Grafting Vinyl Monomers onto Cellulose. IX. Graft Copolymerization of Methyl Methacrylate onto Cellulose Using Peroxydiphosphate-Fe(ll) and Mn(ll) Redox Systems

The vacuum or inert-atmosphere condensation of diphenyl isophthalate and 2,2′,3,3′-tetraaminobiphenyl to poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole has been investigated. Evidence from polymer and model compound (diphenylbibenzimidazole) spectral studies, elemental analysis, and analysis of volatile effluent indicates that the prepolymer formed at 260 to 300°C contains both benzimidazole and hydroxybenzimidazoline but is essentially free from phenoxybenzimidazole structures. A mechanism involving loss of phenol initially, followed by evolution of water to give benzimidazole structures, is established from experimental evidence. Polymerization in vacuum to 400°C gives the polybenzimidazole.     

Studies on Spiroheterocycles,Part III: Synthesis of Diazaspiroundecanetetraone Derivatives Containing Biologically Active Heterocycles

Barbituric acid 2 upon Michael addition with dibenzal acetones 1a–c afforded the corresponding diazaspiro derivatives 3a–c . The base-catalyzed condensation of 3a–c with various aromatic aldehydes produces diarylidine derivatives 4a–l . The diarylidene compounds 4a–l on condensation with hydrazine, phenyl hydrazine, hydroxylamine, urea, guanidine carbonate, and hydrazine hydrate with acetic acid afforded their respective in situ oxidized products 5, 6, 7, 8, 9 , and 10 . The structures of the compounds are ascertained from their analytical and spectral data. Some of the compounds are screened for their biological activities against E. coli, B. cirroflagellosus, A. niger, and C. albicans.     

Bianchi Type-V Cosmology in f(R,T) Gravity with Λ(T)

A new class of cosmological models in f(R,T) modified theories of gravity proposed by Harko et al. (Phys. Rev. D 84:024020, 2011), where the gravitational Lagrangian is given by an arbitrary function of Ricci scalar R and the trace of the stress-energy tensor T, have been investigated for a specific choice of f(R,T)=f ₁(R)+f ₂(T) by considering time dependent deceleration parameter. The concept of time dependent deceleration parameter (DP) with some proper assumptions yield the average scale factor $a(t) = \sinh^{\frac{1}{n}}(\alpha t)$ , where n and α are positive constants. For 0<n≤1, this generates a class of accelerating models while for n>1, the models of universe exhibit phase transition from early decelerating phase to present accelerating phase which is in good agreement with the results from recent astrophysical observations. Our intention is to reconstruct f(R,T) models inspired by this special law for the deceleration parameter in connection with the theories of modified gravity. In the present study we consider the cosmological constant Λ as a function of the trace of the stress energy-momentum-tensor, and dub such a model “Λ(T) gravity” where we have specified a certain form of Λ(T). Such models may display better uniformity with the cosmological observations. The statefinder diagnostic pair {r,s} parameter has been embraced to characterize different phases of the universe. We also discuss the physical consequences of the derived models.     

Mn Oxide‐Silver Composite Nanowires for Improved Thermal Stability,SERS and Electrical Conductivity

Redox transformation reaction between aqueous AgNO₃ and Mn(CH₃COO)₂ at low temperature (～80 °C) has been adopted for industrial‐scale production of uniform Ag–MnOOH composite nanowires for the first time. Varying amounts of incorporated Ag in the composite retain the 1D morphology of the composite. Nanowires upon annealing evolve Ag–MnO₂ nanocomposites, once again with the retention of the parental morphology. Just 4 % of silver incorporation in the composite demonstrates metal‐like conducting performance from the corresponding semiconducting material. Transition of MnO₂ to Mn₂O₃ to Mn₃O₄ takes place upon heat treatment in relation to successive increase in Ag concentrations in the nanowires. The composites offer resistance to the observed oxide transformation. This is evidenced from the progressive increase in transition temperature. In situ Raman, ex situ thermal and XRD analysis corroborate the fact. The composite with 12 % Ag offers resistance to the transformation of MnO₂, which is also verified from laser heating. Importantly, Ag nanoparticle incorporation is proved to offer a thermally stable and better surface enhanced Raman scattering (SERS) platform than the individual components. Both the Ag–MnOOH and Ag–MnO₂ nanocomposites with 8 atomic % Ag show the best SERS enhancement (enhancement factor ～10¹⁰). The observed enhancement relates to charge transfer as well as electromagnetic effects.     

