicos Aromáticos/análise , Hidrocarbonetos Policíclicos Aromáticos/química , Compostos Inorgânicos/química , Metalurgia , Formaldeído/química
3.
J Environ Manage ; 332: 117413, 2023 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-36764214

RESUMO

Parabens have been detected in drinking water (DW) worldwide, however, their impact on DW microbial communities remains to be explored. Microorganisms can easily adapt to environmental changes. Therefore, their exposure to contaminants of emerging concern, particularly parabens, in DW distribution systems (DWDS) may affect the microbiological quality and safety of the DW reaching the consumers tap. This work provides a pioneer evaluation of the effects of methylparaben (MP), propylparaben (PP), butylparaben (BP), and their combination (MIX), in bacterial biofilms formed on different surfaces, representative of DWDS materials - high-density polyethylene (HDPE), polypropylene (PPL) and polyvinyl chloride (PVC). Acinetobacter calcoaceticus and Stenotrophomonas maltophilia, isolated from DW, were used to form single and dual-species biofilms on the surface materials selected. The exposure to MP for 7 days caused the most significant effects on biofilms, by increasing their cellular culturability, density, and thickness up to 233%, 150%, and 224%, respectively, in comparison to non-exposed biofilms. Overall, more pronounced alterations were detected for single biofilms than for dual-species biofilms when HDPE and PPL, demonstrating that the surface material used affected the action of parabens on biofilms. Swimming motility and the production of virulence factors (protease and gelatinase) by S. maltophilia were increased up to 141%, 41%, and 73%, respectively, when exposed to MP for 7 days. The overall results highlight the potential of parabens to interfere with DW bacteria in planktonic state and biofilms, and compromise the DW microbiological quality and safety.


Assuntos
Água Potável , Parabenos , Polietileno , Biofilmes , Bactérias
4.
Molecules ; 29(1)2023 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-38202769

RESUMO

Speciation analysis is a relevant topic since the (eco)toxicity, bioavailability, bio (geo)chemical cycles, and mobility of a given element depend on its chemical forms (oxidation state, organic ligands, etc.). The reliability of analytical results for chemical species of elements depends mostly on the maintaining of their stability during the sample pretreatment step and on the selectivity of further separation step. Solid-phase extraction (SPE) is a matter of choice as the most suitable and widely used procedure for both enrichment of chemical species of elements and their separation. The features of sorbent material are of great importance to ensure extraction efficiency from one side and selectivity from the other side of the SPE procedure. This review presents an update on the application of polymeric materials in solid-phase extraction used in nonchromatographic methods for speciation analysis.

5.
Molecules ; 28(15)2023 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-37570741

RESUMO

Migration studies are one of the few domains of pharmaceutical analysis employing wide-scope screening methodologies. The studies involve the detection of contaminants within pharmaceutical products that arise from the interaction between the formulation and materials. Requiring both qualitative and quantitative data, the studies are conducted using Liquid Chromatography or Gas Chromatography coupled to a mass spectrometer (LC-MS and GC-MS). While mass spectrometry allows wide-scope analyte detection and identification at the very low Analytical Evaluation Threshold (AET) levels used in these studies, MS detectors are far from "universal response" detectors. Regulation brings the application of uncertainty factors into the picture to limit the risk of potential analytes detected escaping report and further evaluation; however, whether the application of a default value can cover any or all relevant applications is still debatable. The current study evaluated the response of species usually detected in migration studies, generating a suitable representative sample, analyzing said species, and creating a strategy and evaluation mechanism for acceptable classification of the detected species. Incorporating novel methodologies, i.e., Design of Experiments (DoE) for Design Space generation, the LC-MS-based methodology is also evaluated for its robustness in changes performed.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas , Espectrometria de Massas , Cromatografia Líquida/métodos
6.
Molecules ; 28(3)2023 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-36770748

