Effect of Physical Properties and Emulsification Conditions on the Microsphere Size Prepared Using a Solvent Extraction Process

Microspheres were prepared using a hydrocarbon-perfluorocarbon solvent extraction process. The effect of the physical properties and the emulsification conditions on the mean microsphere size was investigated. The viscosity of the dispersed and the continuous phase greatly affected the microsphere size. Smaller microspheres were produced at the same mixing intensity when the viscosity of the dispersed phase decreased. Increased continuous phase viscosity reduced the coalescenceof the droplets and hence smaller microspheres were produced. The mean microsphere size first decreased as the volume ratio of the dispersed phase to the continuous phase increased but upon further increase the mean microsphere size increased. The effect of the volume ratio on the microsphere size was linked to the surfactant concentration. The stability of the studied hydrocarbon-in-fluorocarbon emulsion is poor. One reason for the poor stability is the high density difference between the phases. The emulsion droplets were solidified by siphoning part of the emulsion in the fresh continuous phase, which extracted the solvent from the dispersed phase. The effect of emulsion transfer time between the emulsification and solidification steps on the particle size was studied but no significant effect was observedduring the controlled time interval.     

Evaluation and Optimization of the Oxidation efficiency of a UV-Persulphate-Oxidation Toc-Analyzer for the Determination of Oil Contamination from Forestry in Ground Water

Different chain oils (tall, rape seed and mineral oils) have been used as model compounds to evaluate and optimize the applicability of UV-persulphate TOC-analyzer for quantitative determination of forestry oils and to follow the progress of their biodegradability. It was shown, that K 2 S 2 O 8 -UV-oxidation method is not sufficient to oxidize chain oils completely. There were differences in oxidation efficiency between different oils, changing from about 46% measured for tall oil to about 25% observed for rape seed chain oil. The addition of Triton X-100 surfactant up to 2% (w/w) was observed to increase the oxidation efficiency, e.g. to 75% for tall oil. The observations can be explained by assuming that in the presence of surfactant the emulsions are more homogeneous and stable. Optimization using two-level full factorial design (temperature of the oxidation chamber and the amount of persulphate) was studied. The results show that the UV-persulphate-oxidation TOC-analyzer is not suitable method to monitor biodegradability of chain oils.     

High strength modified nanofibrillated cellulose-polyvinyl alcohol films

In this study surface-modified nanofibrillated cellulose (NFC) was used at low levels (0.5 to1.5 wt%) as a reinforcement in a polyvinyl alcohol (PVA) matrix. The modified-NFC–PVA composite films prepared using the solution casting technique showed improved mechanical performance. Birch pulp cellulose was initially modified by allylation using a solvent-free, dry modification method followed by subsequent epoxidation of the allyl groups and finally grinding the pulp to yield epoxy-NFC. In order to obtain optimal mechanical performance, epoxy-NFC with different degrees of substitution was evaluated in the reinforcement of PVA. The addition of 1 wt% epoxy-NFC (degree of substitution, DS 0.07) enhanced the modulus, strength, and strain of pure PVA film by 307, 139 and 23 %, respectively, thus producing the best performing film. The results demonstrate the favourable effect of chemically functionalized NFC on the mechanical properties of polyvinyl alcohol compared to unmodified NFC as reinforcement. In order to improve industrial and economic feasibility, the manufacture of the composite was also done in situ by grinding cellulose directly in PVA to produce the new biocomposite in a one-step process.     

A set of triple-resonance nuclear magnetic resonance experiments for structural characterization of organophosphorus compounds in mixture samples

The ¹H, ¹³C correlation NMR spectroscopy utilizes J_CH couplings in molecules, and provides important structural information from small organic molecules in the form of carbon chemical shifts and carbon-proton connectivities. The full potential of the ¹H, ¹³C correlation NMR spectroscopy has not been realized in the Chemical Weapons Convention (CWC) related verification analyses due to the sample matrix, which usually contains a high amount of non-related compounds obscuring the correlations of the relevant compounds. Here, the results of the application of ¹H, ¹³C, ³¹P triple-resonance NMR spectroscopy in characterization of OP compounds related to the CWC are presented. With a set of two-dimensional triple-resonance experiments the J_HP, J_CH and J_PC couplings are utilized to map the connectivities of the atoms in OP compounds and to extract the carbon chemical shift information. With the use of the proposed pulse sequences the correlations from the OP compounds can be recorded without significant artifacts from the non-OP compound impurities in the sample. Further selectivity of the observed correlations is achieved with the application of phosphorus band-selective pulse in the pulse sequences to assist the analysis of multiple OP compounds in mixture samples. The use of the triple-resonance experiments in the analysis of a complex sample is shown with a test mixture containing typical scheduled OP compounds, including the characteristic degradation products of nerve agents sarin, soman, and VX. The viability of the approach in verification analysis is demonstrated in the analysis of the 30th OPCW Proficiency Test sample.     

Simultaneous interaction with base and phosphate moieties modulates the phosphodiester cleavage of dinucleoside 3',5'-monophosphates by dinuclear Zn2+ complexes of di(azacrown) ligands

Five dinucleating ligands (1-5) and one trinucleating ligand (6) incorporating 1,5,9-triazacyclododecan-3-yloxy groups attached to an aromatic scaffold have been synthesized. The ability of the Zn(2+) complexes of these ligands to promote the transesterification of dinucleoside 3',5'-monophosphates to a 2',3'-cyclic phosphate derived from the 3'-linked nucleoside by release of the 5'-linked nucleoside has been studied over a narrow pH range, from pH 5.8 to 7.2, at 90 degrees C. The dinuclear complexes show marked base moiety selectivity. Among the four dinucleotide 3',5'-phosphates studied, viz. adenylyl-3',5'-adenosine (ApA), adenylyl-3',5'-uridine (ApU), uridylyl-3',5'-adenosine (UpA), and uridylyl-3',5'-uridine (UpU), the dimers containing one uracil base (ApU and UpA) are cleaved up to 2 orders of magnitude more readily than those containing either two uracil bases (UpU) or two adenine bases (ApA). The trinuclear complex (6), however, cleaves UpU as readily as ApU and UpA, while the cleavage of ApA remains slow. UV spectrophotometric and (1)H NMR spectroscopic studies with one of the dinucleating ligands (3) verify binding to the bases of UpU and ApU at less than millimolar concentrations, while no interaction with the base moieties of ApA is observed. With ApU and UpA, one of the Zn(2+)-azacrown moieties in all likelihood anchors the cleaving agent to the uracil base of the substrate, while the other azacrown moiety serves as a catalyst for the phosphodiester transesterification. With UpU, two azacrown moieties are engaged in the base moiety binding. The catalytic activity is, hence, lost, but it can be restored by addition of a third azacrown group on the cleaving agent.