全文获取类型
收费全文 | 544篇 |
免费 | 26篇 |
国内免费 | 2篇 |
专业分类
化学 | 425篇 |
晶体学 | 2篇 |
力学 | 8篇 |
数学 | 29篇 |
物理学 | 108篇 |
出版年
2023年 | 3篇 |
2022年 | 10篇 |
2021年 | 14篇 |
2020年 | 13篇 |
2019年 | 14篇 |
2018年 | 7篇 |
2017年 | 14篇 |
2016年 | 26篇 |
2015年 | 10篇 |
2014年 | 18篇 |
2013年 | 30篇 |
2012年 | 44篇 |
2011年 | 54篇 |
2010年 | 28篇 |
2009年 | 15篇 |
2008年 | 43篇 |
2007年 | 28篇 |
2006年 | 33篇 |
2005年 | 25篇 |
2004年 | 23篇 |
2003年 | 19篇 |
2002年 | 19篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1999年 | 7篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有572条查询结果,搜索用时 15 毫秒
71.
YCo 0.88Ga 3Ge has an incommensurately modulated structure that was solved with (3 + 1)D superspace techniques. YCo 0.88Ga 3Ge crystallizes in the orthorhombic superspace group Immm(alpha00)00 s with unit cell constants of a = 4.1639(4), b = 4.1639(4), c = 23.541(2) A and a modulation vector of q = 0.3200(4) a* at 293 K. The incommensurate modulation, which creates a very large supercell ( approximately 25 fold), arises from a charge density wave (CDW) in the square net of Ga atoms that is coupled with a site occupancy wave (SOW) of Co atoms. The distorted Ga net features polygallide ribbons, chains, as well as single atoms. Temperature dependent crystallographic studies of the structure from 100-500 K indicate that the CDW is "locked in". Electrical conductivity and thermopower measurements in the temperature range of 300-500 K show that YCo 0.88Ga 3Ge is a poor metal. 相似文献
72.
Parallel factor analysis (PARAFAC) was used to analyze data from the high throughput screening of an array of organometallic rhodium and iridium complexes as catalysts for the intramolecular hydroamination of 2-(2-phenylethynyl)aniline to give 2-phenylindole. The progress of the hydroamination reactions was monitored using UV-visible spectroscopy. The overlapped UV-visible spectra of the mixture of starting material, product and solvent in the samples taken at different times were deconvoluted using PARAFAC. Unique PARAFAC models led to close approximations of the actual UV-visible spectra of the compounds in the mixture. The performance of the catalysts was then compared by estimating the final concentration of the starting material and product using PARAFAC loadings. A library of 63 complexes generated in situ was examined in a single experiment using this methodology. The complexes were generated from combinations of seven ligands (bis(N-methyl2-imidazolyl)methane, bis(1-pyrazolyl)methane, 1,10-phenanthroline, N,N'-bis(p-tolyl)diazabutadiene, N,N'-bis(p-tolyl)1,2-dimethyldiazabutadiene, N,N'-bis(mesityl)1,2-dimethyldiazabutadiene and bis(2,4,6-trimethylphenylimino)acenapthene) and nine metal precursors ([Ir(COD)Cl](2) (COD = 1,5-cyclooctadiene), [Ir(CO)(2)Cl](n), [Ir(COE)(2)Cl](2), [IrCp*Cl(2)](2) (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene), [Rh(COD)Cl](2), [Rh(CO)(2)Cl](2), [Rh(COE)(2)Cl](2), [RhCp*Cl(2)](2) and [RhCpCl(2)](2)) (Cp = cyclopentadiene)). The proposed method can be used for the fast screening of arrays of metal complexes for identifying effective catalysts, providing information that can augment traditional methods used for the analysis of catalyzed reactions. 相似文献
73.
Kippeny TC Bowers MJ Dukes AD McBride JR Orndorff RL Garrett MD Rosenthal SJ 《The Journal of chemical physics》2008,128(8):084713
The exciton dynamics of CdSe nanocrystals are intimately linked to the surface morphology. Photo-oxidation of the selenium surfaces of the nanocrystal leads to an increase in radiative decay efficiency from both the band edge and deep trap emission states. The addition of the primary amine hexadecylamine curtails nonradiative excitonic decay attributed to the dangling surface selenium orbitals by passivation of those trap sites by the methylene protons on the amine, leading to enhanced band edge emission and the absence of deep trap emission. Furthermore, CdSeZnSe core/shell nanocrystals are not immune from contributions from surface states because of the alignment of the band structures of the core and shell materials. 相似文献
74.
