One-electron bonds as intermolecular bonds for molecular complexes involving Mulliken n-electron donors and as-electron acceptors

1975 ◽  
Vol 28 (4) ◽  
pp. 881 ◽  
Author(s):  
RD Harcourt

For 1 : 1 molecular complexes involving an n-type electron donor and an aσ-type electron acceptor, it is proved that the simplest Mulliken description, ΨN ≈ Ψ(D,A)+λΨ(D+-A-), is equivalent to using a one-electron bond as the intermolecular bond between the donor (D) and the acceptor (A). The theory is illustrated with reference to the Hassel compound Me3N...I2, and the charge-transfer aspects of hydrogen bonding for the water dimer.

2013 ◽  
Vol 295-298 ◽  
pp. 1402-1407
Author(s):  
Rui Wang ◽  
Ming Chen ◽  
Jia Wen Zhang ◽  
Fei Liu ◽  
Hong Han Chen

Effects of different electron donors (acetate and hydrogen), acetate and perchlorate concentrations on microbial perchlorate reduction in groundwater were studied. The results showed that acetate and hydrogen addition as an electron donor can significantly improve perchlorate removal efficiency while a longer period was observed for hydrogen (15 d) than for acetate (8 d). The optical ratio of electron donor (acetate)-to-electron acceptor (perchlorate) was approximately 1.65 mg COD mg perchlorate-1. The highest specific reduction rate of perchlorate was achieved at the acetate-to-perchlorate ratio of 3.80 mg COD mg perchlorate-1. The perchlorate reduction rates corresponded well to the theoretical values calculated by the Monod equation and the parameters of Ks and Vm were determined to be 15.6 mg L-1 and 0.26 d-1, respectively.


2002 ◽  
Vol 68 (5) ◽  
pp. 2445-2452 ◽  
Author(s):  
John D. Coates ◽  
Kimberly A. Cole ◽  
Romy Chakraborty ◽  
Susan M. O'Connor ◽  
Laurie A. Achenbach

ABSTRACT Previous studies have demonstrated that reduced humic substances (HS) can be reoxidized by anaerobic bacteria such as Geobacter, Geothrix, and Wolinella species with a suitable electron acceptor; however, little is known of the importance of this metabolism in the environment. Recently we investigated this metabolism in a diversity of environments including marine and aquatic sediments, forest soils, and drainage ditch soils. Most-probable-number enumeration studies were performed using 2,6-anthrahydroquinone disulfonate (AHDS), an analog for reduced HS, as the electron donor with nitrate as the electron acceptor. Anaerobic organisms capable of utilizing reduced HS as an electron donor were found in all environments tested and ranged from a low of 2.31 × 101 in aquifer sediments to a high of 9.33 × 106 in lake sediments. As part of this study we isolated six novel organisms capable of anaerobic AHDS oxidation. All of the isolates coupled the oxidation of AHDS to the reduction of nitrate with acetate (0.1 mM) as the carbon source. In the absence of cells, no AHDS oxidation was apparent, and in the absence of AHDS, no cell density increase was observed. Generally, nitrate was reduced to N2. Analysis of the AHDS and its oxidized form, 2,6-anthraquinone disulfonate (AQDS), in the medium during growth revealed that the anthraquinone was not being biodegraded as a carbon source and was simply being oxidized as an energy source. Determination of the AHDS oxidized and nitrate reduced accounted for 109% of the theoretical electron transfer. In addition to AHDS, all of these isolates could also couple the oxidation of reduced humic substances to the reduction of nitrate. No HS oxidation occurred in the absence of cells and in the absence of a suitable electron acceptor, demonstrating that these organisms were capable of utilizing natural HS as an energy source and that AHDS serves as a suitable analog for studying this metabolism. Alternative electron donors included simple volatile fatty acids such as propionate, butyrate, and valerate as well as simple organic acids such as lactate and pyruvate. Analysis of the complete sequences of the 16S rRNA genes revealed that the isolates were not closely related to each other and were phylogenetically diverse, with members in the alpha, beta, gamma, and delta subdivisions of the Proteobacteria. Most of the isolates were closely related to known genera not previously recognized for their ability to couple growth to HS oxidation, while one of the isolates represented a new genus in the delta subclass of the Proteobacteria. The results presented here demonstrate that microbial oxidation of HS is a ubiquitous metabolism in the environment. This study represents the first description of HS-oxidizing isolates and demonstrates that microorganisms capable of HS oxidation are phylogenetically diverse.


1999 ◽  
Vol 65 (12) ◽  
pp. 5212-5221 ◽  
Author(s):  
Jan Gerritse ◽  
Oliver Drzyzga ◽  
Geert Kloetstra ◽  
Mischa Keijmel ◽  
Luit P. Wiersum ◽  
...  

ABSTRACT Strain TCE1, a strictly anaerobic bacterium that can grow by reductive dechlorination of tetrachloroethene (PCE) and trichloroethene (TCE), was isolated by selective enrichment from a PCE-dechlorinating chemostat mixed culture. Strain TCE1 is a gram-positive, motile, curved rod-shaped organism that is 2 to 4 by 0.6 to 0.8 μm and has approximately six lateral flagella. The pH and temperature optima for growth are 7.2 and 35°C, respectively. On the basis of a comparative 16S rRNA sequence analysis, this bacterium was identified as a new strain of Desulfitobacterium frappieri, because it exhibited 99.7% relatedness to the D. frappieri type strain, strain PCP-1. Growth with H2, formate,l-lactate, butyrate, crotonate, or ethanol as the electron donor depends on the availability of an external electron acceptor. Pyruvate and serine can also be used fermentatively. Electron donors (except formate and H2) are oxidized to acetate and CO2. When l-lactate is the growth substrate, strain TCE1 can use the following electron acceptors: PCE and TCE (to produce cis-1,2-dichloroethene), sulfite and thiosulfate (to produce sulfide), nitrate (to produce nitrite), and fumarate (to produce succinate). Strain TCE1 is not able to reductively dechlorinate 3-chloro-4-hydroxyphenylacetate. The growth yields of the newly isolated bacterium when PCE is the electron acceptor are similar to those obtained for other dehalorespiring anaerobes (e.g.,Desulfitobacterium sp. strain PCE1 andDesulfitobacterium hafniense) and the maximum specific reductive dechlorination rates are 4 to 16 times higher (up to 1.4 μmol of chloride released · min−1 · mg of protein−1). Dechlorination of PCE and TCE is an inducible process. In PCE-limited chemostat cultures of strain TCE1, dechlorination is strongly inhibited by sulfite but not by other alternative electron acceptors, such as fumarate or nitrate.


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