Extraction-spectrophotometric and radiometric investigation of the ternary ion-association complex of niobium(V) with pyrocatechol and triphenyl-tetrazolium chloride

The optimum conditions for extraction of niobium(V) as a ternary ion-association complex with pyrocatechol and triphenyltetrazolium chloride(TTC) have been determined. The investigation of the composition has shown that the ratio Nb:proocatechol:TTC is 1:2:1 K_ex, K_D and have been determined radiometrically, using the chemical model. The influence of foreign ions on the extraction of the ion-association complex has been studied. A method for artifical mixture and steel containing niobium has been used.     

Synthese von Tetradecano-14-lacton durch Ringerweiterung

Synthesis of Tetradecano-14-lactone by Ring Enlargement The aldehyde 3 , prepared by ozonolysis of 2-allyl-2-nitrocyclododecanone, gave the ring-enlargement product 5 (85%) by treatment with (i-Bu)₂AlH. Its transformation to the tetradecano-14-lactone ( 8 ) via the aldol ester 6 and other routes (best is reduction with Bu₃SnH, AlBN, toluene) was difficult. Remarkable is the smooth denitrification of 3 (loss of HNO₂) to the conjugated dione 4 by chromatography on silica gel or base treatment.     

Synthesis,Structure and Impact of 5-Aminoorotic Acid and Its Complexes with Lanthanum(III) and Gallium(III) on the Activity of Xanthine Oxidase

The superoxide radical ion is involved in numerous physiological processes, associated with both health and pathology. Its participation in cancer onset and progression is well documented. Lanthanum(III) and gallium(III) are cations that are known to possess anticancer properties. Their coordination complexes are being investigated by the scientific community in the search for novel oncological disease remedies. Their complexes with 5-aminoorotic acid suppress superoxide, derived enzymatically from xanthine/xanthine oxidase (X/XO). It seems that they, to differing extents, impact the enzyme, or the substrate, or both. The present study closely examines their chemical structure by way of modern methods—IR, Raman, and ¹H NMR spectroscopy. Their superoxide-scavenging behavior in the presence of a non-enzymatic source (potassium superoxide) is compared to that in the presence of an enzymatic source (X/XO). Enzymatic activity of XO, defined in terms of the production of uric acid, seems to be impacted by both complexes and the pure ligand in a concentration-dependent manner. In order to better relate the compounds’ chemical characteristics to XO inhibition, they were docked in silico to XO. A molecular docking assay provided further proof that 5-aminoorotic acid and its complexes with lanthanum(III) and gallium(III) very probably suppress superoxide production via XO inhibition.     

p-n Multiplets and band-like structures in106Ag

The half-life of a 3^? excited state in¹⁰⁶Ag was measured as T_1/2 (364.4 keV)=0.9±0.1 ns using the¹⁰³Rh(α, n)¹⁰⁶Ag reaction. The intramultiplet transition rate B(M1, 3^?→2^?) indicates that the configuration π(g_9/2)₀ ^?2π(p_1/2)^?1 vd_5/2 can be assigned. A low-lying 3⁺ isomer, as known in^108,110Ag, was not found in¹⁰⁶Ag, what is explained by the raising energy of the vd_3/2 shell with decreasing neutron number. For the 6^? bandhead of a rotational-like structure T_1/2 (765.2 keV)< 0.2 ns was derived in contradiction to an earlier prediction (200 ns). Indirect evidence for a negative sign of the magnetic moment of¹⁰⁵Ag (g.s.) is obtained.     

Photoluminescent layered lanthanide silicates

The hydrothermal synthesis and structural characterization of layered lanthanide silicates, K(3)[M(1-a)Ln(a)Si(3)O(8)(OH)(2)] (M = Y(3+), Tb(3+); Ln = Eu(3+), Er(3+), Tb(3+), and Gd(3+)), named AV-22 materials, are reported. The structure of these solids was elucidated by single-crystal (180 K) and powder X-ray diffraction and further characterized by chemical analysis, thermogravimetry, scanning electron microscopy, (29)Si MAS NMR, and photoluminescence spectroscopy. The Er-AV-22 material is a room-temperature infrared phosphor, while Tb- and Eu-AV-22 are visible emitters with output efficiencies comparable to standards used in commercial lamps. The structure of these materials allows the inclusion of a second (or even a third) type of Ln(3+) ion in the framework and, therefore, the fine-tuning of their photoluminescent properties. For the mixed Tb(3+)/Eu(3+) materials, evidence has been found of the inclusion of Eu(3+) ions in the interlayer space by replacing K+ ions, further allowing the activation of Tb(3+)-to-Eu(3+) energy transfer mechanisms. The occurrence probability of such mechanisms ranges from 0.62 (a = 0.05) to 1.20 ms(-1) (a = 0.1) with a high energy transfer efficiency (0.73 and 0.84, respectively).     

Determination of the stereochemistry of rotenoids by1H-NMR spectroscopy in C6D6

The application of¹H-NMR spectroscopy in C₆D₆ for the determination of configurations at C_12a and C_6a in rotenoids is discussed.

