Surface polarity of cellulose derivates observed by coumarin 151 and 153 as solvatochromic and fluorochromic probes

Solvent‐dependent ultraviolet–visible (UV–vis) absorption and Stokes shifts including strong hydrogen‐bond‐donating (HBD) solvents such as 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol of two coumarine dyes (Co 151 and Co 153) were analyzed with multiple‐square analyses of linear solvation energy relationships and the Kamlet–Taft solvent parameter set to α (HBD capacity), β (hydrogen‐bond‐accepting capacity), and π* (dipolarity/polarizability). The UV–vis absorption and emission spectra of Co 151 and Co 153 were measured when adsorbed on various polysaccharides such as different cellulose batches, carboxymethylcelluloses with different degrees of substitution, and chitine. As a result of this evaluation, Co 153 is recommended as an alternative UV–vis probe for evaluating the dipolarity/polarizability of cellulose and cellulose derivates. Multiple adsorption of Co 153 on Linters cellulose took place indicating a wide‐surface polarity distribution, which makes the determination of a rigid polarity parameter questionable. Thus, fluorescence measurements of adsorbed Co 153 are suitable to detect inhomogenities on a surface but not for the determination of empirical polarity parameters. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1210–1218, 2003     

Microscopic conditions favoring itinerant ferromagnetism: Hund's rule coupling and orbital degeneracy

The importance of Hund's rule coupling for the stabilization of itinerant ferromagnetism is investigated within a two-band Hubbard model. The magnetic phase diagram is calculated by finite-temperature quantum Monte-Carlo simulations within the dynamical mean-field theory. Ferromagnetism is found in a broad range of electron fillings whereas antiferromagnetism exists only near half filling. The possibility of orbital ordering at quarter filling is also analyzed. Received: 26 February 1998 / Accepted: 17 April 1998     

Dispersive anisotropic ballistic phonon propagation in [100] GaAs

We report experimental observations of the phonon focusing pattern in [100] GaAs using low temperature electron beam scanning for phonon generation. The typical dispersive effects for high-frequency phonons expected from the calculations by Tamura have clearly been observed using PbIn tunnel junctions for phonon detection. The quantitative comparison of our experimental results with the frequency dependent calculations by Tamura allowed to determine the dominant phonon frequencies contributing to the detector signal in our different experiments. Above the temperature of the -point the dominant phonon frequencies appear to be shifted considerably to lower values, which could be explained by a heating effect in the liquid-He layer adjacent to the tunnel junction detector. By comparing the observed magnitude of the detector signal with different theoretical treatments of the detector response, we have found satisfactory agreement for a model where the perturbation due to the high-frequency phonons is restricted to the base electrode of the detector reached first by the phonons following their passage through the crystal.     

Accreditation of reference material producers: the example of IRMM's Reference Materials Unit

The potential approaches for third-party assessment of reference material producers are revisited and the activities of the Reference Materials (RM) Unit of the Institute for Reference Materials and Measurements (IRMM) to obtain accreditation to ISO Guide 34 and ISO 17025 are described. Accreditation was related to the Unit as all matrix RM activities of the institute are concentrated there. A management system was established that allows sufficient flexibility to be applicable to a wide range of RMs while being precise enough to ensure compliance with ISO Guides 30, 31 and especially 34 and 35. Accreditation was achieved in 2004 with independent scopes for testing and RM production and was confirmed and extended in 2005. The key aspects of the RM Unit's management system for RM production are presented. Presented at BERM-10, April 2006, Charleston, SC, USA     

Imaging of spatial structures in crystals with ballistic phonons

Ballistic phonon propagation in single crystals has been used for imaging defect structures in bulk material. We have realized this principle by means of low-temperature scanning electron microscopy. As model cases we have imaged laser drilled holes in single-crystalline sapphire and -quartz samples. Comparing the acoustic images with those obtained by optical transmission microscopy, we found that fine structure seen optically was well reproduced acoustically. In addition strain fields due to plastic deformations could clearly be imaged acoustically. The spatial resolution of our imaging technique is estimated to be a few micrometer. By using two or more phonon detectors, three-dimensional imaging of spatial inhomogeneities becomes possible.     

Baylis-Hillman mechanism: a new interpretation in aprotic solvents

Using reaction rate data collected in aprotic solvents, we have determined that the Baylis-Hillman rate-determining step is second order in aldehyde and first order in DABCO and acrylate. On the basis of these data, we have proposed a new mechanism involving a hemiacetal intermediate. The proposed mechanism was then supported using two different kinetic isotope experiments.