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We describe the synthesis of homo-, block, and clickable copolypeptide brushes from low surface area substrates using nickel-mediated surface-initiated polymerization of alpha-amino N-carboxyanhydrides.

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Cylindrical brush polymers with poly-l-lysine side chains were prepared by grafting lysine NCA from a macroinitiator via living ring-opening polymerization. The main chain degree of polymerization of the methacrylate main chain was Pw = 870, the side chains consisted of 25 and 55 lysine repeat units, respectively. Upon deprotection, the cylindrical brush polymers in 0.005 M NaBr exhibited an almost rodlike conformation with a Kuhn statistical segment length of several hundred nanometers. Cryo-TEM as well as AFM in aqueous solution clearly demonstrated pronounced undulations along the main chain at low ionic strength which could not be detected at higher salt concentrations. With increasing concentration of NaClO4 the PLL side chains underwent a coil-to-helix transition as revealed by CD measurements. The effect of the side chain coil-to-helix transition on the main chain stiffness could not be followed by light scattering due to intramolecular attraction (“folding”) of the cylindrical brushes at high salt concentration, which is somewhat more pronounced for the helical as compared to the coiled PLL side chain conformation. Comparison with linear PLL revealed the coil-to-helix transition to be hardly affected by the high grafting density of the PLL side chains in the cylindrical brush structures.

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Amphiphilic block copolypeptides were prepared through transition-metal- mediated polymerization of amino acid N-carboxyanhydrides. In aqueous solution these materials form strong hydrogels at low concentrations. The self-assembly process that is responsible for gelation was investigated by measuring the rheological properties of the gels for a variety of molecular architectures: poly-L-lysine-&-poly-L-leucine diblock and poly-L-lysine-b-poly-L-leucine-b- poly-L-lysine triblock copolypeptides. Experiments showed that the rodlike helical secondary structure of enantionierically pure poly-L-leucine blocks was instrumental for gelation at polypeptide concentrations as low as 0.25 wt %. The hydrophilic polyelectrolyte segments have stretched coil configurations and stabilize the twisted fibril assemblies by forming a corona around the hydrophobic core. The self-assembly of hydrophobic blocks is highly specific and sensitive to the chirality of the helices. It was found that mechanical properties of the gels can be tuned through the molecular architecture of the block copolypeptides and also by carefully mixing different polypeptides in solution.

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Novel hybrid materials are synthesized through the surface selective grafting of poly-l-lysine and thiols from SBA-15. The Royal Society of Chemistry 2010.

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A series of novel disulfide-containing triblock copolymers, poly(ethylene glycol)-b-poly(l-lysine)-b-poly(rac-leucine) (PEG-SS-PLys-PLeu), were prepared. In an aqueous solution, the copolymers could self-assemble to form core-shell-corona micelles with a disulfide-linked detachable PEG corona, since the PLys middle shell with primary amine groups was linked by a disulfide-containing cross-linker. The morphology and stability of self-assembled micelles were characterized by TEM, DLS and SEM. In the intracellular environment, the micelles underwent destruction of the cross-linked shell with detachment of the PEG corona due to the cleavage of disulfide bonds, followed by the collapse of micelles. The in vitro drug release in response to GSH was further studied. Interestingly, it was found that the micelles not only exhibited reduced drug loss in extracellular environments, but also drastically accelerated drug release at the cytoplasmic GSH level, leading to enhanced growth inhibition of HeLa cells. The glutathione-responsive micelles might have great potential in intracellular drug delivery.

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 1676-86-4, name is (S)-Benzyl (4-(2,5-dioxooxazolidin-4-yl)butyl)carbamate, introducing its new discovery. COA of Formula: C15H18N2O5

The preparation method and application of, the nanoparticle prepared from the tumor microenvironment-responsive polymer and the ribonucleoprotein complex by the self-assembly of the nanoparticles realize the effective enrichment of the ribose nucleic acid complex in the tumor, tissue. (by machine translation)

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A series of amphiphilic diblock copolypeptides (K30-b-F15, K30-b-F30, and K30-b-F45) were synthesized via N-carboxy-alpha-amino-anhydride ring-opening polymerization. The copolypeptides had excellent antibacterial efficacy to both Gram positive (S. aureus) and Gram negative (E. coli) bacteria. The minimum inhibitory concentrations (MICs) against E. coli and S. aureus are 8 mug mL?1 and 2 mug mL?1, respectively, lower than most natural and artificial antimicrobial peptides (AMPs). The morphological changes of the bacteria treated with diblock copolypeptides were investigated by transmission electron microscopy; the results proved that the diblock copolypeptides had a similar antibacterial pore-forming mechanism to natural cationic peptides. This was confirmed by laser scanning confocal microscope images. CCK-8 results and the MICs showed that the diblock copolypeptides have high selectivity to bacteria, which suggested that the diblock copolypeptides could be excellent candidates to replace traditional antibiotics in future.

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We describe the application of flash column chromatography on silica gel as a rapid and general method to obtain pure alpha-amino acid-N-carboxyanhydride (NCA) monomers, the widely used precursors for the synthesis of polypeptides, without the need for recrystallization. This technique was effective at removing all common impurities from NCAs and was found to work for a variety of NCAs, including those synthesized using different routes, as well as those bearing either hydrophilic or hydrophobic side chains. All chromatographed NCAs required no further purification and could be used directly to form high molecular weight polypeptides. This procedure is especially useful for the preparation of highly functional and low melting NCAs that are difficult to crystallize and, consequently, to polymerize. This method solves many long-standing problems in NCA purification and provides rapid access to NCAs that were previously inaccessible in satisfactory quality for controlled polymerization. This method is also practical in that it requires less time than recrystallization and often gives NCAs in improved yields.

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Photosensitive multilayered films were fabricated via layer-by-layer (LbL) assembly based on 5-(4-aminophenyl)-10,15,20-triphenyl-porphyrin (APP) terminated poly-l-lysine (APP-PLL) and DNA (herring sperm). It was found that the distinctive absorbance of porphyrin at 425 nm after light illumination decreased linearly with the increasing light illumination time. Profilometry proved that the thickness of the films decreased linearly with the illumination time. During the light illumination, the degradation of APP-PLL and DNA resulted in a porous structure of the multilayered films. Most importantly, the pore size and pore number of the in situ produced pores can be easily controlled by adjusting the illuminating time.

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A near infrared fluorescent polymeric drug delivery system (NIRF DDS) with pH-responsive drug release properties has been designed and developed. This material was prepared by chemical conjugation of the anticancer drug doxorubicin and hydrophobic aminocyanine dye to triblock copolypeptide via hydrazone and amide bonds, respectively. Conjugation with aminocyanine shows almost no toxicity of the material, while conjugation with doxorubicin induces pronounced toxicity on the original biocompatible material. The pH sensitive drug release nature of the near infrared fluorescent polymeric drug (NIRF prodrug) was confirmed by accelerated drug release at pH of 5.0 via an in vitro drug release experiment and gradual drug cleavage from the NIRF prodrug during a confocal laser scanning microscopic (CLSM) experiment. The CLSM experiment also reveals that the released drug subsequently migrated to the nucleus, while the polymeric residue still remained in cytoplasm, indicating that the as-prepared polymer can be a promising candidate for theranosis of cancer.

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