Influence of Thickness and Shade on the Color of Layered Novel Nanohybrid Composite Systems.

The influence of the layer thickness and composite shade on the final color of Ceram.X composites (Dentsply Sirona) was tested, selecting five intermediate-translucency Ceram.X Universal shades, three high-translucency Ceram.X Duo "enamel" shades, and four low-translucency Ceram.X Duo "dentin" shades. Using cylindrical molds, 850 specimens were obtained, representing the whole array of possible Universal single specimens (in seven thicknesses, ranging from 1.0 to 4.0 mm in 0.5-mm increments) and Duo combinations. The CIELAB coordinates of each specimen were determined with a spectrophotometer. Different thicknesses and composites were compared with Clark's ΔE. The difference in color among specimens of different thicknesses was material-dependent. The thickness and shade of the composite markedly affected the color yield of the Ceram.X system. For each shade of the Universal systems, only one Duo enamel-dentin combination corresponded.

Development of di-methacrylate quaternary ammonium monomers with antibacterial activity.

Nine antibacterial di-methacrylate monomers based on bis-quaternary ammonium salts (bis-QAMs) were synthesized and structurally characterized. The biological activity of the bis-QAMs was tested in terms of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) on different bacterial strains achieving promising results and, in most cases, a complete bactericidal effect using a bis-QAM concentration lower than 1 mg/mL. Two of the structures showed comparable and superior activity against S. mutans than the commercial monomer 12-methacryloyloxydodecyl pyridinium bromide (MDBP). All the bis-QAMs here described were able to inhibit S. mutans biofilm formation at a concentration equal to the MIC value. From the analysis of the obtained data, some correlation regarding the structure and the antibacterial activity of the bis-QAMs could be drawn: a flexible alkyl C12 spacer between the two quaternary ammonium moieties increased the monomer antibacterial effect in comparison to the aromatic ones; the equilibrium between hydrophobic and hydrophilic moieties was directly correlated to the bactericidal range of action; the increase of the steric hindrance of the ammonium side groups might be both advantageous or disadvantageous to the antibacterial efficacy depending on the whole monomer chemical structure. Even though the possible correlation between the monomer structures and their bacteriostatic or bactericidal effect is under investigation, the monomers exhibited low cytotoxicity on human dental pulp stem cells, confirming their promising potential in the dental materials' field. STATEMENT OF SIGNIFICANCE: The use of dental resins with antibacterial monomers might prevent the formation of secondary caries at the restoration margins. For this purpose, a series of di-methacrylate bis-quaternary ammonium monomers (QAMs) was developed. Unlike antibacterial mono-methacrylate monomers already described in the literature, the synthesized di-methacrylate monomers have the potential of acting as cross-linkers stabilizing the polymeric network and bear two quaternary ammonium groups that increase their antibacterial ability. The QAMs exert bactericidal activity on both Gram(+) and Gram(-) bacterial strains maintaining at the same time good biocompatibility with the oral environment. Some structural elements of the monomers were clearly related to high antibacterial properties, and this can help design new active structures and better understand their mechanism of action.

In vitro study on conditioned dental root surfaces: evaluation of wettability, smear layer, and blood clot adhesion.

OBJECTIVES: The aim was to investigate the efficacy of citric acid and ethylenediaminetetraacetic acid (EDTA)-based treatments on smear layer removal and blood clot formation and stabilization. METHOD AND MATERIALS: After scaling and root planing, 126 root samples were divided into seven groups treated with: deionized water; saline; citric acid solution; Ultradent Citric Acid gel; EDTA solution; EDTA-based PrefGel; or untreated. Each group was divided into three subgroups: I for the evaluation of smear layer removal and surface wettability, II and III for the evaluation of blood clot formation and stabilization in static or dynamic rinsing conditions. RESULTS: Conditioning agent treatments increased surface wettability with respect to untreated samples (Ultradent: 45 ± 1 degrees, P = 6.2 × 10-3; EDTA: 36 ± 5 degrees, P = 8.9 × 10-7; PrefGel: 47 ± 7 degrees, P = 3.2 × 10-2). Smear layer removal (30% to 60% with respect to untreated samples) was observed for all the conditioning agents. Clot was absent on untreated samples and samples treated with deionized water. Clot quality was significantly higher for samples treated with conditioning agents (P < .05) and similar between group II and III (P > .05). A statistically significant difference (P = .027) was observed for clot coverage of the saline group, comparing static and dynamic rinsing, confirming the positive effect of treatments on clot stabilization. CONCLUSIONS: The use of conditioning agents improves smear layer removal and clot formation and stabilization with respect to scaling and root planing procedure only, which is, however, considered an essential procedure to promote wound healing in periodontal surgery.

