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71.
Toom L Kütt A Kaljurand I Leito I Ottosson H Grennberg H Gogoll A 《The Journal of organic chemistry》2006,71(19):7155-7164
Basicity constants for a series of 3,7-diazabicyclo[3.3.1]nonane derivatives in acetonitrile with a variation over 13 orders of magnitude have been determined using a spectrophotometric titration technique. An excellent correlation between basicity and calculated proton affinities obtained at PCM-B3LYP/6-31+G(d)//B3LYP/6-31G(d) level was found. The results are discussed in terms of substituent effects and compared to (15)N NMR chemical shifts. 相似文献
72.
Epitaxial NiO (1 1 1) and NiO (1 0 0) films have been grown by atomic layer deposition on both MgO (1 0 0) and α-Al2O3 (0 0 l) substrates at temperatures as low as 200 °C by using bis(2,2,6,6-tetramethyl-3,5-heptanedionato)Ni(II) and water as precursors. The films grown on the MgO (1 0 0) substrate show the expected cube on cube growth while the NiO (1 1 1) films grow with a twin rotated 180° on the α-Al2O3 (0 0 l) substrate surface. The films had columnar microstructures on both substrate types. The single grains were running throughout the whole film thickness and were significantly smaller in the direction parallel to the surface. Thin NiO (1 1 1) films can be grown with high crystal quality with a FWHM of 0.02–0.05° in the rocking curve measurements. 相似文献
73.
Capture of CO2 by a Cationic Nickel(I) Complex in the Gas Phase and Characterization of the Bound,Activated CO2 Molecule by Cryogenic Ion Vibrational Predissociation Spectroscopy 下载免费PDF全文
Dr. Fabian S. Menges Stephanie M. Craig Niklas Tötsch Dr. Aaron Bloomfield Subrata Ghosh Prof. Dr. Hans‐Jörg Krüger Prof. Dr. Mark A. Johnson 《Angewandte Chemie (International ed. in English)》2016,55(4):1282-1285
We describe a systematic method for the preparation and spectroscopic characterization of a CO2 molecule coordinated to an activated bisphenoidal nickel(I) compound containing a tetraazamacrocyclic ligand in the gas phase. The resulting complex was then structurally characterized by using mass‐selected vibrational predissociation spectroscopy. The results indicate that a highly distorted CO2 molecule is bound to the metal center in an η2‐C,O coordination mode, thus establishing an efficient and rational method for the preparation of metal‐activated CO2 for further studies using ion chemistry techniques. 相似文献
74.
F Debatin K Behrens J Weber IA Baburin A Thomas J Schmidt I Senkovska S Kaskel A Kelling N Hedin Z Bacsik S Leoni G Seifert C Jäger C Günter U Schilde A Friedrich HJ Holdt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(37):11630-11640
We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1-4, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0-1.7??), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and (1) H?MAS and (13) C?CP-MAS?NMR spectroscopy. All IFPs showed high thermal stability (345-400?°C); IFP-1 and IFP-4 were stable in boiling water for 7?d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO(2) was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH(4) (at 298?K), CO(2) (at 298?K) and H(2) (at 77?K) at high pressure were also investigated. In situ IR spectroscopy showed that CO(2) is physisorbed on IFP-1-4 under dry conditions and that both CO(2) and H(2) O are physisorbed on IFP-1 under moist conditions. 相似文献
75.
Yang B Pan Y Lin X Nilius N Freund HJ Hulot C Giraud A Blechert S Tosoni S Sauer J 《Journal of the American Chemical Society》2012,134(27):11161-11167
Tris(phenylthio)benzene molecules have been synthesized in order to explore their ability to trap single Au adatoms on an Au(111) surface. The resulting metal-organic complexes have been characterized with low-temperature scanning tunneling microscopy and infrared reflection absorption spectroscopy; possible structure models have been derived from density functional calculations. Upon room temperature deposition, the thiophenyl derivatives form dimer structures, comprising two molecules and six Au adatoms. Below 100 K, isolated molecules are found as well that have trapped up to six Au atoms. On the basis of the experimental results and calculated formation energies of the complexes, we discuss potential applications of the thioethers for the redispersion of metals on a catalyst surface. First experiments performed on Au particle ensembles prepared on alumina thin films suggest that the molecular ligands are indeed able to change the distribution of gold on the oxide surface. 相似文献
76.
Julien Andrieu Niklas Kotman Matthias Maier Volker Mailnder Wolfgang S. L. Strauss Clemens K. Weiss Katharina Landfester 《Macromolecular rapid communications》2012,33(3):248-253
The miniemulsion process is used as a new route for the preparation of enzyme‐responsive nanocapsules with payload‐release properties. Peptide‐based hybrid nanocapsules are prepared via interfacial polyaddition containing a water‐soluble dye that is efficiently encapsulated inside. The influence of the synthetic parameters as the functionality of the peptide and the nature of the dispersed phase on the structure of the nanocapsules were investigated. After redispersion in water, the enzymatic cleavage of the peptide sequence and the release of the fluorescent dye are both monitored in real time. This is evidenced because of the quenching FRET system framing the recognition site in the peptide sequence, and the fluorescence recovery of the self‐quenched encapsulated dye respectively. 相似文献
77.
