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.     

Tailoring the optical and magnetic properties of La-BaM hexaferrites by Ni substitution

We investigate the impact of Ni insertion on the structural,optical,and magnetic properties of Ba_0.8La_0.2Fe_12-xNi_xO₁₉hexaferrites(Ni substituted La-BaM hexaferrites).Samples were prepared using the conventional co-precipitation method and sintered at 1000℃for 4 hours to assist the crystallization process.An analysis of the structure of the samples was carried out using an x-ray diffraction(XRD)spectrometer.The M-type hexagonal structure of all the samples was confirmed using XRD spectra.The lattice parameters a and c were found to be in the ranges of 5.8925±0.001 nm–5.8952±0.001 nm and 23.2123±0.001 nm–23.2219±0.001 nm,respectively.The M-type hexagonal nature of the prepared samples was also indicated by the presence of corresponding FT-IR bands and Raman modes in the FT-IR and Raman spectra,respectively.EDX results confirmed the successful synthesis of the samples according to the required stoichiometric ratio.A UV-vis spectrometer was used to record the absorption spectra of the prepared samples in the wavelength range of 200 nm–1100 nm.The optical energy bandgap of the samples was found to be in the range of 1.21 eV–3.39 eV.The M–H loops of the samples were measured at room temperature at an applied magnetic field range of 0 kOe–60 kOe.A high saturation magnetization of 99.92 emu/g was recorded in the sample with x=0 at a microwave operating frequency of 22.2 GHz.This high value of saturation magnetization is due to the substitution of La3+ions at the spin-up(12k,2a,and 2b)sites.The Ni substitution is proven to be a potential candidate for the tuning of the optical and magnetic parameters of M-type hexaferrites.Therefore,we suggest that the prepared samples are suitable for use in magneto-optic applications.     

Influences of Crystal-Field and Interlayer Coupling Interactions on Dynamic Phase Diagrams of a Mixed-Spin(3/2,2) Bilayer System

Influences of crystal-fields(D_A and D_B) and interlayer coupling interactions(J_3) on dynamic magnetic critical behaviors of a mixed-spin(3/2, 2) bilayer system under an oscillating magnetic field are investigated by the Glauber-type stochastic dynamics based on the mean-field theory. For this purpose, dynamic phase diagrams are constructed in the reduced temperature and magnetic field amplitude plane for the ferromagnetic/ferromagnetic(FM/FM),antiferromagnetic/ferromagnetic(AFM/FM) and AFM/AFM interactions in detail. We observe that the influences of D_A, D_B and J_3 interactions parameters on the behavior of the dynamic phase diagrams are very much.     

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.     

Complex macromolecular structures from stable radical containing block copolymers

A novel synthetic strategy for the synthesis of graft copolymers is reported. Block copolymers containing segments with stable nitroxyl radicals side groups were first prepared by anionic polymerization, which were then used as a precursor for the subsequent nitroxide-mediated radical polymerization (NMRP) of styrene. This way, block–graft copolymers with polystyrene side chains grafted from one of the blocks were successfully synthesized in a controlled manner. In addition, block–graft copolymers with grafted polystyrene chains and a poly(tert-butyl methacrylate) block were subjected to hydrolysis to yield the corresponding amphiphilic polymers. The structures and the molecular weight characteristics of the polymers were characterized by spectral and chromatographic analyses. The surface morphology of thus obtained polymers was also investigated by microscopic techniques. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 62–69     

Magnetoresistance and magnetostriction of Co2Cr0.6Fe0.4Al Heusler alloy

We report a study of the magnetotransport properties of the Co₂Cr_0.6Fe_0.4Al Heusler alloy grown by means of the arc-melting technique. X-ray diffraction and energy dispersive X-ray spectroscopy have been used to analyze the crystallographic structure and the sample stoichiometry. Temperature-dependent magnetization measurements have been carried out in the range 300-850 K. Co₂Cr_0.6Fe_0.4Al is theoretically predicted to have full positive spin polarization at the Fermi level, and as a consequence its spin-dependent transport properties are being intensively studied. Low field magnetoresistance exceeding 30% has been observed very recently in Co₂Cr_0.6Fe_0.4Al compact pellets. We have performed magnetoresistance and magnetostriction measurements in both the as-grown alloy and compact pellets made of mechanically milled Co₂Cr_0.6Fe_0.4Al. The as-grown and the milled sample show negligible anisotropic magnetostriction (25 μst at saturation), whilst only the milled sample exhibits magnetoresistance (0.65% at 300 K). These results permit us to discard the magnetostrictive effects as the magnetoresistance source.     

Low-temperature neutron diffraction study of La<Subscript>0.95</Subscript>Nd<Subscript>0.05</Subscript>CrO<Subscript>3</Subscript>

We have synthesized polycrystalline La_0.95Nd_0.05CrO₃ sample by doping the La-site of LaCrO₃ with Nd and its magnetic properties have been studied using DC magnetization and neutron diffraction techniques. DC magnetization study shows a paramagnetic to a weak ferromagnetic-like transition at ∼295 K followed by signatures of a spin reorientation phenomenon at 233 and 166 K and, finally a transition to an antiferromagnetic-like phase at ∼21 K. Low-temperature neutron diffraction measurements confirm a weak ferrimagnetic ordering of Cr³⁺ moments at all temperatures below 295 K.     

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.     

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.