Environmental effects in free-radical polymerizations. Part III. Vinyl chloride and n-butyraldehyde

The properties of poly(vinyl chloride) samples prepared by a free-radical process in the presence of n-butyraldehyde have been studied from the point of view of polymer tacticity, branching, molecular weight, and relative crystallinity. The postulate of a polymer radical–aldehyde complex, invoked to explain the increased crystallinity, was tested. The polymers had a lower degree of polymerization and branching than normal, and these parameters rather than increased syndiotacticity were responsible for the high degree of crystallinity. Both molecular weight and branching affect the crystallinity, since polymer samples prepared in the presence of various transfer agents with similar molecular weights were less crystalline than those prepared in aldehyde, but yet more crystalline than high molecular weight bulk polymer. Polymers prepared in aldehyde had a lower degree of branching than those formed in other transfer agents. It was concluded that aldehyde was effective in increasing the crystallinity of poly(vinyl chloride) in these two ways, and so appeared to be unique among the transfer agents. There was no evidence for assuming any complexing between polymer radicals and aldehyde.     

A multiple approach to the determination of radon fluxes from sediments

Determination of sedimentary fluxes of²²²Rn via diffusion was required as an input for a mass balance model of radon in a freshwater lake. We obtained these fluxes by: (1) direct measurement in the laboratory using a simulated sediment bed and water column; (2) a “sediment equilibration” technique; and (3) porewater modeling. The first method, analogous to an in situ benthic chamber approach, uses direct observation of the increasing²²²Rn activity in water overlying a sediment bed packed in plastic columns. This allows one to directly measure the fluxes and determine the effective wet bulk sediment diffusion coefficient (D _s). Radon flux estimates using these three techniques agreed to within approximately 10–15%.     

Arresting cancer proliferation by small-molecule gene regulation

A small library of pyrrole-imidazole polyamide-DNA alkylator (chlorambucil) conjugates was screened for effects on morphology and growth characteristics of a human colon carcinoma cell line, and a compound was identified that causes cells to arrest in the G2/M stage of the cell cycle. Microarray analysis indicates that the histone H4c gene is significantly downregulated by this polyamide. RT-PCR and Western blotting experiments confirm this result, and siRNA to H4c mRNA yields the same cellular response. Strikingly, reduction of H4 protein by >50% does not lead to widespread changes in global gene expression. Sequence-specific alkylation within the coding region of the H4c gene in cell culture was confirmed by LM-PCR. The compound is active in a wide range of cancer cell lines, and treated cells do not form tumors in nude mice. The compound is also active in vivo, blocking tumor growth in mice, without obvious animal toxicity.     

Lipid phosphate phosphatases dimerise,but this interaction is not required for <Emphasis Type="Italic">in vivo</Emphasis> activity

Background  

Lipid phosphate phosphatases (LPPs) are integral membrane proteins believed to dephosphorylate bioactive lipid messengers, so modifying or attenuating their activities. Wunen, a Drosophila LPP homologue, has been shown to play a pivotal role in primordial germ cell (PGC) migration and survival during embryogenesis. It has been hypothesised that LPPs may form oligomeric complexes, and may even function as hexamers. We were interested in exploring this possibility, to confirm whether LPPs can oligomerise, and if they do, whether oligomerisation is required for either in vitroor in vivoactivity.     

A survey of non-conformances raised during accreditation inspections of medical laboratories in South Africa.

Under the auspices of the South African National Accreditation System (SANAS) the South African medical laboratory accreditation programme was established in June 1999. This study reports the non-conformances identified during the assessment of 103 medical laboratories in South Africa between September 1999 and December 2001. Laboratories were assessed by SANAS, which is the single accreditation body in the Republic of South Africa. All documentation relating to the assessment of each laboratory was reviewed in detail by the authors to identify the numbers and classification of non-conformances under each of the 25 points of the check list. A total of 862 non-conformances were raised. The top five non-conformances identified were (1) quality management system, (2) test methods, (3) records and (4) quality control and laboratory safety. The deficiencies identified in South African medical laboratories should be viewed in a positive light and promote a culture of continuous quality improvement with appropriate allocation of resources. SANAS should continue to align its requirements and procedures relating to accreditation of medical laboratories with those of their international counterparts with whom mutual recognition agreements/arrangements exist.     

