Carboxylic fused furans for amino acid fluorescent labelling

Four carboxylic fused furans are presented as new fluorescent labels for the amino and hydroxyl functions of organic molecules. Various representative l-amino acids were chosen as models, labelled at their N-terminus and also at their side-chain. Fluorescent derivatives were obtained in high yields, and their absorption and emission properties were studied.     

Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Robust locally testable codes and products of codes

We continue the investigation of locally testable codes, i.e., error‐correcting codes for which membership of a given word in the code can be tested probabilistically by examining it in very few locations. We give two general results on local testability: First, motivated by the recently proposed notion of robust probabilistically checkable proofs, we introduce the notion of robust local testability of codes. We relate this notion to a product of codes introduced by Tanner and show a very simple composition lemma for this notion. Next, we show that codes built by tensor products can be tested robustly and somewhat locally by applying a variant of a test and proof technique introduced by Raz and Safra in the context of testing low‐degree multivariate polynomials (which are a special case of tensor codes). Combining these two results gives us a generic construction of codes of inverse polynomial rate that are testable with poly‐logarithmically many queries. We note that these locally testable tensor codes can be obtained from any linear error correcting code with good distance. Previous results on local testability, albeit much stronger quantitatively, rely heavily on algebraic properties of the underlying codes. © 2006 Wiley Periodicals, Inc. Random Struct. Alg., 2006     

Bipyridinophane‐containing conjugated polymers modulated with an intramolecular aromatic C?H/π interaction

Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and ¹H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, and Ag⁺ ions. In contrast, only Cu²⁺, Co²⁺, and Ni²⁺ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu²⁺, Co²⁺, and Ni²⁺ ions toward P7 are of the order of 10⁶ M^?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006     

Asymptotic speeds of spread and traveling waves for monotone semiflows with applications

The theory of asymptotic speeds of spread and monotone traveling waves is established for a class of monotone discrete and continuous‐time semiflows and is applied to a functional differential equation with diffusion, a time‐delayed lattice population model and a reaction‐diffusion equation in an infinite cylinder. © 2005 Wiley Periodicals, Inc.     

A Characterization of Cosmological Time Functions

A characterization of time functions on a spacetime is made by using theMöbius equation. It is shown that a time function characterized in this wayyields past timelike geodesic incompleteness and local Lorentzian warpedproduct decomposition of spacetime, provided that the stress-energy tensoris a fluid. Also, by imposing additional assumptions on the stress-energytensor and global analytic structure of the spacetime, more restrictivedecompositions closer to Robertson–Walker spacetimes are obtained.     

Resolution of binary mixtures of cephalothin and clavulanic acid by using first derivative spectrophotometry

First-derivative spectrophotometric method with a “zero-crossing” technique of measurement has been used for the quantification of two-components mixtures of cephalothin and clavulanic acid. As the absorption bands of these drugs overlap, both direct and derivative spectrophotometric methods have been investigated and evaluated by a rigorous statistical analysis of the experimental data. The first-derivative spectrophotometric method was found to be more accurate, direct and reproducible. Beer's law was valid over the concentration range 2.0–28.0 mg/l for both compounds. The detection limits of cephalothin and clavulanic acid, at a 0.05 level of significance, were calculated to be 0.13 and 0.15 mg/l. The method was applied for determining these antibiotics in mixtures, some of them containing inject-able dosage forms of cephalothin, and so to determine both compounds in saline and glucosed physiological sera.     

Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Influence of Particle Morphology and Flow Conditions on the Dispersion Behavior of Fumed Silica in Silicone Polymers

The dispersion behavior of agglomerates of several grades of fumed silica in poly(dimethyl siloxane) liquids has been studied as a function of particle morphology and applied flow conditions. The effects of primary particle size and aggregate density and structure on cohesivity were probed through tensile and shear strength tests on particle compacts. These cohesivity tests indicated that the shear strength of particle compacts was two orders of magnitude higher than the tensile strength at the same overall packing density. Experiments carried out in both steady and time‐varying simple‐shear flows indicate that dispersion occurs through tensile failure. In the steady‐shear experiments,enhanced dispersion was obtained at higher levels of applied stress and, at comparable levels of applied stress, dispersion was found to proceed faster at higher shear rates. Experiments conducted in time‐varying flows further corroborated the results obtained in tensile cohesivity tests. Experiments in which the mean and maximum stresses in the time‐varying flows were matched to the stresses produced in steady shear flows highlight the influence of flow dynamics on dispersion behavior.