Time-delayed map as a model for open fluid flow

It is shown that a time-delayed map for just one (chaotic) element whose feedback is periodically interrupted can be exactly mapped to a coupled map lattice model for open fluid flow.     

The number of components in profile analysis tasks.

The central issue of this paper is how detection of a change in spectral shape depends on the number of components m that define the spectrum. First, a channel theory is reviewed and the predictions relating the detectability of such a change as a function of the number of components are derived. Second, the existing literature is reviewed. Most of it concerns the detection of an increment in a single tone of an m-component, equal-amplitude complex. The data are close (+/- 2 dB) to the predictions of the theory, which suggests that there is a relatively small change in threshold as the number of components increases. The consistency of the data is also discussed and hypotheses for discrepancies are presented. Finally, the results of an experiment measuring the detectability of a special spectral shape change is explored. In this case, all the changes are equal in size but some are opposite in sign, so that the summed change is zero. The results using this "balanced" spectral change are also consistent with the predictions of the theory and show that for this special kind of spectral change thresholds improve by nearly 7 dB as m increases from 4 to 24 components.     

Anti-oxidant and pro-oxidant reactivities of copper(II), manganese(II) and iron(III) 3,5-di-<Emphasis Type="Italic">i</Emphasis>-propylsalicylate chelates during peroxidation of alkylbenzenes

Bioactive copper(II), iron(III), and manganese(II) 3,5-di-i-propylsalicylate (3,5-DIPS) chelates were investigated in order to determine their ability to inhibit the free radical initiated chain reactions leading to the peroxidation of isopropylbenzene (i-PrPh) and ethylbenzene (EtPh). Quantitative kinetic studies of these chelates established the following order of anti-oxidant reactivities: manganese(II)-(3,5-DIPS)₂>iron(III)(3,5-DIPS)₃>copper(II)₂(3,5-DIPS)₄> > 3,5-DIPS acid. The mechanism of anti-oxidant reactivity of these three chelates is established as being due, in part, to their chain-breaking capacity resulting from the chemical reduction of the generated peroxyl radical to yield alkybenzenelhydroperoxides via reaction of the 3,5-DIPS ligand with the peroxyl radical. In the case of manganese(II)3,5-di-i-propylsalicylate, the central metalloelement also interacts with the peroxyl radical. The manganese(II)-(3,5-DIPS)₂ and copper(II)₂(3,5-DIPS)₄ chelates were also found to exhibit alkylhydroperoxide pro-oxidative reactivity leading to the formation of the alkylbenzeneperoxyl radical. In addition, the manganese(II) atom underwent oxidation to manganese(III) with the formation of the alkylbenzenehydroperoxide or superoxide with air oxygen oxidation. Amyl acetate and dipropylamine (n-Pr₂NH) were added to the reaction mixture to model the biochemical presence of ester or amine cellular components. Addition of amyl acetate to the reaction mixture increased the anti-oxidant reactivity of manganese(II)-(3,5-DIPS)₂ while decreasing its pro-oxidant reactivity. The weaker anti-oxidant reactivites of iron(III)(3,5-DIPS)₃ and copper(II)₂(3,5-DIPS)₄ were less affected by the addition of amyl acetate and the pro-oxidant reactivity of copper(II)₂(3,5-DIPS)₄ was not changed by the addition of amyl acetate, while the pro-oxidant property of iron(III)(3,5-DIPS)₃ was eliminated. In contrast to 2,6-di-t-butyl-4-methylphenol, butylated hydroxy toluene (BHT), anti-oxidant reactivities of copper(II), iron(III), and manganese(II) 3,5-DIPS chelates were dramatically enhanced by the addition of n-Pr₂NH to the reaction mixture. It is concluded that all three metalloelement chelates react with and remove alkylbenzeneperoxyl radicals and the hydroperoxyl radical. The manganese(II)-(3,5-DIPS)₂ and copper(II)₂(3,5-DIPS)₄ chelates may also be useful in removing hydroperoxides in vivo. These reactivities, in addition to their established superoxide dismutase (SOD)-mimetic and catalase-mimetic reactivities, are suggested to possibly permit anti-oxidant and pro-oxidant reactivities in aqueous and organic cellular compartments.     

Chemistry of (η5-C5H5)Ru(Ph2PCH2CH2PPh2)Cl: preparation of cationic ruthenium olefin complexes

The cationic ruthenium complexes [(η⁵-C₅H₅)Ru(Ph₂PCH₂CH₂PPh₂)L]PF₆ (L=olefin, CO, pyridine or acetonitrile) have been prepared by treatment of (η⁵-C₅H₅)Ru(Ph₂PCH₂CH₂PPh₂)Cl with L and NH₄PF₆ in methanol of 20°C.     

Rearrangement of epoxynitriles: a convenient homologation of acyclic and cyclic ketones to carboxylic acids

A convenient two-step homologation of both aliphatic and aromatic ketones to the corresponding carboxylic acid has been developed. First ketones were converted to epoxynitriles with the Darzens reaction. Second, a Lewis acid mediated rearrangement of these epoxynitriles with lithium bromide was achieved to give homologated secondary alkanoic acids (as well as aryl-alkanoic) in good yields. The mechanism and the scope of the rearrangement reaction were investigated. This strategy constitutes a two-step homologation of ketones to secondary carboxylic acids.     

