RESUMO Este artigo apresenta um estudo teórico-experimental com o objetivo de determinar o coeficiente de transferência de calor interfacial, as variáveis térmicas de solidificação, os espaçamentos dendríticos primários e secundários bem como a microdureza Vickers da liga Al-11%Si solidificada direcionalmente, sob condições transientes de fluxo de calor, em um dispositivo de configuração horizontal refrigerado a água. Para o monitoramento dos perfis de temperatura utilizou-se um conjunto de termopares tipo K localizados em diferentes posições a partir da interface metal-molde, considerando a linha central correspondente ao eixo longitudinal do lingote. Uma técnica numérica, que compara perfis térmicos teóricos e experimentais, foi utilizada no cálculo do coeficiente de transferência de calor na interface metal/molde durante a solidificação cuja condição transiente é representada por uma equação analítica na forma de potência. Foram aplicadas técnicas experimentais para o cálculo das variáveis térmicas de solidificação, ou seja, deslocamento da frente de solidificação, velocidade da isoterma liquidus e taxa de resfriamento. Os resultados experimentais e simulados apresentaram uma concordância muito boa e possibilitaram estabelecer correlações analíticas entre tais variáveis térmicas e os espaçamentos dendríticos primários e secundários obtidos, por meio de equações na forma de potência representadas por expoentes característicos. Finalmente, são também apresentadas expressões experimentais capazes de correlacionar os valores dos espaçamentos dendríticos estudados com o comportamento da microdureza Vickers da referida liga.

ABSTRACT This paper presents a theoretical-experimental study aiming to determine the interfacial heat transfer coefficient and solidification thermal parameters from experimentally obtained data correlating these with the primary and secondary dendritic spacings as well as microhardness during the horizontal solidification of the Al-11wt.%Si alloy under transient heat flow conditions. For the experimental procedure, a water-cooled solidification device was used which allows the horizontal directional solidification and the monitoring of the temperature profiles in different positions from the metal-mold interface considering the center line corresponding to the longitudinal axis of the ingot. A numerical technique which compares theoretical and experimental thermal profiles has permitted the evaluation of the variation of metal-mold heat transfer coefficient along the solidification. The interfacial heat transfer coefficient of studied alloy is represented by a equation which show the time dependence during the process. The experimental and calculated values have shown a very good agreement. Experimental techniques were applied to calculate the following solidification thermal variables: solidification front displacement, growth rate and cooling rate. The experimental results allowed establishing a quantitative correlation between such thermal variables and the studied structural parameters by means of power type equations represented by characteristic exponents. Finally, correlation between the values of both primary and secondary dendritic spacings found with Vickers microhardness behavior for the studied alloy is also presented.

A biocatalytic cascade process was developed using immobilized cells of the wild type yeast Candida albicans CCT 0776 in calcium alginate beads and a commercially available ketoreductase. The aim was to promote deracemization by stereoinversion of (±)-1-arylethanols in high substrate concentration (above 100 mmol L-1) to prepare the (R)-enantiomers of the alcohols (90-99%), with a high enantiomeric excess (83-99%) after 2 to 19 h. The (R)-1-(3-methoxyphenyl)ethanol, with 70% yield and 91% ee, obtained after 5 h was used to prepare (S)-1-(3-methoxyphenyl)-ethylamine with 60% yield and 91% ee after two steps, a key intermediate in the synthesis of (S)-rivastigmine.

Abstract This systematic review assessed the literature to evaluate the efficiency of polymerization of bulk-fill composite resins at 4 mm restoration depth. PubMed, Cochrane, Scopus and Web of Science databases were searched with no restrictions on year, publication status, or article’s language. Selection criteria included studies that evaluated bulk-fill composite resin when inserted in a minimum thickness of 4 mm, followed by curing according to the manufacturers’ instructions; presented sound statistical data; and comparison with a control group and/or a reference measurement of quality of polymerization. The evidence level was evaluated by qualitative scoring system and classified as high-, moderate- and low- evidence level. A total of 534 articles were retrieved in the initial search. After the review process, only 10 full-text articles met the inclusion criteria. Most articles included (80%) were classified as high evidence level. Among several techniques, microhardness was the most frequently method performed by the studies included in this systematic review. Irrespective to the “in vitro” method performed, bulk fill RBCs were partially likely to fulfill the important requirement regarding properly curing in 4 mm of cavity depth measured by depth of cure and / or degree of conversion. In general, low viscosities BFCs performed better regarding polymerization efficiency compared to the high viscosities BFCs.