RESUMO

Dye and nitro-compound pollution has become a significant issue worldwide. The adsorption and degradation of dyes and nitro-compounds have recently become important areas of study. Different methods, such as precipitation, flocculation, ultra-filtration, ion exchange, coagulation, and electro-catalytic degradation have been adopted for the adsorption and degradation of these organic pollutants. Apart from these methods, adsorption, photocatalytic degradation, and chemical degradation are considered the most economical and efficient to control water pollution from dyes and nitro-compounds. In this review, different kinds of dyes and nitro-compounds, and their adverse effects on aquatic organisms and human beings, were summarized in depth. This review article covers the comprehensive analysis of the adsorption of dyes over different materials (porous polymer, carbon-based materials, clay-based materials, layer double hydroxides, metal-organic frameworks, and biosorbents). The mechanism and kinetics of dye adsorption were the central parts of this study. The structures of all the materials mentioned above were discussed, along with their main functional groups responsible for dye adsorption. Removal and degradation methods, such as adsorption, photocatalytic degradation, and chemical degradation of dyes and nitro-compounds were also the main aim of this review article, as well as the materials used for such degradation. The mechanisms of photocatalytic and chemical degradation were also explained comprehensively. Different factors responsible for adsorption, photocatalytic degradation, and chemical degradation were also highlighted. Advantages and disadvantages, as well as economic cost, were also discussed briefly. This review will be beneficial for the reader as it covers all aspects of dye adsorption and the degradation of dyes and nitro-compounds. Future aspects and shortcomings were also part of this review article. There are several review articles on all these topics, but such a comprehensive study has not been performed so far in the literature.

7.
Polim Med ; 53(1): 47-58, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36637332

RESUMO

In recent years, there has been a great interest in the potential use of contact lenses as eye drug delivery systems. Static (individual layers of the cornea, sclera and retina) as well as dynamic barriers (blood flow) pose a serious challenge to the effective delivery of the drug substance to the eyeball. The current ophthalmic systems are not optimal for patients, especially in the form of eye drops, where almost 95% of the drug contained in them is lost through the process of absorption through the conjunctiva or tear drainage. This article describes in vitro experiments that examined the use of contact lenses in the context of drug treatment in infectious, inflammatory, allergic, and glaucomatous diseases. Various techniques used to modify the materials as well as their impact on drug release kinetics were discussed. It has also been demonstrated that these methods can be used in practice during in vivo research, both in animal models as well as in sick and healthy people. The advantages of using controlled-release drug systems in the form of contact lenses are the drug dosing regimen, bioavailability and the prolonged residence time of drugs in the eyeball.


Assuntos
Lentes de Contato , Glaucoma , Animais , Preparações de Ação Retardada , Sistemas de Liberação de Medicamentos/métodos , Córnea , Soluções Oftálmicas
8.
Chemistry ; 28(39): e202200069, 2022 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-35416347

RESUMO

The rapid development of continuous flow processes is driving innovations in various chemical syntheses and industrial productions. Immobilizing catalysts in flow reactors allows transformations with high-efficiency and excludes the subsequent separation procedures. This concept outlines the approaches to incorporate catalysts within flow reactors, with particular focus on the application of additional supports including inorganic materials like silica, zeolite and reduced graphene oxide, polymeric materials like polymer packings, monoliths, cross-linked gels and polymer brushes, and other materials for specific conditions like transparent glass fibers and glass beads. Furthermore, advanced methods to develop ordered micro-/nanoarrays from internal walls of flow channels for immobilization of catalysts as well as application of innovative vortex fluidic devices are discussed to inspire new designs of supports for novel fluidic reactors with broad applications.

9.
Macromol Rapid Commun ; 43(16): e2200083, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35257443

RESUMO

In both natural and artificial functional systems, the cooperation between different dynamic interactions is of vital importance for realizing complicated functions. Dynamic covalent bonds are one kind of relatively stable dynamic interactions and have shown synergistic effect in natural systems such as functional proteins. However, synergistic interactions between different dynamic covalent bonds in polymeric materials are still unclear. Herein, polymeric materials containing diselenide and imine bonds are prepared, and then the synergistic effect between the two dynamic covalent bonds is quantitatively evaluated in typical processes of dynamic materials. The results reveal that dynamic covalent bonds show weak synergistic effect in the degradation process and have strong synergistic effect in stress relaxation process. Therefore, introducing multiple dynamic covalent bonds in polymeric materials can extensively enhance their dynamic properties.


Assuntos
Iminas , Polímeros , Iminas/química , Polímeros/química , Proteínas
10.
Adv Funct Mater ; 30(37)2020 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-33071713

RESUMO

Autoimmune diseases are a group of debilitating illnesses that are often idiopathic in nature. The steady rise in the prevalence of these conditions warrants new approaches for diagnosis and treatment. Stimuli-responsive biomaterials also known as "smart", "intelligent" or "recognitive" biomaterials are widely studied for their applications in drug delivery, biosensing and tissue engineering due to their ability to produce thermal, optical, chemical, or structural changes upon interacting with the biological environment. This critical analysis highlights studies within the last decade that harness the recognitive capabilities of these biomaterials towards the development of novel detection and treatment options for autoimmune diseases.