Evaluation of degree of conversion, rate of cure, microhardness, depth of cure, and contraction stress of new nanohybrid composites containing pre-polymerized spherical filler.

The aim of the present study was to characterize nanohybrid and nanofilled composites in terms of degree of conversion (DC), rate of cure (RC), microhardness (Vickers hardness number; VHN), depth of cure, and contraction stress (CS). Ceram.X® universal- A3, duo enamel E2, and duo dentin D3 composites were compared to Tetric EvoCeram® and FiltekTMSupreme XTE composites of equivalent dentin and enamel shades under a 40 s photopolymerization protocol. DC was measured by infrared spectroscopy, calculating RC from the kinetic curve. Top and bottom VHN were determined using a Vickers indenter, and bottom/top surface ratio (Vickers hardness ratio; VHR) calculated. CS vs. time was assessed by a universal testing machine and normalized for the specimen bonding area. All materials showed DC < 60%, Ceram.X® composites reaching higher values than the other composites of corresponding shades. RC at 5 s of photopolymerization was always higher than that at 10 s. All the Ceram.X® composites and the lighter-shaded Tetric EvoCeram® and FiltekTMSupreme XTE composites reached the RC plateau after 25 s, the remaining materials showed a slower kinetic trend. Tetric EvoCeram® and FiltekTMSupreme XTE composites displayed the softest and the hardest surfaces, respectively. Differently from darker-shaded materials, the universal and the three enamel-shaded composites resulted optimally cured (VHR > 80%). The tested composites differed in CS both during and after light cure, Tetric EvoCeram® and FiltekTMSupreme XTE composites displaying the highest and the lowest CS, respectively. Only the Ceram.X® universal-A3 reached a CS plateau value. The tested composites exhibited material-dependent chemo-mechanical properties. Increasing the curing time and/or reducing the composite layer thickness for dentin-shaded composites appears advisable.

The role of polymerization in adhesive dentistry.

Adhesive systems are resin-based materials that reach their final mechanical properties through a polymerization process. Previous literature correlated the failure of the adhesive interface to low polymer setting. Adhesives systems are elaborate mixtures of different molecules of both hydrophilic and hydrophobic nature, included in the formulation to adequately infiltrate the complex dental substrate or added to prolong the stability of the adhesive layer over time. Each adhesive component may influence the polymerization reaction of the material. Photopolymerization is a complex reaction that has several clinical implications, and besides the material composition, it is influenced by multiple factors, including the substrate characteristics, the operator technique, and the light cure unit properties. This review is focused on the analysis of factors that have a potential role in the setting of adhesive materials and thus the ultimate characteristics of the adhesive layer and the stability of the resin-dentin interface.

Photobiomodulation at Multiple Wavelengths Differentially Modulates Oxidative Stress In Vitro and In Vivo.

