全文获取类型
收费全文 | 42143篇 |
免费 | 9691篇 |
国内免费 | 1408篇 |
专业分类
化学 | 46342篇 |
晶体学 | 377篇 |
力学 | 539篇 |
数学 | 2730篇 |
物理学 | 3254篇 |
出版年
2023年 | 82篇 |
2022年 | 149篇 |
2021年 | 391篇 |
2020年 | 1405篇 |
2019年 | 2723篇 |
2018年 | 1151篇 |
2017年 | 773篇 |
2016年 | 3560篇 |
2015年 | 3701篇 |
2014年 | 3617篇 |
2013年 | 4459篇 |
2012年 | 3455篇 |
2011年 | 2754篇 |
2010年 | 3153篇 |
2009年 | 3064篇 |
2008年 | 2852篇 |
2007年 | 2282篇 |
2006年 | 1870篇 |
2005年 | 2035篇 |
2004年 | 1744篇 |
2003年 | 1596篇 |
2002年 | 2215篇 |
2001年 | 1509篇 |
2000年 | 1406篇 |
1999年 | 417篇 |
1998年 | 89篇 |
1997年 | 70篇 |
1996年 | 87篇 |
1995年 | 72篇 |
1994年 | 53篇 |
1993年 | 74篇 |
1992年 | 54篇 |
1991年 | 34篇 |
1990年 | 36篇 |
1989年 | 19篇 |
1988年 | 22篇 |
1987年 | 29篇 |
1986年 | 26篇 |
1985年 | 33篇 |
1984年 | 32篇 |
1983年 | 28篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 14篇 |
1977年 | 11篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 281 毫秒
901.
Manuel Cano Beatriz Palenzuela J. Luis Ávila Rafael Rodríguez‐Amaro 《Electroanalysis》2007,19(9):973-977
A PVC/TTF‐TCNQ composite electrode has been employed as detector in a flow injection system. The proposed method allows the simultaneous detection of ascorbic acid (AA) and uric acid (UA) in mixtures by using a FIA system in a simple manner, without pre‐treatment or modified electrode. This method is based on the amperometric determination of (a) ascorbic acid at 0.15 V and (b) both analytes at 0.35 V, being the response linear in the range 1×10?2–4×10?4 M for both analytes with detection limits (S/N=3) of 1.2×10?4 M and 8.1×10?5 M for AA and UA, respectively. 相似文献
902.
Two new uncommon nitrogenous sesquiterpenes, 11‐ethoxy‐3‐formamidotheonellin ( 1 ) and 7‐ethoxy‐3‐formamidobisabolane‐8,10‐diene ( 2 ), together with two known related sesquiterpenes, 3‐formamidotheonellin (=theonellin formamide; 3 ) and theonellin isothiocyanate ( 4 ), were isolated from the Hainan sponge Axinyssa aff. variabilis. Their structures were determined on the basis of extensive spectroscopic analysis and by comparison of their NMR data with those of known compounds. 相似文献
903.
This work was aimed at understanding the structure of SiO2–MO2 (M = Ti, Zr, Hf) and SiO2–HfO2–MO2 (M = Ti, Zr) materials, used as mixed oxide glass hosts for Er3+ ions in the fabrication of optical planar waveguides by sol-gel processing. This structural study was performed by Waveguide
Raman Spectroscopy (WRS), complemented with X-ray diffraction (XRD). The admixture of TiO2 to HfO2, SiO2–HfO2 and HfO2–ZrO2 compositions was found to cause precipitation of nanocrystals of tetragonal HfO2 or ZrO2, or the formation of hafnia-titania mixed crystals, depending on the HfO2/TiO2 molar ratio. 相似文献
904.
Zhan‐Xin Zhang Wei‐Dong Xie Ping‐Lin Li Yan‐Ping Shi Zhong‐Jian Jia 《Helvetica chimica acta》2006,89(12):2927-2933
Six new compounds were isolated from the whole plant of Sonchus uliginosus, including three eudesmane‐type sesquiterpenoids (1β,6α)‐1,6,14‐trihydroxyeudesm‐3‐en‐12‐oic acid γ‐lactone ( 1 ), (1β,6α)‐1,6,14‐trihydroxyeudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 2 ), and (1β,6α)‐1,6‐dihydroxy‐14‐O‐[(4‐hydroxyphenyl)acetyl]eudesma‐3,11(13)‐dien‐12‐oic acid γ‐lactone ( 3 ), and three phenylpropane derivatives, 4‐hydroxy‐γ,3,5‐trimethoxybenzenepropanol ( 6 ), γ,3,4,5‐tetramethoxybenzenepropanol ( 7 ), and γ,3,4,5‐tetramethoxybenzenepropanol acetate ( 8 ), together with the two known compounds 4 and 5 . The new structures were elucidated by means of spectroscopic methods, such as IR, EI‐MS, HR‐ESI‐MS, 1D‐ and 2D‐NMR, and by comparison of the spectroscopic data with those reported for structurally related compounds. 相似文献
905.
