Hydrogenation of ß-Keto Sulfones to ß-Hydroxy Sulfones with Alkyl Aluminum Compounds: Structure of Intermediate Hydroalumination Products.

ß-Hydroxy sulfones are important in organic synthesis. The simplest method of ß-hydroxy sulfones synthesis is the hydrogenation of ß-keto sulfones. Herein, we report the reducing properties of alkyl aluminum compounds R3Al (R = Et, i-Bu, n-Bu, t-Bu and n-Hex); i-Bu2AlH; Et2AlCl and EtAlCl2 in the hydrogenation of ß-keto sulfones. The compounds i-Bu2AlH, i-Bu3Al and Et3Al are the at best reducing agents of ß-keto sulfones to ß-hydroxy sulfones. In reactions of ß-keto sulfones with aluminum trialkyls, hydroalumination products with ß-hydroxy sulfone ligands [R2AlOC(C6H5)CH2S(O)2(p-R1C6H4]n [where n = 1,2; 2aa: R = i-Bu, R1 = CH3; 2ab: R = i-Bu, R1 = Cl; 2ba: R = Et, R1 = CH3; 2bb: R = Et, R1 = Cl] and {[Et2AlOC(C6H5)CH2S(O)2(p-ClC6H4]∙Et3Al}n3bb were obtained. These complexes in the solid state have a dimeric structure, while in solutions, they appear as equilibrium monomer-dimer mixtures. The hydrolysis of both the isolated 2aa, 2ab, 2ba, 2bb and 3bb and the postreaction mixtures quantitatively leads to pure racemic ß-hydroxy sulfones. Hydroalumination reaction of ß-keto sulfones with alkyl aluminum compounds and subsequent hydrolysis of the complexes is a simple and very efficient method of ß-hydroxy sulfones synthesis.

Influence of Ti3C2Tx MXene and Surface-Modified Ti3C2Tx MXene Addition on Microstructure and Mechanical Properties of Silicon Carbide Composites Sintered via Spark Plasma Sintering Method.

This article presents new findings related to the problem of the introduction of MXene phases into the silicon carbide matrix. The addition of MXene phases, as shown by the latest research, can significantly improve the mechanical properties of silicon carbide, including fracture toughness. Low fracture toughness is one of the main disadvantages that significantly limit its use. As a part of the experiment, two series of composites were produced with the addition of 2D-Ti3C2Tx MXene and 2D-Ti3C2Tx surface-modified MXene with the use of the sol-gel method with a mixture of Y2O3/Al2O3 oxides. The composites were obtained with the powder metallurgy technique and sintered with the Spark Plasma Sintering method at 1900 °C. The effect adding MXene phases had on the mechanical properties and microstructure of the produced sinters was investigated. Moreover, the influence of the performed surface modification on changes in the properties of the produced composites was determined. The analysis of the obtained results showed that during sintering, the MXene phases oxidize with the formation of carbon flakes playing the role of reinforcement. The influence of the Y2O3/Al2O3 layer on the structure of carbon flakes and the higher quality of the interface was also demonstrated. This was reflected in the higher mechanical properties of composites with the addition of modified Ti3C2Tx. Composites with 1 wt.% addition of Ti3C2Tx M are characterized with a fracture toughness of 5 MPa × m0.5, which is over 50% higher than in the case of the reference sample and over 15% higher than for the composite with 2.5 wt.% addition of Ti3C2Tx, which showed the highest fracture toughness in this series.

Microstructure and Mechanical Properties of Alumina Composites with Addition of Structurally Modified 2D Ti3C2 (MXene) Phase.

This study presents new findings related to the incorporation of MXene phases into ceramic. Aluminium oxide and synthesised Ti3C2 were utilised as starting materials. Knowing the tendency of MXenes to oxidation and degradation, particularly at higher temperatures, structural modifications were proposed. They consisted of creating the metallic layer on the Ti3C2, by sputtering the titanium or molybdenum. To prepare the composites, powder metallurgy and spark plasma sintering (SPS) techniques were adopted. In order to evaluate the effectiveness of the applied modifications, the emphasis of the research was placed on microstructural analysis. In addition, the mechanical properties of the obtained sinters were examined. Observations revealed significant changes in the MXenes degradation process, from porous areas with TiC particles (for unmodified Ti3C2), to in situ creation of graphitic carbon (in the case of Ti3C2-Ti/Mo). Moreover, the fracture changed from purely intergranular to cracking with high participation of transgranular mode, analogously. In addition, the results obtained showed an improvement in the mechanical properties for composites with Ti/Mo modifications (an increase of 10% and 15% in hardness and fracture toughness respectively, for specimens with 0.5 wt.% Ti3C2-Mo). For unmodified Ti3C2, enormously cracked areas with spatters emerged during tests, making the measurements impossible to perform.

Influence of MXene (Ti3C2) Phase Addition on the Microstructure and Mechanical Properties of Silicon Nitride Ceramics.

