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991.
992.
John J. D'Amico Frederic G. Bellinger John J. Freeman 《Journal of heterocyclic chemistry》1988,25(5):1503-1509
The reaction of the appropriate 2-benzothiazolinone with 2-chloroacetamide under basic conditions afforded the 2-oxo-3(2H)-benzothiazolineacetamides 6–9. The 2-thioxo-3(2H)-benzothiazolineacetamide ( 10 ) was prepared by the reaction of 3-(carbethoxymethyl)benzothiazoline-2-thione with ammonium hydroxide. The reaction of acetamides 6–10 with the appropriate anhydride containing a catalytic amount of the sodium salt of the acid corresponding to the anhydride afforded the titled compounds 11–18 in excellent yields. The omission of the catalyst in the same reaction furnished a mixture containing 57% of the titled compound, 37% of the nitrile and 6% of an unknown. Possible mechanism and supporting nmr, ir and mass spectral data are discussed. 相似文献
993.
Hydrolysis of 1,10-phenanthrolinopyrrole ethyl ester leads to the acid derivative which is unstable at room-temperature releasing CO(2) and forming 1,10-phenanthrolinopyrrole (php). The ligand reacts with ruthenium(II) to form a series of complexes of the general formula [Ru(php)(n)(bpy)(3-n)](2+), where bpy = 2,2'-bipyridine and n = 1-3. The photochemical properties reveal that the complexes have longer-lived excited states than the standard complex, [Ru(bpy)(3)](2+). Their emission lifetimes range from 9.04 micros (n = 1) to 35.5 micros (n = 3) at 77 K compared to 7.57 micros for the standard. Similarly, at room-temperature, emission lifetimes range from 1.20 micros (n = 1) to 1.70 micros (n = 3) relative to the standard (0.56 micros). The emission quantum yields also have higher values than the standard [Ru(bpy)(3)](2+) under similar conditions. The temperature-dependent studies for the complexes establish the distribution among the radiative, nonradiative, and (3)MLCT to (3)d-d decay channels and are in agreement with the energy gap law. 相似文献
994.
Abstract— Most sensitizers used for the photodynamic therapy (PDT) of tumors photobleach on illumination. Thus, it is of interest to examine the photobleaching behavior of new sensitizers proposed for use in PDT. This report surveys the quantum yields and kinetics of the photobleaching of mono- l -aspartyl chlorin e6 (NPe6), a hydrophilic chlorin that has many of the photoproperties desirable in a sensitizer for clinical PDT. It is a very effective sensitizer for the PDT of several types of model tumors in animals and is now in Phase I clinical trials. The quantum yield of NPe6 photobleaching in pH 7.4 phosphate buffer in air was 8.2 × 10−4 ; this is greater than the yields for typical porphyrin photosensitizers. For example, the yields for hematoporphyrin and uroporphyrin are 4.7 × 10 5 and 2.8 × 10−5 , respectively. The yield decreased significantly in organic solvents of low dielectric constant. The Sn derivative of NPe6 was more light stable than NPe6 (yield = 5.7 × 10 −6 ), while the Zn derivative was more sensitive (yield = 1.9 × 10−2 ). Oxygen appeared to be necessary for the photobleaching of NPe6; however, bleaching was not inhibited by 100 mM azide, an efficient quencher of singlet oxygen. The photooxidizable substrates cysteine, dithiothreitol and furfuryl alcohol increased the quantum yield of photoblcaching two- to four-fold, while the electron acceptor, met-ronidazole, increased it almost six-fold. Photobleaching yields for several other chlorins were also measured. 相似文献
995.
John J. Fenske Andrew Hashimoto Michael H. Penner 《Applied biochemistry and biotechnology》1998,73(2-3):145-157
The relative toxicity of the combined nonxylose components in prehydrolysates derived from three different lignocellulosic
biomass feedstocks was determined. One woody (poplar) and two herbaceous (corn stover and switchgrass) feedstocks were dilute-acid
pretreated under temperature and acid conditions chosen to optimize xylose recovery in the liquid prehydrolysate; xylose yields
averaged 96,89,and 87% of theoretical for switchgrass,corn stover,and poplar,respectively. Prehydrolysates from each feedstock
were neutralized,adjusted to equivalent xylose concentrations,and bioassayed for toxicity,using a standardized fermentation
protocol withPichia stipitis NRRL 11545. Full time-courses for ethanol production (30-60 h) clearly illustrate the distinct inhibitory effects of prehydrolysates
from different feedstocks. The relative toxicity of the prehydrolysates,ranked in order of decreasing toxicity,is poplar-derived
prehydrolysates > switchgrass-derived prehydrolysates > corn stover-derived prehydrolysates. The inhibition of ethanol production
appeared to be the result of a general slowdown of yeast metabolism,rather than the result of the production of alternative,
nonethanol end products. Ethanol yields averaged 74,83,and 88% of control values for poplar,switchgrass,and corn stover prehydrolysates,
respectively. Volumetric ethanol productivities (g ethanol L/h) averaged 32,70,and 102% of control values for poplar,switchgrass,and
corn stover prehydrolysates,respectively. Ethanol productivities correlated closely with acetate concentrations in the prehydrolysates;
however, regression lines correlating acetate concentrations and ethanol productivities were found to be feedstock-dependent.
