Encapsulation and release by star‐shaped block copolymers as unimolecular nanocontainers

A five‐arm star‐shaped poly(ethylene oxide) (PEO) with terminal bromide groups was used as a macroinitiator for the atom transfer radical polymerization of tert‐butyl acrylate (tBA), resulting in five‐arm star‐shaped poly(ethylene oxide)‐block‐poly(tert‐butyl acrylate) block copolymers. The polymerization proceeded in a controlled way using a copper(I)bromide/pentamethyl diethylenetriamine catalytic system in acetonitrile as solvent. The hydrolysis of the tBA blocks of the amphiphilic star‐shaped PEO‐b‐PtBA block copolymer resulted in dihydrophilic star structures. The encapsulation of the star‐block copolymers and their release properties in acid environment have been followed by UV‐spectroscopy and color changes, using the dye methyl orange as a hydrophilic guest molecule. Characterization of the structures has been done by ¹H NMR, size exclusion chromatography, MALDI‐TOF, and differential scanning calorimetry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 650–660, 2008     

Determination of phosphorus in waste water by EDXRF

Summary In a method developed for the determination of phosphorus in aqueous solutions, phosphorus was changed to the phosphate form, coprecipitated with hydrated iron(III) oxide, bound with activated charcoal and measured by EDXRF. The detection limit was 0.89 mg P/g activated charcoal. The method was used to determine the total phosphorus content of a waste water sample from a paper mill. Investigation of two sample destruction methods, dry ashing/HCl digestion and persulphate oxidation, showed the former to be more suitable for our purpose.     

Copper(I) complexes of bis(2-(diphenylphosphino)phenyl) ether: synthesis, reactivity, and theoretical calculations

The tricoordinated cationic Cu(I) complex [Cu(kappa2-P,P'-DPEphos)(kappa1-P-DPEphos)][BF4] (1) (DPEphos = bis(2-(diphenylphosphino)phenyl) ether) containing a dangling phosphorus center was synthesized from the reaction of [Cu(CH3CN)4][BF4] with DPEphos in a 1:2 molar ratio in dichloromethane. When complex 1 is treated with MnO2, elemental sulfur, or selenium, the uncoordinated phosphorus atom undergoes oxidation to form a P=E bond resulting in the formation of complexes of the type [Cu(kappa2-P,P'-DPEphos)(kappa2-P,E-DPEphos-E)][BF4] (2, E = O; 3, E = S; 4, E = Se) containing a Cu-E bond. The zigzag polymeric CuI complex [Cu(kappa2-P,P'-DPEphos)(micro-4,4'-bpy)]n[BF4]n (5) was prepared by the reaction of [Cu(CH3CN)4][BF4] with DPEphos and 4,4'-bipyridine in an equimolar ratio. The stereochemical influences of DPEphos on its coordination behavior are examined by density functional theory calculations.     

Thermo-Reversible Cellulose Micro Phase-Separation in Mixtures of Methyltributylphosphonium Acetate and γ-Valerolactone or DMSO

We have identified cellulose solvents, comprised of binary mixtures of molecular solvents and ionic liquids that rapidly dissolve cellulose to high concentration and show upper-critical solution temperature (UCST)-like thermodynamic behaviour - upon cooling and micro phase-separation to roughly spherical microparticle particle-gel mixtures. This is a result of an entropy-dominant process, controllable by changing temperature, with an overall exothermic regeneration step. However, the initial dissolution of cellulose in this system, from the majority cellulose I allomorph upon increasing temperature, is also exothermic. The mixtures essentially act as ‘thermo-switchable’ gels. Upon initial dissolution and cooling, micro-scaled spherical particles are formed, the formation onset and size of which are dependent on the presence of traces of water. Wide-angle X-ray scattering (WAXS) and ¹³C cross-polarisation magic-angle spinning (CP-MAS) NMR spectroscopy have identified that the cellulose micro phase-separates with no remaining cellulose I allomorph and eventually forms a proportion of the cellulose II allomorph after water washing and drying. The rheological properties of these solutions demonstrate the possibility of a new type of cellulose processing, whereby morphology can be influenced by changing temperature.     

