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H.-J. Scheibe D. Drescher A. Kolitsch A. Mensch 《Fresenius' Journal of Analytical Chemistry》1995,353(5-8):690-694
Morphology and structure of amorphous carbon films deposited with a pulsed arc source (LASER-ARC) have been studied using microscopical methods (SEM, TEM and AFM), electron diffraction and spectroscopical investigation (EELS). The parameters of the arc source and the deposition conditions (substrate temperature) influence morphology and structure of deposited amorphous carbon films. Especially the incorporation and growth of particles, embedded in the film have been investigated. By particle analysis using an optical microscope a majority of particles that is smaller than 500 nm has been determined. The morphology has been also demonstrated similar by AFM and TEM images. Their number and size of particles is strongly influenced by the deposition temperature. The structure of amorphous film is characterized by the EELS-spectra, but the particle structure was not detectable. 相似文献
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The structure and stability of classical and bridged C2H
3
+
is reinvestigated. The SCF and CEPA-PNO computations performed with flexibles andp basis sets including twod-sets on carbon confirm our previous results. We find the protonated acetylene structure to be more stable than the vinyl
cation by 3.5–4 kcal/mol. The energy barrier for the interconversion of these two structures is at most a few tenths of a
kcal/mol. The equilibrium SCF geometries of Weberet al. [15] are affected insignificantly by further optimization at the CEPA-PNO level.
Several structures for the interaction of C2H
3
+
with HF have been investigated at the SCF level. With our largest basis set which includes a complete set of polarization
functions we find a remarkable levelling of the stabilities of most of the structures. In these cases the stabilization energy
ΔE ranges from −10 to −13 kcal/mol. 相似文献
7.
Summary The calculation of electronically excited states with the internally contracted multiconfiguration-reference configuration interaction (CMRCI) method is discussed. A straightforward method, in which contracted functions for all states are included in the basis, is shown to be very accurate and stable even in cases of narrow avoided crossings. However, the expense strongly increases with the number of states. A new method is proposed, which employs different contracted basis sets for each state, and in which eigensolutions of the Hamiltonian are found using an approximate projection operator technique. The computational effort for this method scales only linearly with the number of states. The two methods are compared for various applications.Dedicated in honor of Prof. Klaus Ruedenberg 相似文献
8.
LETTUCE SEED GERMINATION: EFFECTS OF HIGH TEMPERATURE AND OF REPEATED FAR-RED TREATMENT IN RELATION TO PHYTOCHROME 总被引:5,自引:0,他引:5
Abstract— At 37°C the active form of phytochrome in lettuce seed cannot function to promote subsequent germination. This effect of high temperature is distinct from thermal acceleration of dark reversion from the active form of phytochrome to the inactive form, and may be due to reversible denaturation of phytochrome.
Repeated brief irradiations with far-red light inhibit subsequent germination in the whole seed, whereas a similar irradiation regime results in a strong enhancement of the development of growth potential (ability to expand against an externally-imposed osmotic restraint) in the excised axial portion of the seed. A possible explanation for these two opposing results, in volving two different pigment systems with effective loci in different parts of the seed, is suggested. 相似文献
Repeated brief irradiations with far-red light inhibit subsequent germination in the whole seed, whereas a similar irradiation regime results in a strong enhancement of the development of growth potential (ability to expand against an externally-imposed osmotic restraint) in the excised axial portion of the seed. A possible explanation for these two opposing results, in volving two different pigment systems with effective loci in different parts of the seed, is suggested. 相似文献
9.
Treatment of the bis(allylsulfoximine)titanium complexes derived from the beta-methyl-substituted acyclic allylic sulfoximines 13a and 13b with aldehydes gave with high selectivities the corresponding sulfoximine-substituted homoallylic alcohols which were isolated as the silyl ethers 15a-h. Methylation of sulfoximines 15a-h afforded the aminosulfoxonium salts 5a-h which upon treatment with LiN(H)tBu gave in high yields the enantio- and diastereomerically pure silyl-substituted 2,3-dihydrofurans 4a-h. Treatment of the titanium complexes derived from the cyclic allylic sulfoximines 17a, 17b, and ent-17c with p-MeOC(6)H(4)CHO delivered with high selectivities the corresponding sulfoximine-substituted cyclic homoallylic alcohols which were isolated as the silyl ethers 18a, 18b, and ent-18c, respectively. Methylation of sulfoximines 18a, 18b, and ent-18c furnished the aminosulfoxonium salts 8a, 8b, and ent-8c, respectively, whose treatment with LiN(H)t-Bu gave the enantio- and diastereomerically pure fused bicyclic 2,3-dihydrofurans 6a, 6b, and ent-6c, respectively, in good yields. It is proposed that the 1-alkenyl aminosulfoxonium salts 5a-h, 8a, 8b, and ent-8c react with the base under alpha-elimination and formation of the acyclic and cyclic beta-silyloxy alkylidene carbenes 2a-h, 7a, 7b, and ent-7c, respectively, which then undergo a 1,5-O,Si-bond insertion and 1,2-silyl migration. The cyclic aminosulfoxonium salts 8a, 8b, and ent-8c upon treatment with 1,8-diazabicyclo[5.4.0]-7-undecene did not undergo an alpha-elimination but suffered a novel migratory cyclization with formation of the enantio- and diastereomerically pure bicyclic tetrahydrofurans 9a, 9b, and ent-9c, respectively. It is proposed that the 1-alkenyl sulfoxonium salts 8a, 8b, and ent-8c are isomerized to the allylic aminosulfoxonium salts 10a, 10b, and ent-10c, respectively, which then suffer an intramolecular substitution of the (dimethylamino)sulfoxonium group by the silyloxy group followed by a desilylation. The syntheses of the 2,3-dihydrofurans 4a-h, 6a, and 6b and of the tetrahydrofurans 9a and 9b are accompanied by the formation of sulfinamide 16 of >or=98% ee, which can be converted via sulfoxide 28 of >or=98% to the starting sulfoximine 11 of >or=98% ee. 相似文献
10.
Alfred Kreutzberger Elfriede Kreutzberger Hans-Joachim Saltler Hayriye Aml Aysel Gürsoy 《Journal of heterocyclic chemistry》1982,19(4):753-755
The three-component reaction comprising the interaction of 2-amino-4-antipyrinyl-5-ethylthiazole (1) with s-triazine (2) and pyrrolidine leads to 4-anitpyrinyl-5-ethyl-2-[(4-pyrrolidinyl)methyleneamino]thiazole (5). Structure 5 is supported by 1H- and 13C-NMR spectroscopy. 相似文献