11.
Biopolymers ; 111(9): e23390, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32640085

RESUMO

Intermolecular cross-linking is one of the most important techniques that can be used to fundamentally alter the material properties of a polymer. The introduction of covalent bonds between individual polymer chains creates 3D macromolecular assemblies with enhanced mechanical properties and greater chemical or thermal tolerances. In contrast to many chemical cross-linking reactions, which are the basis of thermoset plastics, enzyme catalysed processes offer a complimentary paradigm for the assembly of cross-linked polymer networks through their predictability and high levels of control. Additionally, enzyme catalysed reactions offer an inherently 'greener' and more biocompatible approach to covalent bond formation, which could include the use of aqueous solvents, ambient temperatures, and heavy metal-free reagents. Here, we review recent progress in the development of biocatalytic methods for polymer cross-linking, with a specific focus on the most promising candidate enzyme classes and their underlying catalytic mechanisms. We also provide exemplars of the use of enzyme catalysed cross-linking reactions in industrially relevant applications, noting the limitations of these approaches and outlining strategies to mitigate reported deficiencies.


Assuntos
Biocatálise , Materiais Biocompatíveis/química , Reagentes de Ligações Cruzadas/química , Hidrogéis/química , Substâncias Macromoleculares/química , Polímeros/química
12.
Molecules ; 25(7)2020 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-32268518

RESUMO

Crosslinked polymeric materials based on a quaternary trimethylammonium compound were developed and evaluated as potential antifouling coatings. For this purpose, two water-soluble random copolymers, poly(4-vinylbenzyltrimethylammonium chloride-co-acrylic acid) P(VBCTMAM-co-AAx) and poly(N,N-dimethylacrylamide-co-glycidylmethacrylate) P(DMAm-co-GMAx), were synthesized via free radical polymerization. A water based approach for the synthesis of P(VBCTMAM-co-AAx) copolymer was used. Coatings of the complementary reactive copolymers in different compositions were obtained by curing at 120 °C for one day and were used to coat aquaculture nets. These nets were evaluated in respect to their release rate using Total Organic Carbon (TOC) and Total Nitrogen (TN) measurements. Finally, the antifouling efficacy of these newly-composed durable coatings was investigated for 14 days in accelerated conditions. The results showed that this novel polymeric material provides contact-killing antifouling activity for a short time period, whereas it functions efficiently in biofouling removal after high-pressure cleaning.


Assuntos
Incrustação Biológica/prevenção & controle , Metilaminas/química , Polímeros/química , Água/química
13.
Stomatologiia (Mosk) ; 99(2): 79-84, 2020.
Artigo em Russo | MEDLINE | ID: mdl-32441080

RESUMO

OBJECTIVE: Characteristics of the adhesion of yeast fungi and oral bacteria of various types in vitro to samples of polymeric materials for fixed structures of dental prostheses, obtained using various technologies: adjective digital 3D printing and traditional methods. MATERIAL AND METHODS: Conducted model experiments on the adhesion of bacterial (including the main periodontopic-pathogenic species - P. gingivalis, P. intermedia, etc.) and fungal pathogens (C. albicans) to standard samples of polymer materials NextDent C & B Micro Filled Hybrid («NextDent¼, Netherlands), Detax Freeprint temp UV («Detax¼, Germany), obtained by digital additive 3D printing technology, and Luxatemp Automix Plus («DMG¼, Germany) and Acrytemp («Zhermack¼, Italy) - by the traditional method as a control. Removal of adhering microbes from the material was carried out using an ultrasound machine (exposure time 10 minutes, power 60 kHz). RESULTS: The dependence of the degree of microbial adhesion on the nature of the material and processing technology (3D printing, milling) was established. The materials of NextDent C & B Micro Filled Hybrid and Detax Freeprint temp UV showed high resistance to adhesion of clinical isolates of periodontal pathogenic bacteria and C. albicans fungi. CONCLUSION: The lowest adhesion values for periodontopathogenic species and C. albicans fungi were detected when using samples of materials obtained by 3D printing: NextDent C & B Micro Filled Hybrid and Detax Freeprint temp UV compared to Luxatemp Automix Plus and Acrytemp polymers.


