Impact of Multimeric Ferrocene-containing Cyclodecapeptide Scaffold on Host-Guest Interactions at a β-Cyclodextrin Covered Surface

Among non-covalent bonds, the host-guest interaction is an attractive way to attach biomolecules to solid surfaces since the binding strength can be tuned by the nature of host and guest partners or through the valency of the interaction. For that purpose, we synthesized cyclodecapeptide scaffolds exhibiting in a spatially controlled manner two independent domains enabling the multimeric presentation of guest molecules on one face and the other face enabling the potential grafting of a biomolecule of interest. In this work, we were interested in the β-cyclodextrin/ferrocene inclusion complex formed on β-CD monolayers functionalized surfaces. By using surface sensitive techniques such as quartz crystal microbalance and surface plasmon resonance, we quantified the influence of the guest valency on the stability of the inclusion complexes. The results show a drastic enhancement of the affinity with the gradual increase of guest valency. Considering that the sequential binding events are equal and independent, we applied the multivalent model developed by the Huskens group to extract intrinsic binding constants and an effective concentration of host.     

Luminscent graphene quantum dots for organic photovoltaic devices

Recent research in organic photovoltaic (OPV) is largely focused on developing low cost OPV materials such as graphene. However, graphene sheets (GSs) blended conjugated polymers are known to show inferior OPV characteristics as compared to fullerene adduct blended with conjugated polymer. Here, we demonstrate that graphene quantum dots blended with regioregular poly(3-hexylthiophene-2,5-diyl) or poly(2-methoxy-5-(2-ethylhexyloxy)-1,4phenylenevinylene) polymer results in a significant improvement in the OPV characteristics as compared to GSs blended conjugated polymers. This work has implications for inexpensive and efficient solar cells as well as organic light emitting diodes.     

Tuning the Photometric Properties of Ternary Sm3+ Complexes Involving Mixed-Ligands

This research article deals with the synthesis of ternary Sm³⁺ complexes with 6,8-dichlorochromone-3-carboxaldehyde through solution-precipitation method. The photometric properties of resultant complexes were tuned by coordinating N-donor heterocyclic ligands with Sm³⁺ ion. The emission spectra, obtained in the visible region have been studied. Under optical excitation of 370 nm, the complexes displayed characteristic Sm³⁺-centered emission peaks at?~?563, 600 and 647 nm in solution as well as in powder state. The complexes showed thermal stability up to 175 °C. The complexes delivered quantum yield as high as 7.91% and longest emission lifetime of 0.564 ms. The color coordinates of the complexes, located in deep orange (in solution) and red (in powder) spectral region, matched well with the Society of Motion Picture and Television Engineers and European Broadcasting Union. The properties of complexes have been investigated to a significant extent due to their easy synthesis and potential applications as orange-red light emitter in a wide range of photonic applications such as display devices, OLEDs, dashboards, optical systems.

     

Sonochemical degradation of martius yellow dye in aqueous solution

The sonolytic degradation of the textile dye martius yellow, also known as either naphthol yellow or acid orange 24, was studied at various initial concentrations in water. The degradation of the dye followed first-order kinetics under the conditions examined. Based on gas chromatographic results and sonoluminescence measurements of sonicated aqueous solutions of the dye, it is concluded that pyrolysis does not play a significant role in its degradation. The chromatographic identification of hydroxy added species indicates that an OH radical induced reaction is the main degradation pathway of the dye. Considering the non-volatility and surface activity of the dye, the degradation of the dye most probably takes place at the bubble/solution interface. The quantitative and qualitative formation of the degradation intermediates and final products were monitored using HPLC and ESMS. The analytical results suggest that the sonolytic degradation of the dye proceeds via hydroxylation of the aryl ring and also by C-N bond cleavage of the chromophoric ring, either through OH radical attack or through another unidentified process. The identification of various intermediates and end products also imply that the degradation of martius yellow proceeds through multiple reaction pathways. Total organic carbon (TOC) analyses of the dye solutions at various times following sonication revealed that sonolysis was effective in the initial degradation of the parent dye but very slow in achieving mineralization. The slow rate of mineralization is likely to be due to the inability of many of the intermediate products such as, the carboxylic acids, to accumulate at the bubble (air/water) interface and undergo decomposition due to their high water solubility (low surface activity).     

