Chemical synthesis of p-type nanocrystalline copper selenide thin films for heterojunction solar cells

Nanocrystalline thin films of copper selenide have been grown on glass and tin doped-indium oxide substrates using chemical method. At ambient temperature, golden films have been synthesized and annealed at 200 °C for 1 h and were examined for their structural, surface morphological and optical properties by means of X-ray diffraction (XRD), scanning electron microscopy and UV-vis spectrophotometry techniques, respectively. Cu_2−xSe phase was confirmed by XRD pattern and spherical grains of 30 ± 4 - 40 ± 4 nm in size aggregated over about 130 ± 10 nm islands were seen by SEM images. Effect of annealing on crystallinity improvement, band edge shift and photoelectrochemical performance (under 80 mW/cm² light intensity and in lithium iodide electrolyte) has been studied and reported. Observed p-type electrical conductivity in copper selenide thin films make it a suitable candidate for heterojunction solar cells.     

Free-radical polymerization of methyl methacrylate in presence of the Cr(C5H7O2)3–Al(i-C4H9)3 catalyst system

Polymerization of methyl methacrylate has been studied with the chromium acetylacetonate–triisobutyl aluminum catalyst system in benzene medium at 40°C. These studies have been carried out at an Al/Cr ratio of 12 to compare the behavior with the previously studied chromium acetyl acetonate–triethyl aluminum catalyst system. The enhanced yield and gelling of polymer suggests a free-radical mechanism of polymerization. Further, the kinetics of polymerization and the heterotactic structure of polymer as determined by NMR examination have led to confirmation of the freeradical mechanism of polymerization of methyl methacrylate by an excess of triisobutylaluminum in the presence of catalyst complex.     

Macrocycle synthesis strategy based on step-wise “adding and reacting” three components enables screening of large combinatorial libraries

Macrocycles provide an attractive modality for drug development, but generating ligands for new targets is hampered by the limited availability of large macrocycle libraries. We have established a solution-phase macrocycle synthesis strategy in which three building blocks are coupled sequentially in efficient alkylation reactions that eliminate the need for product purification. We demonstrate the power of the approach by combinatorially reacting 15 bromoacetamide-activated tripeptides, 42 amines, and 6 bis-electrophile cyclization linkers to generate a 3780-compound library with minimal effort. Screening against thrombin yielded a potent and selective inhibitor (K_i = 4.2 ± 0.8 nM) that efficiently blocked blood coagulation in human plasma. Structure–activity relationship and X-ray crystallography analysis revealed that two of the three building blocks acted synergistically and underscored the importance of combinatorial screening in macrocycle development. The three-component library synthesis approach is general and offers a promising avenue to generate macrocycle ligands to other targets.

Combination of three efficient chemical reactions allows for solution-phase synthesis of 3780 macrocycles and identification of potent thrombin inhibitor.     

Density and ultrasonic absorption studies of the interaction between polyions and hydrophobic counterions

The volume changes associated with the interaction between tetra-n-propylammonium, propylammonium and butylammonium ions with the polyethylenesulphonate ion (PES) have been determined from density measurements. The excess ultrasonic absorption of solutions of PES and polystyrenesulphonic (PSS) acids has been measured as a function of the neutralization degree by tetramethylammonium (TMA) and tetra-n-butylammonium (TBA) hydroxides. The results confirm that a negligible volume change is associated with the interaction between tetramethylammonium ions and polyions. They indicate that the interaction of large tetraalkylammonium (TAA) ions with polyions gives rise to a small contraction. This effect may be due to [1] disruption of the organisation of the water molecules about the TAA ion alkyl chain when the chains come close enough to polyion charged sites, under the effect of the electrical charges; [2] to enhanced TAA-TAA interactions in the neighbourhood of polyions, owing to the so-called condensation phenomenon; and [3] to hydrophobic interactions between TAA ions and polyions, in the case of hydrophobic polyions such as PSS.     