The isolation and identification of twenty‐one components (including four new triterpenoid saponins and one new triterpenoid acid) from the root of Rhaponticum uniflorum (L.) DC. (Compositae) are described. Their structures were determined on the basis of spectral analysis and chemical trans formation. The new compounds were identified as 3‐O‐α‐L‐arabinopyranosyl‐urs‐12,18(19)‐dien‐28‐oic acid β‐D‐glucopyranosyl ester, 3β‐ hydroxyurs‐12,18(19)‐dien‐28‐oic acid β‐D‐glucopyranosyl ester, 3β‐hydroxyurs‐12,19(29)‐dien‐28‐oic acid β‐D‐glucopyranosylester, 3‐O‐α‐L‐arabinopyranosyl‐urs‐9(11),12‐dien‐28‐oic acid β‐D‐glucopyranosyl ester and 2 α,3 α, 19α,25‐tetrahydroxyurs‐12‐en‐23,28‐dioic acid. 相似文献
906.
Ju‐Yeon Lee Eun‐Ju Park 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1742-1748
Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate ( 3 ) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate ( 2 ). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4 – 6 containing the nonlinear optical chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4 – 6 were soluble in common organic solvents such as acetone and dimethylformamide. Polymers 4 – 6 indicated thermal stability up to 300 °C in thermogravimetric thermograms with glass‐transition temperature values obtained from differential scanning calorimetric thermograms in the range of 78–102 °C. The second‐harmonic generation coefficients (d33) of the poled polymer films were around 6.9 × 10?9 esu. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1742–1748, 2002 相似文献
907.
A. Jeyabharathi M. N. Ponnuswamy S. Nanjundan Hoong‐Kun Fun Suchada Chantrapromma Anwar Usman Ibrahim Abdul Razak 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):o26-o28
Chalcones (α,β‐unsaturated ketones) are effective antitumour agents. It has been proved that having halogen or methoxy groups substituted in various positions of the phenyl ring enhances the activity of chalcones many times. The title compounds, C21H20O5 and C19H15BrO3, respectively, were chosen for crystallographic study in order to determine their structures and conformations. In both compounds, the keto group is in the s‐cis conformation and is almost planar. There are weak intramolecular interactions in both structures. 相似文献
908.
Iris A. Bermejo Claudio D. Navo Jorge Castro-Lpez Ana Guerreiro Ester Jimnez-Moreno Elena M. Snchez Fernndez Fayna García-Martín Hiroshi Hinou Shin-Ichiro Nishimura Jos M. García Fernndez Carmen Ortiz Mellet Alberto Avenoza Jesús H. Busto Gonalo J. L. Bernardes Ramn Hurtado-Guerrero Jesús M. Peregrina Francisco Corzana 《Chemical science》2020,11(15):3996
The Tn antigen (GalNAc-α-1-O-Thr/Ser) is a well-known tumor-associated carbohydrate determinant. The use of glycopeptides that incorporate this structure has become a significant and promising niche of research owing to their potential use as anticancer vaccines. Herein, the conformational preferences of a glycopeptide with an unnatural Tn antigen, characterized by a threonine decorated with an sp2-iminosugar-type α-GalNAc mimic, have been studied both in solution, by combining NMR spectroscopy and molecular dynamics simulations, and in the solid state bound to an anti-mucin-1 (MUC1) antibody, by X-ray crystallography. The Tn surrogate can mimic the main conformer sampled by the natural antigen in solution and exhibits high affinity towards anti-MUC1 antibodies. Encouraged by these data, a cancer vaccine candidate based on this unnatural glycopeptide and conjugated to the carrier protein Keyhole Limpet Hemocyanin (KLH) has been prepared and tested in mice. Significantly, the experiments in vivo have proved that this vaccine elicits higher levels of specific anti-MUC1 IgG antibodies than the analog that bears the natural Tn antigen and that the elicited antibodies recognize human breast cancer cells with high selectivity. Altogether, we compile evidence to confirm that the presentation of the antigen, both in solution and in the bound state, plays a critical role in the efficacy of the designed cancer vaccines. Moreover, the outcomes derived from this vaccine prove that there is room for exploring further adjustments at the carbohydrate level that could contribute to designing more efficient cancer vaccines.An anti-cancer vaccine based on an unnatural antigen with an sp2-iminosugar fragment. 相似文献
909.
Crystalline samples of La3Ni2B2N3 were synthesized using solid state metathesis reactions from combinations of La, LaCl3, NiCl2 together with Li3BN2. The structure was determined by single crystal X‐ray diffraction (I4/mmm (No. 139), a = 372.95(2) pm, c = 2056.3(2) pm, R1 = 0.027, wR2 = 0.062) and confirmed earlier results from neutron powder diffraction. La3Ni2B2N3 contains BN units capping square planar Ni layers. Isolated nitrogen atoms reside in La6 octahedra. Magnetic measurements on several bulk samples exhibit superconductivity at temperatures below 14.6 K. 相似文献
910.
A new triterpenoid, fornicatin C (= (3β)‐3‐hydroxy‐18(13 → 12β)‐abeo‐lanosta‐13(17),24‐dien‐18‐oic acid; 1 ), was isolated from the fruiting bodies of Ganoderma fornicatum, together with the known compounds fornicatin A ( 2 ) and fornicatin B ( 3 ), among other constituents. The structure of 1 was elucidated by means of spectroscopic techniques, and those of 2 and 3 were identified by comparing their spectroscopic data with those reported in the literature. 相似文献