Preparation of hyperbranched polymers by atom transfer radical polymerization

A cheap acrylic AB* monomer, 2‐(2‐chloroacetyloxy)‐isopropyl acrylate (CAIPA), was prepared from 2‐hydroxyisopropyl acrylate with chloroacetyl chloride in the presence of triethylamine. The self‐condensing vinyl polymerization by atom transfer radical polymerization (ATRP), a “living”/controlled radical polymerization, has yielded hyperbranched polymers. All the polymerization products were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR). CAIPA exhibited distinctive polymerization behavior that is similar to a classical step‐growth polymerization in the relationship of molecular weight to polymerization time, especially during the initial stage of the polymerization. However, a significant amount of monomer remained present throughout the polymerization, which is consistent with typical chain polymerization. Also, if a much longer polymerization time was used, the polymer became gel. As a result of the unequal reactivity of group A* and B*, the polymerization is different from an ideal self‐condensing vinyl polymerization: the branch structures of polymers prepared depend dramatically on the ratio of 2,2'‐bipyridyl to CAIPA. Hyperbranched polymers exhibit improved solubility in organic solvent, however, they have lower thermal stability than their linear analogs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2114–2123, 2002     

Structural analysis of cellulose triacetate polymorphs by two-dimensional solid-state C-C and H-C correlation NMR spectroscopies

For the elucidation of the crystal structures of the two crystalline allomorphs of cellulose triacetate (CTA), namely CTA I and CTA II, two-dimensional (2D) solid-state through-bond ¹³C-¹³C and ¹H-¹³C correlations NMR techniques applied to the two crystalline allomorphs of CTA. As a result, the ¹³C and ¹H chemical shifts of the glucopyranose ring of CTA I and CTA II were completely assigned by the 2D NMR spectra of these allomorphs. On the 2D ¹³C-¹³C correlation spectrum of CTA II, two sets of the ¹³C-¹³C correlations from C1 to C6 were observed. This indicated that the CP/MAS ¹³C NMR spectrum of CTA II can be characterized by its overlapping of the ¹³C subspectra of two kinds of 2,3,6-triacetyl-anhydroglucopyranose units and that there are two magnetically non-equivalent sites in the unit cell of CTA II. In the case of CTA I, the numbers of respective ¹³C and ¹H shifts of CTA I agreed with the those of the glucopyranose residue in the allomorph, strongly suggesting that the asymmetric unit of CTA I is only one glucose residue. In addition, conformational differences in the exocyclic C5-C6 bonds between CTA I and CTA II were strongly suggested by the notable differences in the ¹H and ¹³C chemical shifts at the C6 sites of these allomorphs.     

The composition of hydrogenated fats by high-resolution13C nuclear magnetic resonance spectroscopy

The high-resolution¹³C nuclear magnetic resonance spectra of twelve hydrogenated fats have been examined. Each spectrum contains 50–100 signals and reveals much about the nature of the acyl chains of both double-bond position and configuration. The signals for the ω1, ω2 and ω3 carbon atoms give information on thecis andtrans isomers of the Δ15, Δ14, Δ13 and Δ12 18:1 esters, respectively. Allylic signals distinguish betweencis andtrans esters, and the proportion of totalcis to totaltrans isomers can be obtained from these. Olefinic signals are the most informative, and most of these have been assigned. This leads to a semi-quantitative estimate of the various 18:1 isomers present. Assignments are based mainly on information already in the literature, but some were confirmed after urea fractionation of the acids from a hydrogenated oil in whichcis andtrans monoene acids were separately concentrated.     

Zwitterion effect in polyelectrolyte gels based on lithium methacrylate-N,N-dimethyl acrylamide copolymer

Zwitterionic compounds such as those based on 1-butylimidazolium-3-(n-butanesulfonate) have previously been shown to have positive effects on the transport properties of polyelectrolytes. The addition of the zwitterion has been found to, in some cases, increase the dissociation of the lithium ion and enhance the conductivity by almost an order of magnitude. In this work, we report the effects of adding the above-mentioned zwitterion into the polyelectrolyte gel system poly(lithium methacrylate-co-N,N-dimethyl acrylamide); the anionic group being a stronger base leads to different behaviour for this copolymer compared to previous work. Polyelectrolyte gels based on dimethyl sulfoxide and polyether solvents were investigated to determine the breadth of applicability of the zwitterion in improving lithium ion transport. Impedance spectroscopy and pulse field gradient-NMR diffusion indicate an increase in the number of available charge carriers with zwitterion addition in some gel systems, however, the effect is not universal.     

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate: Synthesis, Characterization, and Monomer Reactivity at High Conversions

Homogeneous copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) which form clear aqueous solutions were prepared by free radical polymerization in a solution of isopropanol alcohol, using 2,2-azobisisobutyronitrile as an initiator. They were characterized by FTIR, ¹H-NMR, and element analysis studies. The reactivity ratios of the monomer were computed by the Extended Kelen–Tüdós method at high conversions, using data from both ¹H-NMR and elemental analysis studies. The reactivity ratios of VP and VA in a homogenous copolymer were observed to be very different from that of a heterogeneous copolymer. Additional information was obtained by finding out the sequence length distribution for copolymers.     