Abstract Alternative photoinitiators with different absorption wavelengths have been used in resin composites (RCs), so it is crucial to evaluate the effectiveness of light-curing units (LCUs) on these products. Objective Using Fourier transform infrared analysis (FTIR) in vitro, the effects of varying radiant exposure (RE) values generated by second and third generation LED LCUs on the degree of conversion (DC) and maximum rate of polymerization (Rpmax) of an experimental Lucirin TPO-based RC were evaluated. Material and Methods 1 mm or 2 mm thick silicon molds were positioned on a horizontal attenuated total reflectance (ATR) unit attached to an infrared spectroscope. The RC was inserted into the molds and exposed to varying REs (18, 36 and 56 J/cm2) using second (Radii Plus, SDI) and third generation LED LCUs (Bluephase G2/Ivoclar Vivadent) or a quartz tungsten based LCU (Optilux 501/SDS Kerr). FTIR spectra (n=7) were recorded for 10 min (1 spectrum/s, 16 scans/spectrum, resolution 4 cm-1) immediately after their application to the ATR. The DC was calculated using standard techniques for observing changes in aliphatic to aromatic peak ratios both prior to, and 10 min after curing, as well as during each 1 second interval. DC and Rpmax data were analyzed using 3-way ANOVA and Tukey’s post-hoc test (p=0.05). Results No significant difference in DC or Rpmax was observed between the 1 mm or 2 mm thick specimens when RE values were delivered by Optilux 501 or when the 1 mm thick composites were exposed to light emitted by Bluephase G2, which in turn promoted a lower DC when 18 J/cm2 (13 s) were delivered to the 2 mm thick specimens. Radii Plus promoted DC and Rpmax values close to zero under most conditions, while the delivery of 56 J/cm2 (40 s) resulted in low DC values. Conclusions The third generation LCU provided an optimal polymerization of Lucirin TPO-based RC under most tested conditions, whereas the second generation LED-curing unit was useless regardless of the RE.

Resumo Introdução O consumo de bebidas esportivas contendo maltodextrina durante a atividade física tem aumentado. Geralmente elas são ácidas, podendo causar erosão dentária. Objetivo Avaliar o efeito da diluição sobre o potencial erosivo de bebidas esportivas contendo maltodextrina. Metodologia Cinco amostras de cinco bebidas esportivas contendo maltodextrina [Sports Nutrition (SN), Body Action (BA), New Millen (NM), Atlhetica Nutrition (AN), Integral Medica (IM)] foram diluídas com água destilada em três diferentes proporções: como recomendado pelo fabricante (REC), com 20% a mais de pó (20+) e com 20% a menos de pó (20-) do que o recomendado. Foram determinados o seu pH e titrabilidade ácida (volume de NaOH 1N necessário para elevar o pH para 5,5). Resultado O pH e titrabilidade ácida foram diferentes entre os produtos. Os valores de pH foram diferentes entre as diluições. Todas as bebidas esportivas apresentaram pH abaixo do pH crítico para a desmineralização do esmalte dental. Houve uma correlação negativa significativa entre o pH e a titrabilidade ácida (p <0,01; r = -0,795). Conclusão Pequenas alterações na diluição de bebidas esportivas contendo maltodextrina podem afetar o seu pH, mas não a sua titrabilidade ácida.

Abstract Introduction The increasing consumption of maltodextrin-containing sports drinks, usually acidic, during physical activity may cause dental erosion. Objective To evaluate the effect of dilution on the erosive potential of maltodextrin-containing sports drinks. Methodology Five samples of five maltodextrin-containing sports drinks [Sports Nutrition (SN), Body Action (BA), New Millen (NM), Athletica Nutrition (AN), Integral Medica (IM)] were diluted with distilled water in three different proportions: as recommended by manufacturer (rec), with 20% more powder (20+) and with 20% less powder (20-) than recommended. Their pH and titratable acidity (volume of 1N NaOH necessary to raise pH to 5.5) were determined. Result The pH and titratable acidity differed among the products, and pH values differed among the dilutions. All sports drinks showed pH below the critical pH for dental enamel demineralization. There was a significant negative correlation between pH and titratable acidity (p <0.01; r = -0.795). Conclusion Changes in the dilution of maltodextrin-containing sports drinks affected their pH, but not their titratable acidity.

