Gibberellins and related substances

Conclusions 1. A study of the gibberellin-like substances of the leaves of tobaccoN. tabacum has shown that the latter contains gibberellin A₃ and possibly A₆ in the free state.The amount of GA₃ in the leaves of this plant is approximately 0.2–2 µg/kg.2. In addition, tobacco leaves contain neutral gibberellin-like substances in the bound form which are liberated on hydrolysis.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 296–304, 1969     

Co-hydrolysis products of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions: Part 2 [1]

²⁹Si NMR peaks due to species with the double four-membered ring siloxane backbone composed of both Si(O^–)_4/2 and CH₃Si(O^–)_3/2 units, (CH₃) _n Si₈O _{20 – n} ^{/(8 – n) –} (n=1–3), formed by co-hydrolysis of tetraethoxysilane and methyltriethoxysilane in the presence of tetramethylammonium ions in methanol have been assigned. It has been found that ²⁹Si NMR peaks due to Si(OSi)₃(O^–) units shift to lower frequencies by replacement of the adjacent Si(O^–)_4/2 units by CH₃Si(O^–)_3/2 units, in other words, with increasing m value in Si[OSi(O^–)₃]_{3 – m} [OSi(CH₃) (O^–)₂] _m (O^–) (m=0–2). Peaks from CH₃ Si(OSi)₃ units in the species have also appeared as separated due to the kind of neighbor structural units. On the basis of the assignments, positions of CH₃Si(O^–)_3/2 units in the cubic octameric siloxane framework of (CH₃) _n Si₈O _{20 – n} ^{/(8 – n) –} (n=2, 3), for both of which three isomers are present, have been estimated.     

The alkaloids ofStephania glabra

Summary l-Tetrahydropalmatine and stepharine have been isolated from the tubers ofStephania glabra obtained from India, andl-tetrahydropalmatine and cycleanine have been isolated from the tubers ofStephania cultivated on the Black Sea littoral of the Caucasus.The epigeal parts of the plant cultivated on the Black Sea littoral of the Caucasus have given cycleanine and an alkaloid A of composition C₁₉H₂₁O₄N the study of which is proceeding.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 4, pp. 271–275, 1965     

Alkaloids ofCorydalis pseudoadunca andC. gortschakovii

Conclusions From two species ofCorydalis with different growth sites 11 bases were obtained.FromC. pseudoadunca, collected in the Alai Valley, d-bicuculline, d--hydrastine,l-adlumidine, l-scoulerine, coramine, and protopine were isolated; fromC. pseudoadunca, collected in the Pamir d--hydrastine, protopine, d-bicuculline, coramine, andl-scoulerine; and fromC. gortschakovii, collected in the western Tien-Shan, isocorydine, protopine, sendaverine, d-bicuculline,l-adlumine, and a base with mp 240–242° C.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 4, pp. 438–440, 1970     

New glycosides from the holothurian Cucumaria japonica

Four new compounds have been isolated from the fraction of weakly polar triterpene glycosides of the holothurianCucumaria japonica: cucumariosides A₁-2 (I), A₀-1 (II), A₀-2 (III), and A₀-3 (IV). The structures of these substances have been established by chemical and physical methods.Deceased.Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 242–248, March–April, 1993.     

Energy levels and crystal-field calculations of trivalent ytterbium in yttrium aluminum garnet and yttrium gallium garnet

The splitting of the two ² F states of Yb³⁺:YAlG and Yb³⁺:YGaG, have been determined from fluorescence and absorption spectra at low temperatures. The levels of the ground states of Yb³⁺: YAlG are at: 0, 388, 613, 778 cm^–1, those of Yb³⁺: YGaG at 0, 308, 567, and 672 cm^–1. Crystal field calculations yield the following values for Yb³⁺:YAlG; A ₂ ⁰ =270 cm^–1, A ₄ ⁰ =–165 cm^–1, A ₄ ⁴ =–1155 cm^–1, A ₀ ⁶ =21 cm^–1, A ₄ ⁶ =–304 cm^–1 and for Yb³⁺:YGaG: A ₀ ² =110 cm^–1, A ₀ ⁴ =–125 cm^–1, A ₄ ⁴ =–1250 cm^–1, A ₀ ⁶ =10 cm^–1 and A ₄ ⁶ =–142 ^–1 A satisfactory agreement has been found for calculated and observed splitting patterns.

