Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue

The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd.     

Eye-safe compact scanning LIDAR technology

A 1.5-μm eye-safe, 3-D scanning, and compact Mie LIght Detection and Ranging (LIDAR) is presented. The transmitter of the LIDAR is based on a KTA optical parameter oscillator (OPO) resonator. For detecting return signals, an InGaAs APD is used. The all solid-state OPO laser transmitter has the feature of small volume and lightweight, which allows a 165-lb compact eye-safe scanning LIDAR to be constructed. A system simulation using our own model was conducted to direct the system development. A method to solve the problem with small active area APD detectors was developed and described. The preliminary field-test measurement results indicated that the LIDAR has the capability to detect aerosols and clouds in lower atmospheres up to three dimensions.     

129Xe NMR study of the homogeneity and the size distribution of small sodium metal particles in NaY zeolite

NaY zeolite samples loaded with sodium metal by vapor phase deposition have been investigated using¹²⁹Xe NMR spectroscopy. At low sodium concentration, the¹²⁹Xe NMR spectrum showed three resonance lines which clearly indicate the existence of distinct domains in the zeolite sample. Such an observation suggests that the diffusion of the xenon atoms into each domain only occurs with respect to the NMR time scale (2.9 ms). As the sodium concentration increases, observation of a single broad line indicate a macroscopic homogenization of the system. The shift of this line is explained in part due to a paramagnetic interaction between the xenon atoms and the unpaired electrons of particles containing an odd number of sodium atoms. The linewidth is due to the distribution of the local magnetic fields partially averaged by the rapid motion of the xenon atoms and to the statistical distribution of the sodium particles in the supercage cavities. The paramagnetic interaction vanishes with the oxidation of the sample leading to a narrowing and a shift of the line to higher magnetic fields.     

Spectra and Transport in Almost Periodic Dimers

We study spectral properties of discrete Schrödinger operators with potentials obtained via dimerization of a class of aperiodic sequences. It is shown that both the nature of the autocorrelation measure of a regular sequence and the presence of generic (full probability) singular continuous spectrum in the hull of primitive and palindromic (four block substitution) potentials are robust under dimerization. Generic results also hold for circle potentials. We illustrate these results with numerical studies of the quantum mean square displacement as a function of time. The numerical techniques provide a very fast algorithm for the time evolution of wave packets.     

A dual graph-norm refinement indicator for finite volume approximations of the Euler equations

Summary. We generalise and apply a refinement indicator of the type originally designed by Mackenzie, Süli and Warnecke in [15] and [16] for linear Friedrichs systems to the Euler equations of inviscid, compressible fluid flow. The Euler equations are symmetrized by means of entropy variables and locally linearized about a constant state to obtain a symmetric hyperbolic system to which an a posteriori error analysis of the type introduced in [15] can be applied. We discuss the details of the implementation of the refinement indicator into the DLR--Code which is based on a finite volume method of box type on an unstructured grid and present numerical results. Received May 15, 1995 / Revised version received April 17, 1996