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81.
Alexandra Tsybizova Christopher Brenig Christoph Kieninger Bernhard Kräutler Peter Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(25):7252-7264
Aryl-cobalamins are a new class of organometallic structural mimics of vitamin B12 designed as potential ‘antivitamins B12’. Here, the first cationic aryl-cobinamides are described, which were synthesized using the newly developed diaryl-iodonium method. The aryl-cobinamides were obtained as pairs of organometallic coordination isomers, the stereo-structure of which was unambiguously assigned based on homo- and heteronuclear NMR spectra. The availability of isomers with axial attachment of the aryl group, either at the ‘beta’ or at the ‘alpha’ face of the cobalt-center allowed for an unprecedented comparison of the organometallic reactivity of such pairs. The homolytic gas-phase bond dissociation energies (BDEs) of the coordination-isomeric phenyl- and 4-ethylphenyl-cobinamides were determined by ESI-MS threshold CID experiments, furnishing (Co−C )-BDEs of 38.4 and 40.6 kcal mol−1, respectively, for the two β-isomers, and the larger BDEs of 46.6 and 43.8 kcal mol−1 for the corresponding α-isomers. Surprisingly, the observed (Co−C )-BDEs of the Coβ-aryl-cobinamides were smaller than the (Co−C )-BDE of Coβ-methyl-cobinamide. DFT studies and the magnitudes of the experimental (Co−C )-BDEs revealed relevant contributions of non-bonded interactions in aryl-cobinamides, notably steric strain between the aryl and the cobalt-corrin moieties and non-bonded interactions with and among the peripheral sidechains. 相似文献
82.
Pradip K. Bhowmik Robert W. Lenz 《Journal of polymer science. Part A, Polymer chemistry》1994,32(4):651-659
A series of fully aromatic, thermotropic polyesters based on 1,1′-binaphthyl-4,4′-diol, BND, was prepared by the melt polycondensation method and characterized for their thermotropic behavior by a variety of experimental techniques. The homopolymer of BND with terephthalic acid formed a nematic melt at 353°C. In contrast, the polyester from BND and 2,6-naphthalenedicarboxylic acid had a melting transition, Tm, above 400°C, so it was not possible with the equipment available to determine whether it formed a nematic melt. All of the copolymers of BND formed nematic melts at much lower Tm values than those of its respective homopolymers, as expected, because of the copolymerization effect of the added monomer. Moreover, all of the copolymers had higher glass transition temperatures, Tg, than those of other liquid crystalline polyesters and higher thermal stabilities. © 1994 John Wiley & Sons, Inc. 相似文献
83.
Jerzy Majnusz Robert W. Lenz 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2775-2788
A series of low molecular weight, thermotropic poly(2-alkyl-1,4-phenylene terephthalate)s was prepared by the solution polycondensation reaction of terephthaloyl chloride and alkylhydroquinones containing n-alkyl substituents of increasing size from methyl to dodecyl. Samples of the low molecular weight polymers so obtained were also further polycondensed in the solid state to obtain high molecular weight polymers. The liquid crystalline phase behaviors and textures were determined, and the effects of polymer structure and molecular weight on these properties are discussed. All of the polymers obtained formed thermotropic, nematic mesophases, which were less stable for the lower molecular weight polymers, as expected, than were the mesophases formed by the higher molecular weight polymers. © 1994 John Wiley & Sons, Inc. 相似文献
84.
B. Henc P.W. Jolly R. Salz S. Stobbe G. Wilke R. Benn R. Mynott K. Seevogel R. Goddard C. Krüger 《Journal of organometallic chemistry》1980,191(2):449-475
A series of 1 : 1 adducts have been prepared by treating the bis-η3-allyl complexes of nickel, palladium and platinum with tertiary phosphines. Investigations of their structure in solution as well as in the crystal have shown that both 18-electron (η3-allyl)2ML complexes as well as 16-electron (η1-allyl)-(η3-allyl)ML complexes may be formed. 相似文献
85.
In situ pulsed force mode scanning force microscopy (PFM-SFM) images of phase separated solid-supported lipid bilayers are discussed with the help of computer simulations. Simultaneous imaging of material properties and topography in a liquid environment by means of PFM-SFM is severely hampered by hydrodynamic damping of the cantilever. Stiffness and adhesion images of solid-supported membranes consisting of cholesterol, sphingomyelin, and 1,2-dioleyl-phosphatidylcholine obtained in aqueous solution exhibit contrast inversion of adhesion and stiff. ness images depending on parameters such as driving frequency, amplitude, and trigger setting. Simulations using a simple harmonic oscillator model explain experimental findings and give a deeper insight into the way PFM-SFM experiments have to be performed in order to obtain interpretable results and hence pave the way for reliable material contrast imaging at high speed. 相似文献
86.
