Doping effect of Ag+, Mn2+ ions on Structural and Optical Properties of ZnO nanoparticles

Pure ZnO and co-doped (Mn, Ag) ZnO nanoparticles have been successfully prepared by chemical co-precipitation method without using a capping agent. X-ray diffraction (XRD) studies confirms the presence of wurtzite (hexagonal) crystal structure similar to undoped ZnO, suggesting that doped Mn, Ag ions are substituted to the regular Zn sites. The morphology of the samples were studied by scanning electron microscopy (SEM). The chemical composition of pure and co-doped ZnO nanoparticles were characterized by energy dispersive X-ray analysis spectroscopy (EDAX). Optical absorption properties were determined by UV-vis Diffuse Reflectance Spectrophotometer. The incorporation of Ag+, Mn2+ in the place of Zn2+ provoked to decrease the size of nanocrystals as compared to pure ZnO. Optical absorption measurements indicates blue shift in the absorption band edge upon Ag, Mn ions doped ZnO nanoparticles.

Ag2S sensitized mesoporous Bi2WO6 architectures with enhanced visible light photocatalytic activity and recycling properties

To harvest solar energy more efficiently, novel Ag2S/Bi2WO6 heterojunctions were synthesized by a hydrothermal route. This novel photocatalyst was synthesized by impregnating Ag2S into a Bi2WO6 semiconductor by a hydrothermal route without any surfactants or templates. The as prepared structures were characterized by multiple techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmet-Teller (BET) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), UV-vis diffuse reflection spectroscopy (DRS) and photoluminescence (PL). The characterization results suggest mesoporous hierarchical spherical structures with a high surface area and improved photo response in the visible spectrum. Compared to bare Bi2WO6, Ag2S/Bi2WO6 exhibited much higher photocatalytic activity towards the degradation of dye Rhodamine B (RhB). Although silver based catalysts are easily eroded by photogenerated holes, the Ag2S/Bi2WO6 photocatalyst was found to be highly stable in the cyclic experiments. Based on the results of BET, Pl and DRS analysis, two possible reasons have been proposed for the enhanced visible light activity and stability of this novel photocatalyst: (1) broadening of the photoabsorption range and (2) efficient separation of photoinduced charge carriers which does not allow the photoexcited electrons to accumulate on the conduction band of Ag2S and hence prevents the photocorrosion.

Composition dependent multiple structural transformations of myoglobin in aqueous ethanol solution: A combined experimental and theoretical study

Experimental studies (circular dichroism and ultra-violet (UV) absorption spectra) and large scale atomistic molecular dynamics simulations (accompanied by order parameter analyses) are combined to establish a number of remarkable (and unforeseen) structural transformations of protein myoglobin in aqueous ethanol mixture at various ethanol concentrations. The following results are particularly striking. (1) Two well-defined structural regimes, one at x(EtOH) similar to 0.05 and the other at x(EtOH) similar to 0.25, characterized by formation of distinct partially folded conformations and separated by a unique partially unfolded intermediate state at x(EtOH) similar to 0.15, are identified. (2) Existence of non-monotonic composition dependence of (i) radius of gyration, (ii) long range contact order, (iii) residue specific solvent accessible surface area of tryptophan, and (iv) circular dichroism spectra and UV-absorption peaks are observed. Interestingly at x(EtOH) similar to 0.15, time averaged value of the contact order parameter of the protein reaches a minimum, implying that this conformational state can be identified as a molten globule state. Multiple structural transformations well known in water-ethanol binary mixture appear to have considerably stronger effects on conformation and dynamics of the protein. We compare the present results with studies in water-dimethyl sulfoxide mixture where also distinct structural transformations are observed along with variation of co-solvent composition. (C) 2015 AIP Publishing LLC.

Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Three vinylene linked diketopyrrolopyrrole based donor acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V-1 s(-1).

An enolato-bridged dinuclear Cu(II) complex with a coumarin-assisted precursor: a spectral, magnetic and biological study

A new, phenoxo-bridged Cu-II dinuclear complex Cu-2(L)(2)(DMF)(2)] (1) has been obtained by employing the coumarin-assisted tridentate precursor, H2L, benzoic acid(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-ylmethylene)-hydrazide]. Complex 1 has been systematically characterized by FTIR, UV-Vis, fluorescence and PR spectrometry. The single crystal X-ray diffraction analysis of 1 shows that the geometry around each copper ion is square pyramidal, comprising two enolato oxygen atoms belonging to different ligands (which assemble the dimer bridging the two metal centers), one imine-N and one phenolic-O atoms of the Schiff base and one oxygen atom from the DMF molecule. The temperature dependent magnetic interpretation agrees with the existence of weak ferromagnetic interactions between the bridging dinuclear Cu(II) ions. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy towards M. tuberculosis H37Rv ATCC 27294 and M. tuberculosis H37Ra ATCC 25177 strains. The cytotoxicity study on human adenocarcinoma cell lines (MCF7) suggests that the ligand and complex 1 have potential anticancer properties. Molecular docking of H2L with the enoyl acyl carrier protein reductase of M. tuberculosis H37R(v) (PDB ID: 4U0K) is examined and the best docked pose of H2L shows one hydrogen bond with Thr196 (1.99 angstrom).

