Conformational Properties of 1-Halogenated-1-Silacyclohexanes, CHSiHX (X = Cl, Br, I): Gas Electron Diffraction, Low-Temperature NMR, Temperature-Dependent Raman Spectroscopy, and Quantum-Chemical Calculations.

The molecular structures of axial and equatorial conformers of -CHSiHX (X = Cl, Br, I) as well as the thermodynamic equilibrium between these species was investigated by means of gas electron diffraction, dynamic nuclear magnetic resonance, temperature-dependent Raman spectroscopy, and quantum-chemical calculations applying CCSD(T), MP2, and DFT methods. According to the experimental and calculated results, all three compounds exist as a mixture of two chair conformers of the six-membered ring. The two chair forms of symmetry differ in the axial or equatorial position of the X atom.

Sylow -groups of polynomial permutations on the integers mod [Formula: see text].

We enumerate and describe the Sylow -groups of the groups of polynomial permutations of the integers mod [Formula: see text] for [Formula: see text] and of the pro-finite group which is the projective limit of these groups.

Cyclic Disilylated and Digermylated Germylenes.

The preparation of triethylphosphine adducts of cyclic disilylated or digermylated germylenes was achieved by reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with GeBr·(dioxane) and PEt. Phosphine abstraction with B(CF) allowed formation of the base-free germylenes, which undergo 1,2-trimethylsilyl shifts to the germylene atom to form the respective silagermene or digermene, which further dimerize in [2 + 2] cycloadditions to tricyclic compounds. The reasons responsible for the germylenes' completely different reactivities in comparison to the previously studied analogous stannylenes and plumbylenes were elucidated in a theoretical study.

Coordination Chemistry of Disilylated Germylenes with Group 4 Metallocenes.

Reaction of the PEt adduct of a disilylated five-membered cyclic germylene with group 4 metallocene dichlorides in the presence of magnesium led to the formation of the respective germylene metallocene phosphine complexes of titanium, zirconium, and hafnium. Attempts to react the related NHC adduct of a disilylated four-membered cyclic germylene under the same conditions with CpTiCl did not give the expected germylene NHC titanocene complex. This complex was, however, obtained in the reaction of CpTi(btmsa) with the NHC germylene adduct.

Dynamics of monolayer-island transitions in 2,7-dioctyl-benzothienobenzthiophene thin films.

The order in molecular monolayers is a crucial aspect for their technological application. However, the preparation of defined monolayers by spin-coating is a challenge, since the involved processes are far from thermodynamic equilibrium. In the work reported herein, the dynamic formation of dioctyl-benzothienobenzothiophene monolayers is explored as a function of temperature by using X-ray scattering techniques and atomic force microscopy.

[Working in the magnetic field of ultrahigh field MRI].

Development of magnetic resonance imaging (MRI) device technology continues to increase the static magnetic flux densities applied and consequently leads to considerably increased occupational exposure. This has already made it necessary to review limits of occupational exposure and to postpone European legal regulations for occupational exposure to electromagnetic fields. This raises the question whether and if so which adverse health effects and health risks might be associated with occupational exposure to MRI ultra-high static magnetic fields.

Coordination chemistry of disilylated stannylenes with group 10 d10 transition metals: silastannene vs stannylene complexation.

The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners.

Role of phosphatidylethanolamine in the biogenesis of mitochondrial outer membrane proteins.

The mitochondrial outer membrane contains proteinaceous machineries for the import and assembly of proteins, including TOM (translocase of the outer membrane) and SAM (sorting and assembly machinery). It has been shown that the dimeric phospholipid cardiolipin is required for the stability of TOM and SAM complexes and thus for the efficient import and assembly of β-barrel proteins and some α-helical proteins of the outer membrane. Here, we report that mitochondria deficient in phosphatidylethanolamine (PE), the second non-bilayer-forming phospholipid, are impaired in the biogenesis of β-barrel proteins, but not of α-helical outer membrane proteins.

Context-free pairs of groups I: Context-free pairs and graphs.

