Moment characterization of localized orbitals

The parallel between orbital first and second electric moments and statistical first and second central moments is noted. Three measures of orbital spatial distribution in terms of their moments are proposed, and applied to the LMO's in a series of ten-electron hydrides. Consistent differences between bond and lone pair distributions are found. Using the statistical interpretation, for each LMO an effective solid angle around the central atom is postulated.     

Molecular orbital studies on the conformation of GABA (γ-aminobutyric acid)

In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation.     

Purine Nucleoside Analogs. 12. Synthesis of Novel 8,9-Disubstituted Guanine Derivatives by S-Alkylation of 2-Acetamido-9-(2-acetoxyethoxymethyl)-6-oxo-8-thioxopurine

S-Alkylation of 2-acetamido-9-(2-acetoxyethoxymethyl)-6-oxo-8-thioxopurine was used to synthesize its novel S- and N₍₇₎-substituted derivatives. We have established the effect of the structure of the alkylating agent on the reaction conditions and its regioselectivity. We have shown that the synthesized guanine derivatives can be modified further.     

Molecular structure of potassium [N,N′-bis(salicylideneamino)nitroguanidonate-N,N′,-O,O′]nickel(ii), the product of condensation of (salicylideneamino)nitroguanidine with salicylaldehyde on a Ni2+ ion template

The crystal structure of the product of the condensation of (salicylideneamino)nitroguanidine with salicylaldehyde on a Ni²⁺ ion template, K[Ni(C₁₅H₁₀N₅O₄)] · DMF, has been studied. It was established that a planar Ni complex, consisting of isolated [NiL]^– anions and solvated [K⁺ · DMF] cations, is formed. The negative charge of the anion is localized mainly on the O atoms of the nitro group. The nitroguanidine fragment of the ligand occurs in the tautomeric form, which was not reported previously.Deceased in 1995Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2273–2277, September, 1996.     

Biotechnological storage and utilization of entrapped solar energy

Our laboratory has recently developed a device employing immobilized F₀F₁ adenosine triphosphatase (ATPase) that allows synthesis of adenosine triphosphate (ATP) from adenosine 5′-diphosphate and inorganic phosphate using solar energy. We present estimates of total solar energy received by Earth’s land area and demonstrate that its efficient capture may allow conversion of solar energy and storage into bonds of biochemicals using devices harboring either immobilized ATPase or NADH dehydrogenase. Capture and storage of solar energy into biochemicals may also enable fixation of CO₂ emanating from polluting units. The cofactors ATP and NADH synthesized using solar energy could be used for regeneration of acceptor d-ribulose-1,5-bisphosphate from 3-phosphoglycerate formed during CO₂ fixation.     

Effect of hydrophobic amino acids on the conformational change of decapeptides in micellar environments

A series of peptides containing various hydrophobic amino acids [methionine (Met), leucine (Leu), norleucine (Nle), phenylalanine (Phe), 2-aminooctanoic acid (Aoc), and 2-aminodecanoic acid (Ade)] were synthesized and their conformations were studied using circular dichroism (CD) spectroscopy in different solvents such as water, methanol, and aqueous solution of ammonium tetradecanesulfonate. Peptides containing hydrophobic amino acids with linear side chains formed -sheets in water and methanol. Electrostatic interaction between the charged side chain (lysine) and a micelle consisting of an anionic surfactant, ammonium tetradecanesulfonate, is necessary for the formation of -helices in micellar environments. The conformational transition from -helix to -sheet structure required moderate hydrophobicity and linear side chains. This conformational transition depended on the surfactant concentration.     

Zur Synthese von fungizid wirksamen Isocamphanderivaten: Synthesen in der Isocamphanreihe, 34. Mitt.

Summary Some esters of isocamphenilanic acid (4) have been prepared and tested for their fungicidal and insecticidal activity. Esters of various acids with isocamphanyl ethylalcohol (5) have also been synthesized and included in the fungicidal/acaricidal/insecticidal screening programme. All esters bear a geminal dimethyl group at C-3 of the bicyclus which is important because of its shielding effect.

     

Complexation of Al(III) by 8-Hydroxyquinoline and Drastic Fluorescence Enhancement in Reverse Micelles

Complexation of Al^IIIby 8-hydroxyquinoline and fluorescence behavior of the quinolinate(s) were studied in reverse micellar systems at low water content, and compared to aqueous media. Two surfactants were used: one was cationic (CTAC: cetyltrimethylammonium chloride) and the other was anionic (AOT: sodium bis(2-ethylhexyl)sulfosuccinate). The results obtained in the CTAC/dichloromethane system (W= [H₂O]/[surfactant] = 0.9) showed that complexation occurred very likely in the oil phase and no micellar effect was observed. On the contrary, in the presence of AOT, specific micellar effects were observed due to the presence of the anionic polar heads: stabilization of the positively charged 1:1 and 1:2 chelates, at the expense of the neutral water-insoluble 1:3 chelate which is formed in aqueous solutions under similar conditions;drastic fluorescence enhancement factorsof 120 and 100 in AOT/heptane (W= 1.5) and AOT/dichloromethane (W= 1.6), respectively. Such factors have never been reported so far in either hydroorganic or direct micellar systems. In return, the length of time for the production of the complex(es) is increased because of the microheterogeneity of the medium and the small sizes of the water pools.     

Kraftfeldrechnungen an linearen Oligopyrrolen: 2,2′-Bipyrrol, 2,2′-Furylpyrrol und Prodigiosen

Using a specific force field model, relative stabilities of 2,2-bipyrrole and 2,2-furylpyrrole conformers as well as of prodigiosene tautomers, configurations, and conformations, are studied. 2,2-Bipyrrole adopts anantiperiplanar conformation in accord with other theoretical calculations and experimental findings. Its rotational barrier calculated by this method compares favourably to the one derived by other means. For the parent prodigiosene the (Z)sp,sp arrangement is found to be the most stable one. The two possible tautomers within its dipyrrin fragment do not show a significant energy difference.

     

Products active on mosquitoes,IV: Synthesis and biological activity of 8-propargyloxy-3,7-dimethyl-2,6-octadienyl/6-octenyl ethers

Summary A series of 8-proparglyoxy-3,7-dimethyl-2,6-octadienyl and 8-propargyloxy-3,7-dimethyl-6-octenyl ethers were prepared from 8-hydroxygeranyl and 8-hydroxycitronellyl ethers, respectively. Almost all compounds showed high toxicity toCulex quinquefaciatus larvae at 1 mgl^–1 dose level.

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Gegen Mücken aktive Produkte, 4. Mitt.: Synthese und biologische Aktivität von 8-Propargyloxy-3,7-dimethyl-2,6-octadienyl/6-octenyl-ethern

Zusammenfassung Eine Reihe von 8-Propargyloxy-3,7-dimethyl-2,6-octadienyl- und 8-propargyloxy-3,7-dimethyl-6-octenyl-ethern wurden aus 8-Hydroxygeranyl- bzw. 8-Hydroxycitronellyl-ethern hergestellt. Fast alle Verbindungen zeigten hoch Toxizität gegenüber Larven vonCulex quinquefaciatus in einer Dosierung von 1 mgl^–1.