Poly(glyceryl glycerol): A multi‐functional hydrophilic polymer for labeling with boronic acids

The synthesis of poly(glyceryl glycerol) (PGG), a polymer featuring a polyethylene oxide backbone and 1,2‐diol groups in every repeating unit, is presented. PGG was prepared by monomer‐activated ring‐opening polymerization of (dl ?1,2‐isopropylidene glyceryl) glycidyl ether, introducing a functional azido‐ or bromo‐head group to each chain. The 1,2‐diol groups, which were released by acidic deprotection, readily reacted with boronic acid derivatives, enabling the attachment of functional moieties under mild aqueous conditions. PGG was conjugated to poly(l ‐lactide) (PLLA) via azide‐alkyne cycloaddition and the resulting copolymer assembled into nanoparticles of 70 nm diameter in aqueous solution. Labeling of the PGG–PLLA particles was achieved by simple mixing with a boronic acid‐functional fluorophore. The labeling efficiency was determined by fluorescence spectroscopy to be 85.5% for boronic acid‐functional rhodamine B compared with 0.2% for plain rhodamine B. The strong interaction of PGG with boronic acids is ascribed to its polyol structure. This study demonstrates the usefulness and versatility of PGG as a hydrophilic polymer for possible biomedical applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1822–1830     

Structures and EPR spectra of binary sulfur-nitrogen radicals from DFT calculations

The scattered electron paramagnetic resonance (EPR) spectroscopic data for binary sulfur-nitrogen (S,N) radicals have been compiled and critically assessed.Many of these are inorganic rings or cages.For each species, possible equilibrium structures in the gas phase and the EPR hyperfine coupling (hfc) constants have been calculated with DFT using the B3LYP functional and basis sets of triple-ζ (or better) quality.Good agreement is obtained between calculated and measured values for the well characterized [S₃N₂]⁺, a planar π-radical for which the s-component of the orbitals is likely to be reasonably independent of minor geometrical changes between gas-phase and condensed-phase states.The cage compounds [S₄N₄]⁻ and [S₄N₅]⁻², for which reliable experimental EPR spectra have been reported, show larger variation between calculated and measured hfc, as a consequence of the dependence of the s orbital content of the molecular orbitals on small structural changes.The very large disagreements between the DFT calculated and experimentally claimed hfc constants for [NS], [SNS] and [S₄N₄]⁻³ in condensed phases lead us to question their assignment.Among binary S,N radicals, ³³S hfc data has only been reported for [S₃N₂]⁺ (through isotopic enrichment).These values were essential for the correct identification of the EPR spectra of this important radical, which previously was misassigned to other species.Our results suggest that ³³S data will be equally important for the correct identification of the EPR spectra of other binary S,N species, many of which are cyclic systems, e.g.[S₃N₃], [S₄N₃] and[S₄N₅].     

Well-posedness for the continuity equation for vector fields with suitable modulus of continuity

We prove well-posedness of linear scalar conservation laws using only assumptions on the growth and the modulus of continuity of the velocity field, but not on its divergence. As an application, we obtain uniqueness of solutions in the atomic Hardy space, $H^1$, for the scalar conservation law induced by a class of vector fields whose divergence is an unbounded BMO function.     

Continuous chromatographic protein refolding

Column-based protein refolding requires a continuous processing capability if reasonable quantities of protein are to be produced. A popular column-based method, size-exclusion chromatography (SEC) refolding, employs size-exclusion matrices to separate unfolded protein from denaturant, thus refolding the protein. In this work, we conduct a comparison of SEC refolding with refolding by batch dilution, using lysozyme as a model protein. Lysozyme refolding yield was found to be extremely sensitive to the chemical composition of the refolding buffer and particularly the concentration of dithiothreitol (DTT) introduced from the denatured protein mixture. SEC refolding was not adversely affected by DTT carry-over as small contaminants in the denatured solution are separated from protein during the refolding operation. We also find that, contrary to previous reports, size-exclusion refolding on batch columns leads to refolding yields slightly better than batch dilution refolding yields at low protein concentrations but this advantage disappears at higher protein concentrations. As batch-mode chromatography would be the limiting step in a column based refolding downstream process, the batch column refolding method was translated to a continuously operating chromatography system (preparative continuous annular chromatography, P-CAC). It was shown that the P-CAC elution profile is similar to that of a stationary column, making scale-up and translation to P-CAC relatively simple. Moreover, it was shown that high refolding yields (72%) at high protein concentration (>1 mg ml(-1)) could be obtained.