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1.
J Mater Chem B ; 9(47): 9700-9710, 2021 12 08.
Artigo em Inglês | MEDLINE | ID: mdl-34779468

RESUMO

Gold nanoparticles (AuNPs) were surface-engineered with a cationic corona to enhance the incorporation of photosensitizers for photodynamic therapy (PDT). The cationic corona composed of poly(2-(dimethylamino)ethyl methacrylate) was atom transfer radical-polymerized on the surface of the AuNPs. The cationic corona of the engineered surface was characterized by dynamic light scattering, electron microscopy, Raman spectroscopy, and mass spectroscopy. Chlorin-e6 (Ce6) incorporated onto the surface-engineered AuNPs exhibited higher cell incorporation efficiency than bare AuNPs. Ce6-incorporated AuNPs were confirmed to release singlet oxygen upon NIR irradiation. Compared to Ce6, Ce6-incorporated AuNPs exhibited higher cellular uptake and cytotoxicity against cancer cells in an irradiation time-dependent manner. Near-infrared-irradiated animals administered Ce6-incorporated AuNPs exhibited higher levels of tumor suppression without noticeable body weight loss. This result was attributed to the higher localization of Ce6 at the tumor sites to induce cancer cell apoptosis. Thus, we envision that engineered AuNPs with cationic corona can be tailored to effectively deliver photosensitizers to tumor sites for photodynamic therapy.


Assuntos
Antineoplásicos/uso terapêutico , Nanopartículas Metálicas/uso terapêutico , Neoplasias/tratamento farmacológico , Fármacos Fotossensibilizantes/uso terapêutico , Animais , Antineoplásicos/síntese química , Antineoplásicos/efeitos da radiação , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Clorofilídeos/síntese química , Clorofilídeos/efeitos da radiação , Clorofilídeos/uso terapêutico , Feminino , Ouro/química , Ouro/efeitos da radiação , Humanos , Raios Infravermelhos , Nanopartículas Metálicas/química , Nanopartículas Metálicas/efeitos da radiação , Metacrilatos/síntese química , Metacrilatos/química , Metacrilatos/efeitos da radiação , Camundongos Endogâmicos BALB C , Camundongos Nus , Nylons/síntese química , Nylons/química , Nylons/efeitos da radiação , Fotoquimioterapia , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/efeitos da radiação , Polimerização , Oxigênio Singlete/metabolismo , Ensaios Antitumorais Modelo de Xenoenxerto
2.
ACS Appl Mater Interfaces ; 13(39): 46938-46950, 2021 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-34559507

RESUMO

Smart response hydrogel has a broad application prospect in human health real-time monitoring due to its responses to a variety of stimuli. In this study, we developed a novel smart hydrogel dressing based on conductive MXene nanosheets and a temperature-sensitive PNIPAm polymer. γ-Methacryloxypropyltrimethoxysilane (KH570) was selected to functionalize the surface of MXene further to improve the interface compatibility between MXene and PNIPAm. Our prepared K-M/PNIPAm hydrogel was found to have a strain-sensitive property, as well as a respond to NIR phase change and volume change. When applied as a strain flexible sensor, this K-M/PNIPAm hydrogel exhibited a high strain sensitivity with a gauge factor (GF) of 4.491, a broad working strain range of ≈250%, a fast response of ∼160 ms, and good cycle stability (i.e., 3000 s at 20% strain). Besides, this K-M/PNIPAm hydrogel can be used as an efficient NIR light-controlled drug release carrier to achieve on-demand drug release. This work paved the way for the application of smart response hydrogel in human health real-time monitoring and NIR-controlled drug release functions.


Assuntos
Portadores de Fármacos/química , Hidrogéis/química , Materiais Inteligentes/química , Resinas Acrílicas/química , Resinas Acrílicas/farmacologia , Resinas Acrílicas/efeitos da radiação , Resinas Acrílicas/toxicidade , Animais , Linhagem Celular , Portadores de Fármacos/farmacologia , Portadores de Fármacos/efeitos da radiação , Portadores de Fármacos/toxicidade , Liberação Controlada de Fármacos/efeitos da radiação , Elasticidade , Hidrogéis/farmacologia , Hidrogéis/efeitos da radiação , Hidrogéis/toxicidade , Raios Infravermelhos , Masculino , Metacrilatos/química , Metacrilatos/farmacologia , Metacrilatos/efeitos da radiação , Metacrilatos/toxicidade , Camundongos , Ratos Sprague-Dawley , Silanos/química , Silanos/farmacologia , Silanos/efeitos da radiação , Silanos/toxicidade , Pele/efeitos dos fármacos , Materiais Inteligentes/farmacologia , Materiais Inteligentes/efeitos da radiação , Materiais Inteligentes/toxicidade , Estresse Mecânico , Tetraciclina/química , Titânio/química , Titânio/farmacologia , Titânio/efeitos da radiação , Titânio/toxicidade , Cicatrização/efeitos dos fármacos
3.
ACS Appl Mater Interfaces ; 13(34): 40290-40301, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-34410697

