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1.
G. Richard Geier III 《Tetrahedron》2004,60(50):11435-11444
To better understand the effects of diverse substituents on reactions leading to porphyrins, pyrrole+aldehyde condensations and related reactions of dipyrromethanes were examined. The course of pyrrole+aldehyde condensations was investigated by monitoring the yield of porphyrin (by UV-Vis spectroscopy), reaction of aldehyde (by TLC), and changes in the composition of oligomers (by laser desorption mass spectrometry). Reaction reversibility was examined via exchange experiments. Reversibility of reactions leading to porphyrin was further probed with studies of dipyrromethanes. The reaction course was found to depend on the nature of the substituent and the acid catalyst. Alkyl or electron-donating substituents displayed levels of reversibility (exchange/scrambling) on par or greater than that of the phenyl substituent, whereas electron-withdrawing or sterically bulky substituents exhibited little to no reversibility. The results obtained provide insight into the electronic and steric effects of different substituents and should facilitate the design of synthetic plans for preparing porphyrinic macrocycles. 相似文献
2.
Danny E. Akin W. Herbert Morrison III Luanne L. Rigsby Franklin E. Barton II David S. Himmelsbach Kevin B. Hicks 《Applied biochemistry and biotechnology》2006,129(1-3):104-116
Information is presented on structure, composition, and response to enzymes of corn stover related to barriers for bioconversion
to ethanol. Aromatic compounds occurred in most tissue cell walls. Ferulic acid esterase treatment before cellulase treatment
significantly improved dry weight loss and release of phenolic acids and sugars in most fractions over cellulase alone. Leaf
fractions were considerably higher in dry weight loss and released sugars with esterase treatment, but stem pith cells gave
up the most phenolic acids. Results help identify plant fractions more appropriate for coproducts and bioconversion and those
more suitable as residues for soil erosion control. 相似文献
3.
P. Dawson J. W. Haas III K. B. Alexander J. Thompson T. L. Ferrell 《Surface science》1991,250(1-3):L383-L388
The intensity of surface enhanced Raman scattering from benzoic acid derivatives on mildly roughened, thermally evaporated Ag films shows a remarkably strong dependence on metal grain size. Large grained (slowly deposited) films give a superior response, by up to a factor of 10, to small grained (quickly deposited) films, with films of intermediate grain size yielding intermediate results. The optical field amplification underlying the enhancement mechanism is due to the excitation of surface plasmon polaritons (SPPs). Since surface roughness characteristics, as determined by STM, remain relatively constant as a function of deposition rate, it is argued that the contrast in Raman scattering is due to differences in elastic grain boundary scattering of SPPs (leading to different degrees of internal SPP damping), rather than differences in the interaction of SPPs with surface inhomogeneities. 相似文献
4.
5.
Martin R. Bridson Charles F. Miller III 《Proceedings of the American Mathematical Society》2004,132(1):59-65
We give examples of direct products of three hyperbolic groups in which there cannot exist an algorithm to decide which finitely presented subgroups are isomorphic.
6.
J. D. Petke Gerald M. Maggiora‡ Lester Shipman‡ Ralph E. CHRISTOFFERSEN‡ 《Photochemistry and photobiology》1979,30(2):203-223
Abstract— Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying excited singlet and triplet states of ethyl pheophorbide a (Et-Pheo a) and ethyl chlorophyllide a (Et-Chl a), and are employed in an analysis of the electronic absorption spectra of these systems. In both molecules the visible spectrum is found to consist of transitions to the two lowest-lying 1(π, π*) states, S1 and S2. The configurational compositions of S1 and S2 in both molecules are similar, and are described qualitatively in terms of a four-orbital model. The S1← S0 transition in each case is predicted to be intense, and is largely in-plane y-polarized, while the S2← S0 transition is predicted to be extremely weak and in-plane polarized. The orientation of the S2← S0 transition dipole is not conclusively established in the present calculations. The Soret band in both molecules is composed of transitions to no less than ten states (S3-S12 in Et-Chl a and S3-S7S9-S12. and S14 in Et-Pheo a), which exhibit primarily (π, π*) character. The configurational compositions of these states are generally a complex mixture of excitations from both occupied macrocyclic π molecular orbitals and occupied orbitals with electron density in the cyclopen-tanone ring and the carbomethoxy chain. No clear correspondences are evident between respective Soret states of the two systems. Transitions to these states are generally intense and display a variety of in-plane polarizations. Two additional Soret states of Et-Pheo a, S8 and S13, exhibit primarily (n. π*) character. S8 is characterized by excitations from u and non-bonding regions of the carbomethoxy chain, while S13 is described by n →π* excitations involving the nitrogen atom of ring II. No corresponding (n, π*) states were found for Et-Chl a. In both molecules the lowest two triplet states, T1 and T2, are found to lie lower in energy than S1. while T, and S1 are approximately degenerate. The configurational compositions of T1-T4 of both molecules are nearly identical, and may be described by a four-orbital model. However, the compositions of T1-T4 differ sharply from those of S1 and S2. A number of higher-lying 3(π, π*) states of both molecules (T5-T13 in Et-Chi a and T8-T9, T11-T13 in Et-Pheo a) are found to have energies similar to the singlet Soret states, relative to S0. They are characterized by a complex mixture of configurations which do not include significant contributions involving the four-orbital model. In addition, two 3(n, π*) states of Et-Pheo a, T10 and T14, are found, which are somewhat analogous to S8 and S13. Additional data presented include the charge distributions and molecular dipole moments of the S0. S1, and T1 states of both molecules, as well as energies and oscillator strengths of computed Sn←S1 and Tn←1 transitions. 相似文献
7.
