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91.
Mathilde Rigoulet Olivier Thillaye du Boullay Abderrahmane Amgoune Didier Bourissou 《Angewandte Chemie (International ed. in English)》2020,59(38):16625-16630
Heteroarylation of alkenes with aryl iodides was efficiently achieved with a (MeDalphos)AuCl complex through AuI/AuIII catalysis. The possibility to combine oxidative addition of aryl iodides and π‐activation of alkenes at gold is demonstrated for the first time. The reaction is robust and general (>30 examples including internal alkenes, 5‐, 6‐, and 7‐membered rings). It is regioselective and leads exclusively to trans addition products. The (P,N) gold complex is most efficient with electron‐rich aryl substrates, which are troublesome with alternative photoredox/oxidative approaches. In addition, it provides a very unusual switch in regioselectivity from 5‐exo to 6‐endo cyclization between the Z and E isomers of internal alkenols. 相似文献
92.
Point D Davis WC Garcia Alonso JI Monperrus M Christopher SJ Donard OF Becker PR Wise SA 《Analytical and bioanalytical chemistry》2007,389(3):787-798
Two speciated isotope dilution (SID) approaches consisting of a single-spike (SS) method and a double-spike (DS) method including a reaction/transformation model for the correction of inadvertent transformations affecting mercury species were compared in terms of accuracy, method performance, and robustness for the simultaneous determination of methylmercury (MeHg), inorganic mercury (iHg), and total mercury (HgT) concentrations in five biological Standard Reference Materials (SRMs). The SRMs consisted of oyster and mussel tissue materials displaying different mercury species concentration levels and different textural/matrix properties including freeze-dried (FD) materials (SRMs 1566b, 2976, and 2977) and cryogenically prepared and stored fresh-frozen (FF) materials (SRMs 1974a, 1974b). Each sample was spiked with (201)iHg (Oak Ridge National Laboratory, ORNL) and Me(202)Hg (Institute for Reference Materials and Measurements. IRMM-670) solutions and analyzed using alkaline microwave digestion, ethylation, and gas chromatography inductively coupled plasma mass spectrometry (GC/ICP-MS). The results obtained by the SS-SID method suggested that FF and FD materials are not always commutable for the simultaneous determination of iHg, MeHg, and HgT, due to potential transformation reactions resulting probably from the methodology and/or from the textural/matrix properties of the materials. These transformations can occasionally significantly affect mercury species concentration results obtained by SS-SID, depending on the species investigated and the materials considered. The results obtained by the DS-SID method indicated that the two classes of materials were commutable. The simultaneous and corrected concentrations of iHg, MeHg, and HgT obtained by this technique were not found to be statistically different form the certified and reference concentration together with their expanded uncertainty budgets for the five SRMs investigated, exemplifying the robustness, the accuracy, and the improved commutability of this method compared to SS-SID measurements. 相似文献
93.
Mathilde Triquigneaux Béatrice Tuccio Robert Lauricella Laurence Charles 《Journal of the American Society for Mass Spectrometry》2009,20(11):2013-2020
Mass spectrometry (MS) was used in conjunction with electron paramagnetic resonance (EPR) to characterize products arising
from reactions between reduced glutathione (GSH) and 2-methyl 2-nitroso propane (MNP) in an oxidative medium, to evaluate
the reactivity of this tripeptide as a nucleophile toward a nitroso compound. Depending on the experimental conditions, different
radical species could be detected by EPR, which allowed some structural assumptions. These samples were then submitted to
electrospray ionization, in both positive and negative ion modes, for structural elucidation in tandem mass spectrometry.
Although the primary nitroxide products could not be detected in MS, structurally related compounds such as hydroxylamine
and O-methyl hydroxylamine could be fully characterized. In the absence of light, a S-adduct was formed via a Forrester-Hepburn reaction, that is, a nucleophile addition of MNP onto the thiol function in reduced
glutathione to yield a hydroxylamine intermediate, further oxidized into nitroxide. In contrast, irradiating the reaction
medium with visible light could allow an inverted spin trapping reaction to take place, involving the oxidation of both MNP
and GSH before the nucleophilic addition of the sulfenic acid function onto the nitrogen of MNP, yielding a so-called O-adduct. It was also found that dilution of the reaction medium with methanol for the purpose of electrospray ionization could
allow nitroxides to be indirectly observed either as hydroxylamine or O-methyl hydroxylamine species. 相似文献
94.
Zusammenfassung Eisen und Cer lassen sich in Gegenwart von Ammoniumthiocyanat in salzsaurer Lösung durch Ausschütteln mit Äther + Tetrahydrofuran quantitativ trennen. Die Trennung ist in 8–10 min durchzuführen. 相似文献
95.
An intramolecular [2+2] cycloaddition of ketenes and ketene-iminium was developed for the preparation of GR-24, a synthetic analogue of the family of strigolactone plant hormones. Excellent levels of regioselectivity and of chiral induction were obtained using a bulky chiral amine for the formation of the cyclobutanone and a subsequent regioselective Baeyer-Villiger afforded the tricyclic lactone core of (+)-GR-24. 相似文献
96.
