02476nas a2200205 4500008004100000022001400041245009900055210006900154260011000223300001400333490000700347520165000354100001702004700002402021700003002045700001502075700002602090700002702116856012702143 2015 eng d a1744-683X00aCompact polar moieties induce lipid-water systems to form discontinuous reverse micellar phase0 aCompact polar moieties induce lipidwater systems to form discont aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAY a5417-54240 v113 a

The role of molecular interactions in governing lipid mesophase organization is of fundamental interest and has technological implications. Herein, we describe an unusual pathway for monoolein/water reorganization from a bicontinuous mesophase to a discontinuous reverse micellar assembly, directed by the inclusion of polar macromolecules. This pathway is very different from those reported earlier, wherein the Fd3m phase formed only upon addition of apolar oils. Experiments and molecular dynamics simulations indicate that hydrophilic ternary additives capable of inducing discontinuous phase formation must (i) interact strongly with the monoolein head group and (ii) have a compact molecular architecture. We present a detailed investigation that contrasts a monoolein-water system containing polyamidoamine (PAMAM) dendrons with one containing their linear analogs. The Fd3m phase forms only on the addition of PAMAM dendrons but not their linear analogs. Thus, the dendritic architecture of PAMAM plays an important role in determining lipid mesophase behavior. Both dendrons and their linear analogs interact strongly with monoolein through their amine groups. However, while linear polymers adsorb and spread on monoolein, dendrons form aggregates that interact with the lipid. Dendrons induce formation of an intermediate reverse hexagonal phase, which subsequently restructures into the Fd3m phase. Finally, we demonstrate that other additives with compact structures that are known to interact with monoolein, such as branched polyethylenimine and polyhedral silsesquioxane cages, also induce the formation of the Fd3m phase.

1 aKumar, Manoj1 aPatil, Naganath, G.1 aChoudhury, Chandan, Kumar1 aRoy, Sudip1 aAmbade, Ashootosh, V.1 aKumaraswamy, Guruswamy uhttps://library.ncl.res.in/content/compact-polar-moieties-induce-lipid-water-systems-form-discontinuous-reverse-micellar-001994nas a2200169 4500008004100000022001400041245009700055210006900152260011000221300001400331490000600345520127700351100002001628700002001648700002601668856013001694 2015 eng d a1759-995400aControlled micellar disassembly of photo- and pH-cleavable linear-dendritic block copolymers0 aControlled micellar disassembly of photo and pHcleavable lineard aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcAUG a6826-68350 v63 a

A linear-dendritic block copolymer with both photo-and pH-cleavable linkages at the junction between the hydrophobic dendron and hydrophilic linear polymer was synthesised. The photocleavable o-nitrobenzyl group attached to alkyne was introduced at the focal point of polyester dendron and acid-degradable acetal linkage with terminal azide was introduced at one end of linear polyethylene glycol. The two segments were connected using click chemistry. The copolymer was found to self-assemble into micelle-like aggregates in dilute aqueous solution. Stimuli-responsive disassembly of the aggregates was studied by monitoring fluorescence emission of the encapsulated hydrophobic dye and dynamic light scattering (DLS). Products of acetal cleavage at acidic pH were analyzed by gel permeation chromatography and NMR spectroscopy. The photo and pH stimuli were applied separately as well as simultaneously to study the rate of dye release. The synergistic effect of the two stimuli on dye release was demonstrated and the non-cytotoxic nature of the polymer was shown using the MTT assay. Cell uptake of DOX-loaded micelles and photo-induced release of the drug resulting in significantly higher cytotoxicity than by free DOX was demonstrated using MDA-MB-231 cells.