RESUMO

Hydrogel patches with high toughness, stretchability, and adhesive properties are critical to healthcare applications including wound dressings and wearable devices. Gelatin methacryloyl (GelMA) provides a highly biocompatible and accessible hydrogel platform. However, low tissue adhesion and poor mechanical properties of cross-linked GelMA patches (i.e., brittleness and low stretchability) have been major obstacles to their application for sealing and repair of wounds. Here, we show that adding dopamine (DA) moieties in larger quantities than those of conjugated counterparts to the GelMA prepolymer solution followed by alkaline DA oxidation could result in robust mechanical and adhesive properties in GelMA-based hydrogels. In this way, cross-linked patches with ∼140% stretchability and ∼19 000 J/m3 toughness, which correspond to ∼5.7 and ∼3.3× improvement, respectively, compared to that of GelMA controls, were obtained. The DA oxidization in the prepolymer solution was found to play an important role in activating adhesive properties of cross-linked GelMA patches (∼4.0 and ∼6.9× increase in adhesion force under tensile and shear modes, respectively) due to the presence of reactive oxidized quinone species. We further conducted a parametric study on the factors such as UV light parameters, the photoinitiator type (i.e., lithium phenyl-2,4,6-trimethylbenzoylphosphinate, LAP, versus 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, Irgacure 2959), and alkaline DA oxidation to tune the cross-linking density and thereby hydrogel compliance for better adhesive properties. The superior adhesion performance of the resulting hydrogel along with in vitro cytocompatibility demonstrated its potential for use in skin-attachable substrates.


Assuntos
Adesivos/química , Gelatina/química , Hidrogéis/química , Indóis/química , Metacrilatos/química , Polímeros/química , Adesivos/síntese química , Adesivos/toxicidade , Animais , Sobrevivência Celular/efeitos dos fármacos , Reagentes de Ligações Cruzadas/química , Reagentes de Ligações Cruzadas/efeitos da radiação , Reagentes de Ligações Cruzadas/toxicidade , Dopamina/química , Dopamina/efeitos da radiação , Gelatina/efeitos da radiação , Gelatina/toxicidade , Hidrogéis/síntese química , Hidrogéis/toxicidade , Indóis/síntese química , Indóis/toxicidade , Teste de Materiais , Metacrilatos/efeitos da radiação , Metacrilatos/toxicidade , Camundongos , Células NIH 3T3 , Polimerização/efeitos da radiação , Polímeros/síntese química , Polímeros/toxicidade , Pele/metabolismo , Suínos , Resistência à Tração , Raios Ultravioleta
4.
Macromol Biosci ; 21(1): e2000317, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-33043610

RESUMO

Bioinks play a key role in determining the capability of the biofabricatoin processes and the resolution of the printed constructs. Excellent biocompatibility, tunable physical properties, and ease of chemical or biological modifications of gelatin methacryloyl (GelMA) have made it an attractive choice as bioinks for biomanufacturing of various tissues or organs. However, the current preparation methods for GelMA-based bioinks lack the ability to tailor their physical properties for desired bioprinting methods. Inherently, GelMA prepolymer solution exhibits a fast sol-gel transition at room temperature, which is a hurdle for its use in stereolithography (SLA) bioprinting. Here, synthesis parameters are optimized such as solvents, pH, and reaction time to develop GelMA bioinks which have a slow sol-gel transition at room temperature and visible light crosslinkable functions. A total of eight GelMA combinations are identified as suitable for digital light processing (DLP)-based SLA (DLP-SLA) bioprinting through systematic characterizations of their physical and rheological properties. Out of various types of GelMA, those synthesized in reverse osmosis (RO) purified water (referred to as RO-GelMA) are regarded as most suitable to achieve high DLP-SLA printing resolution. RO-GelMA-based bioinks are also found to be biocompatible showing high survival rates of encapsulated cells in the photocrosslinked gels. Additionally, the astrocytes and fibroblasts are observed to grow and integrate well within the bioprinted constructs. The bioink's superior physical and photocrosslinking properties offer pathways of tuning the scaffold microenvironment and highlight the applicability of developed GelMA bioinks in various tissue engineering and regenerative medicine applications.


Assuntos
Bioimpressão , Gelatina/farmacologia , Metacrilatos/farmacologia , Estereolitografia , Engenharia Tecidual , Sobrevivência Celular/efeitos dos fármacos , Gelatina/síntese química , Gelatina/efeitos da radiação , Humanos , Hidrogéis/química , Hidrogéis/farmacologia , Tinta , Luz , Metacrilatos/síntese química , Metacrilatos/efeitos da radiação , Impressão Tridimensional , Alicerces Teciduais/química
5.
ACS Appl Mater Interfaces ; 12(51): 56805-56814, 2020 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-33289537

RESUMO

There has been significant interest in the use of peptides as antimicrobial agents, and peptide containing hydrogels have been proposed as biological scaffolds for various applications. Limited stability and rapid clearance of small molecular weight peptides pose challenges to their widespread implementation. As a common approach, antibacterial peptides are physically loaded into hydrogel scaffolds, which leads to continuous release through the passive mode with spatial control but provides limited control over drug dosage. Although utilization of peptide covalent linkage onto hydrogels addresses partially this problem, the peptide release is commonly too slow. To alleviate these challenges, in this work, maleimide-modified antimicrobial peptides are covalently conjugated onto furan-based cryogel (CG) scaffolds via the Diels-Alder cycloaddition at room temperature. The furan group offers a handle for specific loading of the peptides, thus minimizing passive and burst drug release. The porous nature of the CG matrix provides rapid loading and release of therapeutic peptides, apart from high water uptake. Interfacing the peptide adduct containing a CG matrix with a reduced graphene oxide-modified Kapton substrate allows "on-demand" photothermal heating upon near-infrared (NIR) irradiation. A fabricated photothermal device enables tunable and efficient peptide release through NIR exposure to kill bacteria. Apart from spatial confinement offered by this CG-based bandage, the selective ablation of planktonic Staphylococcus aureus is demonstrated. It can be envisioned that this modular "on-demand" peptide-releasing device can be also employed for other topical applications by appropriate choice of therapeutic peptides.