TiO2-RGO hybrid nanomaterials for enhanced water splitting reaction

The production of H-2 via photocatalytic water splitting reaction has attracted a great attention as a clean and renewable energy for next generation. Despite tremendous efforts, the present challenge for materials scientist is to develop highly active photo catalysts for splitting of water at low cost. This article reports the synthesis of TiO2-reduced graphene oxide hybrid nanomaterials through ionothermal method using functionalized ionic liquid for the enhanced hydrogen generation via water splitting reaction. The structural and morphological properties of the samples were investigated by XFtD, Raman spectroscopy, TG-DTA, UV-vis spectroscopy and TEM. A substantial increase of H-2 evolution was observed for TiO2-reduced graphene oxide hybrid nanomaterials. This is due to the high migration efficiency of photo-induced electrons and the inhibition of charge carrier recombination due to the electronic interaction between TiO2 and reduced graphene oxide. i.e, reduced graphene oxide acts as an electron-acceptor which effectively hinders the electron hole pair recombination of TiO2. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

Structural diversities in Cu(I) and Ag(I) sulfonate coordination polymers and their anion exchange properties

Two new Cu(I) compounds, namely Cu-2(bds)(bpy)(2)]center dot 2H(2)O (1) and Cu-4(bds)(2)(azpy)(4)]center dot 6H(2)O (3) (where bds = benzene-1,3-disulfonate, bpy = 4,4'-bipyridine and azpy = 4,4'-azopyridine), and four Ag(I) compounds, namely Ag-2(bds)(bpy)(2)]center dot 2H(2)O (2), Ag-2(bds)(azpy)(2)]center dot 4H(2)O (4), Ag(bds)(1/2)(bpe)]center dot 3H(2)O (5), and Ag-4(bds)(2)(tmdp)(4)]center dot 9H(2)O (6) (where bpe = 1,2-di(4-pyridyl) ethylene and tmdp = 4,4'trimethylenedipyridine), have been synthesized, and their structures were determined and characterized by elemental analysis, IR, UV-vis and thermal studies. The structure of the compounds changed from 1D (1 and 2) to 2D (3-5) and interpenetrated 3D (6). In the case of 5, a solid-state 2 + 2] photochemical cycloaddition reaction has been performed. Compound 2 exhibits a reversible anion exchange for perchlorate and permanganate, whereas the other compounds (1, 3-6) exhibit an irreversible anion exchange behaviour for perchlorate. Catalytic studies on 2 indicate Lewis acidity.

Spectral characterizations and photophysical properties of one-step synthesized blue fluorescent 4 `-aryl substituted 2,2 `:6 `,2 `'-terpyridine for OLEDs application

We have synthesized a series of 4'-aryl substituted 2,2':6',2 `'-terpyridine (terpy) derivatives, namely 4'-(4-methylphenyl)-2,2':6',2 `'-terpyridine (C-1), 4'-(2-furyl)-2,2':6'2 `'-terpyridine (C-2), and 4'-(3,4,5-trimethoxyphenyl)-2,2':6',2 `'-terpyridine (C-3). The synthesized terpy compounds were characterized by elemental analyses, FTIR, NMR (H-1 and C-13), and ESI-Mass spectrometry. Photophysical, electrochemical and thermal properties of terpy compounds were systematically studied. Maximum excitation band was observed between 240 and 330 nm using UV-visible spectra, and maximum emission peaks from PL spectra were observed at 385, 405 and 440 nm for C-1, C-2 and C-3 respectively. Fluorescence lifetime (tau) of the fluorophores was found to be 035 and 1.55 ns at the excitation wavelength of 406 nm for C-1 and C-2 respectively, and tau value for C-3 was found to be 0.29 ns at the excitation wavelength of 468 nm. We noticed that the calculated values of HOMO energy levels were increased from 5.96 (C-1) to 6.08 (C-3) eV, which confirms that C-3 derivative is more electrons donating in nature. The calculated electrochemical band gaps were 2.95, 2.82 and 3.02 eV for C-1, C-2 and C-3 respectively. These blue fluorescent emitter derivatives can be used as an electron transport and electroluminescent material to design the blue fluorescent organic light emitting diode (OLED) applications. (C) 2015 Elsevier B.V: All rights reserved.

