Synthesis of tri‐aryl ketone amine isomers and their cure with epoxy resins

Isomeric tri‐aryl ketone amines, 1,3‐bis(3‐aminobenzoyl)benzene (133 BABB), 1,3‐bis(4‐aminobenzoyl)benzene (134 BABB), and 1,4‐bis(4‐aminobenzoyl)benzene (144 BABB) are synthesized and cured with diglycidyl ether of bisphenol A and diglycidyl ether of bisphenol F in this work. Differential scanning calorimetry and near‐infrared spectroscopy reveal higher rate constants and enhanced secondary amine conversion with increasing para substitution attributed to resonance effects and the electron withdrawing nature of the carbonyl linkages. Glass transition temperatures increase from 133 BABB to 134 BABB, but decrease modestly for the 144 BABB hardener. With increasing para substitution, the flexural modulus and strength both decrease while the strain to failure increases but all BABB amines displaying higher mechanical properties than the corresponding 4,4‐diaminodiphenyl sulfone (44 DDS) networks. The thermal stability of the BABB networks is found to be modestly lower than 44 DDS, but char yields are significantly higher. Changes in thermal and mechanical properties are described in terms of molecular structure and equilibrium packing density.     

On the influence of numerical integration on mixed finite element approximations of a Maxwell eigenvalue problem

The behaviour of electromagnetic resonances in cavities is modelled by a Maxwell eigenvalue problem (EVP). In the present work, we rewrite the corresponding variational problem, as it arises with a view to the application of a finite element method, in a mixed formulation. For the modelling of realistic problems the integrals occurring in this mixed formulation often cannot be evaluated exactly. We take into account the error arising from numerical quadrature and show convergence to the approximations using exact integration. Finally, some numerical results are presented.     

Torsional vibrations of wet clutches: influence of mechanical parameters

Using a small scale test-rig a number of experiments were performed in which the imposed disk velocity v _disk, the different mechanical parameters of the test-rig (damping c and tangential stiffness k), and normal load were varied independently.     

Subpicosecond Excited-State Proton Transfer Preceding Isomerization During the Photorecovery of Photoactive Yellow Protein

The ultrafast excited-state dynamics underlying the receptor state photorecovery is resolved in the M100A mutant of the photoactive yellow protein (PYP) from Halorhodospira halophila. The M100A PYP mutant, with its distinctly slower photocycle than wt PYP, allows isolation of the pB signaling state for study of the photodynamics of the protonated chromophore cis-p-coumaric acid. Transient absorption signals indicate a subpicosecond excited-state proton-transfer reaction in the pB state that results in chromophore deprotonation prior to the cis-trans isomerization required in the photorecovery dynamics of the pG state. Two terminal photoproducts are observed, a blue-absorbing species presumed to be deprotonated trans-p-coumaric acid and an ultraviolet-absorbing protonated photoproduct. These two photoproducts are hypothesized to originate from an equilibrium of open and closed folded forms of the signaling state, I(2) and I(2)'.     

Critical scaling in linear response of frictionless granular packings near jamming

We study the origin of the scaling behavior in frictionless granular media above the jamming transition by analyzing their linear response. The response to local forcing is non-self-averaging and fluctuates over a length scale that diverges at the jamming transition. The response to global forcing becomes increasingly nonaffine near the jamming transition. This is due to the proximity of floppy modes, the influence of which we characterize by the local linear response. We show that the local response also governs the anomalous scaling of elastic constants and contact number.     

Polystyrene film-coated glassware: a new means of reducing metal losses in trace metal speciation

A recently developed process for coating a glass surface with polystyrene (PS) film, by use of a simple chemical process has been used to reduce trace metal adsorption by cell components. The glass coating is a two-step procedure consisting of covalent attachment of vinyl-terminated PS to Si atoms on the glass surface then adsorption of PS from solution to create a stable PS film. To assess the quality of the coating we used anodic stripping voltammetry to study the adsorption of lead and cadmium ions in coated and untreated glass cells. In both short and long-term (24 h) experiments we observed that the amount of metal adsorbed was considerably less for the PS film-coated glass cell than for the uncoated cell. Further experiments showed that metal desorption is faster and metal contamination after cleaning is significantly lower for the coated cells. The PS film was, moreover, stable over a period of 6 months within the pH range 3.5–9.     

Transport in Porous Media Contents of Volume 44

Volume Contents

Transport in Porous Media Contents of Volume 44     

Face-Centered and Volume-Centered Discrete Analogs of the Exterior Differential Equations Governing Porous Medium Flow I: Theory

This paper presents a physics-oriented approach to approximate the continuum equations governing porous media flow by discrete analogs. To that end, the continuity equation and Darcys law are reformulated using exterior differential forms. This way the derivation of a system of algebraic equations (the discrete analog) on a finite-volume mesh can be accomplished by simple and elegant translation rules. In the discrete analog the information about the conductivities of the porous medium and the metric of the mesh are represented in one matrix: the discrete dual. The discrete dual of the block-centered finite difference method is presented first. Since this method has limited applicability with respect to anisotropy and non-rectangular grid blocks, the finite element dual is introduced as an alternative. Application of a domain decomposition technique yields the face-centered finite element method. Since calculations based on pressures in volume centers are sometimes preferable, a volume-centered approximation of the face-centered approximation is presented too.     

Mixing of peptides and electrophilic traps gives rise to potent, broad-spectrum proteasome inhibitors

The synthesis and evaluation of hybrid proteasome inhibitors that contain structural elements of the known inhibitors bortezomib, epoxomicin and peptide vinyl sulfones is described. From the panel of 15 inhibitors some structure activity relationships can be deduced with regard to inhibitory activity in relation to peptide recognition element, inhibitor size and nature of the electrophilic trap. Further, the panel contains one of the most potent peptide-based pan-proteasome inhibitors reported to date.     

A DFT conformational analysis and VCD study on methyl tetrahydrofuran-2-carboxylate

DFT calculations were performed on (S)-methyl tetrahydrofuran-2-carboxylate to facilitate the interpretation of IR and VCD spectra. The potential energy surface could not be described unambiguously using the 6-31G* basis set in combination with different density functionals including B1LYP, B3LYP, B3P86, B3PW91, B98, BHandH, BHandHLYP, MPW1PW91 and PBE1PBE. In contrast, a uniform conformational picture could be found using the cc-pVTZ basis set. Using this large basis set and the collection of nine functionals from above, the dipole and rotational strengths were calculated, and compared to experimental values which were extracted from the experimental IR and VCD spectra for (+)-(S)-methyl tetrahydrofuran-2-carboxylate. A detailed analysis on the agreement between experiment and simulated spectra was performed by assigning the experimental bands based on the harmonic fundamentals obtained for all functionals except BHandH, which performs badly over the whole line. Assessing the dipole strengths, all tested functionals perform equally well. For the rotational strengths, differences can be observed: B3LYP, B1LYP and B98 give the highest correlation with experiment, while PBE1PBE gives the lowest correlation. Comparable conclusions are obtained using a neighborhood similarity measure.