Assuntos
Antibacterianos/farmacologia , Peptídeos Catiônicos Antimicrobianos/farmacologia , Criogéis/química , Infecções Estafilocócicas/tratamento farmacológico , Antibacterianos/química , Peptídeos Catiônicos Antimicrobianos/química , Criogéis/síntese química , Criogéis/efeitos da radiação , Reação de Cicloadição , Liberação Controlada de Fármacos , Escherichia coli/efeitos dos fármacos , Furanos/síntese química , Furanos/química , Furanos/efeitos da radiação , Células HeLa , Calefação , Humanos , Raios Infravermelhos , Metacrilatos/síntese química , Metacrilatos/química , Metacrilatos/efeitos da radiação , Testes de Sensibilidade Microbiana , Polietilenoglicóis/síntese química , Polietilenoglicóis/química , Polietilenoglicóis/efeitos da radiação , Staphylococcus aureus/efeitos dos fármacos
6.
Mar Drugs ; 17(10)2019 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-31569386

RESUMO

As an important natural polysaccharide biomaterial from marine organisms, alginate and its derivatives have shown great potential in the fabrication of biomedical materials such as tissue engineering, cell biology, drug delivery, and pharmaceuticals due to their excellent biological activity and controllable physicochemical properties. Ionic crosslinking is the most common method used in the preparation of alginate-based biomaterials, but ionic crosslinked alginate hydrogels are prone to decompose in physiological solution, which hinders their applications in biomedical fields. In this study, dual crosslinked alginate hydrogel microfibers were prepared for the first time. The ionic crosslinked methacrylated alginate (Alg-MA) hydrogel microfibers fabricated by Microfluidic Fabrication (MFF) system were exposed to ultraviolet (UV) light and covalent crosslink between methacrylate groups avoided the fracture of dual crosslinked macromolecular chains in organizational environment. The chemical structures, swelling ratio, mechanical performance, and stability were investigated. Cell-encapsulated dual crosslinked Alg-MA hydrogel microfibers were fabricated to explore the application in tissue engineering for the first time. The hydrogel microfibers provided an excellent 3D distribution and growth conditions for cells. Cell-encapsulated Alg-MA microfibers scaffolds with functional 3D tissue structures were developed which possessed great potential in the production of next-generation scaffolds for tissue engineering and regenerative medicine.


Assuntos
Alginatos/química , Materiais Biocompatíveis/química , Hidrogéis/síntese química , Engenharia Tecidual/métodos , Alginatos/efeitos da radiação , Técnicas de Química Sintética/métodos , Hidrogéis/efeitos da radiação , Metacrilatos/química , Metacrilatos/efeitos da radiação , Microquímica/métodos , Técnicas Analíticas Microfluídicas , Alicerces Teciduais/química , Raios Ultravioleta
7.
Nat Chem ; 11(6): 578-586, 2019 06.
Artigo em Inglês | MEDLINE | ID: mdl-30988414

RESUMO

Polymerization reactions conducted inside cells must be compatible with the complex intracellular environment, which contains numerous molecules and functional groups that could potentially prevent or quench polymerization reactions. Here we report a strategy for directly synthesizing unnatural polymers in cells through free radical photopolymerization using a number of biocompatible acrylic and methacrylic monomers. This offers a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules that have the ability to alter cellular motility, label cells by the generation of fluorescent polymers for long-term tracking studies, as well as generate a variety of nanostructures within cells. It is remarkable that free radical polymerization chemistry can take place within such complex cellular environments. This demonstration opens up a multitude of new possibilities for how chemists can modulate cellular function and behaviour and for understanding cellular behaviour in response to the generation of free radicals.


Assuntos
Radicais Livres/química , Polimerização/efeitos da radiação , Ácidos Polimetacrílicos/síntese química , Poliestirenos/síntese química , Acrilatos/química , Acrilatos/efeitos da radiação , Acrilatos/toxicidade , Citoesqueleto de Actina/efeitos dos fármacos , Compostos de Anilina/química , Compostos de Anilina/efeitos da radiação , Compostos de Anilina/toxicidade , Movimento Celular/efeitos dos fármacos , Fluorescência , Células HeLa , Humanos , Metacrilatos/química , Metacrilatos/efeitos da radiação , Metacrilatos/toxicidade , Propano/análogos & derivados , Propano/química , Propano/efeitos da radiação , Fase S/efeitos dos fármacos , Estirenos/química , Estirenos/efeitos da radiação , Estirenos/toxicidade , Raios Ultravioleta , Compostos de Vinila/química , Compostos de Vinila/efeitos da radiação , Compostos de Vinila/toxicidade
8.
Talanta ; 192: 360-367, 2019 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-30348403

