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91.
Cell Tracking with Caged Xenon: Using Cryptophanes as MRI Reporters upon Cellular Internalization 下载免费PDF全文
Stefan Klippel Jörg Döpfert Dr. Jabadurai Jayapaul Martin Kunth Federica Rossella Matthias Schnurr Dr. Christopher Witte Dr. Christian Freund Dr. Leif Schröder 《Angewandte Chemie (International ed. in English)》2014,53(2):493-496
Caged xenon has great potential in overcoming sensitivity limitations for solution‐state NMR detection of dilute molecules. However, no application of such a system as a magnetic resonance imaging (MRI) contrast agent has yet been performed with live cells. We demonstrate MRI localization of cells labeled with caged xenon in a packed‐bed bioreactor working under perfusion with hyperpolarized‐xenon‐saturated medium. Xenon hosts enable NMR/MRI experiments with switchable contrast and selectivity for cell‐associated versus unbound cages. We present MR images with 103‐fold sensitivity enhancement for cell‐internalized, dual‐mode (fluorescence/MRI) xenon hosts at low micromolar concentrations. Our results illustrate the capability of functionalized xenon to act as a highly sensitive cell tracer for MRI detection even without signal averaging. The method will bridge the challenging gap for translation to in vivo studies for the optimization of targeted biosensors and their multiplexing applications. 相似文献
92.
Back Cover: Cell Tracking with Caged Xenon: Using Cryptophanes as MRI Reporters upon Cellular Internalization (Angew. Chem. Int. Ed. 2/2014) 下载免费PDF全文
93.
A Novel Bismuth‐Based Metal–Organic Framework for High Volumetric Methane and Carbon Dioxide Adsorption 下载免费PDF全文
Mathew Savage Dr. Sihai Yang Dr. Mikhail Suyetin Prof. Dr. Elena Bichoutskaia Dr. William Lewis Prof. Dr. Alexander J. Blake Sarah A. Barnett Prof. Dr. Martin Schröder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(26):8024-8029
Solvothermal reaction of H4L (L=biphenyl‐3,3′,5,5′‐tetracarboxylate) and Bi(NO3)3 ? (H2O)5 in a mixture of DMF/MeCN/H2O in the presence of piperazine and nitric acid at 100 °C for 10 h affords the solvated metal–organic polymer [Bi2(L)1.5(H2O)2] ? (DMF)3.5 ? (H2O)3 (NOTT‐220‐solv). A single crystal X‐ray structure determination confirms that it crystallises in space group P2/c and has a neutral and non‐interpenetrated structure comprising binuclear {Bi2} centres bridged by tetracarboxylate ligands. NOTT‐220‐solv shows a 3,6‐connected network having a framework topology with a {4 ? 62}2{42 ? 65 ? 88}{62 ? 8} point symbol. The desolvated material NOTT‐220a shows exceptionally high adsorption uptakes for CH4 and CO2 on a volumetric basis at moderate pressures and temperatures with a CO2 uptake of 553 g L?1 (20 bar, 293 K) with a saturation uptake of 688 g L?1 (1 bar, 195 K). The corresponding CH4 uptake was measured as 165 V(STP)/V (20 bar, 293 K) and 189 V(STP/V) (35 bar, 293 K) with a maximum CH4 uptake for NOTT‐220a recorded at 20 bar and 195 K to be 287 V(STP)/V, while H2 uptake of NOTT‐220a at 20 bar, 77 K is 42 g L?1. These gas uptakes have been modelled by grand canonical Monte Carlo (GCMC) and density functional theory (DFT) calculations, which confirm the experimental data and give insights into the nature of the binding sites of CH4 and CO2 in this porous hybrid material. 相似文献
94.
