Light-induced electron spin polarization in the ground state of water-soluble copper porphyrins

Light-induced spin-polarized transient EPR spectra are reported for several water-soluble copper porphyrins. The spectra are assigned to the doublet ground state, with emissive spin polarization resulting from photoexcitation and subsequent electronic relaxation. In contrast to other systems for which polarization of a doublet ground state has been observed, the exchange interactions in the copper porphyrins are strong and the geometry is fixed. It is proposed that intersystem crossing from the photoexcited trip-doublet to the trip-quartet state can lead to net polarization of the spin system and that this polarization is maintained during electronic decay, possibly via charge-transfer and exciplex states. The intensity of the observed spin polarization is essentially independent of the molecular orientation in the external field, but is strongly dependent on the nature of the charged peripheral groups. Possible reasons for this behavior are discussed.     

Viral dynamics of primary viremia and antiretroviral therapy in simian immunodeficiency virus infection

Mathematical modeling of viral replication dynamics, based on sequential measurements of levels of virion-associated RNA in plasma during antiretroviral treatment, has led to fundamental new insights into human immunodeficiency virus type 1 pathogenesis. We took advantage of the simian immunodeficiency virus (SIV)-infected macaque model to perform detailed measurements and mathematical modeling during primary infection and during treatment of established infection with the antiretroviral drug (R)-9-(2-phosphonylmethoxypropyl)adenine (PMPA). The calculated clearance half-life for productively infected cells during resolution of the peak viremia of primary infection was on the order of 1 day, with slightly shorter clearance half-lives calculated during PMPA treatment. Viral reproduction rates upon discontinuation of PMPA treatment after 2 weeks were approximately twofold greater than those obtained just prior to initiation of treatment in the same animals, likely reflecting accumulation of susceptible target cells during treatment. The basic reproductive ratio (R0) for the spread of SIV infection in vivo, which represents the number of productively infected cells derived from each productively infected cell at the beginning of infection, was also estimated. This parameter quantifies the extent to which antiviral therapy or vaccination must limit the initial spread of virus to prevent establishment of chronic disseminated infection. The results thus provide an important guide for efforts to develop vaccines against SIV and, by extension, human immunodeficiency virus.     

Scheduling DAG's for asynchronous multiprocessor execution

A new approach is given for scheduling a sequential instruction stream for execution “in parallel” on asynchronous multiprocessors. The key idea in our approach is to exploit the fine grained parallelism present in the instruction stream. In this context, schedules are constructed by a careful balancing of execution and communication costs at the level of individual instructions, and their data dependencies. Three methods are used to evaluate our approach. First, several existing methods are extended to the fine grained situation. Our approach is then compared to these methods using both static schedule length analyses, and simulated executions of the scheduled code. In each instance, our method is found to provide significantly shorter schedules. Second, by varying parameters such as the speed of the instruction set, and the speed/parallelism in the interconnection structure, simulation techniques are used to examine the effects of various architectural considerations on the executions of the schedules. These results show that our approach provides significant speedups in a wide-range of situations. Third, schedules produced by our approach are executed on a two-processor Data General shared memory multiprocessor system. These experiments show that there is a strong correlation between our simulation results, and these actual executions, and thereby serve to validate the simulation studies. Together, our results establish that fine grained parallelism can be exploited in a substantial manner when scheduling a sequential instruction stream for execution “in parallel” on asynchronous multiprocessors     

Effects of citrate on the different phases of calcium oxalate crystallization

Urinary citrate appears to be an important factor in the crystallization process of calcium oxalate and calcium phosphate. The urinary excretion of citrate was found to be significantly lower in patients with calcium oxalate stone disease as compared with normal subjects, and about 30 per cent of the calcium stone formers can be considered as hypocitraturic. The lowest excretion of citrate was recorded in urine collected during the night. Citrate has significant effects on supersaturation with respect to both calcium oxalate and calcium phosphate, it also inhibits the growth of these crystals. In addition, citrate appears to be capable of inhibiting the aggregation of crystals composed of calcium oxalate, brushite, and hydroxyapatite. The heterogenous growth of calcium oxalate on calcium phosphate is also counteracted by citrate. As a consequence of the crucial role of citrate in these processes, stone prevention with alkaline citrate has become an attractive form of treatment in patients with recurrent stone formation. Single evening dose administration of sodium potassium citrate resulted in an of sodium potassium citrate resulted in an increased excretion of citrate, reduced levels of the calcium/citrate ratio as well as supersaturation with respect to calcium oxalate and a decreased rate of stone formation. However, conflicting results of stone preventive treatment with alkaline citrate have been reported by different groups, and long-term follow-up of patients treated in a randomized way is necessary to definitely assess the efficacy of alkaline citrate.     

