全文获取类型
收费全文 | 3664篇 |
免费 | 189篇 |
国内免费 | 94篇 |
专业分类
化学 | 2329篇 |
晶体学 | 53篇 |
力学 | 168篇 |
综合类 | 6篇 |
数学 | 742篇 |
物理学 | 649篇 |
出版年
2024年 | 6篇 |
2023年 | 57篇 |
2022年 | 93篇 |
2021年 | 116篇 |
2020年 | 140篇 |
2019年 | 118篇 |
2018年 | 116篇 |
2017年 | 81篇 |
2016年 | 147篇 |
2015年 | 125篇 |
2014年 | 148篇 |
2013年 | 291篇 |
2012年 | 244篇 |
2011年 | 279篇 |
2010年 | 177篇 |
2009年 | 167篇 |
2008年 | 233篇 |
2007年 | 206篇 |
2006年 | 181篇 |
2005年 | 183篇 |
2004年 | 143篇 |
2003年 | 129篇 |
2002年 | 113篇 |
2001年 | 66篇 |
2000年 | 37篇 |
1999年 | 43篇 |
1998年 | 35篇 |
1997年 | 33篇 |
1996年 | 23篇 |
1995年 | 28篇 |
1994年 | 21篇 |
1993年 | 17篇 |
1992年 | 11篇 |
1991年 | 10篇 |
1990年 | 7篇 |
1989年 | 7篇 |
1988年 | 8篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 17篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1977年 | 4篇 |
1975年 | 3篇 |
1973年 | 4篇 |
1940年 | 2篇 |
排序方式: 共有3947条查询结果,搜索用时 15 毫秒
151.
Monserrat García Gerhard van Vliet Mattijs G. J. ten Cate Francisco Chvez Ben Norder Bart Kooi Werner E. van Zyl Henk Verweij Dave H. A. Blank 《先进技术聚合物》2004,15(4):164-172
Solution impregnations, pulltrusion and film stacking are widely used methods to prepare thermoplastic composite materials. Extruders are used to melt the polymer and to incorporate fibers into the polymer in order to modify physical properties. In this article, the compounding of colloidal silica nanoparticles filled polyamide‐6 (PA‐6) is achieved using a twin‐screw extruder, which has a significant market share due to its low cost and easy maintenance. The experiments were performed at 250 rpm and the bulk throughput was 6 kg h?1 with a pump pressure of 30 bars. The composites were characterized with nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). As determined by WAXD, the PA‐6 showed higher amounts of γ‐phase when compared to other synthesis methods such as in situ polymerization. TEM pictures showed that the silica particles aggregated nevertheless, upon addition of 14% (w/w) silica the E‐modulus increased from 2.7 to 3.9 GPa indicating that an effective mechanical coupling with the polymer was achieved. The behavior, illustrated with dynamic mechanical analysis (DMA) curves, indicated that in general when a filled system is compared to unfilled material, the values of the moduli (E′ and E″) increased and tan δ decreased. Determination of molecular mass distribution of the samples by means of size exclusion chromatography (SEC) coupled to a refractive index (RI), viscosity (DV) and light scattering (LS) detector revealed that the addition of silica did not decrease the average molecular weight of the polymer matrix, which is of importance for composite applications. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
152.
A modified version of the first generation unidirectional molecular motor showed >99% stereoselectivity in photo-induced isomerizations in both directions, thus functioning as a perfect chiroptical molecular switch. 相似文献
153.
Leita BA Moubaraki B Murray KS Smith JP Cashion JD 《Chemical communications (Cambridge, England)》2004,(2):156-157
The dinuclear iron(II) complex [(pypzH)(NCSe)Fe([micro sign]-pypz)(2)Fe(NCSe)(pypzH)].2H(2)O displays a single, sharp spin crossover transition between the [HS-HS] and [LS-LS] states and is structurally characterised above and below the T(1/2)= 225 K value 相似文献
154.
Peña D López F Harutyunyan SR Minnaard AJ Feringa BL 《Chemical communications (Cambridge, England)》2004,(16):1836-1837
Highly enantioselective Cu-catalysed 1,4-addition of diphenylzinc to cyclohexenone has been achieved for the first time using a monodentate phosphoramidite ligand. 相似文献
155.
Ignatov SK Rees NH Tyrrell BR Dubberley SR Razuvaev AG Mountford P Nikonov GI 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):4991-4999
The titanocene silyl hydride complexes [Ti(Cp)2(PMe3)(H)(SiR3)] [SiR3=SiMePhCl (6), SiPh2Cl (7), SiMeCl2 (8), SiCl3 (9)] were prepared by HSiR3 addition to [Ti(Cp)2(PMe3)2] and were studied by NMR and IR spectroscopy, X-ray diffraction (for 6, 8, and 9), and DFT calculations. Spectroscopic and structural data established that these complexes exhibit nonclassical Ti-H-Si-Cl interligand hypervalent interactions. In particular, the observation of silicon-hydride coupling constants J(Si,H) in 6-9 in the range 22-40 Hz, the signs of which we found to be negative for 8 and 9, is conclusive evidence of the presence of a direct Si-H bond. The analogous reaction of [Ti(Cp)2(PMe3)2] with HSi(OEt)3 does not afford the expected classical silyl hydride complex [Ti(Cp)2(PMe3)(H)[Si(OEt)3]], and instead NMR-silent titanium (apparently TiIII) complex(es) and the silane redistribution product Si(OEt)4 are formed. The structural data and DFT calculations for the compounds [Ti(Cp)2(PMe3)(H)(SiR3)] show that the strength of interligand hypervalent interactions in the chlorosilyl complexes decreases as the number of chloro groups on silicon increases. However, in the absence of an Si-bound electron-withdrawing group trans to the Si-H moiety, a silane sigma complex is formed, characterized by a long Ti-Si bond of 2.658 A and short Si-H contact of 1.840 A in the model complex [Ti(Cp)2(PMe3)(H)(SiMe3)]. Both the silane sigma complexes and silyl hydride complexes with interligand hypervalent interactions exhibit bond paths between the silicon and hydride atoms in Atoms in Molecules (AIM) studies. To date a classical titanocene phosphane silyl hydride complex without any Si-H interaction has not been observed, and therefore titanocene silyl hydrides are, depending on the nature of the R groups on Si, either silane sigma complexes or compounds with an interligand hypervalent interaction. 相似文献
156.