Assuntos
Materiais Dentários , Polímeros , Bactérias , Biofilmes , Candida albicans , Boca
14.
Molecules ; 24(14)2019 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-31330957

RESUMO

Massive blood loss is responsible for numerous causes of death. Hemorrhage may occur on the battlefield, at home or during surgery. Commercially available biomaterials may be insufficient to deal with excessive bleeding. Therefore novel, highly efficient hemostatic agents must be developed. The aim of the following research was to obtain a new type of biocompatible chitosan-based hemostatic agents with increased hemostatic properties. The biomaterials were obtained in a quick and efficient manner under microwave radiation using l-aspartic and l-glutamic acid as crosslinking agents with no use of acetic acid. Ready products were investigated over their chemical structure by FT-IR method which confirmed a crosslinking process through the formation of amide bonds. Their high porosity above 90% and low density (below 0.08 g/cm3) were confirmed. The aerogels were also studied over their water vapor permeability and antioxidant activity. Prepared biomaterials were biodegradable in the presence of human lysozyme. All of the samples had excellent hemostatic properties in contact with human blood due to the platelet activation confirmed by blood clotting tests. The SEM microphotographs showed the adherence of blood cells to the biomaterials' surface. Moreover, they were biocompatible with human dermal fibroblasts (HDFs). The biomaterials also had superior antibacterial properties against both Staphylococcus aureus and Escherichia coli. The obtained results showed that proposed chitosan-based hemostatic agents have great potential as a hemostatic product and may be applied under sterile, as well as contaminated conditions, by both medicals and individuals.


Assuntos
Antibacterianos/química , Antibacterianos/farmacologia , Quitosana/química , Hemostáticos/química , Hemostáticos/farmacologia , Antibacterianos/síntese química , Antioxidantes/síntese química , Antioxidantes/química , Antioxidantes/farmacologia , Bactérias/efeitos dos fármacos , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Coagulação Sanguínea/efeitos dos fármacos , Técnicas de Química Sintética , Hemostáticos/síntese química , Teste de Materiais , Testes de Sensibilidade Microbiana , Estrutura Molecular , Porosidade , Análise Espectral , Relação Estrutura-Atividade
15.
Klin Lab Diagn ; 64(12): 758-761, 2019.
Artigo em Russo | MEDLINE | ID: mdl-32040901

RESUMO

Microorganisms are able to form biofilms on surfaces of biotic and abiotic nature. In turn, in human biotopes there are optimal conditions for the implementation of biofilm-forming activity. Moreover, in medical practice, polymeric materials are often used for drainage or prosthetics, which can also be successfully colonized by bacteria. However, in laboratory practice, the formation of biofilms is usually evaluated on glass or polystyrene. The purpose of the study is to evaluate the methodological features of studying the biofilm-forming activity of microorganisms on the surface of synthetic polymeric materials. We used strains of Staphylococcus aureus ATCC 25923, Escherichia coli K-12, Candida albicans ATCC 10231, as well as synthetic polymeric materials - DentLight Flow light-curing composite material (nano-hybrid fluid composite; Russia), glass ionomer chemical curing Fuji 1 (Japan), cement for temporary fixation of orthopedic constructions TempBond NE (USA), acrylic, polyurethane and polyvinyl chloride. The formation of biofilms in flat-bottomed ELISA plates in this study was considered as a control group. If the polymer belonged to cold curing materials, sterile flat-bottomed tablets were used, the bottom of which was filled with a thin layer of plastic. After hardening of the plastic, biofilms were formed in the tablets. In the second series of experiments, hot cured materials cut into equal parts 5×5×1 mm in size were placed in the wells of a plate and again used to determine biofilm formation with subsequent coloring. To extract the dye, the pieces were transferred to a new plate to exclude the amount of film biomass formed on the walls of the plate wells. In both cases, cultivation was carried out at 37° C for 24-48 hours. The biomass of the film was stained with fuchsin. Statistical data processing was performed using t-Student criterion. For the threshold level of significance, the value p <0.05 was taken. It is established that the proposed options for determining biofilm forming ability are available and indicative. It was revealed that the same microorganisms have individual biofilm formation indicators for each polymer material. The light curing dental composite and polyvinyl chloride exhibit the more pronounced antiadhesive properties than cements and polyurethane. Up to date, most of the studies of biofilm formation have been carried out using glass or polystyrene, which, as a rule, are not used for the manufacture of prostheses, catheters, drains, etc., which makes it difficult to assess the true film-forming activity of microorganisms. The proposed methodological approaches, especially the second option for preparing testing samples, solve this problem. In general, the proposed approaches to testing biofilm-forming activity on polymers are very simple to implement and generally available. For an adequate study of the biofilms formation, it will be advisable to use polymer materials, directly used in medicine, rather than polystyrene tablets, the material of which is found exclusively in laboratory practice.