RESUMO

A novel composite monolithic column based on graphene oxide-trimethyl-2-methacroyloxyethylammonium chloride-titania (GO-META-TiO2) was developed for the enrichment of phosphopeptides. META was proposed as a "bridge" to connect GO and TiO2 species to prepare GO-META-TiO2 composite. This high surface area composite (surface area = 196.93 m2 g-1) was fixed in the monolithic column via an in situ UV polymerization process. In-tube solid phase microextraction (IT-SPME) using this composite was coupled with matrix-assisted laser desorption ionization time-of-flight-mass spectrometry (MALDI-TOF-MS) for the enrichment and detection of phosphorylated peptides from a digestion mixture of α-casein, ß-casein, and bovine serum albumin (BSA) in molar ratios of 1:1:1, 1:1:10, and 1:1:100. The key factors affecting the IT-SPME of the phosphopeptides, such as the elution solution concentrations, the extraction flow rate, and the elution flow rate were comprehensively investigated. For further demonstration, this method was employed for the enrichment and detection of phosphorylated peptides from digested chicken egg white. The obtained results indicated that the GO-META-TiO2 composite monolithic column rapidly and efficiently captured the phosphopeptides present in these complex biological samples, even in the 10 fmol ß-casein tryptic digest. We therefore propose that the reported GO-META-TiO2 composite monolithic column possesses a suitable affinity for the selective extraction of phosphopeptides from biological samples. This method paves a way in extending the application of nanomaterials.


Assuntos
Nanocompostos/química , Fosfopeptídeos/análise , Microextração em Fase Sólida/instrumentação , Animais , Sequência de Bases , Caseínas/química , Bovinos , Galinhas , Colina/análogos & derivados , Colina/síntese química , Colina/química , Colina/efeitos da radiação , Clara de Ovo/química , Grafite/síntese química , Grafite/química , Grafite/efeitos da radiação , Metacrilatos/síntese química , Metacrilatos/química , Metacrilatos/efeitos da radiação , Nanocompostos/efeitos da radiação , Polimerização/efeitos da radiação , Soroalbumina Bovina/química , Microextração em Fase Sólida/métodos , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Titânio/química , Titânio/efeitos da radiação , Tripsina/química , Raios Ultravioleta
9.
J Am Chem Soc ; 140(47): 16106-16114, 2018 11 28.
Artigo em Inglês | MEDLINE | ID: mdl-30388369

RESUMO

The current challenge for polymeric nanoreactors is to precisely control the membrane permeability between permeable, impermeable, and semipermeable at defined pH. Additionally, the synthetic methods are obstructed by tedious purification processes, especially when polymer multiblocks are required in the membrane of capsules to achieve different responsiveness and functions. Here, we report a rapid one-pot synthesis of ABA-type triblock copolymer brushes on silica template via surface-initiated single electron transfer living radical polymerization (SI-SET-LRP). It is worth noting that there is no purification between the successive block formation steps, since each step is taken to full translation within 20 min. After removing the template, hollow capsules with cross-linked membrane are obtained and have been used as multiresponsive nanoreactors for enzymatic reactions. Their membrane permeability is triggered primarily by temperature and secondarily by pH to allow controlled enzymatic reactions to be reversibly addressable between "permeable", "semipermeable", and "impermeable" valve-like membrane status. These valve-like features highlight the significant potential of hollow capsules, for example, in the fields of synthetic biology and enzyme-deficient disease therapeutic applications.


Assuntos
Resinas Acrílicas/química , Lipossomos/química , Metacrilatos/química , Nylons/química , Resinas Acrílicas/síntese química , Resinas Acrílicas/efeitos da radiação , Animais , Aspergillus niger/enzimologia , Glucose/química , Glucose Oxidase/química , Guaiacol/química , Cavalos , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Lipossomos/síntese química , Metacrilatos/síntese química , Metacrilatos/efeitos da radiação , Mioglobina/química , Nylons/síntese química , Nylons/efeitos da radiação , Permeabilidade , Polimerização , Dióxido de Silício/química , Temperatura
10.
Braz Oral Res ; 32: e116, 2018 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-30462750

RESUMO

The aim of this study was to analyze the efficiency of experimental light-curing resin cements (ERCs) with a ternary photo-initiator system containing diphenyliodonium hexafluorphosphate (DPI) and different amines on retention of glass-fiber posts to dentin (GFP). ERCs formulations: a 1:1 mass ratio of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenylpropane and triethyleneglycol dimethacrylate. Camphorquinone was used as initiator. Six experimental groups were established according to the amine used: [ethyl-4-(dimethylamino)benzoate-EDMAB or 2-(dimethylamino)ethyl methacrylate-DMAEMA] and the concentration of DPI (0, 0.5 mol%, 1 mol%). The resin cements Variolink II (dual- and light-cured versions) were used as commercial reference. Eighty recently extracted bovine incisors (n = 10) were selected for this study. The roots were prepared and the fiber posts were cemented with the resin cement specified for each experimental group. Specimens from coronal, middle, and apical thirds of the root were subjected to push-out bond strength test 24 hours after bonding. Data were subjected to split-plot ANOVA and the Tukey test (p = 0.05). ERCs containing DPI showed statistically significant higher bond strengths compared with ERCs without DPI. ERCs containing DPI were statistically similar to VARIOLINK II - dual-cured and superior to VARIOLINK II - light-cured (except for EDMAB - 1DPI in the medium third and DMAEMA - 1DPI in the coronal third). Different amines did not influence post retention. The apical root region showed the lowest bond strength for the groups EDAB-0DPI, DMAEMA-0DPI and VARIOLINK II light-cured. Light-cured ERCs containing DPI were efficient for GFP retention to radicular dentin, with similar behaviour to that of dual-curing commercial resin cement.


