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41.
Robinson R Karikachery AR Sharp PR 《Dalton transactions (Cambridge, England : 2003)》2012,41(9):2601-2611
The six-membered platinacycle complex, Pt((t)Bu(2)bpy)(C(6)H(4)OC(6)H(4)) (6) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) has been prepared from Pt((t)Bu(2)bpy)Cl(2) and 2,2'-dilithio-diphenyl ether. Platinacycle 6 and its analogs with X = CH(2) (4) and NMe (5) exhibit intense solid-state photoluminescence and nearly identical crystal structures. The photophysical properties of 4-6 in the visible range are dominated by mixed metal-ligand-to-ligand charge transfer (MLL'CT) transitions involving high-lying filled mixed metal-ligand orbitals (ML), composed primarily of platinacyclic ring-based d- and π-orbitals, and a low lying vacant π* orbital (L') of the (t)Bu(2)bpy ligand. Lone pair donation from the bridging oxygen atom and especially the NMe group increases the energy of the mixed metal-ligand orbital (ML) without altering the energy of the (t)Bu(2)bpy π* orbital. As a result, the MLL'CT state energy decreases and the absorption and emission wavelengths are red-shifted. DFT and TD-DFT calculations support the experimental results. Additional calculations on the unknown platinacycles with X = CO (7) and SO(2) (8) predict a blue-shift for the MLL'CT absorption and emission. Two nearly equal energy triplet minima were located on the DFT triplet surface for 4-6. One of these (4T-6T) has a geometry very similar to the ground-state singlet (as represented by 4-6) and is associated with the emissive (3)MLL'CT excited state. The other triplet-state (4T'-6T') has a distorted structure where the platinacycle ring is twisted out of the Pt((t)Bu(2)bpy) plane. Thermal access to this distorted triplet may be responsible for the loss of photoluminescence in room temperature solutions of 4-6. 相似文献
42.
Dr. Alice C. Harnden Dr. Andrei S. Batsanov Prof. Dr. David Parker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(24):6212-6225
A zinc-selective probe based on a set of rare earth complexes of a modified DO3A macrocyclic ligand incorporating a tris-pyridylamine (TPA) moiety has been structurally characterised in solution and in the solid-state. One pyridine group possesses a tert-butyl substituent to serve as an NMR reporter group. The mono-capped square-antiprismatic Dy complex has a long bond (2.83 Å) to an apical N atom (pKa 5.70 Eu) and binds to one water molecule on zinc binding. Zinc binding is reversible and involves all of the exocyclic ligand N donors; it is signalled by large (ratiometric) changes in Eu emission intensity, and by dramatic changes in the size (>50 ppm) and sign of the chemical shift of the paramagnetically shifted tBu resonances in Tb, Dy and Tm complexes. Slow trans-metallation was observed, leading to formation of an unusual di-zinc species in which one zinc ion is seven-coordinate and the other is six-coordinate. 相似文献
43.
Cover Picture: Densely Packed Hydrophobic Clustering: Encapsulated Valerates Form a High‐Temperature‐Stable {Mo132} Capsule System (Angew. Chem. Int. Ed. 23/2016) 下载免费PDF全文
44.
Carla Alice Carabet Anca Moan Ion Plrie Gabriela Iacobescu Andrei Rotaru Marian Leulescu Mariana Popescu Petre Rotaru 《Molecules (Basel, Switzerland)》2020,25(23)
Two yellow bis-azo dyes containing anthracene and two azodiphenylether groups (BPA and BTA) were prepared, and an extensive investigation of their physical, thermal and biological properties was carried out. The chemical structure was confirmed by the FTIR spectra, while from the UV–Vis spectra, the quantum efficiency of the laser fluorescence at the 476.5 nm was determined to be 0.33 (BPA) and 0.50 (BTA). The possible transitions between the energy levels of the electrons of the chemical elements were established, identifying the energies and the electronic configurations of the levels of transition. Both crystals are anisotropic, the optical phenomenon of double refraction of polarized light (birefringence) taking place. Images of maximum illumination and extinction were recorded when the crystals of the bis-azo compounds rotated by 90° each, which confirms their birefringence. A morphologic study of the thin films deposited onto glass surfaces was performed, proving the good adhesion of both dyes. By thermal analysis and calorimetry, the melting temperatures were determined (~224–225 °C for both of them), as well as their decomposition pathways and thermal effects (enthalpy variations during undergoing processes); thus, good thermal stability was exhibited. The interaction of the two compounds with collagen in the suede was studied, as well as their antioxidant activity, advocating for good chemical stability and potential to be safely used as coloring agents in the food industry. 相似文献
45.