Assuntos
Biofilmes , Candida albicans/crescimento & desenvolvimento , Escherichia coli K12/crescimento & desenvolvimento , Cimentos Dentários , Cimentos de Ionômeros de Vidro , Poliuretanos , Cloreto de Polivinila , Óxido de Zinco
16.
Adv Funct Mater ; 28(20)2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29785178

RESUMO

Critical considerations in engineering biomaterials for rotator cuff repair include bone-tendon-like mechanical properties to support physiological loading and biophysicochemical attributes that stabilize the repair site over the long-term. In this study, UV-crosslinkable polyurethane based on quadrol (Q), hexamethylene diisocyante (H), and methacrylic anhydride (M; QHM polymers), which are free of solvent, catalyst, and photoinitiator, is developed. Mechanical characterization studies demonstrate that QHM polymers possesses phototunable bone- and tendon-like tensile and compressive properties (12-74 MPa tensile strength, 0.6-2.7 GPa tensile modulus, 58-121 MPa compressive strength, and 1.5-3.0 GPa compressive modulus), including the capability to withstand 10 000 cycles of physiological tensile loading and reduce stress concentrations via stiffness gradients. Biophysicochemical studies demonstrate that QHM polymers have clinically favorable attributes vital to rotator cuff repair stability, including slow degradation profiles (5-30% mass loss after 8 weeks) with little-to-no cytotoxicity in vitro, exceptional suture retention ex vivo (2.79-3.56-fold less suture migration relative to a clinically available graft), and competent tensile properties (similar ultimate load but higher normalized tensile stiffness relative to a clinically available graft) as well as good biocompatibility for augmenting rat supraspinatus tendon repair in vivo. This work demonstrates functionally graded, bone-tendon-like biomaterials for interfacial tissue engineering.

17.
Int J Mol Sci ; 19(7)2018 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-30011926

RESUMO

Cell responses depend on the stimuli received by the surrounding extracellular environment, which provides the cues required for adhesion, orientation, proliferation, and differentiation at the micro and the nano scales. In this study, discontinuous microcones on silicon (Si) and continuous microgrooves on polyethylene terephthalate (PET) substrates were fabricated via ultrashort pulsed laser irradiation at various fluences, resulting in microstructures with different magnitudes of roughness and varying geometrical characteristics. The topographical models attained were specifically developed to imitate the guidance and alignment of Schwann cells for the oriented axonal regrowth that occurs in nerve regeneration. At the same time, positive replicas of the silicon microstructures were successfully reproduced via soft lithography on the biodegradable polymer poly(lactide-co-glycolide) (PLGA). The anisotropic continuous (PET) and discontinuous (PLGA replicas) microstructured polymeric substrates were assessed in terms of their influence on Schwann cell responses. It is shown that the micropatterned substrates enable control over cellular adhesion, proliferation, and orientation, and are thus useful to engineer cell alignment in vitro. This property is potentially useful in the fields of neural tissue engineering and for dynamic microenvironment systems that simulate in vivo conditions.


Assuntos
Materiais Biocompatíveis/química , Ácido Láctico/química , Polietilenotereftalatos/química , Ácido Poliglicólico/química , Células de Schwann/citologia , Animais , Axônios/efeitos dos fármacos , Axônios/fisiologia , Materiais Biocompatíveis/farmacologia , Adesão Celular/efeitos dos fármacos , Diferenciação Celular/efeitos dos fármacos , Linhagem Celular , Ácido Láctico/farmacologia , Lasers , Camundongos , Regeneração Nervosa/efeitos dos fármacos , Ácido Poliglicólico/farmacologia , Copolímero de Ácido Poliláctico e Ácido Poliglicólico , Células de Schwann/fisiologia , Silício/química , Propriedades de Superfície , Engenharia Tecidual/instrumentação , Engenharia Tecidual/métodos
18.
Molecules ; 23(5)2018 04 25.
Artigo em Inglês | MEDLINE | ID: mdl-29693614

