全文获取类型
收费全文 | 1082篇 |
免费 | 31篇 |
国内免费 | 7篇 |
专业分类
化学 | 810篇 |
晶体学 | 12篇 |
力学 | 22篇 |
数学 | 91篇 |
物理学 | 185篇 |
出版年
2023年 | 8篇 |
2022年 | 13篇 |
2021年 | 10篇 |
2020年 | 9篇 |
2019年 | 13篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 17篇 |
2015年 | 21篇 |
2014年 | 25篇 |
2013年 | 65篇 |
2012年 | 57篇 |
2011年 | 59篇 |
2010年 | 38篇 |
2009年 | 28篇 |
2008年 | 66篇 |
2007年 | 82篇 |
2006年 | 67篇 |
2005年 | 73篇 |
2004年 | 52篇 |
2003年 | 58篇 |
2002年 | 54篇 |
2001年 | 12篇 |
2000年 | 18篇 |
1999年 | 20篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 4篇 |
1989年 | 11篇 |
1988年 | 5篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 22篇 |
1983年 | 8篇 |
1982年 | 12篇 |
1981年 | 16篇 |
1980年 | 13篇 |
1979年 | 9篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1973年 | 5篇 |
1972年 | 3篇 |
排序方式: 共有1120条查询结果,搜索用时 218 毫秒
91.
Tobe M Isobe Y Tomizawa H Nagasaki T Aoki M Negishi T Hayashi H 《Chemical & pharmaceutical bulletin》2003,51(9):1109-1112
We investigated the chemical modifications of the nitroquinazoline derivative (1) through the replacement of the NH group at the C(4)-position with several N-alkyl groups to increase the lipophilicity at the C(4)-position. Among them, we found that the N-methyl analogue (5a) showed a 2-fold loss in the inhibitory activity toward tumor necrosis factor-alpha (TNF-alpha) production in vitro as compared with the NH analogue (1); however, 5a exhibited an oral inhibitory activity on TNF-alpha production with an ED50 value of 26 mg/kg, whereas 1 did not. Moreover, the oral bioavailability of 5a was higher than that of 1 (1, F=1%; 5a, F=21%), and the calculated ClogP value for 5a was higher than that for 1. These results suggest that the improved lipophilicity of 5a compared with that of 1 reflects its greater inhibitory activity on TNF-alpha production in vivo as well as oral bioavailability. 相似文献
92.
Synthesis of single-wall carbon nanotubes (SWNTs) was carried out by an ablation method using a XeCl excimer laser. It was irradiated onto a graphite target containing Co and Ni at the temperatures of 1073, 1173, 1273, 1373, 1473, 1523 and 1623 K under the atmosphere (0.1 MPa) of Ar gas with the flow rate of 12 ml/min. The measurement by a scanning/transmission electron microscope and Raman spectroscopy found the formation of SWNTs with the diameter of about 1.3 nm and the length of about 2 μm in ablated carbonaceous soot. The ratio of peak intensity of 1590 cm−1 (G band) to that of 1335 cm−1 (D band) in the high frequency Raman spectra increased with increasing the ambient temperature. The radial breathing mode (RBM) in the low frequency Raman spectra shows that the mean diameter of SWNTs increased with increasing the ambient temperature. 相似文献
93.
Yoshiaki Tanaka Tatsuo Fujii Yoshihiro Kusano Yasunori Ikeda 《Solid State Communications》2007,141(3):122-126
Single-phases of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites with various Pb concentrations have been synthesized and the Pb-substitution effects on the structural, electrical and magnetic properties have been systematically investigated. Powder X-ray diffraction analysis showed that the single-phases of Bi1.8−x/2PbxCa2Co2Oz were obtained up to x=0.6-0.7 under the optimized synthesis conditions. The lattice parameters of Bi1.8−x/2PbxCa2Co2Oz continuously changed with increasing Pb concentration. The electron diffraction analysis suggested that the structure consisted of two different sublattices with a rock salt structure (RS) and a hexagonal CdI2 structure (H), respectively, without modulation. In combined with the chemical composition analysis, the chemical formulas of the x=0 and x=0.6 samples were determined approximately as [Bi1.74Co0.31Ca2.01O4]RS[CoO2]1.69 and [Bi1.47Pb0.38Co0.29Ca1.98O4]RS[CoO2]1.71, respectively. The electrical resistivity became more metallic with increasing the Pb concentration up to x=0.6. Moreover, the Pb-substitution simultaneously increased the antiferromagnetic Weiss temperatures and decreased the effective magnetic moments of the Co ions. 相似文献
94.
95.
