Iodine(III)-promoted ring expansion of 1-vinylcycloalkanol derivatives: A metal-free approach toward seven-membered rings

A versatile and metal-free approach for the synthesis of molecules bearing seven- and eight-membered rings is described. The strategy is based on the ring expansion of 1-vinylcycloalkanols (or the corresponding silyl or methyl ether) mediated by the hypervalent iodine reagent HTIB (Phl(OH)OTs). The reaction condition can be easily adjusted to give seven-membered rings bearing different functional groups. A route to medium-ring lactones was also developed.

Room Temperature, Metal-Free Synthesis of Diaryl Ethers with Use of Diaryliodonium Salts

A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky ortho-substituted diaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives, and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in the pharmaceutical industry.

Hydrogen evolution by a metal-free electrocatalyst

Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Growth of single-walled carbon nanotubes from well-defined POSS nanoclusters structure

High-quality single-walled carbon nanotubes (SWNTs) with narrow diameter distribution can be generated from well-defined Si8O12 nanoclusters structure which form from thermal decomposition of chemically modified polyhedral oligomeric silsesquioxane (POSS). The nanosized SixOy particles were proved to be responsible for the SWNT growth and believed to be the reason for the narrow diameter distribution of the as-grown SWNTs. This could be extended to other POSS. The SWNTs grown from the nanosized SixOy particles were found to be semiconducting enriched SWNTs (s-SWNTs). A facile patterning technology, direct photolithography, was developed for generating SWNT pattern, which is compatible to industrial-level fabrication of SWNTs pattern for device applications. The metal-free growth together with preferential growth of s-SWNTs and patterning in large scale from the structure-defined silicon oxide nanoclusters not only represent a big step toward the control growth of SWNTs and fabrication of devices for applications particularly in nanoelectronics and biomedicine but also provide a system for further studying and understanding the growth mechanism of SWNTs from nanosized materials and the relationship between the structure of SWNT and nonmetal catalysts.

Aesthetic posts and cores for metal-free restoration of endodontically treated teeth.

Utilization of contemporary post and core systems has facilitated the aesthetic restoration of endodontically treated teeth. Light transmission and biocompatibility have been enhanced by the introduction of metal-free post systems. The periodontal and endodontic status, root length, and histological structure of the devitalized teeth must be considered in order to achieve successful restoration following endodontic treatment. This article presents various restorative criteria for the aesthetic placement and buildup of post and core materials, as well as the preservation of maximum coronal and root structure.

Evaluation of procera/porcelain interface in metal-free prosthesis

Prosthetic substructures for dental application are veneered by porcelain comprising a structure with different elastic modulus and thermal expansion coefficients layers. This structure may present residual stresses in different layers leading to crack propagation and delamination. Although veneering porcelain remains basically on same strength than standard feldspathic porcelains, new ceramic cores have been developed with higher mechanical properties overcoming metal substructures, improving esthetics and biocompatibility. The interface between the Procera dense sintered alumina core and the manufacturer recommended veneering porcelain (AllCeram-Degussa) were evaluated using SEM in coping shaped specimen simulating the standard dental preparation. There were neither crack presences at the interface nor porcelain delamination.

Avaliação in vitro da translucidez de dois sistemas cerâmicos metal-free: In-Ceram x Empress 2

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Coroas estéticas anteriores em cerâmica metal-free: relato de caso clínico

Society's change of parameters for health and aesthetics has resulted in an increased demand for dental treatments. Nowadays, ceramics systems have shown a substantial development, becoming more reliable and predictable. Dental ceramics, besides being chemically stable, present excellent optical properties when compared to dental structures, thus assuring a special position in the list of aesthetic restorative materials. OBJECTIVE, CASE REPORT AND CONCLUSION: This article describes a successful clinical procedure involving the anterior teeth aesthetics, which were restored with all-ceramic crowns (IPS e.max® Ivoclar Vivadent).

Estética em sistema metal free associado a núcleos metalocerâmicos personalisados

The evolution of ceramic systems currently allows the manufacture of prosthesis similar to the natural teeth, meeting the expectations of patients. However, when using vitreous ceramic the color of substrate is significant for the esthetic result, requiring planning aesthetic cores when involved reconstruction of endodontically treated teeth without coronal structure. Thus, the aim of this study to describe a case report of aesthetic rehabilitation in upper anterior teeths using vitreous ceramic system for the reconstruction of elements: 11, 12, 21 and 22 after endodontically treated. It was emphasized the removal of crowns and manufacture of custom cast post and core with ceramic in coronal portion, prioritizing the aesthetic result. Through the clinical results observed can be seen that the use of custom cast post and core with ceramic in association lithium disilicate glass ceramics provided a satisfactory aesthetic result.

Metal-free catalysts derived from lignin for efficient wet peroxide oxidation

In this work, a wheat and hemp lignin (Sarkanda, Granit S.A.) has been used as raw material for the development of metal-free activated carbons. These materials were tested in the catalytic wet peroxide oxidation (CWPO) of 4-nitrophenol (4-NP; 5 g L-1) during 24 h experiments conducted at relatively mild operating conditions (p = 1 atm, t = 50 °C, pH = 3, catalyst load = 2.5 g L-1 and [H2O2]0 = 17.8 g L-1). First, the lignin was carbonized under N2 atmosphere followed by the activation of the obtained non-porous carbon (LG) under air atmosphere at different temperatures (150 to 350 ºC), leading to the generation of significant porosity.