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Chemistry of Heterocyclic Compounds -     

PMR spectra of some five- and six-membered heterocyclic compounds of silicon and germanium

The PMR spectra of various 1-sila- and 1-germacyclopentanes and also those of some substituted disilacyclohexanes are discussed. The influence of the magnetic field of the aryl and vinyl substituents in 1,1-dialkyl-2,5-diaryl(vinyl)-1-sila(germa)cyclopentanes on the chemical shifts of the protons of the individual groups is studied, the differences found in the position of the PMR lines of the methyl and methylene groups showing the existence of cis-trans isomers in these heterocycles. With 1,1-dimethyl-2,5-divinylsilacyclopentane as an example, an increase in screening due to the magnetism of the multiple bonds for the protons of groups not directly connected with the unsaturated groupings and located in a direction perpendicular to the axis of the double bond has been found experimentally.Lecture at the XI-th Scientific Conference of the Institute of High-Molecular-Weight Compounds of the Academy of Sciences of the USSR (Leningrad, March, 1964) and at the All-Union Conference on the Use of Radiospectroscopy in Chemistry (Moscow, January, 1965).The authors express their gratitude to A. V. Kessenikh for taking several of the PMR spectra and for critical observations on the investigation.     

Crystal violet combined with Merocyanine 540 for the ex vivo purging of hematopoietic stem cell grafts

The purpose of this study was to determine in a preclinical purging model, how effective crystal violet-mediated photodynamic therapy (CV-PDT) is against solid tumor and drug-resistant mutant tumor cells, and if certain limitations of CV-PDT can be overcome by using crystal violet (CV) in combination with the membrane-active photosensitizer, Merocyanine 540 (MC540). When used under conditions that preserved an adequate fraction of normal human granulocyte/macrophage progenitors (CFU-GM), CV-PDT failed to achieve meaningful reductions of DU145 prostate, H69 small cell lung cancer, and MDA-MB-435S breast cancer cells. Melphalan-resistant L1210/L-PAM1, adriamycin-resistant P388/ADR, and adriamycin-resistant HL-60/ADR leukemia cells were markedly less sensitive to CV-PDT than their wild-type counterparts, whereas cisplatin-resistant H69/CDDP cells were more sensitive than wild-type H69 cells. Sequential exposure to MC540- and CV-PDT under conditions that preserved an adequate fraction (73% and 29%, respectively) of normal CD34-positive hematopoietic stem cells and granulocyte/macrophage progenitors was highly effective against H69 (99.997% reduction) and H69/CDDP (99.999% reduction) cells, but ineffective against HL-60/ADR, MDA-MB-435S, and DU145 cells. CV thus shows only limited promise as a single-modality purging agent. However, in certain situations, clinically meaningful tumor cell depletions can be obtained by using CV in combination with a second photosensitizer such as MC540.     

Influence of complexation by metal cations on solvophobic retention of crown compounds in reverse-phase high-performance liquid chromatography

The retention of crown compounds in reverse-phase HPLC is determined by their ability to bind to cations present in the eluent. The dependence of the retention of crown compounds on concentration of the binding cation has a break. This enables the stability constant of the crown-compound-cation complex to be calculated. The retention of the antitumor antibiotic actinomycin D in 75% MeOH is demonstrated to depend on [Na⁺] and not on [K⁺] for concentrations of the latter from 10^–6 to 10^–1 M.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2265–2269, October, 1991.     

THE MAXIMUM EFFICIENCY OF PHOTOSYNTHESIS *

Within the ideal assumptions: (1) two Photosystems for photosynthetic fixation of CO₂, (2) all solar photons with Λ≥ 700 nm are absorbed, (3) the photon requirement is 8 for each CO₂ molecule fixed and O₂ molecule evolved and (4) the principal stable product of photosynthesis is d-glucose, the theoretical maximum efficiency of conversion of light to stored chemical energy in green-plant type (oxygen-evolving) photosynthesis in bright sunlight is calculated to be 13.0%. Thermodynamic arguments are presented which indicate that a photosynthetic system with one Photosystem would be highly unlikely to be able to drive each electron from water to evolve O₂ and reduce CO₂. The practical maximum efficiency of photosynthesis under optimum conditions is estimated to be 8–9%.     

