Temporal evolution of benzenethiolate SAMs on Cu(100)

The structure and thermal stability of self-assembled monolayers (SAMs) of benzenethiolate (BT) on Cu(100) have been studied by means of thermal desorption spectroscopy (TDS), scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), UV photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray adsorption fine structure spectroscopy (NEXAFS). Vapor deposition at room temperature yields a well-ordered, densely packed c(6 × 2) saturation structure. At room temperature, this film is, however, metastable and transforms via partial decomposition by cleavage of the S-C bond into a less densely packed layer that reveals a coexisting p(2 × 2) phase. Such a transition occurs on a time scale of several days and is accompanied by a reduction of the work function change with respect to the bare Cu(100) surface from Δ? = -0.9 eV for a freshly prepared saturated layer to -0.5 eV for an aged film. TDS experiments exhibit the presence of two distinct desorption channels (dissociative and intact desorption) occurring at different temperatures that reflects a variation of the local Cu-S interaction strength of BT at differently coordinated adsorption sites. Heating to above room temperature causes a rapid degradation and continuous thinning of BT films whereas above 500 K all thiolate species have desorbed or dissociated, leaving a sulfide overlayer behind that is accompanied by a substrate reconstruction. Interestingly, the upright orientation of BT adopted in the saturated monolayer remains almost identical upon heating and demonstrates the absence of downward tilting upon thermally induced thinning of the film.     

First examples of oxaphosphirane pentacarbonylchromium(0) and -molybdenum(0) complexes: synthesis, structures and reactions

Synthesis of the first oxaphosphirane chromium(0) and molybdenum(0) complexes of the type [{(R(1)PCH(R(2))-O}M(CO)(5)] (R(1) = C(5)Me(5)) (8a-e, 15a-e) and (R(1) = CH(SiMe(3))(2)) (9a-e, 16a-e) via reaction of dichloro(organo)- (1, 2, 10, 11) and chloro(organo)phosphane complexes (3,4,12) with lithium bases and aldehydes 7a-e is reported. Furthermore, bicyclic 1,3-oxaphospholane complexes 17 and 18 have been obtained via O-protonation of oxaphosphirane complexes 8a and 15a with HCl. All complexes were characterized by NMR, IR spectroscopic, mass spectrometric investigations and, in addition, single-crystal X-ray structures of complexes 8a-e, 9a,c, 15a,b,e, 16a-c, 17, 18 are presented and discussed.     

Position-resolved determination of trace elements in mandibular gnathobases of the Antarctic copepod <Emphasis Type="Italic">Calanoides acutus</Emphasis> using a multimethod approach

Previous studies have revealed silica formation in the teeth of mandibular gnathobases of copepods while significant amounts of zinc and copper are present, which might improve mechanical stability of the teeth and represent an adaptation to compact food particles. The present study aimed at analysing the distribution and concentration of trace elements in the mandibular gnathobases of females of the Antarctic copepod species Calanoides acutus. Because of the low overall masses of few micrograms per specimen the application of a combination of position-resolved micro-beam techniques was necessary and micro-particle-induced X-ray emission spectrometry and laser ablation inductively coupled plasma mass spectrometry were used to determine Ba, Br, Ca, Cl, Cu, Fe, K, Mg, Na, Ni, P, S, Si and Zn in the samples with μm to sub-μm resolution. Calibration strategies were optimised to fit for the carbonate matrix. The analyses revealed a distinct enrichment of Br, Ca, Fe, K, S, Si and Zn in the teeth of the gnathobases.     

Switchings, extensions, and reductions in central digraphs

A directed graph is called central if its adjacency matrix A satisfies the equation A²=J, where J is the matrix with a 1 in each entry. It has been conjectured that every central directed graph can be obtained from a standard example by a sequence of simple operations called switchings, and also that it can be obtained from a smaller one by an extension. We disprove these conjectures and present a general extension result which, in particular, shows that each counterexample extends to an infinite family.     

