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1.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
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. 相似文献
2.
3.
Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time. 相似文献
4.
Julien Ferrari Christian Terreaux Tibor Kurtn Attila Szikszai‐Kiss Sndor Antus JeromeD. Msonthi Kurt Hostettmann 《Helvetica chimica acta》2003,86(8):2768-2778
Investigation of the methanol extract of the roots of Gnidia involucrata (Thymelaeaceae) led to the isolation and characterization of two new 3,8″‐biflavonoid diastereoisomers, named GB‐4 ( 6a ) and GB‐4a ( 6b ). Their absolute configurations were determined in mixture by on‐line LC/CD measurements, which also allowed the revision of absolute configurations of the biflavanoids GB‐1 and GB‐2, and the configurational assignment of GB‐3. 相似文献
5.
Kurt Majewski 《Queueing Systems》2005,50(2-3):199-230
We consider multiclass feedforward queueing networks under first in first out and priority service disciplines driven by long-range dependent arrival and service time processes. We show that in critical loading the normalized workload, queue length and sojourn time processes can converge to a multi-dimensional reflected fractional Brownian motion. This weak heavy traffic approximation is deduced from a deterministic pathwise approximation of the network behavior close to constant critical load in terms of the solution of a Skorokhod problem. Since we model the doubly infinite time interval, our results directly cover the stationary case.AMS subject classification: primary 90B15, secondary 60K25, 68M20 相似文献
6.
Mathematical Methods of Operations Research - 相似文献
7.
Kurt M. Anstreicher 《Mathematical Programming》1997,76(1):245-263
We consider the construction of small step path following algorithms using volumetric, and mixed volumetric-logarithmic, barriers.
We establish quadratic convergence of a volumetric centering measure using pure Newton steps, enabling us to use relatively
standard proof techniques for several subsequently needed results. Using a mixed volumetric-logarithmic barrier we obtain
an O(n
1/4
m
1/4
L) iteration algorithm for linear programs withn variables andm inequality constraints, providing an alternative derivation for results first obtained by Vaidya and Atkinson. In addition,
we show that the same iteration complexity can be attained while holding the work per iteration to O(n
2
m), as opposed to O(nm
2), operations, by avoiding use of the true Hessian of the volumetric barrier. Our analysis also provides a simplified proof
of self-concordancy of the volumetric and mixed volumetric-logarithmic barriers, originally due to Nesterov and Nemirovskii.
This paper was first presented at the 1994 Faculty Research Seminar “Optimization in Theory and Practice”, at the University
of Iowa Center for Advanced Studies. 相似文献
8.
Wally L. Chang Kurt C. Frisch Kaneyoshi Ashida 《Journal of polymer science. Part A, Polymer chemistry》1989,27(11):3637-3649
The anionic polymerization of ?-caprolactam (CLM) has been shown to proceed at high reaction rate when catalyzed by metallic lactamates and initiated by acyllactams. The role of initiator and catalyst concentration on the process of ?-caprolactam anionic polymerization has been explored, with the aim of selecting the most suitable experimental conditions for reaction injection molding (RIM). The overall polymerization rates and physical properties for reaction injection molding of star-shaped nylon 6 homopolymer have been studied by the quasi-adiabatic process. In order to model the actual rapid molding conditions, time vs. temperature reaction profiles were measured, and the relative rates of polymerization subsequently determined from these data. 相似文献
9.
10.
We report spectroscopic ellipsometry studies in the energy range of 0.5-5 eV on samples of 1-10 bilayers of polymer and HgTe nanocrystals, which exhibit strong transitions at higher critical points in the dispersion relation. We show that the dispersion relation for nanocrystals can be modelled with the same concepts for critical points as used in semiconductor bulk optics. We find an energy shift of up to 0.4 eV of the critical points to higher energies compared to the HgTe bulk properties, caused by quantum confinement in the nanocrystals, which increases with decreasing nanocrystal size. 相似文献