Effective stresses — a clarification

Summary Although the phenomenon of effective stresses was known for a long time, the theoretical foundation has remained unsatisfactory until now. Due to new experimental and theoretical findings in the porous media theory, the concept of effective stresses will be reexamined. This is necessary for porous media such as concrete and rock which show at high pressure a significant deviation of the real effective stresses from those calculated with von Terzaghi's concept due to the compressibility of the true material. A second feature of the present paper is the investigation of the effective stress principle in unsaturated porous media.Financial support provided by the Deutsche Forschungsgemeinschaft (DFG) and the Volkswagen-Stiftung is greatly appreciated.     

Function‐Led Design of Aerogels: Self‐Assembly of Alloyed PdNi Hollow Nanospheres for Efficient Electrocatalysis

One plausible approach to endow aerogels with specific properties while preserving their other attributes is to fine‐tune the building blocks. However, the preparation of metallic aerogels with designated properties, for example catalytically beneficial morphologies and transition‐metal doping, still remains a challenge. Here, we report on the first aerogel electrocatalyst composed entirely of alloyed PdNi hollow nanospheres (HNSs) with controllable chemical composition and shell thickness. The combination of transition‐metal doping, hollow building blocks, and the three‐dimensional network structure make the PdNi HNS aerogels promising electrocatalysts for ethanol oxidation. The mass activity of the Pd₈₃Ni₁₇ HNS aerogel is 5.6‐fold higher than that of the commercial Pd/C catalyst. This work expands the exploitation of the electrocatalysis properties of aerogels through the morphology and composition control of its building blocks.     

Poly(caprolactone) containing highly branched segmented poly(ester urethane)s via A2 with oligomeric B3 polymerization

Highly branched, poly(caprolactone) (PCL) containing segmented poly(ester urethane)s were synthesized via polymerization of A₂ and oligomeric B₃ type monomers. An isocyanate functional butanediol‐based A₂ hard segment was synthesized and immediately reacted with a poly(caprolactone)‐based trifunctional (B₃) soft segment. Characterization of thermal properties using DMA and DSC analysis demonstrated that the PCL segment remained amorphous in branched poly(ester urethane)s. Conversely, the crystallinity of PCL segment was retained to some extent in a linear analogue with equivalent soft segment molecular weight. Tensile testing revealed a slight decrease in Young's modulus and tensile strength for the highly branched polymers compared with a linear analogue. However, highly branched poly(ester urethane)s demonstrated lower hysteresis. In addition to synthesis of highly branched polymers, poly(ester urethane) networks were synthesized from a highly branched hydroxyl‐terminated precursor and a low molar mass diisocyanate as the crosslinking agent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6285–6295, 2008     

Positive ion electrospray ionization mass spectrometry of oligonucleotides

Positive ion electrospray ionization mass spectra have been obtained of deoxyribonucleic acids (DNA) and ribonucleic acids (RNA), including transfer RNAs (77-mer, ～ 25 kDa). For several different solution conditions, the charge state distributions of DNA and RNA molecules were determined. It is postulated that the production of the multiply charged positive ions results from gas phase dissociation of complexes between nitrogen-containing bases and oligonucleotides.     

Phase Transitions in Gas- and Liquid-Saturated Porous Solids

Phase transitions in porous media consisting of a porous solid filled with liquid and gas constituents can occur, for example, due to freezing and drying processes. Although these phenomena are of certain relevance in soil mechanics and material sciences, a general thermo-dynamical theory is still awaited. Based on recent findings in the porous media theory, this paper is concerned with the development of thermodynamic restrictions for the constitutive relations of an elastic, incompressible porous solid, filled with an incompressible liquid and a compressible gas. The investigations show that mass conversions are related to the differences of the chemical potentials and energy transitions to the differences of temperatures. Thus, they confirm well-known results in classical thermodynamics of gases.     

On a theorem of Kaufman: Cantor-type construction of linear fractal Salem sets

In this paper we present a deterministic Cantor-type construction of linear fractal Salem sets with prescribed dimension. The construction rests on a paper of Kaufman [10] where he investigated the Fourier dimension of the set of α-well approximable numbers inR. Supported by Deutsche Forschungsgemeinschaft DFG, Grant BL446/1-1.     

Teachers’ Practices in High School Chemistry Just Prior to the Adoption of the Next Generation Science Standards

Effective professional development that influences teachers’ classroom practices starts with what teachers know, understand, and do in their classroom. The Next Generation Science Standards (NGSS) challenge teachers to make changes to their classroom; to help teachers make these changes, it is necessary to know what they are doing in their classrooms just prior to NGSS adoption. An online survey was distributed to high school chemistry teachers to understand their teaching practices before NGSS was adopted as state standards. This article presents the findings of the survey in terms of the chemistry content, science and engineering practices, and engineering content currently taught in chemistry. Gaps in the current teaching practices as they relate to the standards at the time of the study and NGSS are discussed, which show a challenge for the transformation of science education, which the implementation of NGSS hopes to achieve. Implications for professional development are included.     

K‐edge XANES analysis of sulfur compounds: an investigation of the relative intensities using internal calibration

Sulfur K‐edge XANES (X‐ray absorption near‐edge structure) spectroscopy is an excellent tool for determining the speciation of sulfur compounds in complex matrices. This paper presents a method to quantitatively determine the kinds of sulfur species in natural samples using internally calibrated reference spectra of model compounds. Owing to significant self‐absorption of formed fluorescence radiation in the sample itself the fluorescence signal displays a non‐linear correlation with the sulfur content over a wide concentration range. Self‐absorption is also a problem at low total absorption of the sample when the sulfur compounds are present as particles. The post‐edge intensity patterns of the sulfur K‐edge XANES spectra vary with the type of sulfur compound, with reducing sulfur compounds often having a higher post‐edge intensity than the oxidized forms. In dilute solutions (less than 0.3–0.5%) it is possible to use sulfur K‐edge XANES reference data for quantitative analysis of the contribution from different species. The results show that it is essential to use an internal calibration system when performing quantitative XANES analysis. Preparation of unknown samples must take both the total absorption and possible presence of self‐absorbing particles into consideration.