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133.
Adamczyk K Candelaresi M Kania R Robb K Bellota-Antón C Greetham GM Pollard MR Towrie M Parker AW Hoskisson PA Tucker NP Hunt NT 《Physical chemistry chemical physics : PCCP》2012,14(20):7411-7419
The ultrafast equilibrium fluctuations of the Fe(III)-NO complex of a single point mutation of Myoglobin (H64Q) have been studied using Fourier Transform 2D-IR spectroscopy. Comparison with data from wild type Myoglobin (wt-Mb) shows the presence of two conformational substates of the mutant haem pocket where only one exists in the wild type form. One of the substates of the mutant exhibits an almost identical NO stretching frequency and spectral diffusion dynamics to wt-Mb while the other is distinctly different in both respects. The remarkably contrasting dynamics are largely attributable to interactions between the NO ligand and a nearby distal side chain which provides a basis for understanding the roles of these side chains in other ferric haem proteins. 相似文献
134.
Thomas Heinze Taha Genco Katrin Petzold-Welcke Holger Wondraczek 《Cellulose (London, England)》2012,19(4):1305-1313
Amino cellulose sulfate (ACS); namely 6-deoxy-6-(ω-aminoethyl) amino cellulose-2,3(6)-O-sulfate (AECS) and 6-deoxy-6-(2-(bis-N′,N′-(2-aminoethyl)aminoethyl)) amino cellulose-2,3(6)-O-sulfate (BAECS) were prepared by a three step synthesis starting with the functionalization of microcrystalline cellulose with p-toluenesulfonyl (tosyl) groups (degree of substitution, DSTos between 0.55 and 1.37). Subsequently the introduction of the sulfate moieties was carried out (DSSulf between 1.09 and 1.27) and the tosyl groups at position 6 were replaced by a nucleophilic substitution reaction. As nucleophilic agents 1,2-diaminoethane and tris-(2-aminoethyl)amine were applied, yielding AECS (DSAEA values between 0.41 and 0.86) and BAECS (DSBAEA values between 0.32 and 0.74), respectively. The ACS samples were characterized by means of elemental analysis, 13C-NMR-, FT-IR-, and UV–Vis spectroscopy. Moreover, the solubility of the samples in water at different pH values and the molecular weights of the samples in aqueous solution were studied. 相似文献
135.
Christian Mitterdorfer Jürgen Bernard Frederik Klauser Katrin Winkel Ingrid Kohl Klaus R. Liedl Hinrich Grothe Erwin Mayer Thomas Loerting 《Journal of Raman spectroscopy : JRS》2012,43(1):108-115
Two different polymorphs of carbonic acid, α‐ and β‐H2CO3, were identified and characterized using infrared spectroscopy (FT‐IR) previously. Our attempts to determine the crystal structures of these two polymorphs using powder and thin‐film X‐ray diffraction techniques have failed so far. Here, we report the Raman spectrum of the α‐polymorph, compare it with its FT‐IR spectrum and present band assignments in line with our work on the β‐polymorph [Angew. Chem. Int. Ed. 48 (2009) 2690–2694]. The Raman spectra also contain information in the wavenumber range ∼90–400 cm−1, which was not accessible by FT‐IR spectroscopy in the previous work. While the α‐polymorph shows Raman and IR bands at similar positions over the whole accessible range, the rule of mutual exclusion is obeyed for the β‐polymorph. This suggests that there is a center of inversion in the basic building block of β‐H2CO3 whereas there is none in α‐H2CO3. Thus, as the basic motif in the crystal structure we suggest the cyclic carbonic acid dimer containing a center of inversion in case of β‐H2CO3 and a catemer chain or a sheet‐like structure based on carbonic acid dimers not containing a center of inversion in case of α‐H2CO3. This hypothesis is strengthened when comparing Raman active lattice modes at < 400 cm−1 with the calculated Raman spectra for different dimers. In particular, the intense band at 192 cm−1 in β‐H2CO3 can be explained by the inter‐dimer stretching mode of the centrosymmetric RC(OHO)2 CR entity with ROH. The same entity can be found in gas‐phase formic acid (RH) and in β‐oxalic acid (RCOOH) and produces an intense Raman active band at a very similar wavenumber. The absence of this band in α‐H2CO3 confirms that the difference to β‐H2CO3 is found in the local coordination environment and/or monomer conformation rather than on the long range. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
136.