Catalytic cyclopropanation of olefins using copper(I) diphosphinoamines

Catalytic cyclopropanation reactions of olefins with ethyl diazoacetate were carried out using copper(I) diphosphinoamine (PPh₂)₂N(R) (R = ⁱPr, H, Ph and –CH₂–C₆H₄–CHCH₂) complexes at 40 °C in chloroform. High yields of the cyclopropanes were obtained in all cases. The rate of the reaction was influenced by the nuclearity of the complex and the binding mode of the ligand which was either bridging or chelating. Comparison of isostructural complexes shows that the rate follows the order R = ⁱPr > H > Ph, where R is the substituent on the N. However, cyclopropane formation versus dimerization of the carbene, and trans to cis ratios of cyclopropane was similar in all cases. The nearly identical selectivity for different products formed was indicative of a common catalytic intermediate. A labile “copper–olefin” complex which does not involve the phosphine or the counterion is the most likely candidate. The differences in the reaction rates for different complexes are attributed to differences in the concentration of the catalytically active species which are in equilibrium with the catalytically inactive copper–phosphinoamine complex. To test the hypothesis a diphosphinoamine polymer complexed to copper(I) was used as a heterogeneous catalyst. Leaching of copper(I) and deactivation of the catalyst confirmed the proposed mechanism.     

Structural investigations on Quinone Methides for understanding their properties in confined media

Encapsulation of 4−[(4′-hydroxy−3′,5′-dimethylphenyl)(aryl)-methylene]−2,6−dimethyl-cyclohexa−2,5−dienones (when aryl=4−hydroxyphenyl 1, 4−methoxyphenyl 2, 2,3,4-trimethoxy phenyl 3) by β-cyclodextrin is studied. The compound 2 is selectively encapsulated by β-cyclodextrin. The result is rationalised by analysing the structural parameters from the crystal structure of 1–3. The visible spectra of the compounds 2 and 3 at pH 9.0 show red shifts on the absorption maxima upon addition of cetyltrimethylammonium bromide (CTAB). For example, addition of a solution of CTAB to aqueous ethanolic solution of 2 at pH 9 causes shift of the absorption at 578–593 nm (Δλ_max=15 nm). The advantage of this observation is taken to use 2 and 3 to determine the critical micelle concentration of CTAB in basic medium.Graphical Abstract Structural investigations on quinone methides for understanding their properties in confined media Rupam J. Sarma, Andrei S. Batsanov, Ritu Kataky, Jubaraj B. Baruah      

Measuring microelastic properties of stratum corneum

We explore the compression moduli of a thin biological tissue through probe microscopy. The elastic modulus (E') of isolated stratum corneum is measured at varying depths through the use of an atomic force microscope (AFM) as well as a nano-indentor (Hysitron Triboscope). In addition, a nano-DMA is used to measure visco-elastic properties. Measurements on dry and hydrated stratum corneum show an order of magnitude difference in E' and the measured tandelta (E'/E') is seen to increase from approximately 0.1 to 0.25. In addition, extensive validation of the experiments is conducted with different indentation probes at different force ranges to reveal the effects of indentor geometry and indentation depth on the measured elastic modulus. The sensitivity of the measurements is tested with applying known treatments to stratum corneum and exploring their effects on biomechanical parameters.     

The constituents of phebalium nudum hook-I The bark

A large number of natural essentially non-terpenoid compounds contain isoprene units. The C₅ units may have their origin based on senecioic acid, or mevalonic acid, but the fundamental stage seems to be an -hydroxy-γ,γ-dimethylallyl system, which can undergo a number of modifications giving rise to types of compounds listed below under (A) to (F) in increasing order of complexity. The simpler furan derivatives are also now considered to be derived from C₅ units by the loss of three carbon atoms by oxidation. This is based not only on co-occurrence of types but also on the experimental feasibility of converting the dimethylallyl (C₅) and allyl groups into furans. In this connection, syntheses of angelicin and psoralen are described. Further the furan rings of furanoquinolines should be considered to have a similar origin.     

Anomalously large contributions of vacancies and dislocations to Hall coefficient and thermoelectric power of copper films

Effect of vacancies and dislocations on Hall coefficient (R_H) and thermoelectric power (TEP) of copper films has been deduced from annealing behaviour of various transport properties. The large contributions of these defects may be attributed to variations in the density of hole-like states and/or the energy dependence of conductivity (at the Fermi surface), caused by changes in the extent and/or degree of curvature of the necks at Fermi surface.