Danielle Promé Catherine Deon Jean-Claude Promé Henri Wajcman Frédéric Galacteros Yves Blouquit 《Journal of the American Society for Mass Spectrometry》1996,7(2):163-167
Hemoglobin Villeparisis was found during a systematic measurement of glycated hemoglobin. Electrospray mass spectra of the globin indicate an apparently unchanged molecular weight within the error range (0.01%). The tryptic digest of the β chain shows a chromatographically abnormal βT-9 peptide. The mass-to-charge ratio value of its [M+H]+ ion, as measured by liquid secondary ionization mass spectrometry, is one mass unit lower than that of the normal βT-9. However, the electrospray mass spectrum of this peptide exhibits mainly a doubly charged ion, whereas the normal βT-9 gives a triply charged ion. None of the allowed single amino acid substitutions for a 1-u shift down (Glu → Gln, Asp → Asn, or Asn → Ile) can explain the suppression of one protonation site. This can be due only to the replacement of the internal histidine by a nonbasic residue. Thus at least two amino acid exchanges occur within the same peptide: one involves the internal histidine, and the sum of the mass shifts is ?1 u. Consideration of the βT-9 sequence and taking account for the genetic code rules, the only possibility was 11His → Tyr (+26 mass shift) associated with 14Asn → Ser (?27 mass shift). This conclusion was consistent with the tandem mass spectrum of the [M+H]+ ion and was further confirmed by chemical microsequencing. 相似文献
75.
76.
77.
Mulet X Kaasgaard T Conn CE Waddington LJ Kennedy DF Weerawardena A Drummond CJ 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):18415-18423
Three nucleoside lipids have been synthesized: 3'-oleoylthymidine, 3',5'-dioleoylthymidine, and 3'-phytanoylthymidine. Differential scanning calorimetry and X-ray diffraction have been employed to characterize the physical properties of these neat lipids. Polarizing optical microscopy, small-angle X-ray scattering, and cryo-transmission electron microscopy techniques have been used to investigate the phase behavior in aqueous systems. Both oleoyl-based nucleoside lipids adopted a lamellar crystalline phase in the neat form at room temperature, and the phytanoyl derivative exhibited a fluid isotropic phase. Under excess water conditions, the presence of one branched (phytanoyl) or one unsaturated (oleoyl) chain promoted the formation of a liquid-crystalline lamellar phase at physiological temperatures. In contrast, the 3',5'-dioleoylthymidine derivative is nonswelling and does not exhibit lyotropic liquid-crystalline phase behavior. The nucleolipids' propensity for DNA-type binding and recognition has been evaluated by using a monolayer system to measure surface pressure-area isotherms in a Langmuir trough and indicates that the nucleoside base is available for nonspecific hydrogen bonding in the monolayer liquid expanded state for the single-chain nucleolipids but not for the dual-chain amphiphile. 相似文献
78.
Danielle Vellucci Athit Kao Robyn M. Kaake Scott D. Rychnovsky Lan Huang 《Journal of the American Society for Mass Spectrometry》2010,21(8):1432-1445
Protein-protein interaction is one of the key regulatory mechanisms for controlling protein function in various cellular processes.
Chemical cross-linking coupled with mass spectrometry has proven to be a powerful method not only for mapping protein-protein
interactions of all natures, including weak and transient ones, but also for determining their interaction interfaces. One
critical challenge remaining in this approach is how to effectively isolate and identify cross-linked products from a complex
peptide mixture. In this work, we have developed a novel strategy using conjugation chemistry for selective enrichment of
cross-linked products. An azide-tagged cross-linker along with two biotinylated conjugation reagents were designed and synthesized.
Cross-linking of model peptides and cytochrome c as well as enrichment of the resulting cross-linked peptides has been assessed. Selective conjugation of azide-tagged cross-linked
peptides has been demonstrated using two strategies: copper catalyzed cycloaddition and Staudinger ligation. While both methods
are effective, Staudinger ligation is better suited for enriching the cross-linked peptides since there are fewer issues with
sample handling. LC MSn analysis coupled with database searching using the Protein Prospector software package allowed identification of 58 cytochrome
c cross-linked peptides after enrichment and affinity purification. The new enrichment strategy developed in this work provides
useful tools for facilitating identification of cross-linked peptides in a peptide mixture by MS, thus presenting a step forward
in future studies of protein-protein interactions of protein complexes by cross-linking and mass spectrometry. 相似文献
79.
Luu T Medos BJ Graham ER Vallee DM McDonald R Ferguson MJ Tykwinski RR 《The Journal of organic chemistry》2010,75(24):8498-8507
Terminal di-, tri-, tetra-, and pentaynes substituted with a variety of functional groups react with benzyl azide in the presence of CuSO(4)·5H(2)O and ascorbic acid to give derivatives of 4-ethynyl-, 4-butadiynyl-, 4-hexatriynyl-, and 4-octatetraynyl-1,2,3-triazoles in moderate to good yields. These reactions appear to proceed regioselectively, and functionalization occurs exclusively at the terminal alkyne moiety. As well, no evidence of multiple azide additions to the polyyne framework is observed. X-ray crystallographic analysis of nine derivatives is used to document the regioselectivity of the reaction as well as outline structural characteristics of the 1,2,3-triazole products. 相似文献
80.
Huang J Wang AM Shetty A Maitz AH Yan D Doyle D Richey K Park S Pieper DR Chen PY Grills IS 《Magnetic resonance imaging》2011,29(7):993-1001