W. Krätschmer 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,19(4):405-408
At the beginning two remarks. One to the nomenclature: Fullerite does not name a specific substance; it names a solid entirely consisting of fullerenes, i.e. closed-cage all-carbon molecules. When our method of synthesis is applied, a solid is obtained in which C60 is the most abundant species. This material may thus be called C60-fullerite. The other remark regarding the production of fullerite: in view of the ease with which this could be achieved, I have the feeling that fullerene molecules must belong to a very frequently overlooked molecular species in carbon chemistry. Since the synthesis is simple and does not require many words to be described, I thought it might be interesting to tell how we came to make fullerite. 相似文献
87.
G. Basar H-D Kronfeldt S. Kröger 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1996,36(1):35-39
The hyperfine structure of the odd configurations 5d 96p and 5d 86s6p was studied with laser optogalvanic spectroscopy and high resolution interferometry in a platinum hollow cathode. A parametric hyperfine structure analysis for the configurations (5d+6s)96p with 10 excited odd-parity levels was performed for195Pt. We obtained one-electron hfs parameters,a 5d 01 =1160(320) MHz,a 6s 10 =35600(5300) MHz anda 6p 01 =1300(780) MHz for the configuration 5d 86s6p. The corresponding $\left\langle {r^{ - 3} } \right\rangle _{nl}^{k_s k_l } $ values are compared with those known for other 5d-elements. 相似文献
88.
Robert W. Lenz Lars C. Westfelt 《Journal of polymer science. Part A, Polymer chemistry》1976,14(9):2147-2153
The cationic polymerization of p-chloro-α-methylstyrene was investigated for the effect of initiator and solvent on polymer tacticity, molecular weight, and molecular weight distribution. The products were generally crystalline polymers of 80–90% syndiotactic content with fairly high molecular weights and broad molecular weight distributions. Tacticities and molecular weight distributions followed similar patterns suggesting that the effect of reaction conditions on ionpair end-group structures was the dominant factor. 相似文献
89.
Zusammenfassung Das Verhalten von Polypropylen im elektrischen Wechselfeld wurde im Frequenzbereich von 0,15 kHz bis 300 kHz und im Temperaturbereich von –75 C bis +140 C untersucht. Es konnte sowohl ein Tieftemperaturdispersionsgebiet —-Absorption — als auch ein Hochtemperaturdispersionsgebiet —-Absorption — beobachtet werden. Die Untersuchungsergebnisse wurden, um die Breite des Dispersionsgebietes und die zugehörigen -Stufen zu bestimmen, nach demCole-Cole-Kreisbogengesetz analysiert. Aus dem Anstieg der Geraden: logf
max 1/T
K wurden sowohl für die- als auch fur die-Absorption die experimentellen Aktivierungsenergien berechnet. Eine Deutung der Ergebnisse wurde versucht. 相似文献
90.
Marian Čerňanský Přemysl Vaněk Karel Král Radmila Krupková 《Monatshefte für Chemie / Chemical Monthly》2002,133(6):799-806
Summary. In this investigation the crystallization of PbTiO3 upon annealing of pure nanopowders and PbTiO3–SiO2 (1:1 v/v) nanocomposite powders prepared by the sol-gel technique was studied. Using X-ray diffraction phase analysis, the
start of PbTiO3 crystallization in pure PbTiO3 powders was detected at 400°C. Distinct crystallization of PbTiO3 in PbTiO3–SiO2 nanocomposites starts at 700°C, whereas SiO2 remains amorphous. There are indications that an interface interaction between the PbTiO3 and the SiO2 phase plays an important role in hindering the crystallization of PbTiO3. The particle size (size of coherently scattering regions) was estimated from the broadening of the X-ray diffraction line
profiles. The average size of PbTiO3 nanocrystallites increases with temperature and time of annealing, the influence of temperature being more significant than
that of the annealing time. Differential scanning calorimetry confirmed the results of the X-ray diffraction with respect
to the start of the crystallization. Laser beam scattering and scanning electron microscopy provided the statistical distribution
of the grain size and the morphology of the powder grains, showing that each grain of the powders contains several nanocrystallites
(coherently scattering regions).
Received October 4, 2001. Accepted (revised) December 14, 2001 相似文献