Oregon State University Agricultural Experiment Station Technical Publication Number 11114 相似文献
996.
Wilson Cunico Claudia R. B. Gomes Solange M. S. V. Wardell John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):o411-o414
rac‐2‐Isopropyl‐3‐(2‐nitrobenzyl)‐1,3‐thiadiazolin‐4‐one, C13H16N2O3S, is a rare example of a racemate crystallizing in the space group P212121, with one molecule each of S and R configurations, whose conformations are almost mirror images, within the asymmetric unit. The molecules of S configuration are linked by two C—H...O hydrogen bonds into a three‐dimensional framework, and the molecules of R configuration are linked by two further C—H...O hydrogen bonds into a different type of three‐dimensional framework; the two frameworks are linked by a fifth C—H...O hydrogen bond. 相似文献
997.
Pamela M. St. John Rainer D. Beck Robert L. Whetten 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,26(1):226-228
We review the processes which have been observed from collisions between alkali-halide clusters and solid surfaces. Soft impact of nanocrystalline NanF n?1 + clusters against solid surfaces causes them to cleave along the lowest energy (100) plane. At higher collision energies (Ei>1 eV/atom), an evaporative cascade occurs which is characteristic of a transformation of the nanocrystal to a molten state. Efficient F? transfer from the cluster to the surface can occur for the larger clusters (>60 atoms) scattering from Si(111), in direct competition with the cleaving channel at low energies. In this regime, strong bonds can form between the F? and silicon surface. The reaction probability increases with cluster size indicating that an impact-initiated shock wave is needed to enhance the reactive process. 相似文献
998.
John Mullay 《Journal of computational chemistry》1988,9(4):399-405
A simple electronegativity method is used to calculate atomic charges for molecules of interest to biochemistry. These include purines, pyrimidines, and amino acids. Results are compared to those obtained from other theoretical methods (ab initio and semiempirical) as well as to nuclear magnetic resonance (NMR) data. Correlation is fair with CNDO results but very good for ab initio, DelRe, and other electronegativity methods. Good correlation was also achieved with NMR data. It is shown that a correction factor may be required in some cases and that important resonance effects need to be taken into account. Because of the small amount of calculational effort involved, these results suggest that this method could be quite useful in this field. 相似文献
999.
Athinoula L. Petrou Maria V. Koromantzou John M. Tsangaris 《Transition Metal Chemistry》1991,16(1):48-52
Summary The preparation of complexes of 3,4-dihydroxyphenylpropoionic acid (hydrocaffeic acid): K2[Cu2(hydcafH)2-Cl2]·2KCl·2MeOH, K2[Co(hydcafH)2]·2KCl, K2[Ni2(hydcafH)2Cl2]·2KCl·2MeOH and Fe2 (hydcafH)2Cl2·2KCl·2H2O was achieved. Spectroscopic and magnetic studies are commensurate with tetrahedral structures for the prepared complexes in which the catechol-like coordination is present. 相似文献
1000.
Phillip T. Mead John C. Traeger John R. Christie Peter. J. Derrick 《Journal of mass spectrometry : JMS》1978,13(7):386-388
The internal energies of [C3H7]+ ions contributing to the metastable peak [C3H7]+ → [C3H5]+ + H2 are higher (by perhaps > 100 kJ mol?1) than those of the ion contributing to the threshold current in appearance energy measurements on [C3H5]+. The measured appearance energy may lead to an underestimation of the activation energy, i.e. negative ‘kinetic shift’, due to quantum, mechanical tunnelling. The distribution of energy released in the decomposition can be explained on the basis that much of the reverse activation energy and a statistical proportion of the excess energy is released as translation. 相似文献