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Zusammenfassung Die Aufspaltung der ² F-Zustände von Yb³⁺:YAlG(I) und Yb³⁺:YGaG (II) wurde bei tiefen Temperaturen aus Fluoreszenz- und Absorptionsspektren bestimmt. Die Niveaus des Grundzustandes von (I) liegen bei 0, 388, 613, 778 ^–1, die von (II) bei 0, 308, 567 und 672 ^–1. Die Ligandenfeldtheorie ergibt folgende Werte für die Kristallfeldparameter: für (I) A ₂ ⁰ =270 cm^–1, A ₄ ⁰ =–165 cm^–1, A ₄ ⁴ =–1155 cm^–1, A ₀ ⁶ =21 cm^–1, A ₄ ⁶ =–304 cm^–1 unf für (II) A ₀ ² =110 cm^–1, A ₀ ⁴ =–125 cm^–1, A ₄ ⁴ =–1250 cm^–1, A=10 cm^–1 and A ₄ ⁶ =–142 ^–1. Die Übereinstimmung zwischen berechneter und beobachteter Aufspaltung war befriedigend.

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Résumé La division, par le champ de ligandes, des états ² F _7/2 et ² F _5/2 dans Yb³⁺:YAlG et Yb³⁺:YGaG a été déterminée des spectres de fluorescence et d'absorption. Les sous-niveaux de l'état fordamental se situent à 0, 388, 613, 778 cm^–1 dans Yb³⁺:YAlG, à 0, 308, 567, 672 cm^–1 Yb³⁺: YGaG. Le calcul fournit les valeurs suivantes pour les paramètres: Yb³⁺: YAlG A ₂ ⁰ =270 cm^–1, A ₄ ⁰ =–165 cm^–1, A ₄ ⁴ =–1155 cm^–1, A ₀ ⁶ =21 cm^–1, A ₄ ⁶ = -304 cm^–1 Yb³⁺:YGaG: A ₀ ² =110 cm^–1, A ₀ ⁴ =–125 cm^–1, A ₄ ⁴ =–1250 cm^–1, A ₀ ⁶ =10 cm^–1 et A ₄ ⁶ =–142 ^–1. L'accord entre les spectres calculé et observé est satisfaisant.

     

Structures of four new triterpene glycosides from the holothurian Cucumaria japonica

Four new triterpene glycosides of the holostane series have been isolated from an alcoholic extract of the economically important Pacific Ocean holothurianCucumaria japonica: cucumariosides A₁-2 (I), A₂-3 (II), A₂-4 (III), and A₄-2 (IV). The structures of these substances have been established by the methods of carbohydrate chemistry and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 787–793, November–December, 1990.     

Crystal-field studies of trivalent Thulium in Yttrium Aluminum Garnet

CF parameters have been calculated from the splitting of some of the manifolds of Tm³⁺ in Yttrium Aluminum Garnet (YAlG). Values of these parameters are: A ₂ ⁰ =270 cm^–1, A ₂ ² =± 95 cm^–1, A ₄ ⁰ =–170 cm^–1, A ₄ ² =± 410 cm^–1, A ₄ ⁴ =–1020 cm^–1, A ₆ ⁰ =30 cm^–1, A ₆ ² =± 115 cm^–1, and A ₆ ⁴ =–475 cm^–1. There are indications that these parameters do not describe the splitting patterns of excited states with higher energy.

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Zusammenfassung Aus der Aufspaltung entarteter Zustände von Tm³⁺ in YAlG sind Kristallfeldparameter berechnet worden. Die Werte dieser Parameter sind: A ₂ ⁰ =270 cm^–1, A ₂ ² =± 95 cm^–1, A ₄ ⁰ =–170 cm^–1, A ₄ ² =± 410 cm^–1, A ₄ ⁴ =–1020 cm^–1, A ₆ ⁰ =30 cm^–1, A ₆ ² =± 115 cm^–1, und A ₆ ⁴ =–475 cm^–1. Es gibt Anzeichen dafür, daß diese Parameter nicht das Aufspaltungsmuster angeregter Zustände höherer Energie beschreiben.

