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.     

Bis(μ6‐cis‐2,4,6,8,10,12,14,16‐octa­methyl­cyclo­octa­siloxane‐2,4,6,8,10,12,14,16‐octolato)octa­kis[(dimethyl­formamide)copper(II)] dimethyl­formamide solvate enclosing a pyrazine mol­ecule

The title compound, [Cu₈(C₈H₂₄O₂Si)₂(C₃H₇NO)₈]·C₄H₄N₂·C₃H₇NO, features a sandwich‐like cage enclosing a pyrazine mol­ecule, both situated on a centre of inversion. In addition, the crystal structure contains one dimethyl­formamide mol­ecule which is disordered over a centre of inversion. The copper layer, containing eight atoms, is located between two siloxanolate fragments. The whole structure of Cu atoms and siloxanolate rings is distorted by the pyrazine mol­ecule, leading to an oval form. As a result, the angles between the Cu atoms differ at the copper layer. The difference in the angles could lead to some deviations in the Cu–Cu exchange inter­actions within the copper ring, which is of inter­est for mol­ecular magnetism.     

Zur quantitativen Eiweissbestimmung im Harn

Ohne Zusammenfassung     

Zur Sch?nbein'sehen Reaction auf Blaus?ure

Ohne Zusammenfassung     

Eine neue Reaction des Phenacetins

Ohne Zusammenfassung     

Quantitative Bestimmungen mittels cyclischer Voltammetrie an der Phasengrenze zweier mischbarer Elektrolytl?sungen

Summary This paper presents some applications of cyclic voltammetry at the interface of two immiscible electrolyte solutions by means of an experimental set-up described in a former publication. When using special sample preparation good results are obtained for the determination of iodide and quinine in pharmaceutical products as well as for the determination of quinine in tonic water and dodecylsulfate in a tooth-salt.

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Herrn Prof. Dr. Günther Tölg zum 60. Geburtstag gewidmet     

Untersuchungen zur Wechselwirkung von gasf?rmigem molekularem Iod mit Silberoberfl?chen mittels XPS und AES

Summary The adsorption of gaseous molecular iodine on clean silver surfaces proceeds in the first stage by dissociative chemisorption. After the formation of half a monolayer of chemisorbed iodine atoms the formation of silver iodide begins, which forms a very regular overlayer on top of the substrate. Both iodine species can be distinguished due to a difference in chemical shift of the M₄N₄, ₅N₄, ₅-Auger transitions. After completion of this overlayer further iodine uptake is slowed down significantly. Above an overlayer thickness of about 10 nm a further progress of the reaction cannot be followed anymore due to the limited information depth of XPS.     

Ueber Bestimmung der Harns?ure im Urin

Ohne Zusammenfassung