Multiple Electron Donors Research Articles

Derivatized Fullerenes Bearing Multiple Electron Donors: Synthesis and Charge Transfer Properties

A series of methano-C60 adducts bearing up to six electron donating N,N-dimethylaniline units (denoted as D compounds), along with their analogues without the dimethylamino groups as references (R compounds), were synthesized. The redox properties of the D compounds in solutions were evaluated spectroscopically in reference to the R compounds. According to UV/vis absorption results, there are obviously ground-state intramolecular charge-transfer complexes in the D series, and the charge-transfer effects apparently become saturated with only two donor units in the molecule. The photoinduced intramolecular electron-transfer properties of the D compounds were investigated via fluorescence measurements. The emission from intramolecular exciplexes can be found only in the D molecule with two electron donor units. Throughout the D series, the fluorescence properties are highly sensitive to the solvent polarity, with the emission completely quenched for all of the molecules in a polar solvent like methylene chloride. Mechanistic implications of the results are discussed.

Novel Physiological Features of Carboxydothermus hydrogenoformans and Thermoterrabacterium ferrireducens

Carboxydothermus hydrogenoformans is able to grow by conversion of CO to H2 and CO2. Besides CO, only pyruvate was described as serving as an energy source. Based on 16S rRNA gene sequence similarity, C. hydrogenoformans is closely related to Thermoterrabacterium ferrireducens. T. ferrireducens is like C. hydrogenoformans a gram-positive, thermophilic, strict anaerobic bacterium. However, it is capable of using various electron donors and acceptors for growth. Growth of C. hydrogenoformans with multiple electron donors and acceptors was tested. C. hydrogenoformans oxidized formate, lactate, glycerol, CO, and H2 with 9,10-anthraquinone-2,6-disulfonate as an electron acceptor. Sulfite, thiosulfate, sulfur, nitrate, and fumarate were reduced with lactate as an electron donor. T. ferrireducens oxidized CO with 9,10-anthraquinone-2,6-disulfonate as an electron acceptor but did not produce H2 from CO. In contrast to what was published before, T. ferrireducens was able to grow on lactate with sulfite, sulfur, and nitrate as electron acceptors.

Intramolecular electron transfer in fullerene derivatives with multiple donors

Electronic absorption and emission properties of the fullerene derivatives with multiple electron donors, ( N, N-dimethylaniline) N -[60]fullerene ( N=0,1,2,4, and 6), were investigated. The results show that there are both ground-state and excited-state electron transfers from the dimethylaniline moiety to the fullerene and that the electron transfers are dependent on the number of intramolecular electron donors on the fullerene cage. The results also show that the absorption and emission properties of these molecules are extremely solvent polarity dependent, consistent with the presence of significant electron transfer processes.

Anaerobic biotransformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) by aquifer bacteria using hydrogen as the sole electron donor

RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) is a nitramine explosive that has contaminated soil and groundwater at military installations throughout the US. Although anaerobic RDX metabolism has been reported, the process is not well understood, as past studies have typically involved complex, undefined media with multiple potential electron donors and acceptors. In this study, bacteria enriched from RDX-contaminated aquifer sediments consumed RDX in a defined, bicarbonate-buffered, anaerobic medium containing hydrogen as the sole electron donor and RDX as a potential electron acceptor and sole nitrogen source. RDX was not consumed in live controls that did not contain hydrogen. Transient formation of mononitroso- and dinitroso-RDX metabolites (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine and hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine, respectively) was documented by liquid chromatography-mass spectrometry. However, studies with 14C-labeled RDX suggested that mineralization to carbon dioxide was negligible (<2%), which is consistent with cometabolic transformation. Several lines of evidence suggest that the RDX-transforming bacteria under study were homoacetogens, including correlations between RDX consumption and acetate production. Methanogens were unlikely to be responsible for RDX metabolism, as the presence of 2-bromoethanesulfonate, an inhibitor of methanogenesis, did not appear to affect RDX metabolism. The presence of nitrate reversibly halted RDX metabolism, whereas ammonium had no discernible effect, which implies that: (i) nitrate, which commonly occurs in RDX-contaminated groundwater, may inhibit in situ RDX metabolism, and (ii) although RDX may act as both a nitrogen source and cometabolic electron sink, the latter role predominates, as RDX reduction will proceed regardless of whether or not a more favorable nitrogen source is present.