Asahi Motoshige Yasuteru Mawatari Yoshiaki Yoshida Chigusa Seki Haruo Matsuyama Masayoshi Tabata 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3008-3015
Polymerization of p‐n‐hexyloxyphenylacetylene (pHPA) by using a [Rh(norbornadine)Cl]2‐triethylamine catalyst was carried out at room temperature to afford stereoregular helical poly(p‐n‐hexyloxyphenylacetylene)s (PpHPAs). When ethanol and n‐hexane were used as polymerization solvents, a bright yellow PpHPAs, poly( Y ) with Mn = 8.5 × 104 and its purple red polymer, poly( R ) with Mn = 5.3 × 104 were obtained in 95% yields and 84% yields, respectively. Diffuse reflective UV–vis spectra of poly( Y ) and poly( R ) in solid phase showed different broad absorption peaks at 445 and 575 nm, respectively. X‐Ray diffraction patterns of poly( Y ) and poly( R ) showed typical columnar structures assignable to cis‐transoid and cis‐cisoid structures, respectively, which were also supported by molecule mechanics calculation. Poly( Y ) was irreversibly transformed to a reddish‐black polymer, poly( Y‐B ), which columnar diameter was nearly the same as that of poly( R ). Further, poly( Y ) showed an exothermic peak in the differential scanning calorimetry trace at 80 °C for 1 h in N2 gas. Thus, these findings suggest a thermally irreversible rearrangement from an unstable cis‐transoid form, poly( Y ) with a stretched cis‐transoid helix to a stable cis‐cisoid form, poly( R ), with a contracted cis‐cisoid helix in the solid phase to give poly( Y → B ) with the cis‐cisoid form. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
96.
The charmonium and bottomonium mass spectra are investigated systematically in potential nonrelativistic QCD with the heavy quark potential computed by lattice QCD simulations nonperturbatively. The potential consists of a static potential and relativistic corrections classified in powers of the inverse of heavy quark mass m, and the effects of the O(1/m) correction, the O(1/m 2) spin–orbit and spin–tensor corrections on the mass spectra are examined systematically. The pattern of the mass spectra is found to be in fairly good agreement with the experimental data, in which the O(1/m) correction gives an important contribution. 相似文献
97.
Tetsuya Yuasa Shinji Tanosaki Yoshiaki Sasaki Michiaki Takagi Akira Ishikawa Hiroshi Taniguchi Balasigamani Devaraj Takao Akatsuka 《Analytical sciences》2002,18(12):1329-1333
The coherent detection imaging (CDI) method uses the optical heterodyne detection technique. CW and single frequency lasers having long coherence lengths are used to exploit the maximum advantages of heterodyne detection, such as high directionality, selectivity and sensitivity. The CDI method based on optical heterodyne detection enables selective filtering of the directional coherence-retaining emergent photons, which leads to image reconstruction from projections, similar to X-ray computed tomography (CT). So far we have demonstrated the advantages and capabilities of the measurement technique for transillumination optical computed tomography in biomedicine. Here, we investigate the fundamental imaging properties of CDI method, such as its high directionality and quantitativeness, with preliminary physical phantom experiments. The results show that the CDI method satisfies the requirements for CT reconstruction under the first order approximation, and enables quantitative measurements in the sense that the relationship between estimated and actual concentration retains a satisfactory linearity. 相似文献
98.
Kazuhiko Kandori Kazunao Hayashi Masaki Matsukawa Masao Fukusumi Yoshiaki Morisada 《Colloid and polymer science》2010,288(10-11):1071-1079
The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl3 solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) x –(PPO) y –(PEO) x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) x –(PEO) y –(PPO) x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N2 adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h~3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles. 相似文献
99.
Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane gave zinc alkoxides of cis-5,6-dialkylcyclohepta-3,7-diene-1,3-diol in good yields at room temperature. The reaction proceeded with high stereospecificity. Bis(iodozincio)methane converted the diketone into the cis-divinylcyclopropane-1,2-diol stereoselectively; this diol transformed into the corresponding cycloheptane derivative stereospecifically via Cope rearrangement. 相似文献
100.
Kanyiva KS Kashihara N Nakao Y Hiyama T Ohashi M Ogoshi S 《Dalton transactions (Cambridge, England : 2003)》2010,39(43):10483-10494
A combination of Ni(cod)(2) and PCyp(3) is found to be an effective catalyst for chemoselective activation of the C-H bond of fluoroarenes over C-F bonds followed by insertion of alkynes to allow direct alkenylation of the electron-deficient arenes. The characteristics of the reactions are: a C-H bond ortho to a fluorine substituent is selectively activated; the reactivity of fluorobenzenes is roughly proportional to the number of fluorine atoms. The reaction conditions tolerate a broad range of both alkynes and fluoroarenes containing both electron-withdrawing and -donating groups, thus allowing efficient synthesis of a variety of substituted ethenes containing a fluoroaryl motif in high regio- and stereoselective manners. Mechanistic studies including both labeling experiments and stoichiometric reactions reveal that oxidative addition of C-H bonds in fluoroarenes to nickel(0) is kinetically highly facile whereas that of C-F bonds is thermodynamically favoured. 相似文献