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71.
α-Methylstyrene/isobutene, α-methylstyrene/diisobutene, cyclopentadiene/isobutene, and cyclopentadiene/α-methylstyrene were copolymerized by cationic polymerization techniques. Several properties of the copolymers such as softening ranges and oxidation stability depend on their constitutional composition, and were controlled by variation of the conditions of their synthesis. 相似文献
72.
An intramolecular, organocatalyzed Michael addition has been developed to obtain biologically important 2,3‐disubstituted cis‐2,3‐dihydrobenzofurans. By using mandelic acid salts of primary aminocatalysts, derived from cinchona alkaloids, the intramolecular cyclization reaction has been developed to proceed in high yield, with moderate to good diastereoselectivity, and up to 99 % ee. Based on the absolute configuration of the formed 2,3‐disubstituted‐cis‐2,3‐dihydrobenzofurans and by considering the observed substrate scope restrictions, a mechanistic rationalization has been presented. 相似文献
73.
Krzysztof Kaczmarek Barbara Pacholczyk-Sienicka ukasz Albrecht Janusz Zabrocki Ronald J. Nachman 《Molecules (Basel, Switzerland)》2021,26(11)
A facile solid-phase synthetic method for incorporating the imidazoline ring motif, a surrogate for a trans peptide bond, into bioactive peptides is reported. The example described is the synthesis of an imidazoline peptidomimetic analog of an insect pyrokinin neuropeptide via a cyclization reaction of an iminium salt generated from the preceding amino acid and 2,4-diaminopropanoic acid (Dap). 相似文献
74.
The stable isotopic composition (delta(2)H and delta(18)O) of short-term (daily) precipitation collected from October 2002 to September 2003 at two stations in a coastal, karstic area in south-western Slovenia was investigated. In addition, monthly composite samples were collected and analysed for comparison with amount-weighted monthly means. The delta(2)H and delta(18)O values obtained show a wide range and reflect seasonal climatic variations. Deuterium excess and local meteoric water lines (LMWLs) were determined and cumulative frequency analysis and coincidence tests were performed. The statistical coincidence test showed that the LMWLs calculated from monthly data for Portoroz and Kozina are coincident, but the LMWLs calculated from daily precipitation events are not. This difference could be explained by the greater variance of the isotopic composition of daily precipitation in comparison to monthly composite samples and also to the influence of evaporation during events below<1 mm at Portoroz during the extremely dry and warm spring-summer season of 2003. Finally, synoptic maps and backward trajectories of a selected precipitation event showed that changes of isotopic composition are related to mixing of air masses originating from the continent and Mediterranean cyclogenesis. 相似文献
75.
Metalation of CH2OH-substituted triazolium salts with CoCl2 under basic conditions affords C,O-bidentate chelating carbene Co(III) complexes ( 3a , 3b ), while analogous phenyl-substituted triazolium salts produce monodentate carbene Co(II) complexes ( 3c , 3d ). The distinct substituent-induced properties of the metal centers were demonstrated by electrochemical measurements and catalytic activities in two specific processes. The complexes showed appreciable activity in the reduction of C=O bonds through hydrosilylation, with methoxybenzene-functionalized triazolylidene Co(III) complex 3a achieving a high selectivity towards aldehydes vs. ketones with turnover frequencies (TOFs) up to 200 h−1. The C,O-chelate systems were also active catalysts in the Biginelli process, a one-step three-component reaction for efficient dihydropyrimidinone synthesis. Optimization of reaction conditions provides high activity with complex 3a , reaching TOFs of 800 h−1, the highest activity known for cobalt NHC complexes to date. 相似文献
76.
Matthias Krumb Dr. Maximilian Jäger Alice Voss Loreen Immig Dr. Karin Peters Danuta Kowalczyk Prof. Dr. Albrecht Bufe Prof. Dr. Till Opatz Prof. Dr. Otto Holst Prof. Dr. Christian Vogel Dr. Marcus Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):928-933
Arabinogalactan, a microheterogeneous polysaccharide occurring in plants, is known for its allergy-protective activity, which could potentially be used for preventive allergy treatment. New treatment options are highly desirable, especially in a preventive manner, due to the constant rise of atopic diseases worldwide. The structural origin of the allergy-protective activity of arabinogalactan is, however, still unclear and isolation of the polysaccharide is not feasible for pharmaceutical applications due to a variation of the activity of the natural product and contaminations with endotoxins. Therefore, a pentasaccharide partial structure was selected for total synthesis and subsequently coupled to a carrier protein to form a neoglycoconjugate. The allergy-protective activity of arabinogalactan could be reproduced with the partial structure in subsequent in vivo experiments. This is the first example of a successful simplification of arabinogalactan with a single partial structure while retaining its allergy-preventive potential. 相似文献
77.
