Reduced inorganic phosphorus in the natural environment: significance, speciation and determination

It is commonly assumed that phosphorus occurs almost exclusively in the environment as fully oxidized phosphate (primarily H₂PO₄⁻ and HPO₄²⁻, where the oxidation state of phosphorus is +V). Recent developments in the field of microbiology and research on the origin of life have suggested a possibly significant role for reduced, inorganic forms of phosphorus in bacterial metabolism and as evolutionary precursors of biological phosphate compounds. Reduced inorganic forms of phosphorus include phosphorus acid (H₃PO₃, P(+III)), hypophosphorus acid (H₃PO₂, P(+I)) and various forms of phosphides (P(−III)). Reduced phosphorus has been detected in anaerobic sediments, sewage treatment facilities and in industrial and agricultural processes.Microbiological evidence suggests a significant role for reduced phosphorus species in metabolic processes and raises interesting questions regarding the biogeochemistry of this nutrient in the environment. However, the paucity of data on the presence and cycling of reduced phosphorus compounds in the environment requires attention in order to elucidate the role of these compounds in natural systems. This paper discusses the significance of reduced phosphorus in the natural environment, its speciation and methods of detection.     

Structure and dynamics of metallomacrocycles: recognition of zinc xylyl-bicyclam by an HIV coreceptor

As platforms for the design of metal-based therapeutic and diagnostic agents, macrocycles are rigid enough to provide strong metal binding sites and orient functional groups stereoselectively, yet flexible enough to accommodate structural changes required for induced-fit recognition of biological targets. We consider the recognition of the Zn(II) complex of the bis-tetraazamacrocycle xylyl-bicyclam, a potent anti-HIV agent, by the coreceptor CXCR4, a G-protein-coupled receptor used by HIV for membrane fusion and cell entry. NMR studies show that the macrocycles of Zn(II)(2)-xylyl-bicyclam perchlorate exist in aqueous solution as two major configurations, trans-I (nitrogen chirality R,S,R,S), and trans-III (S,S,R,R). Acetate addition induced a major structural change. X-ray crystallography shows that the acetate complex contains the unusual cis-V cyclam configuration (R,R,R,R and folded) with bidentate coordination of acetate to Zn(II) plus second-coordination-sphere double H-bond formation between diagonal NH protons on the opposite cyclam face and acetate carboxylate oxygens. Detailed 1D and 2D NMR studies show that the major configuration of Zn(II)(2)-xylyl-bicyclam acetate in aqueous solution is cis-V/trans-I. Molecular modeling shows that an analogous cis-V site can be formed when Zn(II)(2)-xylyl-bicyclam binds to CXCR4, involving the carboxylate groups of Asp262 (Zn(II) coordination) and Glu288 (double H-bonding). The second cyclam can adopt the trans-I (or trans-III) configuration with Zn(II) binding to Asp171. These interactions are consistent with the known structure-activity relationships for bicyclam anti-HIV activity and receptor mutation. Consideration of the anti-HIV activity of xylyl-bicyclam complexes of other metal ions suggests that affinity for carboxylates, configurational flexibility, and kinetic factors may all play roles in receptor recognition. For example, Pd(II) cyclam complexes interact only weakly with axial ligands and are inflexible and inactive, whereas Co(III) cyclams bind carboxylates strongly, are configurationally flexible, and yet have low activity. Our findings should aid the design of new generations of active macrocycles including highly specific chemokine receptor antagonists.     

The potentiometric determination of insecticides: Part I. Organophosphorus insecticides inhibiting cholinesterase

A potentiometric method for the determination of organophosphorus insecticides based on the inhibition of cholinesterase is presented. The acetic acid formed by hydrolysis of acetylcholine is sensed by a glass electrode in a weakly buffered system. The insecticide is incubated with cholinesterase for 1 h at 25°C or 37°C before addition to the substrate. The effects of incubation time and temperature are discussed. The method is applied to the insecticides bromophos and dichlorvos. The detection limits are 2 × 10^-5 M (7 ppb) for bromophos and 1 × 10^-7 M (22 ppb) for dichlorvos. The initial rates of hydrolysis decrease linearly up to 2 × 10^-7 M and 1 × 10^-6 M, respectively.     

Selenirene as an intermediate in the pyrolysis of 1,2,3-selenadiazole. Microwave spectra of 13C labelled selenoketene

Microwave Spectra of ¹³CH₂¹²C^80,78Se and ¹²CH₂¹³C^80,78Se (selenoketene) are recorded. B 5-¹³C-1,2,3-selenadiazole all four species are formed. The ¹³C scrambling may take place via a three-membered ring, selenirene, but as expected its microwave spectrum was not observed.     

Formation and stability of N-heterocyclic carbenes in water: the carbon acid pKa of imidazolium cations in aqueous solution

We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes.     

