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   2949篇
  免费   443篇
  国内免费   335篇
化学   3037篇
晶体学   27篇
力学   34篇
综合类   28篇
数学   5篇
物理学   596篇
  2024年   11篇
  2023年   38篇
  2022年   105篇
  2021年   102篇
  2020年   160篇
  2019年   124篇
  2018年   98篇
  2017年   90篇
  2016年   162篇
  2015年   135篇
  2014年   140篇
  2013年   374篇
  2012年   192篇
  2011年   152篇
  2010年   132篇
  2009年   139篇
  2008年   132篇
  2007年   182篇
  2006年   143篇
  2005年   160篇
  2004年   139篇
  2003年   123篇
  2002年   134篇
  2001年   60篇
  2000年   58篇
  1999年   35篇
  1998年   50篇
  1997年   41篇
  1996年   67篇
  1995年   53篇
  1994年   23篇
  1993年   19篇
  1992年   25篇
  1991年   16篇
  1990年   14篇
  1989年   16篇
  1988年   12篇
  1987年   8篇
  1986年   3篇
  1985年   7篇
  1984年   3篇
  1983年   8篇
  1982年   7篇
  1980年   2篇
  1979年   2篇
  1977年   2篇
  1975年   7篇
  1974年   6篇
  1973年   8篇
  1972年   2篇
排序方式: 共有3727条查询结果,搜索用时 15 毫秒
61.
A new fertilizer of cocrystal type,known as durably efficacious ammonium bicarbonate (DEAB),has been developed by adding a certain amount of dicyandiamide (DCD) as an ammonia-stabilizing agent to ammonium bearbenate(AB)during the process of its production.As compared with AB,DEAB was found to have a reduction of direct volatilization loss by 53%,a fertilizer availability period prolonged from 35-45 to 90-110 d,and an increase in the rate of nitrogen in fertilizer being utilized by 5.9%-10.2%,and a saving of the amount of fertilizer to be ap-phed by 20%-30% for the same level of yield,or an increase of the crop yield by over 10% for the same level of ni-tregen fertilization;in addition,it was found to show usually a function of promoting the crop to early mature.It can be apptied as basal dressing all in one time to soil and thus also used as a labour-saving and crop yield-increasing fertil-izer for is non-mtertillage,plastics film covering and water-saving agriculture  相似文献   
62.
Storage-reduction of NOx by carbon monoxide was investigated over combined catalysts of Mn/Ba/Al2O3-Pt/Ba/Al2O3. Combination of Mn/Ba/Al2O3 and Pt/Ba/Al2O3 catalysts in different ways showed excellent NOx storage-reduction performance and the content of Pt could be reduced by 50%. Not only the addition of 5Mn/15Ba/Al2O3 to lPt/15Ba/Al2O3 could improve its storage ability, but also enhance the NOx conversion consequently. NOx conversion over the combined catalysts (the combined catalysts I and II) was increased under dynamic lean-rich burn conditions, the maximum NOx conversion increased from 69.4% to respectively 78.8% and 75.7% over two combined catalysts.  相似文献   
63.
Efforts were made to assess the efficiency of an anaerobic filter packed with porous floating ceramic media and to identify the optimum operational condition of anaerobic filter as a pretreatment of swine wastewater for the subsequent biological removal of nitrogen and phosphorus. A stepwise decrease in hydraulic retention time (HRT) and an increase in organic loading rate (OLR) were utilized in an anaerobic filter reactor at mesophilic temperature (35°C). The optimum operating condition of the anaerobic filter was found to be at an HRT of 1 d. A soluble chemical oxygen demand (COD) removal efficiency of 62% and a total suspended solids removal efficiency of 39% at an HRT of 1 d were achieved with an OLR of 16.0 kg total COD/(m3·d), respectively. The maximum methane production rate approached 1.70 vol of biogas produced per volume of reactor per day at an HRT of 1 d. It was likely that the effluent COD/total Kjeldahl nitrogen ratio, of 22, the COD/total phosphorous ratio of 47, and the high effluent alkalinity >2500 mg/L as CaCO3 of the anaerobic filter operated at an HRT of 1 d was adequate for the subsequent biological removal of nitrogen and phosphorus.  相似文献   
64.
The structure of Ph[PhC(O)NH]2P=NC(O)Ph (2) in solid state and in solution is discussed on the basis of a crystal structure analysis and IR and Raman spectra. In crystalline state 2 forms dimers which are associated via two pairs of bifurcated (N–H)2O=C hydrogen bonds. The spectroscopic data are in good agreement with the crystallographic results with respect to the hydrogen bonding and they suggest that 2 also in solution is associated.  相似文献   
65.
本文利用诱导效应指数建立了含硫含氮的低碳直链有机物的标准汽化热的简单估算方法,我们利用此法计算了一些含硫含氮的直链有机物的标准汽化热,41个可比较值的相对误差均在5%以内。  相似文献   
66.
