Structure of cucumarioside G1 — A new triterpene glycoside from the holothurianCucumaria fraudatrix

A new triterpene glycoside — cucamarioside G₁ — has been isolated from the Pacific Ocean holothurianCucumaria fraudatrix. On the basis of physicochemical characteristics and the results of chemical transformations, its structure has been established as 16-acetoxy-3-[O-(3-O-methyl--D-xylopyranosyl)-(1 3)-O--D-glucopyranosyl-(1 4)--D-quinovopyranosyl-(1 2)-(4-O-sulfato--D-xylopyranosyloxy)]-holosta-7,24-diene.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 244–248, March–April, 1985.     

Study of the non-adiabatic transitions with application to NO

An expression for the non-adiabatic transition probability is derived from the viewpoint of the non-stationary character of the adiabatic approximation. A numerical calculation has been made for the free NO molecule. The non-adiabatic transition probability for the transition (B ² =0)(a ⁴ =9) is estimated to be 10^–6 sec^–1 by using the wave functions proposed by Moser et al.

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Zusammenfassung Für die nicht adiabatische Übergangswahrscheinlichkeit wurde aus dem nicht-stationären Charakter der adiabatischen Näherung ein Ausdruck hergeleitet, der für den Fall des NO-Moleküls numerisch ausgewertet wurde. Dabei ergab sich unter Verwendung der Wellenfunktionen von Moser u. Mitarb. eine Wahrscheinlichkeit für den Übergang (B ² =0) (a ⁴ =9) von der Größenordnung von 10^–6 sec^–1.

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Résumé Une expression pour la probabilité de la transition non adiabatique est obtenue du point de vue du caractère non stationnaire de l'approximation adiabatique. Un calcul numérique a été effectué pour la molécule NO isolée. La probabilité de transition non adiabatique pour la transition (B ² =0)(a ⁴ =9) est évaluée à 10^–6 sec^–1 en utilisant les fonctions d'onde proposées par Moser et al.

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This work was supported by The Faculty Grant of Arizona State University.     

Metal bioaccumulation by the freshwater algaScenedesmus quadricauda

Bioaccumulation of six metals (Cu²⁺, Cu⁺, Mo⁶⁺, Mn²⁺, V⁵⁺, Ni²⁺) and their combinations by algaScenedesmus quadricauda was determined by using radio nuclide X-ray fluorescence (RXFA). The metals were added into the cultivation medium in concentrations corresponding with EC₅₀ value for each metal. The obtained results indicate that Ni²⁺, Cu²⁺ and Cu⁺ were accumulated in high amounts (20%, 17.5% and 15.19%) the Mo⁶⁺ ion (<0.2%) was accumulated in the lowest amount. For metal-metal interactions in accumulation of metal ions by algaS. quadricauda three types of answers were determined: inhibition (MoCu²⁺, Ni, Mn, V; VNi, Mn; MnNi, Cu²⁺, Cu⁺; Cu⁺Ni; Cu²⁺Ni; NiMn, V), enhancement (VCu⁺; Cu²⁺Mn;Cu⁺V, Mn; MnV; NiCu²⁺, Cu⁺) and neutral effect (VMo; Cu²⁺Mo; Cu⁺Mo; MuMo; NiMo).     

Cardiac glycosides of Cheiranthus allioni. V

Conclusions Two additional cardiac glycosides, glucoerysimoside and glucoerysimosol, have been isolated from the seeds ofCheiranthus allioni Hort. Glucoerysimoside is strophanthidin 3-[O--D-digitoxopyranosyl-(4 1)-O--D-glucopyranosyl-(4 1)--D-glucopyranoside]. Glucoerysimosol is a new cardenolide having the same carbohydrate component, but its aglycone is strophanthidol. From these glycosides a new trisaccharide has been obtained which has been characterized as 4-O--cellobiosyl-D-digitoxose.Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 566–571, September–October, 1970.     

Ein einfacher Zugang zu (R)-γ-Amino-β-hydroxybuttersäure (GABOB) aus natürlichem (2S, 4R)-4-Hydroxyprolin

The oxidative decarboxylation sequence (1a 2a 3a 4a 5a) affording -aminobutanoic acid (5a) is adapted to the synthesis of its hydroxy derivative5b. A facile high yield conversion of (2S, 4R)-4-hydroxyproline-methylester-hydrochloride (7) to (R)-GABOB (5b) on a preparative scale is reported with the hydroxypyrrolidone8 as the intermediate.

