Mössbauer study of the three-coordinate planar Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)): model for the trigonal iron sites of the MoFe(7)S(9):homocitrate cofactor of nitrogenase

The cofactor (M-center) of the MoFe protein of nitrogenase, a MoFe(7)S(9):homocitrate cluster, contains six Fe sites with a (distorted) trigonal sulfido coordination. These sites exhibit unusually small quadrupole splittings, Delta E(Q) approximately 0.7 mm/s, and isomer shifts, delta approximately 0.41 mm/s. M?ssbauer and ENDOR studies have provided the magnetic hyperfine tensors of all iron sites in the S = 3/2 state M(N). To assess the intrinsic zero-field splittings and hyperfine parameters of the cofactor sites, we have studied with M?ssbauer spectroscopy two salts of the three-coordinated Fe(II) thiolate complex [Fe(SR)(3)](-) (R = C(6)H(2)-2,4,6-tBu(3)). One of the salts, [Ph(4)P][Fe(SR)(3)] x 2MeCN x C(7)H(8), 1, has a planar geometry with idealized C(3h) symmetry. This S = 2 complex has an axial zero-field splitting with D = +10.2 cm(-1). The magnetic hyperfine tensor components A(x) = A(y) = -7.5 MHz and A(z) = -29.5 MHz reflect an orbital ground state with d(z(2)) symmetry. A(iso) = (A(x) +A(y) +A(z))/3 = -14.9 MHz, which includes the contact interaction (kappa P = -21.9 MHz) and an orbital contribution (+7 MHz), which is substantially smaller than A(iso) approximately -22 MHz of the tetrahedral Fe(II)(S-R)(4) sites of both rubredoxin and [PPh(4)](2)[Fe(II)(SPh)(4)]. The largest component of the electric field gradient (EFG) tensor is negative, as expected for a d(z(2)) orbital. However, Delta E(Q) = -0.83 mm/s, which is smaller than expected for a high-spin ferrous site. This reduction can be attributed to a ligand contribution, which in planar complexes provides a large positive EFG component perpendicular to the ligand plane. The isomer shift of 1, delta = 0.56 mm/s, approaches the delta-values reported for the six trigonal cofactor sites. The parameters of 1 and their importance for the cofactor cluster of nitrogenase are discussed.     

Determination of anabolic androgenic steroids as imidazole carbamate derivatives in human urine using liquid chromatography–tandem mass spectrometry

Anabolic androgenic steroids are widely abused substances in sports doping. Their detection present limitations regarding the use of soft ion sources such as electrospray or atmospheric pressure chemical ionization by liquid chromatography–tandem mass spectrometry. In the current study, a novel derivatization method was developed for the ionization enhancement of selected anabolic androgenic steroids. The proposed method aims at the introduction of an easily ionizable moiety into the steroid molecule by converting the hydroxyl groups into imidazole carbamates using 1,1′‐carbonyldiimidazole as derivatization reagent. The proposed method was applied to water and urine samples spiked with exogenous anabolic androgenic steroids in various concentration levels. Steroid imidazole carbamate derivatives have shown intensive [M+H]⁺ signals under electrospray ionization and common fragmentation patterns in tandem mass spectrometry mode with [M‐CO₂+H]⁺ and [M‐ΙmCO₂+H]⁺ as major ions with low collision energy. The obtained results showed that the majority of steroids were detectable at concentrations equal or lower to their minimum required performance level according to the World Anti‐Doping Agency technical document. The proposed method is sensitive with a preparation procedure that could be easily applied to the analysis of doping control samples.     

Two theorems about projective sets

In this paper we prove two (rather unrelated) theorems about projective sets. The first one asserts that subsets of ℵ₁ which are in the codes are constructible; thus it extends the familiar theorem of Shoenfield that subsets of ω are constructible. The second is concerned with largest countable sets and establishes their existence under the hypothesis of Projective Determinacy and the assumption that there exist only countably many ordinal definable reals. Y. N. Moschovakis is a Sloan Foundation Fellow. During the preparation of this paper, both authors were partially supported by NSF Grant GP-27964.     