Structure of microemulsions with gemini surfactant studied by solvatochromic probe and diffusion NMR
Ben Moshe M Magdassi S Cohen Y Avram L 《Journal of colloid and interface science》2004,276(1):221-226
The structure of microemulsions prepared by the anionic gemini surfactant didodecyl diphenyl ether disulfonate (C12-DADS) was investigated by a solvatochromic probe and nuclear magnetic resonance (NMR) diffusion measurements. The NMR measurements indicate the presence of bicontinuous and oil-in-water microemulsions depending on microemulsion composition. The absorbance spectra of the solvatochromic probe, Nile red, indicate the solubilization of the probe in different sites, in agreement with the NMR findings. It was also found that the microemulsions were capable of dissolving the hydrophobic probe, Nile red, up to four times better than expected if it were simply dissolved in the toluene phase. 相似文献
157.
Tuttolomondo ME Fernández LE Navarro A Varetti EL Altabef AB 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):611-619
The infrared spectra of 2,2,2-trifluoroethyl trifluoromethanesulfonate (CF3SO2OCH2CF3) were obtained in the gaseous, liquid and solid states as well as the Raman spectrum of the liquid. Quantum chemistry calculations using the density functional theory were used to predict the most stable geometry and conformation of the studied molecule. Subsequently, the harmonic vibrational frequencies and force field were calculated. An assignment of the observed spectral features made after comparison with the related molecules and with the predicted frequencies was used as the basis of a scaling of the original force field in order to reproduce as well as possible the experimental frequencies. With this purpose a set of scale factors was calculated by a least square procedure, leading to a final root mean square deviation (RMSD) of 9.7 cm(-1). 相似文献
158.
In a follow-up of the earlier characterisation of botulinum toxins type A and B (BTxA and BTxB) by mass spectrometry (MS), types C, D, E, and F (BTxC, BTxD, BTxE, BTxF) were now investigated. Botulinum toxins are extremely neurotoxic bacterial toxins, likely to be used as biological warfare agent. Biologically active BTxC, BTxD, BTxE, and BTxF are comprised of a protein complex of the respective neurotoxins with non-toxic non-haemagglutinin (NTNH) and, sometimes, specific haemagglutinins (HA). These protein complexes were observed in mass spectrometric identification. The BTxC complex, from Clostridium botulinum strain 003-9, consisted of a 'type C1 and D mosaic' toxin similar to that of type C strain 6813, a non-toxic non-hemagglutinating and a 33 kDa hemagglutinating (HA-33) component similar to those of strain C-Stockholm, and an exoenzyme C3 of which the sequence was in full agreement with the known genetic sequence of strain 003-9. The BTxD complex, from C. botulinum strain CB-16, consisted of a neurotoxin with the observed sequence identical with that of type D strain BVD/-3 and of an NTNH with the observed sequence identical with that of type C strain C-Yoichi. Remarkably, the observed protein sequence of CB-16 NTNH differed by one amino acid from the known gene sequence: L859 instead of F859. The BTxE complex, from a C. botulinum isolated from herring sprats, consisted of the neurotoxin with an observed sequence identical with that from strain NCTC 11219 and an NTNH similar to that from type E strain Mashike (1 amino acid difference with observed sequence). BTxF, from C. botulinum strain Langeland (NCTC 10281), consisted of the neurotoxin and an NTNH; observed sequences from both proteins were in agreement with the gene sequence known from strain Langeland. As with BTxA and BTxB, matrix-assisted laser desorption/ionisation (MALDI) MS provided provisional identification from trypsin digest peptide maps and liquid chromatography-electrospray (tandem) mass spectrometry (LC-ES MS) afforded unequivocal identification from amino acid sequence information of digest peptides obtained in trypsin digestion. 相似文献
159.
160.
Ben Shi Ning Ren Luyan Gu Ge Xu Rongchen Wang Tianli Zhu Ying Zhu Chunhai Fan Chunchang Zhao He Tian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(47):16982-16986
NIR light responsive nanoplatforms hold great promise for on‐demand drug release in precision cancer medicine. However, currently available systems utilize “always‐on” photothermal transducers that lack target specificity, and thus inaccurately differentiate tumors from normal tissues. Developed here is a theranostic nanoplatform featuring H2S‐mediated in situ production of NIR photothermal agents for imaging‐guided and photocontrolled drug release. The system targets H2S‐rich cancers. This nanoplatform shows H2S‐activatable NIR‐II emission and NIR light controllable release of the drug Camptothecin‐11. Upon administering the system to HCT116 tumor‐bearing mice, the tumor is greatly suppressed with minimal side effects, arising from the synergy of the cancer‐specific and NIR light activated therapy. This theranostic nanoplatform thus sheds light on precision medicine with guidance through NIR‐II imaging. 相似文献