Assuntos
Compostos de Bifenilo/química , Dentina/efeitos dos fármacos , Cura Luminosa de Adesivos Dentários/métodos , Oniocompostos/química , Fotoiniciadores Dentários/química , Técnica para Retentor Intrarradicular , Cimentos de Resina/química , Ápice Dentário/efeitos dos fármacos , Análise de Variância , Compostos de Bifenilo/efeitos da radiação , Lâmpadas de Polimerização Dentária , Dentina/efeitos da radiação , Vidro/química , Vidro/efeitos da radiação , Teste de Materiais , Metacrilatos/química , Metacrilatos/efeitos da radiação , Oniocompostos/efeitos da radiação , Fotoiniciadores Dentários/efeitos da radiação , Polimerização , Cimentos de Resina/efeitos da radiação , Fatores de Tempo , Ápice Dentário/efeitos da radiação , Fraturas dos Dentes , para-Aminobenzoatos/química , para-Aminobenzoatos/efeitos da radiação
11.
Eur J Pharm Sci ; 123: 217-227, 2018 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-30048800

RESUMO

UV-curable gels, which polymerise into long-lasting films upon exposure to UVA, have been identified as potential topical drug carriers for the treatment of nail diseases. Limitations of such films include incomplete drug release and low ungual drug permeation. The aim of the work herein was therefore to investigate two strategies, namely: (1) increasing drug release from the film, and (2) increasing nailplate permeability, with the ultimate goal of enhancing ungual drug permeation. To increase drug release via Strategy 1, a UV-LED lamp (whose emitted light was suboptimal for gel polymerisation) was used, and it was hypothesised that such a lamp would result in films that are less polymerised/cross-linked and where the drugs are less 'trapped'. Indeed, the suboptimal lamp influenced polymerisation, such that the films were thinner, had lower glass transition temperatures and enabled a slightly greater (by 15%) drug release of one of the two drugs tested. However, the greater drug release had only a modest impact on ungual drug permeation. To evaluate Strategy 2, i.e. increase nailplate permeability, chemical ungual enhancers, 2-mercaptoethanol (ME), 2-methyl pyrrolidone (NMP), PEG 200 and water were incorporated within the UV-cured films. These chemicals caused increased ungual drug permeation, with ME showing the greatest (by 140%), and water showing the least (by 20%) increase in the amount of drug permeated by day 30. Surprisingly, these chemicals also caused increased drug release from the films, with ME once again having the greatest effect (by 51%) and water the least effect (by 12%). It seems that these chemicals were increasing ungual drug permeation via their influence on drug release (i.e. via their impact on the film) as well as via their influence on the nail itself. We conclude that, of the two strategies tested, the second strategy proved to be more successful at enhancing ungual drug permeation.


Assuntos
Portadores de Fármacos , Mercaptoetanol/farmacologia , Morfolinas/administração & dosagem , Unhas/efeitos dos fármacos , Polímeros/efeitos da radiação , Terbinafina/administração & dosagem , Raios Ultravioleta , Absorção Fisiológica/efeitos dos fármacos , Administração Tópica , Adolescente , Adulto , Idoso , Composição de Medicamentos , Liberação Controlada de Fármacos , Humanos , Cinética , Mercaptoetanol/química , Metacrilatos/química , Metacrilatos/efeitos da radiação , Pessoa de Meia-Idade , Morfolinas/química , Morfolinas/metabolismo , Unhas/metabolismo , Permeabilidade , Polietilenoglicóis/química , Polietilenoglicóis/farmacologia , Polimerização , Polímeros/química , Pirrolidinas/química , Pirrolidinas/farmacologia , Solubilidade , Tecnologia Farmacêutica/métodos , Terbinafina/química , Terbinafina/metabolismo , Uretana/análogos & derivados , Uretana/química , Uretana/efeitos da radiação , Água/química , Água/farmacologia , Adulto Jovem
12.
Phys Med Biol ; 63(6): 06NT01, 2018 03 12.
Artigo em Inglês | MEDLINE | ID: mdl-29528035

RESUMO

Recent developments in radiation therapy aimed at more precise dose delivery along with higher dose gradients (dose painting) and more efficient dose delivery with higher dose rates e.g. flattening filter free (FFF) irradiation. Magnetic-resonance-imaging based polymer gel dosimetry offers 3D information for precise dose delivery techniques. Many of the proposed polymer gels have been reported to exhibit a dose response, measured as relaxation rate ΔR2(D), which is dose rate dependent. A lack of or a reduced dose-rate sensitivity is very important for dosimetric accuracy, especially with regard to the increasing clinical use of FFF irradiation protocols with LINACs at high dose rates. Some commonly used polymer gels are based on Methacrylic-Acid-Gel-Initiated-by-Copper (MAGIC). Here, we report on the dose sensitivity (ΔR2/ΔD) of MAGIC-type gels with different oxygen scavenger concentration for their specific dependence on the applied dose rate in order to improve the dosimetric performance, especially for high dose rates. A preclinical x-ray machine ('Yxlon', E = 200 kV) was used for irradiation to cover a range of dose rates from low [Formula: see text] min = 0.6 Gy min-1 to high [Formula: see text] max = 18 Gy min-1. The dose response was evaluated using R2-imaging of the gel on a human high-field (7T) MR-scanner. The results indicate that all of the investigated dose rates had an impact on the dose response in polymer gel dosimeters, being strongest in the high dose region and less effective for low dose levels. The absolute dose rate dependence [Formula: see text] of the dose response in MAGIC-type gel is significantly reduced using higher concentrations of oxygen scavenger at the expense of reduced dose sensitivity. For quantitative dose evaluations the relative dose rate dependence of a polymer gel, normalized to its sensitivity is important. Based on this normalized sensitivity the dose rate sensitivity was reduced distinctly using an increased oxygen scavenger concentration with reference to standard MAGIC-type gel formulation at high dose rate levels. The proposed gel composition with high oxygen scavenger concentration exhibits a larger linear active dose response and might be used especially in FFF-radiation applications and preclinical dosimetry at high dose rates. We propose in general to use high dose rates for calibration and evaluation as the change in relative dose sensitivity is reduced at higher dose rates in all of the investigated gel types.


