01346nas a2200169   4500008004100000022001400041245004700055210004600102260011000148300001200258490000700270520075200277100002001029700002601049700001701075856008401092       2011                        eng d  a0306-001200aMain-chain supramolecular block copolymers0 aMainchain supramolecular block copolymers  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN  a129-1370 v403 a<p>Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.</p>1 aYang, Si, Kyung1 aAmbade, Ashootosh, V.1 aWeck, Marcus  uhttps://library.ncl.res.in/content/main-chain-supramolecular-block-copolymers-001683nas a2200205   4500008004100000022001400041245011400055210006900169260007100238300001400309490000800323520088500331100001801216700002001234700001601254700002701270700002201297700002601319856013201345       2012                        eng d  a0002-786300aMultiple topologies from glycopolypeptide-dendron conjugate self-assembly: nanorods, micelles, and organogels0 aMultiple topologies from glycopolypeptidedendron conjugate selfa  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAPR  a7796-78020 v1343 a<p>Glycopolypeptides (GPs) were synthesized by ring-opening polymerization of glycosylated N-carboxyanhydride monomer and attached to hydrophobic dendrons at one chain end by ``click'' reaction to obtain amphiphilic anisotropic macromolecules. We show that by varying polypeptide chain length and dendron generation, an organogel was obtained in dimethylsulfoxide, while nanorods and micellar aggregates were observed in aqueous solutions. Assemblies in water were characterized by electron microscopy and dye encapsulation. Secondary structure of the GP chain was shown to affect the morphology, whereas the chain length of the poly(ethylene glycol) linker between the GP and dendron did not alter rod-like assemblies. Bioactive surface chemistry of these assemblies displaying carbohydrate groups was demonstrated by interaction of mannose-functionalized nanorods with ConA.</p>1 aPati, Debasis1 aKalva, Nagendra1 aDas, Soumen1 aKumaraswamy, Guruswamy1 aGupta, Sayam, Sen1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/multiple-topologies-glycopolypeptide-dendron-conjugate-self-assembly-nanorods-micelles-and-001765nas a2200229   4500008004100000022001400041245012100055210006900176260007700245300001400322490000800336520087100344653002301215653003201238653001301270653002301283653003301306100002001339700002101359700002601380856012901406       2014                        eng d  a1022-135200aEffect of the branching pattern of hydrophobic dendrons on the core structure of linear-dendritic copolymer micelles0 aEffect of the branching pattern of hydrophobic dendrons on the c  aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcAUG  a1456-14650 v2153 a<p>Hydrophobic dendrons based on different branching patterns, viz. 3,5-di- and 3,4,5-trisubstituted phenyl rings, consist of the same backbone but exhibit different sizes, shapes, and hydrophobic densities. These dendrons are attached to poly(ethylene glycol) and the core properties of the copolymer micelles are investigated in tetrahydrofuran (THF)/water mixtures by neutron scattering. Two polymers with intermediate hydrophobicity are studied further with variations in the solvent composition and the temperature. The aggregation numbers for 3,4,5-based dendron copolymers are lower, with more THF molecules of solvation compared with the 3,5-based dendron copolymer, the difference being greater at higher generations due to different molecular shapes. The micellar core size increases in small steps with dendron size so that dye encapsulation is tuned.</p>10adiblock copolymers10alinear-dendritic copolymers10amicelles10aneutron scattering10astructure-property relations1 aKalva, Nagendra1 aAswal, Vinod, K.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/effect-branching-pattern-hydrophobic-dendrons-core-structure-linear-dendritic-copolymer-002476nas 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<p>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.</p>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<p>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.</p>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-002651nas a2200241   4500008004100000022001400041245011100055210006900166260007100235300001400306490000800320520176800328100002202096700001802118700002502136700002002161700002402181700002402205700002602229700001802255700001702273856011902290       2015                        eng d  a1089-563900aTerahertz spectroscopy and solid-state density functional theory calculations of cyanobenzaldehyde isomers0 aTerahertz spectroscopy and solidstate density functional theory   a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL  a7991-79990 v1193 a<p>Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (&lt;3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.