Partial molal volumes of ions in organic solvents from ultrasonic vibration potential and density measurements. III. Dimethylsulfoxide

The partial molal volumes of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Cl^–, Br^–, I^–, and NO ₃ ^- in DMSO at 25°C have been determined from ultrasonic vibration potential data and density data for solutions of uni-univalent electrolytes. Hepler's semiemprirical equation has been used to split ionic partial molal volumes into geometric and electrostrictive contributions. The results obtained in this work confirm the conclusion of our previous studies, namely, that the contribution of electrostriction is essentially determined by the properties of that layer of atoms, 0.3 to 0.4 nm thick, in contact with the ion and by the degree of steric hindrance of the poles of the dipole of the solvent molecule. On the other hand, the geometric contribution depends on the size of the solvent molecule and also on the arrangement of the solvent molecules about the ions. It is shown that the geometric contribution to the partial molal volume of ions is largely increased when ions cannot come close enough to the poles of the solvent-molecule dipole, owing to steric hindrance.     

New copper (II) complexes of tridentate dibasic ONO donor ligands derived from salicylaldehyde or substituted salicylaldehydes ando-hydroxybenzylamine

Summary Copper(II) complexes with the Schiff bases derived from Salicylaldehyde and its 5-chloro-, 5-bromo-, 5-nitro-, 3-ethoxy- and 3,5-dichloro derivatives, or from 2-hydroxy-1-naphthaldehyde ando-hydroxybenzylamine, have been synthesized and characterized on the basis of elemental analysis, i.r. and electronic spectra and magnetic susceptibility measurements. The Schiff bases behave as tridentate dibasic O, N and O donor ligands and form complexes with 11 metal: ligand stoichiometry which exhibit subnormal magnetic moments ( _eff=0.88–0.98 B.M.) and are involved in strong antifer-romagnetic exchange (–J=482–525 cm^–1). The complexes exhibit a d-d band atca. 1600 cm^–1. A dimeric structure with aminophenolic oxygen atoms as the bridging atoms is proposed on the basis of i.r. and magnetic data.     

Strategic engineering of alkyl spacer length for a pH-tolerant lysosome marker and dual organelle localization

Long-term visualization of lysosomal properties is extremely crucial to evaluate diseases related to their dysfunction. However, many of the reported lysotrackers are less conducive to imaging lysosomes precisely because they suffer from fluorescence quenching and other inherent drawbacks such as pH-sensitivity, polarity insensitivity, water insolubility, slow diffusibility, and poor photostability. To overcome these limitations, we have utilized an alkyl chain length engineering strategy and synthesized a series of lysosome targeting fluorescent derivatives namely NIMCs by attaching a morpholine moiety at the peri position of the 1,8-naphthalimide (NI) ring through varying alkyl spacers between morpholine and 1,8-naphthalimide. The structural and optical properties of the synthesized NIMCs were explored by ¹H-NMR, single-crystal X-ray diffraction, UV-Vis, and fluorescence spectroscopy. Afterward, optical spectroscopic measurements were carefully performed to identify a pH-tolerant, polarity sensitive, and highly photostable fluoroprobes for further live-cell imaging applications. NIMC6 displayed excellent pH-tolerant and polarity-sensitive properties. Consequently, all NIMCs were employed in kidney fibroblast cells (BHK-21) to investigate their applicability for lysosome targeting and probing lysosomal micropolarity. Interestingly, a switching of localization from lysosomes to the endoplasmic reticulum (ER) was also achieved by controlling the linker length and this phenomenon was subsequently applied in determining ER micropolarity. Additionally, the selected probe NIMC6 was also employed in BHK-21 cells for 3-D spheroid imaging and in Caenorhabditis elegans (C. elegans) for in vivo imaging, to evaluate its efficacy for imaging animal models.

A series naphthalimide-based fluorophores were designed by alkyl spacer length engineering to discover a pH-tolerant lysosomal marker. This approach also allows to probe lysosome-related organelles in C. elegans and communication between organelles.     

