On the Synthesis of Chloro Derivatives of Five-Membered Heterocyclics via the Lithium Derivatives

In connection with our ¹³C NMR investigations we were interested in obtaining pure samples of 2- and 3-chlorofuran and 2- and 3-chloroselenophene. While direct chlorination with molecular chlorine or other chlorinating agents can successfully be used for the preparation of 2-chlorothiophene,¹ we could not reproduce either yields or isomeric purity in the corresponding chlorination of selenophene.^2,3     

The initial transient of natural convection during copper electrolysis in the presence of an opposing Lorentz force: Current dependence

Magnetic fields are well-established in electrochemistry as an attractive tool to improve both the quality of the deposit as well as the deposition rate. The key mechanism is a mass transfer enhancement by Lorentz-force-driven convection. However, during electrolysis this convection interacts with buoyancy-driven convection, which arises from concentration differences, in a sometimes intriguing way. In the case of a Lorentz force opposing buoyancy, this is due to the growth of a bubble-like zone of less-concentrated cupric ion solution at the lower part of the vertical cathode when copper electrolysis is performed. If buoyancy is strong enough to compete with the Lorentz force, this zone rises along the cathode and causes surprisingly unsteady initial transient behaviour. We explore this initial transient under galvanostatic conditions by analyzing the development of the concentration and velocity boundary layers obtained by Mach-Zehnder interferometry and particle image velocimetry. Particular attention is also paid to higher current densities above the limiting current, obtained from potentiodynamic measurements, at which a chaotic advection takes place. The results are compared by scaling analysis.     

Textile‐Compatible Substrate Electrodes with Electrodeposited ZnO—A New Pathway to Textile‐Based Photovoltaics

A strategy is presented to realize textile‐based photovoltaic cells motivated by developments of textile‐based electronics and their demand of grid‐independent energy supply. Beyond this, a development of textile‐based photovoltaics also represents an attractive pathway towards very flexible and rugged solar cells. The need for compatibility of an appropriate photovoltaic technology with the physical limitations of textiles is stressed. Electrodeposition from aqueous solutions is presented as a successful strategy to realize semiconductor structures on textiles and detailed control and influence of the deposition conditions is discussed. The role of microelectrode effects, options of forced convection, deposition under pulsed potential, alternative deposition baths and different substrate metals are emphasized. An active electrode material is presented which reaches a conversion efficiency close to the 1 % limit under AM 1.5 illumination conditions and thereby opens the door for a further optimization towards devices of technical interest.     

Aerogels from Unaltered Bacterial Cellulose: Application of scCO2 Drying for the Preparation of Shaped,Ultra‐Lightweight Cellulosic Aerogels

Bacterial cellulose produced by the gram‐negative bacterium Gluconacetobacter xylinum was found to be an excellent native starting material for preparing shaped ultra‐lightweight cellulose aerogels. The procedure comprises thorough washing and sterilization of the aquogel, quantitative solvent exchange and subsequent drying with supercritical carbon dioxide at 40 °C and 100 bar. The average density of the obtained dry cellulose aerogels is only about 8 mg · cm^?3 which is comparable to the most lightweight silica aerogels and distinctly lower than all values for cellulosic aerogels obtained from plant cellulose so far. SEM, ESEM and nitrogen adsorption experiments at 77 K reveal an open‐porous network structure that consists of a comparatively high percentage of large mesopores and smaller macropores.

     

MALDI produced ions inspected with a linear ion trap-orbitrap hybrid mass analyzer

A MALDI source is interfaced to a modified LTQ Orbitrap XL instrument. This work gives insight into the MALDI source design and shows results obtained with the MALDI source coupled to an accurate mass, high-resolution hybrid mass spectrometer. MALDI-produced ions and fragment ions thereof produced in the mass spectrometer may be analyzed and detected by the Orbitrap analyzer at a maximum mass resolution of 100,000 (FWHM) at m/z 400 with high mass accuracy. An accuracy of ≤2 ppm is achieved by internal mass calibration using lock mass functionality; using external mass calibration, an accuracy of ≤3 ppm is routinely obtained. External mass calibration of the hybrid mass spectrometer is performed using a standard calibration mixture of different peptides and matrix components. The instrumental capabilities are demonstrated for analytical methodologies such as Protein ID using Peptide Mass Fingerprint (PMF) and MS/MS analyses of small molecule samples. Stability of mass accuracy and signal-to-noise ratio for low samples loads (on plates) are demonstrated as well as the experimental dynamic range using α-cyano-4-hydroxy cinnamic acid (CHCA) matrix.     

Hydrogen network fluctuations of associating liquids: dielectric relaxation of ethylene glycol oligomers and their mixtures with water

Complex dielectric spectra of ethylene glycol and of various derivatives as well as of mixtures of water with an ethylene glycol oligomer and with a poly(ethylene glycol) dimethyl ether oligomer have been measured. The spectra can be well represented by a Cole-Cole [Cole and Cole, J. Chem. Phys. 9, 341 (1941)] spectral function. The extrapolated low frequency (static) permittivity of this function has been evaluated to yield the effective dipole orientation correlation factor of the liquids. The relaxation time of the ethylene glycols displays a characteristic dependence upon the ratio of concentrations of hydrogen bond donating and accepting groups, indicating two opposing effects. With increasing availability of hydrogen bonding sites effects of association and also of dynamical destabilization increase. Both effects exist also in the mixture of water with the oligomers. They are discussed in terms of a wait-and-switch model of dipole reorientation in associating liquids. Another feature in the dependence of the dielectric relaxation time of poly(ethylene glycol)/water mixtures upon mixture composition has been tentatively assigned to precritical demixing behavior of the binary liquids in some temperature range.     

Numerical and experimental investigations of phase segragation effects in binary brazing solders

Solder materials occupy many of fields for technical application (e.g. solder joints in automotive control units or in microelectronic packages). They are required to provide electrical and mechanical connections between different components. Due to their wide range of applications solder alloys are subject to a great variety of microstructural changes such as phase separation and coarsening processes. The micromorphological variations influence strength and life expectation of solder materials, in particular, in very small components such as solder joints in microelectronic packages. In order to analyze the microstructural evolution with a diffusion theory of heterogeneous solid mixtures we employ an extended Cahn-Hilliard phase field model. The diffusion equation under consideration constitutes a partial differential equation involving spatial derivatives of fourth order. Thus, the variational formulation of the problem requires approximation functions which are piecewise smooth and globally C1-continuous. In our contribution we fulfil the continuity requirement by means of rational B-spline finite element basis functions. To illustrate the versatility of this approach numerical simulations of phase decomposition and coarsening controlled by diffusion and by mechanical loading are discussed and compared with experimental results. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silver(I) complexation of linked 2,2'-dipyridylamine derivatives. Synthetic, solvent extraction, membrane transport and X-ray structural studies

Synthesis of the 2,2'-dipyridylamine derivatives di-2-pyridylaminomethylbenzene 1, 1,2-bis(di-2-pyridylaminomethyl)benzene 2, 1,3-bis(di-2-pyridylaminomethyl)benzene 3, 2,6-bis(di-2-pyridylaminomethyl)pyridine 4, 1,4-bis(di-2-pyridylaminomethyl)benzene 5, and 1,3,5-tris(di-2-pyridylaminomethyl)benzene 6 are reported together with the single-crystal X-ray structures of 2, 3, and 5. Reaction of individual salts of the type AgX (where X = NO(3)(-), PF(6)(-), ClO(4)(-), or BF(4)(-)) with the above ligands has led to the isolation of thirteen Ag(I) complexes, nine of which have also been characterised by X-ray diffraction. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a range of coordination arrangements. A series of liquid-liquid (H(2)O/CHCl(3)) extraction experiments of Ag(I) with varying concentrations of 1-6 in the organic phase have been undertaken, with the counter ion in the aqueous phase being respectively picrate, perchlorate and nitrate. In general, extraction efficiencies for a given ionophore followed the Hofmeister order of picrate > perchlorate > nitrate; in each case the tris-dpa derivative 6 acting as the most efficient extractant of the six systems investigated. Competitive seven-metal bulk membrane transport experiments (H(2)O/CHCl(3)/H(2)O) employing the above ligands as the ionophore in the organic phase and equimolar concentrations of Co(II), Ni(II), Zn(II), Cu(II), Cd(II), Pb(II) and Ag(I) in the aqueous source phase were also undertaken, with transport occurring against a pH gradient. Under the conditions employed 1 and 5 yielded negligible transport of any of the metals present in the source phase while sole transport selectivity for Ag(I) was observed for 2-4 and 6.