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1.
Regul Toxicol Pharmacol ; 124: 104965, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34038774

RESUMO

In an experimental setting a laboratory analysis of substances migrating from UV prints under mechanical stress into sweat and saliva simulant was performed. The influence of paper type and curing degree on UV prints was investigated. Five substances were identified at concentrations above the limit of detection in the simulants PPG-3 glyceryl triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, 2/4-isopropylthioxanthone (ITX), and 2,4-diethylthioxanthone (DETX). Migration of the acrylates and photoinitiators into saliva and sweat simulants were increased when the UV inks were printed on uncoated paper in comparison to coated paper. With an exposure scenario considering a person to leaf through 80 pages of UV-printed paper per day while touching each page with a licked fingertip, Risk Characterisation Ratios (RCR) for oral exposure well below 1 were obtained for all five substances indicating no risk for the general population. The three acrylates are classified for skin sensitisation. The migrated amounts per skin surface area of these three were compared with the EC3 value for a hypothetical substance that could be categorised as strong sensitiser (EC3 = 0.1%). The results show that the risk of skin sensitisation even under worst case conditions can be considered as negligible.


Assuntos
Acrilatos/toxicidade , Tinta , Impressão/métodos , Raios Ultravioleta , Acrilatos/farmacocinética , Acrilatos/efeitos da radiação , Adulto , Simulação por Computador , Humanos , Modelos Biológicos , Permeabilidade , Impressão/instrumentação , Saliva/metabolismo , Pele/metabolismo , Suor/metabolismo
2.
Org Biomol Chem ; 19(8): 1835-1846, 2021 03 04.
Artigo em Inglês | MEDLINE | ID: mdl-33565564

RESUMO

Donor-π-acceptor (D-π-A) fluorophores consisting of a donor unit, a π linker, and an acceptor moiety have attracted attention in the last decade. In this study, we report the synthesis, characterization, optical properties, TD-DFT, and cytotoxicity studies of 17 near infrared (NIR) D-π-A analogs which have not been reported so far to the best of our knowledge. These fluorophores have chloroacrylic acid as the acceptor unit and various donor units such as indole, benzothiazole, benzo[e]indole, and quinoline. The fluorophores showed strong absorption in the NIR (700-970 nm) region due to their enhanced intramolecular charge transfer (ICT) between chloroacrylic acid and the donor moieties connected with the Vilsmeier-Haack linker. The emission wavelength maxima of the fluorophores were in between 798 and 870 nm. Compound 20 with a 4-quinoline donor moiety showed an emission wavelength above 1000 nm in the NIR II window. The synthesized fluorophores were characterized by 1H NMR and 13C NMR, and their optical properties were studied. Time dependent density functional theory (TD-DFT) calculations showed that the charge transfer occurs from the donor groups (indole, benzothiazole, benzo[e]indole, and quinoline) to the acceptor chloroacrylic acid moiety. Fluorophores with [HOMO] to [LUMO+1] transitions were shown to possess a charge separation character. The cytotoxicity of selected fluorophores, 4, 7, 10 and 12 was investigated against breast cancer cell lines and they showed better activity than the anti-cancer agent docetaxel.


Assuntos
Acrilatos/farmacologia , Antineoplásicos/farmacologia , Corantes Fluorescentes/farmacologia , Compostos Heterocíclicos com 2 Anéis/farmacologia , Acrilatos/síntese química , Acrilatos/efeitos da radiação , Antineoplásicos/síntese química , Antineoplásicos/efeitos da radiação , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Teoria da Densidade Funcional , Ensaios de Seleção de Medicamentos Antitumorais , Estabilidade de Medicamentos , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/efeitos da radiação , Compostos Heterocíclicos com 2 Anéis/síntese química , Compostos Heterocíclicos com 2 Anéis/efeitos da radiação , Humanos , Luz , Modelos Químicos , Fenômenos Ópticos
3.
Macromol Rapid Commun ; 41(15): e2000289, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32638497

RESUMO

Free radical polymerization upon near-infrared (NIR) light is still the subject of intense research efforts and remains a huge challenge particularly for long wavelengths (>1000 nm). In this study, a NIR sensitizer operating upon long wavelength (1064 nm) is proposed for an efficient polymerization of acrylate monomers. A new three-component photoinitiating system is developed comprising the NIR sensitizer in combination with an Iodonium salt (Iod) and an amine. Remarkably, the NIR sensitizer (IR 1064) absorbing strongly in all the near infrared region (700-1200 nm) offers the possibility to use a broad range of irradiation wavelengths, i.e., examples are provided at 785 and 1064 nm. Such long wavelengths are characterized by many advantages such as a deeper penetration of light and therefore a better curing of the monomer but it is also much safer than UV light. Excellent performance is observed for the three-component IR 1064/Iod/Amine system under air: high conversion of acrylate functions associated with a fast polymerization time. The use of IR 1064 as NIR sensitizer with a broad NIR absorption is-to the best of current knowledge-never proposed in the literature. The photoinitiating performances are studied using real-time Fourier transform infrared spectroscopy.