</p>1 aDash, Jyotirmayee1 aRay, Shaurnik1 aNallappan, Kathirvel1 aKaware, Vaibhav1 aBasutkar, Nitin, B.1 aGonnade, Rajesh, G.1 aAmbade, Ashootosh, V.1 aJoshi, Kavita1 aPesala, Bala  uhttps://library.ncl.res.in/content/terahertz-spectroscopy-and-solid-state-density-functional-theory-calculations-001033nas a2200157   4500008004100000245011300041210006900154260000800223300001600231490000700247520042000254100002400674700002400698700002600722856012700748       2015                        eng d00aVisible light-triggered disruption of micelles of an amphiphilic block copolymer with BODIPY at the junction0 aVisible lighttriggered disruption of micelles of an amphiphilic   cOCT  a17708-177110 v513 a<p>A visible light-cleavable polymer is synthesised to overcome the limitations of UV-sensitive polymers. Photocleavable BODIPY functionalized with an ATRP initiator and alkyne was used to obtain an amphiphilic block copolymer by conducting the click reaction and polymerization simultaneously. Micellar assembly of the polymer was disintegrated under visible light irradiation with controlled release of cargo.</p>1 aPatil, Naganath, G.1 aBasutkar, Nitin, B.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/visible-light-triggered-disruption-micelles-amphiphilic-block-copolymer-bodipy-junction02081nas a2200169   4500008004100000022001400041245017800055210006900233260011000302300001600412490000600428520128300434100002001717700002401737700002601761856012401787       2016                        eng d  a2046-206900aPhotoresponsive assemblies of linear-dendritic copolymers containing azobenzene in the dendron interior: the effect of the dendron structure on dye encapsulation and release0 aPhotoresponsive assemblies of lineardendritic copolymers contain  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcAPR  a43163-431700 v63 a<p>Hydrophobic dendrons with different numbers and positions of azobenzenes as well as different groups benzyl and dodecyl, on the periphery were synthesised and attached to poly(ethylene glycol) using copper-catalysed azide-alkyne cycloaddition to obtain linear-dendritic copolymers. Self-assembly of the polymers in aqueous solution was characterised using dynamic light scattering (DLS), transmission electron microscopy (TEM) and critical micelle concentration (cmc). Formation of H-aggregates during micellisation was shown for polymers with a higher number of azobenzene units. Photoisomerisation of azobenzene in the assemblies was studied and the rate constant of thermal photoisomerisation was calculated. Release of hydrophobic dye Nile red upon photoisomerisation of azobenzene occurred without disruption of micellar aggregates. Dye release varied with the pathway - thermal or visible light irradiation, followed for cis-trans isomerisation. The encapsulation capacity of the micelles and extent of dye release in either pathway were found to be influenced by the dendron structure. A polymer with a lower number of azobenzenes and aliphatic periphery on the dendron showed significantly different behaviour than polymers with a larger number of aromatic units.</p>1 aKalva, Nagendra1 aBasutkar, Nitin, B.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/photoresponsive-assemblies-linear-dendritic-copolymers-containing-azobenzene-dendron02126nas a2200229   4500008004100000022001400041245016200055210006900217260007100286300001200357490000700369520122300376100001801599700001601617700002401633700002001657700002301677700002001700700002601720700002201746856012801768       2016                        eng d  a1525-779700aTunable nanocarrier morphologies from glycopolypeptide-based amphiphilic biocompatible star copolymers and their carbohydrate specific intracellular delivery0 aTunable nanocarrier morphologies from glycopolypeptidebased amph  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcFEB  a466-4750 v173 a<p>Nanocarriers with carbohydrates on the surface represent a very interesting class of drug-delivery vehicles because carbohydrates are involved in biomolecular recognition events in vivo. We have synthesized biocompatible miktoarm star copolymers comprising glycopolypeptide and poly(e-caprolactone) chains using ring-opening polymerization and ``click chemistry''. The amphiphilic copolymers were self-assembled in water into morphologies such as nanorods, polymersomes, and micelles with carbohydrates displayed on the surface. We demonstrate that the formation of nanostructure could be tuned by chain length of the blocks and was not affected by the type of sugar residue. These nanostructures were characterized in detail using a variety of techniques such as TEM, AFM, cryogenic electron microscopy, spectrally resolved fluorescence imaging, and dye encapsulation techniques. We show that it is possible to sequester both hydrophobic as well as hydrophilic dyes within the nanostructures. Finally, we show that these noncytotoxic mannosylated rods and polymersomes were selectively and efficiently taken up by MDA-MB-231 breast cancer cells, demonstrating their potential as nanocarriers for drug delivery.