     

Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride)

Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm · HCl) containing Fe^II or Fe^III and M²⁺ (M=Fe, Co, Cu) in a 11 molar ratio were obtained by the reaction of [Fe(CN)₆] ^n– (n=3,4) with M²⁺ ion-PVAm · HCl mixture in aqueous solution. Under a limited polymer concentration (T_VAm/T_Fe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm · HCl was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (Fe^IIFe^III, Co^IIFe^III, Fe^IICu^II) band for MFe(CN)₆]^(n–2)– bound to PVAm · HCl (M=Fe, Co, Cu) were found to be 10,100–9601 · mol^–1 · cm^–1 at 25 C. The formation constants were found to be in the range of 10⁷ to 10¹⁰ M^–1. The changes of enthalpy (H) and entropy (S) were found to be in the range of –10.4 to –22.5 kJ · mol^–1 and 5.7 to 52.9 J · K^–1 mol^–1 respectively, at 25C.     

Steroid saponins X. Glycosides of Allium narcissiflorum the structure of glycosides A and B

Summary FromAllium narcissiflorum Wells have been isolated for the first time trillin and a glycoside B, which proved to be 3-O-[-O-D-glucopyranosyl-(1 3)-O--D-glucopyranosyl-(1 6)-O--D-glucopyranosyl-(1 ]-26-O-[-D-glucopyranosyl-(1 ]-25R-furost-5-ene-3,22 , 26-triol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 55–58, January–February, 1976.     

Sinapoyl ester of glucoerysimoside inErysimum marschallianum

Summary A new cardenolide glycoside — sinapoylglucoerysimoside — having the structure of strophanthidin 3-0-[0-sinapoyl--D-glucopyranosyl-(14) 0--digitoxopyranoside — has been found in the seeds ofErysimum marshallianum.Kiev Institute for the Further Training of Doctors. Translated from Khimiya Prirodnykh Soedinenii No. 5, pp. 603–606, September–October, 1975.     

Coumarin glycosides ofHaplophyllum performatum. structures of haploperosides C,D, and E

New coumarin glycosides — haploperosides C, D, and E — have been isolated from the epigeal part of theHaplophyllum performatum (MB) Kar et Kir. On the basis of chemical transformations and spectral characteristics, haploperoside D has the structure of 6-methoxy-7-[0--L-rhamnopyranosyl-(1 2)--D-glucopyranosyloxy]-2H-benzopyran-2-one, and haploperoside C that of 6-methoxy-7-[0--L-rhamnopyranosyl-(1 6)-(2-0-acetyl--D-glucopyranosyloxy)]-2H-benzopyran-2-one. The structure of haploperoside E has been established as 7-[0--L-rhamnopyranosyl-(1 2)-0--L-rhamnopyranosyl-(1 6)--D-glucopyranosyloxy]-2H-benzopyran-2-one. The structures of haploperosides A and B have been refined. An assignment has been made of the carbon signals in the¹³C NMR spectra of haploperosides A, D, C, and E.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 27–35, January–February, 1985.     

Triterpene glycosides ofHedera helix III. Structure of the triterpene sulfates and their glycosides

From the leaves of English ivyHedera helix L. we have isolated the known 3-sulfates of oleanolic and echinocystic acids and their 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl esters and the new 3-sulfate of 28-O--gentiobiosyl oleanolate — helicoside L-8a. The structures of the compounds isolated were deduced from the results of chemical transformations and NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 87–90, January–February, 1999.     

The triterpene glycosides ofpatrinia intermedia roem et schult

Conclusions It has been established that patrinoside D₁ is the -D-glucopyranosido(13) -D-xylopyranosido(12) -L-rhamnosido(14)--D-xylopyranoside (13) of oleanolic acidKhimiya Prirodnykh Soedinenii, Vol. 5, No. 2, pp. 84–89, 1969     

The electronic spectrum of acrylonitrile

The vapor absorption spectrum of acrylonitrile CH₂CHCN has been measured in the vacuum ultraviolet region. In addition, an all-valence-electron molecular orbital calculation has been used to calculate the electronic structure and spectrum of the molecule. On the basis of the MO calculation, as well as a vibrational analysis of the observed spectrum, several electronic transitions are assigned. The lowest energy absorption band (2107Å, = 150) is assigned as an n ^* transition. Absorption bands at 2030Å (=1600), 1725Å ( = 2100), and 1570Å ( = 1920) are assigned as 0–0 bands associated with transitions that are, respectively, ^*,^*, and ^* in character.