Preparation, characterization, and photocatalytic activity of sulfate-modified titania for degradation of methyl orange under visible light

Hydrated titania was prepared by a sol-gel method, taking tetraisopropyl orthotitanate as starting material, and then promoted with different weight percentages of sulfate by an incipient wetness impregnation method. The materials were characterized by various advanced techniques such as PXRD, BET surface area, N(2) adsorption-desorption measurements, FTIR, and SEM. Analytical results demonstrated that TiO(2) is mesoporous in nature, and sulfate modification could inhibit the phase transformation and enhance the thermal stability of TiO(2). It was also found that sulfate modification could reduce the crystallite size and increase the specific surface area of the catalysts. The degradation of methyl orange under solar radiation was investigated to evaluate the photocatalytic activity of these materials. Effects of different parameters such as pH of the solution, amount of catalyst, additives, and kinetics were investigated. At 2.5 wt% sulfate loading, the average percentage of degradation of methyl orange was nearly two times than that of neat TiO(2). The photocatalytic degradation followed first-order kinetics.     

Syntheses,Structures, and Electronic Properties of Mono- and Bimetallic Thiolato Complexes Containing Unusual Coordination Modes of Thiolato Ligands

Synthesis, bonding and chemistry of mono- and bimetallic complexes supported by chelating thiolato ligands have been established. Treatment of [Cp*VCl₂]₃ ( 1 ) with [LiBH₄ ⋅ THF] followed by the addition of ethane-1,2-dithiol led to the formation of an EPR active bimetallic vanadium thiolato complex [(Cp*V){μ-(SCH₂CH₂S)-κ²S,S′)₂{V(SCH₂CH₂S-SH)}] ( 2 ). In complex 2 , two ethane-1,2-dithiolato ligands are symmetrically coordinated to two vanadium atoms through μ-S atoms. Interestingly, when similar reactions were carried out with heavier group 5 metal precursors, such as [Cp*NbCl₄] ( 3 a ), it afforded monometallic thiolato complex [Cp*Nb(SCH₂CH₂S)(SCH₂CH₂S−CH₂S)] ( 4 a ). On the other hand, the Ta-analogue [Cp*TaCl₄] ( 3 b ) yielded thiolato species [Cp*Ta(SCH₂CH₂S)(SCH₂CH₂S−CH₂S)] ( 4 b ) and [Cp*Ta(SCH₂CH₂S) (SCH₂CH₂S−S)] ( 5 ). In complexes 4 a and 4 b , one ethane-1,2-dithiolato and one trithiolato ligand are coordinated to Nb and Ta centers, respectively. Whereas, in complex 5 , one ethane-1,2-dithiolato and one 2-disulfanylethanethiolato is coordinated to the Ta center. Moreover, the photolytic reaction of 5 with [Mo(CO)₅ ⋅ THF] yielded heterobimetallic thiolato complex [(Cp*Ta){μ-(SCH₂CH₂S)-κ²S,S′}{μ-(SCH₂CH₂S−CH₂(CH₃)S)κ²S′′ : κ¹S-′′′′ : κ¹S′′′′′}{Mo(CO)₃}] ( 6 ). All the complexes have been characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction studies. Further, computational analyses were performed to provide an insight into the bonding of these complexes.     

