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     

Massenspektrometrie isomerer Diazaphenanthrene—I

The mass spectra of five diazaphenanthrenes formed by photochemical cyclodehydrogenation of styryl diazines are investigated. It is shown that fragmentation of these compounds starts almost exclusively at the heterocyclic part of the molecule and proceeds by competitive α-cleavage. From the intensity ratios of the ions [M ? H˙]⁺, [M ? HCN]⁺˙, [M ? N₂]⁺˙ and [M ? 2 HCN]⁺˙ generated in this way, each isomer can unequivocally be identified.     

An addition to the oxoacid family: H2B12(OH)12

The acid H(2)B(12)(OH)(12) can be isolated as a crystalline solid by protonation of the hydroxylated borane anion, B(12)(OH)(12)(2)(-). This acidic compound has low solubility in water, conducts protons in the solid state, and has thermal stability to a temperature of 400 degrees C. The conductivity mechanism is a Grotthuss mechanism with a low activation enthalpy (9-13 kcal/mol). This new acid represents an addition to the class of oxoacids, of which sulfuric and phosphoric acid are the most prominent examples.     

Darstellung und Charakterisierung von Halogeno(diethyldithiocarbamato) (triethyl- und triphenylphosphin)palladium(II)-Komplexen

The Complexes [Pd(PEt ₃)₂ dtc]X (1) and Pd(PR ₃)Xdtc (2, 3) (dtc=S₂CNEt ₃;X=Cl, Br, I;R=Et, Ph) have been prepared. Conductivity, susceptibility, UV and IR measurements show that the cations [Pd(PEt ₃)₂ dtc]⁺ of1 and the complexes2, 3 have square-planar structure.

     

1H, 13C and 15N NMR spectral analysis of substituted 1,2,3,4‐tetrahydro‐pyrido[1,2‐a]pyrimidines

The NMR spectroscopic data of a series of thirty‐four 3‐acylpyrido[1,2‐a]pyrimidinium salts are analyzed, which were prepared as either perchlorates or chlorides. Methyl group substituted 3‐aroyltetrahydropyrido[1,2‐a]pyrimidines with the methyl substituent in positions 6, 8 and 9 as well as both in positions 6 and 8 were investigated bearing various aroyl substituents. Unequivocal assignment of all resonances was achieved via two‐dimensional ¹H,¹H‐COSY measurements, ¹H,¹³C and ¹H,¹⁵N HSQC as well as HMBC experiments, and important diagnostic CH and NH couplings in the heteroaromatic ring system are evaluated. The influence of the methyl substituents was analyzed on the proton, carbon and nitrogen shifts. A significant effect of the counter ion on some chemical shifts of the nuclei under discussion of the pyridopyrimidines is found, allowing the indirect detection of the anion, which is confirmed by direct measurement of the ³⁵Cl nucleus of the perchlorates. Copyright © 2013 John Wiley & Sons, Ltd.     

An experimentally validated rod model for soft continuum robots

Soft robots are bio-inspired, highly deformable robots with the ability to interact with workpieces in a manner that complements their hard robot counterparts. To develop practical applications and reproducible designs of soft robots, new models are necessary to describe their kinematics and dynamics. In the present work, we describe experimental and numerical investigations of a popular pneumatically-actuated soft continuum arm. These works enable us to derive constitutive relations and develop a rod model for large deformations of the arm that faithfully describes its bending behavior. We show how the resulting non-classical constitutive relation can be defined either through experiments or through quasi-static finite element simulations. With the help of this relation, the resulting rod model can be used to study the dynamics of the soft robot arm in a fast and tractable manner. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Validation of a coupled FE-model for the simulation of methane oxidation via thermal imaging

To simulate the processes of methane oxidation in landfill cover layers, a new computational model was created. The purpose of the model is to allow a forecast on the performance of methanotrophic activity in landfill cover layers under changing environmental conditions. Therefore, a thermodynamic consistent model based on the well-known Theory of Porous Media (TPM) combined with the mixture theory was developed, which analyzes the relevant gas productions of methane, oxygen and carbon dioxide. Diffusion, advection and conversion processes are considered as well as the energy production during methane oxidation. With the help of the thermal imaging technique a new experimental setup was developed in order to validate the coupled model in terms of the heat generation. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)