“Grafting through” polymerization involving surface-bound monomers

“Grafting through” polymerization represents copolymerization of free monomers in solution and polymerizable units bound to a substrate. Free polymer chains are formed initially in solution and can incorporate the surface-bound monomers, and thereby, get covalently bonded to the surface during the polymerization process. As more growing chains attach to the surface-bound monomers, an immobilized polymer layer is formed on the surface. We use a combination of computer simulation and experiments to comprehend this process for monomers bound to a flat impenetrable substrate. We concentrate specifically on addressing the effect of spatial density of the surface-bound monomers on the formation of the surface-attached polymers. We employ a lattice-based Monte Carlo model utilizing the bond fluctuation model scheme to provide molecular-level insight into the grafting process. For experimental validation, we create gradients of density of bound methacrylate units on flat silicon wafers using organosilane chemistry and carry out “grafting through” free radical polymerization initiated in bulk. We report that the proximity of the surface-bound polymerizable units promotes the “grafting through” process but prevents more free growing chains to “graft through'' the polymerizable units. The “grafting through” process is self-limiting in nature and does not affect the overall density of the surface-bound polymer layer, except in case of the highest theoretical packing density of surface-bound monomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 263–274     

Assessing G4-Binding Ligands In Vitro and in Cellulo Using Dimeric Carbocyanine Dye Displacement Assay

G-quadruplexes (G4) are the most actively studied non-canonical secondary structures formed by contiguous repeats of guanines in DNA or RNA strands. Small molecule mediated targeting of G-quadruplexes has emerged as an attractive tool for visualization and stabilization of these structures inside the cell. Limited number of DNA and RNA G4-selective assays have been reported for primary ligand screening. A combination of fluorescence spectroscopy, AFM, CD, PAGE, and confocal microscopy have been used to assess a dimeric carbocyanine dye B6,5 for screening G4-binding ligands in vitro and in cellulo. The dye B6,5 interacts with physiologically relevant DNA and RNA G4 structures, resulting in fluorescence enhancement of the molecule as an in vitro readout for G4 selectivity. Interaction of the dye with G4 is accompanied by quadruplex stabilization that extends its use in primary screening of G4 specific ligands. The molecule is cell permeable and enables visualization of quadruplex dominated cellular regions of nucleoli using confocal microscopy. The dye is displaced by quarfloxin in live cells. The dye B6,5 shows remarkable duplex to quadruplex selectivity in vitro along with ligand-like stabilization of DNA G4 structures. Cell permeability and response to RNA G4 structures project the dye with interesting theranostic potential. Our results validate that B6,5 can serve the dual purpose of visualization of DNA and RNA G4 structures and screening of G4 specific ligands, and adds to the limited number of probes with such potential.     

Where is SUSY?

The searches for supersymmetry at the Large Hadron Collider (LHC) have so far yielded only null results and have considerably tightened the bounds on the sparticle masses. This has generated some skepticism in the literature regarding the ‘naturalness of SUSY’ which qualitatively requires some sparticles to be relatively light. Re-examining some of the bounds from LHC searches, it is argued with specific examples that the above skepticism is a red herring because (i) a quantitative and universally accepted definition of ‘naturalness’ is not available and (ii) even if some conventional definitions of naturalness is accepted at their face values, the alleged tension with the apparently stringent LHC bounds wither away once the strong assumptions, by no means compelling, underlying such bounds are relaxed.     

Figures of merit of magnetostrictive single crystal iron-gallium alloys for actuator and sensor applications

Energy density, magnetomechanical coupling factor and a dimensionless sensing gage factor of 〈1 0 0〉 oriented single crystal iron-gallium alloys with 16, 17.5, 19, 24.7 and 29 at% gallium were studied as functions of stress and magnetic field. To estimate these quantities, the samples were characterized under different quasi-static stress and magnetic field conditions. The experimental behavior was modeled using an energy-based non-linear approach. Both the experimental data and the model simulations were used to calculate material parameters such as magnetic permeability, piezo-magnetic strain coefficient (d₃₃), inverse piezo-magnetic coefficient (stress sensitivity, d*₃₃) and Young's modulus in the material. These quantities were used to obtain energy density, magnetomechanical coupling factor and sensing gage factor as functions of magnetomechanical conditions. Maximum energy density of around 3 kJ/m³, magnetomechanical coupling factor higher than 0.75 and sensing gage factor on the order of 10³ were calculated.     