This paper discusses the influence of Ti3C2 (MXene) addition on silicon nitride and its impact on the microstructure and mechanical properties of the latter. Composites were prepared through powder processing and sintered using the spark plasma sintering (SPS) technic. Relative density, hardness and fracture toughness, were analyzed. The highest fracture toughness at 5.3 MPa·m1/2 and the highest hardness at HV5 2217 were achieved for 0.7 and 2 wt.% Ti3C2, respectively. Moreover, the formation of the Si2N2O phase was observed as a result of both the MXene addition and the preservation of the α-Si3N4→ß-Si3N4 phase transformation during the sintering process.

Ti2C MXene Modified with Ceramic Oxide and Noble Metal Nanoparticles: Synthesis, Morphostructural Properties, and High Photocatalytic Activity.

Among two-dimensional (2D) materials, such as graphene, a new family of 2D anisotropic carbides and nitrides of early transition metals (MXenes) is very interesting because of the potential applications in electronics, medicine, and photocatalysis. In this paper, preparation, morphostructural characterization, band gaps determination, and salicylic acid photodegradation ability of Ti2C MXene and six nanocomposites consisting of the MXene modified by TiO2, Ag2O, Ag, PdO, Pd, and Au are reported. It was confirmed using electron diffraction studies, energy dispersive X-ray spectroscopy, and high-resolution transmission microscopy that metals and metal oxides occur on the MXene flakes as nanoparticles in a shape of spots. The band gaps determined experimentally using Tauc's method are placed in the region of 0.90-1.31 eV. In recent years, the method of photocatalytic decomposition of pollutants using semiconductor photocatalysts and UV-vis energy has become increasingly important. The MXene based nanocomposites revealed high activity in the salicylic acid (SA) photodegradation reaction (86.1-97.1% of degraded SA after 3 h, concentration of SA initial solution 100 µM, the circulation rate of the SA solution 0.875 cm3/min). The interfacial charge transfer mechanism and the role of the metallic and metal oxide nanoparticles in the photocatalytic activity of the MXene based nanocomposites are presented and discussed.

2D Ti2C (MXene) as a novel highly efficient and selective agent for photothermal therapy.

Photothermal therapy (PTT) has shown significant potential for anti-cancer modality. In this report, according to our best knowledge, we explore for the first time Ti2C-based MXene as a novel, highly efficient and selective agent for photothermal therapy (PTT). Ti2C superficially modified with PEG was obtained from the layered, commercially available Ti2AlC MAX phase in the process of etching aluminum layers using concentrated HF, and characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HREM) as well as X-ray photoelectron spectroscopy for chemical analysis (ESCA-XPS). The PEG-coated Ti2C flakes showed a satisfactory photothermal conversion efficacy (PTCE) and good biocompatibility in wide range of the tested concentrations. Through in vitro studies, the PEG-modified Ti2C demonstrated notable NIR-induced ability to cancerous cells' ablation with minimal impact on non-malignant cells up to the concentration of 37.5 µg mL-1. The applied doses of Ti2C_PEG in our work were even 24 times lower comparing other MXene-based photothermal agents. This work is expected to expand the utility of 2D MXenes to biomedical applications through the development of entirely novel agents for photothermal therapy. This work is expected to expand the utility of 2D MXenes to biomedical applications through the development of entirely novel agents for photothermal therapy.

Changes in the microbiological and chemical characteristics of white bread during storage in paper packages modified with Ag/TiO2-SiO2, Ag/N-TiO2 or Au/TiO2.

Microbiological and chemical characteristics of white bread during storage in paper-packages modified with Ag/TiO2-SiO2, Ag/N-TiO2 or Au/TiO2 were investigated. The whiteness and the water retention of the modified packages were slightly superior to those exhibited by the reference sample, as the color of the composite was lighter. The water retention was very good especially for the Ag/TiO2-SiO2-paper. These improvements can be associated with the high specific surface area and with the low agglomeration tendency of Ag nanoparticles in comparison with the Au ones. The preservation activity of the composites for the bread storage is positively influenced by photoactivity and presence of nano-Ag. Packages Ag/TiO2-SiO2-paper and Ag/N-TiO2-paper can find their applicability for extending the shelf life of bread by 2 days as compared with the unmodified paper-package. No influence of the Au/TiO2 on the extending the shelf life of bread was observed.

Alkylaluminum derivatives of diphenic acid: novel aluminum carboxylates.

The reaction of trialkylaluminum compounds with diphenic acid in a 2:1 molar ratio results in the formation of novel dialkylaluminum dicarboxylates [Et(4)Al(2)(OOCC(12)H(8)COO)](3) (1) and [(i)Bu(4)Al(2)(OOCC(12)H(8)COO)](2) (2). Molecular structures of the compounds have been determined by X-ray crystallography. Compound 1 is a hexamer with a skeleton framework consisting of four fused heterocyclic rings, one 27-membered and three Al(2)O(4)C(2) 8-membered. Compound 2 is a centrosymmetric tetramer with a skeleton framework consisting of three fused heterocyclic rings, one 18-membered and two Al(2)O(4)C(2) 8-membered. The structures of the compounds reveal R(4)Al(2)O(4)C(2) subunits, each linked through diphenyl C(12)H(8) bridges. Each of the aluminum atoms is bonded to two alkyl groups and two oxygen atoms originating from two different dicarboxylate moieties.