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851.
A gas chromatographic system with wide-bore capillary columns and synchronized accumulating radioisotope detector (SARD) was developed. A direct injection method and constant-flow regulation were applied. The performance of wide-bore capillary columns was good and the correspondence of the resolution obtained with SARD and that with mass detection was excellent. It was proved that the apparatus could detect of the order of 1 pg of 3H-labelled substances (3.7 TBq/mmol) and compete in terms of sensitivity with gas chromatography-mass spectrometry. 相似文献
852.
Ikue Homma Takuya Isogai Tsuguyuki Saito Akira Isogai 《Cellulose (London, England)》2013,20(2):795-805
The biodegradation behavior of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose fibers (TOCs) suspended in water and TEMPO-oxidized cellulose nanofibrils (TOCNs) dispersed in water by a commercial crude cellulase was studied. Products crude cellulase-treated for 0–7 days were separated into water/ethanol-insoluble and -soluble fractions. Weight recovery ratios and viscosity-average degrees of polymerization of the water/ethanol-insoluble fractions clearly decreased with crude cellulase-treatment time, showing that both TOCs and TOCNs have biodegradability. Water/ethanol-soluble fractions were subjected to size-exclusion chromatography (SEC) with photodiode array (PDA) detection to obtain SEC elution patterns detected by reflective index and UV spectra of each SEC pattern elution slice. SEC–PDA and 13C-NMR analyses showed that glucuronosyl unit-containing molecules present on microfibril surfaces in TOCs and TOCNs were primarily cleaved by hydrolyzing enzymes present as contaminants in the crude cellulase to form glucuronic acid as one of the major water-soluble degradation compounds. After the glucuronosyl units in TOCs and TOCNs were degraded and removed from microfibril surfaces by the hydrolyzing enzymes, cellulose chains newly exposed on the microfibril surfaces were rapidly hydrolyzed by cellulases predominantly present in the crude cellulase to form cellobiose. Both TOCs and TOCNs having sodium carboxyl groups are thus biodegradable, but TOCN having free carboxyl groups had clearly low biodegradability by the crude cellulase. Thus, biodegradation behavior may be controllable by controlling the structure of carboxyl group counter ions in TOCs and TOCNs. 相似文献
853.
Tetsuya Nanba Shoichi Masukawa Junko Uchisawa Akira Obuchi 《Journal of Thermal Analysis and Calorimetry》2013,113(2):793-802
We studied the temperature-programmed reduction by NH3 (NH3-TPR) as a supplement to the temperature-programmed reduction by H2 (H2-TPR) for the characterization of supported Cu species. The NH3-TPR profile of Cu/SiO2, which contained only bulk CuO, exhibited two peaks for N2 formation in equal amounts, suggesting stepwise reduction of the bulk CuO. In contrast, the H2-TPR profile exhibited only one H2 consumption peak. We also studied Cu-NaZSM-5 samples with various Cu and Na loadings. The Cu ions on ZSM-5 were reduced to Cu+ but no further. Kinetic analysis revealed that the NH3-TPR profile exhibited peaks for separate reductions of isolated and binuclear Cu2+ ions. Thus, we found NH3-TPR to be useful for detailed analysis of the reducibility of Cu2+ to Cu+ in zeolite pores. 相似文献
854.
Akira Harada 《Journal of polymer science. Part A, Polymer chemistry》2009,47(18):4469-4481
Cyclodextrins (CDs) were found to initiate polymerization of lactone to give polyesters with a CD ring at the end of the polymer chain in high yields only by mixing and heating with monomer without cocatalysts or solvents. CD‐tethered polyester propagates with the formation of poly‐pseudorotaxane, which is necessary to initiate further polymerization. CDs threaded onto the polymer chain are also essential for maintaining the propagating state of the polyester. By polymerizing with CD, switching the activity of the polymerization by photoisomerization was demonstrated. This polymerization system showed specific substrate recognition, releasing the products from the active site. By using the above polymerization system, β‐CD nanospheres which initiates the oligomerization of lactone were constructed. It was found that the formation of poly‐pseudorotaxane on the nanosphere enabled further polymerization activity for lactone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4469–4481, 2009 相似文献
855.