Assuntos
Acrilatos/efeitos da radiação , Radicais Livres/química , Processos Fotoquímicos , Acrilatos/química , Aminas/química , Cinética , Polimerização/efeitos da radiação , Radiação não Ionizante , Espectroscopia de Infravermelho com Transformada de Fourier/instrumentação , Raios Ultravioleta
4.
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
5.
Phys Med Biol ; 63(17): 175009, 2018 08 30.
Artigo em Inglês | MEDLINE | ID: mdl-30088807

RESUMO

Propagation of ultrasound through a complex composite sample may exhibit phase interference between two or more sonic-rays if differences in transit time are less than the pulse length. The transit time spectrum of a test sample, equivalent to its impulse response, was derived through active-set deconvolution of ultrasound signals with, and without, the test sample. The aim of this study was to test the hypothesis that in cases where only the transmit ultrasound transducer's digitally-coded excitation signal is available, hence not the input ultrasound signal without the test sample, incorporation of the transducer impulse response may increase both accuracy and precision of ultrasound transit time spectroscopy. A digital 1 MHz sinusoid signal was used to create an ultrasound pulse that was propagated through a 5 step-wedge acrylic sample immersed in water. Transit time spectra were obtained through deconvolution utilising an ultrasound input signal, along with a digital input signal, with and without incorporation of the transducer impulse response. Incorporation of the transducer impulse response reduced a quantitative measure of noise-to-signal ratio by a factor of 12. The paper has demonstrated the potential for increased accuracy and precision of transit time spectroscopy when the transducer impulse response is incorporated within active-set deconvolution analysis.


Assuntos
Análise Espectral/normas , Transdutores/normas , Ultrassonografia/normas , Acrilatos/efeitos da radiação , Razão Sinal-Ruído , Análise Espectral/instrumentação , Tempo , Ondas Ultrassônicas , Ultrassonografia/instrumentação
6.
Eur J Pharm Sci ; 121: 309-318, 2018 08 30.
Artigo em Inglês | MEDLINE | ID: mdl-29874551

RESUMO

BACKGROUND: The growing incidence of photodamaging effects caused by UV radiation (e.g. sunburn, skin cancer) has increased the attention from health authorities which recommend the topical application of sunscreens to prevent these skin damages. The economic stakes for those companies involved in this international market are to develop new UV filters and innovative technologies to provide the most efficient, flexible and robust sunscreen products. Today the development of innovative and competitive sunscreen products is a complex formulation challenge. Indeed, the current sunscreens must protect against skin damages, while also being safe for the skin and being sensory and visually pleasant for the customers when applied on the skin. Organic UV filters, while proposing great advantages, also present the risk to penetrate the stratum corneum and diffuse into underlying structures with unknown consequences; moreover, their photo-stability are noted thorny outcomes in sunscreen development and subsequent performance. In recent years, the evaluation of the interaction between skin and sunscreen in terms of penetration after topical application has been considered from European authority but still its testing as their photo-stability assessment are not mandatory in most countries. OBJECTIVE: This study, based on in-vitro approaches, was performed to evaluate and compare the retention and the penetration of organic UV filters in free or encapsulated form inside the skin as well as their respective photo-stability. METHODS: Sunscreen formulation with a combination of Avobenzone and Octocrylene in "free form" and a formulation using the same UV filters but encapsulated in a sol-gel silica capsule, were analyzed and compared by FTIR Imaging Spectroscopy. Tape stripping method was used to investigate the penetration of these UV filters inside the stratum corneum. Their photo-stabilities were evaluated by spectroscopic measurements (FTIR, UV/Vis) and standard measurements were calculated: AUC (Area Under the Curve) and SPF (Sun Protection Factor). RESULT: With traditional formulation, the organic UV filters penetrated significantly into the stratum corneum while the same UV filters combined with encapsulation technology remained on the skin surface. The encapsulation technology also improved significantly their stability. CONCLUSION: Encapsulation technology is a promising strategy to improve the efficacy of sunscreen product using organic UV filters and to reduce safety problem. On the other hand, this study highlighted the pertinence of the FTIR Spectroscopy to test, compare and investigate sunscreen formulations.


