Gram Matrices of Mixed-State Ensembles

International Journal of Theoretical Physics - Gram matrices arise naturally in the consideration of pair-wise overlap of a family of vectors or quantum pure states, and play an important role in...     

Determination of 5-nitroindazole using silver solid amalgam electrode

Monatshefte für Chemie - Chemical Monthly - The voltammetric behavior of 5-nitroindazole was investigated at polished (p-AgSAE) and at mercury meniscus-modified (m-AgSAE) silver solid amalgam...     

Random copolymerization of macromonomers as a versatile strategy to synthesize mixed-graft block copolymers

The random copolymerization of norbornene-functionalized macromonomers was explored as a method of synthesizing mixed-graft block copolymers (mGBCPs). The copolymerization kinetics of a model system of polystyrene (PS) and poly(lactic acid) (PLA) macromonomers was first analyzed, revealing a gradient composition of side chains along the mGBCP backbone. The phase separation behavior of mGBCPs with PS and PLA side chains of various backbone lengths and side chain molar ratios was investigated, and increasing the backbone length was found to stabilize the phase-separated nanostructures. The graft architecture was also demonstrated to improve the processability of the mGBCP, compared to a linear counterpart. Investigations of mGBCPs comprised of polydimethylsiloxane and poly(ethylene oxide) side chains exemplified the diverse self-assembled morphologies, including a Frank-Kasper A15 phase, that can be obtained with mGBCPs synthesized by random copolymerization of macromonomers. Lastly, a ternary mGBCP was synthesized by the copolymerization of three macromonomers.     

Physicochemical properties and bio-interfacial interactions of surface modified PDLLA-PAMAM linear dendritic block copolymers

Here, we demonstrate the applicability of self-assembling linear-dendritic block copolymers (LDBCs) and their nanoaggregates possessing varied surfaces as therapeutic nanocarriers. These LDBCs are comprised of a hydrophobic, linear polyester chemically coupled to a hydrophilic dendron polyamidoamine (PAMAM)—the latter of which acts as the surface of the self-assembled nanoaggregate in aqueous media. To better understand how surface charge density affects the overall operability of these nanomaterials, we modified the nanoaggregate surface to yield cationic (NH₃⁺), neutral (OH), and anionic (COO⁻) surfaces. The effect of these modifications on the physicochemical properties (i.e., size, morphology, and surface charge density), colloidal stability, and cellular uptake mechanism of the polymeric nanocarrier were investigated. This comparative study demonstrates the viability of nanoaggregates formed from PDLLA-PAMAM LDBCs to serve as nanocarriers for applications in drug delivery.     

DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex

DFT computations have been performed to investigate the mechanism of H₂‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H₂ can react with the deactivated [Zr]?pMS?PP_n facilely, which displace functionalized pMS?PP_n chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585