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.     

Dynamically Induced Excitonic Instability in Pumped Dirac Materials

Driven and non-equilibrium quantum states of matter have attracted growing interest in both theoretical and experimental studies in condensed matter physics. Recent progress in realizing transient collective states in driven or pumped Dirac materials (DMs) is reviewed herein. In particular, the focus is on optically pumped DMs which are a promising platform for transient excitonic instabilities. Optical pumping combined with the linear (Dirac) dispersion of the electronic spectrum offers a knob for tuning the effective interaction between the photoexcited electrons and holes, and thus provides a way of reducing the critical coupling for excitonic instability. As a result, a transient excitonic condensate could be achieved in a pumped DM while it is not feasible in equilibrium. A unifying theoretical framework is provided for describing transient collective states in 2D and 3D DMs. The experimental signatures are described and numerical estimates of the size of the dynamically induced excitonic gaps and the values of the critical temperatures for several specific systems, are summarized. In addition, general guidelines for identifying promising material candidates are discussed. Finally, comments are provided regarding recent experimental efforts in realizing transient excitonic condensate in pumped DMs, and outstanding issues and possible future directions are outlined.     

Stability testing in an integrated scheme

ISO Guide 35 deals with RM stability issues and scrutinizes the evaluation of stability testing results under the assumption that either there is no trend at all (a rather rare situation), or any observed deterministic change is insignificant and thus can be neglected. However, market demands for reliable reference materials are obviously not limited to stable or at least seemingly stable materials. In many analytical applications, analytes and measurands under consideration are known, or at least suspected, to be unstable on time scales that may vary widely from measurand to measurand. The Federal Institute for Materials Research and Testing (BAM) has developed (and successfully uses) an integrated approach in its certification practice. The approach is based on an initial stability study and subsequent post-certification monitoring. Data evaluation is model-based and takes advantage of all information collected in the stability testing scheme(s). It thus allows one to deal with any kind of instability observed, to assess limiting time intervals at any stress condition in the range tested, to estimate a final expiry date for materials with detected instabilities or the maximum admissible re-testing interval for seemingly stable materials, and to assess maximum admissible stress loads during delivery of the material to the customer. The article describes (and exemplifies) typical study layout, the model selection, and the integrated data assessment.     

Structures and stability of Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>C and Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>N clusters

We report results of the atomic and electronic structures of Al₇C cluster using ab initio molecular dynamics with ultrasoft pseudopotentials and generalized gradient approximation. The lowest energy structure is found to be the one in which carbon atom occupies an interstitial position in Al₇ cluster. The electronic structure shows that the recent observation [Chem. Phys. Lett. 316, 31 (2000)] of magic behavior of Al₇C^- cluster is due to a large highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) gap which makes Al₇C^- chemically inert. These results have further led us to the finding of a new neutral magic cluster Al₇N which has the same number of valence electrons as in Al₇C^- and a large HOMO-LUMO gap of 1.99 eV. Further, calculations have been carried out on (Al₇N)₂ to study interaction between magic clusters. Received 28 July 2001     

一类潜热型功能液固两相流体的定压比热研究

应用两相流与热物理理论，严格推导出一类潜热型功能液固两相流体的定压比热计算公式．     

Linear and nonlinear optical susceptibilities of orthorhombic rare earth molybdates RE2(MoO4)3

The dielectric responses (i.e. the refractive indices and the second order nonlinear susceptibilities) of all orthorhombic rare earth molybdates have been studied on the basis of the relationship between dielectric responses and the average atomic number of constituent atoms of crystals. Both the linear and second order nonlinear optical responses at 1.064 μm decrease with increasing atomic number from La to Lu.     

Radiochemical proton activation analysis for the determination of cadmium and lead in sediment reference materials

Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the^111,112Cd(p, xn)¹¹¹ In and the^206,207,208Pb(p, xn)²⁰⁶Bi reactions.¹¹¹In and²⁰⁶Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values.     

Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine

Random copolymers of poly{(methacrylamide)-co-(vinyl trimethoxysilane)} and poly{(methacrylic acid)-co-(vinyl trimethoxysilane)} were synthesized via a free radical polymerization reaction. Acid catalyzed sol-gel process of tetraethylorthosilicate (TEOS) with aforementioned polymers in the presence of methyl xanthine class of alkaloid like caffeine resulted in the formation of highly transparent monoliths. Solvent extraction of the template leaves behind the recognition sites intact with high selectivity towards the print molecule. The ionic and non-specific adsorptions, which are considered to be the main disadvantages of the molecularly imprinted polymers (MIP), are prevented to a considerable extent by the end capping of surface silanol groups. The template binding efficiencies of MIP were determined by HPLC analysis.     

New poly(butylene succinate)/layered silicate nanocomposites. II. Effect of organically modified layered silicates on structure,properties, melt rheology,and biodegradability

A series of new poly(butylene succinate) (PBS)/layered silicate nanocomposites were prepared successfully by simple melt extrusion of PBS and organically modified layered silicates (OMLS). Three different types of OMLS were used for the preparation of nanocomposites: two functionalized ammonium salts modified montmorillonite and a phosphonium salt modified saponite. The structure of the nanocomposites in the nanometer scale was characterized with wide-angle X-ray diffraction and transmission electron microscopic observations. With three different types of layered silicates modified with three different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, materials properties, melt rheological behavior, and biodegradability. Interestingly, all these nanocomposites exhibited concurrent improvements of material properties when compared with pure PBS. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3160–3172, 2003     

A relaxed model and its homogenization for nematic liquid crystals in composite materials

We analyse a model for equilibrium configurations of composite systems of nematic liquid crystal with polymer inclusions, in the presence of an external magnetic field. We assume that the system has a periodic structure, and consider the relaxed problem on the unit length constraint of the nematic director field. The relaxation of the Oseen–Frank energy functional is carried out by including bulk as well as surface energy penalty terms, rendering the problem fully non‐linear. We employ two‐scale convergence methods to obtain effective configurations of the system, as the size of the polymeric inclusions tends to zero. We discuss the minimizers of the effective energies for, both, the constrained as well as the unconstrained models. Copyright © 2004 John Wiley & Sons, Ltd.