Direct counting of soil wafers: An improved total alpha/beta screening analysis

Although potentially very useful as a screening tool, currently-applied “gross” alpha/beta analyses are often considered unreliable by the environmental monitoring community. We describe here an alternative approach based on direct counting of pressed soil “wafers” to estimate total alpha/beta activities. The system was calibrated using a series of natural soils and sediment standards with total α/β activities estimated by use of a combination of available certified values, equilibrium assumptions, and our own measurements. A set of 10 such standards that span a wide range of activities were prepared by thoroughly mixing several grams of selected NIST and IAEA natural matrix standards together with reagent grade cellulose in a 4∶1 sample-to-binder ratio and pressing in a 40-mm stainles steel die. The resulting wafers, assumed to be at infinite thickness for expected radionuclides, were counted in a gas flow proportional counter set for simultaneous α/β counting. Both the alpha and beta count rates increased in a linear, systematic manner with increasing total estimated activities. This technique should prove to be an inexpensive, simple, and waste-free approach for screening total radioactivity in soil samples.     

Characterization of the emulsification properties of 2S albumins from sunflower seed

The ability of 2S albumins from sunflower seeds to stabilize oil-in-water emulsions has been investigated, demonstrating that one of the proteins (SFA8) effectively stabilizes emulsions, while another (SF-LTP) does not stabilize emulsions. The surface tension and surface dilation viscosity of these two proteins were measured, rationalizing the emulsifying ability of SFA8 in terms of its ability to form a strongly elastic monolayer at interfaces. The secondary structure changes that occur upon adsorption of SFA8 to the oil/water interface have also been studied by fluorescence, circular dichroism (CD), and Fourier-transform infrared (FT-IR) spectroscopy. It was found that the beta-sheet content of the protein increased upon adsorption at the expense of alpha-helix and random structure. Moreover, FT-IR measurements indicate the presence of intermolecular beta-sheet formation upon adsorption. Fluorescence studies with an oil-soluble fluorescence quencher indicate that the single tryptophan residue present in SFA8 may become located in the oil-phase of the emulsion. This residue is thought to be partially buried in the native protein, and these data suggest that changes in the polypeptide region flanking this residue may play an important role in the molecular rearrangement that occur on or following adsorption to the oil/water interface.     

UV damage and photoreactivation: timing and age are everything

Aquatic organisms, ranging from bacteria to fish, living in clear lakes are presently receiving damaging levels of UV radiation. Photoreactivation is a light-dependent mechanism by which some organisms deal with DNA damage caused by UV radiation. Yet, photoreactivation is a mechanism that confounds long-term predictive modeling of UV effects on the survival of these organisms. Here we show that a short-lived rotifer species, Asplanchna girodi, previously thought to have little to no photoreactivation, does indeed have a significant amount of it. The ability to undergo photoreactivation in A. girodi is dependent on age and becomes apparent only after several days of observation after UV exposure.     

Geochemical partitioning of actinides using sequential chemical extractions: Comparison to stable elements

We have developed a sequential extraction technique for determining the geochemical partitioning of Am, Pu, and U in soils and sediments. Stable element analyses were combined with radiometric measurements to determine the most probable geochemical host phases of these actinides in reference sediment IAEA-135.²⁴¹ Am results indicate an association with carbonate minerals and organic matter. The extraction profile of²³⁸U was similar to that of refractory elements Al, Ti, and K.^239/240Pu data suggest a fractionation of Pu into Fe-bearing phases of varying solubility. The reproducibility of the method was quite good (replicates agreed to within 10% at a 95% confidence level).     

Study of crosslink formation by partial conversion properties. IV. Copolymerization of styrene with poly(ethylene fumarate)

The mechanism of the crosslinking reaction in the copolymerization of poly(ethylene fumarate) and styrene has been studied by using partial conversion number-average molecular weights and viscosities. In dilute solution the reaction is mainly the formation of intramolecular crosslinks, illustrated by a reduced dependence of \documentclass{article}\pagestyle{empty}\begin{document}$\overline{\overline M}_n$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$[\overline{\overline \eta}]$\end{document} on conversion. Increasing the monomer concentrations increases the contribution from intermolecular reactions and gives a much greater dependence of \documentclass{article}\pagestyle{empty}\begin{document}$\overline{\overline M}_n$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$[\overline{\overline \eta}]$\end{document} on conversion.