全文获取类型
收费全文 | 6611篇 |
免费 | 680篇 |
国内免费 | 455篇 |
专业分类
化学 | 4856篇 |
晶体学 | 74篇 |
力学 | 359篇 |
综合类 | 38篇 |
数学 | 745篇 |
物理学 | 1674篇 |
出版年
2024年 | 15篇 |
2023年 | 82篇 |
2022年 | 115篇 |
2021年 | 238篇 |
2020年 | 208篇 |
2019年 | 233篇 |
2018年 | 206篇 |
2017年 | 179篇 |
2016年 | 297篇 |
2015年 | 248篇 |
2014年 | 304篇 |
2013年 | 512篇 |
2012年 | 470篇 |
2011年 | 516篇 |
2010年 | 327篇 |
2009年 | 316篇 |
2008年 | 353篇 |
2007年 | 335篇 |
2006年 | 323篇 |
2005年 | 234篇 |
2004年 | 222篇 |
2003年 | 202篇 |
2002年 | 236篇 |
2001年 | 171篇 |
2000年 | 151篇 |
1999年 | 127篇 |
1998年 | 117篇 |
1997年 | 102篇 |
1996年 | 75篇 |
1995年 | 91篇 |
1994年 | 82篇 |
1993年 | 61篇 |
1992年 | 63篇 |
1991年 | 50篇 |
1990年 | 50篇 |
1989年 | 31篇 |
1988年 | 26篇 |
1987年 | 26篇 |
1986年 | 35篇 |
1985年 | 46篇 |
1984年 | 35篇 |
1983年 | 33篇 |
1982年 | 29篇 |
1981年 | 24篇 |
1980年 | 17篇 |
1979年 | 18篇 |
1977年 | 13篇 |
1975年 | 12篇 |
1974年 | 11篇 |
1973年 | 12篇 |
排序方式: 共有7746条查询结果,搜索用时 161 毫秒
91.
Kamal Y. El-Baradie Tarek M. Fayed Ibrahim M. El-Mehasseb 《Monatshefte für Chemie / Chemical Monthly》2005,96(3):1157-1169
Mono- and homobinuclear complexes of Mn(II), Co(II), Ni(II), and Cu(II) with phthalein purple are prepared and characterized by elemental analysis, thermal studies (TGA and DTA), spectral methods (IR, UV/Vis, and ESR), magnetic moment determination, and electrochemical reduction (DC polarography at DME and CV at HMDE). Thermal degradation of the complexes was studied by TGA and DTA where some thermodynamic parameters were determined. The mode of bonding and geometry of the complexes were determined from the spectral studies. Magnetic moment values showed some antiferromagnetism in the homobinuclear complexes. The reduction of the metal ions proceeds to the metallic state along an irreversible process. 相似文献
92.
Square-planar copper(II) and nickel(II) derivatives of the cis-dithiolate N(2)S(2) ligand bis(N,N'-2-mercapto-2-methylpropyl)-1,5-diazocyclooctane, (bme*daco)M, nucleate four Cu(I)Cl moieties, forming M(II)(2)Cu(I)(4)S(4) clusters with unusual triply bridging thiolates, mu(3)-SR, in the topological form of adamantane. As determined by X-ray crystallography, the (bme*daco)M (M = Cu or Ni) metallothiolate serves as a bidentate ligand that bridges four Cu(I) ions, utilizing all lone pairs on sulfurs. Further characterization by electrochemical and electronic spectral measurements suggests greater electron delocalization in the all-copper complex as compared to the NiCu heterometallic complex. Mass spectral data imply that the mixed-metal Ni(II)(2)Cu(I)(4)S(4) is more stable toward CuCl loss than Cu(II)(2)Cu(I)(4)S(4), a result that is corroborated by extraction of Cu(I) by 1,2-bis(diphenylphosphino)ethane in the latter but not the former. 相似文献
93.
Determination of enantiomeric purity is most often done under overload conditions, which leads to deformed peaks. In general, the best resolutions are obtained when the small peak appears before the large peak in the electropherogram. To be able to determine the R(+)-impurity in the S(-)-form as well as the S(-)-impurity in the R(+)-form the elution orders have to be reversed. The present paper describes reversal of enantiomeric elution order for the basic analyte propranolol and the acidic analyte ibuprofen. For propranolol, a charged heptakis-(6-sulfo)-beta-cyclodextrin (CD) is used in the background electrolyte. For ibuprofen, a mix of the charged heptakis-(6-sulfo)-beta-CD and the uncharged heptakis-(2,3,6-tri-O-methyl)-beta-CD is used in the background electrolyte. The use of a coated capillary and reversal of the polarity shift the elution order, buffer composition is unchanged in both cases. The enantiomers of propranolol and ibuprofen are well separated on both the coated and uncoated capillaries. Detection limits of enantiomer impurities are investigated using spiked samples of both propranolol and ibuprofen. 相似文献
94.
Dispersion of MoO3, NiO, ZnO on rutile TiO2 with low specific surface area was studied with Mercury Porosimeter, SEM, XPS and Ammonia Extraction method. The dispersion thresholds of MoO3, NiO, ZnO on three rutile TiO2 carriers were obtained with XPS, and com-pared with those on anatase TiO2 with high specific surf are area. Ammonia Extraction method was used to identify the surface oxide species interarting with support surface in different strength and it was found that the proportions of oxides that can not be extracted by ammonia extraction are different for MoO3, NiO and ZnO which are supported on rutile TiO2. 相似文献
95.