Assuntos
Ácido Ascórbico/química , Sulfato de Cobre/química , Sequestradores de Radicais Livres/química , Gelatina/química , Hidroquinonas/química , Imageamento por Ressonância Magnética/métodos , Metacrilatos/química , Oxigênio/química , Polímeros/química , Radiometria/métodos , Ácido Ascórbico/efeitos da radiação , Calibragem , Sulfato de Cobre/efeitos da radiação , Gelatina/efeitos da radiação , Humanos , Hidroquinonas/efeitos da radiação , Metacrilatos/efeitos da radiação , Polímeros/efeitos da radiação , Dosagem Radioterapêutica , Planejamento da Radioterapia Assistida por Computador
13.
Braz. oral res. (Online) ; 32: e116, 2018. tab, graf
Artigo em Inglês | LILACS | ID: biblio-974442

RESUMO

Abstract The aim of this study was to analyze the efficiency of experimental light-curing resin cements (ERCs) with a ternary photo-initiator system containing diphenyliodonium hexafluorphosphate (DPI) and different amines on retention of glass-fiber posts to dentin (GFP). ERCs formulations: a 1:1 mass ratio of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenylpropane and triethyleneglycol dimethacrylate. Camphorquinone was used as initiator. Six experimental groups were established according to the amine used: [ethyl-4-(dimethylamino)benzoate-EDMAB or 2-(dimethylamino)ethyl methacrylate-DMAEMA] and the concentration of DPI (0, 0.5 mol%, 1 mol%). The resin cements Variolink II (dual- and light-cured versions) were used as commercial reference. Eighty recently extracted bovine incisors (n = 10) were selected for this study. The roots were prepared and the fiber posts were cemented with the resin cement specified for each experimental group. Specimens from coronal, middle, and apical thirds of the root were subjected to push-out bond strength test 24 hours after bonding. Data were subjected to split-plot ANOVA and the Tukey test (p = 0.05). ERCs containing DPI showed statistically significant higher bond strengths compared with ERCs without DPI. ERCs containing DPI were statistically similar to VARIOLINK II - dual-cured and superior to VARIOLINK II - light-cured (except for EDMAB - 1DPI in the medium third and DMAEMA - 1DPI in the coronal third). Different amines did not influence post retention. The apical root region showed the lowest bond strength for the groups EDAB-0DPI, DMAEMA-0DPI and VARIOLINK II light-cured. Light-cured ERCs containing DPI were efficient for GFP retention to radicular dentin, with similar behaviour to that of dual-curing commercial resin cement.


Assuntos
Oniocompostos/química , Compostos de Bifenilo/química , Técnica para Retentor Intrarradicular , Ápice Dentário/efeitos dos fármacos , Cimentos de Resina/química , Dentina/efeitos dos fármacos , Cura Luminosa de Adesivos Dentários/métodos , Fotoiniciadores Dentários/química , Oniocompostos/efeitos da radiação , Fatores de Tempo , Fraturas dos Dentes , Compostos de Bifenilo/efeitos da radiação , Teste de Materiais , Análise de Variância , Ápice Dentário/efeitos da radiação , Cimentos de Resina/efeitos da radiação , Dentina/efeitos da radiação , Lâmpadas de Polimerização Dentária , Fotoiniciadores Dentários/efeitos da radiação , Polimerização , para-Aminobenzoatos/efeitos da radiação , para-Aminobenzoatos/química , Vidro/efeitos da radiação , Vidro/química , Metacrilatos/efeitos da radiação , Metacrilatos/química
14.
J Dent ; 65: 101-109, 2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28750778

RESUMO

OBJECTIVE: 1) to determine the moment during the redox polymerization reaction of dual cure cements at which to photo-activate the material in order to reduce the polymerization stress, and 2) to evaluate possible synergistic effects between adding chain transfer agents and delayed photo-activation. METHODS: The two pastes of an experimental dual-cure material were mixed, and the polymerization kinetics of the redox phase was followed. The moment when the material reached its maximum rate of redox polymerization (MRRP) of cement was determined. The degree of conversion (DC) and maximum rates of polymerization (Rpmax) were assessed for materials where: the photoactivation immediately followed material mixing, at MRRP, 1min before and 1min after MRRP. Thio-urethane (TU) additives were synthesized and added to the cement (20% wt), which was then cured under the same conditions. The polymerization kinetics was evaluated for both cements photo-activated immediately or at MRRP, followed by measurements of polymerization stress, flexural strength (FS) and elastic modulus (EM). Knoop hardness was measured before and after ethanol storage. RESULTS: Photo-activating the cement at or after MRRP reduced the Rpmax and the polymerization stress. Addition of TU promoted additional and more significant reduction, while not affecting the Rpmax. Greater hardness loss was observed for cements with TU, but the final hardness was similar for all experimental conditions. Addition of TU slightly reduced the EM and did not affect the FS. CONCLUSION: Delayed photo-activation and addition of TU significantly reduce the polymerization stress of dual-cured cements.


