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991.
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993.
Dr. Friedrich Wossidlo Daniel S. Frost Jinxiong Lin Dr. Nathan T. Coles Katrin Klimov Manuela Weber Dr. Tobias Böttcher Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(50):12788-12795
The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of 1JP,Se=883 Hz is in line with a P−Se bond of high s-character. The σ-electron donating Me3Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C5H5P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I)Cl as well as iPrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination. 相似文献
994.
Carolin Rieg Daniel Dittmann Zheng Li Dr. Robert Lawitzki Katrin Gugeler Sarah Maier Prof. Guido Schmitz Prof. Johannes Kästner Prof. Deven P. Estes Dr. Michael Dyballa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17012-17023
We compare three methods for quantitatively distinguishing the location of noble metal (NM) particles in mesopores from those found on the external support surface. MCM-41 and SBA-15 with NM located in mesopores or on the external surface were prepared and characterized by TEM. 31P MAS NMR spectroscopy was used to quantify arylphosphines in complexes with NM. Phosphine/NM ratios drop from 2.0 to 0.2 when increasing the probe diameter from 1.08 to 1.54 nm. The reaction between NM and triphenylphosphine (TPP) within 3.0 nm MCM-41 pores takes due to confinement effects multiple weeks. In contrast, external NM react with TPP instantly. A promising method is filling the pores by using the pore volume impregnation technique with tetraethylorthosilicate (TEOS). TPP loading revealed that 66 % of NMs are located on the external surface of MCM-41. The pore filling method can be used in association with any probe molecule, also for the quantification of acid sites. 相似文献
995.
Benjamin Assarf Ewgenij Gawrilow Katrin Herr Michael Joswig Benjamin Lorenz Andreas Paffenholz Thomas Rehn 《Mathematical Programming Computation》2017,9(1):1-38
The main purpose of this paper is to report on the state of the art of computing integer hulls and their facets as well as counting lattice points in convex polytopes. Using the polymake system we explore various algorithms and implementations. Our experience in this area is summarized in ten “rules of thumb”. 相似文献
996.
Katrin Kittler Holger Hoffmann Franziska Lindemann Matthias Koch Sascha Rohn Ronald Maul 《Analytical and bioanalytical chemistry》2014,406(24):5765-5774
Cylindrospermopsin (CYN) is a cyanobacterial toxin associated with human and animal poisonings. Due to its toxicity in combination with its widespread occurrence, the development of reliable methods for selective, sensitive detection and accurate quantification is mandatory. Liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis using stable isotope dilution analysis (SIDA) represents an ideal tool for this purpose. U-[15N5]-CYN was synthesized by culturing Aphanizomenon flos-aquae in Na15NO3-containing cyanobacteria growth medium followed by a cleanup using graphitized carbon black columns and mass spectrometric characterization. Subsequently, a SIDA-LC-MS/MS method for the quantification of CYN in freshwater and Brassica matrices was developed showing satisfactory performance data. The recovery ranged between 98 and 103 %; the limit of quantification was 15 ng/L in freshwater and 50 μg/kg dry weight in Brassica samples. The novel SIDA was applied for CYN determination in real freshwater samples as well as in kale and in vegetable mustard exposed to toxin-containing irrigation water. Two of the freshwater samples taken from German lakes were found to be CYN-contaminated above limit of quantification (17.9 and 60.8 ng/L). CYN is systemically available to the examined vegetable species after exposure of the rootstock leading to CYN mass fractions in kale and vegetable mustard leaves of 15.0 μg/kg fresh weight and 23.9 μg/kg fresh weight, respectively. CYN measurements in both matrices are exemplary for the versatile applicability of the developed method in environmental analysis. 相似文献
997.
Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis,Photophysics, and Light Microscopy Applications
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Dr. Vladimir N. Belov Dr. Gyuzel Yu. Mitronova Prof. Mariano L. Bossi Prof. Vadim P. Boyarskiy Elke Hebisch Dr. Claudia Geisler Dr. Kirill Kolmakov Dr. Christian A. Wurm Dr. Katrin I. Willig Prof. Stefan W. Hell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13162-13173
Caged rhodamine dyes (Rhodamines NN) of five basic colors were synthesized and used as “hidden” markers in subdiffractional and conventional light microscopy. These masked fluorophores with a 2‐diazo‐1‐indanone group can be irreversibly photoactivated, either by irradiation with UV‐ or violet light (one‐photon process), or by exposure to intense red light (λ~750 nm; two‐photon mode). All dyes possess a very small 2‐diazoketone caging group incorporated into the 2‐diazo‐1‐indanone residue with a quaternary carbon atom (C‐3) and a spiro‐9H‐xanthene fragment. Initially they are non‐colored (pale yellow), non‐fluorescent, and absorb at λ=330–350 nm (molar extinction coefficient (ε)≈104 M?1 cm?1) with a band edge that extends to about λ=440 nm. The absorption and emission bands of the uncaged derivatives are tunable over a wide range (λ=511–633 and 525–653 nm, respectively). The unmasked dyes are highly colored and fluorescent (ε= 3–8×104 M?1 cm?1 and fluorescence quantum yields (?)=40–85 % in the unbound state and in methanol). By stepwise and orthogonal protection of carboxylic and sulfonic acid groups a highly water‐soluble caged red‐emitting dye with two sulfonic acid residues was prepared. Rhodamines NN were decorated with amino‐reactive N‐hydroxysuccinimidyl ester groups, applied in aqueous buffers, easily conjugated with proteins, and readily photoactivated (uncaged) with λ=375–420 nm light or intense red light (λ=775 nm). Protein conjugates with optimal degrees of labeling (3–6) were prepared and uncaged with λ=405 nm light in aqueous buffer solutions (?=20–38 %). The photochemical cleavage of the masking group generates only molecular nitrogen. Some 10–40 % of the non‐fluorescent (dark) byproducts are also formed. However, they have low absorbance and do not quench the fluorescence of the uncaged dyes. Photoactivation of the individual molecules of Rhodamines NN (e.g., due to reversible or irreversible transition to a “dark” non‐emitting state or photobleaching) provides multicolor images with subdiffractional optical resolution. The applicability of these novel caged fluorophores in super‐resolution optical microscopy is exemplified. 相似文献
998.
Raina Seupel Alexander Roth Katrin Steinke Dieter Sicker Hans‐Ullrich Siehl Klaus‐Peter Zeller Stefan Berger 《Chemie in Unserer Zeit》2015,49(1):60-72
Cork of the cork oak is a fascinating natural material, used since ancient times. According to a close sight at cork, in 1665 the term “cell” was coined for use in biology. Friedelin, a complex pentacyclic triterpene ketone, is a constituent of cork. The isolation of friedeline is described as well as its history. All analytical spectra were recorded and are reproduced either in the main part or in the supporting information. The NMR‐ and mass‐spectra have been interpreted and compared with theoretical calculations of the 13C chemical shifts. The project is a follow up of the recent book “Classics in Spectroscopy” by S. Berger und D. Sicker (Wiley‐VCH 2009). 相似文献
999.
1000.
Source of Selectivity in Oxidative Cross‐Coupling of Aryls by Solvent Effect of 1,1,1,3,3,3‐Hexafluoropropan‐2‐ol
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Dr. Bernd Elsler Anton Wiebe Dr. Dieter Schollmeyer Dr. Katrin M. Dyballa Prof. Dr. Robert Franke Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12321-12325
Solvents such as 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) with a high capacity for donating hydrogen bonds generate solvates that enter into selective cross‐coupling reactions of aryls upon oxidation. When electric current is employed for oxidation, reagent effects can be excluded and a decoupling of nucleophilicity from oxidation potential can be achieved. The addition of water or methanol to the electrolyte allows a shift of oxidation potentials in a specific range, creating suitable systems for selective anodic cross‐coupling reactions. The shift in the redox potentials depends on the substitution pattern of the substrate employed. The concept has been expanded from arene–phenol to phenol–phenol as well as phenol–aniline cross‐coupling. This driving force for selectivity in oxidative coupling might also explain previous findings using HFIP and hypervalent iodine reagents. 相似文献