ABSTRACT Objective This in vitro study evaluated the effect of two different shades of resin cement (RC- A1 and A3) layer on color change, translucency parameter (TP), and chroma of low (LT) and high (HT) translucent reinforced lithium disilicate ceramic laminates. Material and Methods One dual-cured RC (Variolink II, A1- and A3-shade, Ivoclar Vivadent) was applied to 1-mm thick ceramic discs to create thin RC films (100 µm thick) under the ceramics. The RC was exposed to light from a LED curing unit. Color change (ΔE) of ceramic discs was measured according to CIEL*a*b* system with a standard illuminant D65 in reflectance mode in a spectrophotometer, operating in the light range of 360-740 nm, equipped with an integrating sphere. The color difference between black (B) and white (W) background readings was used for TP analysis, while chroma was calculated by the formula C*ab=(a*2+b*2)½. ΔE of 3.3 was set as the threshold of clinically unacceptable. The results were evaluated by two-way ANOVA followed by Tukey's post hoc test. Results HT ceramics showed higher ΔE and higher TP than LT ceramics. A3-shade RC promoted higher ΔE than A1-shade cement, regardless of the ceramic translucency. No significant difference in TP was noted between ceramic discs with A1- and those with A3-shade cement. Ceramic with underlying RC showed lower TP than discs without RC. HT ceramics showed lower chroma than LT ceramics, regardless of the resin cement shade. The presence of A3-shade RC resulted in higher chroma than the presence of A1-shade RC. Conclusions Darker underlying RC layer promoted more pronounced changes in ceramic translucency, chroma, and shade of high translucent ceramic veneers. These differences may not be clinically differentiable.

This study examined the effect of cariogenic and erosive challenges (CCs and ECs, respectively) on the degradation of copper-nickel-titanium (CuNiTi) orthodontic wires. Sixty wire segments were divided into four treatment groups and exposed to CCs, ECs, artificial saliva, or dry storage (no-treatment control). CC and EC were simulated using a demineralizing solution (pH 4.3) and a citric acid solution (pH 2.3), respectively. Following treatment, the average surface roughness (Ra) of the wires was assessed, and friction between the wires and a passive self-ligating bracket was measured. CuNiTi wires subjected to ECs exhibited significantly higher Ra values than did those that were stored in artificial saliva. In contrast, surface roughness was not affected by CCs. Finally, friction between the treated wires and brackets was not affected by ECs or CCs. Our results indicate that CuNiTi orthodontic wires may suffer degradation within the oral cavity, as ECs increased the surface roughness of these wires. However, rougher surfaces did not increase friction between the wire and the passive self-ligating bracket.

OBJETIVO: O objetivo do presente estudo foi investigar os efeitos térmicos do laser de Er,Cr:YSGG (1,5W/20Hz) em zircônia tetragonal policristalina estabilizada com ítrio (Y-TZP). MATERIAL E MÉTODO: Quinze discos de Y-TZP (AS Technology Titanium FIX, São José dos Campos, Brasil) com 5 mm de diâmetro e 3 mm de altura padronizados com CAD-CAM (computer-aided design e computer-aided manufacturing) foram usados. Os discos de Y-TZP foram randomicamente distribuídos em três grupos (n=5): Y-TZP-G1 = controle (sem irradiação); Y-TZP-G2 = Y-TZP + Er,Cr:YSGG (proporção resfriamento ar-água 80%/25%); Y-TZP-G3 = Y-TZP + Er,Cr:YSGG (proporção resfriamento ar-água 80%/0%). Um termopar (SmartMether, Novus, Porto Alegre, RS, Brasil) acoplado a um termômetro digital (SmartMether, Novus, Porto Alegre, RS, Brasil) foi fixado na face oposta à superfície irradiada. Os gradientes de temperatura ΔT foram calculados (ΔT = Temperatura final - Temperatura inicial) para cada grupo. Os valores foram analisados estatisticamente por one-way ANOVA com 95% de confiança e comparados pelo teste Tukey (α=0,05). Uma amostra de cada grupo foi analisada por microscopia confocal de luz branca. RESULTADO: O teste ANOVA mostrou diferenças significativas para o fator "laser" (p< 0,001). Os gradientes de temperatura (valores de ΔT) apresentaram os seguintes resultados: Y-TZP-G1 = 0 ºC; Y-TZP-G2 = -1,4 ºC e Y-TZP-G3= 21,4 ºC. O valor de ΔT (ºC) do grupo sem refrigeração foi maior do que o grupo refrigerado. Os valores de rugosidade (Ra) variaram de 4,50 até -33,65 µm. CONCLUSÃO: A refrigeração com água para a irradiação do laser de Er,Cr:YSGG é essencial para evitar o aumento de temperatura de Y-TZP.

