Reversible Dimerization and Polymerization of a Janus Diradical To Produce Labile C−C Bonds and Large Chromic Effects

Conducting polymers can be synthesized by irreversible diradical monomer polymerization. A reversible version of this reaction consisting of the formation/dissociation of σ‐dimers and σ‐polymers from a stable quinonoidal diradical precursor is described. The reaction reversibility is made by a quinonoidal molecule which changes its structure to an aromatic species by forming weak and long intermolecular C?C single bonds. The reaction provokes a giant chromic effect of about 2.5 eV. The two opposite but complementary quinonoidal and aromatic tautomers provide the Janus faces of the reactants and products which produces the observed chromic effect. A reaction mechanism is proposed to explain the variety of final products starting with structurally very similar reactants. These reversible reactions, covering an unusual regime of weak covalent supramolecular bonding, yield products which might be envisaged as novel molecular and polymeric soft matter phases.     

Dimensional changes as a function of charge injection in single-walled carbon nanotubes

Motivated by the central importance of charge-induced dimensional changes for carbon nanotube electromechanical actuators, we here predict changes in nanotube length and diameter as a function of charge injection for armchair and zigzag nanotubes having different diameters. Density functional theory with periodic boundary conditions is used, which we show provides results consistent with experimental observations for intercalated graphites. Strain-versus-charge relationships are predicted from dimensional changes calculated with a uniform background charge ("jellium") for representing the counterions. These jellium calculations are consistent with presented calculations that include specific counterions for intercalated graphite, showing that hybridization between the ions and the graphite sheets is unimportant. The charge-strain relationships calculated with the jellium approximation for graphite and isolated single-walled nanotubes are asymmetric with respect to the sign of charge transfer. The dependence of nanotube strain on charge approaches that for a graphite sheet for intermediate-sized metallic nanotubes and for larger diameter semiconducting nanotubes. However, the strain-charge curves strongly depend on nanotube type when the nanotube diameter is small. This reflects both the dependence of the frontier orbitals for the semiconducting nanotubes on the nanotube type and the pi-sigma mixing when the nanotube diameter is small.     

HPTLC/DESI-MS imaging of tryptic protein digests separated in two dimensions

Desorption electrospray ionization mass spectrometry (DESI-MS) was demonstrated as a method to detect and identify peptides from two-dimensional separations of cytochrome c and myoglobin tryptic digests on ProteoChrom HPTLC Cellulose sheets. Data-dependent tandem mass spectra were acquired during lane scans across the TLC plates. Peptides and the corresponding proteins were identified using a protein database search software. Two-dimensional distributions of identified peptides were mapped for each separated protein digest. Sequence coverages for cytochrome c and myoglobin were 81 and 74%, respectively. These compared well with those determined using the more standard HPLC/ESI-MS/MS approach (89 and 84%, respectively). Preliminary results show that use of more sensitive instrumentation has the potential for improved detection of peptides with low R(f) values and improvement in sequence coverage. However, less multiple charging and more sodiation were seen in HPTLC/DESI-MS spectra relative to HPLC/ESI-MS spectra, which can affect peptide identification by MS/MS. Methods to increase multiple charging and reduce the extent of sodiation are currently under investigation.     

Minimizing analyte electrolysis in electrospray ionization mass spectrometry using a redox buffer coated emitter electrode

An emitter electrode with an electroactive poly(pyrrole) (PPy) polymer film coating was constructed for use in electrospray ionization mass spectrometry (ESI‐MS). The PPy film acted as a surface‐attached redox buffer limiting the interfacial potential of the emitter electrode. While extensive oxidation of selected analytes (reserpine and amodiaquine) was observed in positive ion mode ESI using a bare metal (gold) emitter electrode, the oxidation was suppressed for these same analytes when using the PPy‐coated electrode. A semi‐quantitative relationship between the rate of oxidation observed and the interfacial potential of the emitter electrode was shown. The redox buffer capacity, and therefore the lifetime of the redox buffering effect, correlated with the oxidation potential of the analyte and with the magnitude of the film charge capacity. Online reduction of the PPy polymer layer using negative ion mode ESI between analyte injections was shown to successfully restore the redox buffering capacity of the polymer film to its initial state. Published in 2010 by John Wiley & Sons, Ltd.     

Unique expansions of real numbers

It was discovered some years ago that there exist non-integer real numbers q>1 for which only one sequence (ci) of integers ci∈[0,q) satisfies the equality . The set of such “univoque numbers” has a rich topological structure, and its study revealed a number of unexpected connections with measure theory, fractals, ergodic theory and Diophantine approximation.In this paper we consider for each fixed q>1 the set Uq of real numbers x having a unique representation of the form with integers ci belonging to [0,q). We carry out a detailed topological study of these sets. For instance, we characterize their closures, and we determine those bases q for which Uq is closed or even a Cantor set. We also study the set consisting of all sequences (ci) of integers ci∈[0,q) such that . We determine the numbers r>1 for which the map (defined on (1,∞)) is constant in a neighborhood of r and the numbers q>1 for which is a subshift or a subshift of finite type.     

Asymptotics for the ratio of leading coefficients of orthonormal polynomials on the unit circle

Consider a system {φ _n } of polynomials orthonormal on the unit circle with respect to a measuredμ, withμ′>0 almost everywhere. Denoting byk _n the leading coefficient ofφ _n , a simple new proof is given for E. A. Rakhmanov's important result that lim _n→∞,k _n /k _n+1=1; this result plays a crucial role in extending Szegö's theory about polynomials orthogonal with respect to measuresdμ with logμ′∈L ¹ to a wider class of orthogonal polynomials.     

Electronic structures and charge transport properties of the organic semiconductor bis[1,2,5]thiadiazolo-p-quinobis(1,3-dithiole), BTQBT, and its derivatives

We analyze the correlation between crystal and film structures and charge transport of an important organic semiconductor, bis[1,2,5]thiadiazolo-p-quinobis(1,3-dithiole) (BTQBT), and its derivatives 4,8-bis(1,3-dithiol-2-ylidene)-4H,8H-[1,2, 5]selenadiazolo[3,4-f]-2,1,3-benzothiadiazole, 4,8-bis(1,3-diselenol-2-ylidene)-4H,8H-benzo[1,2-c:4,5-c']bis[1,2,5]thiadiazole, and tetramethyl-BTQBT. We present first-principles density functional theory (DFT) calculations that agree well with earlier angle-resolved photoelectron spectroscopy (ARPES) experiments on BTQBT films, strongly supporting that the BTQBT films adopt the same layered structure as in the single crystals. Qualitative charge transport properties based on presented DFT results agree with experiments regarding the sign of the charge carriers and the unusually small anisotropy of conductivity. These agreements indicate that accurate electronic structure calculations, when coupled with ARPES, help establish the correlation between intermolecular packing and charge transport, which is one of the central but elusive aspects of organic molecular materials. Predictions are made for derivatives of BTQBT, and calculations agree with available experimental information on the conductivities. Comparisons are made with pentacene, one of the most widely studied organic molecular materials.     

Reactions of 5-Acetyl-10, 11-epoxy-10, 11-dihydro-5H-dibenz [b,f] Azepine with Alcohols and Trialkyl Orthoformates

The title compound (1) was reacted with trialkyl orthoformates and alcohols in the presence of boron trifluoride etherate. Depending on the solvent and temperature 10-acetyl-9-(dialkoxy)- methyl-9, 10-dihydroacridines(2) and/or 5-acetyl-10-alkoxy-11-hydroxy-10, 11-dihydro-5H-dibenz[b,f] azepines were formed (3).