Orientational order parameter studies on 3.Om and 3O.Om liquid crystals

Orientational order parameter S is evaluated in the nematic phase of six liquid crystal compounds, N-(p-n-propyl benzylidene)-p-n-alkoxy anilines, 3.Om and N-(p-n-propyloxy benzylidene)-p-n-alkoxy anilines, 3O.Om compounds with m = 6, 7 and 8, using different methods. The techniques employed are S from birefringence δn, Haller's approximation from (1?T/T_c) ^β, effective geometry parameter α_g and Vuks’ scaling factor S_C. The values of S obtained using the above methods are compared with one another and with the results on a number of liquid crystals; the liquid crystals favor isotropic Vuks’ method.     

Acid-Catalyzed Hydrolysis of Some N,N-Dibenzylalkanesulfinamides in 50% Acetonitrile–Water

Abstract

The hydrolysis of some N,N-dibenzylalkanesulfinamides (RSONH(CH₂Ph)₂; 1, R = Me; 2, R = ⁱPr; 3, R = ^tBu; 4, R = 1-adamantyl) has been studied in 50% (v:v) acetonitrile–water solutions of hydrobromic and hydrochloric acids, mainly at 44.8 °C, using ultraviolet (UV) spectrophotometry to determine pseudo first-order rate constants. The compounds were found to hydrolyze by concurrent bimolecular neutral, acid-catalyzed, and acid-dependent nucleophilic (halide ion) catalysis pathways. The last-named is predominant in reactions in HBr solutions, but in HCl solutions, the acid-catalyzed pathway is predominant. The results indicate that both steric and electronic effects are important in these reactions. There appears to be no mechanistic switchover in the series 1→4.     

Octahedral CuII and NiII complexes manifesting with N′-[1-(pyridin-2-yl)ethylidene] acetohydrazide: Structural outlooks and spectral characteristics

A tridentate hydrazone precursor, N′-[1-(pyridin-2-yl)ethylidene]acetohydrazide (L) (1:1 refluxed product of acetichydrazide and 2-acetylpyridine), produced two octahedral Cu^II and Ni^II derivatives, [CuL₂]·NO₃ (1) and [NiL₂]·ClO₄·H₂O (2). Both are subjected to X-ray diffraction system, and structural investigation shows that the central metal atom (Cu^II or Ni^II) adopts a distorted octahedral geometry with N₄O₂ donor sets by coordination of a pair of independent hydrazone precursors. Besides X-ray study, IR and UV-vis spectra, thermal analysis and room temperature magnetic moments are utilized for establishing significant characteristics of both complexes. It is apparent that the M-N_pyridine bonds are slightly longer than the M-N_imino bonds, Cu1-N1 and Cu1-N4 [2.300(2) and 2.038(2) ?] for 1 and Ni1-N1 and Ni1-N4 [2.075(2) and 2.084(1) ?] for 2, Cu1-N2 and Cu1-N5 [2.062(1) and 1.932(1) ?] for 1 and Ni1-N2 and Ni1-N5 [2.008(2) and 1.975(2) ?] for 2, respectively. As per our observation, the effective magnetic moment value (μ_eff) is found to be 1.77 B.M. for 1 and 3.06 BM for 2, respectively.     

A Simple,Efficient and Green Procedure for the Knoevenagel Condensation of Aldehydes with N-Methylpiperazine at Room Temperature under Solvent-Free Conditions

Knoevenagel condensation of aromatic, aliphatic, and heteroaromatic aldehydes with active methylene compounds such as ethylcyanoacetate, malononitrile, and cyanoacetamide proceed very smoothly at room temperature by simply mixing the ingredients together under solvent-free conditions in the presence of N-methylpiperazine in excellent yields of the E-configured products.     

Synthesis,Characterization, and Possible Applications of ZnO Nanocrystals

ZnO nanocrystals are synthesized using the quenching method. The properties of the grown nanocrystals are studied using ultraviolet-vis spectroscopy, x-ray diffraction, photoluminescence, electron diffraction, energy dispersive x-ray spectroscopy, and high resolution transmission electron microscopy. Current-voltage characteristics of the prepared samples are studied for investigating the possible application of the samples as switch and memristor.     

Role of Solvent in Electron-Phonon Relaxation Dynamics in Core-Shell Au−SiO2 Nanoparticles

Relaxation dynamics of plasmons in Au−SiO₂ core-shell nanoparticles have been followed by femtosecond pump-probe technique. The effect of excitation pump energy and surrounding medium on the time constants associated with the hot electron relaxation has been elucidated. A gradual increase in the electron-phonon relaxation time with pump energy is observed and can be attributed to the higher perturbation of the electron distribution in AuNPs at higher pump energy. Variation in time constants for the electron-phonon relaxation in different solvents is rationalized on the basis of their thermal conductivities, which govern the rate of dissipation of heat of photoexcited electrons in the nanoparticles. On the other hand, phonon-phonon relaxation is found to be much less effective than electron-phonon relaxation for the dissipation of energy of the excited electron and the time constants associated with it remain unaffected by thermal conductivity of the solvent.