A mild deprotection strategy for allyl-protecting groups and its implications in sequence specific dendrimer synthesis

A mild deprotection strategy for allyl ethers under basic conditions in the presence of a palladium catalyst is described. Under these conditions, aryl allyl ethers can be cleaved selectively in the presence of alkyl allyl ethers. These conditions are also effective in the deprotection of allyloxycarbonyl groups. The utility of the current methodology in sequence specific dendrimer synthesis is demonstrated.     

Direct asymmetric organocatalytic Michael reactions of alpha,alpha-disubstituted aldehydes with beta-nitrostyrenes for the synthesis of quaternary carbon-containing products

[reaction: see text] Direct asymmetric catalytic Michael reactions have been performed using chiral-amine/acid bifunctional catalysts. Performed with 0.3 equiv of (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine and 0.3 equiv of trifluoroacetic acid as the catalyst, the reaction of alpha,alpha-dialkylaldehydes with (E)-beta-nitrostyrene provided the alpha,alpha-dialkyl Michael products in up to 96% yield with up to 91% ee. With respect to enantioselectivity, l-proline was a poor catalyst of this class of Michael reactions.     

Synthesis and characterization of phenol‐based biaryl proton conducting polymers

Biaryl hydroxy polymers with orthogonal disposition of proton transporting ? OH moieties have been synthesized via conventional free radical polymerization. The polymers are characterized for their thermal stability and proton conductivity, and the results are compared with the corresponding styrenic hydroxy polymers. The orthogonal disposition of ? OH moieties in biaryl polymers does result in lower E_a for proton transport. However, the lower E_a values in biaryl polymers did not translate into a net increase in proton conductivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Sequences in dendrons and dendrimers

Sequential incorporation of a variety of functional groups forms the basis for specificity in biomacromolecules. Introduction of such diversity and sequencing ability in artificial macromolecules is fundamentally interesting. In this paper, three different synthetic approaches have been used to build dendrons and dendrimers in which all the monomer units are different from each other. The synthetic strategies described in this paper involve the use of (i) an ABB(p) monomer, (ii) an ABB' monomer, and (iii) an ABB(m) monomer. The complementarity and the versatility of these synthetic approaches should render them useful for a variety of applications.     

Redox,ionic strength,and pH sensitive supramolecular polymer assemblies

Formation of micelle‐type assembly from supramolecular complexation of a surfactant and an oppositely charged homopolymer is demonstrated. The lower CAC observed for these assemblies suggest that the electrostatic interaction provides an amphiphilic homopolymer‐like structure. The stimulus‐induced disassembly of these supramolecular structures has been accomplished with variations in redox characteristics, ionic strength, and pH of the medium. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1052–1060, 2009     

Influence of substrate temperature on the properties of electron beam evaporated ZnSe films

ZnSe films were deposited on glass substrates keeping the substrate temperatures, at room temperature (RT), 75, 150 and 250 °C. The films have exhibited cubic structure oriented along the (111) direction. Both the crystallinity and the grain size increased with increasing deposition temperature. A very high value of absorption co‐efficient (10⁴ cm^‐1) is observed. The band gap values decrease from a value of 2.94 eV to 2.69 eV with increasing substrate temperature. The average refractive index value is in the range of 2.39 – 2.41 for the films deposited at different substrate temperatures. The conductivity values increases continuously with temperature. Laser Raman spectra showed peaks at 140.8 cm^‐1, 246.7 cm^‐1and 204.5 cm^‐1which are attributable to 2TA LO phonon and TO phonon respectively. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth mechanism and optoelectronic properties of nanocrystalline In2O3 films prepared by chemical spray pyrolysis of metal-organic precursor

Thin films of indium oxide, In₂O₃, were deposited by chemical spray pyrolysis technique, using aqueous alcoholic solutions of indium acetylacetonate (In-acac) precursor, on glass substrates kept at temperatures between 300 and 500 °C. The structural, optical, and electrical properties have been investigated as a function of deposition temperature, precursor concentration, carrier gas pressure, and substrate-to-nozzle distance. X-ray diffraction studies showed that the formation of nanocrystalline In₂O₃ films is preferentially oriented along (2 2 2) plane. The surface morphological modifications with substrate temperature were observed using scanning electron and atomic force microscopic studies. Optical transmittance behavior of the films in the visible and IR region was strongly affected by the deposition parameters. The optical band gap values observed are between 3.53 and 3.68 eV. The long wavelength limit of refractive index is 1.83. The Hall mobility is found to vary from 23 to 37 cm²/V s and carrier density is found nearly constant at about 10²⁰ cm⁻³.     

Effective Tuning of Ketocyanine Derivatives through Acceptor Substitution

A series of ketocyanine derivatives possessing bis(diarylamino)fluorenyl donors and variable acceptors installed at the bridging carbon atom were synthesized to investigate how the electronic structure of the dye can be systemically tuned through stabilization of the cyanine‐like character of the donor by increasing the acceptor strength. Analysis of the ¹H NMR spectra indicates that the “charge‐separated” species dominates in these dyes, given that carbons possessing a positive or negative charge in the resonance structures of this state purposefully shift downfield or upfield, respectively, depending on the strength of the acceptor moiety. In DAA‐Fl‐PI, the acceptor strength and the gain of acceptor aromaticity indicates a predisposition of the separated state, indicated by asymmetry in the ¹H NMR spectrum, as well as uneven distribution of the HOMO on the fluorenyl donor.     

Propagation of Enzyme‐Induced Surface Events inside Polymer Nanoassemblies for a Fast and Tunable Response

We report a new molecular design strategy that allows for the propagation of surface enzymatic events inside a supramolecular assembly for accelerated molecular release. The approach addresses a key shortcoming encountered with many of the currently available enzyme‐induced disassembly strategies, which rely on the unimer–aggregate equilibria of amphiphilic assemblies. The enzymatic response of the host to predictably tune the kinetics of guest‐molecule release can be programmed by controlling substrate accessibility through electrostatic complexation with a complementary polymer. Accelerated guest release in response to the enzyme is shown to be accomplished by a cooperative mechanism of enzyme‐triggered supramolecular host disassembly and host reorganization.     

Recognition and modulation of cytochrome c's redox properties using an amphiphilic homopolymer

An amphiphilic homopolymer scaffold has been used to bind to the protein, cytochrome c. This interaction is analyzed using cyclic voltammetry, native gel electrophoresis, UV-visible absorption, and circular dichroism spectroscopy. The polymer binds to cytochrome c with micromolar affinity and the association of polymer with cytochrome c leads to a structural change of the protein. This conformational change exposes the heme unit of the protein, which affords an opportunity to reversibly modulate its electron-transfer properties. We have also shown that the electrostatic binding of polymer to cytochrome c can be used to disrupt its interaction with its natural partner, cytochrome c peroxidase.