Assuntos
Acrilatos/administração & dosagem , Propiofenonas/administração & dosagem , Protetores Solares/administração & dosagem , Acrilatos/química , Acrilatos/efeitos da radiação , Animais , Composição de Medicamentos , Estabilidade de Medicamentos , Propiofenonas/química , Propiofenonas/efeitos da radiação , Pele/metabolismo , Absorção Cutânea , Protetores Solares/química , Protetores Solares/efeitos da radiação , Suínos , Raios Ultravioleta
7.
Anal Chem ; 90(1): 1014-1020, 2018 01 02.
Artigo em Inglês | MEDLINE | ID: mdl-29182316

RESUMO

Cysteine (Cys), as an important biothiol, plays a major role in many physiological processes like protein synthesis, detoxification and metabolism, and also is closely associated with a variety of diseases; thus the design of novel highly selective and sensitive near-infrared (NIR) fluorescent probes for Cys detection in vivo is of great significance. Herein, we report a selective and sensitive NIR turn-on fluorescent probe (CP-NIR) with large Stokes shift for detecting Cys in vivo. Upon addition of Cys to the solution of the probe, it is absorption wavelength shifts from 550 to 600 nm, accompanying with an obvious enhancement of NIR fluorescence emission centering around 760 nm. This Michael-addition reaction-based probe shows a large Stokes shift (160 nm), low detection limit (48 nM), fast response time, and low toxicity. Moreover, this novel NIR probe with good cell permeability was successfully applied to monitoring endogenous Cys in living cells and in a mouse model.


Assuntos
Cisteína/análise , Corantes Fluorescentes/química , Acrilatos/síntese química , Acrilatos/química , Acrilatos/efeitos da radiação , Animais , Cisteína/metabolismo , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/efeitos da radiação , Células HeLa , Humanos , Raios Infravermelhos , Limite de Detecção , Camundongos Endogâmicos BALB C , Microscopia de Fluorescência/métodos
8.
Dent Mater ; 31(12): 1474-86, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26515541

RESUMO

OBJECTIVES: To evaluate the chemical, mechanical, and biological properties of modern composite surface sealers (CSS) having different compositions. METHODS: The CSS products tested were Biscover LV (BC), Durafinish (DF), G-Coat Plus (GC), and Permaseal (PS). The tests performed were: (A): degree of conversion (DC%) by ATR-FTIR spectroscopy; (B): thickness of O2-inhibition layer by transmission optical microscopy; (C): surface hardness, 10 min after irradiation and following 1 week water storage, employing a Vickers indenter (VHN); (D): color (ΔE*) and gloss changes (ΔGU) after toothbrush abrasion, using L*a*b* colorimetry and glossimetry; (E): accelerated wear (GC,PS only) by an OHSU wear simulator plus 3D profilometric analysis, and (F): cytotoxicity testing of aqueous CSS eluents on human gingival fibroblast cultures employing the methyl-(3)H thymidine DNA labeling method. Statistical analyses included 1-way (A, B, ΔE*, ΔGU) and 2-way (C, F) ANOVAs, plus Tukey post hoc tests. Student's t-test was used to evaluate the results of the accelerated wear test (α=0.05 for all). RESULTS: The rankings of the statistical significant differences were: (A) PS (64.9)>DF,BC,GC (56.1-53.9) DC%; (B) DF,PS (12.3,9.8)>GC,BC (5.2,4.8) µm; (C): GC (37.6)>BC,DF (32.6,31.1)>PS (26.6) VHN (10 min/dry) and BC,DF (29.3,28.7)>GC(26.5)>PS(21.6) VHN (1w/water), with no significant material/storage condition interaction; (D): no differences were found among GC,DF,BC,PS (0.67-1.11) ΔE*, with all values within the visually acceptable range and PS,BC (32.8,29.4)>GC,DF (19.4,12.9) ΔGU; (E): no differences were found between GC and PS in volume loss (0.10,0.11 mm(3)), maximum (113.9,130.5 µm) and mean wear depths (30.3,27.5 µm); (F): at 1% v/v concentration, DF showed toxicity (23% vital cells vs 95-102% for others). However, at 5% v/v concentration DF (0%) and BC (9%) were the most toxic, whereas GC (58%) and PS (56%) showed moderate toxicity. SIGNIFICANCE: Important chemical, mechanical, and biological properties exist among the CSS tested, which may affect their clinical performance.


Assuntos
Acrilatos/química , Materiais Dentários/química , Cimentos de Resina/química , Acrilatos/efeitos da radiação , Acrilatos/toxicidade , Materiais Dentários/efeitos da radiação , Materiais Dentários/toxicidade , Fibroblastos/efeitos dos fármacos , Gengiva/citologia , Dureza , Humanos , Teste de Materiais , Fenômenos Mecânicos , Metilmetacrilato , Cimentos de Resina/efeitos da radiação , Cimentos de Resina/toxicidade , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície
9.
Minerva Stomatol ; 64(6): 323-33, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26486206

