全文获取类型
收费全文 | 276篇 |
免费 | 6篇 |
专业分类
化学 | 187篇 |
力学 | 6篇 |
数学 | 14篇 |
物理学 | 75篇 |
出版年
2020年 | 4篇 |
2016年 | 7篇 |
2014年 | 4篇 |
2013年 | 11篇 |
2012年 | 6篇 |
2011年 | 10篇 |
2009年 | 4篇 |
2008年 | 10篇 |
2007年 | 13篇 |
2006年 | 9篇 |
2005年 | 8篇 |
2004年 | 7篇 |
2003年 | 6篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1982年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1975年 | 9篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1971年 | 2篇 |
1970年 | 2篇 |
1969年 | 3篇 |
1965年 | 2篇 |
1958年 | 3篇 |
1938年 | 3篇 |
1937年 | 2篇 |
1936年 | 2篇 |
1934年 | 9篇 |
1933年 | 6篇 |
1932年 | 2篇 |
1931年 | 3篇 |
1930年 | 2篇 |
1929年 | 3篇 |
1928年 | 4篇 |
1926年 | 2篇 |
排序方式: 共有282条查询结果,搜索用时 15 毫秒
1.
2.
Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of 1H{27Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A 27Al offset-dependent data set yields for each resolved 1H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring 27Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the 1H–27Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of 27Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them. 相似文献
3.
R. Resel M. Oehzelt O. Lengyel T.U. Schülli G. Hlawacek C. Teichert G. Koller 《Surface science》2006,600(19):4645-4649
A para-sexiphenyl monolayer of near up-right standing molecules (nominal thickness of 30 Å) is investigated in-situ by X-ray diffraction using synchrotron radiation and ex-situ by atomic force microscopy. A terrace like morphology is observed, the step height between the terraces is approximately one molecular length. The monolayer terraces, larger than 20 μm in size, are extended along the [0 0 1] direction of the TiO2(1 1 0) substrate i.e. along the Ti-O rows of the reconstructed substrate surface. The structure of the monolayer and its epitaxial relationship to the substrate is determined by grazing incidence X-ray diffraction. Extremely sharp diffraction peaks reveal high crystalline order within the monolayer, which was found to have the bulk structure of sexiphenyl. The monolayer terraces are epitaxially oriented with the (0 0 1) plane parallel to the substrate surface (out-of-plane order). Four epitaxial relationships are observed. This in-plane alignment is determined by the arrangement of the terminal phenyl rings of the sexiphenyl molecules parallel to the oxygen rows of the substrate. 相似文献
4.
Brick DH Widgoff M Beilliere P Lutz P Narjoux JL Gelfand N Alyea ED Bloomer M Bober J Busza W Cole B Frank TA Fuess TA Grodzins L Hafen ES Haridas P Huang D Huang HZ Hulsizer R Kistiakowsky V Ledoux RJ Milstene C Noguchi S Oh SH Pless IA Steadman S Stoughton TB Suchorebrow V Tether S Trepagnier PC Wadsworth BF Wu Y Yamamoto RK Cohn HO Calligarich E Castoldi C Dolfini R Introzzi G Ratti S Badiak M DiMarco R Jacques PF Kalelkar M Plano RJ Stamer PE Brucker EB Koller EL Alexander G Grunhaus J 《Physical review D: Particles and fields》1990,41(3):765-773
5.
6.
M. Mintas Z. Orhanović K. Jakopčić H. Koller G. Stühler A. Mannschreck 《Tetrahedron》1985,41(1):229-233
N-Aryl-4-pyridones 1–6 were synthesized by condensation of the corresponding 4-pyrone with anilines. The enrichment of the enantiomers was achieved by liquid chromatography on triacctylcellulose, enantiomeric purities of(+)-1 and (+ )-2 being measured by 1H-NMR in the presence of an optically active auxiliary. Barriers to partial rotation about the C-N bond in 1-4 were determined and compared with corresponding biphenyls. 相似文献
7.
