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1.
Zenon Moszner 《Aequationes Mathematicae》2018,92(4):617-625
We give the form of the output function in Ginsburg’s machine in which the input and output dictionaries are abelian groups and the transition function is of a special form. 相似文献
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3.
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
4.
Dominik Lungerich Jakob F. Hitzenberger Wolfgang Donaubauer Prof. Thomas Drewello Prof. Norbert Jux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16755-16759
A feasible two‐step synthesis and characterization of a full series of hexaarylbenzene (HAB) substituted porphyrins and tetrabenzoporphyrins is presented. Key steps represent the microwave‐assisted porphyrin condensation and the statistical Diels–Alder reaction to the desired HAB‐porphyrins. Regarding their applications, they proved to be easily accessible and effective high molecular mass calibrants for (MA)LDI mass spectrometry. The free‐base and zinc(II) porphyrin systems, as well as the respective tetrabenzoporphyrins, demonstrate in solid state experiments strong red‐ and near‐infrared‐light emission and are potentially interesting for the application in “truly organic” light‐emitting devices. Lastly, they represent facile precursors to large polycyclic aromatic hydrocarbon (PAH) substituted porphyrins. We prepared the first tetra‐hexa‐peri‐hexabenzocoronene substituted porphyrin, which represents the largest prepared PAH‐porphyrin conjugate to date. 相似文献
5.
Jieping Wang Norbert Moszner Kurt Dietliker Hansjörg Grützmacher Robert Liska 《Journal of polymer science. Part A, Polymer chemistry》2016,54(4):473-479
The monoacylphosphineoxide (MAPO) salts Na‐TPO and Li‐TPO and the bisacylphosphineoxide (BAPO) salts BAPO‐ONa and BAPO‐OLi define an important and in the latter case a new class of water‐soluble photoinitiators (PIs) for radical polymerization. These compounds showed excellent water‐solubility of at least 29 g/L for Na‐TPO and up to 60 g/L for BAPO‐ONa in deionized water, thus exceeding the solubility of the state of the art PI for water‐based systems Irgacure 2959 ( I2959 ) 6‐ to 12‐fold. However, biocompatibility, storage stability, and reactivity were equally important to replace the state of the art compounds. Concerning these properties, the MAPO and BAPO salts were at least in the same range (biocompatibility, stability) or showed even better results (reactivity) and had the additional advantage of visible light initiation. Na‐TPO and Li‐TPO achieved double bond conversions of an aqueous solution of N‐acryloylmorpholine over 97% with broad band irradiation (320–500 nm), Li‐TPO showed additionally very good biocompatibility (LC50 = 3.1 mmol/L) and BAPO‐OLi showed highest reactivity with visible light irradiation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 473–479 相似文献
6.
Samuel Clark Ligon Konstanze Seidler Christian Gorsche Markus Griesser Norbert Moszner Robert Liska 《Journal of polymer science. Part A, Polymer chemistry》2016,54(3):394-406
The rapid and uncontrolled nature of network formation from di(meth)acrylate monomers produces high shrinkage stress and results in polymers with oftentimes brittle mechanical properties. Methods for regulating polymerization and network formation are sought. One option is the use of addition–fragmentation chain transfer (AFCT) agents, which are well known to control molecular weight and molecular weight distribution of monofunctional (meth)acrylates. A series of novel and previously described AFCT reagents were synthesized and screened with laser flash photolysis to determine reactivity. Well‐performing AFCT reagents were then tested in polymerizations with monofunctional and difunctional methacrylates. With monofunctional monomers, the molecular weight and polydispersity of the resultant linear polymers tend to decrease with the addition of AFCT agent. In copolymerization with dimethacrylate monomers, the AFCT agents were found to substantially lower and sharpen the glass transition. Sharpness of the glass transition is here indicative of a more regular and homogenous network. After coupling of the instruments, photorheology was performed simultaneously with real‐time IR to show an increase in monomer conversion at the time of gelation, which appears to have a positive effect on reducing shrinkage stress. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 394–406 相似文献
7.
