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991.
Jane Y. Liew Joshua J. Brown Dr. Evan G. Moore Dr. Matthias Schwalbe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(45):16178-16186
An asymmetric ‘Pacman’ metalloligand, [Zn(PXT)], which features a cofacial ZnII–porphyrin unit (P) covalently attached to a terpyridine (T) chelating group via a rigid xanthene (X) moiety has been prepared, and its interactions with several different trivalent LnIII cations (NdIII, GdIII, YbIII and LuIII) have been examined. The formation of 1:1 metal–ligand complexes was monitored by 1H NMR spectroscopy and corroborated by HRMS data. Solution‐stability constants were determined by UV/Vis titration, and the resulting complexes with NdIII or YbIII demonstrated sensitised emission in the NIR region due to energy transfer from the ZnII–porphyrin donor to LnIII acceptor. The energy transfer was investigated by transient absorption techniques, which provided insight into the kinetics and efficiency of the antenna effect. 相似文献
992.
Stereochemical Definition of the Natural Product (6R,10R,13R, 14R,16R,17R,19S,20S,21R,24S,25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 by Total Synthesis and Comparative Analyses 下载免费PDF全文
Nathaniel T. Kenton Dr. Daniel Adu‐Ampratwum Dr. Antony A. Okumu Dr. Pearse McCarron Dr. Jane Kilcoyne Prof. Dr. Frode Rise Prof. Dr. Alistair L. Wilkins Dr. Christopher O. Miles Prof. Dr. Craig J. Forsyth 《Angewandte Chemie (International ed. in English)》2018,57(3):810-813
The previously accepted structure of the marine toxin azaspiracid‐3 is revised based upon an original convergent and stereoselective total synthesis of the natural product. The development of a structural revision hypothesis, its testing, and corroboration are reported. Synthetic (6R,10R,13R,14R,16R,17R,19S,20S,21R,24S,25S,28S,30S,32R, 33R,34R,36S,37S,39R)‐azaspiracid‐3 chromatographically and spectroscopically matched naturally occurring azaspiracid‐3, whereas the previously assigned 20R epimer did not. 相似文献
993.
Sediment has been considered to be one of the most important mercury methylation sites, but recent studies have demonstrated a new site that is relevant, i.e. the roots of floating aquatic macrophytes, where high methylation is observed. The effects of temperature, pH and electric conductivity on net mercury methylation were studied in the roots of the water‐hyacinth Eichhornia crassipes of a freshwater coastal lagoon (Lagoinha, RJ, Brazil). Root samples were incubated, over three days, with 203HgCl2 addition, at different temperatures (10–90 °C), pH values (3–8) and different electrolytic solutions (KClO4, KCl and CaCl2, at 1, 5, 10, 25 and 50 mM , ranging between 18 and 760 µS cm−1). 203Hg‐labeled methylmercury (Me203Hg) was extracted in toluene, after acid leaching, and measured by β‐counting. Up to 35% of mercury added was converted to MeHg Methylation increased from 10 to 35 °C, and decreased thereafter. The process was completely inhibited at 90 °C. At pH values of 6 and 7 methylation was stimulated and a significant decrease was verified at pH 8. Increasing KClO4 concentrations led to a significant decrease in the methylation rates, while for KCl and CaCl2 solutions only a slight decrease was observed. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
994.
While negative staining can provide detailed, two-dimensional images of biological structures, the potential of combining tomography with negative staining to provide three-dimensional views has yet to be fully realized. Basic requirements of a negative stain for tomography are that the density and atomic number of the stain are optimal, and that the stain does not degrade or rearrange with the intensive electron dose (~10? e/nm2) needed to collect a full set of tomographic images. A commercially available, tungsten-based stain appears to satisfy these prerequisites. Comparison of the surface structure of negatively stained influenza A virus with previous structural results served to evaluate this negative stain. The combination of many projections of the same structure yielded detailed images of single proteins on the viral surface. Corresponding surface renderings are a good fit to images of the viral surface derived from cryomicroscopy as well as to the shapes of crystallized surface proteins. Negative stain tomography with the appropriate stain yields detailed images of individual molecules in their normal setting on the surface of the influenza A virus. 相似文献
995.
