Quantum dot-polymer nanocomposites : new materials for dispersion, encapsulation, and electronic applications.

Tremendous advances in the synthesis and functionalization of nanoparticles over the past twenty years have resulted in remarkable discoveries in the field of nanotechnology. One such development is found in quantum dots, semiconductor nanoparticles that exhibit unique optical and electronic properties not found in the bulk. Research efforts associated with the combination of quantum dots and polymers center on uniting the mechanical or processing properties of the polymer with the optical properties of the quantum dot. Simply blending polymers with nanoparticles typically leads to nanoparticle aggregation, which negates the inherent advantageous properties of the quantum dots. The development of organic and polymer ligands for nanoparticle surface modification enables the preparation of dispersed nanocomposites that retain, or even enhance, the original nanoparticle properties. Presented here is the synthesis of functionalized nanoparticles that are tailored for the growth of polymers directly from the particle surface. Initial studies focused on the preparation of nanoparticle-polymer hybrid materials where the nanoparticles were evenly dispersed throughout the polymer. A method was developed to cross-link polymers grafted from the nanoparticle in an encapsulating shell, with the goal of minimizing nanoparticle degradation. In addition, polymerization chemistry from quantum dot surfaces was modified and optimized to produce conjugated polymer-quantum dot composites. The coupling of these two electronically active components gave composite materials with very unique optical properties that hold potential as displays, sensors, and light-emitting materials

Melanocortin 1 receptor ligands and methods of use

The subject invention pertains to a modified MC1R peptide ligand comprising a peptide that is a melanocortin 1 receptor (MC1R) ligand and a functionality or linker, such as a click functionality, for conjugation to a surface or agent. The modified MC1R peptide ligand can be coupled, e.g., via a click reaction with a complementary click functionality attached, to a moiety to form an MC1R-targeted agent. Drugs, contrast agents, polymers, particles, micelles, surfaces of larger structures, or other moieties can be targeted to the MC1R. The subject invention also pertains to a MC1R peptide ligand-micelle complex comprising a peptide that is a melanocortin 1 receptor ligand connected via a click reaction product to a micelle. The micelle is stable in vivo and can target melanoma tumor cells by association of the peptide ligand with the MC1R or the tumor and selectively provide a detectable and/or therapeutic agent (such as an imageable contrast agent and/or anti-cancer agent) selectively to the tumor cell.Board of Regents, University of Texas Syste

Large-scale synthesis of α-amino acid-<i>N</i>-carboxyanhydrides

<p>Hetero- and homopolymers prepared from α-amino acid-<i>N</i>-carboxyanhydrides (NCAs) monomers are widely useful products. The preparation of pure NCA monomers has been extensively studied in the past. Purification methods including repeated crystallizations, extraction, and flash column chromatography have been devised. However, these methods are not easily amendable to large-scale NCA preparations. This article describes the synthesis of numerous highly purified NCAs on a >100 g scale using a simple filtration step through diatomaceous earth (celite). The resulting NCAs provided polyethylene glycol (PEG)–amino acid triblock polymers devoid of low-molecular-weight by-products that were routinely observed when unfiltered batches of NCAs were used. Also disclosed is the preparation of NCAs at ambient temperature. Traditionally, NCA reactions using a phosgene source are heated. This study shows these reactions can be driven by the slight exotherm that forms upon reagent mixing. This eliminates the need for an external heating source, simplifying large-scale reactions.</p

Synthesis and Characterization of Micelle-Forming PEG-Poly(Amino Acid) Copolymers with Iron-Hydroxamate Cross-Linkable Blocks for Encapsulation and Release of Hydrophobic Drugs

Described is the development of a polymeric micelle drug delivery platform that addresses the physical property limitations of many nanovectors. The system employs triblock copolymers comprised of a hydrophilic poly­(ethylene glycol) (PEG) block, and two poly­(amino acid) (PAA) blocks: a stabilizing cross-linking central block, and a hydrophobic drug encapsulation block. Detailed description of synthetic strategies and considerations found to be critical are discussed. Of note, it was determined that the purity of the α-amino acid-<i>N</i>-carboxyanhydrides (NCA) monomers and PEG macroinitiator are ultimately responsible for impurities that arise during the polymerization. Also, contrary to current beliefs in the field, the presence of water does not adversely affect the polymerization of NCAs. Furthermore, we describe the impact of poly­(amino acid) conformational changes, through the incorporation of d-amino acids to form mixed stereochemistry PAA blocks, with regard to the physical and pharmacokinetic properties of the resulting micelles

Development and <i>in Vivo</i> Quantitative Magnetic Resonance Imaging of Polymer Micelles Targeted to the Melanocortin 1 Receptor

Recent emphasis has focused on the development of rationally designed polymer-based micelle carriers for drug delivery. The current work tests the hypothesis that target specificity can be enhanced by micelles with cancer-specific ligands. In particular, we describe the synthesis and characterization of a new gadolinium texaphyrin (Gd-Tx) complex encapsulated in an IVECT micellar system, stabilized through Fe­(III) cross-linking and targeted with multiple copies of a specific ligand for the melanocortin 1 receptor (MC1R), which has been evaluated as a cell-surface marker for melanoma. On the basis of comparative MRI experiments, we have been able to demonstrate that these Gd-Tx micelles are able to target MC1R-expressing xenograft tumors <i>in vitro</i> and <i>in vivo</i> more effectively than various control systems, including untargeted or un-cross-linked Gd-Tx micelles. Taken in concert, the findings reported herein support the conclusion that appropriately designed micelles are able to deliver contrast agent payloads to tumors expressing the MC1R

Measurement of charged-particle multiplicities in gluon and quark jets in p(p)over-bar collisions at root s=1.8 TeV

We report the first largely model independent measurement of charged particle multiplicities in quark and gluon jets, N-q and N-g, produced at the Fermilab Tevatron in p (p) over bar collisions with a center-of-mass energy of 1.8 TeV and recorded by the Collider Detector at Fermilab. The measurements are made for jets with average energies of 41 and 53 GeV by counting charged particle tracks in cones with opening angles of θ(c)=0.28, 0.36, and 0.47 rad around the jet axis. The corresponding jet hardness Q=E-jetθ(c) varies in the range from 12 to 25 GeV. At Q=19.2 GeV, the ratio of multiplicities r=N-g/N-q is found to be 1.64&PLUSMN; 0.17, where statistical and systematic uncertainties are added in quadrature. The results are in agreement with resummed perturbative QCD calculations