The einstein a-coefficient of spontaneous emission: a relativistic calculation in the Heisenberg representation

We present a simple approach to the relativistic calculation of the rates of spontaneous emission starting from the Heisenberg picture formula for the power radiated by a charged particle undergoing acceleration, and evaluate atomic decay rates using relativistic Dirac-Coulomb wavefunctions. The spin of the electron, embedded in its relativistic wavefunction, is shown to correctly provide the two polarization states of the emitted radiation. We discuss selection rules and calculate the Hydrogen 2P → 1S transition rate, among others, to be Γ=(6.2650±0.0007)×10⁸ s^?1 in good agreement with the full field theory calculation as well as with experiment.     

New details concerning the reactions of nitric oxide with vanadium tetrachloride

The slow addition of NO to a CCl(4) solution of VCl(4) reproducibly forms the known polymer [V(NO)(3)Cl(2)](n)() as a dark brown powder. Treatment of a CH(2)Cl(2) suspension of [V(NO)(3)Cl(2)](n)() with excess THF generates mer-(THF)(3)V(NO)Cl(2) (1) which can be isolated as an orange crystalline material in 55% yield. The reaction of 1 with excess MeCN or 1 equiv of trimpsi (trimpsi = (t)BuSi(CH(2)PMe(2))(3)) provides yellow-orange (MeCN)(3)V(NO)Cl(2)xMeCN (2xMeCN) and yellow (trimpsi)V(NO)Cl(2) (3), respectively. A black, crystalline complex formulated as [NO][VCl(5)] (4) is formed by the slow addition of NO to neat VCl(4) or by the reaction of excess ClNO with neat VCl(4). Complex 4 is extremely air- and moisture-sensitive, and IR spectroscopy suggests that in solutions and in the gas phase it dissociates back into VCl(4) and ClNO. Reaction of 4 with excess [NEt(3)(CH(2)Ph)]Cl generates [NEt(3)(CH(2)Ph)](2)[VCl(6)]x2CH(2)Cl(2) (5x2CH(2)Cl(2)), which can be isolated as deep-red crystals in 51% yield. All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of 1, 2xMeCN, and 5x2CH(2)Cl(2) have been established by single-crystal X-ray diffraction analyses.     

Interactions magnétiques dans des groupements binucléaires du Ruthénium +V

The cationic ordering in the $\text{Ba}\text{M}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Ru}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{O}{}_3\text{(M =}\text{Mg, Ca, Cd, Sr}\text{)}$ oxides which crystallize with the 6H structure gives rise to Ru⁵⁺Ru⁵⁺ pairs in (Ru₂O₉) clusters. The magnetic properties have been analyzed on the basis of the Heisenberg-Dirac-Van Vleck model: The d electrons are localized on each Ru⁵⁺ ion and interact strongly through antiferromagnetic exchange. The susceptibility curves agree with the H.D.V.V. model. The values of the exchange integrals have been determined by fitting the experimental values.     

Isonitrile complexes derived from the nucleophilic attack of primary amines on the dithiomethyl ester complex,RuI(CO)(PPh3)2 (CS2Me)

The bidentate dithiomethyl ester complex, RuI(CO)(PPh₃)₂ (CS₂Me) reacts with primary amines affording a series of novel dimeric isonitrile complexes, [RuI(CO)(CNR)(PPh₃)₂SH]₂.     

Synthetic studies in the field of the curare alkaloids

By oxidation and the identification of the oxidation products, it has been shown that the -[4-(2-alkoxy-5-alkoxycarbonylmethylphenoxy)-3-methoxyphenyl] ethylamides of 4-benzyloxyphenylacetic acid obtained previously and differing in their physicochemical properties are based on the same skeleton and differ only in their spatial configuration, since on Bischler-Napieralski cyclization they give isomeric dihydroisoquinoline compounds. The structure of the latter was established by oxidation to the isomeric acids 2,2-dimethoxy-3,4,5-tricarboxy(diphenyl ether) and 2,2-dimethoxy-4,5,5-tricarboxy-(diphenyl ether); the latter is identical with the compound obtained by the degradation of the methyl ester of natural tubocurarine. 1-(4Benzyloxybenzyl)-6-methoxy-7-(2-methoxy-5-methoxycarbonyl methylphenoxy)-N-methyl-1,2,3,4-tetrahydroisoquinoline and a compound isomeric with it have also been synthesized, and the former has been shown to be identical with a substance obtained by independent synthesis from the 4-benzyl ether of N-methylcoclaurine. During the synthesis of the latter it was shown that cyclization takes place unambiguously without the formation of isomeric compounds.For part XIII, see [2].