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121.
Schmidt H Böttcher C Trampczynska A Clemens S 《Analytical and bioanalytical chemistry》2011,399(3):1355-1361
Nicotianamine (NA) is an important metal chelator, implicated in the intra- and intercellular trafficking of several transition
metal ions in plants. To decipher its roles in physiological processes such as micronutrient acquisition, distribution or
storage, fast and sensitive analytical techniques for quantification of this non-proteinogenic amino acid will be required.
The use of a recombinant Schizosaccharomyces pombe strain expressing a nicotianamine synthase (NAS) gene allowed for the production of [15N3]-NA, which was enriched from cell extracts through cation exchange and used for stable isotope dilution analysis of NA. Such
an approach should be widely applicable to important bioanalytes that are difficult to synthesize. The analytical procedure
comprises mild aqueous extraction and rapid Fmoc derivatization, followed by fast separation using ultra-performance liquid
chromatography (UPLC) and sensitive detection by positive ion electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS)
with a chromatographic cycle time of only 8 min. Derivatization was optimized with respect to incubation time and species
suitable for quantification. The limit of detection was 0.14 to 0.23 pmol in biological matrices with the response being linear
up to 42 pmol. Recovery rates were between 83% and 104% in various biological matrices including fission yeast cells, fungal
mycelium, plant leaves and roots. 相似文献
122.
In this article, we give a new rigorous condition number estimate of the finite element tearing and interconnecting (FETI)
method and a variant thereof, all-floating FETI. We consider a scalar elliptic equation in a two- or three-dimensional domain
with a highly heterogeneous (multiscale) diffusion coefficient. This coefficient is allowed to have large jumps not only across but also along subdomain interfaces and in the interior of the subdomains. In other words, the subdomain partitioning does not need to resolve
any jumps in the coefficient. Under suitable assumptions, we derive bounds for the condition numbers of one-level and all-floating
FETI that are robust with respect to strong variations in the contrast in the coefficient, and that are explicit in some geometric
parameters associated with the coefficient variation. In particular, robustness holds for face, edge, and vertex islands in
high-contrast media. As a central tool we prove and use new weighted Poincaré and discrete Sobolev type inequalities that
are explicit in the weight. Our theoretical findings are confirmed in a series of numerical experiments. 相似文献
123.
Reggie L Lopez JJ Collinson I Glaubitz C Lorch M 《Journal of the American Chemical Society》2011,133(47):19084-19086
Dynamic nuclear polarization (DNP) has made it possible to record 2D double-quantum-filtered (DQF) solid-state NMR (ssNMR) spectra of a signal peptide bound to a lipid-reconstituted SecYEG translocon complex. The small quantity of peptide in the sample (~40 nmol) normally prohibits multidimensional ssNMR experiments. Such small amounts are not the exception, because for samples involving membrane proteins, most of the limited sample space is occupied by lipids. As a consequence, a conventional 2D DQF ssNMR spectrum with the sample used here would require many weeks if not months of measurement time. With the help of DNP, however, we were able to acquire such a 2D spectrum within 20 h. This development opens up new possibilities for membrane protein studies, particularly in the exploitation of high-resolution spectroscopy and the assignment of individual amino acid signals, in this case for a signal peptide bound to the translocon complex. 相似文献
124.
Bhowmick R Rajasekaran S Friebel D Beasley C Jiao L Ogasawara H Dai H Clemens B Nilsson A 《Journal of the American Chemical Society》2011,133(14):5580-5586
Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. 相似文献
125.
Bailey AS Hughes RW Hubberstey P Ritter C Smith RI Gregory DH 《Inorganic chemistry》2011,50(19):9545-9553
New ternary and quaternary nitride halides, Ba(2)N(X,X') (X = F, Cl, Br; X' = Br, I), have been synthesized from the high temperature reactions of barium subnitride with the respective barium halides under an inert atmosphere. The former include the first fully characterized barium nitride halides for X other than F, and the latter are the first examples of barium nitride mixed halides. The variation in structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques. The heavier ternary and quaternary nitride halides (X, X' = Cl, Br, I) crystallize in the hexagonal space group R3m, with the anti-α-NaFeO(2) structure. Ba(2)NF forms with both an anti-α-NaFeO(2) structure, in which N(3-) and F(-) are ordered and an anion-disordered simple rock salt structure. The hexagonal polymorph of Ba(2)NF is the only example to date of a nitride fluoride adopting this layered structure. Both the ternary and the quaternary compounds display very weak, temperature independent paramagnetism. 相似文献
126.
