全文获取类型
收费全文 | 7477篇 |
免费 | 230篇 |
国内免费 | 48篇 |
专业分类
化学 | 5524篇 |
晶体学 | 71篇 |
力学 | 175篇 |
综合类 | 1篇 |
数学 | 792篇 |
物理学 | 1192篇 |
出版年
2023年 | 33篇 |
2022年 | 31篇 |
2021年 | 62篇 |
2020年 | 97篇 |
2019年 | 115篇 |
2018年 | 85篇 |
2017年 | 58篇 |
2016年 | 154篇 |
2015年 | 142篇 |
2014年 | 145篇 |
2013年 | 323篇 |
2012年 | 447篇 |
2011年 | 548篇 |
2010年 | 264篇 |
2009年 | 221篇 |
2008年 | 465篇 |
2007年 | 540篇 |
2006年 | 530篇 |
2005年 | 508篇 |
2004年 | 475篇 |
2003年 | 367篇 |
2002年 | 332篇 |
2001年 | 117篇 |
2000年 | 82篇 |
1999年 | 84篇 |
1998年 | 88篇 |
1997年 | 65篇 |
1996年 | 92篇 |
1995年 | 85篇 |
1994年 | 75篇 |
1993年 | 52篇 |
1992年 | 55篇 |
1991年 | 56篇 |
1990年 | 51篇 |
1989年 | 48篇 |
1988年 | 45篇 |
1987年 | 37篇 |
1986年 | 39篇 |
1985年 | 64篇 |
1984年 | 66篇 |
1983年 | 57篇 |
1982年 | 61篇 |
1981年 | 57篇 |
1980年 | 59篇 |
1979年 | 52篇 |
1978年 | 66篇 |
1977年 | 54篇 |
1976年 | 49篇 |
1975年 | 37篇 |
1974年 | 32篇 |
排序方式: 共有7755条查询结果,搜索用时 302 毫秒
71.
Dario Braga Fabrizia Grepioni Paul J. Dyson Brian F. G. Johnson 《Journal of Cluster Science》1992,3(3):297-311
The molecular and crystal structures of a number of ruthenium and osmium clusters of nuclearity between three and six containing arene fragments such as C6H6, C6H3Me3, C6H4Me2 and C6H5Me have been investigated. Attention has been focused on the relationship between the terminal (
6-coordination) and face-capping (
3:
2:
2:
2-coordination) bonding modes. Empirical packing potential energy calculations have been employed to investigate the intermolecular organization in the crystal. It has been shown that the arene fragments in mono-arene clusters form ribbons, while in bis-arene clusters graphitic-like interactions throughout the crystal are established. The factors controlling the ease of arene reorientational motion in the solid state has also been investigated in relation to the shape, size and geometry of the molecules and of their interlocking modes. 相似文献
72.
The interaction of solvent with a polypeptide chain is one of the primary factors controlling protein folding and stability. In biologically relevant systems, this solvent is most often water. Experimental estimates of the role of water in peptide folding can be obtained from solvent perturbation experiments. The simplest perturbant for H2O water is its isotopic D2O form. The solvation of peptides known to form PII helices with D2O versus H2O increases their propensity to adopt the PII conformation. 相似文献
73.
Plumb RS Stumpf CL Gorenstein MV Castro-Perez JM Dear GJ Anthony M Sweatman BC Connor SC Haselden JN 《Rapid communications in mass spectrometry : RCM》2002,16(20):1991-1996
The application of liquid chromatography/mass spectrometry (LC/MS) followed by principal components analysis (PCA) has been successfully applied to the screening of rat urine following the administration of three candidate pharmaceuticals. With this methodology it was possible to differentiate the control samples from the dosed samples and to identify the components of the mass spectrum responsible for the separation. These data clearly show that LC/MS is a viable alternative, or complementary, technique to proton NMR for metabonomics applications in drug discovery and development. 相似文献
74.
Field-portable, high-speed GC/TOFMS 总被引:1,自引:0,他引:1
Syage JA Nies BJ Evans MD Hanold KA 《Journal of the American Society for Mass Spectrometry》2001,12(6):648-655
This work is focused on developing a fast gas chromatograph, time-of-flight mass spectrometer (GC/TOFMS) for man-portable field use. The goal is to achieve a total system solution for meeting performance, size, weight, power, cost, and ruggedness requirements for a laboratory in the field. The core technology will also be adaptable to specific applications including real-time point detection for hazardous chemical releases (e.g., chemical weapons), for biological agent signature identification, and for mobile monitoring platforms (e.g., air, ship, truck). Previously we presented results of a feasibility demonstration for a 30-lb field-portable TOFMS system. In this work we present recent progress in integrating a low-power, high-speed GC and show the capability for accurately recording fast GC transients for targeted compound detection using a quadrupole ion trap, time-of-flight instrument (QitTof). 相似文献
75.