Alexander G. Sturm Tobias Santowski Julia I. Schweizer Dr. Lioba Meyer Dr. Kenrick M. Lewis Dr. Thorsten Felder Prof. Dr. Norbert Auner Prof. Dr. Max C. Holthausen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8499-8502
The industrial production of monosilanes MenSiCl4−n (n=1–3) through the Müller–Rochow Direct Process generates disilanes MenSi2Cl6−n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si−Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions. 相似文献
8.
Dr. Lucas Wickemeyer Prof. Dr. Israel Fernández Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel 《Angewandte Chemie (International ed. in English)》2023,62(11):e202216943
The reaction of the oxygen-bridged frustrated Lewis pairs (FLPs) tBu2P−O−Si(C2F5)3 ( 1 ) and tBu2P−O−AlBis2 ( 2 ) with azobenzene, promoted by UV irradiation, led to a selective complexation of the cis-isomer. The addition product of 2 is stable, while the adduct of 1 isomerizes in solution in an ortho-benzidine-like [3,3]-rearrangement by cleavage of the N−N bond, saturation of the nitrogen atoms with hydrogen atoms and formation of a new bond between two phenyl ortho-carbon atoms. Similar rearrangements take place with different para-substituted azobenzenes (R=Me, OMe, Cl) and di(2-naphthyl)diazene, while ortho-methylated azo compounds do not form adducts with 1 . All adducts were characterized by multinuclear NMR spectroscopy and elemental analyses and the mechanism of the rearrangement was explored by quantum-chemical calculations. 相似文献
9.
Matthias Mawick Carolin Jaworski Jens Bittermann Dr. Ljuba Iovkova Yinglan Pu Prof. Dr. Carmen Wängler Prof. Dr. Björn Wängler Prof. Dr. Klaus Jurkschat Prof. Dr. Norbert Krause Prof. Dr. Ralf Schirrmacher 《Angewandte Chemie (International ed. in English)》2023,62(50):e202309002
The ring-opening Si-fluorination of a variety of azasilole derivatives cyclo-1-(iPr2Si)−4-X−C6H3−2-CH2NR ( 4 : R=2,6-iPr2C6H3, X=H; 4 a : R=2,4,6-Me3C6H2, X=H; 9 : R=2,6-iPr2C6H3, X=tBuMe2SiO; 10 : R=2,6-iPr2C6H3, X=OH; 13 : R=2,6-iPr2C6H3, X=HCCCH2O; 22 : R=2,6-iPr2C6H3, X=tBuMe2SiCH2O) with different 19F-fluoride sources was studied, optimized and the experience gained was used in a translational approach to create a straightforward 18F-labelling protocol for the azasilole derivatives [18F] 6 and [18F] 14 . The latter constitutes a potential clickable CycloSiFA prosthetic group which might be used in PET tracer development using Cu-catalysed triazole formation. Based on our findings, CycloSiFA has the potential to become a new entry into non-canonical labelling methodologies for radioactive PET tracer development. 相似文献
10.
Johannes Oschwald Dr. David Reger Dr. Stefan Frühwald Vera Warmbrunn Prof. Dr. Andreas Görling Prof. Dr. Norbert Jux Prof. Dr. Thomas Drewello 《Chemphyschem》2023,24(21):e202300496
Gas-phase complexes of [n]helicenes with n=6, 7 and 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI-MS). Besides the well-established [1 : 1] helicene/Ag+-complex in which the helicene provides a tweezer-like surrounding for the Ag+, there is also a [2 : 1] complex formed. Density functional theory (DFT) calculations in conjunction with energy-resolved collision-induced dissociation (ER-CID) experiments reveal that the second helicene attaches via π-π stacking to the first helicene, which is part of the pre-formed [1 : 1] tweezer complex with Ag+. For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2 : 1] complex with silver(I) is typically structured as an Ag+-bound dimer in which the Ag+ would bind to both PAHs as the central metal ion (PAH–Ag+–PAH). For helicenes, the Ag+-bound dimer is of similar thermochemical stability as the π-π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison to the helicenes as an essentially planar PAH. In analogy to the π-π stacked dimer of the helicenes, the Cor−Ag+−Cor−Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag+ are preferably formed with the larger helicenes, with n=6 being entirely ignored as the host for Ag+ in the presence of n=7 or 8. 相似文献