Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities

Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710     

Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

Preparation and Eh--pH diagrams of Fe(II)--Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and -carbonate

Fe(II)--Fe(III) hydroxy-chloride, -sulphate and -carbonate were prepared by oxidation of a ferrous hydroxide precipitate in anion-containing aqueous solutions. The compounds are characterized by monitoring the redox potential E_h and the pH of stochiometric suspension vs time with the appropriate concentration ratios. X-ray diffraction allows us to characterize the crystal structure by distinguishing “green rust one” (GR1) from “green rust two” (GR2). Since green rusts (GRs) are of a pyroaurite-sjögrenite-like structure, i.e., consisting of intercalated foreign anions and water molecules in the interlayers between the brucite-like layers of Fe(OH)₂, their chemical formulae can be determined from the Mössbauer spectra. Three quadrupole doublets are observed: D₁ and D₂ correspond to a ferrous state with isomershift IS of about 1.27 mm s^-1 and quadrupole splittings QS of about 2.85 and 2.60 mm s^-1, respectively, whereas D₃ corresponds to a ferric state with IS and QS of about 0.4 mm s^-1. The hyperfine parameters of these doublets are similar from one green rust to another but their intensity ratios vary considerably. Finally, E_h and pH equilibrium diagrams of the Fe species in the presence of chloride, sulphate and carbonate anions contained within the water solution are drawn and the thermodynamic conditions of existence and degrees of oxidation of green rusts are discussed.     

Synthesis and antimycobacterial activity of alkyl 1‐heteroaryl‐1H‐1,2,3‐triazole‐4‐carboxylates

A series of alkyl l‐heteroaryl‐1H‐1,2,3‐triazole‐4‐carboxylates 6a‐u were synthesised in four steps from methyl (Z)‐2‐benzyloxycarbonylarmino‐3‐(dimethylamino)prop‐2‐enoate ( 1 ) and heterocyclic amines 2a‐s. Triazoles 6a‐o were tested against antimycobacterial activity. For the most active compound, n‐pentyl 1‐(6‐phenylpyridazin‐3‐yl)‐1H‐1,2,3‐triazole‐4‐carboxylate ( 6n ), minimum inhibitory concentration 3.13 μg/ml was determined.     

Sets of permutations that generate the symmetric group pairwise

The paper contains proofs of the following results. For all sufficiently large odd integers n, there exists a set of ²n−1 permutations that pairwise generate the symmetric group Sn. There is no set of ²n−1+1 permutations having this property. For all sufficiently large integers n with n≡2mod4, there exists a set of ²n−2 even permutations that pairwise generate the alternating group An. There is no set of ²n−2+1 permutations having this property.     

Connectedness of the Isospectral Manifold for One-Dimensional Half-Line Schrödinger Operators

Journal of Statistical Physics - Let V 0be a real-valued function on [0,∞) and V∈L 1([0,R]) for all R&;gt;0 so that H(V 0)=? $\frac{{d^2 }}{{dx^2 }}$ +V 0in L 2([0,∞))...