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211.
Stephan Brox Axel P. Ritter Eberhard Küster Thorsten Reemtsma 《Analytical and bioanalytical chemistry》2014,406(20):4831-4840
An analytical method using high-performance liquid chromatography–tandem mass spectrometry was developed to determine internal concentrations of 34 test compounds such as pharmaceuticals and pesticides in zebrafish embryos (ZFE), among them, cimetidine, 2,4-dichlorophenoxyacetic acid, metoprolol, atropine and phenytoin. For qualification and quantification, multiple reaction monitoring mode was used. The linear range extends from 0.075 ng/mL for thiacloprid and metazachlor and 7.5 ng/mL for coniine and clofibrate to 250 ng/mL for many of the test compounds. Matrix effects were strongest for nicotine, but never exceeded ±20 % for any of the developmental stages of the ZFE. Method recoveries ranged from 90 to 110 % from an analysis of nine pooled ZFE. These findings together with the simple sample preparation mean this approach is suitable for the determination of internal concentrations from only nine individual ZFE in all life stages up to 96 h post-fertilization. Exemplarily, the time course of the internal concentrations of clofibric acid, metribuzin and benzocaine in ZFE was studied over 96 h, and three different patterns were distinguished, on the basis of the speed and extent of uptake and whether or not a steady state was reached. Decreasing internal concentrations may be due to metabolism in the ZFE. Figure
Quantification of polar pollutants in different life stages of the zebrafish embryo by LC-MS/MS 相似文献
212.
Jan Rosenboom Dr. Lukas Chojetzki Dr. Tim Suhrbier Dr. Jabor Rabeah Dr. Alexander Villinger Dr. Ronald Wustrack Dr. Jonas Bresien Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202200624
The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)2P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)2P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)2P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)2P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)2P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)2P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)2P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)2P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)2P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity. 相似文献
213.
Dr. Giambattista Testolin Dr. Jana Richter Antje Ritter Dr. Hans Prochnow Prof. Dr. Jesko Köhnke Prof. Dr. Mark Brönstrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(54):e202201297
The rise of antibiotic resistance causes a serious health care problem, and its counterfeit demands novel, innovative concepts. The combination of photopharmacology, enabling a light-controlled reversible modulation of drug activity, with antibiotic drug design has led to first photoswitchable antibiotic compounds derived from established scaffolds. In this study, we converted cystobactamids, gyrase-inhibiting natural products with an oligoaryl scaffold and highly potent antibacterial activities, into photoswitchable agents by inserting azobenzene in the N-terminal part and/or an acylhydrazone moiety near the C-terminus, yielding twenty analogs that contain mono- as well as double-switches. Antibiotic and gyrase inhibition properties could be modulated 3.4-fold and 5-fold by light, respectively. Notably, the sensitivity of photoswitchable cystobactamids towards two known resistance factors, the peptidase AlbD and the scavenger protein AlbA, was light-dependent. While irradiation of an analog with an N-terminal azobenzene with 365 nm light led to less degradation by AlbD, the AlbA-mediated inactivation was induced. This provides a proof-of-principle that resistance towards photoswitchable antibiotics can be optically controlled. 相似文献
214.
Jie Zhang Yuyin Wang Yun Wang Yang Bai Xin Feng Jiahua Zhu Xiaohua Lu Liwen Mu Tingzhen Ming Renaud de Richter Wei Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202201984
Methane (CH4) is a potent greenhouse gas and the second highest contributor to global warming. CH4 emissions are still growing at an alarmingly high pace. To limit global warming to 1.5 °C, one of the most effective strategies is to reduce rapidly the CH4 emissions by developing large-scale methane removal methods. The purpose of this perspective paper is threefold. (1) To highlight the technology gap dealing with low concentration CH4 (at many emission sources and in the atmosphere). (2) To analyze the challenges and prospects of solar-driven gas phase advanced oxidation processes for CH4 removal. And (3) to propose some ideas, which may help to develop solar-driven gas phase advanced oxidation processes and make them deployable at a climate significant scale. 相似文献
215.
The application of ionic liquids for the dissolution of metal oxides is a promising field for the development of more energy- and resource-efficient metallurgical processes. Using such solutions for the production of valuable chemicals or electrochemical metal deposition requires a detailed understanding of the chemical system and the factors influencing it. In the present work, several compounds are reported that crystallize after the dissolution of copper(II) oxide in the ionic liquid [Hbet][NTf2]. Dependent on the initial amount of chloride, the reaction temperature and the purity of the reagent, copper crystallizes in complexes with varying coordination geometries and ligands. Subsequently, the influence of these different complex species on electrochemical properties is shown. For the first time, copper is deposited from the ionic liquid [Hbet][NTf2], giving promising opportunities for more resource-efficient copper plating. The copper coatings were analyzed by SEM and EDX measurements. Furthermore, a mechanism for the decomposition of [Hbet][NTf2] in the presence of chloride is suggested and supported by experimental evidence. 相似文献
216.
Dr. Uttam Chakraborty Patrick Bügel Lorena Fritsch Dr. Florian Weigend Prof. Dr. Matthias Bauer Prof. Dr. Axel Jacobi von Wangelin 《ChemistryOpen》2021,10(2):265-271
The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe4, Fe6, and Fe7 nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles. 相似文献
217.
218.
Niedzwiedz K Wischnewski A Monkenbusch M Richter D Genix AC Arbe A Colmenero J Strauch M Straube E 《Physical review letters》2007,98(16):168301
We present a neutron scattering investigation on a miscible blend of two polymers with greatly different glass-transition temperatures Tg. Under such conditions, the nearly frozen high-Tg component imposes a random environment on the mobile chain. The results demand the consideration of a distribution of heterogeneous mobilities in the material and demonstrate that the larger scale dynamics of the fast component is not determined by the average local environment alone. This distribution of mobilities can be mapped quantitatively on the spectrum of local relaxation rates measured at high momentum transfers. 相似文献
219.
We study the link between three seeming-disparate cases of self-avoiding polymers: strongly overlapping multiple chains in dilute solution, chains under spherical confinement, and the onset of semidilute solutions. Our main result is that the free energy for overlapping n chains is independent of chain length and scales as n9/4, slowly crossing over to n3, as n increases. For strongly confined polymers inside a spherical cavity, we show that rearranging the chains does not cost an additional free energy. Our results imply that, during cell cycle, global reorganization of eukaryotic chromosomes in a large cell nucleus could be readily achieved. 相似文献
220.
Byelikov A Adachi T Fujita H Fujita K Fujita Y Hatanaka K Heger A Kalmykov Y Kawase K Langanke K Martínez-Pinedo G Nakanishi K von Neumann-Cosel P Neveling R Richter A Sakamoto N Sakemi Y Shevchenko A Shimbara Y Shimizu Y Smit FD Tameshige Y Tamii A Woosley SE Yosoi M 《Physical review letters》2007,98(8):082501
The Gamow-Teller strength distributions below the particle threshold in 138La and 180Ta, deduced from high-resolution measurements of the (3He,t) reaction at 0 degrees, allow us to evaluate the role of charged-current reactions for the production of these extremely rare nuclides in neutrino-nucleosynthesis models. The analysis suggests that essentially all 138La in the Universe can be made that way. Neutrino nucleosynthesis also contributes significantly to the abundance of 180Ta but the magnitude depends on the unknown branching ratio for population of the long-lived isomer. 相似文献