8.
Joze Kobe D. E. O'Brien R. K. Robins Thomas Novinson 《Journal of heterocyclic chemistry》1974,11(6):991-996
The reaction of 4-hydrazino-7-phenylpyrazolo[1,5-a]-1,3,5-triazine ( 4 ) with nitrous acid gave 8-phenyltetrazolo[1,5-e]pyrazolo[1,5-a]-1,3,5-triazine ( 5b ), which was determined by pmr and ir spectra to be in equilibrium with 4-azido-7-phenylpyrazolo[1,5-a]-1,3,5-triazine ( 5a ). The equilibrium between the tetrazolo ( 5b ) and azido ( 5a ) forms was studied by pmr and an attempt was made to determine if substituents in the pyrazole nucleus could sufficiently stabilize the tricyclic tetrazolo form ( 5b ) over the bicyclic azido form ( 5a ). Thermal degradation of 5 (a ? b) in an aprotic solvent gave 4-amino-7-phenylpyrazolo[1,5-a]-1,3,5-triazine ( 7 ), indicating the probability of a nitrene mechanism involved in the decomposition. Heating 5 in aqueous base gave both 7 and the “hydroxy” analog, 7-phenylpyrazolo[1,5-a]-1,3,5-triazin-4(3H)one ( 6 ), further substantiating the existence of a nitrene intermediate with a competing nucleophilic displacement of the azido group by a hydroxyl group. Cyclization of 4 with diethoxymethylacetate (DEMA) gave 8-phenyl-s-triazolo[4,3-e]pyrazolo[1,5-a]-1,3,5-triazine ( 8 ), which underwent thermal rearrangement to 8-phenyl-s-triazolo[2,3-e]pyrazolo[1,5-a]-1,3,5-triazine ( 9 ). Acid catalyzed ring opening of 9 with formic acid gave 3-N-formamido-5-phenyl-2(2-s-triazolyl)pyrazole ( 10 ). The failure of 10 to recyclize to 9 with the resultant loss of water, supported the theory that the rearrangement of 8 to 9 might occur simply as a concerted, thermally induced “anhydrous” rearrangement rather than via a covalently hydrated intermediate or a Dimroth type mechanism (in the base catalyzed rearrangement). 相似文献
9.
Kraka E Cremer D Koller J Plesnicar B 《Journal of the American Chemical Society》2002,124(28):8462-8470
The HOOO(-) anion (1) can adopt a triplet state (T-1) or a singlet state (S-1), where the former is 9.8 kcal/mol (DeltaH(298) = 10.3 kcal/mol) more stable than the latter. S-1 possesses a strong O-OOH bond with some double bond character and a weakly covalent OO-OH bond (1.80 A) according to CCSD(T)/6-311++G(3df,3pd) calculations (the longest O-O bond ever found for a peroxide). In aqueous solution, S-1 adopts a geometry closely related to that of HOOOH (OO(O), 1.388 A; (O)OO(H), 1.509 A; tau(OOOH), 78.3 degrees ), justifying that S-1 is considered the anion of HOOOH. Dissociation into HO anion and O(2)((1)Delta(g)) requires 15.4 (DeltaH(298) = 14.3; DeltaG(298) = 8.9) kcal/mol. Structure T-1 corresponds to a van der Waals complex between HO anion and O(2)((3)Sigma(g)(-)) having a binding energy of 2.7 (DeltaH(298) = 2.1) kcal/mol. Modes of generating S-1 in aqueous solution are discussed, and it is shown that S-1 represents an important intermediate in ozonation reactions. 相似文献
10.
Anab initio crystal orbital method is used to calculate the energies of an infinite chain of H atoms and of linear arrangements of H2 molecules with different interatomic distances. The H2 arrangements are not stable in respect to isolated molecules. The cohesive energy of an optimized arrangement of H atoms chain is 0.0354 a.u. 相似文献