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901.
We investigate triplet-triplet annihilation in molecular host-guest systems where triplets are localized on spatially separated guest molecules. Our results indicate that the dominant mechanism of annihilation is single-step long-range (F?rster-type) energy transfer between two excited guests. This mechanism leads to a fundamental limit for the efficiency of phosphorescent organic light emitting diodes at high luminance. Our model is confirmed by photoluminescence decay experiments on 2,3,7,8,12,13,17,18-octaethylporphine platinum as guest in a host matrix of 4,4'-N,N'-dicarbazole-biphenyl. 相似文献
902.
Contado C Dalpiaz A Leo E Zborowski M Williams PS 《Journal of chromatography. A》2007,1157(1-2):321-335
Poly(lactic acid) (PLA) nanoparticles were synthesized using a modified evaporation method, testing two different surfactants (sodium cholate and Pluronic F68) for the process. During their formulation the prodrug 5'-octanoyl-CPA (Oct-CPA) of the anti-ischemic N(6)-cyclopentyladenosine (CPA) was encapsulated. Three different purification methods were compared with respect to the influence of surfactant on the size characteristics of the final nanoparticle product. Flow and sedimentation field-flow fractionation techniques (FlFFF and SdFFF, respectively) were used to size characterize the five poly(lactic acid) particle samples. Two different combinations of carrier solution (mobile phase) were employed in the FlFFF analyses, while a solution of poly(vinyl alcohol) was used as mobile phase for the SdFFF runs. The separation performances of the two techniques were compared and the particle size distributions (PSDs), derived from the fractograms, were interpreted with the support of observations by scanning electron microscopy. Some critical aspects, such as the carrier choice and the channel thickness determination for the FlFFF, have been investigated. This is the first comprehensive comparison of the two FFF techniques for characterizing non-standard particulate materials. The two FFF techniques proved to be complementary and gave good, congruent and very useful information on the size distributions of the five poly(lactic acid) particle samples. 相似文献
903.
A synthesis of the ABC framework of dumsin is described. The optically active intermediate 9b, which is expeditiously assembled from 5-oxobornyl pivalate by the sequential implementation of an oxy-Cope rearrangement and an intramolecular ene reaction, proved to be suitably functionalized for ultimate conversion to 5. The synthesis plan relies on two approaches to this targeted intermediate. In the first, the exocyclic double bond introduced during EtAlCl2-promoted closure of aldehyde 10b is cleaved to leave a carbonyl group that is amenable to hydride reduction and elimination of water. Cleavage of the resulting double bond with ruthenium tetroxide provided the seco ketoacid. The same advanced intermediate was obtained by initially positioning the double bond internal to the five-membered ring in advance of transient ring expansion via diketone formation and intramolecular aldolization. Both of these approaches bypass the complications arising from the substantial steric congestion prevailing in these structural networks. The task of covalently positioning an oxygen atom adjacent to the gem-dimethyl-substituted carbon in 5 was properly realized by oxidative decarboxylation. The stereochemical assignments to many of the intermediates were confirmed by an X-ray crystallographic analysis of 43. 相似文献
904.
The ultraviolet spectroscopy of m- and p-divinylbenzene isomers (mDVB and pDVB) was studied by a combination of methods, including resonance-enhanced two-photon ionization (R2PI), laser-induced fluorescence (LIF), UV-UV hole-burning spectroscopy (UVHB), and single vibronic level fluorescence spectroscopy (SVLF). In mDVB, there are three low-energy conformations, cis-cis, cis-trans, and trans-trans whose S1 <-- S0 origins occur at 31,408, 31,856, and 32,164 cm(-1), respectively, as confirmed by UVHB spectroscopy. There are two possible conformations in pDVB, cis and trans. UVHB studies confirm the S1 <-- S0 origin of trans-pDVB occurs at 32,553 cm(-1), and the corresponding cis-pDVB origin is tentatively assigned to a transition at 32 621 cm(-1). SVLF studies were used to determine several of the vinyl torsional levels of the isomers of mDVB and pDVB. A two-dimensional flexible model was used to fit these levels in mDVB to a potential form and determine the barriers to isomerization. 相似文献
905.
Quantum chemistry calculations have been used to study the uncatalyzed transfer hydrogenation between a range of hydrogen donors and acceptors, in the gas phase and in solution. Our study shows in the first place that in order to obtain reliable condensed-phase transition structures, it is necessary to perform geometry optimization in the presence of a continuum. In addition, the use of a free energy of solvation obtained with the UB3-LYP/6-31+G(d,p)/IEF-PCM/UA0 combination, in conjunction with UMPWB1K/6-311+G(3df,2p)//B3-LYP/6-31+G(d,p) gas-phase energies, gives the best agreement with experimental barriers. In condensed phases, the geometries and energies of the transition structures are found to relate to one another in a manner consistent with the Hammond postulate. There is also a correlation between the barriers and the energies of the radical intermediates in accord with the Bell-Evans-Polanyi principle. We find that in the gas phase, all the transfer-hydrogenation reactions examined proceed via a radical pathway. In condensed phases, some of the reactions follow a radical mechanism regardless of the solvent. However, for some reactions there is a change from a radical mechanism to an ionic mechanism as the solvent becomes more polar. Our calculations indicate that the detection of radical adducts by EPR does not necessarily indicate a predominant radical mechanism, because of the possibility of a concurrent ionic reaction. We also find that the transition structures for these reactions do not necessarily have a strong resemblance to the intermediates, and therefore one should be cautious in utilizing the influence of polar effects on the rate of reaction as a means of determining the mechanism. 相似文献
906.
