Interaction of CO2 with MnOx/Pd(111) Reverse Model Catalytic Interfaces

Understanding the activation of CO₂ on the surface of the heterogeneous catalysts comprised of metal/metal oxide interfaces is of critical importance since it is not only a prerequisite for converting CO₂ to value-added chemicals but also often, a rate-limiting step. In this context, our current work focuses on the interaction of CO₂ with heterogeneous bi-component model catalysts consisting of small MnO_x clusters supported on the Pd(111) single crystal surface. These metal oxide-on-metal ‘reverse’ model catalyst architectures were investigated via temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) techniques under ultra-high vacuum (UHV) conditions. Enhancement of CO₂ activation was observed upon decreasing the size of MnO_x nanoclusters by lowering the preparation temperature of the catalyst down to 85 K. Neither pristine Pd(111) single crystal surface nor thick (multilayer) MnO_x overlayers on Pd(111) were not capable of activating CO₂, while CO₂ activation was detected at sub-monolayer (∼0.7 ML) MnO_x coverages on Pd(111), in correlation with the interfacial character of the active sites, involving both MnO_x and adjacent Pd atoms.     

Design and Development of D‒α‒Tocopheryl Polyethylene Glycol Succinate‒block‒Poly(ε-Caprolactone) (TPGS−b−PCL) Nanocarriers for Solubilization and Controlled Release of Paclitaxel

The objective of this study was to synthesize and characterize a set of biodegradable block copolymers based on TPGS-block-poly(ε-caprolactone) (TPGS-b-PCL) and to assess their self-assembled structures as a nanodelivery system for paclitaxel (PAX). The conjugation of PCL to TPGS was hypothesized to increase the stability and the drug solubilization characteristics of TPGS micelles. TPGS-b-PCL copolymer with various PCL/TPGS ratios were synthesized via ring opening bulk polymerization of ε-caprolactone using TPGS, with different molecular weights of PEG (1–5 kDa), as initiators and stannous octoate as a catalyst. The synthesized copolymers were characterized using ¹H NMR, GPC, FTIR, XRD, and DSC. Assembly of block copolymers was achieved via the cosolvent evaporation method. The self-assembled structures were characterized for their size, polydispersity, and CMC using dynamic light scattering (DLS) technique. The results from the spectroscopic and thermal analyses confirmed the successful synthesis of the copolymers. Only copolymers that consisted of TPGS with PEG molecular weights ≥ 2000 Da were able to self-assemble and form nanocarriers of ≤200 nm in diameter. Moreover, TPGS₂₀₀₀-b-PCL₄₀₀₀, TPGS₃₅₀₀-b-PCL₇₀₀₀, and TPGS₅₀₀₀-b-PCL₁₅₀₀₀ micelles enhanced the aqueous solubility of PAX from 0.3 µg/mL up to 88.4 ug/mL in TPGS₅₀₀₀-b-PCL₁₅₀₀₀. Of the abovementioned micellar formulations, TPGS₅₀₀₀-b-PCL₁₅₀₀₀ showed the slowest in vitro release of PAX. Specifically, the PAX-loaded TPGS₅₀₀₀-b-PCL₁₅₀₀₀ micellar formulation showed less than 10% drug release within the first 12 h, and around 36% cumulative drug release within 72 h compared to 61% and 100% PAX release, respectively, from the commercially available formulation (Ebetaxel^®) at the same time points. Our results point to a great potential for TPGS-b-PCL micelles to efficiently solubilize and control the release of PAX.     

Mixed Dimensional Nanostructure (UiO-66-Decorated MWCNT) as a Nanofiller in Mixed-Matrix Membranes for Enhanced CO2/CH4 Separation

Mixed-matrix membranes (MMMs) with combination of two distinct dimensional nanofillers (such as 1D-3D, 2D-3D, or 3D-3D, etc.) have drawn special attention for gas separation applications due to their concerted effects on gas permeation and mechanical properties. An amine-functionalized 1D multiwalled carbon nanotube (NH₂-MWCNT) with exceptional mechanical strength and rapid gas transport was crosslinked with an amine-functionalized 3D metal-organic framework (UiO-66-NH₂) with high CO₂ affinity in a Schiff base reaction. The resultant crosslinked mixed-dimensional nanostructure was used as a nanofiller in a polysulfone (PSf) polymer matrix to explore the underlying synergy between 1D and 3D nanostructures on the gas separation performance of MMMs. Cross-sectional scanning electron microscopy and mapping revealed the homogenous dispersion of UiO-66@MWCNT in the polymer matrix. The MMM containing 5.0 wt. % UiO-66@MWCNT demonstrated a superior permeability 8.3 Barrer as compared to the 4.2 Barrer of pure PSf membrane for CO₂. Moreover, the selectivity (CO₂/CH₄) of this MMM was enhanced to 39.5 from the 28.0 observed for pure PSf under similar conditions of pressure and temperature.     

