PMR investigation of the structure of native and iodine doped polyacetylene films

The second moment of the proton magnetic resonance line of native cis- polyacetylene, thermally isomerized trans-polyacetylene, and iodine doped initially cis-polyacetylene has been measured by a pulse technique. The results differ qualitatively and quantitatively from previous reports. They are discussed in terms of the proposed crystalline structures of (CH)_x.     

Bright,Highly Water‐Soluble Triazacyclononane Europium Complexes To Detect Ligand Binding with Time‐Resolved FRET Microscopy

Luminescent europium complexes are used in a broad range of applications as a result of their particular emissive properties. The synthesis and application of bright, highly water‐soluble, and negatively charged sulfonic‐ or carboxylic acid derivatives of para‐substituted aryl–alkynyl triazacyclononane complexes are described. Introduction of the charged solubilizing moieties suppresses cellular uptake or adsorption to living cells making them applicable for labeling and performing assays on membrane receptors. These europium complexes are applied to monitor fluorescent ligand binding on cell‐surface proteins with time‐resolved Förster resonance energy transfer (TR‐FRET) assays in plate‐based format and using TR‐FRET microscopy.     

Destabilization of a viscous film flowing down in the form of a vertical cylindrical curtain

In this Letter, we study experimentally a viscous liquid curtain in an annular geometry. Gap and median radius can be varied in such a way that the base of the initially stationary cylindrical curtain is led to oscillate by decreasing the flow rate. Standing and traveling waves in the plane of the annulus are observed and a nontrivial expression linking pulsation to flow rate per surface unit and viscosity can be defined.     

Amorphous blends of poly(zwitterions) and zwitterionomers of the ammonioalkoxydicyanoethenolate type with some alkali metal salts

Poly(zwitterions) and zwitterionomers of the ammonioethoxydicyanoethenolate type (functional dipolar unit R ₃N⁺–(CH ₂) ₂–O–CO–C^?–(CN) ₂, µ = 25.9 D) show the very specific property of solvation of some alkali metal salts to yield amorphous blends. For homopolymers in the (meth)acrylic series, solvation is observed up to a ratio r = [salt]/[zwitterion] of 1 for LiClO ₄ and NaSCN and of 0.5 for NaCF ₃SO ₃: it results in a significant plasticization (increasing order LiClO ₄ < NaSCN < NaCF ₃SO ₃) and in the development in some cases of a poorly defined (lamellar?) local order, as evidenced by the presence of a single broad peak in the small‐angle x‐ray scattering (SAXS) patterns (Bragg distances of about 15–20 Å). For the amorphous blend of a biphasic poly(tetramethyleneoxide) segmented zwitterionomer and NaCF ₃SO ₃ (r = 0.5), selective solvation of the salt in the hard zwitterionic domains induces a transition from a lamellar structure (zwitterionic sublayer of about 9 Å thickness) to an hexagonal packing of ionic‐zwitterionic cylinders (radius of about 15 Å). Ionic conductivity, measured in a narrow range of temperature just above the glass transition temperature, is characterized for most systems by an activation energy of about 1–1.8 eV; the drastic decrease of the conductivity by a factor of 10 ³, when going from the homopolymer to the zwitterionomer blends, is typical of the inhibition of the ionic percolation process by the lack of connectivity of the ionic‐zwitterionic domains. Copyright © 2001 John Wiley & Sons, Ltd.     

Automated Trimethyl Sulfonium Hydroxide Derivatization Method for High-Throughput Fatty Acid Profiling by Gas Chromatography–Mass Spectrometry

Fatty acid profiling on gas chromatography–mass spectrometry (GC–MS) platforms is typically performed offline by manually derivatizing and analyzing small batches of samples. A GC–MS system with a fully integrated robotic autosampler can significantly improve sample handling, standardize data collection, and reduce the total hands-on time required for sample analysis. In this study, we report an optimized high-throughput GC–MS-based methodology that utilizes trimethyl sulfonium hydroxide (TMSH) as a derivatization reagent to convert fatty acids into fatty acid methyl esters. An automated online derivatization method was developed, in which the robotic autosampler derivatizes each sample individually and injects it into the GC–MS system in a high-throughput manner. This study investigated the robustness of automated TMSH derivatization by comparing fatty acid standards and lipid extracts, derivatized manually in batches and online automatically from four biological matrices. Automated derivatization improved reproducibility in 19 of 33 fatty acid standards, with nearly half of the 33 confirmed fatty acids in biological samples demonstrating improved reproducibility when compared to manually derivatized samples. In summary, we show that the online TMSH-based derivatization methodology is ideal for high-throughput fatty acid analysis, allowing rapid and efficient fatty acid profiling, with reduced sample handling, faster data acquisition, and, ultimately, improved data reproducibility.     

Measurement of Nanometer Distances in Solution via 13C NMR Spectroscopy—Shrinking of Macrocycles with Increasing Temperature

For a molecular system, size and shape are of elementary importance for its function and properties. Therefore, the determination of distances within a molecule is essential. However, the commonly used methods are only suitable for distances smaller than 4 Å or larger than 15 Å. Here, we show that by incorporating a molecular spring, we can measure distances in macrocycles in the range of 10 Å using ¹³C NMR spectroscopy. The accuracy of the method also allows to determine the temperature dependence of the distances. In one case, we find a contraction of the length by almost 10 % upon heating. This shrinking due to heating can be considered as inverse thermoelasticity at the molecular level and is a previously completely overlooked phenomenon that can be used in the future as a tool to change the length and, thus, the function of a system.     

Encapsulation of magnetic self-assembled systems in thermoreversible gels

We describe two different ways of encapsulating within the fibrils of thermoreversible polymer gels the filaments of a supermolecular polymer formed by self-assembly of a bicopper complex. Heterogeneous nucleation is brought about with gels made from isotactic poly(styrene) while compound formation occurs with gels made from poly(hexyl isocyanate). These ways depend upon the interaction between the wings of the supermolecular polymer and the side groups of the polymer. In all cases, the filaments retain their 1-D structure. Preliminary results from magnetic susceptibility measurements show a striking difference between the pure and the encapsulated supermolecular polymer.