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Résumé On a calculé les paramètres du champ cristallin à partir de la séparation obtenue par levée de dégénerescence pour les niveaux de Tm³⁺ dans le grenat d'yttrium aluminium (YAlG). Les valeurs de ces paramètres sont: A ₂ ⁰ =270 cm^–1, A ₂ ² =±95 cm^–1, A ₄ ⁰ =–170 cm^–1, A ₄ ² = ± 410 cm^–1, A ₄ ⁴ =–1020 cm^–1, A ₆ ⁰ =30 cm^–1, A ₆ ² =± 115 cm^–1 et A ₆ ⁴ =–475 cm^–1. Il existe des indications selon lesquelles ces paramètres ne décrivent pas l'aspect des séparations des états excités d'énergies plus élevées.

     

Alkaloids of Stephania hernandifolia VI. Hernandifoline

Summary A new hasubanan alkaloid with the composition C₂₉H₃₃O₉N, mp 128–129°C₉ from ether), [] _D ²⁰ – 25° (c 2; ethanol) containing an ester group has been isolated from the herbStephania hernandifolia and has been called hernandifoline.All-Union Scientific-Research Institute for Medicinal Plants. Translated from Khimiya Prirodynkh Soedinenii, No. 2, pp. 158–164, March, 1971.     

The structure of gummosin

Summary From the neutral fraction of an acetone extract of the roots of plants of the genusFerula,F. gummosa Boiss.,F. pseudoreoselinum Rgl. et Schmalh. (K-Pol.) andF. Samarkandica Eug. Kor., we have isolated a coumarin gummosin with the composition C₂₄H₃₀O₄, mp 176–177°C, [a]_D –54°C. The structure of gummosin corresponds to formula (III).With respect to structure, gummosin is a spatial isomer of farnesiferol A; it differs from the latter by the fact that the secondary OH group in gummosin is axial.Khimiya Prirodynkh Soedinenii, Vol. 2, No. 6, pp. 383–387, 1966     

A study of the alkaloids of plants of the genusStephania

Summary Four alkaloids have been isolated from the tubers ofStephania glabra (Roxb.) Miers. (synonymSt. rotunda Lour.) collected in the Democratic Republic of Vietnam:l-tetrahydropalmatine and three previously undescribed bases (A -C₁₉H₁₈O₂N, C - C₂₀H₂₅O₄N, and D -C₂₁H₂₅O₄N).Khimiya Prirodnykh Soedinenii, Vol. 1, No. 6, pp. 392–394, 1965.The substances in this paper are denoted by letters. The novelty of these substances has not been established, which contradicts the rules of this journal. The paper is printed as an exception (Editiorial Board).     

The structure and dynamic properties of mixed adsorption and penetration layers of α-dipalmitoylphosphatidylcholine/β-lactoglobulin at water/fluid interfaces

The interfacial tensions of mixed α-dipalmitoylphosphatidylcholine (DPPC)/β-lactoglobulin layers at the chloroform/water interface have been measured by the pendent drop and drop volume techniques. In certain intervals, the adsorption kinetics of these mixed layers was strongly influenced by the concentrations of both protein and DPPC. However, at low protein concentration, C_{β-lactoglobulin}=0.1 mg l⁻¹, the adsorption rate of mixed interfacial layers was mainly controlled by the variation of the DPPC concentration. As C_{β-lactoglobulin} was increased to 0.8 mg l⁻¹, the interfacial activity was abruptly increased, and within the concentration range of C_DPPC=10⁻⁴–10⁻⁵ mol l⁻¹, the DPPC has very little effect on the whole adsorption process. In this case, the adsorption rate of mixed layers was mainly dominated by the protein adsorption. This phenomenon also happened as the protein concentration was further increased to 3.6 mg l⁻¹. When C_DPPC>3 · 10^–5 mol l⁻¹, the adsorption behaviour was very similar to that of the pure DPPC although the protein concentration was changed. The equilibrium interfacial tensions of the mixed layers are dramatically effected by the lipid as compared to the pure protein adsorption at the same concentration. It reveals the estimation of which composition of lipid and protein decreases the interfacial tension. The combination of Brewster angle microscopy (BAM) with a conventional LB trough was applied to investigate the morphology of the mixed DPPC/β-lactoglobulin layers at the air/water interface. The mixed insoluble monolayers were produced by spreading the lipid at the water surface and the protein adsorbed from the aqueous buffer subphase. The BAM images allow to visualise the protein penetration and distribution into the DPPC monolayer on compression of the complex film. It is shown that a homogeneous distribution of β-lactoglobulin in lipid layers preferentially happens in the liquid fluid state of the monolayer while the protein can be squeezed out at higher surface pressures.     

