Constructive and Destructive Two-Pulse Excitation Investigated with a White-Light Michelson Interferometer

Linear propagation of two pulses through methanol solution of aluminum phthalocyanine chloride is investigated using a modified white-light Michelson interferometer. The observed coherence time of the white light is 6 fs, and the separation between the two-excitation pulses is set to about 10 fs. The excitation is dependent on the phase-relation between the two pulses. We have observed an enhancement of the excitation when the two pulses are in-phase and strong suppression of the excitation when the two pulses are out of phase by π.     

Addition of benzylic and allylic organozinc and Grignard reagents to resin-bound imines to provide alpha-branched secondary amines bearing a wide variety of functional groups. Utility in the synthesis of beta-3 adrenergic receptor agonists

Benzylic and allylic organozinc and Grignard reagents have been added to resin-bound imines to provide alpha-branched secondary amines. Many functional groups, including electrophilic groups, were compatible with this methodology. Three modules--a resin-bound primary amine, an aromatic aldehyde, and the organometallic--were independently varied to produce a combinatorial library of alpha-branched secondary amines designed as beta-3 adrenergic receptor agonists.     

Electrospinning of poly(lactic acid): Theoretical approach for the solvent selection to produce defect‐free nanofibers

In this study an integrated methodology was proposed for the selection of solvent systems to produce electrospinnable solutions that form defect‐free poly(lactic acid) (PLA) fibers with narrow diameter distributions. The solvent systems were chosen using a thermodynamic approach, combined with electrical and rheological property criteria. More specifically, the three step methodology includes (1) initial choice of solvent by solubility evaluation to meet thermodynamic criteria, (2) electrical properties, that is, conductivity and dielectric constant adjustment by using solvent mixtures to meet electrical property criteria, and (3) critical entanglement concentration (C_e) determination by viscosity measurements, supported by elastic and plastic moduli measurements, followed by concentration adjustment to meet rheological criteria. All three criteria need to be met to ensure defect‐free nanofiber morphology. The methodology was demonstrated using PLA solutions that were characterized in terms of thermodynamic properties, conductivity, surface tension, and viscosity measurements. These data were analyzed and related to the nanofiber morphology and diameter as determined from scanning electron microscopy (SEM). Measurements of the elastic (G′) and the plastic (G″) moduli of PLA solutions showed a sharp increase of G′ at the chain entanglement concentration. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1483–1498     

Tuning the Triplet Excited State of Bis(dipyrrin) Zinc(II) Complexes: Symmetry Breaking Charge Transfer Architecture with Exceptionally Long Lived Triplet State for Upconversion

Zinc(II) bis(dipyrrin) complexes, which feature intense visible absorption and efficient symmetry breaking charge transfer (SBCT) are outstanding candidates for photovoltaics but their short lived triplet states limit applications in several areas. Herein we demonstrate that triplet excited state dynamics of bis(dipyrrin) complexes can be efficiently tuned by attaching electron donating aryl moieties at the 5,5′-position of the complexes. For the first time, a long lived triplet excited state (τ_T=296 μs) along with efficient ISC ability (Φ_Δ=71 %) was observed for zinc(II) bis(dipyrrin) complexes, formed via SBCT. The results revealed that molecular geometry and energy gap between the charge transfer (CT) state and triplet energy levels strongly control the triplet excited state properties of the complexes. An efficient triplet–triplet annihilation upconversion system was devised for the first time using a SBCT architecture as triplet photosensitizer, reaching a high upconversion quantum yield of 6.2 %. Our findings provide a blueprint for the development of triplet photosensitizers based on earth abundant metal complexes with long lived triplet state for revolutionary photochemical applications.     

Sol–gel synthesis and characterization of conducting polythiophene/tin phosphate nano tetrapod composite cation-exchanger and its application as Hg(II) selective membrane electrode

Nano tetrapod based on conducting polythiophene (PTh) and tin-phosphate (SnP) were synthesized by in situ chemical oxidative polymerization. The morphology of the resulting polythiophene tinphosphate composite was characterized by elemental analysis, fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The physico-chemical characterization carried out on the composite showed that SnP was modified by conducting PTh with an enhancement of various properties. On the basis of highest distribution coefficient values for Hg(II), the composite was also used for the preparation of Hg(II) selective membrane electrode. The electrode showed working concentration range of 1 × 10^?1 to 1 × 10^?7 with Nernstian slope of 29.29 mV per decade change in concentration and the electrode may be used for wide working pH range of 4–8 having quick response time about 23 s. The life of electrode is 4 months without any notable drift in potential.     

ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat⁻¹ h⁻¹ under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Isolation and Identification of Bioactive Compounds from Bidens spp. Using HPLC-DAD and GC-MS Analysis and Their Biological Activity as Anticancer Molecules

The genus Bidens a member of family Compositae, is widely documented as an ethno-medicinally important genus of plants. In the present study, anticancer potential of three ethno-medicinally important species i.e., B. bipinnata, B. biternata and B. pilosa were tested. For in-vitro evaluation, an MTT (Thiazolyl blue tetrazolium bromide) assay was performed against cervical cancer cells (HeLa), hepatocellular carcinoma (HepG), and adenocarcinoma human alveolar basal epithelial cells (A549). For in vivo evaluation, Artemia salina, Danio rerio, and Caenorhabditis elegans were used. Among all the tested extracts, the ethanol extract of B. biternata appeared to have highest anticancer activity, and the compounds responsible for this activity were identified to be Tris (2,4-di-tert-butylphenyl), 4-hydroxy-2,4′-dimethoxychalcone, and 2,4-di-tert-butylphenol. This is the first report of the isolation of Tris (2,4-di-tert-butylphenyl) phosphate from the genus Bidens and the first report of 4-hydroxy-2,4′-dimethoxychalcone and 2,4-di-tert-butylphenol from B. biternata. Among the isolated compounds, 4-hydroxy-2,4′-dimethoxychalcone showed the highest anticancer activity with an LD50 value of 236.7 µg/mL. Therefore, this compound carries promising potential for being established as a pharmaceutical for chemoprevention and chemotherapy.