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151.
Kruk M Dufour B Celer EB Kowalewski T Jaroniec M Matyjaszewski K 《The journal of physical chemistry. B》2005,109(19):9216-9225
Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs. 相似文献
152.
The influence of spent catalyst from catalytic cracking in fluidized bed on the hydration process of cement and the properties
of cement mortars were studied. The spent catalyst was used as an additive to cement in the mortars (10 and 20% of cement).
The samples of mortars kept in water for28 days, then they were placed in sulfate and chloride media for 2 months (the control
samples were kept in water for 3 months). After this time they were subjected to bending strength and compressive strength
determinations. Thermogravimetric and infrared absorption studies were performed and capillary elevation, capability of binding
heavy metals, and changes in mass and apparent density were determined too. The studies disclosed the pozzolana nature of
spent catalyst and its influence on cement mortars being in contact with corrosive media.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
153.
Addition of a phenyl Grignard reagent to a toluene solution of the nickel(II) chloride complex of a dimethylated inverted porphyrin, (2-NCH3-21-CH3CTPP)NiIICl (1), at 203 K results in the formation of a rare paramagnetic (sigma-phenyl)nickel(II) species, (2-NCH3-21-CH3CTPP)NiIIPh (2). The coordination of the sigma-phenyl in 2 is determined by a unique pattern of three sigma-phenyl resonances (ortho 375.0 ppm; meta 108.94 ppm; para 35.68 ppm (at 283 K)) in the 1H NMR and 2H NMR spectra. The (sigma-phenyl)nickel(II) compound 2 is in the high-spin ground electronic state (dxy)2(dxz)2(dyz)2(dz2)1(dx2-y2)1, as confirmed by similarity of the NMR spectra of the equatorial ligand in 1 and 2. Titration of 1 with phenyllithium produces (2-NCH3-21-CH3CTPP)NiIIPh (2). One-electron reduction with excess PhLi yields [(2-NCH3-21-CH3CTPP)NiIIPh]- (3), which can be also generated by independent routes, e.g., by reduction of (2-NCH3-21-CH3CTPP)NiIIPh using lithium triethylborohydride or tetrabutylammonium borohydride. The spectroscopic data indicate that (2-NCH3-21-CH3CTPP)NiIIPh (2) undergoes one-electron reduction without a substantial disruption of the molecular geometry. The presence of two paramagnetic centers in 3, i.e., the high-spin nickel(II) and the carbaporphyrin anion radical, produces remarkable variations in a spectral patterns, such as the upfield and downfield positions of pyrrole resonances (103.78, 96.66, -25.35, -50.97, -92.15, -114.83 ppm (at 253 K)) and sign alternations of the meso-phenyl resonances (ortho -77.81, -79.34 ppm; meta 48.77, 48.04 ppm; para -85.65, -86.46 ppm (at 253 K)). A single species, 4, is detected in the 1H NMR titration of 1 with n-butyllithium. The formation of one- or two-electron-reduced species, [(2-NCH3-21-CH3CTPP)NiBu]- or [(2-NCH3-21-CH3CTPP)NiBu]2-, respectively, is considered to account for the spectroscopic properties of 4 (pyrrole 17.33, 15.45, -5.79, -7.74, -14.62, -58.14 ppm; 21-CH3 3 ppm (at 203 K)). The temperature dependence of the hyperfine shifts of 4 demonstrates pronounced anti-Curie behavior, interpreted in terms of a temperature-dependent spin equilibrium between diamagnetic and paramagnetic states with diamagnetic properties approached as the temperature is lowered. Warming of 2-4 results in complete decomposition via homolytic/heterolytic cleavage of an axial nickel-apical carbon bond. In the case of 2 or 3, the process yields a mixture of two compounds, 5 and 6, which are detected by EPR spectroscopy, demonstrating the anisotropy of the g tensor (5, g1 = 2.237, g2 = 2.092, g3 = 2.090; 6, g1 = 2.115, g2 = 2.030, g3 = 1.940 (in frozen toluene solution at 77 K)). 相似文献
154.