OBJECTIVE: The objective of the present study was to investigate the thermal effects of Er,Cr:YSGG laser irradiation (1.5W/20Hz) on yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP). MATERIAL AND METHOD: Fifteen disks of Y-TZP (AS Technology TitaniumFIX, São José dos Campos, Brazil) with 5 mm diameter and 3 mm high standardized with CAD-CAM were used. The Y-TZP disks were randomized in three groups (n=5): Y-TZP-G1 = control (no laser treatment); Y-TZP-G2 = Y-TZP + Er,Cr:YSGG laser (air-water cooling proportion 80%/25%); Y-TZP-G3 = Y-TZP + Er,Cr:YSGG laser (air-water cooling proportion 80%/0%). A thermopar (SmartMether, Novus, Porto Alegre, RS, Brazil) was attached to a digital thermometer (SmartMether, Novus, Porto Alegre, RS, Brazil) fixed to the opposite irradiated surface. The temperature gradients (ΔT) were calculated (ΔT = Final Temperature - Initial Temperature) for each group. Values were statistically analyzed by one-way ANOVA at the 95% confidence level and compared by Tukey post-hoc test (α=0.05) for each material. One sample of each group was analyzed by confocal white light microscopy. RESULT: The ANOVA test showed significant differences for the factor "laser" (p<.001). The temperature gradients (ΔT value) showed the following results: Y-TZP-G1 = 0 ºC; Y-TZP-G2 = -1.4 ºC and Y-TZP-G3 = 21.4 ºC. The ΔT values (ºC) of the non-refrigerated group were higher than the refrigerated group. The roughness value (Ra) ranged from 4.50 to -33.65 µm. CONCLUSION: The water refrigeration for Er,Cr:YSGG irradiation is essential to avoid thermal increase in the Y-TZP.

This study evaluated the effects of the photoactivation source and restorative material on the development of caries-like lesions on human enamel after an in vitro pH challenge. Enamel cavities were prepared in 36 blocks, which were assigned to two groups according to the restorative material: resin-modified glass ionomer (RMGI) and composite resin (CR). Samples were exposed to quartz-tungsten-halogen lamp, argon-ion laser, or light-emitting diode (n = 6). The Knoop microhardness (KHN) values of the top surface of all materials were evaluated. Restored enamel blocks were thermocycled and subjected to 10 demineralization-remineralization cycles at 37°C. KHN analysis of the superficial enamel was performed by four indentations located 100 mm from the restoration margin. The material KHN was not affected by the photoactivation source. No significant difference in KHN was noted between CR and RMGI. The enamel surface around RMGI exhibited a higher KHN (272.8 KHN) than the enamel around CR (93.3 KHN), regardless of the photoactivation source. Enamel demineralization around the dental restoration was not influenced by the photoactivation source. Less enamel demineralization was observed around the RMGI than around the CR restoration.