Reaction of the side-on end-on dinitrogen complex [{(NPN)Ta}(2)(mu-H)(2)(mu-eta(1):eta(2)-N(2))] (1; in which NPN=(PhNSiMe(2)CH(2))(2)PPh), with the Lewis acids XR(3) results in the adducts [{(NPN)Ta}(2)(mu-H)(2)(mu-eta(1):eta(2)-NNXR(3))], XR(3)=GaMe(3) (2), AlMe(3) (3), and B(C(6)F(5))(3) (4). The solid-state molecular structures of 2, 3, and 4 demonstrate that the N-N bond length increases relative to those found in 1 by 0.036, 0.043, and 0.073 A, respectively. In solution complexes 2-4 are fluxional as evidenced by variable-temperature (1)H NMR spectroscopy. The (15)N{(1)H} NMR spectra of 2-4 are reported; furthermore, their vibrational properties and electronic structures are evaluated. The vibrational structures are found to be closely related to that of the parent complex 1. Detailed spectroscopic analysis on 2-4 leads to the identification of the theoretically expected six normal modes of the Ta(2)N(2) core. On the basis of experimental frequencies and the QCB-NCA procedure, the force constants are determined. Importantly, the N-N force constant decreases from 2.430 mdyn A(-1) in 1 to 1.876 (2), 1.729 (3), and 1.515 mdyn A(-1) (4), in line with the sequence of N-N bond lengths determined crystallographically. DFT calculations on a generic model of the Lewis acid adducts 2-4 reveal that the major donor interaction between the terminal nitrogen atom and the Lewis acid is mediated by a sigma/pi hybrid molecular orbital of N(2), corresponding to a sigma bond. Charge analysis performed for the adducts indicates that the negative charge on the terminal nitrogen atom of the dinitrogen ligand increases with respect to 1. The lengthening of the N-N bond observed for the Lewis adducts is therefore explained by the fact that charge donation from the complex fragment into the pi* orbitals of dinitrogen is increased, while electron density from the N-N bonding orbitals p(sigma) and pi(h) is withdrawn due to the sigma interaction with the Lewis acid.  相似文献   
67.
A novel method that allows the determination of the electrical potential of a polymer surface has been applied for polypropylene film treated by N2 + H2 cold plasma. The plasma treatment results in formation on the film surface of NH2 groups, which then gets transformed to NH3+ in contact with an electrolyte and leads to the formation of an electrical double layer. The method consists of theoretical calculation of electrical model potential, using the measurement of the electrical capacitance of the film in contact with an electrolyte by dielectric spectroscopy. Comparison with the results obtained by theoretical model shows similar dependencies of the electrical potential as a function of amino‐groups density and electrolyte concentration, but systematic differences of absolute values are observed. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   
68.
A HPLC method for the analysis of polycyclic aromatic nitrogen heterocyclics (PANHs) in complex sample matrices is presented. It isolated and separated carbazole and acridine type PANHs with an absolute recovery of between 79–98%. Open column chromatography is used as an initial step to isolate a PANH fraction. By applying normal-phase liquid chromatography using a dimethylaminopropyl silica stationary phase and utilising back-flush technique it was possible to separate the PANH fraction into two fractions containing acridine type and carbazole type PANHs, respectively. The method applied on a sample of solvent refined coal heavy distillate (SRC II HD). A number of 3–5 ring acridines and carbazoles were identified with GC–electron impact MS and quantified with GC–nitrogen–phosphorous detection. Polycyclic aromatic hydrocarbons (PAHs) were determined in the SRC II HD sample by automated on-line clean-up and analysis of the obtained PAH fraction with coupled LC–GC–flame ionization detection. There was no overlap between the PANH and the PAH fractions with this method, and carbazoles and acridines were efficiently separated.  相似文献   
69.
3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described.  相似文献   
70.
Specific sorption sites for nitrogen, N2, in NaLSX and LiLSX zeolites were investigated using a DRIFT spectroscopic method. Sorption of molecular hydrogen, H2, by NaLSX or LiLSX zeolite at 77 K with DRIFT control of perturbation of sorbed molecules allowed to discriminate two or three different types of specific sorption sites in the respective zeolites. Their H–H stretching frequencies are 4077 and 4081 cm–1 for NaLSX, and 4061, 4084 and 4129 cm–1 for LiLSX. With reference to an independent investigation by methods of both sorption thermodynamics and molecular modeling for N2 sorption on LiLSX, the first two of the corresponding bands were ascribed to H2 sorption on lithium cations, Li+, localized in supercages of the faujasite, FAU, zeolite framework at sites SIII and SIII, while the latter band most likely belongs to H2 sorption on Li+ cations at sites SII, and on hydroxyl groups, OH. Sorption of N2 by Li+ cations at sites SIII and SIII is the strongest, resulting in a decrease of intensity of the corresponding DRIFT bands that stem from subsequent H2 sorption. Nitrogen sorption by Li+ cations at sites SII is much weaker. Sorption of N2 on Na+ cations at sites SIII in NaLSX zeolite is also stronger than by Na+ cations at sites SII.  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