RESUMO

AIM: Retention is the phase of orthodontic treatment that attempts to hold teeth in their corrected positions after orthodontic therapy is completed. The aim of this study was to consider fiber-reinforced composites (FRC) as a possible alternative to conventional multistranded stainless steel wire for retention through SEM analysis. METHODS: Two different FRC orthodontic retainers were investigated, i.e. Everstick® (Stick Tech Ltd, Turku, Finland) (type A, 24 samples), with a diameter of 0.76 mm made of glass fibers and a Young's modulus of elasticity of 28 gpa, and Ribbond® (Ribbond, Inc., Seattle, Washington, WA, USA) (type B, 24 samples), with ultra high molecular weight and with an high Young's modulus of elasticity by polyethylene fibers cold treated with plasma gas. Six groups were created: control groups A1 and B1, composed by 8 type A and 8 type B samples without impregnation and only with fluid resin before curing; groups A2 and B2, composed respectively by 8 type A and 8 type B samples impregnated with fluid resin Heliobond for 6 seconds; groups A3 and B3, composed respectively by 8 type A and 8 type B samples impregnated with fluid resin Heliobond for 6 minutes before curing. RESULTS: Cross- and lengthwise SEM analysis of the sectioned samples made showed that fiber without impregnation with fluid resin, before curing, showed interwoven and straight directed cylindrical fibers. The SEM analysis denoted that the two types of fiber shows structural characteristics differing in dimension, number, diameter and orientation of FRC without a preliminary treatment through impregnation of the fibers with fluid resin. CONCLUSION: An impregnation time of 6 seconds could considerably reduced voids, crazes and microcracks of the fibers, making them more resistant to the other oral and bacterial agents. A larger time of impregnation (6 minutes), with fluid resin before hardening, further enhances the morphological characteristics of the FRC.


Assuntos
Acrilatos , Resinas Compostas , Materiais Dentários , Contenções Ortodônticas , Polietilenos , Acrilatos/efeitos da radiação , Análise do Estresse Dentário , Módulo de Elasticidade , Vidro , Teste de Materiais , Microscopia Eletrônica de Varredura , Fotoquímica , Polietileno , Propriedades de Superfície , Fatores de Tempo
10.
Colloids Surf B Biointerfaces ; 135: 1-7, 2015 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-26222605

RESUMO

This study addresses the preparation and characterization of hybrid films prepared from Titanium dioxide (TiO2) Pickering stabilized acrylic polymeric dispersion as well as their bacterial inactivation efficiency under sunlight irradiation. Complete bacterial inactivation under low intensity simulated solar light irradiation (55 mW/cm(2)) was observed within 240 min for the films containing 10 weight based on monomers (wbm) % of TiO2, whereas 360 min were needed for the films containing 20 wbm% of TiO2. The hybrid films showed repetitive Escherichia coli (E. coli) inactivation under light irradiation. TiO2 released from the films surfaces was measured by inductively coupled plasma mass spectrometry (IPC-MS), obtaining values of ∼ 0.5 and 1 ppb/cm(2) for the films containing 10 wbm% and 20 wbm% of TiO2, respectively, far below the allowed cytotoxicity level for TiO2 (200 ppb). Transmission electron microscopy (TEM) of the hybrid films showed that TiO2 nanoparticles (NPs) were located at the polymer particle's surface forming a continuous inorganic network inside the film matrix. Atomic force microscopy (AFM) images showed differences in the TiO2 dispersion between the air-film and film-substrate interfaces. Films containing 10 wbm% of TiO2 had higher roughness (Rg) at both interfaces than the one containing 20 wbm% of TiO2 inducing an increase in the bacterial adhesion as well as the bacterial inactivation kinetics. The highly oxidative OH-radicals participating in the bacterial inactivation were determined by fluorescence.


Assuntos
Acrilatos/química , Acrilatos/efeitos da radiação , Antibacterianos/química , Antibacterianos/efeitos da radiação , Luz Solar , Titânio/química , Titânio/efeitos da radiação , Aderência Bacteriana/efeitos dos fármacos , Aderência Bacteriana/efeitos da radiação , Escherichia coli/efeitos dos fármacos , Escherichia coli/efeitos da radiação , Radical Hidroxila/química , Radical Hidroxila/efeitos da radiação , Nanopartículas Metálicas/química , Nanopartículas Metálicas/efeitos da radiação , Microscopia de Força Atômica , Ácidos Ftálicos/química , Propriedades de Superfície
11.
Eur J Pharm Sci ; 78: 79-89, 2015 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-26159738

