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51.
J. B. Westmore Denis C. K. Lin K. K. Ogilvie H. Wayborn J. Berestiansky 《Journal of mass spectrometry : JMS》1972,6(11):1243-1270
The mass spectra of 2,2′-anhydrouridine, 2,2′-anhydrothymidine and 2,2′-anhydro-4-thiouridine are reported. The acetyl, trifluoroacetyl, trityl, pivaloyl and trimethylsilyl ether derivatives were also studied. Deuterium labeling in acetyl and trimethylsilyl groups aided characterization of many ions in the spectra, as well as helping to clarify hydrogen migration processes. The anhydronucleosides and their derivatives are readily distinguished from natural nucleosides by the presence of an ion containing the base moiety plus the anhydro-ring plus one hydrogen atom from the rest of the molecule. As for natural nucleosides the [base + H]+ and [base + 2H]+ ions are usually prominent, but in contrast to natural nucleosides, ions characteristic of the sugar moiety do not retain the 2′-oxygen atom (i.e. the oxygen atom of the anhydro-ring). The mass spectra of deuterium labeled derivatives suggest a test for the presence of a 3′-O-acetyl function (the O-acetyl group is lost from the molecular ion much more readily from the 3′- than from the 5′-carbon atom). The trimethylsilyl derivatives showed evidence in their mass spectra for migration of trimethylsilyl groups in addition to hydrogen atoms. 相似文献
52.
Markov DE Amsterdam E Blom PW Sieval AB Hummelen JC 《The journal of physical chemistry. A》2005,109(24):5266-5274
Exciton diffusion and photoluminescence quenching in conjugated polymer/fullerene heterostructures are studied by time-resolved photoluminescence. It is observed that heterostructures consisting of a spin-coated poly(p-phenylene vinylene) (PPV)-based derivative and evaporated C60 are ill-defined because of diffusion of C60 into the polymer, leading to an overestimation of the exciton diffusion length. This artifact is resolved by the use of a novel, thermally side-chain polymerizing and cross-linking fullerene derivative (F2D) containing two diacetylene moieties, forming a completely immobilized electron acceptor layer. With this heterostructure test system, an exciton diffusion length of 5 +/- 1 nm is derived for this PPV derivative from time-integrated luminescence quenching data. 相似文献
53.
Erilov DA Bartucci R Guzzi R Shubin AA Maryasov AG Marsh D Dzuba SA Sportelli L 《The journal of physical chemistry. B》2005,109(24):12003-12013
Electron spin-echo envelope modulation (ESEEM) spectroscopy of phospholipids spin-labeled systematically down the sn-2 chain was used to detect the penetration of water (D2O) into bilayer membranes of dipalmitoyl phosphatidylcholine with and without 50 mol % cholesterol. Three-pulse stimulated echoes allow the resolution of two superimposed 2H-ESEEM spectral components of different widths, for spin labels located in the upper part of the lipid chains. Quantum chemical calculations (DFT) and ESEEM simulations assign the broad spectral component to one or two D2O molecules that are directly hydrogen bonded to the N-O group of the spin label. Classical ESEEM simulations establish that the narrow spectral component arises from nonbonded water (D2O) molecules that are free in the hydrocarbon chain region of the bilayer membrane. The amplitudes of the broad 2H-ESEEM spectral component correlate directly with those of the narrow component for spin labels at different positions down the lipid chain, reflecting the local H-bonding equilibria. The D2O-ESEEM amplitudes decrease with position down the chain toward the bilayer center, displaying a sigmoidal dependence on position that is characteristic of transmembrane polarity profiles established by other less direct spin-labeling methods. The midpoint of the sigmoidal profile is shifted toward the membrane center for membranes without cholesterol, relative to those with cholesterol, and the D2O-ESEEM amplitude in the outer regions of the chain is greater in the presence of cholesterol than in its absence. For both membrane types, the D2O amplitude is almost vanishingly small at the bilayer center. The water-penetration profiles reverse correlate with the lipid-chain packing density, as reflected by 1H-ESEEM intensities from protons of the membrane matrix. An analysis of the H-bonding equilibria provides essential information on the binding of water molecules to H-bond acceptors within the hydrophobic interior of membranes. For membranes containing cholesterol, approximately 40% of the nitroxides in the region adjacent to the lipid headgroups are H bonded to water, of which ca. 15% are doubly H bonded. Corresponding H-bonded populations in membranes without cholesterol are ca. 20%, of which ca. 6% are doubly bonded. 相似文献
54.
Dr. Valentin Radtke Niklas Gebel Denis Priester Andreas Ermantraut Monika Bäuerle Dr. Daniel Himmel Regina Stroh Prof. Thorsten Koslowski Prof. Ivo Leito Prof. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(40):e202200509
Utilizing the “ideal” ionic liquid salt bridge to measure Gibbs energies of transfer of silver ions between the solvents water, acetonitrile, propylene carbonate and dimethylformamide results in a consistent data set with a precision of 0.6 kJ mol−1 over 87 measurements in 10 half-cells. This forms the basis for a coherent experimental thermodynamic framework of ion solvation chemistry. In addition, we define the solvent independent - and the values that account for the electronating potential of any redox system similar to the value of a medium that accounts for its protonating potential. This scale is thermodynamically well-defined enabling a straightforward comparison of the redox potentials (reducities) of all media with respect to the aqueous redox potential scale, hence unifying all conventional solvents′ redox potential scales. Thus, using the Gibbs energy of transfer of the silver ion published herein, one can convert and unify all hitherto published redox potentials measured, for example, against ferrocene, to the scale. 相似文献
55.
