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Sheshanath Bhosale

Publications and source records attributed to Sheshanath Bhosale.

11 recordsLinked to original sources
PubMed2006

Synthetic functional pi-stack architecture in lipid bilayers.

Neglected until recently, pi-stack architecture is rapidly emerging as a powerful strategy to create function in lipid bilayer membranes. Recent reports describe supramolecular rosettes acting as hosts of intercalating guests, to assemble in bilayer membranes and, in the case of stacked guanosine and folate quartets, to form ion channels. The introduction of rigid-rod pi-stack architecture allowed us to address one of the great challenges in the field, i.e. ligand gating. Inspiring pi-stack chemistry from related fields, covering rainbow coloration, conductivity, as well as the critical dependence of charge mobilities on the precision of supramolecular organization is summarized to zoom in on arguably the most promising application of functional pi-stack architecture in lipid bilayers, that is the creation of multifunctional photosystems.

Circular Dichroism↗
PubMed2006

Photoproduction of proton gradients with pi-stacked fluorophore scaffolds in lipid bilayers.

Rigid p-octiphenyl rods were used to create helical tetrameric pi-stacks of blue, red-fluorescent naphthalene diimides that can span lipid bilayer membranes. In lipid vesicles containing quinone as electron acceptors and surrounded by ethylenediaminetetraacetic acid as hole acceptors, transmembrane proton gradients arose through quinone reduction upon excitation with visible light. Quantitative ultrafast and relatively long-lived charge separation was confirmed as the origin of photosynthetic activity by femtosecond fluorescence and transient absorption spectroscopy. Supramolecular self-organization was essential in that photoactivity was lost upon rod shortening (from p-octiphenyl to biphenyl) and chromophore expansion (from naphthalene diimide to perylene diimide). Ligand intercalation transformed the photoactive scaffolds into ion channels.

Benzene Derivatives↗
PubMed2006

Synthetic ion channels and pores (2004-2005).

This critical review covers synthetic ion channels and pores created between January 2004 and December 2005 comprehensively. The discussion of a rich collection of structural motifs may particularly appeal to organic, biological, supramolecular and polymer chemists. Functions addressed include ion selectivity and molecular recognition, as well as responsiveness to light, heat, voltage and membrane composition. The practical applications involved concern certain topics in medicinal chemistry (antibiotics, drug delivery), catalysis and sensing. An introduction to principles and methods is provided for the non-specialist; some new sources of inspiration from fields beyond chemistry are highlighted.

Ion Channels↗
PubMed2006

Hydrophobic and hydrophilic yoctowells as receptors in water.

Hydrophilic yoctowells (volume = 10-24 L) with OEG walls are introduced, which entrap tobramycin, a tetraamino trisaccharide, in water with a binding constant of 107 M-1 but do not interact with cellobiose. This is in contrast to corresponding hydrophobic yoctowells, which kinetically immobilize cellobiose in water, but do not entrap tobramycin.

Journal Article↗
PubMed2006

A simple method to identify supramolecules in action: Hill coefficients for exergonic self-assembly.

Precise supramolecular architecture is often essential for significant function. Simple methods to reliably and rapidly demonstrate the existence of such supramolecular structure and function at relevant concentrations in complex systems are badly needed. Hill plots, describing the dependence of a signal on the n-th power of the monomer concentration, are compatible only with the identification of supramolecules that do not really exist, that is, endergonic self-assembly (Litvinchuk et al., J Am Chem Soc 2004;126:10067). Here, we show that the artificial increase in monomer concentration by chemical denaturation restores compatibility of Hill plots with exergonic self-assembly and affords Hill coefficients n > 1 for stable supramolecules. Recent rigid-rod pi-stack architecture with photosynthetic and ion channel activity is used as timely example, circular dichroism (CD) spectroscopy as method of choice for both sensitive and selective detection under relevant conditions.

Circular Dichroism↗
PubMed2006

Hydrophobic and hydrophilic yoctowells.

Rigid molecular monolayers made of alpha,omega-diamido lipids form yoctoliter-sized gaps ("yoctowells", 1 yL = 10(-24) L or 1 nm3) around porphyrin islands on smooth surfaces. Their hydrophobic walls adsorb cyclic edge amphiphiles, e.g., trans-1,2-cyclohexanediol, cellobiose, and tyrosine, which fill-up the wells slowly and irreversibly by a process called "kinetic trapping". Wells with oligoethylene or oligoamide walls are effective as 3D-crown ethers or oligoamide barrels for reversible "thermodynamic trapping" of amines or amides. Three porphyrins A, B, and C were sorted as stacks within the yoctowells, and a methylammonium ring was established at their rim to fixate a fourth molecule D at a longer distance. Yoctowells are easy to prepare, characterize, and modify and provide simple models of biological modules.

Amines↗
PubMed2004

Slow motion, trapping, and sorting of water- and chloroform-soluble porphyrins in nanowells.

A two-step self-assembly procedure on smooth, aminated silica particles established holey monolayers. At first, single, flat-lying porphyrin tetraamides (A) were bound covalently, followed by the build-up of a rigid monolayer made of diamido bolaamphiphiles (bolas) around the porphyrin islands. "Nanowells" around porphyrin (A) bottoms with a uniform diameter of 2.2 nm and varying depths of 0.6, 1.0, or 1.5 nm depending on the length of the applied bolas were thus obtained. Oligoethylene headgroups solubilized the particles in water, ethanol, and chloroform/ethanol, and two hydrogen bond chains between the secondary amide groups prevented swelling of the monolayer. Manganese(III) porphyrinates (B) migrated from the bulk solution to the bottom of the form-stable nanowells with a speed of about 1 pm/s and were trapped there above porphyrin (A). After isolation of the (A,B) particles by centrifugation or ultrafiltration, the particles were suspended in a chloroform solution of a chlorin (C), which was also fixated irreversibly on the bottom of the nanowells. The nanowells thus contained three different porphyrins A,B,C in a noncovalent stack. The reverse sequence A,C,B was built-up correspondingly, first in chloroform/ethanol, and then in water. The "sorting" of A,B,C and A,C,B systems was characterized by visible spectra, sequence-dependent fluorescence quenching, and cyclic voltammetry of the top component. The molecular sorting method is the first of its kind and should be generally useful for the production of noncovalent reaction systems on any smooth surface.

Journal Article↗
PubMed2004

Porphyrin-acetylene-thiophene polymer wires.

5,15-Bis[acetylene-4-(ethylenedioxy)thiophene]-10,20-bis(4-carboxyphenyl)porphyrin was synthesized by a Sonogashira coupling and polymerized to fibres; TEM and AFM images show uniform porphyrin wires with a length of several micrometers and a thickness of less than 4 nm.

Journal Article↗