Christian Fiebig J?rg Fricke Mirko Uebernickel Daniel Jedrzejczyk Alexander Sahm Katrin Paschke 《Optical Review》2012,19(6):405-408
Large-area high-resolution displays, using a flying-spot to create the picture, require light sources in the red, green and blue wavelength range with a high optical output power and nearly diffraction limited beam. In this paper we present experimental results of high-brightness distributed Bragg reflector tapered diode lasers at 106x nm that can be used for single-pass second harmonic generation into the green. Based on these lasers we developed compact (2.5 cm3) green laser modules with an output power of 1W at 53x nm and an electro-optical conversion efficiency of about 5%. The output power stability is better than 2% and the wavelength stability is ±10 pm. The excellent beam quality M ?? 2 < 2 of the green light allows operation in flying spot application systems. Furthermore, we estimate that our concept allows power scaling up to 2W by using nonlinear planar waveguide crystals and into the multi-watt level by spectral beam combining. 相似文献
137.
Using density functional theory (DFT) calculations with an on-site Coulomb repulsion term, we study the composition, stability, and electronic properties of the most common FeOOH surfaces goethite(101), akaganeite(100), and lepidocrocite(010), and their interaction with water. Despite the differences in surface structure, the trends in surface stability of these FeOOH polymorphs exhibit remarkable similarities. We find that the reactivity and the binding configuration of adsorbates depend strongly on the coordination of surface iron: at the fourfold coordinated Fe2 site water is chemisorbed, whereas at the fivefold coordinated Fe1 water is only loosely bound with hydrogen pointing towards the surface. Our results show that the oxidation state of surface iron can be controlled by the surface termination where ferryl (Fe4 +) species emerge for oxygen terminated surfaces and ferrous iron (Fe2 +) at iron and water terminations leading to a reduced band gap. In contrast, the fully hydroxylated surfaces, identified as stable surface configurations at standard conditions from the surface phase diagram, show electronic properties and band gaps closest to bulk FeOOH with ferric surface iron (Fe3 +). Only in the case of goethite(101), a termination with mixed surface hydroxyl and aquo groups is stabilized. 相似文献
138.
We present in this Letter experimental results of a Yb:Sc(2)SiO(5) (Yb:SSO) thin-disk laser. To our knowledge, this is the first lasing demonstration of this crystal in thin-disk configuration reported on to date. Preliminary tests regarding the characterization and the laser operation are presented. Two different resonator configurations, a simple linear multimode cavity, and a fundamental-mode folded resonator providing a double pass in the laser crystal were set up. The gain and the small signal gain of the available Yb:SSO sample were calculated using the experimental results of the multimode resonator. The operation in a fundamental-mode resonator with the double pass in the laser crystal led to 9.4 W of output power with an optical efficiency of 25.4%. 相似文献
139.
Dr. Shamil Nizamov Dr. Katrin I. Willig Dipl.‐Chem. Maksim V. Sednev Dr. Vladimir N. Belov Prof. Stefan W. Hell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16339-16348
Photostable and bright fluorescent dyes with large Stokes shifts are widely used as markers in far‐field optical microscopy, but the variety of useful dyes is limited. The present study introduces new 3‐heteroaryl coumarins decorated with a primary phosphate group (OP(O)(OH)2) attached to C‐4 in 2,2,4‐trimethyl‐1,2‐dihydroquinoline fragment fused with the coumarin fluorophore. The general synthetic route is based on the Suzuki reaction of 3‐bromocoumarines with hetarylboronic acids followed by oxidation of the methyl group at the C?C bond with SeO2 (to an aldehyde), reduction with NaBH4 (to an alcohol), and conversion into a primary phosphate. The 4 position in the coumarin system may be unsubstituted or bear a methyl group. Phosphorylated coumarins were found to have high fluorescence quantum yields in the free state and after conjugation with proteins (in aqueous buffers). In super‐resolution light microscopy with stimulated emission depletion (STED), the new coumarin dyes provide an optical resolution of 40–60 nm with a low background signal. Due to their large Stokes shifts and high photostability, phosphorylated coumarins enable to combine multilabel imaging (using one detector and several excitation sources) with diffraction unlimited optical resolution. 相似文献
140.
Dr. Ann‐Katrin Jungton Dr. Christian Herwig Prof. Dr. Thomas Braun Prof. Dr. Christian Limberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(32):10009-10013
1H NMR exchange spectroscopy of a reaction mixture of [Cp*Ir(H)4] ( 1 ; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) and ammonia suggests an exchange of hydrogen atoms between the hydrido ligands and ammonia. Treatment of 1 with ND3 led to an H/D exchange between ND3 and the hydrido ligands of 1 . Subsequent studies showed that photolysis of 1 isolated in frozen argon matrices leads to the formation of the iridium compounds [Cp*Ir(H)2] ( 2 ) and [Cp*Ir(H)3] ( 4 ), as it was confirmed by IR spectroscopy. In the presence of water the aqua complex [Cp*Ir(H)2(OH2)] ( 3 ) was generated simultaneously. Accordingly, photolysis of 1 in an argon matrix doped with ammonia gave rise to the ammine complex [Cp*Ir(H)2(NH3)] ( 5 ). IR assignments were supported by calculations of the gas‐phase IR spectra of 1 – 5 by DFT methods. 相似文献