Solid-state structure of (+)-phendimetrazine bitartarate,an anorexic drug

The anorexic drug (+)-(2S, 3S, 4S)-phendimetrazine-2R, 3R)-bitartarate crystallized in the orthorhombic space groupP2₁2₁2₁ and at 293 Ka=7.7710(4),b=13.1379(7),c=15.9913(9) Å,V=1632.6(2) ų,Z=4,R(F)=0.062, andR _w (F)=0.026. A chair conformation 2,3-trans-1,4-oxazine ring with equatorially oriented 2-phenyl,3-methyl, andN-methyl substituents was found as predicted by an earlier reported solid-state CP-MAS¹³C-NMR investigation of crystalline (±)-phendimetrazine bitartarate. The O-CH₂-CH₂-N torsion angle of –58.4(6)° in the solid-state agrees nicely with the 56.0(7)° dihedral angle value estimated by¹H NMR spectroscopy for the major (equatorialN-methyl) phendimetrazine mesylate species in CD₂Cl₂ solution. A common solid-state conformational arrangement was found for (+)-phendimetrazine and a series of six other anorexic drugs structurally analogous to (+)-(2S, 3S)-pseudoephedrine. In this arrangement, NCH(Me)CPh has (S)-configuration, there is a (–)-gaucheMe-CH-C-Ph torsion angle, an antiperiplanarN-CH-C-Ph torsion angle, and the phenyl ring approximately eclipses the C-H bond of the attached carbon (e.g., H-C-C_ipso-C_ortho ca. 4° for 2,3-transphendimetrazine). Nonbonded interactions involving the 3-methyl and the 2-phenyl groups open up the H-C-C_ipso-C_ortho angle in a series of solid-state structures containing the epimeric (–)-(2R, 3S)-ephedrine moiety (e.g., ca. 45° for molecular mechanics calculated 2,3-cis-phendimetrazine model).     

Alkaloids of Fumaria vaillantii structure of vaillantine

Summary The plantFumaria vaillantii Loisl. has yielded protopine, fumaridine, fumaramine, d--hydrastine,l-adlumine, d-bicuculline, andl-adlumidine (this being the first time thatl-adlumidine has been isolated from the genusFumaria), and the new base vaillantine. On the basis of UV, IR, NMR, and mass spectra, and also the identity of O,O-dimethylvaillantine with muramine, the structure of vaillantine has been established as 2,3-didemethylmuramine.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 476–478, July–August, 1974.     

First and second dissociation constants of deuterio-o-phthalic acid in D2O from 5 to 50°C

The first and second dissociation constants of deuterio-o-phthalic acid in deuterium oxide have been determined by the emf method over the temperature range of 5 to 50°C. The pD values for potassium deuterium phthalate have been calculated from these two constants and experimentally verified. The thermodynamic properties for the dissociation of deuterio-o-phthalic acid have been evaluated. At 25°C, these values in the molality scale are: pK _1A =3.505, pK _2A =5.890, and pD=4.518. From K _1A and K _2A , respectively: G ^o =20.003, 33.582 kJ-mol^–1; H ^o =2.851, 2.208 kJ-mol^–1; S ^o =–76.7, –105.2 J-mol^–1-K^–1; and C _p ^o =–52.7, –315.6 J-mol^–1-K^–1. The isotope effect is discussed.     

