A fast low-pressure transport route to large black phosphorus single crystals

Black phosphorus, a promising candidate for lithium battery electrodes, can be prepared by a low-pressure transport reaction route representing the first effective and scalable access to this element modification. Crystal sizes larger than 1 cm were obtained at low-pressure conditions in silica ampoules. X-ray phase analyses, EDX, ICP-MS and optical microscopy were applied to characterize the resulting black phosphorus. The present method drastically improves the traditional preparation ways like mercury catalysis, bismuth-flux or high-pressure techniques and represents an easy, non-toxic, fast and highly efficient method to achieve black phosphorus. In contrast to a previously reported low-pressure route the present transport reaction allows an up-scaling to higher masses of starting materials, a larger black phosphorus yield and faster reaction time under retention of the high product crystallinity.     

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfur-based ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once.     

On existentially closed and generic nilpotent groups

Letn≧2 be an integer. We prove the following results that are known in casen=2: The upper and the lower central series of an existentially closed nilpotent group of classn coincide. A finitely generic nilpotent group of classn is periodic and the center of a finitely generic torsion-free nilpotent group of classn is isomorphic toQ ⁺, whereas infinitely generic nilpotent groups do not enjoy these properties. We determine the structure of the torsion subgroup of existentially closed nilpotent groups of class 2. Finally we give an algebraic proof that there exist 2^κ non-isomorphic existentially closed nilpotent groups of classn in cardinalityK ≧N ₀. Some results of this paper were contained in [6].     

Über Pterinchemie. 90. Mitteilung. Synthese und Kristallstruktur des ersten chinoiden Dihydropterinmolybdän (IV)-Komplexes

Synthesis and Crystal Structure of the First Quinoid Dihydropterinmolybdenum (IV) Complex The first molybdenum(IV) complex with a quinoid dihydropterin, i.e. 2 , was isolated and characterized by IR, UV and NMR data and single-crystal X-ray diffraction. The reaction of Mo^VIO₂Cl₂ with the biologically important 6β-5,6,7,8-tetrahydro-L-biopterin(²) ( 7 ) in MeOH gave almost quantitatively trichloro(1,5-quinoid-7,8-dihydro-6H-L-biopterin)oxomolybdenLim(IV) ( 2 ). The complex crystallizes with one molecule of MeOH in the noncentrosymmetric orthorhombic space group P2₁2₁2₁ (No. 19) with unit cell dimensions a = 1009.3(3), b = 1104.7(3), and c = 1484.5(4) pm and Z = 4. The Mo-atom has a distorted octahedral geometry (Fig.1). It is coordinated by N(5) and O(4) of the pterin ligand. The distance of the Mo–N(5) bond (202 pm) is unusually short compared to similar complexes. O(4) is located trans to a terminal oxo ligand. The octahedral coordination is completed by three Cl-atoms in a meridional arrangement. Complex 2, with the Mo-atom in the enzyme-relevant oxidation state +IV and the pterin in the intermediate quinoid dihydro form, should lead to an extension of the proposed ‘common molybdenum cofactor’ model.     

Über den Propylidendipropyläther

Ohne ZusammenfassungSchliesslich ist es mir eine angenehme Pflicht, meinem hochverehrten Lehrer, dem Herrn Prof. A. Lieben für die freundliche Unterstützung, welche er mir bei Ausführung vorliegender Arbeit zu Theil werden liess, meinen aufrichtigsten Dank auszusprechen.     

Nuclear coherences in photosynthetic reaction centers following light excitation

Transient electron paramagnetic resonance is used to study the secondary radical pair in plant photosystem I. Nuclear coherences are observed in the transverse magnetization at lower temperatures following light excitation. Comparative studies of deuterated and deuterated¹⁵N-substituted cyanobacteriaS. lividus indicate assignment of these coherences to nitrogen nuclei in the primary donor and deuterons in the secondary acceptor. The modulation amplitude of a deuteron matrix line, as a function of the microwave power, reveals a distinct resonance behavior. The maximum amplitude is obtained when the Rabi frequency equals the nuclear Zeeman frequency.     

Relative elemental sensitivity factors in non-resonant laser-SNMS

Using a reflectron time-of-flight mass spectrometer, the ionization process in non-resonant Laser postionization Secondary Neutral Mass Spectrometry (SNMS) has been investigated. In particular, the postionization efficiencies (PIE) achieved by multi photon and single photon absorption have been compared by ionizing ten elements sputtered from a NIST standard reference material by excimer laser radiation of 248 nm, 193 nm and 157 nm. Only in the case of single photon ionization (SPI) the measured laser intensity dependence of the PIE can be understood quantitatively in terms of corresponding theory. From the results, absolute values of the SPI cross sections have been evaluated for atoms of nine elements, which show a total variation over about two orders of magnitude. Furthermore, even in the regime of high laser intensity, where the ionization of all atoms is completely saturated, different elements have been detected with relative sensitivity factors which scatter over about one order of magnitude. This has been attributed to element dependent variations of the effective ionization volume which are caused by the different kinetic energy and angular distributions of different sputtered atoms.