Self-assembled gold nanofilms as a simple, recoverable and recyclable catalyst for nitro-reduction

Hexaazamacrocycle (L) stabilized gold nanoparticles (AuNPs) were prepared by combining L with HAuCl4 center dot 3H(2)O in a variety of alcohol-water (1 : 1) mixtures. The dual roles of L as a reducing and stabilizing agent were exploited for the synthesis of AuNPs under the optimized ratio of L to Au3+ (2 : 1). Self-assembled gold nanofilms (AuNFs) were constructed at liquid-liquid interfaces by adding equal volumes of hexane to the dispersions of AuNPs in the alcohol-water systems. The nanofilms were formed spontaneously by shaking the two-phase mixture for a minute followed by standing. The alcohols explored for the self-assembly phenomenon were methanol, ethanol, i-propanol and t-butanol. The systems containing methanol or t-butanol resulted in AuNFs at the interfaces, whereas the other two alcohols were found not suitable and the AuNPs remained dispersed in the corresponding alcohol-water medium. The AuNFs prepared under suitable conditions were coated on a variety of surfaces by the dip and lift-off method/solvent removal approach. The AuNFs were characterized by UV-vis, SEM, TEM, AFM and contact angle measurement techniques. A coated glass-vial or cuvette was used as a catalytic reservoir for nitro-reduction reactions under ambient and aqueous conditions using NaBH4 as the reducing agent. The reduced products (amines) were extracted by aqueous work-up using ethyl acetate followed by evaporation of the organic layer; the isolated products required no further purification. The catalyst was recovered by simply decanting the reaction mixture whereupon the isolated catalyst remained coated inside the vessel. The recovered catalyst was found to be equally efficient for further catalytic cycles.

Prediction and validation of gold nanoparticles (GNPs) on plant growth promoting rhizobacteria (PGPR): a step toward development of nano-biofertilizers

Several soil microbes are present in the rhizosphere zone, especially plant growth promoting rhizobacteria (PGPR), which are best known for their plant growth promoting activities. The present study reflects the effect of gold nanoparticles (GNPs) at various concentrations on the growth of PGPR. GNPs were synthesized chemically, by reduction of HAuCl 4, and further characterized by UV-Vis spectroscopy, X-ray diffraction technique (XRD), and transmission electron microscopy (TEM), etc. The impact of GNPs on PGPR was investigated by Clinical Laboratory Standards Institute (CLSI) recommended Broth-Microdilution technique against four selected PGPR viz., Pseudomonas fluorescens, Bacillus subtilis, Paenibacillus elgii, and Pseudomonas putida. Neither accelerating nor reducing impact was observed in P. putida due to GNPs. On the contrary, significant increase was observed in the case of P. fluorescens, P. elgii, and B. subtilis, and hence, GNPs can be exploited as nano-biofertilizers.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Carbon onions: Carriers of the 217.5 nm interstellar absorption feature

The UV-VIS characteristics of carbon ions fabricated by an arch discharge in water or liquid nitrogen show characteristics that are similar to the interstellar absorption feature. Thus, high purity and well separated carbon onion samples prepared by annealing the as-fabricated powder in air at 600°C for 60 showed a constant absorption peak at 4.6 μm-1 with a variable width ranging from 1.2-1.6 μm-1. In addition to the UV-VIS data, the origin of the absorption feature at 4.6 μm-1 in carbon onions can be attributed to the collective excitations of π plasmons.

带电胶体粒子结晶过程的实验研究

利用带电单分散聚苯乙烯胶体粒子,通过自组装机理,制备了体积百分比为4·8%的具有多晶结构的胶体晶体,并用Kossel衍射技术和紫外可见分光光度计分别对晶体的生长过程进行了监测.通过对Kossel的图像分析检测不同阶段相应的晶格结构,发现胶体结晶过程晶体结构演变顺序为由液态—随机层结构—堆无序结构—面心立方孪晶结构到面心立方结构.定量地确定了结晶过程中晶体不同晶面的晶面间距和晶体的晶格常数,通过紫外可见分光光度计测量的晶体透射谱图,计算得到111晶面的晶面间距和晶体的晶格常数,与用Kossel衍射技术得到的结果相一致,还发现随样品放置时间的延长,衰减峰变窄和加深,并向短波方向移动,对应着晶体的晶格常数减小的现象.