Polyester-based Copolymers for Biomaterials Fabrication

Summary: Results on synthesis of poly(3-hydroxybutyrate)s possessing one or two hydroxyl groups at one terminus of the chain and carboxylic group at the other chain end are reported. These polymers were further functionalised via transesterification with dimethyl H-phosphonate thus incorporating a reactive/biodegradable center in the polyester backbone. Block/star-like copolymers composed of hydrophilic PEG and hydrophobic poly(3-hydroxybutyrate) segments linked by phosphoester moiety were also obtained. Chemical structure and composition of the reaction products were analysed applying different spectroscopic techniques (¹H, and ³¹P NMR, IR and ESI-MS) and size exclusion chromatography was applied to describe molecular weight averages and distribution.     

Synthesis of poly(oxyethylene phosphoramidate)s and glycopolymers via Staudinger reaction: Multivalent binding studies with Concanavalin A

A new method for the preparation of poly(oxyethylene phosphoramidate)s and glycopolymers is developed via modification of poly(oxyethylene H‐phosphonate) which is a biodegradable, biocompatible and low toxic polymer. The phosphonate groups of the precursor are converted into tri‐coordinated phosphorus species yielding poly(oxyethylene trimethylsilyl phosphite). The latter is then reacted with different azides, including sugar azides, via Staudinger reaction to furnish the desired poly(oxyethylene phosphoramidate)s and such containing sugar moieties in the side chains attached to the P‐centers. 2002P NMR spectroscopy is applied as a powerful tool for determination of the conversion and structure of the reaction products. Studies on Concanavalin A binding to the obtained glycopolymers are performed using dynamic light scattering and analytical ultracentrifugation techniques. The viability of Human Embryonic Kidney 293 cell line is slightly affected when exposed to polyphosphoramidate glucoconjugate over a broad range of concentrations. The results obtained are encouraging for further investigations on the clustering and bio‐recognition properties of the synthesized glycopolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1730–1741     

Selective Production of Phenol on Bifunctional,Hierarchical ZSM-5 Zeolites

Mono- and bimetallic Ni-, Ru- and Pt-modified hierarchical ZSM-5 materials were prepared by impregnation technique and characterized by X-ray diffraction (XRD), N₂ physisorption, temperature-programmed reduction (TPR–TGA), ATR–FTIR and solid state NMR spectroscopy. Formation of finely dispersed nickel, ruthenium and platinum species was observed on the bimetallic catalysts. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides and their dispersion and reducibility. The samples’ acidity was studied via FTIR spectroscopy of adsorbed pyridine. The changes in the zeolite structure were studied via solid-state NMR spectroscopy. The catalysts were investigated in a gas-phase hydrodeoxygenation, transalkylation and dealkylation reaction of model lignin derivative molecules for phenol production.     

Electrostatic complexation of a double hydrophilic block polyelectrolyte and proteins of different molecular shape

The electrostatic complexation between the polyelectrolyte block of the novel double hydrophilic copolymer quaternized poly(3,5‐bis(dimethylaminomethylene) hydroxystyrene)‐b‐poly(ethylene oxide) (QNPHOS‐PEO) and proteins of different molecular shape, that is globular bovine serum albumin (BSA) or rod‐like bovine fibrinogen (FBG), is investigated by means of dynamic, static, and electrophoretic light scattering, as well as analytical ultracentrifugation measurements. The solution behavior, structure, and properties of the formed complexes at pH 7 and 0.01 M ionic strength, as a function of the protein concentration in the solution (or equivalently the charge ratio of the two components), depend on the protein concentration and molecular characteristics. Moreover, the structure of the complexes is greatly influenced by the intrinsic structure of the block polyelectrolyte, which forms rather loose multichain aggregates, due to hydrophobic interactions. A direct correlation between the stability of the preformed complexes against the increase of the solution ionic strength and their structure is established. Finally, the spectroscopic structural investigation of both complexed proteins reveals no signs of protein denaturation upon complexation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1515–1529     

Fundamental Fermions Fit Inside One <Emphasis Type="Italic">su</Emphasis>(1|5) Irreducible Representation

The Lie superalgebra su(1|5) has irreducible representations of dimension 32, in which the 32 fundamental fermions of one generation (leptons and quarks, of left and right chirality, and their antiparticles) can be accommodated. The branching of these su(1|5) representations with respect to its subalgebra su(3)× su(2)× u(1) reproduces precisely the classification of these fundamental fermions according to the gauge group su(3)^c× su(2)^w× u(1)^w of the Standard Model. Furthermore, a simple construction of the relevant representations is given, and some consequences are discussed.     

