Photoinitiated Free Radical Polymerization Using Benzoxazines as Hydrogen Donors

Summary: Free radical polymerization of methyl methacrylate (MMA) is initiated upon irradiation at λ > 350 nm in CH₂Cl₂ that contains benzoxazine (P‐a) and one of the following photosensitizers: benzophenone (BP), thioxanthone (TX), 2‐chlorothioxanthone (CTX), 2‐isopropyl thioxanthone (ITX), and camphorquinone (CQ). The postulated mechanism is based on the intermolecular reaction of the excited photosensitizer with the tertiary amino moiety of the ground state P‐a and a subsequent hydrogen abstraction reaction. The resulting aminoalkyl radicals initiate the polymerization. The incorporation of P‐a groups into polymers is demonstrated by spectroscopic methods. The possibility of deep curing using the described photoinitiating system followed by the thermal ring opening of the incorporated P‐a groups is also demonstrated.

Schematic of the photoinitiated free radical polymerization using benzoxazines as hydrogen donors.     

Synthesis and characterization of sulfone containing main chain oligobenzoxazine precursors

The preparation of soluble and processable polybenzoxazine precursors capable of forming high performance networks is an important field of research with a broad spectrum of application. This study demonstrates an approach that utilizes aromatic sulfonediamine, bisphenol‐A, and formaldehyde in Mannich‐type polycondesation to prepare polybenzoxazine precursor. The structure of the oligomeric precursor (M_n = 2600) was confirmed by FTIR and ¹H NMR spectral analysis. The precursor contained both sulfone and benzoxazine ring structures in the backbone. It was shown that small amount of ring‐opened phenolic groups were also present. Thermally activated self‐curing behavior of precursor in the absence of catalyst was studied by differential scanning calorimetry. Thermal properties of the cured polymers were also investigated by thermo gravimetric analysis. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Magnetic studies of colossal magnetoresistance perovskites on macroscopic,mesoscopic and microscopic length scales

We have investigated magnetic correlations in various CMR manganites on macroscopic, mesoscopic and microscopic length scales by carrying out DC magnetization, neutron depolarization, and neutron diffraction measurements. We present here the effect of substituting Mn with Fe and La with Dy in the ferromagnetic La_0.7−xCa_xMnO₃ (x ∼ 0.3–0.33) compounds. Neutron diffraction has been used in order to characterize the long-range magnetic order and its gradual suppression by the substitution. Neutron depolarization study has been carried out in order to bridge the gap in our understanding regarding the nature of magnetic correlation obtained from the macroscopic and microscopic measurements. In particular, our study on La_0.67Ca_0.33Mn_0.9Fe_0.1O₃ has established the fact that a true double exchange mediated spin-glass is insulating. In another study of La-site ionic size effect and its disorder in (La_1−x Dy _x )_0.7Ca_0.3MnO₃, we have investigated the evolution of the length scale of magnetic ordering with a possible microscopic explanation and the results have been compared with that for the light rare earth substituted compounds.     

Simple and efficient H2 Raman conversion of a XeCl laser with a variable numerical aperture coupling geometry

A simple combination of a lens-based unstable resonator and an inverted telescope coupling geometry working in a XeCl laser pumped H₂ Raman cell are presented. Raman spectrum optimization is achieved by varying the pump beam numerical aperture. 70% pump depletion and energy conversion efficiencies as high as 66% and 7.8% have been obtained for S₁, S₂ and S₃ respectively.     

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.     

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.     

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.     

Magnetic recyclable eggshell-based mesoporous catalyst for biodiesel production from crude neem oil: Process optimization by central composite design and artificial neural network

A magnetically recyclable eggshell-based catalyst (MKEC) was synthesized to circumvent saponification during the conversion of neem, Jatropha, and waste cooking oils (free fatty acid, 2.3–6.6%) to biodiesel. The characterization results indicated that MKEC had a mesoporous structure with the pore width of 3.24 nm, a specific surface area of 128 m²/g, and a pore volume of 0.045 cm³/g. The results confirmed that the MKEC is more tolerant to fatty acid poisoning than calcined eggshell. The effects of process parameters for maximum fatty acid methyl ester (FAME) content were evaluated by central composite design (CCD) and artificial neural network (ANN). The experimental FAME content of 94.5% was achieved for neem oil with a standard deviation (SD) of 0.68, which was in reasonable agreement with predicted values (CCD, 96.9%; ANN, 95.9%; SD, 0.73). The reusability studies showed that the mesoporous catalyst can be reused efficiently for five cycles without much deterioration in its activity.     

Three novel Cu(II), Cd(II) and Cr(III) complexes of 6−Methylpyridine−2−carboxylic acid with thiocyanate: Synthesis,crystal structures,DFT calculations,molecular docking and α-Glucosidase inhibition studies

Novel complexes of 6?methylpyridine?2?carboxylic acid and thiocyanate {[Cu(NCS)(6-mpa)₂], (1); [Cd(NCS)(6-mpa)]_n, (2); [Cr(NCS)(6-mpa)₂·H₂O], (3)} were synthesized, and their structures were characterized by XRD analysis, FT–IR and UV–Vis spectroscopic techniques. The inhibitory activities of the synthesized complexes (1–3) on α-glucosidase were determined by using genistein reference compound. Furthermore, the optimized geometry and vibrational harmonic frequencies for the complexes 1–3 were obtained by DFT/HSEh1PBE/6–311G(d,p)/LanL2DZ level. Electronic spectral properties were examined by using TD-DFT/HSEh1PBE/6–311G(d,p)/LanL2DZ level with CPCM model. Additionally, major contributions to the electronic transitions were determined via Swizard program. The refractive index, linear optical and non?nonlinear optical parameters of the complexes 1–3 were investigated at HSEh1PBE/6–311G(d,p) level. The docking studies of the complexes 1–3 to the binding site of the target protein (the template structure S. cerevisiae isomaltase are fulfilled. Lastly, natural bond orbital analysis was used to investigate inter- and intra-molecular bonding and interaction among bonds.     

Synthesis,characterization, antioxidant,antimicrobial and DNA binding properties of ruthenium(II), cobalt(II) and nickel(II) complexes of Schiff base containing o-vanillin

Research on Chemical Intermediates - In this study, the complex combinations of Ru(II), Co(II) and Ni(II) with Schiff base obtained through the condensation of (E)-methyl...