全文获取类型
收费全文 | 43643篇 |
免费 | 1294篇 |
国内免费 | 1528篇 |
专业分类
化学 | 27576篇 |
晶体学 | 495篇 |
力学 | 1078篇 |
综合类 | 17篇 |
数学 | 5321篇 |
物理学 | 11978篇 |
出版年
2021年 | 551篇 |
2020年 | 503篇 |
2019年 | 602篇 |
2018年 | 570篇 |
2017年 | 622篇 |
2016年 | 1205篇 |
2015年 | 936篇 |
2014年 | 1165篇 |
2013年 | 2725篇 |
2012年 | 2289篇 |
2011年 | 2476篇 |
2010年 | 1581篇 |
2009年 | 1762篇 |
2008年 | 2055篇 |
2007年 | 2040篇 |
2006年 | 1797篇 |
2005年 | 1713篇 |
2004年 | 1887篇 |
2003年 | 1448篇 |
2002年 | 1349篇 |
2001年 | 1161篇 |
2000年 | 911篇 |
1999年 | 720篇 |
1998年 | 629篇 |
1997年 | 563篇 |
1996年 | 554篇 |
1995年 | 588篇 |
1994年 | 494篇 |
1993年 | 463篇 |
1992年 | 485篇 |
1991年 | 491篇 |
1990年 | 471篇 |
1989年 | 456篇 |
1988年 | 439篇 |
1987年 | 419篇 |
1986年 | 427篇 |
1985年 | 568篇 |
1984年 | 573篇 |
1983年 | 411篇 |
1982年 | 433篇 |
1981年 | 453篇 |
1980年 | 421篇 |
1979年 | 399篇 |
1978年 | 390篇 |
1977年 | 373篇 |
1976年 | 394篇 |
1975年 | 337篇 |
1974年 | 331篇 |
1973年 | 336篇 |
1967年 | 341篇 |
排序方式: 共有10000条查询结果,搜索用时 156 毫秒
991.
Garcia EM Sanchez MD Tonetto G Volpe MA 《Journal of colloid and interface science》2005,292(1):179-185
The preparation of different samples of vanadia supported on ultrastable zeolite (VO(x)/USY) is discussed. The samples were prepared in order to obtain highly dispersed V-species, avoiding the formation of crystalline vanadia and the destruction of the zeolite framework. Two methods were employed for preparing VO(x)/USY samples: an organic route using V(AcAc)3 and an inorganic route using NH4VO3. The characterization of the samples was performed with XRD, TPR, NH3-TPD, and N2 isotherms. From these results it is concluded that when VO(x) is supported on the surface of USY from acidic aqueous solution of ammonium metavanadate, the destruction of the zeolite framework is accomplished. For higher pH values in the impregnating solution, undesired V2O5 is formed on the USY surface. On the other hand, VO(x)/USY prepared from the organic precursor shows no destruction of the USY structure. In addition, highly dispersed VO(x) are formed, though for relatively high V loadings (6%) an obstruction of the zeolite windows takes place. The samples are tested as catalysts for gas phase dehydrogenation of n-butane to olefins. The catalysts prepared from NH4VO3 are almost inactive for the reaction. On the other hand, both samples prepared from V(AcAc)3 present initial conversion levels in the 8-12% range. However, the selectivity depends on the V loading, the catalysts with 6% loading being the most selective (75%). The catalytic patterns of the samples (activity and selectivity) are in agreement with the physicochemical features of the VO(x)/USY surface. 相似文献
992.
The synthesis of 2-phenylsparteine-N16-oxide (7) and its perchlorate salt (7-H+) was carried out. On the basis of spectral data, and by comparison with appropriate sparteine-N-oxides, the mechanism of formation and the structures of the two new compounds were proposed. It was found, the basicity of the new N-oxide is unexpectedly high and comparable to the basicity of quaternary ammonium hydroxides. The structure and the strength of intramolecular H-bond in 7-H+ makes 7 an excellent “catcher” proton or specific ”sponge” proton. 相似文献
993.
Summary Correlations between retention index (RI) and Van der Waals' volume (VW) in homologous series of n-alcohols, n-aldehydes and esters are studied on the stationary phases Carbowax 1540 and squalane. Influence of functional groups is quantified and a method for obtaining one general equation, valid for an indeterminate number of homologous series, is proposed. 相似文献
994.
Casas JS Castaño MV García-Tasende MS Rodríguez-Castellón E Sánchez A Sanjuán LM Sordo J 《Dalton transactions (Cambridge, England : 2003)》2004,(13):2019-2026
Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature. 相似文献
995.
Patel RN Singh N Shukla KK Gundla VL Chauhan UK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2603-2610
X-band electron spin resonance (ESR) and UV-vis spectra of a homobinuclear [(Bipy)2Cu-E-Im-Cu(Bipy)2](BF4)3 and a heterobinuclear [(Bipy)2Cu-E-Im-Zn(Bipy)2](BF4)3 complexes, E-Im=2-ethylimidazolate ion have been described as possible models for superoxide dismutase (SOD). Magnetic moment and ESR spectral measurements of the homobinuclear complex have shown an antiferromagnetic exchange interaction. From pH-dependent ESR and UV-vis spectral measurements studies, these complexes have been found to be stable over 8.5-10.5 pH range. These complexes catalyze the dismutation of superoxide (O2-) at biological pH. All the observations indicate that these complexes act as good possible models for superoxide dismutase. 相似文献
996.
