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Dr. Julian Brunner Britta Maier Rose Rosenberg Sebastian Sturm Prof. Dr. Helmut Cölfen Dr. Elena V. Sturm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15242-15248
Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDIc=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes “colloidal” impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals. 相似文献
3.
Julian P. Edwards William J. Wolf Robert H. Grubbs 《Journal of polymer science. Part A, Polymer chemistry》2019,57(3):228-242
Cyclic polymers have drawn considerable interest for their peculiar physical properties in comparison to linear polymers, despite their equivalent compositions. Synthetically, cyclic polymers can be accessed through either macrocyclic ring‐closure or by ring‐expansion polymerization, but the main challenge with either method is the production of highly pure cyclic polymer samples. This highlight describes advances in the area of cyclic polymer synthesis, with a particular focus on ring‐expansion metathesis polymerization. Methods for characterizing cyclic polymers and assessing their purity are also discussed in order to emphasize the need for additional robust and reliable methods for synthesizing and studying topologically complex macromolecules. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 228–242 相似文献
4.
Dr. Daniel Brodbeck Dr. Sonia Álvarez-Barcia Dr. Jan Meisner Dr. Florian Broghammer Julian Klepp Dr. Delphine Garnier Dr. Wolfgang Frey Prof. Dr. Johannes Kästner Prof. Dr. René Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1515-1524
Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 104. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results. 相似文献
5.
Necessary conditions for the existence of a super‐simple, decomposable, near‐resolvable ‐balanced incomplete block design (BIBD) whose 2‐component subdesigns are both near‐resolvable ‐BIBDs are (mod ) and . In this paper, we show that these necessary conditions are sufficient. Using these designs, we also establish that the necessary conditions for the existence of a super‐simple near‐resolvable ‐RBIBD, namely (mod ) and , are sufficient. A few new pairwise balanced designs are also given. 相似文献
6.
We construct planar bi-Sobolev mappings whose local volume distortion is bounded from below by a given function with . More precisely, for any we construct -bi-Sobolev maps with identity boundary conditions; for , we provide bi-Lipschitz maps. The basic building block of our construction are bi-Lipschitz maps which stretch a given compact subset of the unit square by a given factor while preserving the boundary. The construction of these stretching maps relies on a slight strengthening of the celebrated covering result of Alberti, Csörnyei, and Preiss for measurable planar sets in the case of compact sets. We apply our result to a model functional in nonlinear elasticity, the integrand of which features fast blowup as the Jacobian determinant of the deformation becomes small. For such functionals, the derivation of the equilibrium equations for minimizers requires an additional regularization of test functions, which our maps provide. 相似文献
7.
Rik H. Verschueren Julie Schmauck Dr. Michael S. Perryman Dr. Hui-Lan Yue Julian Riegger Dr. Bertrand Schweitzer-Chaput Dr. Martin Breugst Dr. Martin Klussmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):9088-9097
In this work, the reactivities of acetonyl and benzoyl radicals in aromatic substitution and addition reactions have been compared in an experimental and computational study. The results show that acetonyl is more electrophilic than benzoyl, which is rather nucleophilic. A Hammett plot analysis of the addition reactions of the two radicals to substituted styrenes clearly support the nucleophilicity of benzoyl, but in the case of acetonyl, no satisfactory linear correlation with a single substituent-related parameter was found. Computational calculations helped to rationalize this effect, and a good linear correlation was found with a combination of polar parameters (σ+) and the radical stabilization energies of the formed intermediates. Based on the calculated philicity indices for benzoyl and acetonyl, a quantitative comparison of these two radicals with many other reported radicals is possible, which may help to predict the reactivities of other aromatic radical substitution reactions. 相似文献
8.
Julian G. Sereni 《哲学杂志》2020,100(10):1211-1225
ABSTRACTWith the aim to improve the performance of classical paramagnetic salts for adiabatic refrigeration processes at the sub-Kelvin range, relevant thermodynamic parameters of some new Yb-based intermetallic compounds are analysed and compared. Two main applications are considered: (i) those requiring temperature fixed-points to be reached applying magnetic fields of moderate intensity for satellite applications, and (ii) those which can be used for controlled thermal drifts in laboratory applications. Different thermomagnetic trajectories of the entropy are identified depending on respective specific heat behaviours and the constraints imposed by the Nernst postulate at the sub-Kelvin range. Some simple relationships are proposed to compare the diverse magnetocaloric characteristics of different systems. This procedure allows to include the classical Cerium-Magnesium-Nitride (CMN) salt in that comparison. 相似文献
9.
Inside Back Cover: Univalent Gallium Complexes of Simple and ansa‐Arene Ligands: Effects on the Polymerization of Isobutylene (Chem. Eur. J. 1/2015) 下载免费PDF全文
10.
The Synthesis of B2(SIDip)2 and its Reactivity Between the Diboracumulenic and Diborynic Extremes 下载免费PDF全文
Julian Bhnke Holger Braunschweig Theresa Dellermann William C. Ewing Kai Hammond J. Oscar C. Jimenez‐Halla Thomas Kramer Jan Mies 《Angewandte Chemie (International ed. in English)》2015,54(46):13801-13805
A new compound with the formula L‐B2‐L wherein the stabilizing ligand (L) is 1,3‐bis[diisopropylphenyl]‐4,5‐dihydroimidazol‐2‐ylidene (SIDip) has been synthesized, isolated, and characterized. The π‐acidity of the SIDip ligand, intermediate between the relatively non‐acidic IDip (1,3‐bis[diisopropylphenyl]imidazol‐2‐ylidene) ligand and the much more highly acidic CAAC (1‐[2,6‐diisopropylphenyl]‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) ligand, gives rise to a compound with spectroscopic, electrochemical, and structural properties between those of L‐B2‐L compounds stabilized by CAAC and IDip. Reactions of all three L‐B2‐L compounds with CO demonstrate the differences caused by their respective ligands, as the π‐acidities of the CAAC and SIDip carbenes enabled the isolation of bis(boraketene) compounds (L(OC)B‐B(CO)L), which could not be isolated from reactions with B2(IDip)2. However, only B2(IDip)2 and B2(SIDip)2 could be converted into bicyclic bis(boralactone) compounds. 相似文献