Ajay Kumar Bunha Joey Mangadlao Mary Jane Felipe Katrina Pangilinan Rigoberto Advincula 《Macromolecular rapid communications》2012,33(14):1214-1219
A novel route to synthesize catenated macrocyclic PS–PMMA block copolymers is demonstrated via combination of supramolecular chemistry and controlled radical polymerization (CRP). Polymerization of styrene with bromopropionate ester initiator coupled with phenanthroline Cu(I) complex affords a four arm PS macroinitiator, which upon further chain extension by polymerization of MMA generates a four arm PS–PMMA block copolymer. Intramolecular coupling of PS–PMMA–Br arms via low temperature styrene‐assisted atom transfer radical coupling (ATRC) leads to the formation of PS–PMMA catenand, which generates the metal‐free catenated macrocyclic PS–PMMA block copolymer after removal of Cu metal. The interlocked structures of catenated block copolymers are confirmed by GPC, NMR, and AFM image analysis. 相似文献
996.
Janna Nibbs Sergei A. Vinogradov Jane M. Vanderkool Bogumil Zelent 《Photochemistry and photobiology》2004,80(1):36-40
The heme in horseradish peroxidase (HRP) was replaced by phosphorescent Pt‐mesoporphyrin IX (PtMP), which acted as a phosphorescent marker of oxygen quenching and allowed comparison with another probe, Pd‐mesoporphyrin IX (Khajehpour et al. (2003) Proteins 53, 656–666). Benzohydroxamic acid (BHA), a competitive inhibitor of the enzyme, was also used to monitor its effects on phosphorescence quenching. With the addition of BHA, in the presence of oxygen, the phosphorescence intensity of the protein increased. In contrast, the addition of BHA, in the absence of oxygen, reduced the phosphorescence intensity of the protein. Kd= 18 μM when BHA binds to PtMP‐HRP. The effect of BHA can be explained by two factors: ( 1 ) BHA reduces the accessibility of O2 to the protein interior and ( 2 ) BHA itself quenches the phosphorescence. Consistent with this, the oxygen quenching of the phosphorescence of PtMP‐HRP gave a quenching constant of kq= 234 mm Hg?1 s?1 in the absence of BHA and kq= 28.7 mm Hg?1 s?1 in the presence of BHA. The quenching rate of BHA is 4000 s?1. The relative quantum yield of the phosphorescence of the Pt derivative is about six times that of the Pd derivative, whereas the phosphorescence lifetime is approximately eight times shorter. The high quantum yield and suitable lifetime make Pt‐porphyrins appropriate as sensors of O2 diffusion and flexibility in heme proteins. 相似文献
997.
Remi A. Momo Jane F. Povey C. Mark Smales Christopher J. O’Malley Gary A. Montague Elaine B. Martin 《Analytical and bioanalytical chemistry》2013,405(25):8251-8265
Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF MS) has been exploited extensively in the field of microbiology for the characterisation of bacterial species, the detection of biomarkers for early disease diagnosis and bacterial identification. Here, the multivariate data analysis technique of partial least squares-discriminant analysis (PLS-DA) was applied to ‘intact cell’ MALDI-ToF MS data obtained from Escherichia coli cell samples to determine if such an approach could be used to distinguish between, and characterise, different growth phases. PLS-DA is a technique that has the potential to extract systematic variation from large and noisy data sets by identifying a lower-dimensional subspace that contains latent information. The application of PLS-DA to the MALDI-ToF data obtained from cells at different stages of growth resulted in the successful classification of the samples according to the growth phase of the bacteria cultures. A further outcome of the analysis was that it was possible to identify the mass-to-charge (m/z) ratio peaks or ion signals that contributed to the classification of the samples. The Swiss-Prot/TrEMBL database and primary literature were then used to provisionally assign a small number of these m/z ion signals to proteins, and these tentative assignments revealed that the major contributors from the exponential phase were ribosomal proteins. Additional assignments were possible for the stationary phase and the decline phase cultures where the proteins identified were consistent with previously observed biological interpretation. In summary, the results show that MALDI-ToF MS, PLS-DA and a protein database search can be used in combination to discriminate between ‘intact cell’ E. coli cell samples in different growth phases and thus could potentially be used as a tool in process development in the bioprocessing industry to enhance cell growth and cell engineering strategies. 相似文献
998.