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Zusammenfassung Das UV-Absorptionsspektrum von dampfförmigen Acrylnitril wurde gemessen und eine CNDO/2-Rechnung für die Elektronenstruktur durchgeführt. Auf dieser Basis konnten unter Zuhilfenahme der Analyse der Schwingungsstruktur im beobachteten Spektrum mehrere Banden zugeordnet werden: die 2107-Å-Bande ( = 150) einem n^*-Übergang, die drei Banden bei 2030Å ( = 1600), 1725Å ( = 2100) und 1570 Å ( = 1920)0-0-Übergängen von ^*-, ^*- bzw. ^*-Banden.

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Résumé Mesure du spectre d'absorption en phase vapeur de l'acrilonitrile CH₂CHCN dans la région de l'ultraviolet. Par ailleurs, la structure électronique et le spectre de la molécule ont été calculés à l'aide d'une méthode des orbitales moléculaires semi-empirique pour tous les électrons de valence. Sur cette base, ainsi que sur une analyse vibrationnelle du spectre expérimental, on procède à l'attribution de plusieurs transitions électroniques. La bande d'absorption de plus basse énergie (2107 Å, = 150) est attribuée à une transition n ^*. Les bandes d'absorption à 2030Å ( = 1600), 1275Å ( = 2100) et 1570Å ( = 1920) sont considérées comme des bandes 0 - 0 associées à des transitions ^*, ^* et ^* respectivement.

     

Quantum-chemical calculations and interpretations of electronic spectra of phthalocyanines of transition metals and of their ionic forms

The INDO/S method with Zerner's parametrization has been used to calculate the energies and intensities of electronic transitions for a number of metallophthalocyanines of transition metals and their negatively charged ions: CoPC, FePC·L₂, MnPC·L₂, CoPC^–, FePC^–, MnPC^–·L₂, FePC^2–, FePC^–·L₂, and COPC^2– (PC is the macrocyclic phthalocyanines ligand, and L the molecules of axial ligands, in the present instance ammonia molecules). It is shown that within an isoelectronic series of compounds, having the same total number of electrons and the same disposition of pairs of d orbitals, the laws governing the changes in the electronic spectra, related to changes in the d- interactions, can be described theoretically by allowing for configuration interactions of doubly excited configurations in the basis. It is established that in the visible and near UV and IR regions of the spectrum the allowed electronic transitions in compounds of an isoelectronic series, corresponding to an uncharged state of the phthalocyanine ligand, consist of a superposition of the ^* configuration (2a_1u 6e_g) and two types of intramolecular CT configurations: (d 3b_1u) and the double excitation (2a_1u, d 6e_g, 6e_g). Data are obtained for the energy levels of the even electronic states which are responsible for the rapid radiationless deactivation of excited molecules of the phthalocyanines of transition metals.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 651–658, November–December, 1990.     

PPP and CNDO calculations for protonated molecules

CNDO calculations have been used to obtain the one-centre core integrals for protonated azines required in calculating the ^* absorption spectra of such molecules using the PPP method. Calculated spectra for both the parent and the protonated molecules are obtained in satisfactory agreement with experiment. The changes in the -framework of the molecules on protonation are also discussed in terms of the CNDO results.

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Zusammenfassung CNDO-Rechnungen wurden benutzt, um die Einzentren-Rumpf-Integrale für protonierte Azine zu erhalten, die bei der Berechnung der ^* -Absorptionsspektren mit Hilfe der PPP-Methode benötigt werden.Die berechneten Spektren für die Ausgangsmoleküle und die protonierten Moleküle sind in zufriedenstellender Übereinstimmung mit dem Experiment. Die Veränderungen im -Rumpf der Moleküle bei der Protonierung werden ebenfalls mit Hilfe der CNDO-Resultate diskutiert.

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Résumé Des CNDO ont tét utilisés pour obtenir les intégrales de coeur monocentriques des azines protonées nécessaires au calcul de leur spectre d'absorption ^* par la méthode PPP. Les spectres calculés pour les molécules protonées ou non sont en accord satisfaisant avec l'expérience. Les modifications subies lors de la protonation par le squelette sont discutées en fonction des résultats des calculs CNDO.

     

Conjugated radicals

Restricted open shell CNDO calculations have been carried out on butadiene anion radical (M_–), butadiene cation radical (M⁺), and butadiene dimer cation radical (M ₂ ⁺ ). Calculated transition energies are in agreement with the experimental data. Formation of M ₂ ⁺ and unsuccessful attempts to detect M ₂ ^– have been interpreted by the CNDO and extended Hückel calculations, in light of which the M + M⁺ M ₂ ⁺ process is energetically favourable while the M + M^– (M ₂ ^– ) process is connected with an energy loss. CNDO calculations support the assumed sandwich structure of M ₂ ⁺ .

