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71.
Paulo A. R. Pires Muhammad Imran Carina Loffredo Paulo M. Donate Daniel Previdi Omar A. El Seoud 《Journal of Physical Organic Chemistry》2013,26(3):280-285
The effects of solvents on chemical phenomena (rate and equilibrium constants, spectroscopic transitions, etc.) are conveniently described by solvation free‐energy relationships that take into account solvent acidity, basicity and dipolarity/polarizability. The latter can be separated into its components by manipulating the UV–vis spectra of two solvatochromic probes, 2‐(N,N‐dimethylamino)‐7‐nitrofluorene (DMANF) and a di‐(tert‐butyl)‐tetramethyl docosanonaen probe (ttbP9) whose synthesis is laborious and expensive. Recently, we have shown that the natural dye β‐carotene can be conveniently employed instead of ttbP9 for the determination of solvent polarizability (SP) of 76 molecular solvents and four ionic liquids. In the present work, we report the polarizabilities of further 24 solvents. Based on the solvatochromism of β‐carotene and DMANF, we have calculated solvent dipolarity (SD) for 103 protic and aprotic molecular solvents, and ionic liquids. The dependence of SD and SP on the number of carbon atoms in the acyl‐ or alkyl group of several homologous series (alcohols; 2‐alkoxyethanols; carboxylic acid‐ anhydrides, and esters, ionic liquids) is calculated and briefly discussed. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
72.
The IR spectra have been recorded in the solid state for the parent molecule, 6-(N-pyrrolyl)purine (1) and its N-9-and N-7-substituted derivatives: 9-and 7-(2-hydroxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (2 and 3), 9-and 7-(2-acetoxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (4 and 5), 9-and 7-(2,3-dihydroxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (6 and 7) as well as 9-and 7-(2,3-diacetoxyprop-1-yl)-6-(N-pyrrol-1-yl)purine (8 and 9). Analysis of the characteristic bands has proved to be useful in differentiating between N-9 and N-7 regioisomers. 相似文献
73.
Let K be a field of characteristic p > 0, let L be a restricted Lie algebra and let R be an associative K-algebra. It is shown that the various constructions in the literature of crossed product of R with u(L) are equivalent. We calculate explicit formulae relating the parameters involved and obtain a formula which hints at a noncommutative version of the Bell polynomials. 相似文献
74.
Carina I. Jette Irina Geibel Shoshana Bachman Masaki Hayashi Shunya Sakurai Hideki Shimizu Jeremy B. Morgan Brian M. Stoltz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4341-4345
Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich dialkylphosphine ligand we have been able to construct α‐quaternary centers in good yields (up to 91 % yield) and high enantioselectivities (up to 97 % ee). 相似文献
75.
Olaya Domarco Claudia Kieler Christine Pirker Carina Dinhof Bernhard Englinger Johannes M. Reisecker Gerald Timelthaler Marcos D. García Carlos Peinador Bernhard K. Keppler Walter Berger Alessio Terenzi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8091-8096
Metal‐driven self‐assembly afforded a multitude of fascinating supramolecular coordination complexes (SCCs) with applications as catalysts, host–guest, and stimuli‐responsive systems. However, the interest in the biological applications of SCCs is only starting to emerge and thorough characterization of their behavior in biological milieus is still lacking. Herein, we report on the synthesis and detailed in‐cell tracking of a Pt2L2 metallacycle. We show that our hexagonal supramolecule accumulates in cancer cell nuclei, exerting a distinctive blue fluorescence staining of chromatin resistant to UV photobleaching selectively in nucleolar G4‐rich regions. SCC co‐localizes with epitopes of the quadruplex‐specific antibody BG4 and replaces other well‐known G4 stabilizers. Moreover, the photophysical changes accompanying the metallacycle binding to G4s in solution (fluorescence quenching, absorption enhancement) also take place intracellularly, allowing its subcellular interaction tracking. 相似文献
76.
