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   99355篇
  免费   13691篇
  国内免费   11498篇
化学   68475篇
晶体学   1110篇
力学   6149篇
综合类   992篇
数学   12111篇
物理学   35707篇
  2024年   273篇
  2023年   1664篇
  2022年   2930篇
  2021年   3213篇
  2020年   3281篇
  2019年   3299篇
  2018年   2954篇
  2017年   2722篇
  2016年   4138篇
  2015年   4326篇
  2014年   5234篇
  2013年   6967篇
  2012年   8175篇
  2011年   8505篇
  2010年   6028篇
  2009年   6002篇
  2008年   6474篇
  2007年   5882篇
  2006年   5556篇
  2005年   4785篇
  2004年   3950篇
  2003年   3156篇
  2002年   3193篇
  2001年   2683篇
  2000年   2348篇
  1999年   2230篇
  1998年   1763篇
  1997年   1541篇
  1996年   1546篇
  1995年   1335篇
  1994年   1245篇
  1993年   1085篇
  1992年   963篇
  1991年   811篇
  1990年   683篇
  1989年   594篇
  1988年   445篇
  1987年   415篇
  1986年   353篇
  1985年   351篇
  1984年   232篇
  1983年   198篇
  1982年   161篇
  1981年   128篇
  1980年   100篇
  1978年   81篇
  1977年   62篇
  1976年   61篇
  1975年   63篇
  1973年   64篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
211.
The metabolic response of normal rat brain to photodynamic therapy (PDT) was studied over a 1 week interval using in vivo 31P-NMR spectroscopy. Rats injected with 12.5 mg/kg Photofrin II were submitted to brain photoactivation 48 h after drug administration with either 140 or 70 J/cm2 light (630 +/- 1 nm) from an Argon dye laser. Control studies, animals not given drug or light, animals submitted only to brain illumination without drug, and animals given drug but no light, were also performed. The data revealed a transient metabolic degradation; a decrease in the ratio of beta-nucleotriphosphate to inorganic phosphate (P less than 0.001) at 24 h after PDT treatment was followed by a return to pretreatment spectral values. Brain tissue alkalosis was also noted, with significant (P less than 0.05) differences in brain tissue pH detected at 72 h post treatment between 70 J/cm2 PDT vs control studies and at 1 week post treatment between 140 J/cm2 vs 70 J/cm2, 140 J/cm2 vs no light-no drug and 140 J/cm2 vs drug only. The data suggest that there is no difinitive metabolic marker from 31P-NMR spectroscopy that can identify necrotic brain tissue caused by PDT. Phosphorus-31 NMR data are also presented which suggest that PDT damage to brain is not solely the result of microvascular occlusion causing ischemic necrosis.  相似文献   
212.
The UV and visible spectra of six model compounds were studied. These compounds can be considered as models of polyaniline in the reduced, cation radical, partially oxidized and oxidized forms. After treatment of a mixture of equal molar quantities of the reduced form (DPPD) and the oxidized form (QDIM) with acid, the following reaction was observed: DPPD(I)+QDIM(III)+2H+=2DPPD+(II) After similar treatment of the partially oxidized form (V) with acid, the radical cation salt formed. The UV and visible spectra of polyaniline in the reduced form, oxidized form and conductive form are similar to the spectra of DPPD, QDIM and DPPD+ or radical cation salt of V respectively. We propose that the polyaniline synthesized by chemical oxidation of aniline consists of oxidized and reduced repeat units. Upon protonation a redox reaction (or electron rearrangement) occurs and forms delocalized radical cations (polarons) in the polymer chain which are highly conductive.  相似文献   
213.
This study attempted to comprehend how temperature affects hydrophobic interaction between proteins and hydrophobic adsorbents. By equilibrium batch analysis, we measured the adsorption isotherm to evaluate the protein-adsorbent affinity, while isothermal titration calorimetry was used to measure the adsorption enthalpy. In addition, the affinity and enthalpy differences between two proteins, alpha-chymotrypsinogen A and trypsinogen, with two adsorbents, butyl-Sepharose and octyl-Sepharose gel, under varying temperatures were studied with respect to the exposed hydrophobic segments of the protein and ligand hydrophobicity. The enthalpies obtained in this investigation can be used to more thoroughly understand the hydrophobic interaction between proteins and adsorbents. First, the adsorption isotherm experiments reveal that the adsorption quantity of the proteins with the Sepharose gels increases with temperature. For a microcalorimetric measurement, as temperature is increased from 298 to 310 K, the DeltaH value of alpha-chymotrypsinogen A with butyl-Sepharose increases, while the DeltaH value of trypsinogen is reduced. This is likely due to the fact that alpha-chymotrypsinogen A has a higher area of exposed hydrophobic segments than trypsinogen does. This observation also implies that as temperature increases, the interaction mechanism of alpha-chymotrypsinogen A with butyl-Sepharose changes from an adsorption-dominated process to a partitioning process. In addition, for octyl-Sepharose, the DeltaH value of alpha-chymotrypsinogen A is positive and decreases with temperature increment. However, the DeltaH value of trypsinogen was positive and increased with temperature. Therefore, we conclude that as temperature increases, the interaction mechanism of the proteins for octyl-Sepharose is a partitioning-dominated process. Copyright 2000 Academic Press.  相似文献   
214.