Copper(II) Cyanoacetate Polymer: Synthesis and Structure

A new copper carboxylate polymer with cyanoacetate anion as a ligand was synthesized and studied using X-ray diffraction, IR, and EPR spectroscopy. The crystal is tetragonal: a= 14.702(2) Å, c= 13.470(3) Å, Z= 8, space group I4₁/a, and R= 0.0634. The copper atoms in the centrosymmetric dimeric fragment have a square-pyramidal surrounding with the CuO₄N coordination core and are joined through four bidentate bridging anions of cyanoacetic acid Cu(1)"–O(1A) 1.931(4) Å, Cu(1)"–O(1B) 1.926(4) Å, Cu(1)–O(2B) 2.018(3) Å, Cu(1)–O(2A) 2.036(4) Å, and Cu(1)–N(1A)" 2.206(5) Å). The Cu···Cu" distance in the dimer is 2.709 Å. The copper atom is extended from the mean equatorial plane toward the axial nitrogen atom by 0.23 Å. EPR data confirm strong antiferromagnetic interaction (2J –275 cm^–1) between the copper(II) ions of the dimeric fragment, whereas the interaction between the dimers is significantly weaker (J< 0.3 cm^–1).     

Phospholipase A2 from the venom of the spider Eresus niger

A phospholipase A₂ with a molecular mass of 12–14 kDa has been isolated from the venom of the spiderEresus niger by three-stage column chromatography. Asparagine has been identified as the N-terminal amino acid.Institute of Physiology, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 557–560, July–August, 1991.     

Crystal structures and spectroscopic properties of copper(II) pseudohalide complexes with two sparteine epimers, having a CuN4 chromophore

Tetrahedrally distorted copper(II) sparteine pseudohalide complexes having a CuN₄ chromophore were prepared and characterized by various spectroscopic techniques and X-ray crystallography. Among them, the crystal structures of copper(II) isothiocyanate complexes with two sparteine epimers, (−)-l-sparteine (Sp) and (−)-α-isosparteine (α-Sp), were determined. The N_Sp–Cu–N_Sp plane in copper(II) (−)-l-sparteine isothiocyanate [Cu(Sp)(NCS)₂] and copper(II) (−)-α-isosparteine isothiocyanate [Cu(α-Sp)(NCS)₂] is twisted by 58.2(6)° and 52.2(9)°, respectively, from the N_NCS–Cu–N_NCS plane. Based on the values of the dihedral angles and tilted distances of these two complexes, the geometry around Cu(II) in Cu(α-Sp)(NCS)₂ is more distorted from the perfect tetrahedron than that in Cu(Sp)(NCS)₂. For copper(II) sparteine pseudohalide (NCS⁻ and N₃⁻) complexes having a CuN₄ chromophore, the EPR and the optical spectral data were collected. The results of X-ray crystallography and ESR spectroscopy are in a good agreement with the assumption that the degree of distortion from planarity to tetrahedron will reduce the A_|| value of four-coordinate copper(II) sparteine pseudohalide complexes.     

Kinetics of the thermal decomposition of [Co(NH3)6]2(C2O4)3·4H2O

The thermal decomposition of [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O was studied under isothermal conditions in flowing air and argon. Dissociation of the above complex occurs in three stages. The kinetics of the particular stages thermal decomposition have been evaluated. The R_N and/or A_M models were selected as those best fitting the experimental TG curves. The activation energies,E, and lnA were calculated with a conventional procedure and by a new method suggested by Kogaet al. [10, 11]. Comparison of the results have showed that the Arrhenius parameters values estimated by the use of both methods are very close. The calculated activation energies were in air: 96 kJ mol^–1 (R_1.575, stage I); 101 kJ mol^–1 (Ain1.725 stage II); 185 kJ mol^–1 (A _2.9, stage III) and in argon: 66 kJ mol^–1 (A _1.25, stage I); 87 kJ mol^–1 (A _1.825, stage II); 133 kJ mol^–1 (A _2.525, stage III).