全文获取类型
收费全文 | 595篇 |
免费 | 7篇 |
国内免费 | 5篇 |
专业分类
化学 | 330篇 |
力学 | 16篇 |
数学 | 84篇 |
物理学 | 177篇 |
出版年
2019年 | 4篇 |
2016年 | 6篇 |
2015年 | 8篇 |
2014年 | 7篇 |
2013年 | 23篇 |
2012年 | 10篇 |
2011年 | 28篇 |
2010年 | 8篇 |
2009年 | 6篇 |
2008年 | 33篇 |
2007年 | 21篇 |
2006年 | 29篇 |
2005年 | 21篇 |
2004年 | 19篇 |
2003年 | 19篇 |
2002年 | 21篇 |
2001年 | 10篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 6篇 |
1997年 | 6篇 |
1996年 | 14篇 |
1995年 | 12篇 |
1994年 | 10篇 |
1993年 | 9篇 |
1992年 | 15篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 16篇 |
1981年 | 13篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1975年 | 9篇 |
1974年 | 9篇 |
1973年 | 15篇 |
1972年 | 5篇 |
1971年 | 5篇 |
1970年 | 8篇 |
1968年 | 3篇 |
1961年 | 5篇 |
排序方式: 共有607条查询结果,搜索用时 46 毫秒
11.
Christopher Irwin Angelit Barnes Denise Veres Kays Kaidbey 《Photochemistry and photobiology》1993,57(3):504-507
The wavelength dependence for immediate pigment darkening (IPD) was investigated by exposing the midback skin of volunteers to a series of incremental fluences of narrow waveband radiation isolated by band-pass filters in the310–400 nm region. The threshold IPD fluence for each waveband was determined by visual assessment of the skin responses immediately after each exposure. The action spectrum, constructed from the mean threshold fluences, was broad and extended from 320 nm to 400 nm with a peak at around 340 nm. No IPD could be evoked at 310 nm, even after erythemogenic fluences. The spectrum was similar in each of the three skin types investigated (III, IV, V). The broad nature of the action spectrum within the UVA region suggests that IPD may serve as an alternative endpoint for measuring photoprotection against these wavelengths. 相似文献
12.
Howard C. Haas Monis J. Manning Martin H. Mach 《Journal of polymer science. Part A, Polymer chemistry》1970,8(7):1725-1730
Differential thermal analysis has been used to study the fusion of aqueous thermally reversible gels of gelatin and polyacrylylglycinamide (PAG). In the case of gelatin gels, endotherms close to the melting point are readily observed and these are sometimes preceeded by a small exothermic heat of gel reorganization. Calculations are presented to show that breaking of the gelatin gel network requires only a small fraction of the observed endothermic heat of fusion and that most of the heat is required for melting larger crystallites within gelatin aggregates and for perhaps a helix → coil transition. Failure to observe endotherms by DTA over the known temperature range of fusion of PAG gels is consistent with prior measurements and conclusions. The noncrystallinity of PAG gels and soluble aggregates together with a heat of crosslinking of only ?5 to ?10 kcal/mole of crosslinks places the heat of fusion of PAG gels outside the lower limits of DTA sensitivity. 相似文献
13.
The geometries of ten isomers of dimethyl cyclohexane were determined by ab initio gradient geometry refinement with the 4-21G basis set. It is found that many intramolecular interactions are clearly manifested by correlated structural trends, and that they are consistent with strain energies calculated by employing previously defined ab initio group equivalents. Specifically, non-bonded interactions are found between two adjacent methyl groups in some of the forms, and between axial methyl groups and adjacent axial C? H bonds in others. Unperturbed axial C? H and C? C bonds are consistently longer than equatorial bonds. In general, C? H bonds which are involved in non-bonded repulsive interactions are shortened, i.e., strengthened, and the corresponding H? C? C angles are large, compared to non-interacting parameters. 相似文献
14.