RESUMO

Trans-resveratrol (RES) is used in cosmetic formulations and beta-carotene (BTC) is a classical sunscreen antioxidant, but their photostability in sunscreens, a property directly correlated to performance and safety has not been addressed in the literature. This paper reports the assessment of RES and/or BTC influence on the photostability of five UV-filters (octyl methoxycinnamate - OMC, avobenzone -AVO, octocrylene - OCT, bemotrizinole - BMZ, octyltriazone - OTZ) in three different combinations after UVA exposure followed by the identification of degradation products and the assessment of photoreactivity. The evaluation of sunscreen photostability was performed by HPLC and spectrophotometric analysis, and degradation products were identified by GC-MS analysis. Components RES, BTC, OMC and AVO were significantly degraded after UV exposure (reduction of around 16% in recovery). According to HPLC analysis, all formulations presented similar photostability profiles. Eleven degradation products were identified in GC-MS analysis, among them products of RES, BTC, OMC and AVO photodegradation. All evaluated formulations were considered photoreactive, as well as the isolated compounds RES and AVO. Considering HPLC, spectrophotometric and GC-MS results, it is suggested that formulations containing BMZ were considered the most photostable. The combination RES+BTC in a sunscreen improved the photostability of AVO. The benefits of using a combination of antioxidants in sunscreens was demonstrated by showing that using RES+BTC+studied UV-filters led to more photostable formulations, which in turn implies in better safety and efficacy.


Assuntos
Estilbenos/efeitos da radiação , Protetores Solares/efeitos da radiação , Raios Ultravioleta , beta Caroteno/efeitos da radiação , Acrilatos/efeitos da radiação , Benzoatos/efeitos da radiação , Cromatografia Líquida de Alta Pressão , Cinamatos/efeitos da radiação , Estabilidade de Medicamentos , Cromatografia Gasosa-Espectrometria de Massas , Fenóis/efeitos da radiação , Fotólise , Propiofenonas/efeitos da radiação , Resveratrol , Oxigênio Singlete/química , Espectrofotometria Ultravioleta , Superóxidos/química , Triazinas/efeitos da radiação
12.
ACS Appl Mater Interfaces ; 7(5): 3398-405, 2015 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-25594664

RESUMO

Hydrogels such as poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAM-AAc) can be photopatterned to create a wide range of actuatable and self-folding microstructures. Mechanical motion is derived from the large and reversible swelling response of this cross-linked hydrogel in varying thermal or pH environments. This action is facilitated by their network structure and capacity for large strain. However, due to the low modulus of such hydrogels, they have limited gripping ability of relevance to surgical excision or robotic tasks such as pick-and-place. Using experiments and modeling, we design, fabricate, and characterize photopatterned, self-folding functional microgrippers that combine a swellable, photo-cross-linked pNIPAM-AAc soft-hydrogel with a nonswellable and stiff segmented polymer (polypropylene fumarate, PPF). We also show that we can embed iron oxide (Fe2O3) nanoparticles into the porous hydrogel layer, allowing the microgrippers to be responsive and remotely guided using magnetic fields. Using finite element models, we investigate the influence of the thickness and the modulus of both the hydrogel and stiff polymer layers on the self-folding characteristics of the microgrippers. Finally, we illustrate operation and functionality of these polymeric microgrippers for soft robotic and surgical applications.


Assuntos
Hidrogéis/química , Magnetismo/instrumentação , Nanopartículas de Magnetita/química , Micromanipulação/instrumentação , Procedimentos Cirúrgicos Robóticos/instrumentação , Acrilatos/química , Acrilatos/efeitos da radiação , Resinas Acrílicas/química , Resinas Acrílicas/efeitos da radiação , Desenho de Equipamento , Análise de Falha de Equipamento , Hidrogéis/efeitos da radiação , Campos Magnéticos , Nanopartículas de Magnetita/efeitos da radiação , Temperatura
13.
Eur J Pharm Sci ; 68: 127-36, 2015 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-25533240

RESUMO

This study aimed to assess the phototoxic potential of combined UV-filters and retinyl palmitate (RP) in the presence or not of bemotrizinol (BMTZ), employing photostability and in vitro and in vivo phototoxicity assays. The formulations tested contained octocrylene (OCT), octyl methoxycinnamate (OMC), benzophenone-3 (BZP-3) and RP (photostable) or octocrylene (OCT), octyl methoxycinnamate (OMC), avobenzone (AVO) and RP (less photostable). Both formulations were supplemented with bemotrizinol. Photostability was evaluated by exposing, or not, formulations spread on a glass plate to UVA/UVB irradiation. The resulting products were quantified by HPLC analysis. In vitro phototoxicity of UV-filters and combinations were evaluated using 3T3 viable monolayer fibroblast cultures submitted, or not, to irradiation according to OECD TG 432. In vivo photoallergy and photoxicity were assessed by clinical studies (photopatch test). Photostability assays showed that UV-filter bemotrizinol was a better photostabilizer for RP/benzophenone-3 than for RP/avobenzone. The in vitro phototoxicity of the combination RP/avobenzone was reduced by bemotrizinol. Clinical studies did not indicate phototoxic or photoallergenic potentials in all formulations tested. It is concluded that the 3T3 NRU phototoxicity test may be considered a supplementary assay in formulation developments, since it can detect chemically unstable and potentially phototoxic combinations. However, extrapolation of in vitro positive results to human photopatch tests may be performed only to a limited extent.


