Metallation of Ligands with Biological Activity: Synthesis and X‐Ray Characterization of [UO2(PN)2(H2O)]Cl2{PN = vitamin B6 pyridoxine[2‐methyl‐3‐hydroxy‐4, 5‐bis(hydroxymethyl) pyridine]}

Chloridrate of pyridoxine (vitamin B₆) reacts with UO₂(NO₃)₂·6H₂O in acetonitril containing triethylamine to give the complex salt [UO₂(PN)₂(H₂O)]Cl₂. The structure of the novel compound was analyzed by single crystal X‐ray diffraction affording the centrosymmetric triclinic space group . In [UO₂(PN)₂(H₂O)]²⁺ two zwitterionic pyridoxine molecules complex the uranium atom in a planar manner with a water molecule achieving the coordination of a semi planar pentagon. The two uranyl oxo ligands set the axis of a distorted pentagonal bipyramide. The ability of vitamin B₆ pyridoxine to react with UO₂²⁺ allowing the chelation of one uranium atom represents a very specific model of assimilation of uranium by living beings. It could also explain the serious damages caused by heavy or radioactive metals like uranium since their complexation “in vivo” by enzymatic systems like pyridoxal phosphate‐containing enzymes would lead to a modification of the prosthetic groups of the metalloenzymes with loss of their catalytic activities.     

Total synthesis of thiostrepton. Assembly of key building blocks and completion of the synthesis

The completion of the total synthesis of thiostrepton (1) is described. The synthesis proceeded from key building blocks 2-5, which were assembled into a growing substrate that finally led to the target molecule. Thus, the dehydropiperidine peptide core 2 was, after appropriate manipulation, coupled to the thiazoline-thiazole fragment 3, and the resulting product was advanced to intermediate 11 possessing the thiazoline-thiazole macrocycle. The bis-dehydroalanine tail equivalent 4 and the quinaldic acid fragment 5 were then sequentially incorporated, and the products so obtained were further elaborated to forge the second macrocycle of the molecule. Several roadblocks encountered along the way were systematically investigated and overcome, finally opening the way, through intermediates 20, 32, 44, 45, and 46, to the targeted natural product, 1.     

Reactivity of radicals generated on irradiation of trans-[Ru(NH3)4(NO2)P(OEt)3](PF6)

The electronic absorption spectrum of trans-[Ru(NH(3))(4)(NO(2))(P(OEt)(3)](+) in aqueous solution is characterized by a strong absorption band at 334 nm (lambda(max) = 1800 mol(-1) L cm(-1)). On the basis of quantum mechanics calculations, this band has been assigned to a MLCT transition from the metal to the nitro ligand. Molecular orbital calculations also predict an LF transition at 406 nm, which is obscured by the intense MLCT transition. When trans-[Ru(NH(3))(4)(NO(2))(P(OEt)(3)](+) in acetonitrile is irradiated with a 355 nm pulsed laser light, the absorption features are gradually shifted to represent those of the solventocomplex trans-[Ru(NH(3))(4)(solv)(P(OEt)(3)](2+) (lambda(max) = 316 nm, epsilon = 650 mol(-1) L cm(-1)), which was also detected by (31)P NMR spectroscopy. The net photoreaction under these conditions is a photoaquation of trans-[Ru(NH(3))(4)(NO(2))(P(OEt)(3)](+), although, after photolysis, the presence of the nitric oxide was detected by differential pulse polarography. In phosphate buffer pH 9.0, after 15 min of photolysis, a thermal reaction resulted in the formation of a hydroxyl radical and a small amount of a paramagnetic species as detected by EPR spectroscopy. In the presence of trans-[Ru(NH(3))(4)(solv)P(OEt)(3)](2+), the hydroxyl radical initiated a chain reaction. On the basis of spectroscopic and electrochemical data, the role of the radicals produced is analyzed and a reaction sequence consistent with the experimental results is proposed. The 355 nm laser photolysis of trans-[Ru(NH(3))(4)(NO(2))(P(OEt)(3)](+) in phosphate buffer pH 7.4 also gives nitric oxide, which is readily trapped by ferrihemeproteins (myoglobin, hemoglobin, and cytochrome C), giving rise to the formation of their nitrosylhemeproteins(II), (NO)Fe(II)hem.     

Beiträge zur Analyse nuklearer Rohmaterialien. XV

Zusammenfassung Ein Verfahren zur Bestimmung von mg-Mengen Uran in Natriumdiuranaten wurde beschrieben. Bei dieser Methode wird die Analysenprobe in Mineralsäuren gelöst und danach das Uran nach seiner Reduktion mittels Eisen(II)-Sulfat in phosphorsaurer Lösung titrimetrisch bestimmt, und zwar mittels Standardkaliumdichromatlösung in Gegenwart von Bariumdiphenylaminsulfonat als Indikator. Dieses Titrationsverfahren ist auch zur Uranbestimmung sehr geeignet nach dessen Abtrennung mittels Anionenaustausches in einem gemischt wäßrig-organischen Lösungsmittelsystem aus 50 Vol.% Tetrahydrofuran, 40 Vol.% Methylglykol und 10 Vol.% 6-m Salzsäure. Die Methode wurde zur Bestimmung des Urans in zahlreichen Yellow-Cake-Proben aus Mexiko herangezogen, in denen Urangehalte zwischen 57 und 71% U₃O₈ ermittelt wurden.