</p>1 aPati, Debasis1 aDas, Soumen1 aPatil, Naganath, G.1 aParekh, Nimisha1 aAnjum, Dalaver, H.1 aDhaware, Vinita1 aAmbade, Ashootosh, V.1 aGupta, Sayam, Sen  uhttps://library.ncl.res.in/content/tunable-nanocarrier-morphologies-glycopolypeptide-based-amphiphilic-biocompatible-star-101701nas 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-401877nas a2200145   4500008004100000245015800041210006900199260000800268300001400276490000700290520125800297100002001555700002601575856013001601       2017                        eng d00aSynthesis and tunable thermoresponsive solution morphologies of 2,2-bis-methylolpropionic acid dendron-azobenzene-poly(N-isopropyl acrylamide) copolymers0 aSynthesis and tunable thermoresponsive solution morphologies of   cJUL  a1084-10930 v663 aAmphiphilic temperature- and photoresponsive linear-dendritic block copolymers comprising second-generation acetonide-2,2-bis-methylolpropionic acid-based polyester dendron and linear poly(N-isopropyl acrylamide) (PNIPAM) linked by an azobenzene unit were synthesized using atom transfer radical polymerization (ATRP) followed by click chemistry. Linear PNIPAM precursor was prepared from an azide-functionalized azobenzene containing ATRP initiator. Two polymers obtained by varying the chain length of the PNIPAM block showed different morphologies and lower critical solution temperature (LCST) values in aqueous solution. Complete change in morphology of the two polymers into large spherical aggregates and nanotubes, respectively, was observed upon heating the micellar solution above LCST. The azobenzene unit was found to undergo trans-cis photoisomerization in the assemblies and caused a change in the microenvironment of an encapsulated hydrophobic dye without any release. Acetonide groups on the dendron were deprotected to afford hydroxylated polymer that showed well-defined morphologies above the LCST and after heating-cooling cycle while significant dye encapsulation was seen only above the LCST. (c) 2017 Society of Chemical Industry1 aKalva, Nagendra1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/synthesis-and-tunable-thermoresponsive-solution-morphologies-22-bis-methylolpropionic-acid02351nas a2200181   4500008004100000022001400041245009500055210006900150260000800219300001400227490000700241520169600248100001701944700003201961700002601993700002702019856012302046       2018                        eng d  a0743-746300aLarge PAMAM dendron induces formation of unusual P4332 mesophase in monoolein/water system0 aLarge PAMAM dendron induces formation of unusual P4332 mesophase  cMAY  a6827-68340 v343 aCompact macromolecular dendrons have been shown to induce the formation of discontinuous inverse micellar assemblies with Fd3m symmetry in monoolein/water systems. Here, we demonstrate that a large PAMAM dendron (G5: fifth generation) induces the formation a very unusual mesophase with P4332 symmetry. This mesophase had previously been observed in monoolein/water systems only on addition of cytochrome C. The P4332 mesophase can be considered an intermediate phase between the bicontinuous Ia3d and discontinuous micellar mesophases. In this unusual phase, every third rod junction of the Ia3d mesophase is replaced with a spherical micelle. We present a detailed investigation of the phase behaviour of monoolein/water as a function of G5 concentration and temperature. Addition of 1% G5 in 85/15 monoolein/water system induces a transition from the L to Ia3d phase. Further increase in G5 concentration to above 2% induces the formation of the P4332 phase. Thus, incorporation of G5 yields a qualitatively different phase diagram when compared with incorporation of lower generation PAMAM dendrons (G2 – G4) in monoolein/water, where the reverse micellar Fd3m phase forms. PAMAM dendrons of all generations, G2 – G5, bear terminal amine groups that interact with the monoolein head group. The compact molecular architecture of the dendrons and these attractive interactions induce bending of the monoolein bilayer structure. For smaller dendrons, G2 – G4, this results in the formation of the Fd3m phase. However, the large size of the G5 dendron precludes this and a rare intermediate phase between the Ia3d and discontinuous micellar phase, the P4332 mesophase forms instead.1 aKumar, Manoj1 aPatil, Naganath, Ganapatara1 aAmbade, Ashootosh, V.1 