The Schwartz space of a smooth semi-algebraic stack

Schwartz functions, or measures, are defined on any smooth semi-algebraic (“Nash”) manifold, and are known to form a cosheaf for the semi-algebraic restricted topology. We extend this definition to smooth semi-algebraic stacks, which are defined as geometric stacks in the category of Nash manifolds. Moreover, when those are obtained from algebraic quotient stacks of the form X/G, with X a smooth affine variety and G a reductive group defined over a number field k, we define, whenever possible, an “evaluation map” at each semisimple k-point of the stack, without using truncation methods. This corresponds to a regularization of the sum of those orbital integrals whose semisimple part corresponds to the chosen k-point. These evaluation maps produce, in principle, a distribution which generalizes the Arthur–Selberg trace formula and Jacquet’s relative trace formula, although the former, and many instances of the latter, cannot actually be defined by the purely geometric methods of this paper. In any case, the stack-theoretic point of view provides an explanation for the pure inner forms that appear in many versions of the Langlands, and relative Langlands, conjectures.     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.     

Preventive doping control analysis: liquid and gas chromatography time-of-flight mass spectrometry for detection of designer steroids

A new combined doping control screening method for the analysis of anabolic steroids in human urine using liquid chromatography/electrospray ionization orthogonal acceleration time-of-flight mass spectrometry (LCoaTOFMS) and gas chromatography/electron ionization orthogonal acceleration time-of-flight mass spectrometry (GCoaTOFMS) has been developed in order to acquire accurate full scan MS data to be used to detect designer steroids. The developed method allowed the detection of representative prohibited substances, in addition to steroids, at concentrations of 10 ng/mL for anabolic agents and metabolites, 30 ng/mL for corticosteroids, 500 ng/mL for stimulants and beta-blockers, 250 ng/mL for diuretics, and 200 ng/mL for narcotics. Sample preparation was based on liquid-liquid extraction of hydrolyzed human urine, and the final extract was analyzed as trimethylsilylated derivatives in GCoaTOFMS and underivatized in LCoaTOFMS in positive ion mode. The sensitivity, mass accuracy, advantages and limitations of the developed method are presented.     

Monomeric oxovanadium(IV) compounds of the general formula cis-[V(IV)(=O)(X)(L(NN))(2)](+/0) [X = OH(-), Cl(-), SO(4)(2)(-) and L(NN) = 2,2'-bipyridine (bipy) or 4,4'-disubstituted bipy

Reaction of [V(IV)OCl(2)(THF)(2)] in aqueous solution with 2 equiv of AgBF(4) or AgSbF(6) and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[V(IV)O(OH)(L(NN))(2)]Y [where L(NN) = bipy, Y = BF(4)(-) (1), L(NN) = 4,4'-dtbipy, Y = BF(4)(-) (2.1.2H(2)O), L(NN) = 4,4'-dmbipy, Y = BF(4)(-) (3.2H(2)O), and L(NN) = 4,4'-dtbipy, Y = SbF(6)(-) (4)]. Sequential addition of 1 equiv of Ba(ClO(4))(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of V(IV)OSO(4).5H(2)O yields cis-[V(IV)O(OH)(bipy)(2)]ClO(4) (5). The monomeric compounds 1-5 contain the cis-[V(IV)O(OH)](+) structural unit. Reaction of 1 equiv of V(IV)OSO(4).5H(2)O in water and of 1 equiv of [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4) (9), cis-[V(IV)O(BF(4))(4,4'-dmbipy)(2)]BF(4) (10), and cis-[V(IV)O(SbF(6))(4,4'-dtbipy)(2)]SbF(6) (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF(4) or AgSbF(6) to a dichloromethane solution containing 1 equiv of [V(IV)OCl(2)(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH(3)OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) A, b = 13.33(1) A, c = 27.25(2) A, V = 7851(2) A(3), Z = 8. Compound 6.CH(3)OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) A, b = 14.204(5) A, c = 14.613(6) A, beta = 114.88(1) degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) A, b = 24.176(2) A, c = 13.676(1) A, V = 7628(2) A(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [V(IV)O(bipy)(2)](2+) and [V(IV)OX(bipy)(2)](+/0) species (X = OH(-), SO(4)(2)(-), Cl(-)).