Assuntos
Cura Luminosa de Adesivos Dentários , Polimerização/efeitos da radiação , Cimentos de Resina/efeitos da radiação , Autocura de Resinas Dentárias , Uretana/química , Uretana/efeitos da radiação , Compostos de Bário/química , Compostos de Bário/uso terapêutico , Bis-Fenol A-Glicidil Metacrilato/química , Bis-Fenol A-Glicidil Metacrilato/efeitos da radiação , Hidroxitolueno Butilado , Módulo de Elasticidade , Dureza , Cinética , Teste de Materiais , Metacrilatos/química , Metacrilatos/efeitos da radiação , Oxirredução , Projetos Piloto , Polietilenoglicóis/química , Polietilenoglicóis/efeitos da radiação , Ácidos Polimetacrílicos/química , Ácidos Polimetacrílicos/efeitos da radiação , Dióxido de Silício/química , Dióxido de Silício/uso terapêutico , Estresse Mecânico , Propriedades de Superfície , Resistência à Tração , Fatores de Tempo , para-Aminobenzoatos
15.
J Dent ; 63: 51-59, 2017 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-28576660

RESUMO

OBJECTIVES: to determine the mode of light transmission and its impact on the polymerisation kinetic in modern bulk-fill resin-based composites (B-RBC). MATERIALS AND METHODS: Four low-viscosity methacrylate-based and one high-viscosity ormocer-based B-RBCs were considered. One material was available in three different shades that were all analyzed. Polymerization kinetic and light transmittance were assessed in 2 and 4mm specimen depths. Incident and transmitted irradiance and radiant exposure were measured in real-time on a laboratory-grade spectrometer. RESULTS: A progressive enhanced light transmittance during polymerisation was identified in all materials except for TetricEvoFlow BulkFill, which became progressively opaque in all shades. One-way ANOVA and multivariate analysis (α=0.05) were performed. The parameter material has a significant (p<0.001) effect on DC (ηP2=0.856) and light transmittance parameters (irradiance, ηP2=0.965; radiant exposure, ηP2=0.956); specimen depth influences only transmittance (ηP2=0.978; 0.980). DC variation in time was best described by an exponential sum function (R2>0.95), differentiating between the gel- and the glass-phase and revealing a faster initiation of polymerization and a slower transition into the glass-phase by lowering the filler volume. Depth retarded the transition into the glass-phase, but did not alter DC measured 300s post-irradiation. Moderate inverse correlation was identified among DC and filler volume% (-0.646) or filler weight% (-0.403), while no correlation among DC and light transmittance (p=0.141; 0.125). The maximal rate of carbon-carbon double bond conversion varied within the analyzed materials but was independent from specimen's depths. CONCLUSIONS: Light transmission changes during polymerization do not alter polymerization kinetics in modern B-RBCs. DC 300s post-irradiation was maintained with depth, while light was attenuated, the faster the more translucent the material was. DC and quality of curing cannot be related to light transmittance in B-RBCs.


Assuntos
Resinas Compostas/química , Resinas Compostas/efeitos da radiação , Lâmpadas de Polimerização Dentária , Materiais Dentários/química , Materiais Dentários/efeitos da radiação , Teste de Materiais , Transição de Fase/efeitos da radiação , Polimerização/efeitos da radiação , Cimentos Dentários/química , Cimentos Dentários/efeitos da radiação , Vidro/química , Vidro/efeitos da radiação , Cinética , Cura Luminosa de Adesivos Dentários/métodos , Metacrilatos/química , Metacrilatos/efeitos da radiação , Análise Multivariada , Cerâmicas Modificadas Organicamente , Doses de Radiação , Espectroscopia de Infravermelho com Transformada de Fourier , Estresse Mecânico , Propriedades de Superfície , Fatores de Tempo , Viscosidade
16.
Chem Commun (Camb) ; 53(23): 3315-3318, 2017 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-28078346
17.
Macromol Rapid Commun ; 38(13)2017 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-28004494

RESUMO

Well-defined poly(methyl methacrylate) (PMMA) and poly(methyl acrylate) (PMA) are prepared via photochemically induced atom transfer radical polymerization (photoATRP) using ppm amounts of CuBr2 /tris(2-pyridylmethyl)amine and CuBr2 /tris[2-(dimethylamino)ethyl]amine catalyst complexes, respectively, without degassing of polymerization mixture and with no need to introduce an external reducing agent to the system. The effect of ligand to CuBr2 ratio on kinetic and induction period during the polymerization of MMA and MA is investigated. The induction period is influenced also by the amount of oxygen in the polymerization system. Both the kinetics of MA polymerization and the induction period are affected by light intensity. Finally, the high livingness and initiation efficiency of the photoATRP system in the presence of air are proved by chain extension polymerizations. The presented system is valuable from an industrial point of view, since after optimization, well-defined and high-molar-mass poly(meth)acrylates can be prepared without the necessity of degassing the system, while the polymerization can be proceeded quickly and without an induction period.