aKumaraswamy, Guruswamy  uhttps://library.ncl.res.in/content/large-pamam-dendron-induces-formation-unusual-p4332-mesophase-monooleinwater-system02331nas a2200253   4500008004100000022001300041245010500054210006900159260000800228300001400236490000700250520146200257653002401719653003001743653001901773653002701792100002201819700001701841700001801858700002001876700002401896700002601920856013101946       2018                        eng d  a1866689200aTuning of terahertz resonances of pyridyl benzamide derivatives by electronegative atom substitution0 aTuning of terahertz resonances of pyridyl benzamide derivatives   cJUL  a636–6500 v393 a<p>N-(pyridin-2-yl) benzamide (Ph2AP)-based organic molecules with prominent terahertz (THz) signatures (less than 5 THz) have been synthesized. The THz resonances are tuned by substituting the most electronegative atom, fluorine, at ortho (2F-Ph2AP), meta (3F-Ph2AP), and para (4F-Ph2AP) positions in a Ph2AP molecule. Substitution of fluorine helps in varying the charge distribution of the atoms forming hydrogen bond and hence strength of the hydrogen bond is varied which helps in tuning the THz resonances. The tuning of lower THz resonances of 2F-Ph2AP, 3F-Ph2AP, and 4F-Ph2AP has been explained in terms of compliance constant (relaxed force constant). Four-molecule cluster simulations have been carried out using Gaussian09 software to calculate the compliance constant of the hydrogen bonds. Crystal structure simulations of the above molecules using CRYSTAL14 software have been carried out to understand the origin of THz resonances. It has been observed that THz resonances are shifted to higher frequencies with stronger hydrogen bonds. The study shows that 3F-Ph2AP and 4F-Ph2AP have higher hydrogen bond strength and hence the THz resonances originating due to stretching of intermolecular hydrogen bonds have been shifted to higher frequencies compared to 2F-Ph2AP. The methodology presented here will help in designing novel organic molecules by substituting various electronegative atoms in order to achieve prominent THz resonances.</p>10aCompliance constant10aDensity functional theory10aPh2AP molecule10aTerahertz spectroscopy1 aDash, Jyotirmayee1 aRay, Shaumik1 aDevi, Nirmala1 aBasutkar, Nitin1 aGonnade, Rajesh, G.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/tuning-terahertz-resonances-pyridyl-benzamide-derivatives-electronegative-atom-substitution02413nas a2200253   4500008004100000022001400041245008700055210006900142260000800211300001200219490000900231520156800240653002401808653003401832653003001866653002701896100002201923700001701945700001801962700002001980700002602000700001702026856011602043       2019                        eng d  a0022-286000aFine-tuning of Terahertz resonances in hydrogen-bonded organic molecular complexes0 aFinetuning of Terahertz resonances in hydrogenbonded organic mol  cMAY  a495-5020 v11843 a<p>Novel organic molecular complexes have been designed and synthesized to obtain prominent Terahertz (THz) resonances in the low-frequency region. Intermolecular hydrogen bonds give rise to low-frequency THz resonances and hence binary organic molecular complexes of pyridyl alkylamide/benzamide (DAP) and hexyl thymine (C6THY) with multiple strong intermolecular hydrogen bonds (N-H–-O and N-H–-N) are designed and synthesized. THz resonances of the complexes are fine-tuned by varying the number of benzene rings in the DAP moiety (PrDAP + C6THY, PrPhDAP + C6THY and PhDAP + C6THY). DFT simulation studies of two molecule clusters have been carried out to understand the origin of low-frequency THz resonances. It has been observed that the lowest THz resonances (&lt; 2 THz) originate due to translation/rotation of the whole crystal structure and the resonances from 2 to 4 THz are mainly due to intermolecular hydrogen bond bending/stretching vibrations. In order to understand the individual hydrogen bond strengths, compliance constants, which are inverse of the force constants are calculated and Natural Bond Orbital (NBO) analysis has been carried out. Comparison of the experimental THz spectra of different complexes shows that there is a small but tunable variation in THz resonances from one complex to another. Tuning of THz resonances has potential applications in designing THz tags, which can be used in various anti-counterfeiting applications such as currency notes, pharmaceutical tablets. (C) 2019 Elsevier B.V. All rights reserved.</p>10aCompliance constant10aNatural bond orbital analysis10aOrganic molecular complex10aTerahertz spectroscopy1 aDash, Jyotirmayee1 aRay, Shaumik1 aDevi, Nirmala1 aBasutkar, Nitin1 aAmbade, Ashootosh, V.1 aPesala, Bala  uhttps://library.ncl.res.in/content/fine-tuning-terahertz-resonances-hydrogen-bonded-organic-molecular-complexes02223nas a2200241   4500008004100000245016000041210006900201260000800270300001100278490000800289520133700297653002101634653002301655653001801678653001601696653001701712653002301729100002901752700002601781700002601807700002601833856012201859       2023                        eng d00aPermeable polymersomes from temperature and pH dual stimuli-responsive PVCL-b-PLL block copolymers for enhanced cell internalization and lysosome targeting0 aPermeable polymersomes from temperature and pH dual stimulirespo  cAUG  a2134540 v1513 a<p>
