Phase behavior at low temperature of poly(tetrafluoroethylene) by temperature-modulated calorimetry

Temperature modulated differential calorimetry (TMDSC) is used to examine the crystal-crystal transitions of poly(tetrafluoroethylene). This study gives new information about the dynamic thermal behavior of such transitions. The involvement of reversible and irreversible processes during the phenomenon is observed, which are related to the order-disorder changes occurring during the transition.This study adds a new example to the response of TMDSC during first order transitions.     

Reactions of ketenes. XX. Phenylketene dimethylacetal as synthon for the introduction of functionalized phenylethyl units

Phenylketene dimethylacetal ( 1 ) reacts with the α-diazoketones to give the dihydrofurans 6 . These compounds, as cyclic ortho esters, can undergo dealcoholation into the furans 2 and hydrolysis into the γ-ketoesters 3 and into the γ-ketoacids 4 . Cyclopropane acetal 8 , obtained starting from acetal 1 and ethyl diazoacetate, by heating leads quantitatively to functionalized ester 9 . These synthetic methods enlarge the sphere of applicability of the electron-rich alkene 1 as synthon in organic synthesis.     

Reactions of ketenes—IX Reactions between ketene acetals and diphenylketene

Monoalkylketene acetals and monoarylketene acetals react with diphenylketene to give acylketene acetals (VII). These compounds can further react with diphenylketene to give 2,4-pyronone 4-acetals (IX), which, by mild acid hydrolysis, yields 2,4-pyronones (X).

Reaction of methylketene diethylacetal with two equivalents of diphenylketene yields 3,3-di-phenyl-5-methyl-6-diphenylmethylentetrahydropyran-2,4-dione 4-diethylacetal (XIV) in addition to small quantities of the pyronone acetal IXb.     

Accurate mass measurements by Fourier transform mass spectrometry in the study of advanced glycation end products/peptides

The Maillard reaction occurring between sugars and amino groups is important in living systems. When amino groups belonging to protein chains are involved, the Maillard reaction has been invoked as responsible for protein cross-linking and the production of 'toxic' compounds. The reaction leads to the production of a heterogeneous group of substances, usually called advanced glycation end products (AGEs). Classical analytical approaches, such as spectroscopic (ultraviolet, fluorescence) and mass spectrometric (matrix-assisted laser desorption/ionization, liquid chromatography/electrospray ionization mass spectrometry) methods, have shown that the digestion mixture is highly complex. However, there are clear differences between the digestion mixtures of glycated and unglycated human serum albumin (HSA). In the former case, possible glycated peptides belonging to the AGE peptide class may be identified. Tandem mass spectrometric experiments on selected species seemed to be promising as regards structural information, but it was thought of interest to undertake the present investigation, based on liquid chromatography/electrospray ionization Fourier transform mass spectrometry, in order to obtain definitive results on their elemental composition. Using this approach, about 20 glycated peptides were detected and their possible structures were postulated by examining the known sequence of HSA.     

Highly Sensitive “Off/On” EPR Probes to Monitor Enzymatic Activity

The assessment of unregulated level of enzyme activity is a crucial parameter for early diagnoses in a wide range of pathologies. In this study, we propose the use of electron paramagnetic resonance (EPR) as an easy method to probe carboxylesterase (CE) enzymatic activity in vitro. For this application, were synthesized two amphiphilic, nitroxide containing esters, namely Tempo-C12 (T-C12) and Tempo-2-C12 (T-2-C12). They exhibit low solubility in water and form stable micelles in which the radicals are EPR almost silent, but the hydrolysis of the ester bond yields narrows and intense EPR signals. The intensity of the EPR signals is proportional to the enzymatic activity. CEs1, CEs2 and esterase from porcine liver (PLE) were investigated. The obtained results show that T-C12 and T-2-C12-containing systems display a much higher selectivity toward the CEs2, with a Limit of Detection of the same order of those ones obtained with optical methods.     

Mikrobestimmung von Siedepunkt und Schmelzpunkt, Mikrosublimation

Ohne Zusammenfassung     

Partial Uniqueness and Obstruction to Uniqueness in Inverse Problems for Anisotropic Elastic Media

We consider the inverse problem of identifying the density and elastic moduli for three-dimensional anisotropic elastic bodies, given displacement and traction measurements made at their surface. These surface measurements are modelled by the dynamic Dirichlet-to-Neumann map on a finite time interval. For linear or nonlinear anisotropic hyperelastic bodies we show that the displacement-to-traction surface measurements do not change when the density and elasticity tensor in the interior are transformed tensorially by a change of coordinates fixing the surface of the body to first order. Our main tool, a new approach in inverse problems for elastic media, is the representation of the equations of motion in a covariant form (following Marsden and Hughes, 1983) that preserves the underlying physics.In the case of classical linear elastodynamics we then investigate how the type of anisotropy changes under coordinate transformations. That is, we analyze the orbits of general linear, anisotropic elasticity tensors under the action by pull-back of diffeomorphisms that fix the surface of the elastic body to first order, and derive a pointwise characterization of parts of the orbits under this action. For example, we show that the orbit of isotropic elastic media, at any point in the body, consists of some transversely isotropic and some orthotropic elastic media. We then derive the first uniqueness result in the inverse problem for anisotropic media using surface displacement-traction data: uniqueness of three elastic moduli for tensors in the orbit of isotropic elasticity tensors. ^†Partially supported by an MSRI Postdoctoral Fellowship. Research at MSRI is supported in part by NSF grant DMS-9850361. This work was conducted while the first author was a Gibbs Instructor at Yale University. ^‡Partially supported by an MSRI Postdoctoral Fellowship, and by NSF grant DMS-9801664 (9996350).     

The variability of composition of the volatile fraction of olive oil

Aroma of olive oil is a very complex mixture of components. Analysis of head space of a series of virgin olive oil samples indicate a great variability of volatile substances composition in olives and these data probably should be related to the story of olives after collecting.     

New insights from X-ray photoelectron spectroscopy into the chemistry of covalent enzyme immobilization, with glutamate dehydrogenase (GDH) on silicon dioxide as an example

A three-step process for immobilization of glutamate dehydrogenase (GDH) on the surface of silicon dioxide has been studied by X-ray photoelectron spectroscopy (XPS). The enzyme layer was deposited on the silicon dioxide surface after first exposing the surface to 3-aminopropyltriethoxysilane (3-APTS) and reacting the silylated surface with glutaraldehyde (GA). Fine XPS analysis, performed after each step of the chemical procedure, revealed unknown details of the step-by-step construction of the enzyme layer under different experimental conditions.     

Boundary determination for an inverse problem in elastodynamics

We consider the unique determination of material properties of an inhomogeneous, isotropic, elastic object from measurements made at the surface. The behavior of the 3-dimensional object is modeled by solutions of the hear. hyperbolic system of equations for elastodynamics. The material properties of the object (its density and elastic properties) correspond to the (leading) coefficients of these diffrential equations. Modeling surface measurements by the Dirichlet-to-Neumann map on a finite time interval, we show here that the Dirichlet-to-Neumann map uniquely determines the density and elastic properties of the surface of the object. Solution of this problem leads to a proof in [R] of unique determination of certain properties(the wave speeds) of the interior of the object. Techniques used here include geometric optics. propagation of singularities for systems of real principal type, and Hamilton-Jacobi theory.