Assuntos
Dermatite Fotoalérgica/etiologia , Dermatite Fototóxica/etiologia , Fenóis/efeitos adversos , Protetores Solares/efeitos adversos , Triazinas/efeitos adversos , Vitamina A/análogos & derivados , Células 3T3 , Acrilatos/efeitos adversos , Acrilatos/farmacologia , Acrilatos/efeitos da radiação , Adolescente , Adulto , Idoso , Animais , Benzofenonas/efeitos adversos , Benzofenonas/farmacologia , Benzofenonas/efeitos da radiação , Cinamatos/efeitos adversos , Cinamatos/farmacologia , Cinamatos/efeitos da radiação , Diterpenos , Método Duplo-Cego , Interações Medicamentosas , Estabilidade de Medicamentos , Humanos , Camundongos , Pessoa de Meia-Idade , Vermelho Neutro/metabolismo , Fenóis/farmacologia , Fenóis/efeitos da radiação , Ésteres de Retinil , Medição de Risco , Protetores Solares/farmacologia , Protetores Solares/efeitos da radiação , Triazinas/farmacologia , Triazinas/efeitos da radiação , Raios Ultravioleta , Vitamina A/efeitos adversos , Vitamina A/farmacologia , Vitamina A/efeitos da radiação , Adulto Jovem
14.
Biomacromolecules ; 16(2): 497-506, 2015 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-25539413

RESUMO

An in situ heparin-based forming hydrogel that cures under visible-light is formulated using eosin Y as a photoinitiator with triethanolamine as an electron donor to initiate reaction of thiolated-heparin with acrylate-ended poly(ethylene glycol). Formulations and irradiation conditions are presented for control of heparin content (1.6 to 3.3% w/v), modulus (100-10,000 Pa), and gelation time (30-600 s). Encapsulation of 3T3 fibroblasts in the hydrogel gave over 96% viability for all conditions examined. In vitro characterization of epidermal growth factor released from the hydrogel confirmed that the growth factor remains bioactive. The ability to deliver growth factors, fast gelation kinetics under visible light, and independent control of physical and biochemical properties makes this system a promising candidate for use in regenerative medicine. In particular, irradiation conditions that achieve gelation in 150s are compatible with the stringent light exposure limits of the retina, which affords a wide safety margin for use with other tissues.


Assuntos
Acrilatos/efeitos da radiação , Heparina/efeitos da radiação , Hidrogéis/efeitos da radiação , Luz , Compostos de Sulfidrila/efeitos da radiação , Acrilatos/química , Acrilatos/farmacologia , Animais , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/fisiologia , Reagentes de Ligações Cruzadas/química , Reagentes de Ligações Cruzadas/farmacologia , Reagentes de Ligações Cruzadas/efeitos da radiação , Heparina/química , Heparina/farmacologia , Hidrogéis/química , Hidrogéis/farmacologia , Camundongos , Células NIH 3T3 , Polimerização , Compostos de Sulfidrila/química , Compostos de Sulfidrila/farmacologia
15.
Acta Odontol Scand ; 72(7): 543-8, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-24490641

RESUMO

OBJECTIVE: The aim of this study was to evaluate the micromechanical properties of different adhesive bonding agents when polymerized through ceramics. MATERIALS AND METHODS: Sixty sound extracted human third molars were selected and the crowns were sectioned perpendicular to the long axis in order to obtain dentin slices to be bonded with one of the following adhesives: Syntac/Heliobond (Ivoclar-Vivadent) or Adper-Scotchbond-1XT (3M-ESPE). The adhesives were cured by using a LED-unit (Bluephase®, Ivoclar Vivadent) with three different curing times (10 s, 20 s and 30 s) under two ceramics (IPS-e.max-Press, Ivoclar-Vivadent; IPS-Empress®CAD, Ivoclar-Vivadent) of different thicknesses (0 mm, 0.75 mm, 2 mm). Thirty groups were included, each containing 60 measurements. Micromechanical properties (Hardness, HV; indentation modulus, E; and creep, Cr) of the adhesives were measured with an automatic microhardness indenter (Fisherscope H100C, Germany). Data were statistically analyzed by using one-way ANOVA and Tukey's post-hoc test, as well as a multivariate analysis to test the influence of the study parameters (SPSS 18.0). RESULTS: Significant differences were observed between the micromechanical properties of the adhesives (p < 0.05). The ceramic type showed the highest effect on HV (Partial-eta squared (η(2)) = 0.109) of the tested adhesives, while E (η(2) = 0.275) and Cr (η(2) = 0.194) were stronger influenced by the adhesive type. Ceramic thickness showed no effect on the E and Cr of the adhesives. CONCLUSIONS: The adhesive bonding agents used in this study performed well by curing through different thicknesses of ceramics. The micromechanical properties of the adhesives were determined by the adhesive type and were less influenced by ceramic type and curing time.