Merchant KA Noid WG Akiyama R Finkelstein IJ Goun A McClain BL Loring RF Fayer MD 《Journal of the American Chemical Society》2003,125(45):13804-13818
Spectrally resolved infrared stimulated vibrational echo data were obtained for sperm whale carbonmonoxymyoglobin (MbCO) at 300 K. The measured dephasing dynamics of the CO ligand are in agreement with dephasing dynamics calculated with molecular dynamics (MD) simulations for MbCO with the residue histidine-64 (His64) having its imidazole epsilon nitrogen protonated (N(epsilon)-H). The two conformational substate structures B(epsilon) and R(epsilon) observed in the MD simulations are assigned to the spectroscopic A(1) and A(3) conformational substates of MbCO, respectively, based on the agreement between the experimentally measured and calculated dephasing dynamics for these substates. In the A(1) substate, the N(epsilon)-H proton and N(delta) of His64 are approximately equidistant from the CO ligand, while in the A(3) substate, the N(epsilon)-H of His64 is oriented toward the CO, and the N(delta) is on the surface of the protein. The MD simulations show that dynamics of His64 represent the major source of vibrational dephasing of the CO ligand in the A(3) state on both femtosecond and picosecond time scales. Dephasing in the A(1) state is controlled by His64 on femtosecond time scales, and by the rest of the protein and the water solvent on longer time scales. 相似文献
76.
Kate J. Graham Chris P. Schaller Brian J. Johnson John B. Klassen 《The Chemical Educator》2002,7(6):376-378
The incorporation of research projects into undergraduate chemistry courses provides a perspective that is fundamentally unavailable in most laboratory experiences. While independent, multistep synthesis projects in organic chemistry have been reported previously, most efforts have been directed at relatively restricted, closely guided research plans with modest student participation in the experimental design. We have implemented a more open-ended synthesis project, limited principally by cost, safety and availability of materials. In the second semester of the sophomore organic sequence, students develop multiple drafts of a plan for a three-to-four-step synthesis. Subsequently, students obtain their own literature protocols for the individual steps. The synthesis is performed over three four-hour laboratory periods. The students conclude this project with a poster presentation of the results at the end of the semester. Evaluation of the students work focuses not only on the successful synthesis of the target but also on planning, troubleshooting, purification, and spectral analysis. 相似文献
77.
Valahovic MT Gunnoe TB Sabat M Harman WD 《Journal of the American Chemical Society》2002,124(13):3309-3315
A series of complexes of the form TpRe(CO)(L)(eta(2)-naphthalene) (Tp = hydridotris(pyrazolyl)borate) undergoes tandem electrophile/nucleophile addition reactions with a high degree of regiocontrol depending on the auxiliary ligand, L. When L = PMe(3), the reaction of the eta(2)-naphthalene complex with triflic acid followed by a silyl ketene acetal favors the 1,4-addition product, whereas when L = pyridine, N,N-dimethylaminopyridine, N-methylimidazole, or NH(3) the 1,2-addition product is favored. These reactions proceed with excellent stereocontrol: both electrophile (H(+), D(+)) and nucleophile (silyl ketene acetal) add anti to the face of metal coordination, and a single coordination diastereomer can be isolated for each reaction. One-electron oxidation of the Re complex affords the corresponding free dihydronaphthalene in good yield. 相似文献
78.
Virgil Percec Brian C. Auman Hildeberto Nava Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》1988,26(3):721-741
Alternating—i.e., -(A-B)n- type—block copolymers of polyisobutylene (PIB) and aromatic polyether sulfone (PSU) have been prepared by phase transfer catalyzed Williamson polyetherification of α,ω-di(phenol)PIB with α,ω-di(chloroallyl)- or -(bromobenzyl)PSU. Block copolymers of the two prepolymers were also synthesized by the phase transfer catalyzed polyetherification of methylene chloride with α,ω-di(phenol)PIB and α,ω-di(phenol)PSU (bisphenol-A-terminated PSU). This method leads to -[(A)x-(B)y]n- block copolymers with formal linkages between segments. At sufficiently high segment lengths, both types of block copolymers exhibit two distinct Tgs, indicating phase separation into rubbery PIB and glassy PSU domains. 相似文献
79.
On the basis of their 1H n.m.r. spectra it is concluded that vinyl alcohol and -1-propenol exist mainly in the -conformation and that -1-propenol and 2-methyl-1-propenyl exist mainly in the conformation. 相似文献
80.
Suspended trapping is used to eject electrons in negative-ion Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometric experiments. In contrast to electron ejection by resonant excitation of the trapping motion, suspended trapping involves allowing the electrons to escape along the z-axis (perpendicular to the trap plates) while the trapping potential is briefly removed. The duration of this event is sufficiently short (~10 μs) so that ion losses are negligible; the overall effect is that of a ‘high-pass mass filter’. Suspended trapping is simpler to implement and more generally applicable to various cell geometries than resonant electron ejection. The effectiveness of the suspended trapping technique is not compromised by the anharmonicity of the potential well in ‘elongated’ ICR traps, but depends simply on the time it takes the electrons to escape the cell. Finally, a small, positive offset potential (~+0.25 V) applied to the trap plates during the suspended trapping event increases the efficiency of the ejection. 相似文献