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Oliver Andler Prof. Dr. Uli Kazmaier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):949-953
Application of ester dienolates as nucleophiles in Matteson homologations allows for the stereoselective synthesis of highly substituted α,β-unsaturated δ-hydroxy carboxyl acids, structural motifs widespread found in polyketide natural products. The protocol is rather flexible and permits the introduction of substituents and functionalities also at those positions which are not accessible by the commonly used aldol reaction. Therefore, this ester dienolate Matteson approach is an interesting alternative to the “classical” polyketide syntheses. 相似文献
145.
Using the nonrenormalization theorem and Pohlmeyer's theorem, it is proven that there cannot be an asymptotic safety scenario for the Wess–Zumino model unless there exists a non-trivial fixed point with (i) a negative anomalous dimension (ii) a relevant direction belonging to the Kähler potential. 相似文献
146.
Soft robots are bio-inspired, highly deformable robots with the ability to interact with workpieces in a manner that complements their hard robot counterparts. To develop practical applications and reproducible designs of soft robots, new models are necessary to describe their kinematics and dynamics. In the present work, we describe experimental and numerical investigations of a popular pneumatically-actuated soft continuum arm. These works enable us to derive constitutive relations and develop a rod model for large deformations of the arm that faithfully describes its bending behavior. We show how the resulting non-classical constitutive relation can be defined either through experiments or through quasi-static finite element simulations. With the help of this relation, the resulting rod model can be used to study the dynamics of the soft robot arm in a fast and tractable manner. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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Dr. William Herzog Dr. Catherine Bronner Susanne Löffler Dr. Bice He Daniel Kratzert Prof. Dietmar Stalke Prof. Andreas Hauser Prof. Oliver S. Wenger 《Chemphyschem》2013,14(6):1168-1176
Two pyridylphenols with intramolecular hydrogen bonds between the phenol and pyridine units have been synthesized, characterized crystallographically, and investigated by cyclic voltammetry and UV/Vis spectroscopy. Reductive quenching of the triplet metal‐to‐ligand charge‐transfer excited state of the [Re(CO)3(phen)(py)]+ complex (phen=1,10‐phenanthroline, py=pyridine) by the two pyridylphenols and two reference phenol molecules is investigated by steady‐state and time‐resolved luminescence spectroscopy, as well as by transient absorption spectroscopy. Stern–Volmer analysis of the luminescence quenching data provides rate constants for the bimolecular excited‐state quenching reactions. H/D kinetic isotope effects for the pyridylphenols are on the order of 2.0, and the bimolecular quenching reactions are up to 100 times faster with the pyridylphenols than with the reference phenols. This observation is attributed to the markedly less positive oxidation potentials of the pyridylphenols with respect to the reference phenols (≈0.5 V), which in turn is caused by proton coupling of the phenol oxidation process. Transient absorption spectroscopy provides unambiguous evidence for the photogeneration of phenoxyl radicals, that is, the overall photoreaction is clearly a proton‐coupled electron‐transfer process. 相似文献
149.
Oliver Wuerfel Markus Greule Frank Keppler Maik A. Jochmann Torsten C. Schmidt 《Analytical and bioanalytical chemistry》2013,405(9):2833-2841
In the environment, the methylation of metal(loid)s is a widespread phenomenon, which enhances both biomobility as well as mostly the toxicity of the precursory metal(loid)s. Different reaction mechanisms have been proposed for arsenic, but not really proven yet. Here, carbon isotope analysis can foster our understanding of these processes, as the extent of the isotopic fractionation allows to differentiate between different types of reaction, such as concerted (SN2) or stepwise nucleophilic substitution (SN1) as well as to determine the origin of the methyl group. However, for the determination of the kinetic isotope effect the initial isotopic value of the transferred methyl group has to be determined. To that end, we used hydroiodic acid for abstraction of the methyl group from methylcobalamin (CH3Cob) or S-adenosyl methionine (SAM) and subsequent analysis of the formed methyl iodide by gas chromatography (GC) isotope ratio mass spectrometry (IRMS). In addition, three further independent methods have been investigated to determine the position-specific δ 13C value of CH3Cob involving photolytic cleavage with different additives or thermolytic cleavage of the methyl-cobalt bonding and subsequent measurement of the formed methane by GC-IRMS. The thermolytic cleavage gave comparable results as the abstraction using HI. In contrast, photolysis led to an isotopic fractionation of about 7 to 9 ‰. Furthermore, we extended a recently developed method for the determination of carbon isotope ratios of organometal(loid)s in complex matrices using hydride generation for volatilization and matrix separation before heart-cut GC and IRMS to the analysis of the low boiling partly methylated arsenicals, which are formed in the course of arsenic methylation. Finally, we demonstrated the applicability of this methodology by investigation of carbon fractionation due to the methyl transfer from CH3Cob to arsenic induced by glutathione.
Position-specific isotope analysis of the methyl group in CH3Cob by abstraction using HI and subsequent analysis of formed CH3I by GC-IRMS 相似文献
150.
Andreas Thomas Matthias Vogel Thomas Piper Oliver Krug Simon Beuck Wilhelm Schänzer Mario Thevis 《Analytical and bioanalytical chemistry》2013,405(30):9703-9709
AICAR (5-amino-4-imidazolecarboxyamide ribonucleoside) arguably provides performance-enhancing properties even in the absence of physical exercise and, therefore, the substance is banned in elite sports since 2009. Due to the natural presence of AICAR in human blood and urine, uncovering the misuse by direct qualitative analysis is not possible. Entering the circulation, the riboside is immediately incorporated into red blood cells (RBCs) and transformed into the corresponding ribotide (5′-monophosphate) form. Within the present study, an analytical method was developed to determine AICAR-ribotide concentrations in RBC concentrates by means of liquid chromatography-tandem mass spectrometry. The method was validated enabling quantitative result interpretation considering the parameters specificity, precision (intra- and interday), linearity, recovery, accuracy (LOD/LOQ), stability and ion suppression. By analysing 99 RBC samples of young athletes, normal physiological levels of AICAR-ribotide were determined (10–500 ng/mL), and individual levels were found to be stable for several days. Employing in vitro incubation experiments with AICAR riboside in fresh whole blood samples, the ribotide concentrations were observed to increase significantly within 30 min from baseline to 1–10 μg/mL. These levels are considered conserved for the lifetime of the erythrocyte and, thus, the results of the in vitro model strongly support the hypothesis that measuring abnormally high AICAR-ribotide concentrations in RBC of elite athletes has the potential to uncover the misuse of this substance for a long period of time. 相似文献