Counting all bent functions in dimension eight 99270589265934370305785861242880

Based on the classification of the homogeneous Boolean functions of degree 4 in 8 variables we present the strategy that we used to count the number of all bent functions in dimension 8. There are $$99270589265934370305785861242880 \approx 2^{106}$$ such functions in total. Furthermore, we show that most of the bent functions in dimension 8 are nonequivalent to Maiorana?CMcFarland and partial spread functions.     

Macroscopic investigation of the transient hydrodynamic memory behavior of preparative packed chromatography beds

The goal of the present work was to examine the hydrodynamic behavior of preparative scale packed chromatography beds during long-term cyclical operation at high loads using an experimental set-up with a high resolution measuring device of bed height. One agarose-based resin and one methacrylic-based resin were examined in a 140 mm column. Both resins exhibited hysteresis behavior during compression/relaxation cycles. The hystereses were less pronounced with decreasing hydrodynamic stress rate. The occurrence of hystereses was an indication for hydrodynamic memory behavior of the chromatography packing. During long-term cyclical operation at high loads of the column filled with methacrylic resin, oscillations of the steadily with time decreasing flow rate were observed for the first time. These oscillations were attributed to the viscoelasticity of the polymer particles network representing a system with materials with fading memory. Such nonlinear systems with feed-back are known to exhibit inherent self-oscillations. A decoupling of the two processes of bed compression and decrease of bed permeability was observed. The presented results explain why preparative packed-bed chromatography often yields unsatisfactory reproducible data and why unwanted phenomena like medium wall detachment or other symptoms of deteriorated chromatography beds are frequently observed.     

Solution synthesis of nanoparticular binary transition metal antimonides

The preparation of nanoengineered materials with controlled nanostructures, for example, with an anisotropic phase segregated structure or a regular periodicity rather than with a broad range of interparticle distances, has remained a synthetic challenge for intermetallics. Artificially structured materials, including multilayers, amorphous alloys, quasicrystals, metastable crystalline alloys, or granular metals, are mostly prepared using physical gas phase procedures. We report a novel, powerful solution-mediated approach for the formation of nanoparticular binary antimonides based on presynthesized antimony nanoparticles. The transition metal antimonides M-Sb (M = Co, Ni, Cu(2), Zn) were obtained with sizes ranging from 20 and 60 nm. Through careful control of the reaction conditions, single-phase nanoparticular antimonides were synthesized. The nanophases were investigated by powder X-ray diffraction and (high resolution) electron microscopy. The approach is based on activated metal nanoparticles as precursors for the synthesis of the intermetallic compounds. X-ray powder diffraction studies of reaction intermediates allowed monitoring of the reaction kinetics. The small particle size of the reactants ensures short diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis.     

Wet chemical synthesis and a combined X-ray and Mössbauer study of the formation of FeSb2 nanoparticles

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 M?ssbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C.     

Freezing of Lennard-Jones-type fluids

We put forward an approximate method to locate the fluid-solid (freezing) phase transition in systems of classical particles interacting via a wide range of Lennard-Jones-type potentials. This method is based on the constancy of the properly normalized second derivative of the interaction potential (freezing indicator) along the freezing curve. As demonstrated recently it yields remarkably good agreement with previous numerical simulation studies of the conventional 12-6 Lennard-Jones (LJ) fluid [S.A.Khrapak, M.Chaudhuri, G.E.Morfill, Phys. Rev. B 134, 052101 (2010)]. In this paper, we test this approach using a wide range of the LJ-type potentials, including LJ n-6 and exp-6 models, and find that it remains sufficiently accurate and reliable in reproducing the corresponding freezing curves, down to the triple-point temperatures. One of the possible application of the method--estimation of the freezing conditions in complex (dusty) plasmas with "tunable" interactions--is briefly discussed.     

The stoichiometry of single nanoparticles of copper zinc tin selenide

Cu(2)ZnSnSe(4) nanoparticles have high potential to be used as ink for printable solar cells. Using transmission electron microscopy we show that these nanoparticles exhibit a broad range of chemical heterogeneity. These results are contrary to the interpretation of previous experimental work and will have considerable impact on the development of these nanoparticles.