Correlated and non-correlated growth kinetics of pentacene in the sub-monolayer regime

We present a study of the growth kinetics of pentacene monolayer islands on SiO₂ in the submonolayer regime by using Atomic Force Microscopy (AFM). Two distinct growth modes, namely correlated growth (CG) and non-correlated growth (NCG), have been identified by Voronoi tesselation. These two modes are characterized by different island growth kinetics. In the case of correlated growth, the average island size 〈A〉 scales with deposition time t i.e. 〈A〉 ∝ t whereas for non-correlated growth, 〈A〉 ∝ t². The CG and NCG regimes are defined by the level of re-evaporation which determines the capture zones around the islands: Wigner-Seitz cells for CG and coronas of width λ_D (λ_D is the mean diffusion distance on SiO₂ before re-evaporation) for NCG. A simple model is proposed to reproduce the experimental growth kinetics in both modes.     

Microsatellite structures in the context of human evolution

Six microsatellite - or short tandem repeat (STR) - systems with uniform repetitive sequences (HumTH01, HumCD4, HumFES/FPS, HumF13B, HumTPO, HumLPL) and three compound repeat systems (HumVWA, HumFIBRA, D21S11) were used, including data from the literature, to determine genetic distances among eight populations worldwide. The TH01- and VWA homologous loci in nonhuman primates (chimpanzees, gorillas, orangutans, rhesus monkeys, ring-tailed lemurs) were compared and found to be shorter than in humans. Microsatellites of lower complexity were most efficient for the separation of major ethnic groups. The loci of higher complexity showed a leveling of the diversity differences among populations, which could be attributed to higher mutation rates.     

Tetraarylester der μ-Imidodiphosphorsäure und ihre Thioderivate — Strukturuntersuchungen

Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by ¹H, ¹³C, and ³¹P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the ²J_{P? N? P} coupling constants were determined by ¹³C{¹H, ³¹P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.     

An investigation of intermittency in proton-gold, oxygen-gold, sulphur-gold and sulphur-sulphur interactions at 200 GeV per nucleon

The intermittency phenomenon is investigated in proton-gold, oxygen-gold, sulphur-gold and sulphur-sulphur collisions at 200 GeV per nucleon. The data were taken with the NA 35 streamer chamber detector at the CERN SPS. The data samples are carefully corrected for double counting of tracks and for contamination from photon conversions, particle decays and secondary interactions. The analysis is carried out in terms of factorial moments, using a new definition, and of correlation integrals. Both methods show the presence of nonstatistical fluctuations (intermittency). The main conclusions are: The observation of the effect for pairs of hadrons with negative charges and its near absence for pairs of opposite charges is consistent with the assumption that Bose-Einstein correlations yield the dominant contribution. The intermittency effect is not proportional to (dn/dy)^–1 which would be expected in superposition models. The measured relation between the second and third factorial moment for negative hadrons indicates that genuine 3-particle correlations are small. The predictions of a Monte Carlo simulation which is based on the Lund Fritiof model with the inclusion of Bose-Einstein correlations agree with the experimental results.Deceased     

Certification of reference materials and accreditation of reference material producers: Questionable terminology leads to confusion

In the view of the Deutscher Kalibrierdienst (DKD) , a certifying body for reference materials can be considered to be a calibration laboratory. Therefore, accreditation of calibration laboratories in accordance with ISO/IEC 17025 is the most appropriate way to establish confidence in certificates for reference materials. If necessary, the criteria of ISO/IEC 17025 can be tailored to specific cases. There is no need to provide any new kind of reference-material specific accreditation. However, in view of the variety of reference materials and the practice existing in other countries, accreditation of testing laboratories and product certification bodies may optionally be acceptable as long as the same stringent principles with respect to traceability and measurement uncertainty are applied. Such accreditations but not accreditations of reference material producers (ISO Guide 34) are also covered by existing international mutual recognition arrangements (MRA).     

Non-linear calibration functions in ion chromatography with suppressed conductivity detection using hydroxide eluents

The linearity of calibration curves in ion chromatography with suppressed conductivity detection using hydroxide eluents was investigated. Theoretical calibration curves were derived for strong electrolytes and weak monobasic acids and the results compared with experimental data. At low concentrations up to 1 micromol l(-1) the autoprotolysis of water induces left-curved calibration functions even for strong electrolytes like nitrate. The experimental data are best described by a quadratic function, the differences between linear and quadratic regression being up to 10%. At higher concentrations the calibration curves for strong electrolytes are linear. Due to incomplete dissociation, the calibration curves for weak mono- and dibasic acids show a right curvature. Thus, depending on the analyte and the concentration range of interest, analysts should carefully choose between a linear and a quadratic regression function.     

Optical tuning of a tellurium cavity: optical modulation and bistability in the infrared region at room temperature

A new optical-optical modulator for the infrared region (4m < < 11m) is described. It is based on the tuning of the transmission of a plane parallel tellurium slab by free carriers created by multiphoton absorption of 10.6m and 5.3m radiation at room temperature. The operation of this device is described by a simple theory using the plane-wave approximation and the Drude-Zehner model. The assumptions of this theory were fulfilled by the experimental conditions, permitting a quantitative analysis of the registered modulations. Under certain working conditions pulse shortening (170 ns pulses of=5.3m were shortened by up to 20 ns) and fast switch-on of the device (switch-on time 2 ns) were observed. Moreover, the modulator exhibits limiter action and optical bistability which, for the first time, is observed in an intrinsic semiconductor device at room temperature.The substance of this paper was presented at the Conference on Ultrafast Phenomena in Spectroscopy at Reinhardsbrunn (GDR), in November 1980, and a preliminary account published in theProceedings of the meeting.     

Divergent Synthesis of Molecular Winch Prototypes

We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties.     

Star-Shaped Ruthenium Complexes as Prototypes of Molecular Gears

The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length.     

Selective Enzymatic Oxidation of Silanes to Silanols

Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450_BM3 from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C?H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C?H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire.