Functionalization of bolalipid nanofibers by silicification and subsequent one-dimensional fixation of gold nanoparticles

In the present work, we describe the successful stabilization of bolalipid nanofibers by sol-gel condensation (silicification) of tetraethoxysilane (TEOS) or 3-mercaptopropyltriethoxysilane (MP-TEOS), respectively, onto the nanofibers. The conditions for an effective and reproducible silicification reaction were determined, and the silicification process was pursued by transmission electron microscopy (TEM). The resulting bolalipid-silica composite nanofibers were characterized by means of differential scanning calorimetry (DSC), TEM, (13)C, and (31)P NMR spectroscopy. Finally, the novel silicified bolalipid nanofibers were used as templates for the fixation of 5 and 2 nm AuNPs, respectively, resulting in one of the rare examples of one-dimensional AuNP arrangements in aqueous suspension.     

Cover Picture: Photoprogrammable Organic Light‐Emitting Diodes (Angew. Chem. Int. Ed. 22/2009)

Programmable organic light‐emitting diodes: UV irradiation converts an oxetane‐functionalized dithienylethene derivative from its colorless open form into a dark blue closed form, while visible light reverses the reaction. In the Communication on page 4038 ff., K. Meerholz and co‐workers describe a reversibly switchable organic light‐emitting diode based on this principle.

     

Artificial Genetic Sets Composed of Size‐Expanded Base Pairs

We describe in this Minireview the synthesis, properties, and applications of artificial genetic sets built from base pairs that are larger than the natural Watson–Crick architecture. Such designed systems are being explored by several research groups to investigate basic chemical questions regarding the functions of the genetic information storage systems and thus of the origin and evolution of life. For example, is the terrestrial DNA structure the only viable one, or can other architectures function as well? Working outside the constraints of purine–pyrimidine geometry provides more chemical flexibility in design, and the added size confers useful properties such as high binding affinity and helix stability as well as fluorescence. These features are useful for the investigation of fundamental biochemical questions as well as in the development of new biotechnological, biomedical, and nanostructural tools and methods.     

High speed coding for velocity by archerfish retinal ganglion cells

ABSTRACT: BACKGROUND: Archerfish show very short behavioural latencies in response to falling prey. This raises the question, which response parameters of retinal ganglion cells to moving stimuli are best suited for fast coding of stimulus speed and direction. RESULTS: We compared stimulus reconstruction quality based on the ganglion cell response parameters latency, first interspike interval, and rate. For stimulus reconstruction of moving stimuli using latency was superior to using the other stimulus parameters. This was true for absolute latency, with respect to stimulus onset, as well as for relative latency, with respect to population response onset. Iteratively increasing the number of cells used for reconstruction decreased the calculated error close to zero. CONCLUSIONS: Latency is the fastest response parameter available to the brain. Therefore, latency coding is best suited for high speed coding of moving objects. The quantitative data of this study are in good accordance with previously published behavioural response latencies.     

Trends in single-cell analysis by use of ICP-MS

The analysis of single cells is a growing research field in many disciplines such as toxicology, medical diagnosis, drug and cancer research or metallomics, and different methods based on microscopic, mass spectrometric, and spectroscopic techniques are under investigation. This review focuses on the most recent trends in which inductively coupled plasma mass spectrometry (ICP-MS) and ICP optical emission spectrometry (ICP-OES) are applied for single-cell analysis using metal atoms being intrinsically present in cells, taken up by cells (e.g., nanoparticles), or which are artificially bound to a cell. For the latter, especially element tagged antibodies are of high interest and are discussed in the review. The application of different sample introduction systems for liquid analysis (pneumatic nebulization, droplet generation) and elemental imaging by laser ablation ICP-MS (LA-ICP-MS) of single cells are highlighted. Because of the high complexity of biological systems and for a better understanding of processes and dynamics of biologically or medically relevant cells, the authors discuss the idea of “multimodal spectroscopies.”     

The Roles of Composition and Mesostructure of Cobalt-Based Spinel Catalysts in Oxygen Evolution Reactions

By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co₃O₄, MgCo₂O₄, Co₂FeO₄, Co₂AlO₄ and CoFe₂O₄. The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H₂O₂ decomposition. Studying the effect of dominant surface termination, isotropic Co₃O₄ and CoFe₂O₄ catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co³⁺ plays the major role for high activity. In H₂O₂ decomposition, Co²⁺ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction.     

Non-Oxido-Vanadium(IV) Metalloradical Complexes with Bidentate 1,2-Dithienylethene Ligands: Observation of Reversible Cyclization of the Ligand Scaffold in Solution

Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)₂Cl₂] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the V^IV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution.     

Schrödinger invariance and strongly anisotropic critical systems

The extension of strongly anisotropic or dynamical scaling to local scale invariance is investigated. For the special case of an anisotropy or dynamical exponent =z=2, the group of local scale transformation considered is the Schrödinger group, which can be obtained as the nonrelativistic limit of the conformal group. The requirement of Schrödinger invariance determines the two-point function in the bulk and reduces the three-point function to a scaling form of a single variable. Scaling forms are also derived for the two-point function close to a free surface which can be either spacelike or timelike. These results are reproduced in several exactly solvable statistical systems, namely the kinetic Ising model with Glauber dynamics, lattice diffusion, Lifshitz points in the spherical model, and critical dynamics of the spherical model with a nonconserved order parameter. For generic values of , evidence from higher-order Lifshitz points in the spherical model and from directed percolation suggests a simple scaling form of the two-point function.     

Direct measurement of the flow field around swimming microorganisms

Swimming microorganisms create flows that influence their mutual interactions and modify the rheology of their suspensions. While extensively studied theoretically, these flows have not been measured in detail around any freely-swimming microorganism. We report such measurements for the microphytes Volvox carteri and Chlamydomonas reinhardtii. The minute (～0.3%) density excess of V. carteri over water leads to a strongly dominant Stokeslet contribution, with the widely-assumed stresslet flow only a correction to the subleading source dipole term. This implies that suspensions of V. carteri have features similar to suspensions of sedimenting particles. The flow in the region around C. reinhardtii where significant hydrodynamic interaction is likely to occur differs qualitatively from a puller stresslet, and can be described by a simple three-Stokeslet model.