Carlos Cativiela Jos Ma Fraile Jos I. García Jos A. Mayoral Juan M. Campelo Diego Luna Jos M. Marinas 《Tetrahedron: Asymmetry》1993,4(12):2507-2512
Reactions of cyclopentadiene with several chiral acrylates are studied and compared with the same reactions catalysed by Zn(II)-exchanged K10 montmorillonite. In general, amorphous AlPO4 is a more efficient catalyst than the clay. In particular, the reaction of cyclopentadiene with (−)-8-phenylmenthyl acrylate leads to 74% diastereomeric excess (d.e.) in methylene chloride at low temperatures. This result constitutes the highest asymmetric induction described to date for a solid-catalysed asymmetric Diels-Alder reaction. When the reactions are carried out in the absence of a solvent a noticeable decrease in selectivity is observed, probably due to an extensive competition of the non-catalysed reaction. 相似文献
997.
Shilov VN Delgado AV González-Caballero F Horno J López-García JJ Grosse C 《Journal of colloid and interface science》2000,232(1):141-148
Electrophoresis is one of the electrokinetic phenomena most widely investigated, both from a fundamental point of view and as a research tool in academia and industry. However, the dependence between electrophoretic mobility and zeta potential is, in a general case, far from simple, because of the many physical processes involved. In this work, we first describe qualitatively and (in some cases) quantitatively the time behavior of the dipole moment induced in the electrical double layer by an applied electric field. Further, a simple relationship is deduced between the dipole moment and the electrophoretic mobility. Through the analysis of the time dependence of the former, it is possible to resolve the different contributions to the stationary values of the mobility. Three characteristic relaxation times are distinguished in the time evolution of the dipole moment: tau(H) (the time needed for hydrodynamic flows to be established), tau(MW) (time for ionic electromigration to develop), and tau(VD) (after this time, diffusion flows are established in the system, and the double layer polarization is complete). This means that different mechanisms are operating on the double layer for different times after the application of the field, and that computing the mobility at such different times is equivalent to calculating the steady-state electrophoretic mobility under different approximations. A comparison is shown between estimated and computed mobility values as functions of time and of zeta potential, confirming the validity of the asymptotic calculations. Copyright 2000 Academic Press. 相似文献
998.
U. Groß P. Dietrich G. Engler D. Prescher J. Schulze K. Lunkwitz A. Ferse 《Journal of fluorine chemistry》1982,20(1):33-52
The present work studies the changes in polymer structure and the mechanism of the decomposition of polytetrafluoroethylene resin (PTFE) exposed to high energy radiation (electron beam). Spectroscopic and kinetic observations are used to interpret the degradation process. For the first time the decomposition of PTFE has been carried out on a preparative scale and new results obtained by analysing the degradation products. The radiation-induced degradation of PTFE is accompanied by thermal degradation under certain irradiation conditions. This is due to an increase in temperature of the polymer caused by retardation of highly accelerated electrons (heat accumulation effect).The kinetics are discussed in terms of the reactions and recombination of radicals produced by high-energy radiation both in the polymer melt and the polymer surface. These are related to the overall rate of decomposition.The primary radicals formed by decomposition of PTFE in an inert atmosphere (N2, Ar) react to produce perfluorinated alkanes and alkenes. In the presence of reactive gases the decomposition fragments originated will react rapidly; e.g. if oxygen is present in the reactive area the radicals form perflourinated peroxyl and oxyl radicals which finally stabilize themselves by CC-scission to perfluorocarbon acid fluorides and carbonyldifluorides. 相似文献
999.
Fuchslueger U Rissler K Grether HJ Grasserbauer M 《Analytical and bioanalytical chemistry》1996,356(8):495-499
High-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) is used to detect 2,4-dinitrophenyl (DNP) derivatives of amines by means of negative chemical ionisation at atmospheric pressure. The high sensitivity and good comparability of UV- and MS-detection of DNP-derivatives of amines is shown by several examples. The high selectivity of the derivatisation and the detection method (UV and MS) is used for the analysis of unknown amines in aqueous phases after hydrolytic degradation of polyamide-amine- or polyamine-epoxide-adducts as well as for the characterisation of commercial products. 相似文献
1000.
Lundström U 《Talanta》1982,29(4):291-296
The optimum conditions for the oxidation of bromide to bromate by peroxodisulphate at 120 degrees as well as for the decomposition of the excess of oxidant have been determined. The predicted advantages of this oxidizing agent, viz. minimal blanks and destruction of small amounts of interfering organic matter and reducing substances, were confirmed. The bromate was determined iodometrically either by titration with thiosulphate or by spectrophotometry in absence of oxygen at 355 nm. The titrimetric finish applied to 0.8-8 micromole of bromide gave a mean yield of 100.0%, s = 6 nmole. The spectrophotometric finish applied to 0.05-0.25 micromole of bromide gave a mean yield of 98.9%, s = 1.1 nmole. Interfering amounts of iodide present in the sample and oxidized to iodate can be corrected for by making use of the pH-dependence of the reaction of iodide with bromate and iodate. 相似文献