Laccase bound to cryogel functionalized with phenylalanine for the decolorization of textile dyes

In this study, amino acid functionalized poly(2-hydroxyethyl methacrylate-N-methacrylolyl-l-phenylalanine) [PHEMAPA] cryogel discs were prepared. In this respect, phenylalanine containing N-methacryloyl-(L)-phenylalanine methyl ester (MAPA) was polymerized with 2-hydroxyethyl methacrylate (HEMA) without requirement of any activation step. Laccase bound poly(2-hydroxyethyl methacrylate-N-methacryloyl-l-phenylalanine) [Lac-PHEMAPA] cryogel discs were applied for decolorization of Reactive Blue-247 (RB-247). The ability of Lac-PHEMAPA cryogel discs on dye decolorization was found to be as 90% in 2 h and even more within 4h. The decolorization activities of 86% and 73% were observed at relatively low (4°C) and high (60°C) temperatures, respectively. The effect of dye concentration on dye decolorization and 100% decolorization activity was achieved in dye concentration between 50–300 ppm. Lac-PHEMAPA cryogel discs maintained 80% of its decolorization activity after six cycles. Consequently, the PHEMAPA cryogel discs are promising materials for immobilizing laccase. The Lac-PHEMAPA has a rapid dye decolorization in a broad range of temperature. The preparation is furthermore very stable and activity is preserved during storage.     

Initiation of cationic polymerization by photoinduced electron transfer

The objective of this paper is to discuss: (i) the general approaches to the initiation of cationic polymerization by photinduced electron transfer reactions (ii) the use of photoinduced electron transfer reactions for block copolymer synthesis. For the first, it is concluded that three general methods are currently available which involve reduction of onium salts by (a) photogenerated radicals, (b) photoexcited sensitizers or (c) electron donor compounds in charge transfer complexes. According to this view, a variety of initiating systems are discussed. For the second, recent developments on the application of photoinduced electron transfer reactions to the synthesis of block copolymer of monomers polymerizable with different mechanisms are presented.     

Two interface effects: Exchange bias and magnetic proximity

Exchange bias and magnetic proximity effects are two novel phenomena that are in the limelight because of their fundamental and technological importance. Since both phenomena are interfacial in origin, we review these together. In the first part of this review, we have discussed the basics of these two phenomena. Subsequently, we have described numerous experimental examples involving a variety of composite magnetic materials and heterostructures. The recent theoretical models of these two interface phenomena have also been described. Finally, we have shed light on an obvious question: can one expect both these phenomena to occur together in any magnetically coupled system? We conclude that one can enhance the operating temperature of an exchange biased device by exploiting the magnetic proximity effect.     

Dynamics of optical solitons and nonautonomous complex wave solutions to the nonlinear Schrodinger equation with variable coefficients

Variable coefficients nonlinear evolution equations offer us with more real aspects in the inhomogeneities of media and nonuniformities of boundaries than their counter constant coefficients in some real-world problems. Under consideration is a nonlinear variable coefficients Schrödinger’s equation with spatio-temporal dispersion in the Kerr law media. We are aimed at constructing novel solutions to the equation under consideration. Bright and combined dark–bright optical solitons are successfully revealed with aid of the complex amplitude ansatz scheme. Using two test functions, two nonautonomous complex wave solutions in dark and bright optical solitons forms are successfully revealed. The effect of the variable coefficients on the reported results can be clearly seen on the 3-dimensional and contour graphs.

     

Determination of the chemical composition and Raman characterization of barite samples from Denizli and Akdamadeni,Turkey, using Energy Dispersive X-ray fluorescence and Raman microscopy

Accurate analysis of samples is very important for scientists working in many fields. XRF device is used very frequently especially in mine analysis. However, researchers are trying to reach accurate results with many different analysis methods. In addition to the known analysis methods, alternative research methods also guide the studies. In this study, two barite ore samples, collected from two regions of different nature (Denizli and Akda?madeni) by following specified sampling methods, were analyzed using Confocal Raman Spectroscopy (CRS) and Polarized Energy Dispersive X-Ray Fluorescence (PEDXRF) spectrometer. The first sample was from a metamorphic basement, and the second was from an alkali syenite rock unit. The main objective of this paper is to compare the optical characteristics of these two different barite samples collected from different regions under a polarized microscope, using CRS and PEDXRF. The results of polarized microscopy analysis showed that the barite taken from Denizli is associated with calcite. On the other hand, the barite taken from Akda?madeni is associated with galena, celestite, and quartz. Two different colors were observed in the barite samples. CRS and PEDXRF results showed that the barites collected from two regions differed in mineral association, chemical composition, and physical properties. The accuracy of the chemical analysis technique was ensured by following USGS standards, GBW 7109, and GBW-7309 Sediment. Barite ores were analyzed using HR-800 (HORIBA-Jobin Yvon) CRS and a polarized microscope (Leica DMLP). Thanks to this study, it has been shown that mineral analyzes can be performed with an accuracy close to XRF with Confocal Raman spectroscopy. Confocal Raman spectroscopy will also guide researchers for mineral analysis.     

Fatty Acid Composition of the Seeds of Vicia faba var. major Genotypes from Turkey

Chemistry of Natural Compounds -