Assuntos
Metacrilatos/síntese química , Oxigênio/química , Fotoquímica , Polimerização , Catálise , Cinética , Metacrilatos/efeitos da radiação
18.
ScientificWorldJournal ; 2016: 6389347, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27722199

RESUMO

The aim of this study was to evaluate the radiopacity of silorane and methacrylate resin composites, comparing them to the enamel, dentin, and aluminum penetrometer using a digital image. From six resin composites (Filtek™ P90, Filtek Z350, Filtek Z350 XT flow, Tetric Ceram, TPH Spectrum, and SureFil SDR flow) cylindrical disks (5 × 1 mm) were made and radiographed by a digital method, together with a 15-step aluminum step-wedge and a 1 mm slice of human tooth. The degree of radiopacity of each image was quantified using digital image processing. The mean values of the shades of gray of the tested materials were measured and the equivalent width of aluminum was calculated for each resin. The results of our work yielded the following radiopacity values, given here in descending order: Tetric Ceram > TPH > SDR > Z350 > Z350 flow > P90 > enamel > dentin. The radiopacity of the materials was different both for the enamel and for the dentin, except for resin P90, which was no different than enamel. In conclusion, silorane-based resin exhibited a radiopacity higher than dentin and closest to the enamel; a large portion of the methacrylate-based flow and conventional resins demonstrated greater radiopacity in comparison to dentin and enamel.


Assuntos
Resinas Compostas/efeitos da radiação , Metacrilatos/efeitos da radiação , Radiografia Dentária Digital , Resinas Sintéticas/efeitos da radiação , Resinas de Silorano/efeitos da radiação , Esmalte Dentário/efeitos da radiação , Dentina/efeitos da radiação , Humanos , Teste de Materiais
19.
J Appl Oral Sci ; 24(4): 338-43, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27556204

RESUMO

OBJECTIVE: The aim of this study was to evaluate cytotoxicity and cytokine production induced by light-cured or non-light-cured methacrylate-based and silorane composite resins in RAW 264.7 macrophages. MATERIAL AND METHODS: Cells were stimulated with the extracts from light-cured or non-light-cured composite resins. After incubation for 24 h, cytotoxicity was assessed with the lactate dehydrogenase (LDH) and methyl thiazolyl tetrazolium (MTT) assays, and total protein was quantified using the Lowry method. TNF-α detection was examined with an enzyme-linked immunosorbent assay (ELISA) conducted with cell supernatants after cell stimulation for 6, 12, and 24 h. Data were analyzed using one-way analysis of variance (ANOVA) and Tukey's post hoc test (α=0.05). RESULTS: KaloreTM and FiltekTM Silorane were cytotoxic with or without light curing (p<0.05) after 24 h of incubation. KaloreTM stimulated the early production of TNF-α in comparison with control (p<0.05), whereas FiltekTM Silorane did not affect TNF-α levels after 6 and 12 h (p>0.05). However, after 24 h FiltekTM Silorane inhibited the production of TNF-α (p<0.05). CONCLUSIONS: KaloreTM and FiltekTM Silorane were cytotoxic regardless of light curing. The extract obtained from KaloreTM after 15 days of incubation stimulated the production of TNF-α, unlike that obtained from FiltekTM Silorane.


Assuntos
Resinas Compostas/toxicidade , Metacrilatos/toxicidade , Resinas de Silorano/toxicidade , Fator de Necrose Tumoral alfa/análise , Animais , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Células Cultivadas , Resinas Compostas/efeitos da radiação , Lâmpadas de Polimerização Dentária , Ensaio de Imunoadsorção Enzimática , L-Lactato Desidrogenase , Teste de Materiais , Metacrilatos/efeitos da radiação , Camundongos , Valores de Referência , Reprodutibilidade dos Testes , Resinas de Silorano/efeitos da radiação , Fatores de Tempo
20.
J. appl. oral sci ; 24(4): 338-343, July-Aug. 2016. tab, graf
Artigo em Inglês | LILACS, BBO - Odontologia | ID: lil-792602

RESUMO

ABSTRACT The successful use of composite resins in Dentistry depends on physicochemical properties, but also on the biological compatibility of resins, because of the close association between pulp and dentin. Objective The aim of this study was to evaluate cytotoxicity and cytokine production induced by light-cured or non-light-cured methacrylate-based and silorane composite resins in RAW 264.7 macrophages. Material and Methods Cells were stimulated with the extracts from light-cured or non-light-cured composite resins. After incubation for 24 h, cytotoxicity was assessed with the lactate dehydrogenase (LDH) and methyl thiazolyl tetrazolium (MTT) assays, and total protein was quantified using the Lowry method. TNF-α detection was examined with an enzyme-linked immunosorbent assay (ELISA) conducted with cell supernatants after cell stimulation for 6, 12, and 24 h. Data were analyzed using one-way analysis of variance (ANOVA) and Tukey’s post hoc test (α=0.05). Results KaloreTM and FiltekTM Silorane were cytotoxic with or without light curing (p<0.05) after 24 h of incubation. KaloreTM stimulated the early production of TNF-α in comparison with control (p<0.05), whereas FiltekTM Silorane did not affect TNF-α levels after 6 and 12 h (p>0.05). However, after 24 h FiltekTM Silorane inhibited the production of TNF-α (p<0.05). Conclusions KaloreTM and FiltekTM Silorane were cytotoxic regardless of light curing. The extract obtained from KaloreTM after 15 days of incubation stimulated the production of TNF-α, unlike that obtained from FiltekTM Silorane.


Assuntos
Animais , Camundongos , Fator de Necrose Tumoral alfa/análise , Resinas Compostas/toxicidade , Resinas de Silorano/toxicidade , Metacrilatos/toxicidade , Valores de Referência , Fatores de Tempo , Teste de Materiais , Ensaio de Imunoadsorção Enzimática , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Células Cultivadas , Reprodutibilidade dos Testes , Resinas Compostas/efeitos da radiação , Lâmpadas de Polimerização Dentária , Resinas de Silorano/efeitos da radiação , L-Lactato Desidrogenase , Metacrilatos/efeitos da radiação
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