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Contributions to the analysis of nuclear raw materials. XV

Summary A procedure to determine mg amounts of uranium in sodium diuranate samples was described. In this method the sample is dissolved in mineral acids and the uranium then determined titrimetrically after its reduction by means of ferrous sulfate in phosphoric acid solution. The titration was performed with standard potassium dichromate solution in the presence of barium diphenylamine sulphonate as indicator. This titration procedure is also very suitable for determination of uranium after its separation by means of anion exchange in a mixed aqueous-organic solvent system of 50 vol% tetrahydrofuran, 40 vol% methylglycol and 10 vol% 6M hydrochloric acid. The method was used to determine the uranium in numerous yellow-cake samples from Mexico; uranium contents between 57% and 71% U₃O₈ were found.

     

A two-parameter spectral theorem

Summary We study the characteristic set of a couple (A, B) of selfadjoint compact operators on a real Hilbert spaceH. We prove thatC is the union of a sequence of characteristic curvesC _n in the (, ) plane. Each curve is the analytic image of an open interval and it is either closed or it goes to infinity at both ends of the interval. Moreover, it may intersect either itself or other characteristic curves in an at most countable set of points, which may accumulate only at infinity. Finally, to each characteristic curve one can associate an analytic function E_n, which gives the eigenprojection onto the eigenspace attached to each point of the characteristic curve, except at the intersection points, where the eigenspace is the direct sum of the projection relevant to each branch passing through the point. The dimension of the eigenprojection is constant along each curve and it is called the multiplicity of the characteristic curve.     

Acyl complexes of molybdenum: structural and reactivity studies

The following structural peculiarities of the agostic acyl structure ₂R) (R = H, SiMe₃) and some characteristic chemical reactivity of the M-η²-acyl and iminoacyl linkage are described. (i) A structural comparison of the bonding parameters within three agostic acetyl Mo complexes containing the dithioacid ligand, indicates that the agostic interaction strengthens upon increasing the electron-releasing properties of the S-chelating ligand. (ii) The acyl-xanthate complex Mo(C(O)Me)(S₂COR)(CO)(PMe₃)₂ undergoes loss of a sulfur atom from the coordinated xanthate and coupling with the acyl ligand to form complexes containing coordinated alkoxythiocarbonyl and monothioacetate ligands. The latter can be metathetically replaced by KS₂COR. (iii) Upon heating at 70°C η²-acyl-dicarbonyl bispirazolilborate complexes of molybdenum of the type Mo(H₂B(pz^*)₂)(η²-C(O)Me)(CO)₂(PMe₃) (pz^* = 3,5-dimethyl-pyrazol-1-yl) yield functionalized acyl ligands derived from the stereo- and regioselective intramolecular addition of one of the B---H bonds of the H₂B(pz^*)₂ group across the C=O moiety of the η²-acyl group. (iv) The η²-acyl-isocyanide complexes {Mo}(η²-C(O)R)(CNR′) ({Mo} = Mo(H₂B(pz^*)₂)(CO)(PMe₃)) undergo irreversible thermal isomerization to the corresponding η²-iminoacyl-carbonyl derivatives {MO}(η²-C(NR′)R)(CO). This isomerization reaction follows first-order kinetics.     

Oxidative behaviour of 3-aryl-2H-1,4-benzoxazines

Autoxidation of 3 - phenyl - 2H - 1,4-benzoxazine 8 gives 2 - hydroxy -3 - phenyl - 2H - 1,4-benzoxazine 13, 3 - phenyl - 2H - 1,4-benzoxazin - 2 - one 11, and 2 - phenylbenzoxazole 10 according to the conditions. Oxidation of 8 with DDQ in the presence of air gave mainly the bisacetal 17 but in the absence of air the major product was trans-Δ^2,2′-bi-(3-phenyl-2H-1,4-benzoxazine) 21a. Corresponding dimers were obtained from the 3-p-bromophenylbenzoxazine 9. The trans-isomers 21a and 22a are photochromic and change into their cis-isomers on exposure in solution to direct sunlight.     

Lanthanide complexes of new polyaminocarboxylate complexes with two chromophores derived from bispyrazolylpyridine and aceto or benzophenone: synthesis, characterization and photophysical properties

New ionophores derived from 2,6-bis(N-pyrazolyl)pyridine and aceto/benzophenone have been synthesized and fully characterized. The lanthanide complexes of these new ligands were studied from their UV-vis and fluorescence data. Eu³⁺ and Tb³⁺ complexes were easily formed and their photophysical properties measured. In all cases, lanthanide emission lifetimes were in the range of ms albeit quantum yields were relatively low. Possible flaws in the energy-transfer mechanisms are discussed.     

Photostability and photoprotection factor of boldine and glaucine

Boldine hydrochloride was more photounstable than boldine after irradiation with UVB (lambda = 300 nm). However, photoconsumption quantum yields, for glaucine hydrochloride (6.5 x 10(-2)) and boldine hydrochloride (6.7 x 10(-2)) in air, were quite similar. The photolysis was oxygen dependent in both cases, and the effect over the kinetics after the addition of 2,2,6,6-tetramethyl-1-piperidinyloxy suggested free radicals participation. The fact that the antioxidative capacity of boldine and boldine hydrochloride did not change during the photolysis, suggests that the phenolic structure remains unchanged in the photoproducts, corroborated with the photoproducts analysis. The photoprotection capacity was evaluated before and after irradiation. Results indicate that the values before irradiation are similar for all three compounds, only glaucine increasing its capacity with length of irradiation time.