Synthesis and characterization of fluorescently labeled core cross‐linked star polymers

A series of fluorescently labeled core cross‐linked star (CCS) polymers were synthesized via the “arm‐first” approach, employing atom transfer radical polymerization (ATRP) to control the resulting architecture. The initiator p‐toluenesulfonyl chloride (TsCl) was used to synthesize “living” poly(methyl methacrylate) (PMMA) macroinitiator, which was subsequently cross‐linked to generate the CCS polymers. Divinylbenzene (DVB) was used as the cross‐linker and 7‐[4‐(trifluoromethyl)coumarin] methacrylamide ( F₁ , λ_ex = 343 nm) was added as a fluorescent labeling monomer. A range of PMMA/DVB/ F₁ based CCS polymers were synthesized with the core domain made selectively fluorescent by using varying amounts of monomer F₁ . The core functionalized stars were characterized using gel permeation chromatography (GPC) equipped with multi‐angle laser light scattering (MALLS), refractive index (RI), and UV–visible detectors. The fluorescence quantum yield (Φ_F) and the amount of fluorescent monomer incorporated into the core were quantified by UV–visible and fluorescence spectrophotometry. It was recognized that the overall molecular weights of the stars produced, along with their core molecular weight, decreased as the mol % of monomer F₁ was increased relative to cross‐linker. Visual confirmation of F₁ incorporation was obtained by fluorescence microscopy of thin polymer films cast on glass substrates. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2422–2432, 2008     

SQUID-based measuring systems

A program has been developed and initiated at the Indira Gandhi Centre for Atomic Research (IGCAR) for the utilization of SQUID sensors in various application areas. DC SQUID sensors based on Nb-AlO _x -Nb Josephson junctions have been designed and developed inhouse along with associated flux-locked loop (FLL) electronics. A compact low field SQUID magnetometer insertible in a liquid helium storage dewar has also been developed inhouse and is in use. Efforts to build a high field SQUID magnetometer, SQUID-DAC system, are in progress. A planar gradiometric DC SQUID sensor for non-destructive evaluation (NDE) application to be used in relatively unshielded environment has been designed and developed. An easily portable NDE cryostat with a small lift-off distance, to be used in external locations has been designed and tested. The magnetic field produced by a given two-dimensional current density distribution is inverted using the Fourier transform technique.     

ATRP-mediated continuous assembly of polymers for the preparation of nanoscale films

The continuous assembly of polymers (CAP) via atom transfer radical polymerisation (ATRP) is reported as an efficient approach for the preparation of dense, cross-linked, nanoscale engineered films as surface coatings, hollow capsules and replica particles. These films can be reinitiated to allow the preparation of thicker films without loss of film growth efficiency while maintaining similar film density.     

Nanoelectromechanical systems

Nanoelectromechanical systems (NEMS) are nano-to-micrometer scale mechanical resonators coupled to electronic devices of similar dimensions. NEMS show promise for fast, ultrasensitive force microscopy and for deepening our understanding of how classical dynamics arises by approximation to quantum dynamics. This article begins with a survey of NEMS and then describes certain aspects of their classical dynamics. In particular, we show that for weak coupling the action of the electronic device on the mechanical resonator can be effectively that of a thermal bath, this despite the device being a driven, far-from-equilibrium system.     

Anatomy of a polarization switch of a vertical-cavity semiconductor laser

Using a streak camera we have measured the three Stokes polarization parameters during a polarization switch of a vertical-cavity semiconductor laser. The switch occurs along a corkscrew path on the Poincare sphere and takes on average a few nanoseconds; this value agrees with a theoretical treatment based upon the Fokker-Planck equation.     

Soft nanoparticles assembled from linear poly(ethylene glycol) and linear brush polydimethylsiloxane diblock copolymers

A series of novel amphiphilic diblock copolymers composed of hydrophilic linear poly(ethylene glycol) (PEG) and linear brush hydrophobic polydimethylsiloxane (PDMS) were synthesized. Three different molecular weights of monomethyl ether PEG were initially functionalized with 2‐bromoisobutyryl bromide to afford macroinitiators suitable for atom‐transfer radical polymerization. The macroinitiators were characterized by gel permeation chromatography, ¹H and ¹³C nuclear magnetic resonance spectroscopic analysis and matrix‐assisted laser desorption ionization time‐of‐flight mass spectroscopy. The three different molecular weight macroinitiators were then chain extended with monomethacryloxypropyl‐terminated PDMS and photoactive 2‐(methylacyloyloxy)ethyl anthracene‐9‐carboxylate in different molar ratios to afford a series of photoresponsive amphiphilic diblock copolymers with high conversions. Self‐assembly of these linear–linear brush diblock copolymers in N,N‐dimethylformamide afforded nanoparticles with hydrodynamic diameters (d_H) ranging from 41 to 268 nm, as determined by dynamic light scattering analysis. Crosslinking and stabilization of the nanoparticles was achieved via [4+4] photodimerization of the anthracene moieties upon exposure to UV radiation at 365 nm with the reverse reaction studied at a wavelength of 254 nm. Transmission electron microscopy revealed that the self‐assembled nanoparticles and their crosslinked derivatives had spherical morphologies. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1251–1262