Let [Formula: see text] be a finitely generated group, [Formula: see text] a finite set of generators and [Formula: see text] a subgroup of [Formula: see text]. We define what it means for [Formula: see text] to be a context-free pair; when [Formula: see text] is trivial, this specializes to the standard definition of [Formula: see text] to be a context-free group. We derive some basic properties of such group pairs.

Processing and topology of the yeast mitochondrial phosphatidylserine decarboxylase 1.

The inner mitochondrial membrane plays a crucial role in cellular lipid homeostasis through biosynthesis of the non-bilayer-forming lipids phosphatidylethanolamine and cardiolipin. In the yeast Saccharomyces cerevisiae, the majority of cellular phosphatidylethanolamine is synthesized by the mitochondrial phosphatidylserine decarboxylase 1 (Psd1). The biogenesis of Psd1 involves several processing steps.

Life-long accumulation of 137Cs and 40K in the vertebral column of a cow.

We have investigated the accumulation of (137)Cs and (40)K in all the tissues and organs of an adult slaughtered Austrian "mountain pasture cow". In this paper we present measured (137)Cs- and (40)K-activity concentrations in different tissues of the vertebral bodies, in their other bony components and in all the vertebrae forming the vertebral column. Data are also given for activity concentrations of adherent tissues, and for activities of both the components and the whole vertebral column.

[Working in the magnetic field of ultrahigh field MRI].

Development of magnetic resonance imaging (MRI) device technology continues to increase the static magnetic flux densities applied and consequently leads to considerably increased occupational exposure. This has already made it necessary to review limits of occupational exposure and to postpone European legal regulations for occupational exposure to electromagnetic fields. This raises the question whether and if so which adverse health effects and health risks might be associated with occupational exposure to MRI ultra-high static magnetic fields.

Coordination chemistry of cyclic disilylated stannylenes and plumbylenes to group 4 metallocenes.

Reduction of group 4 metallocene dichlorides with magnesium in the presence of cyclic disilylated stannylene or plumbylene phosphine adducts yielded the respective metallocene tetrylene phosphine complexes. Under the same conditions the use of the respective dimerized stannylene or plumbylene gave metallocene ditetrylene complexes. A computational analysis of these reactions revealed for all investigated compounds multiple-bonded character for the M-E(II) linkage, which can be rationalized in the case of the monotetrylene complex with the classical σ-donor/π-acceptor interaction.

Dispersion energy enforced dimerization of a cyclic disilylated plumbylene.

By reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with PbBr(2) in the presence of triethylphosphine a base adduct of a cyclic disilylated plumbylene could be obtained. Phosphine abstraction with B(C(6)F(5))(3) led to formation of a base-free plumbylene dimer, which features an unexpected single donor-acceptor PbPb bond. The results of density functional computations at the M06-2X and B3LYP level of theory indicate that the dominating interactions which hold the plumbylene subunits together and which define its actual molecular structure are attracting van der Waals forces between the two large and polarizable plumbylene subunits.

Observation of complex bound states in the spin-1/2 Heisenberg XXZ chain using local quantum quenches.

We consider the nonequilibrium evolution in the spin-1/2 XXZ Heisenberg chain for fixed magnetization after a local quantum quench. This model is equivalent to interacting spinless fermions. Initially an infinite magnetic field is applied to n consecutive sites and the ground state is calculated.

Cycle decompositions: From graphs to continua.

We generalise a fundamental graph-theoretical fact, stating that every element of the cycle space of a graph is a sum of edge-disjoint cycles, to arbitrary continua. To achieve this we replace graph cycles by topological circles, and replace the cycle space of a graph by a new homology group for continua which is a quotient of the first singular homology group [Formula: see text]. This homology seems to be particularly apt for studying spaces with infinitely generated [Formula: see text], e.

Context-free pairs of groups II - Cuts, tree sets, and random walks.