	A series of dual stimuli-responsive block copolymers comprising temperature-responsive poly(N-vinyl-caprolactam) (PVCL) and biodegradable pH-responsive poly(L-lysine) (PLL) of varying chain length were syn-thesized by a combination of free radical polymerization and ring opening polymerization. The block copolymers formed micelles and vesicles (polymersomes) in response to temperature and pH, respectively, in aqueous so-lution. The nanoassemblies were characterized by transmission electron microscopy and dynamic light scattering techniques. Encapsulation of both hydrophobic and hydrophilic dyes in the polymersomes was shown. Doxo-rubicin (DOX) was loaded in the polymersomes and its controlled release in response to the two stimuli, inde-pendently and jointly, was studied. The drug was found to be released due to stimuli-induced increased permeability without disassembly of the polymersomes. A significant increase in the cellular uptake of the drug-loaded polymersomes at hyperthermia conditions was demonstrated at 41 degrees C and release of the drug upon localization in lysosomes was observed. Cellular internalization pathway of the polymersomes was investigated by competitive inhibition assay and a combination of endocytic pathways dominated by caveolae-mediated mechanism was found to be operative.</p>
10ablock copolymers10aControlled release10adrug delivery10aendocytosis10aPolymersomes10aStimuli-responsive1 aSurapaneni, Sai, Geetika1 aChoudhari, Shakeb, N.1 aAvhad, Shankarrao, V.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/permeable-polymersomes-temperature-and-ph-dual-stimuli-responsive-pvcl-b-pll-block02477nas 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<p>
	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.</p>
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-sulfones02411nas a2200265   4500008004100000022001400041245012700055210006900182260000900251300001400260490000600274520146900280653002201749653003301771653003801804653001801842653001701860653001701877100002701894700002001921700002701941700002601968700002701994856012402021       2024                        eng d  a2637-610500aNonedible thevetia peruviana oil for the synthesis of biobased thermosets and vitrimers with tunable mechanical properties0 aNonedible thevetia peruviana oil for the synthesis of biobased t  cFEB   a2695-27080 v63 a<p>
	Current attempts to replace fossil-derived materials with vegetable oils for polymer production mainly rely on edible oils. This approach raises sustainability concerns due to potential food security risks. This report introduces the first in-depth examination of Thevetia peruviana oil (TPO) epoxidation, an easily accessible nonedible vegetable oil, utilizing diverse acidic ion-exchange resins as catalysts. It is followed by the development of vitrimers based on epoxidized oil (ETPO) with various dicarboxylic acid hardeners. Amberlite IRC120H emerged as the most effective catalyst for the epoxidation of the oil, allowing for repeated catalyst reusability for up to five cycles. An impressive relative oxirane conversion of 98.9% was achieved after optimization. DSC analysis revealed that among the diacids, 2,2'-dithiodibenzoic acid (DTBZ) has the lowest activation energy with ETPO. Additionally, the ETPO-DTBZ-based thermosets displayed exceptional solvent resistance and thermal stability, indicative of a high degree of cross-linked networks within the system. Mechanical analyses revealed that all aliphatic hardeners resulted in soft materials, while DTBZ resulted in thermosets with tensile stress and modulus of 15 and 843 MPa, respectively. Consequently, DTBZ-ETPO thermosets were successfully recycled, repaired, and reshaped with minimal changes in the mechanical properties. The shape memory of the thermosets was also established.</p>