17O MAS NMR study of 12-molybdophosphoric acid

¹⁷O MAS NMR spectra for¹⁷O enriched solid heteropoly acid H₃PMo₁₂O₄₀ are reported. The oxygen exchange between solid H₃PMo₁₂ ¹⁷O₄₀ and H₂ ¹⁶O vapor at 200–250°C is shown to be accompanied by fast mixing of terminal Mo=O and bridging Mo-O-Mo oxygens in the Keggin unit. The oxygen exchange in H₃PMo₁₂ ¹⁷O₄₀ is much faster than in H₃PW₁₂ ¹⁷O₄₀ in solution as well as in the gas phase.     

Structure of resorcinol,phenol, and furan resins by MALDI‐TOF mass spectrometry and 13C NMR

The structure of traditional, linear phenol–resorcinol–formaldehyde (PRF) resins, urea‐branched PRF resins, and phenol–resorcinol–furfural (PRFuran) resins has been investigated in depth by both matrix‐assisted laser desorption/ionization time of flight (MALDI‐TOF) mass spectroscopy and ¹³C NMR. The structure of a variety of oligomers has been obtained, and the structures present in each of the three types of resins related to the very different percentages of resorcinol needed for their equal performance as adhesives. The oligomers type and species distribution appeared very different for each case. PRF resins performance is improved by maximizing either the proportion of resorcinol‐containing oligomers or methylol‐groups containing oligomers, even without any resorcinol, or both. It is equally obtained by the minimization of the relative proportion of the low reactivity Phenol (CH₂ Phenol) species in which resorcinol is not present, this being the most important parameter. This can be obtained by more effective use of the resorcinol by just modifying the resin manufacturing procedure. This parameter instead does not appear to be determinant in PRFuran resins. In these, it is the higher molecular weight of furfural in relation to formaldehyde that engenders for the same manufacturing procedure a correspondingly lower proportion of resorcinol in the resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2665–2674, 2004     

Study of Ozonated Sunflower Oil Using 1H NMR and Microbiological Analysis

Prior studies have proven that ozonated vegetable oils present a high germicidal power. Ozonation of sunflower oil at different applied ozone dosage was carried out and peroxide and aldehydes indices along with antimicrobial activity were determined. The reaction products were identified using Proton Nuclear Magnetic Resonance Spectroscopy (¹H NMR). The principal signals intensity values were used for following the reaction course between ozone and sunflower oil. The reaction was following up to peroxide index values of 1202 mmol-equi/kg. The intensities of olefinic proton signals decreased with the gradual increase in ozone concentration but without disappearing completely. The Criegee ozonides obtained at 107.1 mg/g of ozone doses were approximately 3.9-fold higher than that at beginning of the reaction. The aldehyde protons were observed as a weak intensity signal in all the spectra. The signals belonging to olefinic protons from hydroperoxides appeared weak and increased with the increase in ozone doses. Signals from other oxygenated groups were assigned. The highest action spectrum of antimicrobial activity was obtained with the higher peroxide index. It was concluded that at higher applied ozone doses, the higher the antimicrobial activity potential of ozonized sunflower oil     

Over-production of 5-enolpyruvylshikimate-3-phosphate synthase in Escherichia coli: use of the T7 promoter

5-Enolpyruvylshikimate-3-phosphate (EPSP) synthase, the productof the Escherichia coli aroA gene, has been overproduced inE.coli BL21(DE3) under the control of the T7 gene 10 promoterand ribosome binding site, to a level of {small tilde}50% oftotal cell protein. EPSP synthase is the primary target of thepost-emergence herbicide, glyphosate, commonly known as Roundup^TM.A simple two step purification is described, which results in99% pure homogeneous protein (as determined by PAGE). The integrityof the protein has been compared with previously characterizedprotein from .E.coli AB2829(pKD501) by determination of itskinetic parameters, N-terminal protein and DNA sequences, aminoacid analysis and ¹³C-NMR spectroscopy. This new overproducingstrain readily provides the gram quantities of highly pure proteinrequired for NMR studies of the active site and the developmentof novel time-resolved solid-state NMR techniques currentlyunderway in this laboratory.     

Influence of catalyst type on the curing process and network structure of alkyd coatings

Recent studies have shown that cobalt catalysts, used for curing of alkyd coatings, are potentially carcinogenic, and hence replacement by new environmental friendly catalysts is needed. The influence of different metal based catalysts on the oxidation process has been studied extensively in model systems, consisting of unsaturated oils. However, these results may not be representative for real coatings, since in these systems the oxygen diffusion is much lower than in model systems and therefore may have a large effect on the curing. In this paper, we will show how the curing of an alkyd coating depends on the type of catalyst (cobalt or manganese based). The curing process is studied using a high spatial resolution nuclear magnetic resonance (NMR) setup. The final network structure and cross-link density are found to be correlated with the catalyst used, i.e. a cobalt based catalyst and two manganese based catalysts. The difference in final network structure is investigated by NMR T₂ relaxation analysis and the glass transition temperature T_g measured using a differential scanning calorimeter (DSC). In case of the cobalt based catalyst a cross-linking front was observed and a high cross-link density was found, compared to the manganese based catalysts, in which case no sharp cross-linking front was observed. To interpret the observed NMR profiles in more detail, simulations based on a reaction-diffusion model were performed. From the results of these simulations estimates were obtained for the reaction constants and the diffusion of oxygen for the different catalysts.