全文获取类型
收费全文 | 5512篇 |
免费 | 104篇 |
国内免费 | 14篇 |
专业分类
化学 | 3632篇 |
晶体学 | 46篇 |
力学 | 79篇 |
数学 | 918篇 |
物理学 | 955篇 |
出版年
2019年 | 41篇 |
2016年 | 82篇 |
2015年 | 61篇 |
2014年 | 81篇 |
2013年 | 162篇 |
2012年 | 162篇 |
2011年 | 190篇 |
2010年 | 115篇 |
2009年 | 104篇 |
2008年 | 180篇 |
2007年 | 173篇 |
2006年 | 179篇 |
2005年 | 166篇 |
2004年 | 174篇 |
2003年 | 151篇 |
2002年 | 144篇 |
2001年 | 96篇 |
2000年 | 122篇 |
1999年 | 83篇 |
1998年 | 83篇 |
1997年 | 74篇 |
1996年 | 96篇 |
1995年 | 124篇 |
1994年 | 105篇 |
1993年 | 76篇 |
1992年 | 88篇 |
1991年 | 84篇 |
1990年 | 76篇 |
1989年 | 92篇 |
1988年 | 93篇 |
1987年 | 75篇 |
1986年 | 76篇 |
1985年 | 110篇 |
1984年 | 82篇 |
1983年 | 98篇 |
1982年 | 111篇 |
1981年 | 98篇 |
1980年 | 88篇 |
1979年 | 99篇 |
1978年 | 76篇 |
1977年 | 78篇 |
1976年 | 68篇 |
1975年 | 61篇 |
1974年 | 72篇 |
1973年 | 72篇 |
1972年 | 44篇 |
1971年 | 56篇 |
1970年 | 41篇 |
1968年 | 41篇 |
1966年 | 39篇 |
排序方式: 共有5630条查询结果,搜索用时 15 毫秒
51.
[reaction: see text] The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by nucleotides has been studied. The quenching mechanism was analyzed on the basis of deuterium isotope effects, tendencies for exciplex formation, and the quenching efficiency in the presence of a molecular container (cucurbit[7]uril). Exciplex-induced quenching appears to prevail for adenosine, cytidine, and uridine, while hydrogen abstraction becomes competitive for thymidine and guanosine. Compared to other fluorescent probes, DBO responds very selectively to the type of nucleotide. 相似文献
52.
The reaction of C5H5Rh(CO)(PiPr3) (1] which is prepared from C5H5Rh(CO)2 and neat P1Pr3, with the nitriloxides 2-RC6H4CNO (R = H, Cl) leads to the formation of the metallaheterocycles C5H5(P1Pr3)
) (2, 3) in 90–95% yield. Compound 1 reacts with tosylazide to give the C,N-bound isocyanate complex C5 H5(PiPr3)Rh(η2-TosN=C=O) (6). Analogously, on treatment of C5Me5Co(CO)(PMe3) with phenylazide the phenylisocyanate derivative C5Me5(PMe3)Co(η2-PhN=C=O) (7) is formed. Protonation of 7 with CF3CO 2H affords the non-ionic carbamoylcobalt complex C5Me5(PMe3)Co[C(O)NHPh](O2CCF3) (8). The X-ray structural analysis of 2 reveals the presence of an almost planar
heterocycle in which the two Rh-C distances differ by 0.045 Å 相似文献
53.
Five different structures of CH5
+ and one structure of CH5
– are calculated using a gaussian basis both in the SCF approximation and with the inclusion of electron correlation in the independent electron pair approximation (IEPA). While on SCF level the C
sstructure of CH5
+ has to lowest energy, the energy difference between the C
sand C
2vstructures becomes negligible if correlation is included. In contrast to this the approach of a proton to CH4 at large and intermediate distances is most favorable towards a corner of the CH4 tetrahedron which means a structure. The decomposition of CH5
+ into CH3
+ and H2 requires 20kcal/mol on SCF level and 40 kcal/mol if correlation is included. 相似文献
54.
Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered. 相似文献
55.
Fabiano Molinos de Andrade Clovis Peppe Werner Uhl 《Journal of organometallic chemistry》2005,690(5):1294-1299
The reaction of bromomethyl-dibromo-indium(III), Br2InCH2Br with dialkylselenides, R1SeR2 (R1 = CH3, R2 = CH2C6H5; R1 = C2H5, R2 = CH2C6H5; R1 = R2 = CH2C6H5) afforded the corresponding dialkylselenonium methylide complexes of indium tribromide, Br3InCH2SeR1R2, which were fully characterized by NMR spectroscopy and single crystal X-ray diffraction studies. 相似文献
56.