Dr. Lydia M. Peschel Carina Vidovič Dr. Ferdinand Belaj Dr. Dmytro Neshchadin Prof. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3893-3902
The synthesis and structural determination of four tungsten alkyne complexes coordinated by the bio-inspired S,N-donor ligand 2-(4′,4′-dimethyloxazoline-2′-yl)thiophenolate (S-Phoz) is presented. A previously established protocol that involved the reaction of the respective alkyne with the bis-carbonyl precursor [W(CO)2(S-Phoz)2] was used for the complexes [W(CO)(C2R2)(S-Phoz)2] (R=H, 1 a ; Me, 1 b ; Ph, 1 c ). Oxidation with pyridine-N-oxide gave the corresponding W-oxo species [WO(C2R2)(S-Phoz)2] (R=H, 2 a ; Me, 2 b ; Ph, 2 c ). All W-oxo-alkyne complexes ( 2 a , b , c ) were found to be capable of alkyne release upon light irradiation to afford five-coordinate [WO(S-Phoz)2] ( 3 ). The photoinduced release of the alkyne ligand was studied in detail by in situ 1H NMR measurements, which revealed correlation of the photodissociation rate constant ( 2 b>2 a>2 c ) with the elongation of the alkyne C≡C bond in the molecular structures. Oxidation of [WO(S-Phoz)2] ( 3 ) with pyridine-N-oxide yielded [WO2(S-Phoz)2] ( 4 ), which shows highly fluxional behavior in solution. Variable-temperature 1H NMR spectroscopy revealed three isomeric forms with respect to the ligand arrangement versus each other. Furthermore, compound 4 rearranges to tetranuclear oxo compound [W4O4(μ-O)6(S-Phoz)4] ( 5 ) and dinuclear [{WO(μ-O)(S-Phoz)}2] ( 6 ) over time. The latter two were identified by single-crystal X-ray diffraction analyses. 相似文献
77.
The so-called ‘soldering’ procedure performed by Polyakov (Int J Math Phys A5, 833–842, 1990) for a -gauge theory is geometrically explained in terms of a Cartan connection on second-order frames of the projective space P1. The relationship between a Cartan connection and the usual (Ehresmann) connection on a principal bundle allows to gain an
appropriate insight into the derivation of the genuine ‘diffeomorphisms out of gauge transformations’ given by Polyakov himself.
Unité Mixte de Recherche (UMR 6207) du CNRS et des Universités Aix-Marseille I, Aix-Marseille II et de l’Université du Sud
Toulon-Var. Unité affiliée à la FRUMAM Fédération de Recherche 2291. 相似文献
78.
Molina FD Bertollo EM Assis CM Falleiros LR Campos SG Maniglia JV Taboga SR 《Micron (Oxford, England : 1993)》2008,39(7):910-914
Squamous cell carcinoma of the tongue is one of the most common head and neck cancer. Treatment in the early stages is still controversial. This study aims to correlate the apoptosis rate of primary tongue cancer with cervical node metastasis, found in the histopathological studies of specimens obtained from neck dissections or during clinical follow-up. Twenty patients, 65% males, mean age 64.5 years, without clinical evidence of cervical metastasis was included. Eighty-five percent were smokers and 40% were alcohol abusers. Mann-Whitney test was used for statistical analysis (p=0.05). Five patients with clinically occult cervical metastases had metastasis in the histopathological specimens (25%) occult metastasis. The mean apoptosis rate in patients without cervical metastasis was 9.43%. Twenty-five percent of the patients had occult cervical metastasis. High apoptosis rate in tongue cancer, even in the absence of palpable neck nodes, correlates with the presence of occult metastasis. 相似文献
79.
We consider the problem of sending a message from a sender to a receiver through an unreliable network by specifying in a protocol what each vertex is supposed to do if it receives the message from one of its neighbors. A protocol for routing a message in such a graph is finite if it never floods with an infinite number of copies of the message. The expected reliability of a given protocol is the probability that a message sent from reaches when the edges of the network fail independently with probability .We discuss, for given networks, the properties of finite protocols with maximum expected reliability in the case when is close to 0 or 1, and we describe networks for which no one protocol is optimal for all values of . In general, finding an optimal protocol for a given network and fixed probability is challenging and many open problems remain. 相似文献