10abiobasedvitrimers10aenvironmental sustainability10aepoxidizedThevetial peruviana oil10anonedible oil10aOptimization10ashape memory1 aOlosho, Adebayo, Isaac1 aAlam, Md, Shafi1 aNair, Kiran, Sukumaran1 aAmbade, Ashootosh, V.1 aAdekola, Folahan, Amoo  uhttps://library.ncl.res.in/content/nonedible-thevetia-peruviana-oil-synthesis-biobased-thermosets-and-vitrimers-tunable01982nas a2200241   4500008004100000022001400041245013900055210006900194260000900263300001200272490000700284520113000291653001101421653001901432653001301451653001801464653002901482100002401511700002901535700002101564700002601585856012901611       2024                        eng d  a1060-132500aVisible light and pH-responsive star copolymer and doxorubicin-polymer conjugate micelles for combination drug delivery and bioimaging0 aVisible light and pHresponsive star copolymer and doxorubicinpol  cFEB   a105-1160 v613 a<p>
	Amphiphilic 3-arm star copolymer containing visible light-cleavable BODIPY group and pH-responsive imine bonds at the junction of hydrophilic poly(ethylene glycol) (PEG) and two poly(epsilon-caprolactone) (PCL) arms was synthesized by the combination of ring-opening polymerization (ROP) and click chemistry. The formation and stimuli-responsive disruption of micelles were analyzed using dynamic light scattering and transmission electron microscopy. Dual stimuli-responsive release of anticancer drugs Doxorubicin (Dox) and Camptothecin (CPT) from the micelles was studied. Micellar assemblies containing Dox conjugated to PEG-BODIPY through imine bonds were prepared and controlled release of Dox in response to visible light and pH was shown. CPT and Dox-loaded star copolymer micelles as well as CPT loaded Dox-conjugated micelles were used in cellular uptake studies on MDA-MB 231 cells, and the synergistic effect of the two stimuli on the release of the two drugs was demonstrated inside the cells. Micellar assemblies also showed excellent bioimaging properties in the cellular uptake studies. [GRAPHICS]</p>
10aBODIPY10adrug conjugate10amicelles10apH-responsive10avisible light-responsive1 aBasutkar, Nitin, B.1 aSurapaneni, Sai, Geetika1 aAlam, Md., Shafi1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/visible-light-and-ph-responsive-star-copolymer-and-doxorubicin-polymer-conjugate-micelles02083nas a2200241   4500008004100000022001400041245015700055210006900212260000900281300001200290490000700302520118800309653002201497653002301519653002101542653002801563653002301591100002501614700002401639700002701663700002601690856012501716       2025                        eng d  a1060-132500aBio-based poly(isobornyl acrylate)-b-(citronellyl methacrylate) block copolymers by PET-RAFT polymerization: thiol-ene modification and adhesion studies0 aBiobased polyisobornyl acrylatebcitronellyl methacrylate block c  cSEP   a728-7360 v623 a<p>
	In this study, poly(isobornyl acrylate)-b-poly(citronellyl methacrylate) (PIBA-b-PCMA) block copolymers were synthesized with controlled molecular weights and low dispersity using photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of isobornyl acrylate (IBA) and citronellyl methacrylate (CMA), both terpene-derived monomers. A series of block copolymers was obtained by varying the chain length of PCMA block. Kinetics study of the polymerization of IBA and CMA using 4-cyano-(((dodecylthio)carbonothioyl)thio)pentanoic acid (CDTPA) as chain transfer agent showed a linear plot of ln[M]0/[M]t vs time indicating first order reaction. Distinct glass transition temperatures were observed for the individual blocks and enhanced thermal stability was seen with increasing PCMA content. Post-polymerization modification of the polymer was demonstrated using thiol-ene reaction with the vinyl group in the pendent citronellyl moiety. Adhesion performance, evaluated through lap shear test on aluminum substrates, showed that the block copolymers achieved peak shear strengths of 1.74 MPa at a 38:62 PIBA:PCMA mole ratio.</p>
10aadhesion strength10aBio-based polymers10ablock copolymers10aPET-RAFT polymerization10aThiol-ene reaction1 aHetkale, Pragati, M.1 aPurohit, Poorvi, M.1 aNair, Kiran, Sukumaran1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/bio-based-polyisobornyl-acrylate-b-citronellyl-methacrylate-block-copolymers-pet-raft02157nas a2200181   4500008004100000022001400041245015100055210006900206260000800275300001400283490000700297520144000304100002001744700002801764700002701792700002601819856013001845       2025                        eng d  a0024-929700aSquaraine dyes as efficient photoredox catalysts for PET-RAFT polymerization in batch and flow modes accelerated by suppression of dye aggregation0 aSquaraine dyes as efficient photoredox catalysts for PETRAFT pol  cMAR  a2850-28590 v583 a<p>
