02087nas a2200193 4500008004100000022001400041245006800055210006700123260007100190300001400261490000700275520140500282100002001687700002201707700002001729700002001749700002201769856010201791 2013 eng d a0743-746300aSynthesis and self-assembly of amphiphilic homoglycopolypeptide0 aSynthesis and selfassembly of amphiphilic homoglycopolypeptide a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY a5659-56670 v293 a

The synthesis of the amphiphilic homoglycopolypeptide was carried out by a combination of NCA polymerization and click chemistry to yield a well-defined Polypeptide having an amphiphilic carbohydrate on its side chain. The amphiphilicity of the carbohydrate was achieved by incorporation of an alkyl chain, at the C-6 position of the carbohydrate thus also rendering the homoglycopolypeptide amphiphilic. The homoglycopolypeptide formed multimicellar aggregates in water above a critical concentration of 0.9 mu M due to phase separation. The multimicellar aggregates were characterized by DLS, TEM, and AFM. It is proposed that hydrophobic interactions of the aliphatic chains at the 6-position of the sugar moieties drives the assembly of these rod-like homoglycopolypeptide into large;spherical aggregates. These multimicellar aggregates encapsulate both hydrophilic as well as hydrophobic dye as was confirmed by confocal microscopy. finally, amphiphilic random polypeptides containing 10% and 20% alpha-D-mannose in addition to glucose containing a, hydrophobic alkyl chain at its 6 position were synthesized by our methodology, and these polymers Were also found to assemble into spherical nanostructures. The spherical assemblies Of amphiphilic random glycopolypeptides containing 10% and 20% mannose were found to be surface bioactive and were found, to interact with the lectin Con-A.

1 aDhaware, Vinita1 aShaikh, Ashif, Y.1 aKar, Mrityunjoy1 aHotha, Srinivas1 aGupta, Sayam, Sen uhttps://library.ncl.res.in/content/synthesis-and-self-assembly-amphiphilic-homoglycopolypeptide-002237nas a2200205 4500008004100000022001400041245012400055210006900179260007100248300001400319490000700333520144600340100002201786700001601808700001801824700002001842700002201862700002001884856012701904 2014 eng d a1525-779700aCationic charged helical glycopolypeptide using ring opening polymerization of 6-deoxy-6-azido-glyco-N-carboxyanhydride0 aCationic charged helical glycopolypeptide using ring opening pol a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcOCT a3679-36860 v153 a

Glycopolypeptides with a defined secondary structure are of significance in understanding biological phenomena. Synthetic glycopolypeptides, or polypeptides featuring pendant carbohydrate moieties, have been of particular interest in the field of tissue engineering and drug delivery. In this work, we have synthesized charged water-soluble glycopolypeptides that adopt a helical conformation in water. This was carried out by the synthesis of a glyco-N-carboxyanhydride (glyco-NCA) containing an azide group at the sixth position of the carbohydrate ring. Subsequently, the NCA was polymerized to obtain azide-containing glycopolypeptides having good control over molecular weight and polydispersity index (PDI) in high yields. We were also able to control the incorporation of the azide group by synthesizing random co-glycopolypeptide containing 6-deoxy-6-azido and regular 6-OAc functionalized glucose. This azide functionality allows for the easy attachment of a bioactive group, which could potentially enhance the biological activity of the glycopolypeptide. We were able to obtain water-soluble charged glycopolypeptides by both reducing the azide groups into amines and using CuAAC with propargylamine. These charged glycopolypeptides were shown to have a helical conformation in water. Preliminary studies showed that these charged glycopolypeptides showed good biocompatibility and were efficiently taken up by HepG2 cells.

1 aShaikh, Ashif, Y.1 aDas, Soumen1 aPati, Debasis1 aDhaware, Vinita1 aGupta, Sayam, Sen1 aHotha, Srinivas uhttps://library.ncl.res.in/content/cationic-charged-helical-glycopolypeptide-using-ring-opening-polymerization-6-deoxy-6-002126nas 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

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.

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-102469nas a2200193 4500008004100000022001400041245010500055210006900160260000800229520178200237653001302019653001502032653002602047653001402073100002002087700002202107700002202129856012402151 2019 eng d a1861-472800aBiopolymer/glycopolypeptide-blended scaffolds: synthesis, characterization and cellular interactions0 aBiopolymerglycopolypeptideblended scaffolds synthesis characteri cDEC3 a

Three-dimensional (3D) scaffolds formed from natural biopolymers gelatin and chitosan that are chemically modified by galactose have shown improved hepatocyte adhesion, spheroid geometry and functions of the hepatocytes. Galactose specifically binds to the hepatocytes via the asialoglycoprotein receptor (ASGPR) and an increase in galactose density further improves the hepatocyte proliferation and functions. In this work, we aimed to increase the galactose density within the biopolymeric scaffold by physically blending the biopolymers chitosan and gelatin with an amphiphlic beta-galactose polypeptide (PPO-GP). PPO-GP, is a di-block copolymer with PPO and beta-galactose polypeptide, exhibits lower critical solution temperature and is entrapped within the scaffold through hydrophobic interactions. The uniform distribution of PPO-GP within the scaffold was confirmed by fluorescence microscopy. SEM and mechanical testing of the hybrid scaffolds indicated pore size, inter connectivity and compression modulus similar to the scaffolds made from 100 % biopolymer. The presence of the PPO-GP on the surface of the scaffold was tested monitoring the interaction of an analogous mannose containing PPO-GP scaffold and the mannose binding lectin Con-A. In vitro cell culture experiments with HepG2 cells were performed on GLN-GP and CTS-GP and their cellular response was compared with GLN and CTS scaffolds for a period of seven days. Within three days of culture the Hep G2 cells formed multicellular spheroids on GLN-GP and CTS-GP more efficiently than on the GLN and CTS scaffolds. The multicellular spheroids were also found to infiltrate more in GLN-GP and CTS-GP scaffolds and able to maintain their round morphology as observed by live/dead and SEM imaging.

