Extrathermodynamic approach to the study of the adsorption of organic compounds by macromolecules

By using substituent constants and regression analysis, an analysis has been made of the binding of derivatives of aniline and acetanilide to nylon and rayon, the experimental data of Ward and Upchurch being used. The amount of organic compounds bound from an aqueous solution by these two types of synthetic macromolecules is shown to be related to the octanol–water partition coefficients P. In the case of the aniline derivatives, where the basicity of the compounds varied considerably, a good model describing binding results from the linear combination of the two parameters related to free energy, i.e., log P and ΔpK_a. The latter term is the difference between pK_a for aniline and a particular derivative. For the neutral acetanilides a simple linear free-energy relation between log P and log K is found. Of special note is the fact that the dependence of binding of these two classes of compounds to two classes of synthetic macromolecules as indicated by the coefficient with the log P term very closely parallels that found for a variety of biopolymers. The mechanism of hydrophobic binding seems to be the same in both the synthetic and natural polymers.     

Neuronal expression of muskelin in the rodent central nervous system

Background  

The kelch repeat protein muskelin mediates cytoskeletal responses to the extracellular matrix protein thrombospondin 1, (TSP1), that is known to promote synaptogenesis in the central nervous system (CNS). Muskelin displays intracellular localization and affects cytoskeletal organization in adherent cells. Muskelin is expressed in adult brain and has been reported to bind the Cdk5 activator p39, which also facilitates the formation of functional synapses. Since little is known about muskelin in neuronal tissues, we here analysed the tissue distribution of muskelin in rodent brain and analysed its subcellular localization using cultured neurons from multiple life stages.     

Elliptic Curves Suitable for Pairing Based Cryptography

For pairing based cryptography we need elliptic curves defined over finite fields whose group order is divisible by some prime with where k is relatively small. In Barreto et al. and Dupont et al. [Proceedings of the Third Workshop on Security in Communication Networks (SCN 2002), LNCS, 2576, 2003; Building curves with arbitrary small Mov degree over finite fields, Preprint, 2002], algorithms for the construction of ordinary elliptic curves over prime fields with arbitrary embedding degree k are given. Unfortunately, p is of size .We give a method to generate ordinary elliptic curves over prime fields with p significantly less than which also works for arbitrary k. For a fixed embedding degree k, the new algorithm yields curves with where or depending on k. For special values of k even better results are obtained.We present several examples. In particular, we found some curves where is a prime of small Hamming weight resp. with a small addition chain.AMS classification: 14H52, 14G50     

Shape-persistent linear, kinked, and cyclic oligo(phenylene-ethynylene-butadiynylene)s: self-assembled monolayers

Shape-persistent rigid phenylene-ethynylene-butadiynylenes form lamellar self-assembled monolayers (SAMs) at the HOPG/TCB interface, which were studied by scanning tunneling microscopy (STM) with submolecular resolution. Substitution of the terminating acetylene functions with polar cyanopropyldimethylsilyl groups leads to 2D phase separation and defined rod-rod interactions, which determine the packing distances between the rigid rods. The results stimulated the connection of rigid rods via septiarylene clamp units. They covalently link two rigid rod units and define the intramolecular rod-rod distance that matches the alkoxy substituent chain lengths. The systems can be described as half-ring structures of two rigid rods connected via a rotatable joint unit. These acetylene-terminated half-ring structures were also oligomerized under Cu and Pd catalysis to yield defined acyclic and cyclic oligomers. Detailed STM studies decoded the molecular origin of the surface patterning of such systems. The dodecyloxy side chains are adsorbed along the HOPG main axes and, together with the alkoxy backbone angle, determine the adsorption direction of the adlayers.     

Parametrization of multiply differential cross sections

Multiply differential cross sections for two- and three-electron escape are parametrised in terms of generalised tensorial asymmetry parameters. The analysis is based exclusivly on rotational invariance as an exact symmetry for the experimental set up. No approximate assumptions are made on the correlated dynamics of many- electron systems. Results are valid for any atomic and molecular target. The new parameters may be used to describe experimental and theoretical data in a compact way, but also to link e.g. coincidence and non-coincidence measurements with each other.     

Sensory Perception of Non-Deuterated and Deuterated Organic Compounds

The chemical background of olfactory perception has been subject of intensive research, but no available model can fully explain the sense of smell. There are also inconsistent results on the role of the isotopology of molecules. In experiments with human subjects it was found that the isotope effect is weak with acetone and D₆-acetone. In contrast, clear differences were observed in the perception of octanoic acid and D₁₅-octanoic acid. Furthermore, a trained sniffer dog was initially able to distinguish between these isotopologues of octanoic acid. In chromatographic measurements, the respective deuterated molecule showed weaker interaction with a non-polar liquid phase. Quantum chemical calculations give evidence that deuterated octanoic acid binds more strongly to a model receptor than non-deuterated. In contrast, the binding of the non-deuterated molecule is stronger with acetone. The isotope effect is calculated in the framework of statistical mechanics. It results from a complicated interplay between various thermostatistical contributions to the non-covalent free binding energies and it turns out to be very molecule-specific. The vibrational terms including non-classical zero-point energies play about the same role as rotational/translational contributions and are larger than bond length effects for the differential isotope perception of odor for which general rules cannot be derived.     

Monitoring the heterogeneity in single cell responses to drugs using electrochemical impedance and electrochemical noise

Impedance spectroscopy is a widely used technique for monitoring cell–surface interactions and morphological changes, typically based on averaged signals from thousands of cells. However, acquiring impedance data at the single cell level, can potentially reveal cell-to-cell heterogeneity for example in response to chemotherapeutic agents such as doxorubicin. Here, we present a generic platform where light is used to define and localize the electroactive area, thus enabling the impedance measurements for selected single cells. We firstly tested the platform to assess phenotypic changes in breast cancer cells, at the single cell level, using the change in the cell impedance. We next show that changes in electrochemical noise reflects instantaneous responses of the cells to drugs, prior to any phenotypical changes. We used doxorubicin and monensin as model drugs and found that both drug influx and efflux events affect the impedance noise signals. Finally, we show how the electrochemical noise signal can be combined with fluorescence microscopy, to show that the noise provides information on cell susceptibility and resistance to drugs at the single cell level. Together the combination of electrochemical impedance and electrochemical noise with fluorescence microscopy provides a unique approach to understanding the heterogeneity in the response of single cells to stimuli where there is not phenotypic change.

A light addressable single-cell impedance technique for cell adhesion monitoring and measurement of a cell''s drug response based on electrochemical noise is introduced.     

Synthesis of (-)-Vulcanolide by enantioselective protonation

Two efficient enantioselective syntheses of the more active (S,S)-enantiomer of the powerful musk odorant Vulcanolide are described. In both syntheses, the key step is an enantioselective protonation of a ketone enolate. A third enantioselective protonation, of a thiol ester enolate, was applied for the determination of the absolute configuration of Vulcanolide by comparison with a known compound.