Role of PVA in synthesis of nano Co3O4‐decorated graphene oxide

Polymeric materials have been found to be ideal candidates for the synthesis of organic–inorganic nanomaterials. We have obtained Co₃O₄‐decorated graphene oxide (GO) nanocomposites by a simple polymer combustion method. Polyvinyl alcohol (PVA) of two different molecular weights, 14,000 and 125,000, was used for the synthesis. The pristine sample was annealed at 300, 500, and 800°C. PVA has played an important role in the formation of GO and Co₃O₄ nanoparticles. Synthesized Co₃O₄–GO nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared, Raman, electron paramagnetic resonance, transmission electron microscopy, and vibrating sample magnetometry. Reflection peaks at 12° and 37° in an X‐ray study confirm the formation of Co₃O₄–GO. Raman study validates the presence of GO in nanocomposites of Co₃O₄–GO. Room temperature ferromagnetism was observed in all annealed samples. The highest coercivity of 462 G was observed for 300°C annealed samples as compared with bulk Co₃O₄. On the basis of the results obtained, a mechanism of formation is proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Straightforward Approach for Preparing Durable Antibacterial ZnO Nanoparticle Coatings on Flexible Substrates

Flexible antibacterial materials have gained utmost importance in protection from the distribution of bacteria and viruses due to the exceptional variety of applications. Herein, we demonstrate a readily scalable and rapid single-step approach for producing durable ZnO nanoparticle antibacterial coating on flexible polymer substrates at room temperature. Substrates used are polystyrene, poly(ethylene-co-vinyl acetate) copolymer, poly(methyl methacrylate), polypropylene, high density polyethylene and a commercial acrylate type adhesive tape. The deposition was achieved by a spin-coating process using a slurry of ZnO nanoparticles in toluene. A stable modification layer was obtained when toluene was a solvent for the polymer substrates, namely polystyrene and poly(ethylene-co-vinyl acetate). These coatings show high antibacterial efficiency causing >5 log decrease in the viable counts of Gram-negative bacteria Escherichia. coli and Gram-positive bacteria Staphylococcus aureus in 120 min. Even after tapping these coated surfaces 500 times, the antibacterial properties remained unchanged, showing that the coating obtained by the presented method is very robust. In contrast to the above findings, the coatings are unstable when toluene is not a solvent for the substrate.     

Effect of Cold Atmospheric Plasma Jet and Gamma Radiation Treatments on Gingivobuccal Squamous Cell Carcinoma and Breast Adenocarcinoma Cells

Surgery, chemotherapy and radiotherapy, the conventional treatment modalities of cancer though successful are limited by presence of residual tumor cells, toxic side-effects and treatment resistance, thus raising the need for investigating other novel approaches. Here, we have used a cold atmospheric plasma (CAP) jet and assessed the in vitro efficacy in gingivobuccal squamous cell carcinoma (GB-SCC) – ITOC-03, breast adenocarcinoma—MCF7 and HEK293 cells. Cells lines were subjected to varying doses of ionizing radiation (0, 2, 4, 6, 8 Gy) and CAP jet treatment (0, 60, 180, 240, 300 s). CAP jet treatment showed time dependent increase in H₂O₂ and NO₂^? concentration. Cell viability assay showed potent effect of CAP jet on all three cell lines in comparison to radiation treatment, while helium gas treatment showed minimal inhibitory effect. Irradiated, CAP jet and helium gas treated cells showed loss of nucleic acid features, 788 cm^?1 and 1340 cm^?1 in Raman spectra, indicating DNA damage. Principal Component Analysis (PCA) showed distinct classification of CAP-treated and control cells, while Principal Component – Linear Discriminant Analysis (PC-LDA) based classification of Raman spectra showed ITOC-03 and HEK293 cells to be sensitive to CAP jet and radiation treatment in comparison to MCF7 cells. Collectively, cell viability assay and Raman spectroscopy have shown potent effect of CAP jet in GB-SCC and breast adenocarcinoma cells.