Photobiomodulation (PBM) is emerging as an effective strategy for the management of multiple inflammatory conditions, including oral mucositis (OM) in cancer patients who receive chemotherapy or radiotherapy. Still, the poor understanding of the mechanisms by which the light interacts with biological tissues and the heterogeneity of light sources and protocols employed worldwide significantly limits its applicability. Reactive oxygen species (ROS) are massively generated during the early phases of OM and play a major role in the pathogenesis of inflammation in general. Here, we report the results of a clinical and experimental study, aimed at evaluating the effect of laser light at different wavelengths on oxidative stress in vivo in oncologic patients suffering from OM and in vitro in two cell types abundantly present within the inflamed oral mucosa, neutrophil polymorphonuclear (PMN) granulocytes, and keratinocytes. In addition to standard ROS detection methods, we exploited a roGFP2-Orp1 genetically encoded sensor, allowing specific, quantitative, and dynamic imaging of redox events in living cells in response to oxidative stress and PBM. We found that the various wavelengths differentially modulate ROS production. In particular, the 660 nm laser light increases ROS production when applied either before or after an oxidative stimulus. In contrast, the 970 nm laser light exerted a moderate antioxidant activity both in the saliva of OM patients and in both cell types. The most marked reduction in the levels of ROS was detected in cells exposed either to the 800 nm laser light or to the combination of the three wavelengths. Overall, our study demonstrates that PBM exerts different effects on the redox state of both PMNs and keratinocytes depending on the used wavelength and prompts the validation of a multiwavelength protocol in the clinical settings.

Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters.

The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral ß-ketosulfones, and the reductive elimination of related α-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of α-amino aldehydes.

Impact of Stereochemistry on Ligand Binding: X-ray Crystallographic Analysis of an Epoxide-Based HIV Protease Inhibitor.

A new pseudopeptide epoxide inhibitor, designed for irreversible binding to HIV protease (HIV-PR), has been synthesized and characterized in solution and in the solid state. However, the crystal structure of the complex obtained by inhibitor-enzyme cocrystallization revealed that a minor isomer, with inverted configuration of the epoxide carbons, has been selected by HIV-PR during crystallization. The structural characterization of the well-ordered pseudopeptide, inserted in the catalytic channel with its epoxide group intact, provides deeper insights into inhibitor binding and HIV-PR stereoselectivity, which aids development of future epoxide-based HIV inhibitors.

Efficient synthesis of new fluorinated building blocks by means of hydroformylation.

Hydroformylation of fluorinated alkenes is an efficient method for the preparation of fluorinated functionalized building blocks for the synthesis of biologically active target structures. In this article we summarize known hydroformylation reactions of fluorinated olefins and we add new results from our research groups. Particular attention is paid to the remarkable influence of organofluorine substituents on catalyst activity, regio- and stereoselectivity of the hydroformylation reaction.

New chiral P-N ligands for the regio- and stereoselective Pd-catalyzed dimerization of styrene.

Two new chiral, enantiomerically pure, hybrid P-N ligands, namely (2R,5S)-2-phenyl-3-(2-pyridyl)-1,3-diaza-2-phosphanicyclo[3,3,0]octan-4-one (1) and (2R,5S)-2-phenyl-3-(2-pyridyl)-1,3-diaza-2-phosphanicyclo[3,3,0]octane (2), have been synthesized starting from L-proline. The two ligands differ in the presence or not of a carbonyl group in the diazaphosphane ring. Their coordination chemistry towards Pd(II) was studied by reacting them with [Pd(CH3)Cl(cod)]. A different behaviour was observed: ligand 2 shows the expected bidentate chelating behaviour leading to the mononuclear Pd-complex, while ligand 1 acts as a terdentate ligand giving a dinuclear species. The corresponding cationic derivatives were obtained from the palladium neutral complexes, both as mono- and dinuclear derivatives, and tested as precatalysts for styrene dimerization, yielding E-1,3-diphenyl-1-butene regio- and stereoselectively as the sole product. A detailed analysis of the catalytic behaviour is reported.

Efficient chemoenzymatic synthesis of chiral pincer ligands.

Chiral, nonracemic pincer ligands based on the 6-phenyl-2-aminomethylpyridine and 2-aminomethylbenzo[h]quinoline scaffolds were obtained by a chemoenzymatic approach starting from 2-pyridyl and 2-benzoquinolyl ethanone. In the enantiodifferentiating step, secondary alcohols of opposite absolute configuration were obtained by a baker's yeast reduction of the ketones and by lipase-mediated dynamic kinetic resolution of the racemic alcohols. Their transformation into homochiral 1-methyl-1-heteroarylethanamines occurred without loss of optical purity, giving access to pincer ligands used in enantioselective catalysis.