Kenji Hotta Hideharu Ishida Makoto Kiso Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(4-5):491-506
Abstract A first total synthesis of a cholinergic neuron-specific ganglioside, GQ1bα (IV3Neu5Acα, III6Neu5Acα, II3Neu5Acα2-Gg4Cer) is described. Regio- and stereo-selective monosialylation of the hydroxyl group at C-6 of the GalNAc residue in 2-(trimethylsilyl)ethyl O-(2-acetamido-2-deoxy-3,4-O-isopropylidene-β-d-galactopyranosyl)-(1→4)-O-(2,6-di-O-benzyl-β-dgalactopyranosyl)-(1→4)- O-2,3,6-tri-O-benzyl-β-dglucopyranoside (4) with methyl (phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-d glycero-d galacto-2-nonulopyranosid) onate (5), and subsequent dimericsialylation of the hydroxyl group at C-3 of the Gal residue with methyl [phenyl 5-acetamido-8-O-(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d glycero-α-d galacto-2-nonulopyranosylono-1′,9-lactone)-4, 7-di-O-acetyl-3,5-dideoxy-2-thio-d glycero-d galacto-2-nonulopyranosid]onate (7), using N-iodosuccinimide (NIS)-trifluoromethanesulfonic acid (TfOH) as a promoter, gave the desired hexasaccharide 8 containing α-glycosidically-linked mono- and dimeric sialic acids. This was transformed into the acceptor 9 by removal of the isopropylidene group. Condensation of methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-d glycero-α-d galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-dgalactopyranoside (10) with 9, using dimethyl(methylthio)sulfonium triflate (DMTST) as a promoter, gave the desired octasaccharide derivative 11 in high yield. Compound 11 was converted into α-trichloroacetimidate 14, via reductive removal of the benzyl groups, O-acetylation, removal of the 2-(trimethylsilyl)ethyl group, and treatment with trichloroacetonitrile, which, on coupling with (2S,3R,4E)-2-azido-3-O-benzoyl-4-octadecene-1,3-diol (15), gave the β-glycoside 16. Finally, 16 was transformed, via selective reduction of the azido group, coupling with octadecanoic acid, O-deacylation, and hydrolysis of the methyl ester group, into the title ganglioside 18 in good yield. 相似文献
856.
Nobuaki Kambe Akira Nishiyama Shin-Ichi Fujiwara Tsutomu Shin-Ike Noboru Sonoda 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):1001-1005
Abstract Lithium enolates of esters, amides, and an acylsilane undergo carbonylation with carbon monoxide with the aid of selenium under mild conditions to yield the corresponding selenol esters after trapping with alkyl iodides. 相似文献
857.
Jennifer Coyne Albrecht Akira Kotani Jennifer S. Lin Annelise E. Barron 《Electrophoresis》2013,34(4):590-597
We demonstrate here the power and flexibility of free‐solution conjugate electrophoresis (FSCE) as a method of separating DNA fragments by electrophoresis with no sieving polymer network. Previous work introduced the coupling of FSCE with ligase detection reaction (LDR) to detect point mutations, even at low abundance compared to the wild‐type DNA. Here, four large drag‐tags are used to achieve free‐solution electrophoretic separation of 19 LDR products ranging in size from 42 to 66 nt that correspond to mutations in the K‐ras oncogene. LDR‐FSCE enabled electrophoretic resolution of these 19 LDR‐FSCE products by CE in 13.5 min (E = 310 V/cm) and by microchip electrophoresis in 140 s (E = 350 V/cm). The power of FSCE is demonstrated in the unique characteristic of free‐solution separations where the separation resolution is constant no matter the electric field strength. By microchip electrophoresis, the electric field was increased to the maximum of the power supply (E = 700 V/cm), and the 19 LDR‐FSCE products were separated in less than 70 s with almost identical resolution to the separation at E = 350 V/cm. These results will aid the goal of screening K‐ras mutations on integrated “sample‐in/answer‐out” devices with amplification, LDR, and detection all on one platform. 相似文献
858.
Elucidation of codoping effects on the solubility enhancement of Er3+ in SiO2 glass: striking difference between Al and P codoping 总被引:1,自引:0,他引:1
Saitoh A Matsuishi S Se-Weon C Nishii J Oto M Hirano M Hosono H 《The journal of physical chemistry. B》2006,110(15):7617-7620
The codoping effect mechanism of Al and P on the solubility enhancement of Er(3+) ion in SiO(2) glass was clarified by electron spin-echo envelope modulation spectroscopy. It turned out that doped P ions preferentially coordinate to the Er(3+) ion to form a "solvation shell structure", and the environment is similar to that in phosphate glass, while doped Al ions do not form such a selective solvation structure, taking octahedral coordination. This striking difference indicates that the primary roles of the P-doping and the Al-doping are attributed to "enthalpy of mixing" and to "entropy of mixing", respectively. 相似文献
859.
Lee VY Fukawa T Nakamoto M Sekiguchi A Tumanskii BL Karni M Apeloig Y 《Journal of the American Chemical Society》2006,128(35):11643-11651
((t)Bu(2)MeSi)(2)Sn=Sn(SiMe(t)Bu(2))(2) 1, prepared by the reaction of (t)Bu(2)MeSiNa with SnCl(2)-diox in THF and isolated as dark-green crystals, represents the first example of acyclic distannene with a Sn=Sn double bond that is stable both in the crystalline form and in solution. This was proved by the crystal and NMR spectral data of 1. Distannene 1 has these peculiar structural features: a shortest among all acyclic distannenes Sn=Sn double bond of 2.6683(10) A, a nearly planar geometry around both Sn atoms, and a highly twisted Sn=Sn double bond. The reactions of 1 toward carbon tetrachloride and phenylacetylene also correspond to the reactivity anticipated for the Sn=Sn double bond. The one-electron reduction of 1 with potassium produced the distannene anion radical, the heavy analogue of alkene ion radicals, for which the particular crystal structure and low-temperature EPR behavior are also discussed. 相似文献
860.