Stewart KD Steffy K Harris K Harlan JE Stoll VS Huth JR Walter KA Gramling-Evans E Mendoza RR Severin JM Richardson PL Barrett LW Matayoshi ED Swift KM Betz SF Muchmore SW Kempf DJ Molla A 《Journal of computer-aided molecular design》2007,21(1-3):121-130
Two new proteins of approximately 70 amino acids in length, corresponding to an unnaturally-linked N- and C-helix of the ectodomain
of the gp41 protein from the human immunodeficiency virus (HIV) type 1, were designed and characterized. A designed tripeptide
links the C-terminus of the C-helix with the N-terminus of the N-helix in a circular permutation so that the C-helix precedes
the N-helix in sequence. In addition to the artificial peptide linkage, the C-helix is truncated at its N-terminus to expose
a region of the N-helix known as the “Trp-Trp-Ile” binding pocket. Sedimentation, crystallographic, and nuclear magnetic resonance
studies confirmed that the protein had the desired trimeric structure with an unoccupied binding site. Spectroscopic and centrifugation
studies demonstrated that the engineered protein had ligand binding characteristics similar to previously reported constructs.
Unlike previous constructs which expose additional, shallow, non-conserved, and undesired binding pockets, only the single
deep and conserved Trp-Trp-Ile pocket is exposed in the proteins of this study. This engineered version of gp41 protein will
be potentially useful in research programs aimed at discovery of new drugs for therapy of HIV-infection in humans. 相似文献
907.
The addition rate constants of radicals to alkenes are strongly substituent dependent because of enthalpic, polar and steric effects. Recent absolute experimental and high level ab initio data for many prototype additions of small radicals are analyzed with the aid of the state correlation diagram. This leads to a unifying rationalization of the various effects and allows the prediction of rate constants to one order of magnitude or better. Propagation rate coefficients of homo- and copolymerizations and penultimate effects are also discussed. 相似文献
908.
The durability of topcoats is dependent on a large number of factors as polymer composition, stabilization package and the conditions during the weathering process. For obvious reasons prediction of the long-term (5-10 year) durability of coatings is very important. The rate-determining factor for the degradation of PUR coatings is photo-oxidation. The photo-oxidation rate is controlled by the polymer structure but also stabilizers as HALS has a large influence. The prediction of the durability of clearcoats is based on tracing of the photo-oxidation rate and of the HALS longevity during exposure. The photo-oxidation rate is measured using FTIR-PAS. The results show that degradation can be detected much earlier compared with classical methods as gloss loss. Moreover detection of differences between systems after short exposure times as well as prediction of the long-term durability are possible. 相似文献
909.
910.
H. Ackermann G. Geiseler K. Harms R. Leo W. Massa F. Weller K. Dehnicke 《无机化学与普通化学杂志》1999,625(9):1500-1506
Triethylphosphanimine Complexes of the Acetates of Copper(II) and Zinc. Crystal Structures of [Zn(O2C–CH3)2(HNPEt3)], [Cu5(O2C–CH3)10(HNPEt3)2], and [Cu(O2C–CH3)2(HNPEt3)2] The title compounds originate from the anhydrous acetates of zinc and copper(II) with trimethylsilyl-triethylphosphanimine, Me3SiNPEt3, in the presence of water in dichloromethane. They form colourless ( 1 ), bluish-green ( 2 ), and blue ( 3 ), respectively, single crystals, which were characterized by IR spectroscopy and by crystal structure analyses. [Zn(O2C–CH3)2(HNPEt3)] ( 1 ): Space group P 4 21c, Z = 8, lattice dimensions at –83 °C: a = b = 1709.6(2), c = 982.4(1) pm, R = 0.0551. 1 has a polymeric chain structure in which the zinc atoms are μ2-bridged via the oxygen atoms of one of the two acetato groups, while the second acetato group and the phosphanimine are bonded terminally. [Cu5(O2C–CH3)10(HNPEt3)2]( 2 · 4 CH2Cl2): Space group P21/c, Z = 8, lattice dimensions at –80 °C: a = 1761.18(13), b = 4074.5(2), c = 1733.34(15) pm, β = 91.383(10)°, R = 0.0413. 2 consists of the two structural units [Cu2(O2C–CH3)4] and [Cu3(O2C–CH3)6(HNPEt3)2], which are connected via two of the acetato groups of the Cu3-unit along the crystallographic a-axis to form three crystallographically independent polymeric strands. [Cu(O2C–CH3)2(HNPEt3)2] ( 3 ): Space group P21/n, Z = 2, lattice dimensions at 20 °C: a = 695.49(8), b = 1217.85(10), c = 1380.05(7) pm, β = 96.451(7)°, R = 0.0291. 3 forms monomeric, centrosymmetric molecules with a square planar environment at the Cu atoms. 相似文献