RESUMO

We report the synthesis and characterization of synthetic polymer aerogels based on dendritic-type urethane-norbornene monomers. The core of those monomers is based either on an aromatic/rigid (TIPM/Desmodur RE), or an aliphatic/flexible (Desmodur N3300) triisocyanate. The terminal norbornene groups (three at the tip of each of the three branches) were polymerized via ROMP using the inexpensive 1st generation Grubbs catalyst. The polymerization/gelation conditions were optimized by varying the amount of the catalyst. The resulting wet-gels were dried either from pentane under ambient pressure at 50 °C, or from t-butanol via freeze-drying, or by using supercritical fluid (SCF) CO2. Monomers were characterized with high resolution mass spectrometry (HRMS), ¹H- and solid-state 13C-NMR. Aerogels were characterized with ATR-FTIR and solid-state 13C-NMR. The porous network was probed with N2-sorption and SEM. The thermal stability of monomers and aerogels was studied with TGA, which also provides evidence for the number of norbornene groups that reacted via ROMP. At low densities (<0.1 g cm−3) all aerogels were highly porous (porosity > 90%), mostly macroporous materials; aerogels based on the aliphatic/flexible core were fragile, whereas aerogels containing the aromatic/rigid core were plastic, and at even lower densities (0.03 g cm−3) foamy. At higher densities (0.2⁻0.7 g cm−3) all materials were stiff, strong, and hard. At low monomer concentrations all aerogels consisted of discrete primary particles that formed spherical secondary aggregates. At higher monomer concentrations the structure consisted of fused particles with the size of the previous secondary aggregates, due to the low solubility of the developing polymer, which phase-separated and formed a primary particle network. Same-size fused aggregates were observed for both aliphatic and aromatic triisocyanate-derived aerogels, leading to the conclusion that it is not the aliphatic or aromatic core that determines phase separation, but rather the solubility of the polymeric backbone (polynorbornene) that is in both cases the same. The material properties were compared to those of analogous aerogels bearing only one norbornene moiety at the tip of each branch deriving from the same cores.


Assuntos
Norbornanos/química , Polímeros/síntese química , Uretana/química , Géis/síntese química , Géis/química , Estrutura Molecular , Tamanho da Partícula , Polímeros/química
19.
Mol Pharm ; 14(10): 3609-3616, 2017 10 02.
Artigo em Inglês | MEDLINE | ID: mdl-28872319

RESUMO

Injectable biomaterials play a critical role in many biomedical applications. These materials, however, often have limitations in mechanical and drug-eluting properties attributed to their high water content and the weak secondary forces holding them together. Here we describe a new injectable material based on two complementary water-free, prepolymers modified with succinimidyl carbonate (SC) or with NH2 end groups that form a stiff matrix upon mixing. Cross-linking involves an immediate reaction between PEG4-SC and PEG4-NH2 that forms carbamate bonds and a delayed reaction of PEG4-SC with hydroxyl functional groups that forms carbonate bonds. The mechanical properties, swelling, and erosion kinetics of this biomaterial can be fine-tuned by varying the ratio between the two prepolymers. Bovine serum albumin and poorly water-soluble free base doxorubicin were readily loaded into this system, resulting in a high drug loading content attributed to the absence of water in the formulation. Controlled release over a period of 1 to 30 days was observed, depending on mixture composition and drug properties. The injectable nature of the formulation, its tailored mechanical properties, the fact that it can be cross-linked by two separate mechanisms, and its ability to incorporate and release hydrophilic and hydrophobic drugs make it very attractive as a drug delivery system.


Assuntos
Materiais Biocompatíveis/química , Sistemas de Liberação de Medicamentos/métodos , Hidrogéis/química , Carbonatos/química , Química Farmacêutica , Reagentes de Ligações Cruzadas/química , Doxorrubicina/farmacologia , Composição de Medicamentos/métodos , Liberação Controlada de Fármacos , Injeções , Polietilenoglicóis/química , Succinimidas/química
20.
Anal Bioanal Chem ; 408(12): 3165-75, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-26892638

RESUMO

The uptake calibration of more than 12 non-polar organic contaminants by 3 polymeric materials is shown: bare polydimetilsiloxane (PDMS, stir-bars), polyethersulfone tubes and membranes (PES) and polyoxymethylene membranes (POM), both in their free form and membrane-enclosed sorptive coating (MESCO). The calibration process was carried out exposing the samplers to a continuous flow of contaminated water at 100 ng mL(-1) for up to 28 days, and, consequently, the sampling rates (Rs, mL day(-1)) of several organic microcontaminants were provided for the first time. In situ Rs values were also determined disposing the samplers in the effluent of a wastewater treatment plant. Finally, these passive samplers were applied to monitor the effluents of two wastewater treatment plants. This application lead to the confirmation of the presence of galaxolide, tonalide and 4-tert-octylphenol at high ng mL(-1) levels, as well as the identification of compounds like some phthalates and alkylphenols at levels below the detection limits for active sampling methods.

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