Self-similar scaling of density in complex real-world networks

Despite their diverse origin, networks of large real-world systems reveal a number of common properties including small-world phenomena, scale-free degree distributions and modularity. Recently, network self-similarity as a natural outcome of the evolution of real-world systems has also attracted much attention within the physics literature. Here we investigate the scaling of density in complex networks under two classical box-covering renormalizations–network coarse-graining–and also different community-based renormalizations. The analysis on over 50 real-world networks reveals a power-law scaling of network density and size under adequate renormalization technique, yet irrespective of network type and origin. The results thus advance a recent discovery of a universal scaling of density among different real-world networks [P.J. Laurienti, K.E. Joyce, Q.K. Telesford, J.H. Burdette, S. Hayasaka, Universal fractal scaling of self-organized networks, Physica A 390 (20) (2011) 3608–3613] and imply an existence of a scale-free density also within–among different self-similar scales of–complex real-world networks. The latter further improves the comprehension of self-similar structure in large real-world networks with several possible applications.     

NMR,IR and DFT studies of phenylplatinum complexes with O-monodentate coordinated silsesquioxanate and auxiliary phosphine ligands

The molecular structure and spectroscopic properties of a series of phenylplatinum complexes containing silsesquioxanate and phosphine ligands with general formula trans-[Pt{O₁₀Si₇(R)₇(OH)₂}(Ph)(L)₂] (1: R = cyclo-C₅H₉, L = PEt₃; 2: R = iso-C₄H₉, L = PEt₃; 3: R = CH₃, L = PEt₃; 4: R = cyclo-C₅H₉, L = PMe₃; 5: R = cyclo-C₅H₉, L = PMe₂Ph; 6: R = cyclo-C₅H₉, L = PPh₂Me; 7: R = cyclo-C₅H₉, L = PPh₃) have been investigated by DFT/OPW91/6-31G(d) calculations, ¹H, ¹³C, ²⁹Si and ³¹P NMR and IR spectroscopy. DFT molecular modeling based on available X-ray and NMR data for complexes 1 and 2 allowed deriving structure-NMR spectra correlations. It was found that the alkyl substituents (R) attached to Si atoms, cyclo-C₅H₉, iso-C₄H₉ and CH₃, slightly influence the geometry and multinuclear NMR parameters of the complexes in the series studied. The molecular structures of the Pt(II) complexes with R = cyclo-C₅H₉ (4–7) were predicted by DFT calculations of their simplified models with R = CH₃ (4′?7′). The geometry optimizations of 4′?7′ showed square-planar configuration of Pt(II) center bonded to two trans phosphine ligands, a phenyl group and an O-monocoordinated silsesquioxanate. The structures 4′?6′ are stabilized by two intramolecular hydrogen bonds similar to 1 and 2. A fast conformer exchange process A?B and switching of H-bonds in solution of 1–6 were suggested based on (i) the calculated conformer energies and small barrier of the process, and (ii) the observed single ¹H NMR signal at low magnetic field. The stability of the Pt(II) complexes depends on the nature of the phosphine ligands and decreases in the order PMe₂Ph > PMe₃ > PPh₂Me > PEt₃ > PPh₃. The PPh₃ ligands attached to Pt(II) in 7 cause the largest geometry changes and a new set of weaker hydrogen bonds. The comparison of the calculated NMR and IR parameters with the experimental spectroscopic data reveals good coincidence and thus confirmed the suggested molecular structures.     

Quantitative determination of jatrophone in "cachaça" prepared with Jatropha elliptica

A method for sample preparation and analysis by high performance liquid chromatography with UV detection (HPLC-UV) was developed for analysis of jatrophone in "cacha?a" prepared with Jatropha elliptica, administered orally, employed in Brazil for the treatment of venomous snake bites. The linearity, accuracy, precision of the procedure was evaluated. Analytical curve for jatrophone was linear in the range of 16.24-81.20 microg ml(-1). The recovery of the jatrophone in the samples analyzed was 98.99-99.89%. The percent coefficient of variation for the quantitative analysis of the "cacha?a" in the analyses was under 2%.     

A method for quantitative determination of furanocoumarins in capsules and tablets of phytochemical preparations

A method for sample preparation and analysis by high-performance liquid chromatography with UV detection (HPLC-UV) was developed for analysis of psoralen, bergapten and 5-[3-(4,5-dihydro-5,5-dimethyl-4-oxo-2-furanyl)-butoxy]-7H-furo[3-2-g][1]benzopyran-7-one in capsules and tablets employed in Brazil for certain illnesses. The linearity, accuracy, the inter- and intra-day precision of the procedure were evaluated. Analytical curves for furanocoumarins were linear in the range of 1.0-50.0 microg/ml. The recoveries of the furanocoumarins in the products analyzed were 97.3-99.5%, and the percent coefficient of variation for the quantitative analysis of the furanocoumarins in the analyses was under 5%. For inter-equipment study gas chromatography (GC) was employed.