This paper presents results from seven experimental facilities on the co-current flow of air and water in downward sloping pipes. As a function of the air flow rate, pipe diameter and pipe slope, the required water discharge to prevent air accumulation was determined. In case the water discharge was less than the required water discharge, the air accumulation and additional gas pocket head loss were measured. Results show that volumetric air discharge as small as 0.1% of the water discharge accumulate in a downward sloping section. The experimental data cover all four flow regimes of water-driven air transport: stratified, blow-back, plug and dispersed bubble flow. The analysis of the experimental results shows that different dimensionless numbers characterise certain flow regimes. The pipe Froude number determines the transition from blow-back to plug flow. The gas pocket head loss in the blow-back flow regime follows a pipe Weber number scaling. A numerical model for the prediction of the air discharge as a function of the relevant system parameters is proposed. The novelty of this paper is the presentation of experimental data and a numerical model that cover all flow regimes on air transport by flowing water in downward inclined pipes. 相似文献
127.
D. Clemens K. Bongartz W. Speier R. J. Hussey W. J. Quadakkers 《Fresenius' Journal of Analytical Chemistry》1993,346(1-3):318-322
Summary The oxidation behaviour of a number of FeCrAl-based oxide dispersion strengthened (ODS) alloys of the type MA 956 was investigated at temperatures between 1100°C and 1200°C. The main emphasis was placed on the effect of alloy yttria content on scale composition and structure. Studies of three model alloys with various alloy yttria contents in the range 0.02–0.7% showed an increase in the oxide growth rate with increasing yttria content. Alumina scales on alloys with 0.17% and 0.7% yttria grow almost exclusively by oxygen diffusion, whereas the scale on the alloy with 0.02% yttria exhibits a significant contribution from cation diffusion. By using SIMS depth-profiling and SIMS-imaging it was found that the oxygen diffuses through the alumina scale via oxide grain boundaries. TEM-studies revealed that the yttria is incorporated in the scale grain boundaries as precipitations and as a segregation layer. This behaviour of the yttrium is believed to be responsible for its influence on scale growth mechanisms. A mathematical model has been developed which describes the alumina scale growth by oxygen diffusion through grain boundaries. The model accounts for the observed increase in aluminium oxide grain size in scale growth direction. 相似文献
128.
Aurélien A L Nicolet Clemens Hofmann Mikhail A Kol'chenko Boleslaw Kozankiewicz Michel Orrit 《Chemphyschem》2007,8(8):1215-1220
We study single dibenzoterrylene molecules in an anthracene single crystal at 1.4 K in two insertion sites at 785.1 and 794.3 nm. The single-molecule zero-phonon lines are narrow (about 30 MHz), intense (the detected fluorescence rates at saturation reach 100,000 counts s(-1)), and very photostable. The intersystem-crossing yield is extremely low (10(-7) or lower). All of these features are hallmarks of an excellent system for high-resolution spectroscopy and nanoscale probing at cryogenic temperatures. 相似文献
129.
Many families of parametrized Thue equations over number fields have been solved recently. In this paper we consider for the
first time a family of Thue equations over a polynomial ring. In particular, we calculate all solutions of
X(X-Y)(X-(T+x)Y)+Y3=1+xT(1-T)X(X-Y)(X-(T+\xi)Y)+Y^3=1+\xi T(1-T)
over
\Bbb C[T]{\Bbb C}[T]
for all
x ? \Bbb C\xi\in{\Bbb C}
. 相似文献
130.
The crystal structures of [pipH]2[WS4] ( 1 ) and the new compounds [pipH]3[WS4](HS) ( 2 ) and [pipH]4[WS4][WOS3] ( 3 ) (pip = piperidine) were determined. Hydrogen bonds between the piperidinium cations and the thiotungstate anions play a dominant structural role. Their strength and number correlates with the degree of distortion found for the tetrahedral anions. Unshared hydrogen bonds have a considerably stronger effect than bifurcated ones; the effect of trifurcated hydrogen bonds is extremely weak. HS? and [WOS3]2? are considerably stronger H bond acceptors than the [WS4]2? anion. 相似文献