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Zusammenfassung Restricted open shell CNDO-Rechnungen für das Butadien-Radikalanion (M^–), das Butadien-Radikalkation (M⁺) und das dimere Butadien-Radikalkation (M ₂ ⁺ ) wurden durchgeführt. Die berechneten Übergangsenergien stimmen mit den experimentellen Daten überein. Die Bildung von M ₂ ⁺ einerseits und die erfolglosen Versuche, das dimere Radikalanion M ₂ ^– herzustellen, andererseits wurden mittels CNDO- und EHT-Berechnungen gedeutet. Es zeigte sich hierbei, daß der Prozeß M + M⁺ M ₂ ⁺ energetisch möglich sein, die Reaktion M + M ₂ ^– M ₂ ^– dagegen mit einem Energieverlust ablaufen sollte. Die CNDO-Rechnungen sprechen für die Annahme einer Sandwich-Struktur von M ₂ ⁺ .

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Résumé On a effectué des calculs avec restricted open shell d'après la méthode CNDO sur l'anion radical du butadiène (M^–) sur le cation radical du butadiene (M⁺) et sur le cation radical du dimère du butadiène (M ₂ ⁺ ). Les énergies de transition calculées sont en accord avec les données expérimentales. La formation de M ₂ ⁺ et les efforts sans succès à prouver la présence de M ₂ ⁺ ont été interprétés par la méthode de CNDO et par les calculs étendus d'après Hückel. De ce point de vue le procès M + M⁺ M ₂ ⁺ est énergétiquement favorable pendant que le procès M + M^– M ₂ ^– est accompagné d'une perte d'énergie. Les calculs d'après la méthode de CNDO soutiennent la structure supposée deM ₂ ⁺ .

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Part XI: ársky, P., Hobza, P., Zahradnik, R.: Collect. Czechoslov. Chem. Commun., in press.     

Error of Atomic Charges Derived from Electrostatic Potential

The purpose of this article is to show that CHELP, CHELPG, and Merz and Kollman undergo error for the charge on atoms of HCOO^– (H₂O) _n for n = 1 6. We also demonstrate that the CHELP, CHELPG, and Merz and Kollman show error for the tendency toward change in the charges on carbons for CH₃NH⁺ ₃ (CH₃)₂NH⁺ ₂ (CH₃)₃NH⁺ (CH₃)₄N⁺.     

UV spectra and basicity constants of 2-substituted quinoxalines

The UV spectra of the bases and cations of a number of 2-substituted quinoxaline derivatives were investigated, and their basicity constants were determined. The investigated compounds were divided into two series, characterized, respectively, by ortho and meta orientations of the substituent and cationoid center, on the basis of correlations of the pKa values with the Hammett—Taft constants. The effect of the position of the protonation center relative to the substituent on the energy of the ^* transitions was examined within the framework of the simple MO LCAO method. The results of the calculations are compared with the experimentally observed shift in the¹L_b band in the UV spectra of some 2-substituted quinoxalines on passing from the bases to the monocations.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 398–403, March, 1973.     

A structural investigation of a D-glucan fromYersinia pseudotuberculosis of serotype VI

It has been established that an -D-glucan isolated fromYersinia pseudotuberculosis, serotype VI, is branched and contains -14- and -16-bound D-glucopy-ranose residues in the main chain and the side chains, respectively.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostock. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 151–154, March–April, 1981.     

Calculation of σ→π* and π→σ* transitions in vinylboranes

Calculations are presented of the energies of the ground and excited and electronic states of ethylene and substituted vinylboranes. The Pople-Segal-Santry method was employed throughout. It is concluded that the excited state of lowest energy in ethylene has * character whilst the lowest energy ultra-violet spectral bands of the latter compounds stem from ^* transitions.

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Zusammenfassung Valenzelektronenrechnungen nach Pople-Segal-Santry wurden für Äthylen und Vinylborane durchgeführt. Danach hat der niedrigste angeregte Zustand von Äthylen ^*-Charakter, während die längstwellige UV-Bande der Vinylborane einem ^* -Übergang entspricht.

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Résumé Calculs de l'énergie pour les états fondamentaux et excités et de l'éthylène et des vinylboranes substitués. Utilisation de la méthode de Pople-Ségal-Santry. L'état excité le plus bas pour l'éthylène résulte d'une transition ^* , alors qu'il résulte d'une transition ^* pour les vinylboranes.