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.     

Generalized quasilinearization method for reaction-diffusion equations under nonlinear and nonlocal flux conditions

In this paper we consider an initial boundary value problem for a reaction-diffusion equation under nonlinear and nonlocal Robin type boundary condition. Assuming the existence of an ordered pair of upper and lower solutions we establish a generalized quasilinearization method for the problem under consideration whose characteristic feature consists in the construction of monotone sequences converging to the unique solution within the interval of upper and lower solutions, and whose convergence rate is quadratic. Thus this method provides an efficient iteration technique that produces not only improved approximations due to the monotonicity of its iterates, but yields also a measure of the convergence rate.     

Ueber die Möglichkeit,einen Linienzug ohne Wiederholung und ohne Unterbrechung zu umfahren

Ohne ZusammenfassungDie folgende Untersuchung trug der leider so früh dem Dienste der Wissenschaft durch den Tod entrissene Privatdocent Dr. Hierholzer dahier (gest. 13. Sept. 1871) einem Kreise befreundeter Mathematiker vor. Um sie vor Vergessenheit zu bewahren, musste sie bei dem Mangel jeder schriftlichen Aufzeichnung aus dem Gedächtniss wieder hergestellt werden, was ich unter Beihilfe meines verehrten Collegen Lüroth durch das Folgende möglichst getreu auszuführen suchte.     

Enclosure results for quasilinear systems of variational inequalities

In this paper we consider systems of quasilinear elliptic variational inequalities, and prove the existence of minimal and maximal (in the set theoretical sense) solutions within some ordered interval of an appropriately defined pair of sub- and supersolutions. We show that the notion of sub- and supersolutions of variational inequalities introduced here is consistent with the usual notion of sub-supersolutions for (variational) equations. For weakly coupled quasimonotone systems of variational inequalities the existence of smallest and greatest solutions is proved.     

Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Sprouting side chain conformations in X-PLOR simulations of peptides

A scheme for sprouting peptide side chains using X-PLOR is introduced using an example from the collagen system to show how reasonable starting structures for minimization studies may be created. © 1993 John Wiley & Sons, Inc.     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Variant superfield representations

We discuss some variant superfield representations which can arise by the replacement of some of the usual fields in a multiplet with p-form gauge fields.