ESCA: Eine Methode zur Bestimmung von Elementen und ihren Bindungszust?nden in der Oberfl?che von Festk?rpern

Zusammenfassung ESCA (nach Siegbahn: Electron Spectroscopy for Chemical Analysis) beruht auf dem Photoeffekt an inneren Atomorbitalen und ist auf alle Substanzen anwendbar. Die Routineuntersuchungen werden überwiegend an Festkörpern durchgeführt. Informationsträger sind Photo- und Augerelektronen, die verlustfrei von der Festkörperoberfläche emittiert werden. Auf Grund der Oberflächenempfindlichkeit gehört ESCA zu den mikrochemischen Verfahren. Die erfaßte Schichtdicke ist gegeben durch die Austrittstiefe der Photo- und Augerelektronen. Sie beträgt einige Monolagen, maximal 100 Å. Man kann davon ausgehen, daß bei einer untersuchten Fläche von 0,5 cm² und homogener Verteilung eines Elementes in den obersten 100 Å eine Konzentration von 1 % noch sicher nachgewiesen wird. Die Empfindlichkeitsunterschiede von Element zu Element liegen innerhalb eines Faktors 10. Matrixeffekte sind noch wesentlich geringer. Deshalb sind gute Voraussetzungen für eine quantitative Analyse gegeben. ESCA ist zwar nicht direkt ein Verfahren zur Spurenanalyse, wohl aber nach geeigneter Anreicherung. Der besondere Vorteil von ESCA liegt darin, daß man nicht nur Elemente nachweist, sondern an Hand von chemischen Verschiebungen, Linienaufspaltungen und Shake-up-Satelliten zuverlässige Aussagen über ihren Bindungszustand erhält. Weiterhin kann innerhalb des Bereiches der Austrittstiefe der Photoelektronen differenziert werden; dadurch ergeben sich Möglichkeiten zur zerstörungsfreien Aufnahme von Tiefenverteilungen von Elementen und Verbindungen. Zum Vordringen in tiefere Schichten kann ESCA mit abbauenden Verfahren gekoppelt werden. Nach Ionenbeschußabbau ist wegen ioneninduzierter Reaktionen in der Regel jedoch kein Verbindungsnachweis mehr möglich.

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ESCA: A method for the determination of elements and their valence states in the surfaces of solids

Summary ESCA — or Electron Spectroscopy for Chemical Analysis (the term used by its inventor, Siegbahn)-is based on the effects of X-rays on the inner orbitals of atoms and is applicable to all substances. Routine ESCA investigations are carried out chiefly on solids. The information is provided by photo- and Auger electrons, which are emitted from the surfaces of solids without energy losses. Because of its surface sensitivity ESCA may be regarded as a microchemical method. The comprehended layer thickness is given by the escape depths of the photo- and Auger electrons. The range is from a few monolayers to 100 Å. As a rule, an element that is distributed homogeneously in the uppermost 100 Å of an area of 0.5 cm² can still be detected reliably at a concentration of 1%. The differences in sensitivity from element to element are within a factor of ten. Matrix effects are considerably smaller still. ESCA is therefore well suited for quantitative analysis. Though not directly suitable for trace analysis, ESCA can be used for that purpose after appropriate enrichment techniques have been applied. The special advantage of ESCA is that, in addition to detecting elements, it provides reliable information on their valence states by means of chemical shifts, line splitting and shake-up satellites. Apart from this, ESCA permits in-depth discrimination within the range of the escape depths of the photo electrons; it therefore provides opportunities for the non-destructive recording of the depth distributions of elements and compounds. For investigation of lower layers, ESCA can be combined with methods which involve the removal of outer layers. After removal of layers by ion bombardment, however, ion-induced reactions generally prevent the detection of compounds.

Hauptvortrag auf dem Internationalen Symposium für mikrochemische Arbeitsmethoden (ISM) Davos, Mai 1977     

Rearrangement of symmetrical dicubane clusters into topological analogues of the P cluster of nitrogenase: nature's choice?

Reaction schemes have been developed that lead to clusters having the topology of the PN cluster of nitrogenase. The single cubane clusters [(Tp)MFe3S4Cl3]z (M = Mo, z = 1-; M = V, z = 2-) react with PEt3 to give [(Tp)MFe3S4(PEt3)3]1+, which are reduced to the neutral edge-bridged double cubanes [(Tp)2M2Fe6S8(PEt3)4] with highly reduced (2[MFe3S4]1+) cores. Reaction of these clusters in acetonitrile with (Et4N)(HS) results in the formation of [(Tp)2Mo2Fe6S9(SH)2]3- and [(Tp)2V2Fe6S9(SH)2]4-. X-ray structures of the Et4N+ salts reveal the bridging pattern M2Fe6(mu2-S)2(mu3-S)6(mu6-S) in which two cuboidal MFe3(mu3-S)3 units share the common bridge atom mu6-S and are externally bridged by two mu2-S atoms. The M sites possess trigonal octahedral, and the Fe sites, distorted tetrahedral coordination. Hydrosulfide ligands and sulfide atoms simulate terminal cysteinate ligation and mu2 bridges, respectively, in the protein-bound cluster Fe8S7(mu2-SCys)2(SCys)4. The synthetic clusters have the same bridging pattern as the PN cluster and approach congruency with it. These clusters are the first molecular topological analogues of a PN cluster. Like the latter, they are substantially reduced (majority of Fe(II)).     

Two-electron-transfer redox systems,part 7: two-step electrochemical oxidation of the boron subhalide cluster dianions B6X 2- 6 (X = Cl,Br, I)

Boron subhalide cluster dianions B6X 2- 6 (X = Cl, Br, I) are electrochemically oxidized in two steps. According to cyclic voltammograms, the first step is chemically reversible and yields the corresponding radical anions B6X .- 6. The electron transfer is nearly diffusion controlled. The second, slower electron-transfer step leads to a species which we assume to be the hitherto not yet described neutral compounds B6X 2- 6. The voltammograms indicate a coupled fast catalytic reaction, producing the radical anions in a reduction by an electrolyte component. Computer simulations of the cyclic voltammograms reveal mechanistic details of the redox reactions, as well as quantitative values for formal potentials, rate constants, and diffusion coefficients. The results are compared to other BnXn redox systems.