We have evaluated the potential of near-infrared spectroscopy (NIRS) as a technique for rapid analysis of lactate in whole blood. To test the NIRS technique, a comparison was made with a standard clinical method using whole blood samples taken from five exercising human subjects at three different stage of exercise. To expand lactate concentration within the physiological range, standard additions method was used to generate 45 unique data points. Spectra were collected over the 2050-2400 nm spectral range with a 1 mm optical path length quartz cell. Reference lactate concentrations in the samples were determined by enzymatic measurements. Estimates and calibration of the lactate concentration with NIRS was made using partial least squares (PLS) regression analysis and leave-N-out cross validation on second derivative spectra. Separate calibrations were determined from each of the subject samples and cumulative PRESS was used to determine the number of PLS factors in the final model. The results from the PLS model presented are generated from the five individual calibration coefficient vectors and provided a correlation coefficient of 0.978 and a standard error of cross validation of 0.65 mmol l−1 between the enzymatic assay and the NIRS technique. To study the parameters that impact the spectra baseline and the correlation between the calculated model and the data, referenced measurements of lactate against baseline spectrum were made for each individual. A correlation coefficient of 0.992 and a standard error of cross validation of 0.21 mmol l−1 were found. The results suggest that NIRS may provide a valuable tool to assess physiological status for both research and clinical needs. 相似文献
56.
Various enantiopure fluorous bis(oxazolines) with fluorine content between 52.7 and 58.7% have been synthesized by a simple reaction sequence that involved the introduction of two fluorinated ponytails by alkylation of the corresponding nonfluorous bis(oxazolines). These new ligands have been used in palladium-catalyzed alkylation of rac-(E)-1,3-diphenylpropenyl acetate with carbon nucleophiles and in copper-catalyzed oxidation of cycloalkenes; these ligands exhibited enantioselectivities up to 98 and 77%, respectively, quite close to the values obtained using the analogous nonfluorous bis(oxazolines). These ligands could be easily recovered by liquid-liquid extraction or solid-liquid separation and reused with the same enantioselectivities. 相似文献
57.
A novel terminal hydroxide containing dinuclear alumoxane LAl(OH)OAlL(OCH=N-tBu) (3; L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3) was prepared by treatment of aluminum dihydride LAlH2 (1) and tert-butyl isocyanate in the presence of trace amounts of water and alternatively from 1 and LAlH(OCH=N-tBu) (2) with water. Compound 2 was obtained from the reaction of 1 and tert-butyl isocyanate. 相似文献
58.
J. Barcicki A. Denis W. Grzegorczyk D. Nazimek T. Borowiecki 《Reaction Kinetics and Catalysis Letters》1976,5(4):471-478
The influence of additives (Cu, Fe and Al2O3) on the textural and catalytic properties of nickel in steam reforming of methane is described. The effects of structural promoting by Al2O3 and of electronic promoting by copper are reported. The rate of steam reforming of methane was measured in a gradientless reactor at atmospheric pressure.
(Cu, Fe Al2O3) . Al2O3 . .相似文献
59.
Tandem cuprate addition-Dieckmann condensation is featured in the construction of the polyketide metabolite tetracenomycin A(2). Thus, cyclization substrate 11 was treated with Gilman cuprate Me(2)CuLi to afford anthracene 12. The phenolic acetate protecting group of 12ensured its chemoselective oxidation to reveal terminal quinone 13, which intercepts the previously reported synthesis of tetracenomycin A(2). 相似文献
60.
Stochastic detection of motor protein-RNA complexes by single-channel current recording. 总被引:1,自引:0,他引:1
Yann Astier Denis E Kainov Hagan Bayley Roman Tuma Stefan Howorka 《Chemphyschem》2007,8(15):2189-2194
A label- and immobilization-free approach to detecting the reversible formation of complexes between nucleic acids and proteins at the single-molecule level is described. The voltage-driven translocation of individual oligoribonucleotides through a nanoscale protein pore is observed by single-channel current recordings. The oligoribonucleotide 5'-C25A(25)-3' gives rise to current blockades with an average duration of approximately 0.5 ms. In the presence of the RNA-binding ATPase P4, a viral packaging motor from bacteriophage phi8, longer events of tens to hundreds of milliseconds are observed. Upon addition of ATP the long events disappear, indicating the dissociation of the P4RNA complex. The frequency of events also depends on the concentration of P4 and the length of the oligoribonucleotide, thereby confirming the specificity of the P4RNA events. This study shows that single-channel current recordings can be used to monitor RNA-protein complex formation, thus opening up a new means to examine the motor activity of RNA- or DNA-processing enzymes. 相似文献