[reaction: see text] The complexation of p-sulfonatocalix[4]arene (CX4) with 2,3-diazabicyclo[2.2.1]hept-2-ene (1), 2,3-diazabicyclo[2.2.2]oct-2-ene (2), 2,3-diazabicyclo[3.2.2]non-2-ene (3), 1-methyl-4-isopropyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4), and 1-phenyl-2,3-diazabicyclo[2.2.2]oct-2-ene (5) was studied in D2O at pD 7.4 by 1H NMR spectroscopy. The formation of deep inclusion complexes was indicated by large upfield 1H NMR shifts of the guest protons (up to 2.6 ppm), which were also used to assign, in combination with 2D ROESY spectra, a preferential inclusion of the isopropyl group of 4 and a dominant inclusion of the azo bicyclic residue for 5. The bicyclic azoalkanes 1-3 showed exceptionally high binding constants on the order of 1000 M(-1), 1-2 orders of magnitude larger than for previously investigated noncharged organic guest molecules. The strong binding was attributed to the spherical shape complementarity between the guest and the conical cavity offered by CX4. Interestingly, although the derivatives 4 and 5 are more hydrophobic, they showed a 2-3 times weaker binding, which was again attributed to the deviation from spherical shape in these bridgehead-substituted derivatives. The preferential inclusion of the hydrophilic but spherical bicyclic residue of 5 rather than the hydrophobic aromatic phenyl group provides a unique observation in aqueous host-guest chemistry and corroborates the pronounced spherical shape affinity of CX4. 相似文献
57.
ICP-MS (inductively coupled plasma mass spectrometry) is shown as a very sensitive method for quantitative determination of Th and U concentration and excretion analysis in urine without any sample pretreatment. The current standard method for incorporation monitoring applies alpha-spectrometry, a very tedious and time consuming technique. ICP-MS offers an attractive alternative for monitoring of thorium and uranium body burdens in occupationally exposed subjects and also larger groups of the general population. A limit of determination of 0.5 ng/L in aqueous solutions and 1 ng/L in urine samples for both elements was achieved, with a precision of about ± 10% in the concentration range of appr. 10 ng/L. Due to the lack of a suitable reference material, the accuracy of the method was tested by comparing some of the results with those obtained by -spectrometry, especially for U. There was a sufficient agreement on both results. 相似文献
58.
Herbert Muffler Guenter Siegemund Werner Schwertfeger 《Journal of fluorine chemistry》1982,21(2):107-132
4.5-Perfluoro-1.3-dioxolanes are available by reaction of 2(α-chloroalkoxy)perfluoro-carbonyl halides or -ketone with fluoride ions. A mechanism for the intramolecular ring- closure-reaction is proposed. Hydrogen atoms at C-2 in can be exchanged photochemically by chlorine. Starting from the 2-monochloro-derivatives the 2-monofluoro-4.5-perfluoro- 1.3-dioxolanes are formed by reaction with triethylamine- hydrofluoride. 相似文献
59.
Roger Kalbermatten Werner Stdeli Jost H. Bieri Max Viscontini 《Helvetica chimica acta》1981,64(8):2627-2635
13C- and 15N-NMR.-Spectroscopic Studies on (6RS)-5, 10-Methylene-5, 6, 7, 8-tetrahydro-L -folic Acid; Unequivocal Proof of thier Structure The existence of a 5, 10-methylene bridge in the title compound has been established with the help of 15N-NMR, and 13C-NMR. spectroscopy. The simultaneous coupling of 13C(11) with 15N(5) and 15N(10) proves that C(11) must be bound as a methylene bridge to both N-atoms. Some other aspects of the NMR. spectra of the compound are discussed. Synthesis of the title product with the label 15N is described. 相似文献
60.
It is shown unequivocally by chemical correlations (cf. Schemes 1--3) and Raman optical activity spectra (cf. Fig. 1 and 2) that the (R)-configuration has to be attributed to (+)-1-methylindane ((+)- 1 ). This is in contradiction to an earlier assignment of the (R)-configuration to (?)- 1 [2] which was based on the (R)-configuration of (+)-indane-1-carboxylic acid ( 3 ) [11]. 相似文献