Alice Merca Jürgen Schnack Joris van Slageren Thorsten Glaser Hartmut Bögge Veronika Hoeke Mechtild Läge Achim Müller Bernt Krebs 《Journal of Cluster Science》2013,24(4):979-988
The gadolinium (Gd) member of a new type of heteropolytungstates that contain one lanthanide and two transition metal ions in a triangular arrangement is reported. The compound NaK6Gd0.33 [((VO)2Gd(H2O)4K2(H2O)2(Na)(H2O)2)(α-B-AsW9O33)2]·24H2O (1) was prepared from acidified aqueous solutions of Na2WO4·2H2O, As2O3 and VOSO4·5H2O to which Gd3+ ions were added. The single crystal X-ray structure analysis (monoclinic, space group P21/m) shows that the anion consists of two [α-B-AsIIIW9O33]9? trilacunary Keggin-type units linked by two VO2+, one Gd3+ as well as weakly by two K+ and one Na+ ions, resulting in a sandwich-type structure with idealized C 2v symmetry. The problem of positioning crystal lattice and special polyoxometalate sites with different cations is discussed also in connection with supramolecular chemistry aspects and as an option for further research. A fit of the magnetic susceptibility yielded exchange coupling constants of J VV = ?2.55 cm?1 (anti-ferromagnetic) between the vanadium ions and J GdV = 0.6 cm?1 (ferromagnetic) between the Gd and each of the two vanadium ions. The complete magnetochemical analysis also revealed a partial occupancy of the Na+ sites in the counter-cation–water system by Gd3+ ions (0.33 Gd3+ ions in total). 相似文献
46.
A new linker cis-5-aminopent-3-enoic acid (cis-Apa) was prepared for the synthesis of cyclic pseudopeptides by cyclization-cleavage by using ring-closing methatesis (RCM). We developed a new synthetic pathway for the preparation of the cis-Apa linker that was tested in the cyclization-cleavage process of different RGD peptide sequences. Different macrocyclic peptidomimetics were prepared by using this integrated microwave-assisted method, showing that the readily available cis-Apa amino acid is well adapted as a linker in the cyclization-cleavage process. 相似文献
47.
A capillary electrophoresis method with UV detection was developed for the determination of 8-hydroxy-2'-deoxyguanosine (8-OHdG) in untreated urine samples. The calibration graph for 8-OHdG in urine is linear in the concentration range 10-500 mg/l. and the detection limit is 5 mg/l (17 microM). 8-OHdG was determined in urine from oncological patients treated by radiation therapy. Its concentrations relative to creatinine were found to be in the range 10-47 microg 8-OHdG/l mg creatinine (4-19 micromol 8-OHdG/mmol creatinine). The overall time of the analysis of a urine sample was less than 15 min. 相似文献
48.
Ali Mohammad Akbar Edwards Alice A. Tuah Jauyah Hossain Mir Ezharul Nazimuddin Mohamed 《Transition Metal Chemistry》1997,23(1):41-44
A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has
been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−,
NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via
the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure
for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes
of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each
of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical
techniques.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
49.
A liquid chromatography–electrospray-tandem mass spectrometry (ES-MS/MS) method was developed for the speciation analysis of four organic selenium species of relevance to human urinary metabolism, namely trimethylselenomium ion (TMSe+), selenomethionine (SeMet) and the two selenosugars, methyl 2-acetamido-2-deoxy-1-seleno-β-d-galactos/-glucos-amine (SeGalNAc and SeGluNAc, respectively). Their chromatographic separation was achieved by using a cation exchange pre-column coupled in-series with a reversed-phase high-performance liquid chromatography column, along with an isocratic mobile phase. Online detection was performed using ES-MS/MS in selective reaction monitoring mode. SeGalNAc was detected as the major human urinary metabolite of selenium in the samples analysed, whereas TMSe+ was detected in the urine of one volunteer before and after receiving a selenium supplement. SeMet was not detected as a urine excretory metabolite in this study. Spiking experiments performed with the urine samples revealed significant signal suppression caused by coeluting matrix constituents. To overcome such interferences, isotopically labelled 13CD382SeGalNAc was used as an internal standard, whereas in the absence of an isotopically labelled internal standard for TMSe+, the standard addition method was applied. Quality control for the accurate quantitation of TMSe+ and SeGalNAc was carried out by analysing spiked human urine samples with appropriate selenium standards over a concentration range of 10–50 μg Se L−1. The method has achieved a limit of detection in the presence of urine matrix comparable to that of HPLC-inductively coupled plasma-mass spectrometry for the four selenium species: 1.0 μg Se L−1 for TMSe+, 5.6 μg Se L−1 for SeMet, and 0.1 μg Se L−1 for both SeGalNAc and SeGluNAc. 相似文献
50.
Bartlett PA Yusuff N Rico AC Lindvall MK 《Journal of the American Chemical Society》2002,124(15):3853-3857
The hydrophobic component to the binding affinities of one acyclic phosphinate (4) and three macrocyclic phosphonamidate inhibitors (1-3) to the zinc peptidase thermolysin was probed by varying the solvent composition. Increasing the percentage of ethanol in the buffer solution over the range 0-9% increases the inhibition constants, K(i), by up to an order of magnitude. This approach represents an experimental method for distinguishing solvation from conformational or other effects on protein-ligand binding. The size of the "antihydrophobic effect" is correlated with the amount of hydrophobic surface area sequestered from solvent on association of the inhibitor and enzyme, although it is attenuated from that calculated from the surface tension of ethanol-water mixtures. The results are consistent with the Lum-Chandler-Weeks explanation for the size dependence of the hydrophobic effect. 相似文献