Expression Analysis of the nrdHIEF Operon fromEscherichia coli: CONDITIONS THAT TRIGGER THE TRANSCRIPT LEVEL IN VIVO

Escherichia coli has two aerobic ribonucleotide reductases encoded by the nrdAB and nrdHIEF operons. While NrdAB is active during aerobiosis, NrdEF is considered a cryptic enzyme with no obvious function. Here, we present evidence that nrdHIEF expression might be important under certain circumstances. Basal transcript levels were dramatically enhanced (25-75-fold), depending on the growth-phase and the growth-medium composition. Likewise, a large increase of >100-fold in nrdHIEF mRNA was observed in bacteria lacking Trx1 and Grx1, the two main NrdAB reductants. Moreover, nrdHIEF expression was triggered in response to oxidative stress, particularly in mutants missing hydroperoxidase I and alkyl-hydroperoxide reductase activities (69.7-fold) and in cells treated with oxidants (up to 23.4-fold over the enhanced transcript level possessed by cells grown on minimal medium). The mechanism(s) that triggers nrdHIEF expression remains unknown, but our findings exclude putative global regulators like RpoS, Fis, cAMP, OxyR, SoxR/S, or RecA. What we have learned about nrdHIEF expression indicates strong differences between its regulation and that of the nrdAB operon and of genes coding for components of both thioredoxin/glutaredoxin pathways. We propose that E. coli might optimize the responses to different stimuli by co-evolving the expression levels for its multiple reductases and electron donors.

Technetium-99m chelators in nuclear medicine. A review.

Nuclear medicine is a branch of medical imaging that uses radioactive tracers to examine the function of body systems. The radionuclide used in about 90% of all examinations is 99Tcm, which is available from 99Mo/99Tcm generators at most nuclear medicine departments. In aqueous medium, technetium is chemically stable as pertechnetate, 99TcmO4-. Injected into the human body, pertechnetate will be absorbed by the thyroid gland because of the similarity to iodide in its radius and charge. To reach targets in the human body other than glandula thyreoidea, 99Tcm needs a carrier molecule, usually a chelating agent. Many chelators that form stable complexes with 99Tcm have affinities for certain tissues in the human body. Other chelators can be manipulated by pharmaceutical formation to be retained in certain body systems. In order to form bonds with technetium, the chelator must contain electron donors like nitrogen, oxygen and sulfur. Space between multiple electron donor atoms is required to allow several bonds to form with the central metal. The stability of the complex increases with increasing number of bonds. Today, chelators for the use with 99Tcm exist for a number of highly sensitive scintigraphic studies of the brain, heart, skeleton, kidneys, hepatobiliary system and lungs. This includes chelators such as dimercaptosuccinic acid, 1,2-ethylenediylbis-L-cysteine diethyl ester, methylenediphosphonate, hexamethylpropyleneamineoxime and hexakis(methoxy isobutyl isonitrile).

Natural denitrification in the saturated zone: A review

Denitrification is increasingly recognized for its ability to eliminate or reduce nitrate concentrations in groundwater. With this awareness comes a desire to predict the rate and extent of denitrification in aquifers. The limiting factor in making predictive models, however, is our limited knowledge of the physical characteristics of this process. This review synthesizes the published literature on natural aquifer denitrification. A background section discusses denitrification requirements and dissimilatory nitrate reduction to ammonium, which occurs in environments similar to those where denitrification occurs, and gives a historical perspective on denitrification. Other sections discuss denitrification with organic carbon serving as the electron donor (heterotrophic denitrification) and with reduced inorganic compounds serving as the electron donor (autotrophic denitrification). The section on heterotrophic denitrification is structured around two tables that summarize natural aquifer denitrification rates reported by laboratory studies and natural aquifer denitrification rates reported by field studies. The section on autotrophic denitrification discusses denitrification with reduced iron and reduced sulfur. Thus far, most studies only consider a single electron donor or donor type, whether heterotrophic or autotrophic. This review demonstrates, however, that multiple electron donors may be present in a given aquifer. Future research efforts are recommended to determine the factors affecting the availability of electron donors and their denitrification rates. Additional research is also suggested on how dissolved oxygen affects denitrification rates and on the factors influencing the partitioning of nitrate reduction products to nitrous oxide, a potential contributor to the destruction of the ozone layer, and to ammonium.

The use of a metabolically structured model in the study of growth, nitrification, and denitrification by Thiosphaera pantotropha

Thiosphaera pantotropha is capable of aerobic heterotrophic nitrification and both aerobic and anaerobic denitrification. These phenomena have been studied in acetate-limited aerobic and anaerobic continuous cultures supplied with ammonia and nitrate. The internal reaction rates were defined, based on biochemical knowledge. The observable external conversion rates are related through a linear equation on the basis of the specified internal reaction rates. The linear equation is a Pirt relation extended for microbial systems with multiple electron donors (acetate and ammonia) and electron acceptors (oxygen and nitrate). The coefficients in this equation were estimated from the continuous culture measurements, and are composed of parameters involved in ATP production and consumption by the microorganism. It is shown that with realistic values for these parameters, the metabolically structured model describes the aerobic as well as the anaerobic experiments.