Genetic algorithms have properties which make them attractive in de novo drug design. Like other de novo design programs, genetic algorithms require a method to reduce the enormous search space of possible compounds. Most often this is done using information from known ligands. We have developed the ADAPT program, a genetic algorithm which uses molecular interactions evaluated with docking calculations as a fitness function to reduce the search space. ADAPT does not require information about known ligands. The program takes an initial set of compounds and iteratively builds new compounds based on the fitness scores of the previous set of compounds. We describe the particulars of the ADAPT algorithm and its application to three well-studied target systems. We also show that the strategies of enhanced local sampling and re-introducing diversity to the compound population during the design cycle provide better results than conventional genetic algorithm protocols. 相似文献
15.
Batinić-Haberle I Spasojević I Stevens RD Hambright P Neta P Okado-Matsumoto A Fridovich I 《Dalton transactions (Cambridge, England : 2003)》2004,(11):1696-1702
Three new Mn(III) porphyrin catalysts of O2.-dismutation (superoxide dismutase mimics), bearing ether oxygen atoms within their side chains, were synthesized and characterized: Mn(III) 5,10,15,20-tetrakis[N-(2-methoxyethyl)pyridinium-2-yl]porphyrin (MnTMOE-2-PyP(5+)), Mn(III)5,10,15,20-tetrakis[N-methyl-N'-(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTM,MOE-2-ImP(5+)) and Mn(III) 5,10,15,20-tetrakis[N,N'-di(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTDMOE-2-ImP(5+)). Their catalytic rate constants for O2.-dismutation (disproportionation) and the related metal-centered redox potentials vs. NHE are: log k(cat)= 8.04 (E(1/2)=+251 mV) for MnTMOE-2-PyP(5+), log k(cat)= 7.98 (E(1/2)=+356 mV) for MnTM,MOE-2-ImP(5+) and log k(cat)= 7.59 (E(1/2)=+365 mV) for MnTDMOE-2-ImP(5+). The new porphyrins were compared to the previously described SOD mimics Mn(III) 5,10,15,20-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP(5+)), Mn(III) 5,10,15,20-tetrakis(N-n-butylpyridinium-2-yl)porphyrin (MnTnBu-2-PyP(5+)) and Mn(III) 5,10,15,20-tetrakis(N,N'-diethylimidazolium-2-yl)porphyrin (MnTDE-2-ImP(5+)). MnTMOE-2-PyP(5+) has side chains of the same length and the same E(1/2), as MnTnBu-2-PyP(5+)(k(cat)= 7.25, E(1/2)=+ 254 mV), yet it is 6-fold more potent a catalyst of O2.-dismutation , presumably due to the presence of the ether oxygen. The log k(cat)vs. E(1/2) relationship for all Mn porphyrin-based SOD mimics thus far studied is discussed. None of the new compounds were toxic to Escherichia coli in the concentration range studied (up to 30 microM), and protected SOD-deficient E. coli in a concentration-dependent manner. At 3 microM levels, the MnTDMOE-2-ImP(5+), bearing an oxygen atom within each of the eight side chains, was the most effective and offered much higher protection than MnTE-2-PyP(5+), while MnTDE-2-ImP(5+) was of very low efficacy. 相似文献
16.
Balakin V Alexandrov VA Mikhailichenko A Flöttmann K Peters F Voss G Bharadwaj V Halling M Holt JA Buon J Jeanjean J LeDiberder F Lepeltier V Puzo P Heimlinger G Settles R Stierlin U Hayano H Ishihara N Nakayama H Oide K Shintake T Takeuchi Y Yamamoto N Bulos F Burke D Field R Hartman S Helm R Irwin J Iverson R Rokni S Roy G Spence W Tenenbaum P Wagner SR Walz D Williams S 《Physical review letters》1995,74(13):2479-2482
17.
Belz J Cousins RD Diwan MV Eckhause M Ecklund KM Hancock AD Highland VL Hoff C Hoffmann GW Irwin GM Kane JR Kettell SH Klein JR Kuang Y Lang K Martin R May M McDonough J Molzon WR Riley PJ Ritchie JL Schwartz AJ Trandafir A Ware B Welsh RE White SN Witkowski MT Wojcicki SG Worm S 《Physical review letters》1996,76(18):3277-3280
18.