Taxumairols X--Z,new taxoids from Taiwanese Taxus mairei   总被引:1,自引:0,他引:1  
In addition to 19-dydroxybaccatin III, 1beta-hydroxy-5 alpha-deacetylbaccatin I, taxayuntin G and 13-O-deacetyltaxumairol Z (4), three new taxane diterpenoids, taxumairols X (1), Y (2), Z (3) have been isolated from extracts of the Formosan Taxus mairei (LEMEE & LEVL.) S. Y. HU. Compounds 1-2 belong to the 11(15-->1)-abeo-taxane system, having a tetrahydrofuran ring at C-2, C-3, C-4 and C-20. The new compound 3 and 4, which was misidentified previously are derivatives of 11(15-->1)-abeo-taxane with an intact oxirane system. The structures of compounds 1-4 were elucidated on the basis of extensive two dimensional (2D)-NMR analysis.  相似文献   
215.
Yong He  H.V. Rasika Dias 《Tetrahedron》2006,62(37):8755-8769
N-Alkyl acryloylamides derived from o-aminobenzaldehyde derivatives react with N-alkyl glycine derivatives to provide cis-fused pyrrole[3,2-c]quinolones in moderate yield and high diastereoselectivity. These same substrates engage in a tandem Michael-Mannich pathway on treatment with a secondary amine, providing corresponding quinolone derivatives. The elaboration of a pyrroloquinolone derivative via addition of an in situ generated functionalized copper acetylide to an in situ generated iminium ion provided the C2-substituted derivative. Global deprotection and reduction of the alkyne afford the tricyclic triamine core (as the HCl salt) found in martinellic acid.  相似文献   
216.
α—Fe_2O_3是多种工业催化剂的主要成分,有反铁磁结构的特殊性.张和Matijevie的实验曾经发现,草酸在均匀α-Fe_2O_3胶体粒子上的吸附随温度的升高而增加,这可能暗示着草酸从物理吸附向化学吸附的过渡.考虑到磁学测量需要更为明显的表面效应,我们制备了较小的α-Fe_2O_3粒子,并测定其吸附草酸前后的磁化率变化。  相似文献   
217.
MINDO/3 method has been used to study the mechanism of the consecutive addition ofHCN to aminoacetonitrile.The results obtained for the first three steps show that the reaction isexothermic,and step I is the rate determining step.  相似文献   
218.
EDTA, the target compound of this study from the effluent of secondary biotreatment units, can be biodegraded by special microorganisms. So far, there are three species of microorganisms—Agrobacterium, Gram-negative BNCI, and DSM9103—that can degrade EDTA and are published in the literature. We have successfully isolated a bacterial strain that can degrade EDTA. It was identified as Burkhol cepacia, an aerobic species, elliptically shaped with a length of 5–15 μm. The growth medium contains 1000 mg/L of ferric-EDTA as carbon source, 750 mg/L of (NH4)2SO4+(NH2)2CO as nitrogen source, and 1000 mg/L of KH2PO4 as phosphorus source, and mineral factors such as Fe and Mg. Incubated at pH, 7.0, 30°C, and 150 rpm on a shaker for 15 d, the average specific growth rate of this microbe is 0.135 d−1, which shows that the respective degradation efficiency of Fe-EDTA and Cu-EDTA is 90 and 75% individually.  相似文献   
219.
Three new β-dihydroagarofuran sesquiterpene polyol esters,one alkaloid andtwo non-alkaloids,were isolated from the MeOH extract of seed oil of Celastrus angulatus.Their structures were elucidated on the basis of UV,IR,mass,NOE difference,~1H-NMR,~(13)C-NMR and ~1H-~(13)C long-range correlation spectroscopy.  相似文献   
220.
A new thiol weak-fluorescence probe, 5-maleimidyl-2-(m-methylphenyl)benzoxazole (MMPB), gives a highly fluorescence product in the presence of Cys. In this paper, MMPB has been developed for the fluorimetric determination of cysteine (Cys). At lambda(ex)/lambda(em) = 305.6/425.6 nm, the linear range is from 0 to 3.3 x 10(-7) mol l(-1) and the detection limit (sigma = 3) of 6.2 x 10(-10) mol l(-1). The main advantage of this method lies in the relative high selectivity compared with the methods using other N-substituted maleimide type of thiol reagents, in which 0.15-fold (molar ratio) of GSH is allowed and most of other amino acids at 100-fold (molar ratio) level had no obvious effect on the results. The proposed method has been applied to the determination of Cys in real samples.  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