Guan Z Roland JT Bai JZ Ma SX McIntire TM Nguyen M 《Journal of the American Chemical Society》2004,126(7):2058-2065
A long lasting challenge in polymer science is to design polymers that combine desired mechanical properties such as tensile strength, fracture toughness, and elasticity into one structure. A novel biomimetic modular polymer design is reported here to address this challenge. Following the molecular mechanism used in nature, modular polymers containing multiple loops were constructed by using precise and strong hydrogen bonding units. Single-molecule force-extension experiments revealed the sequential unfolding of loops as a chain is stretched. The excellent correlation between the single-molecule and the bulk properties successfully demonstrates our biomimetic concept of using modular domain structure to achieve advanced polymer properties. 相似文献
999.
Mahandru GM Skauge AR Chowdhury SK Amarasinghe KK Heeg MJ Montgomery J 《Journal of the American Chemical Society》2003,125(44):13481-13485
A new strategy for effecting cascade cyclization processes using nickel enolates has been developed. Nickel enolates may be cleanly generated by the oxidative cyclization of an enal and alkyne with Ni(0), and the resulting enolate may be functionalized by a variety of alkylation processes. Partially and fully intramolecular versions of the process allow the rapid synthesis of complex polycyclics from simple achiral, acyclic precursors. 相似文献
1000.
Hailin Wang Meiling Lu Nan Mei Jane Lee Michael Weinfeld X. Chris Le 《Analytica chimica acta》2003,500(1-2):13-20
Human DNA is exposed to a variety of endogenous and environmental agents that may induce a wide range of damage. The critical role of DNA damage in cancer development makes it essential to develop highly sensitive and specific assays for DNA lesions. We describe here ultrasensitive assays for DNA damage, which incorporate immuno-affinity with capillary electrophoresis (CE) separation and laser induced fluorescence (LIF) detection. Both competitive and non-competitive assays using CE/LIF were developed for the determination of DNA adducts of benzo[a]pyrene diol epoxide (BPDE). A fluorescently labeled oligonucleotide containing a single BPDE adduct was synthesized and used as a fluorescent probe for competitive assay. Binding between this synthetic oligonucleotide and a monoclonal antibody (MAb) showed both 1:1 and 1:2 complexes between the MAb and the oligonucleotide. The 1:1 and 1:2 complexes were separated by CE and detected with LIF, revealing binding stoichiometry information consistent with the bidentate nature of the immunoglobulin G antibody. For non-competitive assay, a fluorescently labeled secondary antibody fragment F(ab′)2 was used as an affinity probe to recognize a primary antibody that was specific for the BPDE-DNA adducts. The ternary complex of BPDE-DNA adducts with the bound antibodies was separated from the unbound antibodies using CE and detected with LIF for quantitation of the DNA adducts. The assay was used for the determination of trace levels of BPDE-DNA adducts in human cells. Analysis of cellular DNA from A549 human lung carcinoma cells that were incubated with low doses of BPDE (32 nM–1 μM) showed a clear dose–response relationship. BPDE is a potent environmental carcinogen, and the ultrasensitive assays for BPDE-DNA adducts are potentially useful for monitoring human exposure to this carcinogen and for studying cellular repair of DNA damage. 相似文献