Ag-Doped Free-Standing 2D TiO2 Sheets: Electronic,Optical, Magnetic,and Self-Healing Behaviour

Beyond a critical doping level, Ag–2D TiO₂ sheets (ATO) are deemed to be a flexible transparent conductor, useful for visible-range functional photonic/optoelectronic devices/sensors, sunlight-sensitive catalysis, and light-activated resistive switching. Due to the lack of control of surface energy which often leads to the formation of structural defects and even dimensionality crossover (2D to 0D) of materials during doping reaction, it is challenging to obtain ATO with a controlled doping level. Gauging the urgency, therefore we report the surface energy-controlled synthesis of ATO employing liquid phase exfoliation of TiO₂ and subsequent hydrothermal Ag-doping in the presence of Hexamethylenetetramine (HMTA). Electron microscopy and atomic force microscopy reveal ATO sheets with large lateral dimensions. 6-fold, 4-fold, and strain-mediated crystallographic phases of 2D ATO have been revealed by high-resolution electron imaging. Successful tuning of the band gap down to ~2 eV with Ag doping up to ~10 % is obtained. Synthesized 2D ATO have been investigated for their electrical, optical, optoelectronic, photoluminescence, and ferromagnetic behaviour. Visible light-sensitive thermally/structurally robust semiconductor/conductor via tuneable doping will pave the way for their flexible as well as wearable device applications. Self-healing effect of AFM tip-generated mechanical stress has also been demonstrated.     

Intramolecular charge transfer reaction, polarity, and dielectric relaxation in AOT/water/heptane reverse micelles: pool size dependence

Intramolecular charge transfer (ICT) reaction in a newly synthesized molecule, of 4-(1-morpholenyl) benzonitrile (M6C), in AOT/water/heptane reverse micelles at different pool sizes has been studied by using steady-state and time-resolved fluorescence emission spectroscopy. The pool size dependences of the reaction equilibrium constant and reaction rate have been explained in terms of the average polarity of the confined solvent pools estimated from the fluorescence emission Stokes shift of a nonreactive probe, coumarin 153, dissolved in these microemulsions. The complex permittivity measurements in the frequency range 0.01相似文献   

Excited state intramolecular charge transfer reaction in binary mixtures of water and tertiary butanol (TBA): alcohol mole fraction dependence

The excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) has been studied in water-tertiary butanol (TBA) mixtures at different alcohol mole fractions by using steady state and time-resolved fluorescence spectroscopy. The ratio between the areas under the locally excited (LE) and charge transferred (CT) emission bands is found to exhibit a sharp rise at alcohol mole fraction approximately 0.04, a value at which several thermodynamic properties of this mixture is known to show anomalous change due to the enhancement of H-bonding network. The radiative rate associated with the LE emission also shows a maximum at this TBA mole fraction. Although the structural transition from the water-like tetrahedral network to the alcohol-like chain is reflected in the red shift of the absorption spectrum up to TBA mole fraction approximately 0.10, the emission bands (both LE and CT) show the typical nonideal alcohol mole fraction dependence at all TBA mole fractions. Quantum yield, CT radiative rate as well as transition moments also exhibit a nonideal alcohol mole fraction dependence. The time-resolved emission decay of P4C has been found to be biexponential at all TBA mole fractions, regardless of emission collection around either the LE or the CT bands. The time constant associated with the slow component (tau(slow)) shows a minimum at TBA mole fraction approximately 0.04, whereas such a minimum for the fast time constant, tau(fast) (representing the rate of LE --> CT conversion reaction) is not observed. The nonobservation of the minimum in tau(fast) might be due to the limited time resolution employed in our experiments.     

Selective and sensitive recognition of Cu2+ in an aqueous medium: a surface-enhanced Raman scattering (SERS)-based analysis with a low-cost Raman reporter

In the present study, surface-enhanced Raman spectra of a bifunctional Raman reporter, 2-mercaptobenzimidazole, has been found to be responsive exclusively towards Cu(2+) ions while the reporter remains anchored on the Au nanoparticle surface. Thus a specific Cu(2+)-ion-detection protocol emerges. The simplicity, sensitivity, and reproducibility of the method allow routine and quantitative detection of Cu(2+) ions. An interference study involving a wide number of other metal ions shows the procedure to be uniquely selective and analytically rigorous. A theoretical study was carried out to corroborate the experimental results. Finally, the method is promising for real-time assessment of Cu(2+) ions in aqueous samples and also has the ability to discriminate Cu(I) and Cu(II) ions in solution.