1 aKalva, Nagendra1 aParekh, Nimisha1 aAmbade, Ashootosh, V. uhttps://library.ncl.res.in/content/controlled-micellar-disassembly-photo-and-ph-cleavable-linear-dendritic-block-copolymers-001701nas a2200157 4500008004100000245012600041210006900167260000800236300001400244490000700258520107200265100002401337700002401361700002601385856013201411 2017 eng d00aCopper and silver nanoparticles stabilized by bistriazole-based dendritic amphiphile micelles for 4-nitrophenol reduction0 aCopper and silver nanoparticles stabilized by bistriazolebased d cJUN a4546-45540 v413 aCopper and silver nanoparticles were fabricated in aqueous solution using micellar assemblies of dendritic amphiphiles containing triazole rings. Dendritic amphiphiles displaying a bistriazole unit between a hydrophobic benzyl ether dendron and two oligo(ethylene glycol) (OEG) chains were synthesized using click chemistry. Micelles were characterized by DLS, TEM, CMC determination, and dye encapsulation. Micellar size was dependent on the dendron backbone structure and OEG chain length. Metal nanoparticles were characterized by TEM and UV-Vis spectroscopy. The Cu NPs had a smaller average particle diameter than the Ag NPs. The micelle-stabilized nanoparticles, at a concentration of 7.5 ppm, were shown to efficiently catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 in aqueous solution without stirring, using up to 1 ppm of substrate. The reaction catalyzed by Cu NPs followed zero order kinetics (k = 3.48 x 10(-3) M s(-1)), while the Ag NP-catalyzed reaction followed pseudo-first order kinetics (k = 1.28 x 10(-3) s(-1)).1 aPatil, Naganath, G.1 aBasutkar, Nitin, B.1 aAmbade, Ashootosh, V. uhttps://library.ncl.res.in/content/copper-and-silver-nanoparticles-stabilized-bistriazole-based-dendritic-amphiphile-micelles-402477nas a2200301 4500008004100000022001400041245012900055210006900184260000800253300001100261490000800272520146800280653002901748653001301777653001801790653001601808653001401824653001401838653002301852100002201875700002301897700002601920700002301946700002501969700002601994700002802020856012702048 2024 eng d a0014-305700aCatechol- and phenolic hydroxyl-functionalized partially bio-based (Co) poly(ether sulfone)s with multifarious applicability0 aCatechol and phenolic hydroxylfunctionalized partially biobased  cNOV a1134840 v2203 a

A largely bio-based new bisphenol, namely, 4,4 `-((3,4-dimethoxyphenyl)methylene)-bis(2-methoxyphenol) (DMBM) was synthesized by the reaction of veratraldehyde with guaiacol. DMBM and varying compositions of DMBM and bisphenol A were polycondensed with bis(4-fluorophenyl) sulfone to afford reasonably high molecular weight film-forming (co)poly(ether sulfone)s possessing built-in methoxyl groups. T10 and Tg values of (co)poly(ether sulfone)s were in the range 382-478 degrees C and 171-187 degrees C, respectively indicating their good thermal stability and the values decreased with increase in mol % incorporation of DMBM. The methoxyl groups present in (co)poly (ether sulfone)s were quantitatively de-blocked resulting in the formation of corresponding polymers possessing pendant catechol moieties and free phenolic hydroxyl groups. By virtue of the presence of these functional moieties, (co)poly(ether sulfone)s are amenable for post-polymerization modifications, and exhibited properties such as antimicrobial (23 mm against Staphylococcus aureus and 18 mm against Escherichia coli)), antioxidant (72 % scavenger of free radicals), adhesive (2.24 MPa lap shear strength) and usefulness as redox-active agent in zinc-ion batteries. These data underscore the promise of DMBM as a versatile monomer of wider utility for the synthesis of functional (co)poly(ether sulfone)s capable of expanding their applicability beyond the conventional ones.

10a(Co)poly(ether sulfone)s10aadhesive10aAntimicrobial10aAntioxidant10abio-based10abisphenol10aZinc-ion batteries1 aWale, Apparav, K.1 aJagtap, Ashish, S.1 aPandey, Priyanshi, R.1 aDastager, Syed, G.1 aShelke, Manjusha, V.1 aAmbade, Ashootosh, V.1 aWadgaonkar, Prakash, P. uhttps://library.ncl.res.in/content/catechol-and-phenolic-hydroxyl-functionalized-partially-bio-based-co-polyether-sulfones