Abbau von Palustrin zu (−)-Dihydropalustraminsäure ((2R, 6S, 1′S)-[6-(1′-Hydroxypropyl)-2-piperidyl]essigsäure) und Struktur von Palustrin und Palustridin. Mitteilung über Schachtelhalmalkaloide

Degradation of palustrin to (?)-dihydropalustramic acid ((2R,6S,1′S)-[6-(1′-hydroxypropyl)-2-piperidyl]acetic acid), and the structure of palustrin and palustridin The structure of the macrocyclic alkaloid palustrin is shown to be 1a . Its piperidine unit can be obtained as (?)-dihydropalustramic acid ( 6a ) by the following sequence of degradation reactions (Scheme 1): catalytic hydrogenation of 1a followed by methylation and Hofmann degradation provides the allyl base 4 . the regioselectivity of the Hofmann elimination is explained by intramolecular proton abstraction at C(3) by C(18)-O^?. Catalytic reduction of 4 and subsequent acidic hydrolysis yielded 6a and N, N-dimethylputrescine (?N,N-dimethyl-1,4-butanediamine; 7 ). Loss of the N-alkyl group in the formation of 6a occurs during the catalytic hydrogenation step. This interpretation is supported by the results of model experiments. The position of the double bond in 1a is deduced from the IR. spectrum of the bromo-δ-lactone 19 prepared by treatment of 1a with N-bromosuccinimide at pH 4 (Scheme 3). Some of our previously published results on the degradation of dihydropalustrin ( 2a ) are obviously at variance with the newly proposed structure for palustrin ( 1a ). They can easily be explained by assuming a partial hydrogenolysis of the C(17)-N(1) bond during the preparation of dihydropalustrin from palustrin. Periodate cleavage of dihydropalustramic acid methyl ester ( 6b ) liberates propionaldehyde, which can be trapped by working at pH 7.5 (Scheme 2); at lower pH values it condenses rapidly with the simultaneously generated 3,4,5,6-tetrahydropyridine derivative 15 . The structure of the condensation product is proposed to be 16 on the basis of the isolation of its hydrogenation product, an isomeric dihydropalustramic acid ( 17 ).     

Influence of dipolar interactions on radical pair recombination reactions subject to weak magnetic fields

Monte Carlo simulations of the effects of weak magnetic fields on the recombination of interacting radical pairs undergoing free diffusion in solution have been performed, with the aim of determining the influence on the low field effect of the magnetic dipolar coupling between the radicals. The suppression of singlet-triplet interconversion in the radical pair by the dipolar interaction is found to be pronounced at magnetic field strengths comparable to the hyperfine interactions in the radicals, to the extent that the low field effect is completely abolished. The averaging of the dipolar coupling by the translational diffusion of the radicals around one another is relatively efficient in the presence of strong magnetic fields but becomes ineffective in weak applied fields where the strength of the dipolar interaction is independent of the orientation of the inter-radical vector. Low field effects are only likely to be observed if the motion of the radical pair is restricted in some way so as to increase the likelihood that, having separated to the large distance required for the dipolar interaction to have a negligible effect, the radicals subsequently encounter and have the opportunity to recombine.     

Quantitative tests of mixed crystal excition theory. I. Naphthalene monomer1B2u and 3B1u spectra

A quantitative, computer processed spectroscopic study, using photon counting, on the first excited triplet and singlet states of dilute isotopic mixed crystals of naphthalene at 2 K is presented for C₁₀H₈; 1-DC₁₀H₇; 2-DC₁₀H₇; 1,4-D₂C₁₀H₆; 1,4,5-D₃C₁₀H₅; 1,4,5,8-D₄C₁₀H₄; 1,2,4,5,8-D₅C₁₀H₃; a β-D₄C₁₀H₄ and a β₂-D₆C₁₀H₂ as guests in C₁₀D₈ host crystals (and, for comparison, also for the same guests in a durene host crystal). The guest—host relative polarization Rashba formula has been verified quantitatively, and, as an added bonus, the elusive polarization ratio of the pure naphthalene crystal singlet Davydov components has been found to be 80 ± 20 (b/a), which is in poor agreement with the transition octupole—transition octupole model. The experimental guest energies and their concomitant quasiresonance shifts for bound singlet states (as well as the occurrences of unbound states) are in excellent quantitative agreement (about 1 cm^?1) with those calculated using a Green's function formalism based on the ideal mixed crystal approximation and on a restricted Frenkel type dispersion relation derived from resonance pairs. The same Green's function also accounts quantitatively (within 10%) for the guest singlet state exciton localizations (guest excitation amplitudes). The triplet exciton state reveals an orientational site splitting (about 0.7 cm^?1) for the 0—0 transition of the I-DC₁₀H₇ guest in C₁₀D₈ host. The order of the α and β substituted deuteronaphthalenes in the triplet state is reversed from that of the singlet state. The last two observations are related to the different nature of the lowest Π-Π^* singlet and triplet states of naphthalene.     

Synthesis of some pyridylamino-1,4-disubstituted phthalazines

Two general procedures involving the condensation of phthalonitrile or 1,3-diiminoisoindoline with various aminopicolines, followed by ring expansion with hydrazine to the corresponding phthalazine are described. Syntheses are reported of 1, 4-di(3′-methyl-2′-pyridyl) aminophthalazine, 1,4-di(5′-methyl-2′-pyridyl)aminophthalazine, and 1,4-di(4′, 6′-dimethyl-2′-pyridyl)aminophthalazine.