Condensações de Knoevenagel de aldeídos aromáticos com 4-cloro-3-oxobutanoato de etila catalisadas por morfolina/ácido acético foram conduzidas em líquidos iônicos para fornecerem 2-cloroacetil-3-arilpropenoatos de etila em 44 a 84% de rendimentos após 0,5 a 2 h à temperatura ambiente (25-28 ºC). Estas condições representam um protocolo mais verde para a condensação de Knoevenagel do que aquelas realizadas com refluxo de benzeno e tolueno, utilizados como solventes. Aldeídos aromáticos contendo grupos arila, 4-clorofenila, 4-metoxifenila, 2-tiofuranila, 2-furanila, fenila e 3,4-metilenodioxifenila apresentaram razões diastereoméricas (E)/(Z) de 56/44 a 85/15. A estrutura do isômero-(E) do 2-cloroacetil-3-(3',4'-metilenodioxifenil)propenoato de etila foi determinada por difração de raio X, e uma metodologia inequívoca da análise estrutural-(E)/(Z) por RMN de 13C (ressonância magnética nuclear) é apresentada.

Knoevenagel condensations of aromatic aldehydes with ethyl 4-chloro-3-oxobutanoate catalyzed by morpholine/acetic acid were carried out in ionic liquids to give ethyl 2-chloroacetyl-3-arylpropenoates in 44-84% yield after 0.5 to 2 h at room temperature (25-28 ºC). These conditions represent a greener protocol for the Knoevenagel condensation than those using refluxing benzene or toluene as solvent. Aromatic aldehydes having aryl groups 4-chlorophenyl, 4-methoxyphenyl, 2-thiofuranyl, 2-furanyl, phenyl and 3,4-methylenedioxyphenyl gave (E)/(Z) diastereomeric ratios of products from 56/44 to 85/15. The two isomers of each compound were separately isolated and characterized. The structure of the (E)-isomer of ethyl 2-chloroacetyl-3-(3',4' methylenedioxyphenyl)propenoate was determined by X-ray crystallography and an unequivocal methodology of (E)/(Z)-structural analysis by 13C NMR (nuclear magnetic resonance) is presented.

This study evaluated the effects of resin luting agents (LA) polymerized using increased temperature on the in vitro microtensile bond strength (mTBS) of indirect restorations to dentin. The occlusal dentin surfaces of 40 human third molars were exposed and flattened. The teeth were assigned to 8 groups (n = 5) according to the LA temperature (25°C o r 50°C), curing mode (dual- or self-curing mode), and product (Excite DSC/Variolink II [VII] and XP Bond/Calibra [Cal]). The bonding agents were applied to the dentin surfaces according to manufacturers' instructions. For preheated groups, the LAs were heated to 50°C, subsequently mixed on a heated stirrer surface, and applied to the previously heated pre-polymerized resin discs (2 mm thickness, TPH-Spectrum). The discs were bonded to the dentin surfaces, and the LAs were either exposed to a curing light according to manufacturers' instructions or allowed to self-cure. Specimens were stored in relative humidity at 37°C for 7 days. Specimens were mesio-distally and bucco-lingually sectioned to obtain multiple bonded beams with a 1-mm² cross-sectional area for mTBS testing. Data (MPa) were analyzed by 2-way ANOVA and Tukey's post hoc test (a = 5%) for each product. Specimen failure patterns were analyzed using a scanning electron microscope. VII groups showed higher mTBS at 50°C than at 25°C regardless of curing mode (p = 0.05). Cal groups showed similar mTBS at 25°C and 50°C in all activation modes. The use of some dual-polymerizing LAs at 50°C may improve the mTBS of indirect restorations to dentin.

The wide use of dental bleaching treatment has brought concern about the possible effects of hydrogen peroxide on dental tissue and restorative materials. The objective of this study was to evaluate in vitro the effect of nightguard bleaching on the surface roughness of dental ceramics after different periods of bleaching treatment. Fifteen specimens of 5 × 3 × 1 mm were created with three dental ceramics following the manufacturers' instructions: IPS Classic (Ivoclar-Vivadent); IPS d.Sign (Ivoclar-Vivadent); and VMK-95 (Vita). A profilometer was used to evaluate baseline surface roughness (Ra values) of all ceramics by five parallel measurements with five 0.25 mm cut off (Λc) at 0.1 mm/s. Afterwards, all specimens were submitted to 6-h daily bleaching treatments with 10% or 16% carbamide peroxide (Whiteness- FGM) for 21 days, while control groups from each ceramic system were stored in artificial saliva. The surface roughness of all groups was evaluated after 18 h, 42 h, 84 h, and 126 h of bleaching treatment. The surface roughness of each specimen (n = 5) was based on the mean value of five parallel measurements in each time and all data were submitted to two-way repeated measures ANOVA and Tukey's post-hoc test (α = 0.05). No significant differences in ceramic surface roughness were observed between untreated and bleached ceramic surfaces, regardless of bleaching intervals or bleaching treatments. This study provided evidence that at-home bleaching systems do not cause detrimental effects on surface roughness of dental ceramics.