	Organic photoredox catalysts (PCs) based on squaraine dyes are investigated for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization under visible-light (lambda max = 485 nm) irradiation in the presence of triethylamine that suppresses self-aggregation of dye and accelerates the polymerization. Several commonly used PCs are also screened, and self-aggregation is found to be reduced with triethylamine, thus providing a simple and effective approach to reduce aggregation of PCs. There is no induction period, and total polymerization time is shorter for squaraine dye PCs than for reported PCs under similar conditions. The photocatalyst system is amenable to polymerization by using different RAFT agents. Methyl methacrylate and a range of functional methacrylates are polymerized with good control over molecular weight and narrow dispersity in a first-order reaction with a random switch ``ON-OFF'' of the light source and even without an inert atmosphere. The mechanism of polymerization without and with requirement of triethylamine is elucidated using control experiments and found to be an oxidative and reductive electron transfer, respectively. A series of diblock and random copolymers of methyl methacrylate with methacrylate monomers are synthesized. Controlled polymerization is also demonstrated using a continuous-flow method and in an aqueous medium.</p>
1 aPatil, Anil, M.1 aNawghare, Indrajeet, S.1 aNithyanandhan, Jayaraj1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/squaraine-dyes-efficient-photoredox-catalysts-pet-raft-polymerization-batch-and-flow-modes02183nas a2200169   4500008004100000022001400041245012100055210006900176260000800245300001400253490000700267520154000274100002601814700001701840700002601857856013001883       2025                        eng d  a0743-746300aVisible light-responsive composition-dependent morphology and cargo release in mixed micelles of dendron amphiphiles0 aVisible lightresponsive compositiondependent morphology and carg  cJAN  a1957-19670 v413 a<p>
	2,2-Bis-(methylol)propionic acid-based second-generation polyester dendron amphiphile (T-D) containing visible light-responsive donor-acceptor Stenhouse adduct (DASA) as hydrophobic tails is synthesized. Micelles of T-D amphiphile and its mixed micelles of varying compositions with nonresponsive dendron amphiphile containing lauryl groups are prepared in aqueous solution. In transmission electron microscopy and atomic force microscopy analyses, T-D amphiphiles show rice grain-like ellipsoidal micelles as the predominant morphology. Mixed micelles display a composition-dependent morphology gradient such that the morphology changes from rice grain like to mixed to completely spherical with decreasing content of the T-D amphiphile. Complete morphology change to spherical micelles and partial reversal to ellipsoidal micelles, finally leading to ill-defined aggregates, are observed when the T-D amphiphile micelles are subjected to visible light-dark storage photoswitching cycles. Small-angle neutron scattering (SANS) analysis of 1 wt.% micellar solution in THF:water (10:90) reveals only a minor change in shape and size upon photoirradiation, and the data could be fitted to spherical or ellipsoidal model. Release of hydrophobic dye from mixed micelles is tuned by the content of the photoresponsive amphiphile. Cellular uptake and visible light-triggered release of hydrophobic drug from mixed micelles are demonstrated using MDA-MB-231 cells, suggesting their applicability for photoresponsive drug delivery.</p>
1 aAvhad, Shankarrao, V.1 aKumar, Sugam1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/visible-light-responsive-composition-dependent-morphology-and-cargo-release-mixed-micelles01927nas a2200157   4500008004100000022001400041245013400055210006900189260000900258300001400267490000700281520130500288100002601593700002601619856012401645       2026                        eng d  a1525-779700aEffect of shape on cellular uptake of visible-light- and redox-responsive biodegradable linear-dendritic block copolymer micelles0 aEffect of shape on cellular uptake of visiblelight and redoxresp  cMAR   a1969-19840 v273 a<p>
	Linear-dendritic block copolymers comprising poly(epsilon-caprolactone) attached to hydrophilic 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) ester dendron via a disulfide and containing a defined number of pendent visible-light-responsive donor-acceptor Stenhouse adduct (DASA) groups are synthesized using click chemistry and postpolymerization modification. Self-assembly in aqueous solution selectively affords rice grain-like ellipsoidal, rod-like, and spherical micelles, governed by the number of DASA groups. Progressive disassembly of the micelles is observed during photoswitching cycles. Release of camptothecin depends on the DASA content under light irradiation and is enhanced by the synergistic effect of two stimuli. Cellular uptake quantified by FACS analysis is demonstrated to be influenced by the shape of the micelles, with ellipsoidal micelles exhibiting higher efficiency than spherical micelles by following clathrin- and caveolae-mediated endocytosis as major pathways for internalization. Both types of micelles were found to maintain the particle size in Dulbecco's modified Eagle's medium containing 10% fetal bovine serum at 37 degrees C. Doxorubicin (DOX)-loaded ellipsoidal micelles under photoirradiation show significantly higher apoptosis than free DOX.</p>