Reaction of laser-ablated Zr with CH(4) ((13)CH(4), CD(4), and CH(2)D(2)) in excess neon during condensation at 5 K forms CH(2)=ZrH(2), the simplest alkylidene hydride complex, which is identified by infrared absorptions at 1581.0, 1546.2, 757.0, and 634.5 cm(-)(1). Density functional theory electronic structure calculations using a large basis set with polarization functions predict a C(1) symmetry structure with agostic C-H- - -Zr bonding and distance of 2.300 A. Identification of the agostic CH(2)=ZrH(2) methylidene complex is confirmed by an excellent match of calculated and observed isotopic frequencies particularly for the four unique CHD=ZrHD isotopic modifications. The analogous reactions in excess argon give two persistent photoreversible matrix configurations for CH(2)=ZrH(2). Finally, methane activation by CH(2)=ZrH(2) gives the new (CH(3))(2)ZrH(2) molecule. 相似文献
8.
Fluorescence-dip infrared spectroscopy and predissociation dynamics of OH A 2Sigma+ (v = 4) radicals
Derro EL Pollack IB Dempsey LP Greenslade ME Lei Y Radenović DC Lester MI 《The Journal of chemical physics》2005,122(24):244313
Fluorescence-dip infrared spectroscopy, an UV-IR double-resonance technique, is employed to characterize the line positions, linewidths, and corresponding lifetimes of highly predissociative rovibrational levels of the excited A (2)Sigma(+) electronic state of the OH radical. Various lines of the 4 <--2 overtone transition in the excited A (2)Sigma(+) state are observed, from which the rotational, centrifugal distortion, and spin-rotation constants for the A (2)Sigma(+) (v = 4) state are determined, along with the vibrational frequency for the overtone transition. Homogeneous linewidths of 0.23-0.31 cm(-1) full width at half maximum are extracted from the line profiles, demonstrating that the N = 0 to 7 rotational levels of the OH A (2)Sigma(+) (v = 4) state undergo rapid predissociation with lifetimes of < or =23 ps. The experimental linewidths are in near quantitative agreement with first-principles theoretical predictions. 相似文献
9.
The mass spectra of aluminum isopropoxide show that polymers, [Al(OC3H7)3]x where x = 1 to 7, can be present in the vapor and are, therefore, probably present in the bulk sample. The polymeric composition of the vapor depends on the previous history of the sample. Exact mass measurements on many of the ions along with data on a number of metastable peaks support the proposed fragmentation mechanisms. Loss of 102 mass units between intense peaks in the mass range above 500 a.m.u. leads to the suggestion that the higher polymers may be used as high mass marking substances. 相似文献
10.
C. E. Aalseth F. T. Avignone III R. L. Brodzinski H. S. Miley J. H. Reeves 《Journal of Radioanalytical and Nuclear Chemistry》1998,233(1-2):119-125
A fast digital oscilloscope based pulse shape discrimination (PSD) system has been tested with intrinsic germanium detectors
large enough to allow ionizing events which generate localized electron-hole pairs at a single site to be segregated from
those depositing energy at several different sites in the crystal. Drift velocities of the electrons and holes result in pulses
several hundred nanoseconds long. Since the electric field varies by almost a factor of 10 between the outer and inner surfaces,
collection of electrons and holes can frequently be dinstinguished, and pulses due to multi-site events can be distinguished
from single site events. 相似文献