首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   28694篇
  免费   1031篇
  国内免费   161篇
化学   19126篇
晶体学   233篇
力学   475篇
综合类   4篇
数学   4826篇
物理学   5222篇
  2023年   175篇
  2022年   305篇
  2021年   535篇
  2020年   500篇
  2019年   540篇
  2018年   546篇
  2017年   504篇
  2016年   987篇
  2015年   833篇
  2014年   916篇
  2013年   1712篇
  2012年   1819篇
  2011年   2047篇
  2010年   1259篇
  2009年   1221篇
  2008年   1777篇
  2007年   1658篇
  2006年   1551篇
  2005年   1408篇
  2004年   1142篇
  2003年   965篇
  2002年   836篇
  2001年   579篇
  2000年   498篇
  1999年   401篇
  1998年   313篇
  1997年   308篇
  1996年   386篇
  1995年   273篇
  1994年   292篇
  1993年   271篇
  1992年   263篇
  1991年   206篇
  1990年   200篇
  1989年   151篇
  1988年   140篇
  1987年   156篇
  1986年   152篇
  1985年   184篇
  1984年   189篇
  1983年   127篇
  1982年   152篇
  1981年   122篇
  1980年   127篇
  1979年   96篇
  1978年   82篇
  1977年   82篇
  1976年   74篇
  1975年   59篇
  1973年   72篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
992.
Relationships between lattice parameters of manganese dioxides and their surface properties at the solid-aqueous solution interface were investigated. The studied series ranged from ramsdellite to pyrolusite and encompassed disordered MD samples. The structural model used takes into account structural defects: Pr (rate of pyrolusite intergrowth) and Tw (rate of microtwinning). Water adsorption isotherms showed that the cross sectional area of water molecules adsorbed in the first monolayer is positively correlated to Pr. Titration of the surface charge of the MD series evidenced a positive linear relationship between the PZC and Pr (Pr=0, Tw=0, PZC=1 for ramsdellite; Pr=1, Tw=0, PZC=7.3 for pyrolusite; gamma-MD with intermediate values of Pr (0.2 to 0.45) have increasing PZC values). The rate of microtwinning appeared as a secondary factor for the increase of the PZC. The above correlations are explained by the chemical defects at the origin of the structural disorder, respectively Mn(3+)/Mn4+ substitution for Pr and Mn vacancies for Tw, which result in proton affinity and thus in increased PZC. The experimental results are compared with data collected in the literature for manganese dioxides as well as for dioxides of transition elements with tetragonal structure.  相似文献   
993.
Aconitine, mesaconitine, and a new alkaloid, which has been called altaconitine, have been isolated from the total alkaloids of the epigeal part ofAconitum altaicum. Altaconitine has the structure of 8-acetoxy-14-benzoyloxy-2,3,13,-15-tetrahydroxy-1,6, 16-trimethoxy-4-methoxymethy-N-ethylaconitan, which was established on the basis of a study of IR, PMR,13C NMR, and mass spectra and by the x-ray structural method.Institute of Chemistry, Mongolian Peoples' Republic Academy of Sciences, Ulan-Bator. Institute of the Chemistry of Plant Substances of the Uzbekistan Republic of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 47–53, January–February, 1993.  相似文献   
994.
It was demonstrated that adsorbed CO is obtained from the reduction of NaHCO3 solution when Pt(100), Pt(110), disordered Pt(111) and polycrystalline electrodes are employed. Reduction of CO2 coming from the dissociation of the hydrogencarbonate anion is proposed as the reaction that produces CO. By using Fourier transform infrared spectroscopy, linear and multi-bonded CO were detected on polycrystalline platinum electrodes. The shape of the band associated with linearly adsorbed CO is monopolar as a consequence of the partial overlapping, at lower wavenumbers, of the absolute bands at both potentials (0.05 and 0.35 V).  相似文献   
995.
Summary The interaction of non-anhydrous solutions of the ligand 1,3-bis-(2-hydroxyphenyl)-1,3-propanedione (bhppH3) with hydrated rare earth chlorides resulted in the formation of anhydrous, non-solvated, complexes M(bhppH2)3 (M=Y, La, Nd, Pr, Sm or Yb). The complexes have been characterized by elemental analysis, t.g., i.r. and1H n.m.r. spectroscopy. The evidence suggests that the coordination is through the -diketone site.  相似文献   
996.
Abstract— We determined the polarized and isotropic visible/UV absorption spectra of chlorophyll a (Chi a ) and pheophytin a (Pheo a ) oriented in the lamellar phase of glycerylmonooctanoate/H2O. Resolution into mutually perpendicular X- and Y-polarized absorption spectra of the pigments was achieved assuming that the transition moments of Chi a and Pheo a are located in the plane of the chromophores. The polarized spectra were deconvoluted into harmonic progressions and the resultant assignment of band positions in the long-wavelength region was found to correlate well with independent spectral measurements, such as the polarisation of fluorescence. However, the correlation of the experimentally determined transitions with the results of theoretical calculations is not straightforward. The overall conclusions are of fundamental interest in the determination of orientations of the tetrapyrrole macrocycle in lipid lamellae and pigment-protein structures of photosynthetic membranes.  相似文献   
997.
The reaction of the dimer complex [{Ru(CO)3Cl2}2] with the ligands 4,6-dichloroquinoline-5,8-dione and 6-methoxybenzo[g]quinoline-5,10-dione in ethanol solution led to the neutral mononuclear complexes of general formula [Ru(CO)2Cl22-quinolinedione-N,O)]. The complexes were characterized by elemental analysis, IR and RMN spectroscopy, and the molecular structure of [Ru(CO)2Cl2(6-methoxybenzo[g]quinoline-5,10-dione)] was determined by single-crystal X-ray diffraction. The redox chemistry of ligands and complexes was investigated by cyclic voltammetry, and their potential antitumor activity was also evaluated.  相似文献   
998.
999.
A new method based on matrix solid-phase dispersion (MSPD) extraction was studied to determine aflatoxin B1, B2, G1 and G2 from peanuts. Optimization of different parameters, such as type of solid supports for matrix dispersion and elution solvents were carried out. The method used 2 g of peanut sample, 2 g of C18 bonded silica as MSPD sorbent and acetonitrile as eluting solvent. Recoveries of each aflatoxin spiked to peanut samples at 2.5 ng/g (5 ng/g for aflatoxin G2) level were between 78 and 86% with relative standard deviations ranging from 4 to 7%. The limits of quantification ranged from 0.125 to 2.5 ng/g for the four studied aflatoxins using liquid chromatography (LC) with fluorescence detection. In addition, LC coupled to mass spectrometry with an electrospray interface was used for confirmation of aflatoxins present in real samples. Eleven peanut samples from different countries were analyzed by the proposed method and by using an enzyme-linked immunosorbent assay (ELISA). ELISA test is a good screening method for investigation of these mycotoxins in peanut samples.  相似文献   
1000.
The manganese carbonyl complex [MnBr(CO)3 L ] ( 1 ), where L = Ph2POCH2CH2OPPh2, was prepared by reacting [MnBr(CO)5] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)2 LL ′], where L ′ = P(OMe)3 ( 2 ) or P(OEt)3 ( 3 ) and [MnBr(CO)3 L ′2], where L ′ =PPh(OEt)2 ( 4 ) or PPh2(OEt) ( 5 ). The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (1H, 13C and 31P) spectroscopies and X‐ray diffractometry for the complexes 1 , 4 and 5 .  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号