Tawarah Khalid M. Jibril Ibrahim Bani-Fwaz Mutasem Z. 《Transition Metal Chemistry》2000,25(6):659-663
The kinetics of the photolytic CO-substitution of CpFe(CO)2SCOR [Cp = C5H5, Bu
t
C5H4, 1,3-Bu2
t
C5H3; R = Me, Bu
t
, Ph, 2-(O2N)C6H4, 3-(O2N)C6H4, 4-(O2N)C6H4, 3,5-(O2N)2C6H3] with PPh3 were studied in CH2Cl2 at 0 °C by i.r. spectroscopy. The reactions yielded exclusively the mono-CO-substituted derivatives, CpFe-(CO)(PPh3) SCOR, and were found to follow second order kinetics with first order dependence on the concentration of each reactant. The differences in rates are discussed in terms of current knowledge pertaining to such reactions. An associative mechanism is proposed to account for the kinetic data of the reactions described. 相似文献
96.
A series of chiral aromatic imides and diimides were synthesized and their electrochemical, absorption, fluorescent, and chiroptical properties were examined for their potential application as molecular chiroptical switches. These compounds exhibit strong UV-vis absorptions, and can be electrochemically reduced to radical anions that absorb in the near infrared (NIR) region. Further reduction to the dianionic states results in new absorptions in the visible region. The changes in circular dichroism upon redox switching were apparent in the UV-vis region but were absent in the NIR region. 相似文献
97.
Three lanthanide coordination polymers were prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. [Pr2(mBDC)3(phen)(H2O)]n·0.5nH2O (1) (mBDC=isophthalate, phen=1,10-phenanthroline) exhibits two kinds of metal environments (coordination numbers 7 and 8). In complex 1, mBDC ligands adopt the tetradentate (bridging and bridging) coordination mode and connect Pr ions into an undulating layer, and a 3D supramolecular structure is formed via hydrogen bonds between adjacent layers. [Tb4(mBDC)6(phen)]n (2) has three types of metal environments (coordination numbers 6, 7 and 8) and is composed of a 3D network formed by mBDC linking Tb ions via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. There are two kinds of small quadrilateral channels along the a-axis. [Er4(mBDC)6(phen)]n (3) is isostructural to complex 2. 相似文献
98.
杂多化合物的酸催化特性及其在有机合成反应中的应用 总被引:12,自引:0,他引:12
杂多化合物在各个研究领域中的实际应用日趋广泛。特别是在催化领域内,对杂多化合物催化性能和研究越来越引起人们的关注。本文对在均相和非均相体系中杂多化合物的酸催化的最新研究成果和应用进行了综述,对杂多化合物的酸行为进行了简要的概括,并介绍了作者在这方面的工作。 相似文献
99.
Li BS Kang SZ Cheuk KK Wan L Ling L Bai C Tang BZ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7598-7603
In the present work, we investigated self-assembling of a poly(phenylacetylene) carrying L-valine pendants (PPA-Val) in a water/methanol solution, upon evaporation of the solution on mica, and on the water surface. With intercalation of a fluorescence probe of Ru(phen)2(dppx)2+ (phen = 1,10-phenanthroline, dppx=7,8-dimethyldipyridophenazine) into the hydrophobic cavities associated by the PPA-Val chains, their helical structures were directly detected in solution with an in situ fluorescence microscope. Helical aggregates were observed with AFM upon evaporation of the solvents, suggesting that the helical structures in the solution are the building blocks of the helical aggregates. Self-assembling structures of PPA-Val on the water surface were, however, very different from that formed upon evaporation of its THF solution on the mica surface. The polymer chains associated into a monolayer of extended fibers on the water surface, whereas superhelical fibers formed on the mica surface. Water molecules play a critical role in inducing the polymer to form diverse morphological structures in its bulk solution and on its surface. In solution, the isotropic hydrophobic effect drove the polymer chains to form superhelical aggregates, while on the water surface, the hydrophobic effect concentrated mainly on the lateral part of the polymer, thus giving a monolayer of extended fibers. 相似文献
100.
M. E. Kassem T. G. Abdel-Malik M. El-Shabasy R. M. Abdel-Latif A. A. Ibrahim 《Journal of Thermal Analysis and Calorimetry》1987,32(5):1531-1537
The influence of chloroacetic acid amide (AC) on the temperature-dependence of the electrical conductivity (), thermal expansion (ij) and specific heat ((C
p) of triglycine sulphate crystals was studied in the phase transition range (T
c=49°). The addition of isostructural AC increased the electrical conductivity, decreased the thermal expansion and changed theC
p peak. The mechanism is discussed on a thermodynamic basis.
Zusammenfassung Der Einfluß der Zumischung von Chloressigsäureamid (AC) auf die Temperaturabhängigkeit der elektrischen Leitfähigkeit, der Wärmeausdehnung ij und der spezifischen WärmeC p von Triglycinsulfat-Kristallen wurde im Phasenübergangsgebiet (T c=49 °C) untersucht. Die Beimischung von isostrukturellem AC erhöht die elektrische Leitfähigkeit und vermindert die Wärmeleitfähigkeit, während derC p-Peak verändert wird. Der Mechanismus kann thermodynamisch diskutiert werden.
(), () ij) () , T c=49°. , , , , C p. .相似文献