A Bioorthogonal Small‐Molecule‐Switch System for Controlling Protein Function in Live Cells 下载免费PDF全文
Dr. Peng Liu Abram Calderon Dr. Georgios Konstantinidis Dr. Jian Hou Dipl. Stephanie Voss Dr. Xi Chen Fu Li Soumya Banerjee Dr. Jan‐Erik Hoffmann Christiane Theiss Dr. Leif Dehmelt Dr. Yao‐Wen Wu 《Angewandte Chemie (International ed. in English)》2014,53(38):10049-10055
Chemically induced dimerization (CID) has proven to be a powerful tool for modulating protein interactions. However, the traditional dimerizer rapamycin has limitations in certain in vivo applications because of its slow reversibility and its affinity for endogenous proteins. Described herein is a bioorthogonal system for rapidly reversible CID. A novel dimerizer with synthetic ligand of FKBP′ (SLF′) linked to trimethoprim (TMP). The SLF′ moiety binds to the F36V mutant of FK506‐binding protein (FKBP) and the TMP moiety binds to E. coli dihydrofolate reductase (eDHFR). SLF′‐TMP‐induced heterodimerization of FKBP(F36V) and eDHFR with a dissociation constant of 0.12 μM . Addition of TMP alone was sufficient to rapidly disrupt this heterodimerization. Two examples are presented to demonstrate that this system is an invaluable tool, which can be widely used to rapidly and reversibly control protein function in vivo. 相似文献
95.
96.
Aleksandr Zaichenko Dr. Daniel Schröder Prof. Dr. Jürgen Janek Prof. Dr. Doreen Mollenhauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(11):2395-2404
Recent experimental investigations demonstrated the generation of singlet oxygen during charging at high potentials in lithium/oxygen batteries. To contribute to the understanding of the underlying chemical reactions a key step in the mechanism of the charging process, namely, the dissociation of the intermediate lithium superoxide to oxygen and lithium, was investigated. Therefore, the corresponding dissociation paths of the molecular model system lithium superoxide (LiO2) were studied by CASSCF/CASPT2 calculations. The obtained results indicate the presence of different dissociation paths over crossing points of different electronic states, which lead either to the energetically preferred generation of triplet oxygen or the energetically higher lying formation of singlet oxygen. The dissociation to the corresponding superoxide anion is energetically less preferred. The understanding of the detailed reaction mechanism allows the design of strategies to avoid the formation of singlet oxygen and thus to potentially minimize the degradation of materials in alkali metal/oxygen batteries. The calculations demonstrate a qualitatively similar but energetically shifted behavior for the homologous alkali metals sodium and potassium and their superoxide species. Fundamental differences were found for the covalently bound hydroperoxyl radical. 相似文献
97.
Nuclear emulsions processed in discriminating developers, intended to suppress small latent image sites, exhibit supralinear sensitometric blackness-exposure curves, whose character varies according to developing time, concentration, and composition, yielding hittedness ranging from 1 to 8, singly and in combination. These emulsion-processing combinations display the phenomena called ion-kill (sensitization by the transit of a single charged particle) and gamma- kill (sensitization by the overlap of secondary electron paths, whether from x-rays or from the delta-rays of heavy ions) in radiobiology. Here emulsions are blackened by x-rays when these same plates reveal no electron tracks, or no alpha-particle tracks, or even no fission fragment tracks. The supralinearity of the emulsion response to x-rays, and the consequent suppression of low LET radiations suggest that these materials have the potential to mimic the response of biological systems to particulate radiations of different charge and speed. 相似文献
98.
In the spirit of the Hamiltonian QR algorithm and other bidirectional chasing algorithms, a structure-preserving variant of
the implicit QR algorithm for palindromic eigenvalue problems is proposed. This new palindromic QR algorithm is strongly backward
stable and requires less operations than the standard QZ algorithm, but is restricted to matrix classes where a preliminary
reduction to structured Hessenberg form can be performed. By an extension of the implicit Q theorem, the palindromic QR algorithm
is shown to be equivalent to a previously developed explicit version. Also, the classical convergence theory for the QR algorithm
can be extended to prove local quadratic convergence. We briefly demonstrate how even eigenvalue problems can be addressed
by similar techniques.
D. S. Watkins partly supported by Deutsche Forschungsgemeinschaft through Matheon, the DFG Research Center Mathematics for key technologies in Berlin. 相似文献
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