International legislation on trace elements as contaminants in food: a review

Environmental contaminants such as trace elements may be present in all foods. Foods, raw materials and ingredients for food production are to an increasing extent traded across borders. Hence, there is a need for international legislation on trace elements as contaminants in food. In 1961, the FAO and WHO established the Codex Alimentarius to elaborate international food legislation. Contaminants in food are handled by the Codex Committee for Food Additives and Contaminants (CCFAC). The Codex Alimentarius system for developing legislation concerning trace elements as contaminants in food is based upon the Codex General Standard for Contaminants and Toxins in Food (GSCTF). By October 2001, the principles for setting maximum limits (MLs) for contaminants in food are agreed, and work is in progress on MLs for trace elements such as lead and cadmium in the various food categories. The status for the proposals is presented and discussed. The EU Regulation 466/2001 of 8 March 2001 sets MLs for lead and cadmium in various foods. This regulation will apply from 5 April 2002. The EU regulation is more detailed but similar to the Codex draft standards for lead and cadmium in food. In future, legislators and administrators in the Codex and EU and analytical chemists will discuss how to use more and better analytical data as risk-management tools to protect public health. Trace elements' speciation is an important aspect of this discussion.     

The effects of pressure on the isothermal fluid behavior of bituminous coals

An investigation into the effects of pressure (helium gas) on the isothermal fluid behavior includes: (1) the effect of pressure on the rate of melting and coking as evidenced by the rate constants k(melt) and k(coke); (2) the effect of pressure on the energies of activation of melting and coking; (3) the effects of pressure on the characteristic times; (4) the effects of pressure on the maximum isothermal fluidity. Results from the effects of pressure on k(melt) revealed that it was generally the high total sulfur, low nitrogen, low reactives/mineral matter ratio, medium rank coals which show the greatest increase in k(melt), whereas the highest rank coals show the least decrease in k(coke). The energies of activation of melting and coking were not significantly affected by pressure. The investigation also reveals increases or decreases in the respective times of softening, maximum fluidity, resolidification and total time of fluid behavior under isothermal pressurized conditions. There appears the possibility that these shifts may be rank dependent. Additionally, the lower rank coals show the largest relative increase in their fluidities when subjected to pressure. Empirical relationships were derived in order to quantitatively predict the maximum isothermal fluidity for most (fluid) coals at a given pressure.     

Intramolecular crosslinking of poly(vinyl alcohol)

Poly(vinyl alcohol) is crosslinked in dilute solution (c=0.1 wt%) with glutaraldehyde. The reaction product is characterized by viscometry and gel permeation chromatography (g.p.c.). The intrinsic viscosity decreases with increasing degree of crosslinking and does not depend on temperature. G.p.c. reveals that the reaction product is not homogeneous, but consists of a mixture of particles with different sizes, possibly both intra- and intermolecularly crosslinked molecules. The intramolecularly crosslinked molecules are smaller in size than the initial polymer molecules and their size depends on the degree of crosslinking. They possess a narrow particle size distribution even if the initial polymer sample had a broad molecular weight distribution.     

Miniature in vivo robots for remote and harsh environments

Long-term human space exploration will require contingencies for emergency medical procedures including some capability to perform surgery. The ability to perform minimally invasive surgery (MIS) would be an important capability. The use of small incisions reduces surgical risk, but also eliminates the ability of the surgeon to view and touch the surgical environment directly. Robotic surgery, or telerobotic surgery, may provide emergency surgical care in remote or harsh environments such as space flight, or extremely forward environments such as battlefields. However, because current surgical robots are large and require extensive support personnel, their implementation has remained limited in forward environments, and they would be difficult, or impossible, to use in space flight or on battlefields. This paper presents experimental analysis of miniature fixed-base and mobile in vivo robots to support MIS surgery in remote and harsh environments. The objective is to develop wireless imaging and task-assisting robots that can be placed inside the abdominal cavity during surgery. Such robots will provide surgical task assistance and enable an on-site or remote surgeon to view the surgical environment from multiple angles. This approach is applicable to long-duration space flight, battlefield situations, and for traditional medical centers and other remote surgical locations.     

Analytical pyrolysis as a tool for the study of plastic coals

The technique of analytical pyrolysis has been used to characterize 40 similar mid-rank western Kentucky coals of widely differing ASTM Gieseler plasticity. Certain pyrolysis/g.c. variables were shown to correlate well with both ASTM Gieseler and isothermal plasticity. Highly plastic coals were shown to exhibit certain characteristic peaks in the 450 °C pyrogram which were absent in the pyrogram of the non-plastic coals. Two coals, representing the two extremes in plasticity, were selected for further study. After extraction with solvents such as DMF the characteristic peaks were absent in the 450 °C pyrogram of the extraction residue of the highly plastic coal. These peaks were also shown to decrease with increasing severity of air oxidation of the plastic coal. This technique appears to be a useful tool for the analysis of mid-rank plastic coals and supports the view that the substances contained in the bitumen fraction of these coals are involved in the development of the plastic state.     

Biological rhythms as organization and information

The purpose of the current study was to describe four models of cognitive deficit and to outline the statistical hypotheses underlying each model. The four models of cognitive deficit were (a) specific deficit; (b) subgroup deficit; (c) a syndrome dissociation model; and (d) a global function dissociation model. Neuropsychological data are analyzed to examine each of these four models in a sample of mild Multiple Sclerosis (MS) patients. The results suggest that for these subjects and tests, the specific deficit model best fits the data. The results are reviewed initially in the context of MS. There follows a consideration of statistical caveats and finally, general applications of the proposed procedures.