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The synthesis and structural characterization of four novel supramolecular hydrogen-bonded arrangements based on self-assembly from molecular `[Cu(2,2'-biimidazole)]' modules and malonate anions are presented, namely, tetrakis(2,2'-biimidazole)di-µ-chlorido-dimalonatotricopper(II) pentahydrate, [Cu3(C3H2O4)2Cl2(C6H6N4)4]·5H2O or [Cu(H2biim)2(µ-Cl)Cu0.5(mal)]2·5H2O, aqua(2,2'-biimidazole)malonatocopper(II) dihydrate, [Cu(C3H2O4)(C6H6N4)(H2O)]·2H2O or [Cu(H2biim)(mal)(H2O)]·2H2O, bis[aquabis(2,2'-biimidazole)copper(II)] dimalonatodiperchloratocopper(II) 2.2-hydrate, [Cu(C6H6N4)2(H2O)]2[Cu(C3H2O4)(ClO4)2]·2.2H2O or [Cu(H2biim)2(H2O)]2[Cu(mal)2(ClO4)2]·2.2H2O, and bis(2,2'-biimidazole)copper(II) bis[bis(2,2'-biimidazole)(2-carboxyacetato)malonatocopper(II)] tridecahydrate, [Cu(C6H6N4)2][Cu(C3H2O4)(C3H3O4)(C6H6N4)2]·13H2O or [Cu(H2biim)2][Cu(H2biim)2(Hmal)(mal)]2·13H2O. These assemblies are characterized by self-complementary donor-acceptor molecular interactions, demonstrating a recurrent and distinctive pattern of hydrogen-bonding preferences among the carboxylate, carboxylic acid and N-H groups of the coordinated 2,2'-biimidazole and malonate ligands. Additionally, coordination of the carboxylate group with the metallic centre helps sustain remarkable supramolecular assemblies, such as layers, helices, double helix columns or 3D channeled architectures, including mixed-metal complexes, into a single structure.

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Using a 1:1 cocrystal of (E)-N-(3,4-difluorophenyl)-1-(pyridin-4-yl)methanimine with acetic acid, C12H8F2N2·C2H4O2, we investigate the influence of F atoms introduced to the aromatic ring on promoting π-π interactions. The cocrystal crystallizes in the triclinic space group P1. Through crystallographic analysis and computational studies, we reveal the molecular arrangement within this cocrystal, demonstrating the presence of hydrogen bonding between the acetic acid molecule and the pyridyl group, along with π-π interactions between the aromatic rings. Our findings highlight the importance of F atoms in promoting π-π interactions without necessitating full halogenation of the aromatic ring.

RESUMO

To evaluate the effect of adhesive coats application on the enamel microtensile bond strength (µTBS) of universal adhesives, morphological etching pattern and their chemical interaction with hydroxyapatite (HA). Two universal adhesives were investigated: Scotchbond Universal (SBU, 3 M) and Prime&Bond Universal (PBU, Dentsply). The adhesives were applied in self-etching mode on bovine enamel (n = 8) in one (1L), two (2L) or three coats (3L) and light-cured as per manufacturers' instructions. As controls adhesives were applied to etched enamel (H3PO4-37% phosphoric acid). Bonded specimens were cut into sticks that were stored in deionized water for 24 h or 6 months prior to µTBS testing. Two-way ANOVA and Tukey's test were used for statistical analysis of bond strength with α = 5%. For morphological SEM analysis, enamel surfaces were treated as aforementioned and immediately rinsed with acetone. The intensity of monomer-calcium salt formation from each treatment was measured via infrared spectroscopy (ATR-FTIR). All treatments presented no significant reduction on µTBS after aging (p > 0.05). However, SBU attained highest µTBS when applied in 3L. PBU showed higher µTBS when applied to H3PO4 etched enamel than 1L or 2L. Etching pattern was enhanced by 3L application, particularly with PBU. Chemical interaction was notably higher for SBU than PBU, with no relevant differences with more layers or prior H3PO4-etching. The application of three adhesive coats of universal adhesives in self-etch mode using may enhance the bonding performance and etching pattern to enamel, surpassing the H3PO4-etched enamel bond for SBU. The chemical interaction with calcium from enamel is not affected by number of coats or prior phosphoric acid etching.