1 aAvhad, Shankarrao, V.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/effect-shape-cellular-uptake-visible-light-and-redox-responsive-biodegradable-linear02255nas a2200277   4500008004100000022001400041245012900055210006900184260000800253300001100261490000800272520131600280653001801596653001501614653001801629653002601647653001701673653001301690653001801703653002101721100002601742700002901768700002401797700002601821856013001847       2026                        eng d  a0021-899500aRedox- and pH-responsive block copolymer nanocarriers with dual drug conjugation through dynamic covalent and hydrogen bonds0 aRedox and pHresponsive block copolymer nanocarriers with dual dr  cMAR  ae702050 v1433 a<p>
	Loading of multiple drugs in a nanocarrier with high entrapment efficiency is important for combination therapy in cancer treatment. Here, a block copolymer comprising hydrophobic poly(epsilon-caprolactone) block with a defined number of pendent propargyl groups, polyethylene glycol monomethyl ether as a hydrophilic block, and a redox-responsive disulfide group at the block junction is synthesized using click chemistry and ring-opening polymerization (ROP). Benzaldehyde and thymine groups are introduced in the side chains for selective attachment of anti-cancer drugs, doxorubicin (DOX) and methotrexate (MTX), via the formation of pH-responsive imine linkage and hydrogen bonds, respectively. The drug-conjugated block copolymers are assembled into spherical micelles of &lt; 200 nm, and the preferential release of DOX and MTX in response to acidic pH and redox conditions is shown. At pH 5, DOX release was 59.5%, and MTX release was 40% compared to 13% and 12% at pH 7.4, whereas at pH 5 with 10 mM GSH, a DOX release of 81.5% was observed after 48 h. Cellular uptake of drug-conjugated micelles and their apoptosis compared to free DOX in the MDA-MB-231 breast cancer cells is demonstrated. Caveolae-mediated endocytosis was found to be the major pathway used by drug-loaded nanocarriers.</p>
10abiodegradable10acopolymers10aDOX-conjugate10adrug delivery systems10amethotrexate10amicelles10apH-responsive10aredox-responsive1 aAvhad, Shankarrao, V.1 aSurapaneni, Sai, Geetika1 aPurohit, Poorvi, M.1 aAmbade, Ashootosh, V.  uhttps://library.ncl.res.in/content/redox-and-ph-responsive-block-copolymer-nanocarriers-dual-drug-conjugation-through-dynamic02136nas a2200229   4500008004100000022001400041245012600055210006900181260000800250300001000258490000700268520133600275653002401611653001401635653001401649653001301663653002301676100002201699700002601721700002801747856013101775       2026                        eng d  a1060-132500aUtilization of bisphenol based on lignin-derived chemicals for the synthesis of partially bio-based aromatic copolyesters0 aUtilization of bisphenol based on ligninderived chemicals for th  cJAN  a83-900 v633 a<p>
	New aromatic copolyesters were synthesized by phase-transfer catalyzed interfacial polycondensation of 4,4 `-((3,4-dimethoxyphenyl)methylene)bis(2-methoxyphenol) (DMBM) with isophthaloyl chloride (IPC) and a mixture of (50:50 mol %) IPC and terephthaloyl chloride (TPC). Additionally, a series of copolyesters was synthesized by polycondensation of varying compositions of DMBM and bisphenol A with IPC. Copolyesters exhibited inherent viscosity and Mn values in the range 0.59-0.98 dL/g and 15,840-49,460 g/mol, respectively, indicating formation of reasonably high molecular weight polymers. Copolyesters could be cast into tough, transparent and flexible films from chloroform solution. UV-vis measurements on films gave values of T400, T450 and cut-off wavelength in the range 80-84 %, 83-89 % and 324-334 nm, respectively. The formation of random copolyesters was evidenced by 13C NMR spectroscopic studies. Copolyesters exhibited good thermal stability with 10% weight loss temperature in the range 391-438 degrees C. The Tg values of copolyesters were in the range 162-180 degrees C and Tg values decreased with an increase in mol% content of DMBM. Copolyesters exhibited tensile strength, Young's modulus and elongation at break values in the range 83.55-70.68 MPa, 2.11-1.31 GPa and 10.52-5.45 %, respectively.</p>
10aAromatic polyesters10abio-based10abisphenol10amethoxyl10aThermal properties1 aWale, Apparav, K.1 aAmbade, Ashootosh, V.1 aWadgaonkar, Prakash, P.  uhttps://library.ncl.res.in/content/utilization-bisphenol-based-lignin-derived-chemicals-synthesis-partially-bio-based-aromatic