Gunnar Brinkmalm Erik Portelius Annika Öhrfelt Niklas Mattsson Rita Persson Mikael K. Gustavsson Charles H. Vite Johan Gobom Jan‐Eric Månsson Jonas Nilsson Adnan Halim Göran Larson Ulla Rüetschi Henrik Zetterberg Kaj Blennow Ann Brinkmalm 《Journal of mass spectrometry : JMS》2012,47(5):591-603
Amyloid precursor protein (APP) is the precursor protein to amyloid β (Aβ), the main constituent of senile plaques in Alzheimer's disease (AD). Endogenous Aβ peptides reflect the APP processing, and greater knowledge of different APP degradation pathways is important to understand the mechanism underlying AD pathology. When one analyzes longer Aβ peptides by low‐energy collision‐induced dissociation tandem mass spectrometry (MS/MS), mainly long b‐fragments are observed, limiting the possibility to determine variations such as amino acid variants or post‐translational modifications (PTMs) within the N‐terminal half of the peptide. However, by using electron capture dissociation (ECD), we obtained a more comprehensive sequence coverage for several APP/Aβ peptide species, thus enabling a deeper characterization of possible variants and PTMs. Abnormal APP/Aβ processing has also been described in the lysosomal storage disease Niemann–Pick type C and the major large animal used for studying this disease is cat. By ECD MS/MS, a substitution of Asp7 → Glu in cat Aβ was identified. Further, sialylated core 1 like O‐glycans at Tyr10, recently discovered in human Aβ (a previously unknown glycosylation type), were identified also in cat cerebrospinal fluid (CSF). It is therefore likely that this unusual type of glycosylation is common for (at least) species belonging to the magnorder Boreoeutheria. We here describe a detailed characterization of endogenous APP/Aβ peptide species in CSF by using an online top‐down MS‐based method. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
78.
Lucas Wickemeyer Niklas Aders Andreas Mix Beate Neumann Hans-Georg Stammler Jorge J. Cabrera-Trujillo Israel Fernndez Norbert W. Mitzel 《Chemical science》2022,13(27):8088
The reaction of tBu2P(O)H with Bis2AlH (Bis = CH(SiMe3)2) afforded the adduct tBu2P(H)–O–Al(H)Bis2 (3). It slowly releases H2 to form the first oxygen-bridged geminal Al/P frustrated Lewis pair tBu2P–O–AlBis2. It is capable of reversibly binding molecular hydrogen to afford 3, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO2. Importantly, the H2 adduct 3 reduces CO2 in a stoichiometric reaction leading to the formic acid adduct tBu2P(H)–O–Al(CO2H)Bis2. The formation of the different species was explored by density functional theory calculations which provide support for the experimental results. All products were characterized by NMR spectroscopy as well as X-ray diffraction experiments and elemental analyses.Addition vs. reduction: the geminal FLP Bis2Al–O–PtBu2 can reversibly bind molecular hydrogen, it reacts with CO2 to give an adduct, and its hydrogen adduct reduces CO2 to an adduct of formic acid. 相似文献
79.
Dr. You-Quan Zou Dr. Niklas von Wolff Dr. Michael Rauch Dr. Moran Feller Dr. Quan-Quan Zhou Dr. Aviel Anaby Dr. Yael Diskin-Posner Dr. Linda J. W. Shimon Dr. Liat Avram Yehoshoa Ben-David Prof. Dr. David Milstein 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4715-4722
Glycolic acid is a useful and important α-hydroxy acid that has broad applications. Herein, the homogeneous ruthenium catalyzed reforming of aqueous ethylene glycol to generate glycolic acid as well as pure hydrogen gas, without concomitant CO2 emission, is reported. This approach provides a clean and sustainable direction to glycolic acid and hydrogen, based on inexpensive, readily available, and renewable ethylene glycol using 0.5 mol % of catalyst. In-depth mechanistic experimental and computational studies highlight key aspects of the PNNH-ligand framework involved in this transformation. 相似文献
80.
Niklas O. Thiel Benyapa Kaewmee Trung Tran Ngoc Prof. Dr. Johannes F. Teichert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(7):1597-1603
Stereoselective alkyne semihydrogenations are attractive approaches to alkenes, which are key building blocks for synthesis. With regards to the most atom-economic reducing agent dihydrogen (H2), only few catalysts for the challenging E-selective alkyne semihydrogenation have been disclosed, each with a unique substrate scope profile. Here, we show that a commercially available nickel catalyst facilitates the E-selective alkyne semihydrogenation of a wide variety of substituted internal alkynes. This results in a simple and broadly applicable overall protocol to stereoselectively access E-alkenes employing H2, which could serve as a general method for synthesis. 相似文献