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The first step in comprehending the properties of Au10 clusters is understanding the lowest energy structure at low and high temperatures. Functional materials operate at finite temperatures; however, energy computations employing density functional theory (DFT) methodology are typically carried out at zero temperature, leaving many properties unexplored. This study explored the potential and free energy surface of the neutral Au10 nanocluster at a finite temperature, employing a genetic algorithm coupled with DFT and nanothermodynamics. Furthermore, we computed the thermal population and infrared Boltzmann spectrum at a finite temperature and compared it with the validated experimental data. Moreover, we performed the chemical bonding analysis using the quantum theory of atoms in molecules (QTAIM) approach and the adaptive natural density partitioning method (AdNDP) to shed light on the bonding of Au atoms in the low-energy structures. In the calculations, we take into consideration the relativistic effects through the zero-order regular approximation (ZORA), the dispersion through Grimme's dispersion with Becke-Johnson damping (D3BJ), and we employed nanothermodynamics to consider temperature contributions. Small Au clusters prefer the planar shape, and the transition from 2D to 3D could take place at atomic clusters consisting of ten atoms, which could be affected by temperature, relativistic effects, and dispersion. We analyzed the energetic ordering of structures calculated using DFT with ZORA and single-point energy calculation employing the DLPNO-CCSD(T) methodology. Our findings indicate that the planar lowest energy structure computed with DFT is not the lowest energy structure computed at the DLPN0-CCSD(T) level of theory. The computed thermal population indicates that the 2D elongated hexagon configuration strongly dominates at a temperature range of 50-800 K. Based on the thermal population, at a temperature of 100 K, the computed IR Boltzmann spectrum agrees with the experimental IR spectrum. The chemical bonding analysis on the lowest energy structure indicates that the cluster bond is due only to the electrons of the 6 s orbital, and the Au d orbitals do not participate in the bonding of this system.

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This report describes multidisciplinary care combining orthodontics and restorative dentistry for a patient with Class II occlusion and stained mandibular and maxillary resin composite veneers. The orthodontic treatment improved severe overjet and malocclusion prior to restorative care. Occlusal assessment was provided with a novel digital device (PlaneSystem, Zirkonzahn) that is integrated with digital workflows for the evaluation of the occlusal plane and condylar path inclination. Diagnostic digital impressions and digital wax-up for intraoral mock-ups led to the patient's treatment acceptance. Minimally invasive tooth preparation, final digital impressions, and bonding under dental dam isolation fulfilled the patient's esthetic and functional demands with all-ceramic restorations.

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The (R,R)-Teth-TsDPEN-Ru(II) complex promoted the one-pot double C=O reduction of α-alkyl-ß-ketoaldehydes through asymmetric transfer hydrogenation/dynamic kinetic resolution (ATH-DKR) under mild conditions. In this process, ten anti-2-benzyl-1-phenylpropane-1,3-diols (85:15 to 92:8 dr) were obtained in good yields (41-87%) and excellent enantioselectivities (>99% ee for all compounds). Notably, the preferential reduction of the aldehyde moiety led to the in situ formation of 2-benzyl-3-hydroxy-1-phenylpropan-1-one intermediates. These intermediates played a crucial role in enhancing both reactivity and stereoselectivity through hydrogen bonding.

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This systematic review evaluated the effect of different hydrofluoric acid (HF) etching regimens and a self-etch ceramic primer (SECP) on the flexural strength (FS) and fatigue failure load (FFL) of glass-ceramic materials.The identification of relevant studies was conducted by two authors in five databases: PubMED, Scopus, Web Of Science, LILACS and Virtual Health Library (BVS) until July 2022 with no year limit. The analysis was conducted in RevMan 5.4.1 Software (Cochrane Collaboration) using Random effect model at 5 %. The risk of bias of the included studies were assessed. From the 5349 articles identified, 34 were included for quantitative analysis. Meta-analysis showed that for predominantly glassy ceramics, etching with HF 5 % had no significant impact on FS, however, HF acid etching with concentrations greater than 5 % negatively impacted FS. For lithium disilicate glass-ceramics (LDGC) HF acid etching, negatively influenced FS, while increasing the FFL. HF etching negatively affected FS of hybrid ceramics. The self-etch ceramic primer and HF acid etching showed a similar impact on FFL and FS. This meta-analysis indicates that the impact of SECP and HF acid etching on the mechanical behavior of glass ceramics is material-dependent.

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Mother-infant bonding is influenced by several risk and protective factors, and the literature has investigated the relationships between these factors independently. This study aimed to verify the interrelationships of some of these factors and how they influence mother-infant bonding in Brazil. In this study, 361 mothers participated, and the outcome variable of mother-infant bonding was assessed using the Postpartum Bonding Questionnaire (PBQ). Multivariate regression analysis was performed using a hierarchical model with three blocks structured according to the influence exerted on mother-infant bonding. The PBQ's factor scores were estimated and used in the subsequent analyses to decrease measurement error. The variable "violence experienced by mothers" was statistically significant for explaining the second block model but not significant for the third block. Network analysis was performed after multiple regression, showing that the violence experienced by mothers does not directly influence mother-infant bonding but rather is mediated by postpartum depression. This explains why violence is not significant in the hierarchical multiple regression when maternal depression is added to the model. This study's strengths lie in its utilization of PBQ factor scores and network analysis, enabling the estimation of conditional relationships among variables. This approach provides deeper insights into factors affecting mother-infant bonding.

