Thermal degradation of ammonium polymethacrylate and polymethacrylamide

The degradation of ammonium polymethacrylate and polymethacrylamide has been studied by a combination of thermal analysis methods (TVA and TG) and examination of volatile and involatile products by infrared analysis. It is shown that total reaction comprises an initial cyclization and further fragmentation of the modified chain at higher temperatures to yield gaseous volatiles. The partially degraded NH₄PMA contains anhydride ring and cyclic imide structures in the chain. Quantitative comparison of yields of isocyanic acid and carbon dioxide has shown that imidization is the major reaction and anhydride formation is of less importance. The mechanisms of the various reactions are discussed.     

Degradation of polymer mixtures—Part 10: The thermal degradation of blends of polyacrylonitrile and poly(methyl methacrylate)

Although the thermal degradation of polyacrylonitrile (PAN) is unchanged by blending with poly(methyl methacrylate) (PMMA), the degradation of PMMA is profoundly altered in the presence of PAN. The low temperature phase of the reaction is hindered although monomer is still the predominating product. At higher temperatures the monomer production gives way to the appearance of methanol, carbon dioxide, carbon monoxide and chain fragments which incorporate a variety of carbonyl structures.These results are interpreted in terms of initial reaction of methyl methacrylate units with the ammonia formed by degradation of the PAN. The amide-ester copolymer thus formed undergoes a complex degradation process at higher temperatures which includes inter unit cyclisations, chain fragmentation and the formation of methanol and oxides of carbon. Mechanisms are proposed and discussed.     

Isolation and synthesis of glutamine and glutarimide derivatives fromCroton humilis

Extract ofCroton humilis L. were shown to contain N - [N - (2 - methylpropanoyl) -l - glutaminoyl] - 2 - phenylethylamine, N - [N - 2R - methylbutanoyl) -l - glutaminoyl] - 2 - phenylethylamine, 2 - [N- (2 - methylpropanoyl)] - N - phenylethylglutarimide and 2 - [N- (2R - methylbutanoyl)] - N - phenylethylglutarimide. Structural proof was based on acid degradation, spectral studies as well as the synthesis of N - [N- (2- methylpropanoyl) -l - glutaminoyl] - 2 - phenylethylamine and 2 - [N - (2 - methylpropanoyl] - N - phenylethylglutarimide.     

Generalized weak peripheral multiplicativity in algebras of Lipschitz functions

Let (X, d _X ) and (Y,d _Y ) be pointed compact metric spaces with distinguished base points e _X and e _Y . The Banach algebra of all $\mathbb{K}$ -valued Lipschitz functions on X — where $\mathbb{K}$ is either?or ? — that map the base point e _X to 0 is denoted by Lip₀(X). The peripheral range of a function f ∈ Lip₀(X) is the set Ran_µ(f) = {f(x): |f(x)| = ‖f‖_∞} of range values of maximum modulus. We prove that if T ₁, T ₂: Lip₀(X) → Lip₀(Y) and S ₁, S ₂: Lip₀(X) → Lip₀(X) are surjective mappings such that $Ran_\pi (T_1 (f)T_2 (g)) \cap Ran_\pi (S_1 (f)S_2 (g)) \ne \emptyset $ for all f, g ∈ Lip₀(X), then there are mappings φ₁φ₂: Y → $\mathbb{K}$ with φ₁(y)φ₂(y) = 1 for all y ∈ Y and a base point-preserving Lipschitz homeomorphism ψ: Y → X such that T _j (f)(y) = φ _j (y)S _j (f)(ψ(y)) for all f ∈ Lip₀(X), y ∈ Y, and j = 1, 2. In particular, if S ₁ and S ₂ are identity functions, then T ₁ and T ₂ are weighted composition operators.     

Exploring the Limits of Förster Theory for Energy Transfer at a Separation of 20 Å

Cutting the corner : An excellent agreement has been obtained between experimental and computed coulombic coupling matrix elements for donor–spacer–acceptor systems, which consist of a boron dipyrromethane donor and acceptor in various stages of protonation. This correlation occurs in spite of reservations about the validity of Förster theory being applied to intramolecular electronic energy transfer (ET) over short (e.g., 20 Å) distances (see picture).

     

Energy transfer mediated fluorescence from blended conjugated polymer nanoparticles

Nanoparticles consisting of a derivative of the blue-emitting conjugated polymer polyfluorene doped with green-, yellow-, and red-emitting conjugated polymers were prepared by a reprecipitation method. The nanoparticles can be described as a system of densely packed chromophores that exhibit efficient energy transfer from the host to the dopant polymers. Fluorescence quenching analysis of the host polymer as a function of the dopant concentration indicates that one energy acceptor molecule can effectively quench 90% of the fluorescence of a nanoparticle consisting of 100-200 host conjugated polymer molecules. A nanoparticle energy transfer model was developed that successfully describes the quenching behavior of a small number of highly efficient energy acceptors per nanoparticle. The fluorescence brightness of the blended polymer nanoparticles was determined to be much higher than that of inorganic quantum dots and dye-loaded silica particles of similar dimensions. The combination of high fluorescence brightness and tunable fluorescence of these blended nanoparticles is promising for ultrasensitive fluorescence-based assays.     

Tarski's theorem on intuitionistic logic,for polyhedra

In 1938, Tarski proved that a formula is not intuitionistically valid if, and only if, it has a counter-model in the Heyting algebra of open sets of some topological space. In fact, Tarski showed that any Euclidean space ${\mathbb{R}}^n$ with $n?1$ suffices, as does e.g. the Cantor space. In particular, intuitionistic logic cannot detect topological dimension in the Heyting algebra of all open sets of a Euclidean space. By contrast, we consider the lattice of open subpolyhedra of a given compact polyhedron $P?{\mathbb{R}}^n$, prove that it is a locally finite Heyting subalgebra of the (non-locally-finite) algebra of all open sets of P, and show that intuitionistic logic is able to capture the topological dimension of P through the bounded-depth axiom schemata. Further, we show that intuitionistic logic is precisely the logic of formulæ valid in all Heyting algebras arising from polyhedra in this manner. Thus, our main theorem reconciles through polyhedral geometry two classical results: topological completeness in the style of Tarski, and Ja?kowski's theorem that intuitionistic logic enjoys the finite model property. Several questions of interest remain open. E.g., what is the intermediate logic of all closed triangulable manifolds?     

Measurements of fluoride in bone biopsies by neutron activation analysis for the clinical study of osteoporosis

A procedure has been developed to measure fluoride concentration in bone biopsies by neutron activation analysis /NAA/. The NAA procedure is non-destructive so that the bone biopsies can be used subsequently for histological evaluation. The fluoride content is expressed as F/Ca ratio in the bone samples. The fluoride and calcium are measured using the reactions:¹⁹F/n, /²⁰F /t=11.2 s/ and⁴⁸Ca/n,/⁴⁹Ca/t=8.8 m/, respectively. The F/Ca ratio normalizes the fluoride to bone mineral avoiding the use of bone weight which is unreliable with fresh biopsy samples. This ratio also corrects for variations in neutron flux and gamma counting efficiencies. Results by this procedure were compared to biochemical determinations using an ion-selective electrode for fluoride and atomic absorption for calcium. The two methods gave results which agreed within ±5% which is the precision of the NNA procedure. The NAA method provides a simple and non-destructive procedure for fluoride measurement in bone biopsies for clinical studies. The method is now routinely used in our clinical studies for the fluoride measurements on biopsies from osteoporotic patients treated with fluoride therapy for nearly four years.