Cationic polymerization of 1,4,6-trioxaspiro [4,4]-nonane ( 1 ) with (CH3)3O+SbF6?(2) and CH3OSO2CF3(3) initiators has been investigated. Although the observed rates of initiation and propagation are relatively slow, they consist of rapid reversible elementary reactions. In 1H-NMR spectra, a broadening of the monomer signal was observed, indicating a fast exchange between “free” monomer and monomer engaged in the active species. The variety of orthoester bonds were observed in the polymer formed at the early stages of monomer conversion. The final polymer has, however, structure of a linear poly(ester–ether) including two subsequent ester or ether linkages. To account for these new facts, the mechanism of polymerization was proposed, consisting of a rapid reversible opening of one of the rings in the monomer molecule involved in the growing species, followed by the slower opening of the second ring with formation of the ester linkages. It appears that the rings originally present in the chains rearrange into the linear units intramolecularly. 相似文献
155.
Alicja Wawrzynów Adam Liwo Ewa Kaczmarczyk Lech Chmurzyński 《Journal of solution chemistry》1998,27(5):463-472
Cationic heteroconjugation equilibria of more than ninety systems consisting of substituted pyridines, their N-oxides, and trimethylamine N-oxide, i. e., in systems with mixed hydrogen bridges of type OHN+ (NHO+) were studied in propylene carbonate. Both experimental systems without proton transfer, BH+/B1, and those with proton transfer, B1H+/B, were explored. The stability of the mixed hydrogen bridges, OHN+ (NHO+), is compared with that of the OHC+-type bridges. The influence of the difference in basicity of the conjugate base of the proton donor and the proton acceptor on the presence of the proton transfer equilibria, and, consequently, the possibility of determination of the cationic heteroconjugation constant values is discussed. 相似文献
156.
This work was done while the second author visited Toru. This research was partially supported by the Polish Scientific Grant KBN No. 1222/2/91 相似文献
157.
Krzysztof Ciesielski 《Periodica Mathematica Hungarica》1995,31(1):11-20
In the paper we prove that the complex analytic functions are (ordinarily) density continuous. This stays in contrast with the fact that even such a simple function asG:22,G(x,y)=(x,y
3
), is not density continuous [1]. We will also characterize those analytic functions which are strongly density continuous at the given pointa . From this we conclude that a complex analytic functionf is strongly density continuous if and only iff(z)=a+bz, wherea, b andb is either real or imaginary. 相似文献
158.
Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by1H and13C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.
Die räumliche Struktur von Methylierungsprodukten des Multiflorins
Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (1H und13C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.相似文献
159.
The153/151Eu isotope separation factor (q) for the Eu(II)/Eu(III) chemical exchange in the liquid-liquid extraction system, containing Eu (III) in di (2-ethylhexyl) phosphoric acid (HDEHP) and Eu(II) in water acidified with hydrochloric acid, was found to be 0.9993±0.0002 (2) for the single stage. Some theoretical aspects of separation of the Eu isotopes are discussed. The decisive role of the electron exchange reaction and complexation by the counter-ion in the aqueous phase is emphasized. 相似文献
160.
A. Baranowski M. Dębowska K. Jerie J. Rudzińska-Girulska Z. Paweŀka R. T. Sikorski 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):463-467
Results of angular correlation of annihilation radiation (ACAR) and positron annihilation lifetime (PAL) measurements are presented for five styrene copolymers: poly(co-styrene-phenylmaleimide) and its three derivatives with chlorine as well as for one with the OH group substituted at the benzene ring. It occurs that the chlorine substituted at three different positions at the benzene ring poly(co-styrene-o (or-m,-p)-chlorophenylmaleimide) inhibits the formation of the positronium to different extent. The greatest effect is observed in case of the chlorine atom substituted at the benzene ring at the ortho-position towards the nitrogen atom. The two long lifetimes (3 and 4) observed in the lifetime spectra are connected with the bimodal distributions of the free volume radius in the samples. 相似文献