Varios factores de riesgo y de protección ejercen influencia sobre la unión afectiva madre­infante; la literatura disponible ha investigado las relaciones entre estos factores de una manera independiente. Este estudio se propuso verificar las interrelaciones de algunos de estos factores y cómo ellos influyen en la unión afectiva madre­infante. Se consultó un total de 361 madres y el variable resultado de afectividad madre­infante se evaluó por medio del Cuestionario de Afectividad de Postparto (PBQ). Se llevaron a cabo análisis de regresión multivariados usando un modelo jerárquico con tres estructuras de bloques de acuerdo con la influencia ejercida sobre la unión afectiva madre­infante. Se estimaron y usaron los puntajes de factores del PBQ en los análisis subsecuentes para disminuir el error en la medida. La variable "violencia experimentada por las madres" fue estadísticamente significativa para explicar el segundo modelo de bloque, pero no significativa para el tercer bloque. Se llevó a cabo un análisis de interrelaciones después de la regresión múltiple, demostrando que la violencia experimentada por las madres no influye directamente la afectividad madre­infante, sino que la misma es mediada por la depresión posterior al parto. Esto explica por qué la violencia no es significativa en la jerárquica regresión múltiple cuando la depresión materna se le agrega al modelo. Entre los puntos fuertes de este estudio se incluye el uso de los puntajes de factores del PBQ y el análisis de interrelaciones, lo cual permitió que se estimaran las relaciones condicionales existente dentro del grupo de variables, aportando una mayor comprensión de algunos factores que interfieren en la unión afectiva madre­infante.

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RESUMO

Objective: This study aimed to evaluate the bond strength of a universal adhesive to dentin (µTBS) using different time periods of airborne particle abrasion (APA) and two types of acid etching. Methods: Seventy-two human third molars were divided into 9 groups (n=8) according to dentin pretreatment: APA duration (0, 5, or 10s) and acid etching (no acid - NA, 37% phosphoric acid - PhoA, or 1% phytic acid - PhyA). APA was performed at a 0.5 cm distance and air pressure of 60 psi using 50 µm aluminum oxide particles. Afterwards, two coats of Single Bond Universal adhesive (3M) were applied to the dentin surface. Composite blocks were built using the incremental technique, sectioned into 1×1 mm slices and subjected to microtensile bond strength (µTBS) testing. Fracture patterns and surface topography of each dentinal pretreatment were evaluated using a Scanning electron microscope (SEM). Bond strength data were analyzed using two-way ANOVA and Bonferroni post-hoc tests. Results: The group that received pretreatment with 5s APA and PhoA presented higher µTBS values among all groups, which was statistically different when compared with the PhoA, 10APA+PhoA, and 5APA+PhyA groups. PhyA did not significantly influence the bond strength of the air-abraded groups. Finally, adhesive failure was considered the predominant failure in all groups. Conclusion: Dentin pretreated by airborne particle abrasion using aluminum oxide demonstrated an increase in bond strength when abraded for 5 seconds and conditioned with phosphoric acid in a universal adhesive system.

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La estética ha llegado a formar una parte muy importante en la odontología actual. Sin embargo, no debemos sobreponer las necesidades estéticas sobre las necesidades funcionales. La pérdida de estructura dental asociada a bruxismo puede ser considerada patológica cuando compromete la guía anterior, la cual es la influencia en los movimientos mandibulares que proveen las superficies contactantes de los dientes maxilares anteriores con los mandibulares anteriores y evita contactos excéntricos dañinos en los dientes posteriores. El objetivo de este reporte de caso es presentar una alternativa conservadora para restablecer tanto la estética como la funcionalidad de una paciente de 34 años de edad que acudió a la Clínica de Prostodoncia de la Universidad Autónoma de Guadalajara en busca de rehabilitación estética de dientes anteriores. Una vez realizada su evaluación inicial se llegó al diagnóstico de pérdida de guía anterior por desgaste patológico asociado a bruxismo. El tratamiento incluyó tratamientos de conductos, remoción de caries y restauraciones mal ajustadas, coronas y carillas para restablecer la guía anterior. Se cumplieron con las expectativas estéticas que tenía la paciente al igual que con las necesidades funcionales que fueron objetivo desde el inicio, logrando un restablecimiento de la guía anterior de manera conservadora (AU)

Esthetics has become a very important part of dentistry today. However, we should not superimpose esthetic needs over functional needs. The loss of tooth structure associated with bruxism can be considered pathologic when it compromises the anterior guidance, which is the influence on mandibular movements that provides the contacting surfaces of the maxillary anterior teeth with the mandibular anterior teeth and avoids damaging eccentric contacts in the posterior teeth. The aim of this case report is to present a conservative way to restore both esthetics and function in a 34-year-old patient who came to the Prosthodontics Clinic of the Universidad Autónoma de Guadalajara in search of an esthetic appearance of her anterior teeth. After her initial evaluation, a diagnosis of anterior guide loss due to pathological wear associated with bruxism was made. Treatment included root canal treatment, removal of caries, and ill-fitting restorations, crowns, and veneers to reestablish the anterior guidance. The aesthetic expectations of the patient have met as well as the functional needs that were aimed from the beginning, achieving a conservative reestablishment of the anterior guidance system (AU)

Assuntos