The aim of this study was to evaluate the degree of conversion by Knoop microhardness (KHN) and FT-Raman spectroscopy (FTIR) of one nanofilled (Filtek Supreme-3M-ESPE [FS]) and one microhybrid composite (Charisma-Heraeus-Kulzer [CH]), each with different opacities, namely enamel, dentin, and translucent, which were photo-activated by a quartz-tungsten-halogen lamp (QTH) and a light-emitting diode (LED). Resin was bulk inserted into a disc-shaped mold that was 2.0 mm thick and 4 mm in diameter, obtaining 10 samples per group. KHN and FTIR values were analyzed by two-way ANOVA and Tukey's tests (α = 0.05). Nanofilled resin activated by a LED presented higher microhardness values than samples activated by a QTH for dentin opacity (p < 0.05). The microhybrid resin showed no differences in KHN or FTIR values with different activation sources or opacity. The nanofilled dentin and enamel resins showed lower FTIR values than the translucent resin. The KHN values of the translucent resins were not influenced by the light source.

This study evaluated the degree of conversion (DC) and ultimate tensile strength (UTS) of dual-cured resin cements heated to 50º C prior to and during polymerization. Disc- and hourglass-shaped specimens of Rely X ARC (RX) and Variolink II (VII) were obtained using addition silicon molds. The products were manipulated at 25º C or 50º C and were subjected to 3 curing conditions: light-activation through a glass slide or through a pre-cured 2-mm thick resin composite disc, or they were allowed to self-cure (SC). All specimens were dark-stored dry for 15 days. For DC analysis, the resin cements were placed into the mold located on the center of a horizontal diamond on the attenuated total reflectance element in the optical bench of a Fourier Transformed Infrared spectrometer. Infrared spectra (n = 6) were collected between 1680 and 1500 cm-1, and DC was calculated by standard methods using changes in ratios of aliphatic-to-aromatic C=C absorption peaks from uncured and cured states. For UTS test, specimens (n = 10) were tested in tension in a universal testing machine (crosshead speed of 1 mm/min) until failure. DC and UTS data were submitted to 2-way ANOVA, followed by Tukey's test (α= 5%). Both products showed higher DC at 50º C than at 25º C in all curing conditions. No significant difference in UTS was noted between most light-activated groups at 25º C and those at 50º C. VII SC groups showed higher UTS at 50º C than at 25º C (p < 0.05). Increased temperature led to higher DC, but its effects on resin cement UTS depended on the curing condition.

Fosfolipase A2 colhida da serpente Crotalus durissus terrificus foi empregada pela primeira vez para testar sua enantiosseletividade na hidrólise de diferentes ésteres não-naturais. Foi observado que a estrutura desta pequena enzima tem sua ação lipase dependente da escolha dos substratos não-naturais. Foram usadas duas formas da enzima; livre e como agregado enzimático formado com ligações cruzadas, CLEA. Com todos os substratos, a enzima livre mostrou atividade similar a da preparada CLEA. A vantagem da fosfolipase CLEA é que permite sua reutilização em várias reações consecutivas sem demonstrar diminuição de atividade e seletividade, propiciando rendimentos bons e superiores, e ee similares quando comparados com os da enzima livre.

Phospholipase A2 from the rattlesnake Crotalus durissus terrificus was employed for the first time to test its enantioseletivity on the hydrolysis of different non-natural esters. It was observed that the structure of this small enzyme is restrictive in the choice of its lipase action with non-natural substrates. Two forms of the enzyme were used; free and as its cross-linked enzyme aggregate (CLEA). With all substrates, the free enzyme showed activity similar to the CLEA preparation. The advantage of the CLEA phospholipase is the possibility to reuse it in several consecutive reactions without a decrease of activity and selectivity with good but higher yields and ee than with the free enzyme.