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71.
Dmytro Neshchadin Dr. Rebecca Levinn Georg Gescheidt Prof. Dr. Stephen N. Batchelor Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):7008-7016
Polyphenols occur naturally in a vast variety of plants. One of their predominant properties is their antioxidant activity. To provide a deeper understanding of the antioxidant mechanism, 1H CIDNP spectroscopy (CIDNP=chemically induced dynamic nuclear polarization) is used to study model hydrogen abstraction reactions with four catechin‐based polyphenols: catechin (CA), gallocatechin (GC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG). The experiments involve photoinduced hydrogen‐atom transfer to a hydrogen abstractor (e.g., excited isopropylthioxanthone) followed under steady‐state conditions and in a time‐resolved fashion (resolution 500 ns–1 ms). It is found that hydrogen abstraction is an essentially stochastic process with a slight preference for the B rings in the catechin‐based polyphenols. Remarkably, analogous reactivity patterns could be followed in the “real systems”, green tea and red wine. We also show that CIDNP can be used as a semiquantitative tool to assess chemical reactivity. 相似文献
72.
Kurosaki Hiromu Mueller Rebecca J. Lambert Susan B. Rao Govind R. 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(1):323-329
Journal of Radioanalytical and Nuclear Chemistry - An alternate method of preparing actinide alpha counting sources was developed in place of electrodeposition or lanthanide fluoride... 相似文献
73.
CO(2) capture by a task-specific ionic liquid 总被引:20,自引:0,他引:20
Reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, followed by workup and anion exchange, yields a new room temperature ionic liquid incorporating a cation with an appended amine group. The new ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The new ionic liquid, which can be repeatedly recycled in this role, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents, and yet is nonvolatile and does not require water to function. 相似文献
74.
75.
Basabe-Desmonts L Beld J Zimmerman RS Hernando J Mela P García Parajó MF van Hulst NF van den Berg A Reinhoudt DN Crego-Calama M 《Journal of the American Chemical Society》2004,126(23):7293-7299
Self-assembled monolayers (SAMs) on glass were used as a platform to sequentially deposit fluorophores and small molecules for ion sensing. The preorganization provided by the surface avoids the need for complex receptor design, allowing for a combinatorial approach to sensing systems based on small molecules. The resulting libraries are easily measured and show varied responses to a series of both cations and anions. This technology is transferable from the macro- to the microscale both via microcontact printing (microCP), where the fluorophore is printed onto a glass surface, and via direct attachment of the fluorophore to microchannel walls. The ease of miniaturization of this technology may make the generation of a wide variety of simple yet efficient microarrays possible. 相似文献
76.
Moss RJ Wadsworth KJ Chapman CJ Frost CG 《Chemical communications (Cambridge, England)》2004,(17):1984-1985
The rhodium catalysed addition of potassium trifluoro(organo)borates to dimethyl itaconate generates an intermediate complex which on protonation provides enantioenriched succinic esters. 相似文献
77.
78.
An approach toward the synthesis of the antifungal and cytotoxic pseudolaric acids based on the tandem metal carbene cyclization-cycloaddition reaction is described. Using this strategy, the advanced intermediate 3a bearing three of the four stereocenters of the target molecules has been synthesized. The substrate-controlled diastereoselectivity of the tandem carbene cyclization-cycloaddition was preferential for the undesired diastereomer, but reagent control through the use of Hashimoto's chiral rhodium catalyst Rh(2)(S-BPTV)(4) reversed the selectivity in favor of 3a. Ring opening of the oxabicyclic nucleus to give a hydroxycycloheptene has been demonstrated in a model study. 相似文献
79.
An evaluation of alpha-aryl-alpha-diazodiones in tandem carbonyl ylide formation-enantioselective [3 + 2]-cycloaddition reactions is described. Such substrates were designed to allow investigation of the electronic characteristics of the dipole upon asymmetric induction. Intramolecular cycloadditions (with a tethered alkene dipolarophile) were found to occur in good to quantitative yields, with a difference in ee exhibited by the two electronically different diazodiones 8 and 9. Intermolecular cycloadditions using diazodiones 12 and 13 with DMAD and arylacetylenes 16-18 again demonstrated that electronics play a key role in determining the outcome of the cycloaddition reactions. Enantioselectivities of up to 76% were observed. 相似文献
80.
Synthesis, cyclic voltammetric studies, and electrogenerated chemiluminescence of a new phenylquinoline-biphenothiazine donor-acceptor molecule 总被引:1,自引:0,他引:1
We report the synthesis, electrochemistry, and luminescence of a novel ECL emitting compound containing two electron-accepting hexyl-phenylquinoline groups covalently attached to the 3,3'-positions of the electron-donating 10,10'-dimethylbiphenothiazine group. The optimized geometry as determined from semiempirical MNDO calculations shows that the two quinoline groups are twisted 82.5 degrees from the two phenothiazine rings, indicating a lack of electron delocalization among these groups. This unique geometry allows generation of localized radical cations and radical anions capable of generating ECL upon annihilation. However, the phenothiazine rings are twisted 46.5 degrees relative to each other, suggesting possible interactions between the two moieties. This is evident in the electrochemical behavior in which two closely spaced one-electron oxidations, rather than a single two-electron oxidation wave, were observed. The photophysical properties of BHQ-BPZ show strong resemblances to the parent compound, BPQ-PTZ, which contains a single phenothiazine moiety. In addition, the ECL spectrum produced via radical ion annihilation shows good agreement with the fluorescence emission of the compound. 相似文献