Assuntos
Cerâmica/química , Colagem Dentária , Adesivos Dentinários/química , Cura Luminosa de Adesivos Dentários/métodos , Acrilatos/química , Acrilatos/efeitos da radiação , Silicatos de Alumínio/química , Silicatos de Alumínio/efeitos da radiação , Cerâmica/efeitos da radiação , Lâmpadas de Polimerização Dentária , Porcelana Dentária/química , Porcelana Dentária/efeitos da radiação , Adesivos Dentinários/efeitos da radiação , Módulo de Elasticidade , Dureza , Humanos , Teste de Materiais , Polimerização , Cimentos de Resina/química , Cimentos de Resina/efeitos da radiação , Estresse Mecânico , Propriedades de Superfície , Fatores de Tempo
16.
Acta Biomater ; 9(9): 8232-44, 2013 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-23770222

RESUMO

Block copolymers of poly(ethylene glycol) and poly(ε-caprolactone) (PCL) with chemically addressable functional groups were synthesized and characterized. Ring-opening polymerization of ε-caprolactone (CL) and 1,4,8-trioxaspiro-[4,6]-9-undecanone (TSU) using α-methoxy, ω-hydroxyl poly(ethylene glycol) as the initiator afforded a copolymer with cyclic ketals being randomly distributed in the hydrophobic PCL block. At an initiator/catalyst molar ratio of 10/1 and a TSU/CL weight ratio of 1/4, a ketal-carrying copolymer (ECT2-CK) with Mn of 52 kDa and a ketal content of 15 mol.% was obtained. Quantitative side-chain deacetalization revealed the reactive ketones without noticeable polymer degradation. In our study, 10 mol.% of cyclic ketals were deprotected and the ketone-containing copolymer was designated as ECT2-CO. Reaction of ECT2-CO with 2-(2-(aminooxy)acetoxy)-ethyl acrylate gave rise to an acrylated product (ECT2-AC) containing an estimated 3-5 acrylate groups per chain. UV-initiated radical polymerization of ECT2-AC in dichloromethane resulted in a crosslinked network (xECT2-AC). Thermal and morphological analyses employing differential scanning calorimetry and atomic force microscopy operated in PeakForce Tapping mode revealed the semicrystalline nature of the network, which contained stiff crystalline lamellae dispersed in a softer amorphous interstitial. Macroscopic and nanoscale mechanical characterizations showed that ECT2-CK exhibited a significantly lower modulus than PCL of a similar molecular weight. Whereas ECT2-CK undergoes a plastic deformation with a distinct yield point and a cold-drawing region, xECT2-AC exhibits a compliant, elastomeric deformation with a Young's modulus of 0.5±0.1 MPa at 37°C. When properly processed, the crosslinked network exhibited shape-memory behaviors, with shape fixity and shape recovery values close to 1 and a shape recovery time of less than 4s at 37°C. In vitro studies showed that xECT2-AC films did not induce any cytotoxic effects on the cultured mesenchymal stem cells. The crosslinkable polyester copolymers can be potentially used as tissue engineering scaffolds and minimally invasive medical devices.


Assuntos
Acrilatos/química , Elastômeros/síntese química , Elastômeros/toxicidade , Células-Tronco Mesenquimais/citologia , Células-Tronco Mesenquimais/efeitos dos fármacos , Poliésteres/síntese química , Poliésteres/toxicidade , Polietilenoglicóis/síntese química , Polietilenoglicóis/toxicidade , Acrilatos/efeitos da radiação , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/efeitos da radiação , Materiais Biocompatíveis/toxicidade , Sobrevivência Celular/efeitos dos fármacos , Células Cultivadas , Reagentes de Ligações Cruzadas/química , Reagentes de Ligações Cruzadas/efeitos da radiação , Cristalização/métodos , Módulo de Elasticidade/efeitos da radiação , Dureza/efeitos da radiação , Humanos , Luz , Teste de Materiais , Poliésteres/efeitos da radiação , Polietilenoglicóis/efeitos da radiação , Resistência à Tração/efeitos da radiação
17.
Biomed Mater ; 8(2): 025001, 2013 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-23343533

RESUMO

Cell behavior is guided by the complex interplay of matrix mechanical properties as well as soluble and immobilized biochemical signals. The development of synthetic scaffolds that incorporate key functionalities of the native extracellular matrix (ECM) for support of cell proliferation and tissue regeneration requires that stiffness and immobilized concentrations of ECM signals within these biomaterials be tuned and optimized prior to in vitro and in vivo studies. A detailed experimental sensitivity analysis was conducted to identify the key polymerization conditions that result in significant changes in both elastic modulus and immobilized YRGDS within visible light photopolymerized poly(ethylene glycol) diacrylate hydrogels. Among the polymerization conditions investigated, single as well as simultaneous variations in N-vinylpyrrolidinone and precursor concentrations of acryl-PEG3400-YRGDS resulted in a broad range of the hydrogel elastic modulus (81-1178 kPa) and YRGDS surface concentration (0.04-1.72 pmol cm(-2)). Increasing the YRGDS surface concentration enhanced fibroblast cell adhesion and proliferation for a given stiffness, while increases in the hydrogel elastic modulus caused decreases in cell adhesion and increases in proliferation. The identification of key polymerization conditions is critical for the tuning and optimization of biomaterial properties and the controlled study of cell-substrate interactions.