Sensing of Phosphates by Using Luminescent EuIII and TbIII Complexes: Application to the Microalgal Cell Chlorella vulgaris 下载免费PDF全文
Sandeep Nadella Jashobanta Sahoo Dr. Palani S. Subramanian Abhishek Sahu Dr. Sandhya Mishra Prof. Dr. Markus Albrecht 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6047-6053
Phenanthroline‐based chiral ligands L1 and L2 as well as the corresponding EuIII and TbIII complexes were synthesized and characterized. The coordination compounds show red and green emission, which was explored for the sensing of a series of anions such as F?, Cl?, Br?, I?, NO3?, NO2?, HPO42?, HSO4?, CH3COO?, and HCO3?. Among the anions, HPO42? exhibited a strong response in the emission property of both europium(III) and terbium(III) complexes. The complexes showed interactions with the nucleoside phosphates adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP). Owing to this recognition, these complexes have been applied as staining agents in the microalgal cell Chlorella vulgaris. The stained microalgal cells were monitored through fluorescence microscopy and scanning electron microscopy. Initially, the complexes bind to the outer cell wall and then enter the cell wall through holes in which they probably bind to phospholipids. This leads to a quenching of the luminescence properties. 相似文献
78.
Dr. Łukasz Albrecht Dr. Hao Jiang Prof. Dr. Karl Anker Jørgensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(2):358-368
This Concept article summarizes recent progress in the field of hydrogen‐bonding aminocatalysis using proline‐derived systems. The aminocatalysts available in the literature are categorized by the incorporated hydrogen‐bonding scaffold and its mode of recognition. Both mono‐ and double‐hydrogen‐bonding motifs are discussed and examples of their application in asymmetric synthesis are given. 相似文献
79.
Green single-crystals of the hydroxochromate(III) CaNa[Cr(OH)6] were grown under highly alkaline hydrothermal conditions at about 200 °C. The starting materials Ca(NO3)2 · 6H2O and Cr(NO3)3 · 9H2O were reacted in a mixture of water and sodium hydroxide with the molar ratio of 2.8:1. CaNa[Cr(OH)6] crystallizes in the non-centrosymmetric trigonal space group R3 with the lattice parameters a = 583.86(2) pm and c = 1428.73(6) pm [T = 100(1) K]. Characteristically, the crystals are reverse-obverse as well as inversion twins. The crystal structure is a stack of uncharged metal hydroxide layers, which can be regarded as a cation-ordered rhombohedral variant of the Mg(OH)2 (brucite) structure type. The oxidation state of chromium(III) and its coordination by hydroxide groups was confirmed by UV/Vis and IR spectroscopy, respectively. Temperature-dependent magnetic measurements revealed paramagnetic behavior with an effective moment of 3.82 μB per chromium atom. The thermal decomposition of CaNa[Cr(OH)6] takes place at about 225 °C, where the fast elimination of 1.5 equivalents of water is followed by the oxidation of chromium(III) to chromium(VI). Upon further heating to 1000 °C and 1200 °C, the intermediate decomposition products CaCrO4 and Na2CrO4 transform into the oxochromates(V) Ca5(CrO4)3O0.5 and Ca3(CrO4)2, respectively. 相似文献
80.
Kathrin Brmmel Sarah Maskri Ivan Maisuls Christian Paul Konken Marius Rieke Zoltan Peth Cristian A. Strassert Oliver Koch Albrecht Schwab Bernhard Wünsch 《Angewandte Chemie (International ed. in English)》2020,59(21):8277-8284
Small‐molecule probes for the in vitro imaging of KCa3.1 channel‐expressing cells were developed. Senicapoc, showing high affinity and selectivity for the KCa3.1 channels, was chosen as the targeting component. BODIPY dyes 15 – 20 were synthesized and connected by a CuI‐catalyzed azide–alkyne [3+2]cycloaddition with propargyl ether senicapoc derivative 8 , yielding fluorescently labeled ligands 21 – 26 . The dimethylpyrrole‐based imaging probes 25 and 26 allow staining of KCa3.1 channels in NSCLC cells. The specificity was shown by removing the punctate staining pattern by pre‐incubation with senicapoc. The density of KCa3.1 channels detected with 25 and by immunostaining was identical. The punctate structure of the labeled channels could also be observed in living cells. Molecular modeling showed binding of the senicapoc‐targeting component towards the binding site within the ion channel and orientation of the linker with the dye along the inner surface of the ion channel. 相似文献