10aadhesion10aAggregates10aCellular infiltration10aSpheroids1 aDhaware, Vinita1 aDiaz, David, Diaz1 aGupta, Sayam, Sen uhttps://library.ncl.res.in/content/biopolymerglycopolypeptide-blended-scaffolds-synthesis-characterization-and-cellular03363nas a2200193 4500008004100000245009100041210006900132260000800201300001600209490000600225520268800231100001902919700001602938700002002954700002002974700002002994700002003014856013503034 2019 eng d00apH-responsive “supra-amphiphilic” nanoparticles based on homoarginine polypeptides0 apHresponsive supraamphiphilic nanoparticles based on homoarginin cAUG a4162–41720 v23 a

pH-responsive “supra-amphiphiles” based on double hydrophilic, positively charged block copolypeptides such as PEG-b-poly-l-lysine together with low molecular weight stimuli-sensitive partners that contain phosphate and carboxylate groups have been widely studied. In contrast, the other widely used cationic polypeptide poly-l-arginine whose cell-penetrating properties are well-known has been much less explored for the synthesis of supra-amphiphile-based nanomaterials. It is also known that the guanidine side chain of arginine binds to carboxylate anions with binding constants that are 2.5 times higher than the corresponding amines of poly-l-lysine. Here, we demonstrate the fabrication of pH-sensitive supra-amphiphilic nanoparticles by simple mixing of PEG2k-b-poly(homoarginine) block copolymer and carboxylic acid containing functional low molecular weight organic compounds. A high yielding three-step methodology was developed for the synthesis of ε-N,N′-di-Boc-l-homoarginine-α-N-carboxyanhydride which was polymerized using amine-terminated PEG (2000 MW) to yield 100% guanine-functionalized polypeptide (PEG2k-b-PHR30) with controlled molecular weights and low PDIs. Incubation of PEG2k-b-PHR30 with four different carboxylic acids (including dexamethasone a glucocorticoid receptor used in cancer therapy) in water leads to the formation of “supra-amphiphilic” nanoparticles (<200 nm size) due to the charge neutralization resulting from the strong interaction between the guanidine group and the carboxylate group. All these nanoparticles were able to encapsulate the hydrophobic dye Nile red with varying efficiency. Although these assemblies were stable at neutral pH, upon lowering the pH of the solution between 4 and 5, the protonation of the carboxylic acids leads to disassembly of these nanoparticles. The cytotoxicity of all four “supra-amphiphilic” nanoparticles varied depending on the carboxylic acid used for their fabrication. While the nanoparticle formed using dioctylbenzoic acid displayed 80% cell viability at concentration of 60 μg/mL, those formed with the steroid deoxycholic acid or dexamethasone showed only 40% cell viability at similar concentrations. Colocalization studies performed using epifluorescence microscopy demonstrate the successful uptake of intact dye-encapsulated nanoparticle inside the cell.

1 aPraveen, Korra1 aDas, Soumen1 aDhaware, Vinita1 aPandey, Bhawana1 aMondal, Basudeb1 aSengupta, Sayam uhttps://library.ncl.res.in/content/ph-responsive-%E2%80%9Csupra-amphiphilic%E2%80%9D-nanoparticles-based-homoarginine-polypeptides02205nas a2200289 4500008004100000022001400041245008700055210006900142260000800211300001100219490000800230520126600238653001601504653001301520653003101533653001701564653003601581653003301617100002001650700002101670700002001691700002101711700001801732700001701750700003101767856011701798 2020 eng d a0927-775700aDual responsive cellulose microspheres with high solid-state fluorescence emission0 aDual responsive cellulose microspheres with high solidstate fluo cAPR a1245100 v5913 a

Materials that respond to multiple stimuli such as magnetic field and light are attractive for security and medical diagnostic applications. One of the major challenges in dual functional microspheres is that the presence of magnetic nanoparticles can quench fluorescence emission. Also, there is a probability of solid-state quenching due to the proximity of the fluorophore. We report here a facile approach to prepare cellulose microspheres with high solid-state fluorescence using 40 % tetrabutylammonium hydroxide (TBAH). The fluorescence quenching effect due to the presence of Fe3O4 nanoparticles and solid-state quenching due to aggregation of fluorophore was systematically investigated. Microspheres with the detectable magnetic response and fluorescence quantum yield as high as 0.57 (FMB 414) was obtained by optimizing the reaction conditions. Such a high quantum yield has not been reported before for dual stimuli-responsive fluorescent microspheres. The magnetic and fluorescent properties were found to be durable even after multiple washing cycles. These dual responsive cellulose microspheres can be added as security features to authenticate documents such as passports, degree certificates, currency notes, financial documents etc.

10aFluorescent10aMagnetic10aMicrocrystalline cellulose10amicrospheres10aStimuli responsive microspheres10aTetrabutylammonium hydroxide1 aYadav, Prashant1 aPrajitha, K., P.1 aDhaware, Vinita1 aSubramani, Mohan1 aJoy, Pattayil1 aAsha, S., K.1 aShanmuganathan, Kadhiravan uhttps://library.ncl.res.in/content/dual-responsive-cellulose-microspheres-high-solid-state-fluorescence-emission