Electronic Structures of Formic Acid (HCOOH) and Formate (HCOO–) in Aqueous Solutions

2012 ◽  
Vol 3 (13) ◽  
pp. 1754-1759 ◽  
Author(s):  
Matthew A. Brown ◽  
Fernando Vila ◽  
Martin Sterrer ◽  
Stephan Thürmer ◽  
Bernd Winter ◽  
...  
1995 ◽  
Vol 60 (4) ◽  
pp. 527-536 ◽  
Author(s):  
Martin Breza ◽  
Alena Manová

Using semiempirical MNDO method of quantum chemistry the optimal geometries and corresponding electronic structures of [Pb3(OH)n]6-n model systems as well as of their hydrated [Pb3(OH)n(H2O)8-n]6-n analogues (n = 4, 5) are investigated. The most stable trinuclear lead(II) complexes present in aqueous solutions correspond to cyclo-(μ3-OH)(μ2-OH)3Pb32+, Pb(μ-OH)2Pb(μ-OH)2Pb2+, cyclo-(μ3-OH)2(μ2-OH)3Pb3+, Pb(OH)(μ-OH)2Pb(μ-OH)Pb(OH)+ and Pb(OH)(μ-OH)2Pb(μ-OH)2Pb+ systems. The key role of OH bridges (by vanishing direct Pb-Pb bonds) on the stability of individual isomers is discussed.


2003 ◽  
Vol 107 (46) ◽  
pp. 12562-12565 ◽  
Author(s):  
Shuji Matsuo ◽  
Ponnusamy Nachimuthu ◽  
Dennis W. Lindle ◽  
Hisanobu Wakita ◽  
Rupert C. C. Perera

1948 ◽  
Vol 39 (3) ◽  
pp. 359-383 ◽  
Author(s):  
J. W. L. Beament

The unspecialised portion of the shell and the cap of Rhodnius eggs are impermeable to almost all hydrophilic and lipophilic liquids. If water and very small ions pass through the chorion they must traverse a wax layer on the inside of the shell. Certain corrosive materials, e.g., glacial formic acid, may pass through the shell slowly.These conclusions, based on experiments with pieces of shell, have been confirmed in ovicidal experiments. A range of materials with widely differing properties enter the embryo only through the micropyles, of which there are approximately fifteen in the rim of each shell. At least one micropyle must be traversed to kill an egg but many eggs were killed when only one had been penetrated.A cement, applied by the female at oviposition, may occlude the outer orifice of a micropyle. The properties of the cement are described; it appears to be a tanned protein. Cement deposits are much more copious on the eggs laid by younger females. Such eggs are more resistant to ovicides because penetration is delayed. This increased resistance is more pronounced when oleophilic liquids are used owing to the rapidity with which they kill eggs from older females. The random distribution of cement is one cause of the variability of replicates in ovicidal tests.A detailed investigation has been made of factors governing liquids traversing the micropyles. Hydrophilic liquids invade the outer lipophilic part of the micropyle slowly; the displacement of air is the most important factor and small changes in the wetting power of the liquid make little difference to the rate of entry.Aqueous liquids aie absorbed into the protein lining of the inner portion of the micropyle. They reach the wax layer on the inside of the shell by migrating into and through the inner protein layer. The area which is invaded increases linearly with time. Mortality, therefore, increases as the square of the time of immersion, but it is proportional to the increase in concentration of a solute if the period of immersion is constant.Oleophilic liquids wet the micropyle actively. They may by-pass air and flow rapidly to the wax at the inner end of the tube. Wax solvents kill very quickly and are much more toxic than other lipophiles.Water in the micropyle and shell may affect the entrance of either type of liquid. In general it increases the toxicity of aqueous solutions and retards the entry of oils.Wax-emulsifying materials added to aqueous solutions do not produce great increases in toxicity. They are “filtered out” at the protein lining of the micropyle and do not reach the wax layer for a considerable period of time.


2002 ◽  
Vol 67 (2) ◽  
pp. 219-227 ◽  
Author(s):  
Martin Breza ◽  
Alena Manová

Optimum geometries based on experimental structures and corresponding electronic structures of [Pb6(μ3-OH)8]4+ and [Pb6O(μ3-OH)6]4+ clusters as well as of their hydrated [Pb6(μ3-OH)8(H2O)6]4+ and [Pb6O(μ3-OH)6(H2O)6]4+ analogues are investigated using the semiempirical MNDO method of quantum chemistry. Direct Pb-Pb and O-O bonds are vanishing in the systems under study. Small differences in interatomic Pb-Pb and Pb-O distances between these clusters indicate that they cannot be distinguished by recent experimental techniques in solution. Both the mentioned structures are stable and might coexist in solution.


1991 ◽  
Vol 36 (5-6) ◽  
pp. 973-978 ◽  
Author(s):  
Kiyochika Yahikozawa ◽  
Yuichi Fujii ◽  
Yoshiharu Matsuda ◽  
Katsunori Nishimura ◽  
Yoshio Takasu

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