In the course of our investigations on the synthesis of original nitrogen heterocyclic derivatives, we were interested in the synthesis and study of original 1,4-dihydropyrazine rings. To this aim the desired bisvinylphosphate derivative was prepared from N-Boc piperazine-2,5-dione and then was engaged in palladium catalyzed reactions (reduction, Suzuki and Stille cross-coupling reactions). The 1,4-dihydropyrazine and the corresponding 2,5-disubstituted derivatives were obtained in fair to good yields and were then functionalized under anionic conditions. Aromatization into 1,4-pyrazines was investigated in a second stage. 相似文献
97.
Maria Mastrangelopoulou Mantas Grigalavicius Kristian Berg Mathilde Mnard Theodossis A. Theodossiou 《Photochemistry and photobiology》2019,95(1):387-396
Cercosporin is a naturally occurring perylenequinone. Although other perylenequinones have been extensively studied as photosensitizers in photodynamic therapy of cancer (PDT), cercosporin has been studied in this light only within the remits of phytopathology. Herein, we investigated the photocytotoxicity of cercosporin against two glioblastoma multiforme (T98G and U87) and one breast adenocarcinoma (MCF7) human cell lines. Cercosporin was found to be a potent singlet oxygen producer upon 532 nm excitation, while its cell loading was similar for MCF7 and U87, but approximately threefold higher for T98G cells. The subcellular localization of cercosporin was in all cases in both mitochondria and the endoplasmic reticulum. Light irradiation of cercosporin‐incubated cells around 450 nm showed that T98G cells were more susceptible to cercosporin PDT, mainly due to their higher cercosporin uptake. Metabolic studies before and 1 h following cercosporin PDT showed that cercosporin PDT instigated a bioenergetic collapse in both the respiratory and glycolytic activities of all cell lines. In the dark, cercosporin exhibited a synergistic cytotoxicity with copper only in the most respiratory cell lines (MCF7 and T98G). Cercosporin is a potent photosensitizer, but with a short activation wavelength, mostly suitable for superficial PDT treatments, especially when it is necessary to avoid perforations. 相似文献
98.
P450Jα: A New,Robust and α-Selective Fatty Acid Hydroxylase Displaying Unexpected 1-Alkene Formation
Julia Armbruster Mathilde Steinmassl Dr. Christina A. Müller Bogotá Prof. Dr. Gabriele Berg Prof. Dr. Bernd Nidetzky Dr. Alexander Dennig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):15910-15921
Oxyfunctionalization of fatty acids (FAs) is a key step in the design of novel synthetic pathways for biobased/biodegradable polymers, surfactants and fuels. Here, we show the isolation and characterization of a robust FA α-hydroxylase (P450Jα) which catalyses the selective conversion of a broad range of FAs (C6:0-C16:0) and oleic acid (C18:1) with H2O2 as oxidant. Under optimized reaction conditions P450Jα yields α-hydroxy acids all with >95 % regioselectivity, high specific activity (up to 15.2 U mg−1) and efficient coupling of oxidant to product (up to 85 %). Lauric acid (C12:0) turned out to be an excellent substrate with respect to productivity (TON=394 min−1). On preparative scale, conversion of C12:0 reached 83 % (0.9 g L−1) when supplementing H2O2 in fed-batch mode. Under similar conditions P450Jα allowed further the first biocatalytic α-hydroxylation of oleic acid (88 % conversion on 100 mL scale) at high selectivity and in good yields (1.1 g L−1; 79 % isolated yield). Unexpectedly, P450Jα displayed also 1-alkene formation from shorter chain FAs (≤C10:0) showing that oxidative decarboxylation is more widely distributed across this enzyme family than reported previously. 相似文献
99.
100.
Dr. Blaise Gatin-Fraudet Mathilde Pucher Dr. Thomas Le Saux Dr. Gilles Doisneau Dr. Yann Bourdreux Prof. Ludovic Jullien Dr. Boris Vauzeilles Prof. Dominique Guianvarc'h Dr. Dominique Urban 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202201543
Arylborinic acids represent new, efficient, and underexplored hydrogen peroxide-responsive triggers. In contrast to boronic acids, two concomitant oxidative rearrangements are involved in the complete oxidation of these species, which might represent a major limitation for an efficient effector (drug or fluorophore) release. Herein, a comprehensive study of H2O2-mediated unsymmetrical arylborinic acid oxidation to investigate the factors that could selectively guide their oxidative rearrangement is described. The o-CF3 substituent was found to be an excellent directing group allowing a complete regioselectivity on borinic acid models. This result was successfully applied to synthesizing new borinic acid-based fluorogenic probes, which exclusively release the fluorescent moiety upon H2O2 treatment. These compounds maintained their superior kinetic properties compared to boronic acids, thus further enhancing the potential of arylborinic acids as valuable new H2O2-sensitive triggers. 相似文献