This is a continuation of the study, begun by Ceccherini-Silberstein and Woess (2009) [5], of context-free pairs of groups and the related context-free graphs in the sense of Muller and Schupp (1985) [22]. The graphs under consideration are Schreier graphs of a subgroup of some finitely generated group, and context-freeness relates to a tree-like structure of those graphs. Instead of the cones of Muller and Schupp (1985) [22] (connected components resulting from deletion of finite balls with respect to the graph metric), a more general approach to context-free graphs is proposed via tree sets consisting of cuts of the graph, and associated structure trees.

Redundancy of minimal weight expansions in Pisot bases.

Motivated by multiplication algorithms based on redundant number representations, we study representations of an integer n as a sum n=∑kεkUk, where the digits εk are taken from a finite alphabet Σ and (Uk)k is a linear recurrent sequence of Pisot type with U0=1. The most prominent example of a base sequence (Uk)k is the sequence of Fibonacci numbers. We prove that the representations of minimal weight ∑k|εk| are recognised by a finite automaton and obtain an asymptotic formula for the average number of representations of minimal weight.

The number of maximum matchings in a tree.

We determine upper and lower bounds for the number of maximum matchings (i.e., matchings of maximum cardinality) [Formula: see text] of a tree T of given order.

Imino sugars and glycosyl hydrolases: historical context, current aspects, emerging trends.

Forty years of discoveries and research on imino sugars, which are carbohydrate analogues having a basic nitrogen atom instead of oxygen in the sugar ring and, acting as potent glycosidase inhibitors, have made considerable impact on our contemporary understanding of glycosidases. Imino sugars have helped to elucidate the catalytic machinery of glycosidases and have refined our methods and concepts of utilizing them. A number of new aspects have emerged for employing imino sugars as pharmaceutical compounds, based on their profound effects on metabolic activities in which glycosidases are involved.

Conformational Control of Polysilanes: Use of CH(2) Spacers in the Silicon Backbone.

By the reaction of a number of oligosilyl potassium compounds with (trimethylsilyl)chloromethane, derivatives containing the (trimethylsilyl)methyl substituent were prepared. Using X-ray single-crystal structure analysis and UV spectroscopy the conformational properties of some of the compounds were studied. It was found that the (trimethylsilyl)methylated examples exhibit UV absorption properties which correspond to lower energy transitions in comparison to those of analogous trimethylsilylated molecules.

Absolute concentration of free volume-type defects in ultrafine-grained Fe prepared by high-pressure torsion.

A maximum excess volume ΔV/V ≈ 1.9 × 10(-3) in ultrafine-grained Fe prepared by high-pressure torsion is determined by measurements of the irreversible length change upon annealing employing a high-resolution differential dilatometer. Since dislocations and equilibrium-type grain boundaries cannot fully account for the observed released excess volume, the present study yields evidence for a high concentration of free volume-type defects inherent to nanophase materials, which is considered to be the main source of their particular properties, such as strongly enhanced diffusivities.

A cyclic disilylated stannylene: synthesis, dimerization, and adduct formation.

Reaction of 1,4-dipotassio-1,1,4,4-tetrakis(trimethylsilyl)tetramethyltetrasilane with [(Me(3)Si)(2)N](2)Sn led to the formation of an endocyclic distannene via the dimerization of a transient stannylene. In the presence of strong donor molecules such as PEt(3), the stannylene could be trapped as adduct. Reaction of the PEt(3) derivative with B(C(6)F(5))(3) gave rise to the formation of the stannylene B(C(6)F(5))(3) adduct.

Analysis of Bonding between Conjugated Organic Molecules and Noble Metal Surfaces Using Orbital Overlap Populations.

The electronic structure of metal-organic interfaces is of paramount importance for the properties of organic electronic and single-molecule devices. Here, we use so-called orbital overlap populations derived from slab-type band-structure calculations to analyze the covalent contribution to the bonding between an adsorbate layer and a metal. Using two prototypical molecules, the strong acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) on Ag(111) and the strong donor 1H,1'H-[4,4']bipyridinylidene (HV0) on Au(111), we present overlap populations as particularly versatile tools for describing the metal-organic interaction.