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Bestimmung der Stereochemie von Rotenoiden mittels¹H-NMR-Spektroskopie in C₆D₆

Zusammenfassung Es wird die Anwendung der¹H-NMR-Spektroskopie in C₆D₆ zur Bestimmung der Konfigurationen an C_12a und C_6a in Rotenoiden diskutiert.

     

Structures of Ring-Enlargement Products

Crystal structures have been determined of methyl trans-1-hydroxy-6-nitro-3-oxobicyclo[4.4.0]decane-2-carboxylate ( 19 ), cis-3-methyl-6-nitro-2-oxabicyclo[4.4.0]decan-1-ol ( 2 ), cis-7-hydroxy-1-nitrobicyclo[5.4.0]undecan-9-one ( 13 ), and the medium-ring compounds 2-acetyl-4-nitrocyclooctanone ( 9 ), methyl 5-nitro-2-oxocyclooctane-carboxylate ( 4 ), 2-acetyl-4-nitrocyclononanone ( 11 ), 2-acetyl-4-nitrocyclodecanone ( 15 ), benzyl 5-nitro-2,11-dioxocycloundecanecarboxylate ( 24 ), methyl 5-nitro-2,12-dioxocyclododecanecarboxylate ( 21 ), and 8-nitro-11-oxo-13-tridecanolide ( 7 ), which are intermediates, side products, or end products of the ‘Zip’ ring-enlargement reaction. The conformations of most of the medium-ring compounds are very similar to equal-sized ring compounds previously determine by other authors.     

Preparation and stereochemical characterization of some N-acyl-[1]benzopyrano[3,4-c]pyrazole derivatives from rotenoids

Summary Several new N-acyl derivatives of 1-(4-hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-di methoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazole-1-ene have been prepared by appropriate chemical transformation of isohydrazones of rotenone and amorphigenin. A study of their¹H- and¹³C-NMR spectra confirmed the presence of the twocis 3a, 9b, 2 and 3a, 9b, 2 diastereomers in the parent isohydrazones and revealed the strong predominance of the conformers withendo orientation of the 3-NAc group. The conformations due to rotation about the 1,5-bond between rings C and D in the 4-OH and 4-O-substituted compounds were also determined by taking into account the anisotropic effect of aromatic rings A and D, and the hydrogen bond between 4-OH and the 2-N atom, as well as by inspecting the Dreiding models.

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Darstellung und stereochemische Charakterisierung einiger N-Acyl-[1]benzopyrano[3,4-c]pyrazol-Derivate von Rotenoiden

Zusammenfassung Mittels geeigneter chemischer Transformationen von Isohydrazonen von Rotenon und Amorphigenin wurden einige neue N-Acyl-Derivate von 1-(4-Hydroxy-2,3-dihydrobenzofuran-5-yl)-7,8-dimethoxy-1,9 b,2,3,3 a,4-hexahydro-[1]benzopyrano[3,4-c]pyrazol-1-en hergestellt. Eine Untersuchung ihrer¹H und¹³C-NMR-Spektren zeigt die Gegenwart von zweicis 3a, 9b, 2- und 3a, 9b, 2-Diastereomeren in den Ausgangs-Isohydrazonen und eine starke Bevorzugung der Konformeren mitendo-Orientierung der 3-NAc-Gruppe. Die Konformationen bezüglich der Rotation um die 1,5-Bindung zwischen Ring C und D werden für die 4-OH und 4-O-substituierten Verbindungen unter Berücksichtigung von Anisotropie-Effekten der aromatischen A- und D-Ringe, der Wasserstoffbrücken zwischen 4-OH und dem 2-N Atom und auch der Betrachtung der entspechenden Dreiding-Modelle diskutiert.

     

Transition probabilities and the structure of some negative-parity states in126,130Xe and132Ba

The lifetimes of several negative-parity states in^126,130Xe and¹³²Ba have been determined by means of the generalized centroid-shift method. The reactions^124,128Te(α,2n) and¹²²Sn(¹³C, 3n) have been used. Following results were obtained:T _1/2(2758 keV)=1.3±0.2 ns in¹²⁶Xe,T _1/2(2060 keV)=0.20±0.10 ns,T _1/2(2104 keV)=0.50±0.10 ns,T _1/2(2376 keV)=0.30±0.10 ns andT _1/2(2973 keV)=4.6±0.4 ns in¹³⁰Xe as well asT _1/2(2120 keV)=0.40 _?0.10 ^+0.20 ns in¹³²Ba. A systematics of the B(E2; 7 _? ¹ ?5 ₁ ^? ) values in theN=76 nuclei is presented. Electric dipole and quadrupole transition rates are discussed in terms of octupole and quadrupole collectivity. The structure of the 5 ₁ ^? and 7 ₁ ^? states is considered. Nuclear reactions:^124,128Te(α, 2 _n ),E=26 MeV,¹²²Sn (¹³C, 3n),E=53 MeV; measuredE _γ I _γ , γ-r.f. DeducedT _1/2, B(σL) in^126,130Xe and¹³²Ba. Ge detectors. Generalized centroid-shift analysis.