Arisaka K Auerbach LB Axelrod S Belz J Biery KA Buchholz P Chapman MD Cousins RD Diwan MV Eckhause M Ginkel JF Guss C Hancock AD Heinson AP Highland VL Hoffmann GW Horvath J Irwin GM Joyce D Kaarsberg T Kane JR Kenney CJ Kettell SH Kinnison WW Knibbe P Konigsberg J Kuang Y Lang K Lee DM Margulies J Mathiazhagan C McFarlane WK McKee RJ Melese P Milner EC Molzon WR Ouimette DA Riley PJ Ritchie JL Rubin P Sanders GH Schwartz AJ Sivertz M Slater WE Urheim J Vulcan WF Wagner DL Welsh RE Whyley RJ 《Physical review letters》1993,71(24):3910-3913
19.
The phosphorescence and photochemical behavior of the macrocyclic complexes (1,4,7,10,13,16-hexaazacyclooctadecane)chromium(III) (Cr([18]-aneN(6))(3+); 1) and (4,4',4'-ethylidynetris(3-azabutan-1-amine)) chromium(III) (Cr(sen)(3+); 2) have been compared to each other and to the complex Cr(en)(3)(3+). For both macrocyclic complexes, phosphorescence from room temperature aqueous solutions is too weak to be observed, contrasting with Cr(en)(3)(3+), though both had somewhat longer 77 K lifetimes than Cr(en)(3)(3+). Phosphorescence lifetimes for these macrocyclics decreased with increasing temperature much faster than for Cr(en)(3)(3+) and a conventional extrapolation based on a fit of reciprocal lifetimes (corrected for the low-temperature contribution) to the Arrhenius equation gave estimated room temperature phosphorescence lifetimes of a few nanoseconds, consistent with the failure to observe room temperature emission. Fitting of the nonlinearity of the data seen in these plots suggested that two high-temperature processes were occurring with estimated activation parameters (E in kJ mol(-1) and A in s(-1)) for Cr([18]-aneN(6))(3+): E(1) = 40, A(1) = 1 x 10(16); E(2) = 24, A(2) = 1 x 10(14): Cr(sen)(3+); E(1) = 45, A(1) = 2 x 10(15); E(2) = 29, A(2) = 7 x 10(11). Cr([18]-aneN(6))(3+) was photochemically inert on irradiation. On irradiation into the lowest quartet ligand field absorption band, Cr(sen)(3+) photolyzes with a quantum yield of 0.098 +/- 0.001 at room temperature. Laser flash photolysis with conductivity detection showed that this photoreaction occurred faster than protonation of the liberated amine ligand at all practical proton concentrations. The quantum yield for irradiation directly into the doublet absorption band of Cr(sen)(3+) was 0.077 +/- 0.003. Photoaquation of Delta-Cr(sen)(3+) led to loss of optical activity and product analysis by capillary electrophoresis showed that both racemic and Delta-Cr(sen)(3+) photoaquate to a single main product, trans-Cr(sen-NH)(H(2)O)(4+). The product stereochemistry is shown to be consistent with predictions based on the angular overlap model for Cr(III) photochemistry, recognizing the additional constraints imposed by the ligand. The abnormally short room temperature solution lifetime of the doublet state is a result of a radiation-less process that competes with other processes depleting the doublet state. However, this doublet-state deactivation process does not lead to photoaquation but competes with BISC and photoaquation via the quartet state, resulting in an unprecedented reduction in photoaquation quantum yield on direct irradiation into the doublet state. 相似文献
20.
Circular high-performance thin-layer chromatography (HPTLC) has been used to differentiate a series of twelve tricyclic neuroleptics, using both normal phase and reverse phase procedures. The use of normal phase systems also allows the resolution of geometric isomers of chlorprothixene, clopenthixol and flupenthixol. Thirteen sulphonamides and Trirnethoprim may also be distinguished using HPTLC. 相似文献