Assuntos
Adesão Celular/fisiologia , Proliferação de Células , Matriz Extracelular/química , Oligopeptídeos/farmacocinética , Polietilenoglicóis/química , Acrilatos/química , Acrilatos/efeitos da radiação , Animais , Materiais Biomiméticos/química , Módulo de Elasticidade , Dureza/fisiologia , Hidrogéis/química , Hidrogéis/efeitos da radiação , Ligantes , Luz , Teste de Materiais , Camundongos , Células NIH 3T3 , Fotoquímica/métodos , Polietilenoglicóis/efeitos da radiação , Polímeros/química , Polímeros/efeitos da radiação , Propriedades de Superfície , Resistência à Tração/fisiologia
19.
J Prosthet Dent ; 105(4): 236-41, 2011 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-21458648

RESUMO

STATEMENT OF PROBLEM: The color alteration of resin-based materials is one of the most common reasons to replace esthetic dental restorations. PURPOSE: This study assessed the influence of surface sealant (Biscover) on the color stability of nanofilled (Supreme XT) and microhybrid (Vit-l-escence and Opallis) composite resins after artificial aging. MATERIAL AND METHODS: One hundred disc-shaped (6 × 1.5 mm) specimens were made for each composite resin. After 24 hours, all specimens were polished and sealant was applied to 50 specimens of each material. Baseline color was measured according to the CIE L*a*b* system using a reflection spectrophotometer. Ten specimens of each group were aged for 252 h in an ultraviolet (UV)-accelerated aging chamber or immersed for 4 weeks in cola soft drink, orange juice, red wine staining solutions or distilled water as control. Color difference (ΔE) after aging was calculated based on the color coordinates before (baseline) and after aging/staining treatment. Data were analyzed with 2-way ANOVA and Fisher's test (α=.05). RESULTS: The results showed significant changes in color after artificial aging in all the groups (P<.05). Independent of the material studied, red wine resulted in the highest level of discoloration. Intermediate values were found for orange juice, UV accelerated aging, and the cola soft drink. The lowest values of ΔE were found for specimens stored in distilled water. CONCLUSIONS: All composite resins showed some color alteration after the aging methods. The surface sealant did not alter the color stability of the tested materials.


Assuntos
Acrilatos/efeitos da radiação , Resinas Compostas/efeitos da radiação , Restauração Dentária Permanente , Pigmentação em Prótese , Cimentos de Resina/efeitos da radiação , Descoloração de Dente/prevenção & controle , Análise de Variância , Teste de Materiais , Espectrofotometria , Raios Ultravioleta/efeitos adversos
20.
Ultrason Sonochem ; 18(5): 1185-92, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21306934

RESUMO

Ultrasound (US) was used to change the shear viscosity of an aqueous solution of copolymers having acrylic acid (AA) and N-isopropylacrylamide (NIPAM) segments. The US effect on the shear viscosity of the copolymers containing 10, 50 and 90 mol% of the NIPAM group having thermo-responsible property was examined when the US was exposed to the aqueous solution at different temperatures. The shear viscosity of the solution had a significant change at about 30-35°C when the viscosity was measured in the range of 0-60°C. While, the viscosity decreased with the increase of the temperature, the US operated at 28, 45 and 100 kHz also induced significant reduction of the shear viscosity. Evidence of the US effect on the shear viscosity reduction was observed by measurement of FT-IR spectra of the copolymer solution when the US was exposed. It was noted that considerable change of the spectra at the 28 kHz US was observed relative to that of the 45 and 100 kHz US. The tendency of the change in the shear viscosity and IR spectra was almost similar. Furthermore, the shear viscosity and IR spectra changed gradually to recover its original value as the US was stopped. This was due to the breaking and reformation of the hydrogen bonding between NIPAM and AA segments when the US was exposed and stopped, respectively.


Assuntos
Acrilatos/química , Acrilatos/efeitos da radiação , Resinas Acrílicas/química , Resinas Acrílicas/efeitos da radiação , Sonicação/métodos , Termografia/métodos , Água/química , Temperatura Alta , Doses de Radiação , Resistência ao Cisalhamento/efeitos da radiação , Viscosidade/efeitos da radiação
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