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   15721篇
  免费   1776篇
  国内免费   1659篇
化学   12011篇
晶体学   213篇
力学   740篇
综合类   137篇
数学   1509篇
物理学   4546篇
  2024年   31篇
  2023年   203篇
  2022年   407篇
  2021年   531篇
  2020年   526篇
  2019年   538篇
  2018年   426篇
  2017年   461篇
  2016年   684篇
  2015年   657篇
  2014年   812篇
  2013年   1115篇
  2012年   1372篇
  2011年   1443篇
  2010年   1033篇
  2009年   909篇
  2008年   1134篇
  2007年   957篇
  2006年   900篇
  2005年   777篇
  2004年   652篇
  2003年   570篇
  2002年   603篇
  2001年   412篇
  2000年   322篇
  1999年   289篇
  1998年   213篇
  1997年   174篇
  1996年   143篇
  1995年   129篇
  1994年   87篇
  1993年   94篇
  1992年   86篇
  1991年   93篇
  1990年   53篇
  1989年   41篇
  1988年   49篇
  1987年   40篇
  1986年   34篇
  1985年   32篇
  1984年   20篇
  1983年   17篇
  1982年   19篇
  1981年   9篇
  1980年   9篇
  1979年   6篇
  1978年   6篇
  1975年   6篇
  1971年   6篇
  1970年   7篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
High-speed counter-current chromatography (HSCCC) was used to purify salidroside from an extract of Rhodiola crenulata with two steps using a two-phase solvent system composed of ethyl acetate-n-butanol-water (1:4:5, v/v) in the first run and chloroform-methanol-isopropanol-water (5:6:1:4) in the second run. The method yielded 21.9 mg of salidroside from 1.216 g of the crude sample at 98% purity determined by HPLC analyses. Identification was performed by 1H NMR, 13C NMR, and MS.  相似文献   
82.
The hydrosilylation reaction of octa(hydrido)silsesquioxane with ω‐halo‐1‐alkenes and other unsaturated substrates allows attachment of 8 long‐chain functionalized alkyls on the cubic Si8O12 skeleton. Pt/C and H2PtCl6 have been adopted as the catalysts, the yields being 74–98% for compounds 2–9 . For terminal alkenes, the hydrosilylation follows the anti‐Markonikov's rule. The morphological state of 2–9 ranges from viscous liquid to crystalline materials. The pyrolysis results indicate that 7 , a material of hard spherical core and soft flexible shell, may likely act as nanometer‐size ball bearings up to more than 400 °C. The X‐ray structure of 9 reveals that the molecule is required to possess a center of symmetry crystallographically. The linear arms on 9 , except for two of them, are virtually all‐trans in conformation, not counting the ω‐C‐Cl bond.  相似文献   
83.
A novel method, modified matrix solid-phase dispersion (MMSPD), has been developed for quantitative analysis of organophosphorus pesticide residues in soil. It was based on matrix solid-phase dispersion (MSPD) and continuous liquid-solid extraction (continuous LSE), using Florisil as sorbent and dichloromethane as the recycling solvent. Two soils with different texture and physicochemical properties were studied to validate the method. The effect of residence time of pesticides in soil was also studied. MMSPD was compared with MSPD and continuous LSE respectively. Determination was carried out by gas chromatography with nitrogen-phosphorus detection (GC-NPD). The method gave recoveries ranging from 72–105% with relative standard deviations (RSDs) lower than 15% for the pesticides studied. The limits of detection (LODs) ranged from 0.1 to 0.6 ng g−1. Two pesticide residues have been detected in real soil samples from Fujian, China, using MMSPD. The pesticides were confirmed by gas chromatography-mass spectrometry (GC-MS) in a selected-ion monitoring (SIM) mode. Revised: 4 and 9 April 2006  相似文献   
84.
IthasbeenreportedthatTrichosanthi11(TCS),isolatedfromrkiI-ilolt)ii,hasanti-tumorI-4andanti-vira1activities5-'.Someanti-tun1orremedies,whicharedesignedfromTCS,arebeingtestedanddeveloped'-.'.StudyingthebioIogicalphenomenonbyelectrochemicalmethodsisanewhotresearchspotemerginginrecentyears".Manyresultsshowedthatnotonlytheenzymesystemsuchassuccinatedehydrogenasedisplayedthediode-likebehaviorduringtheelectrontransferprocess",butalsothehigh1yorganizedorganeIle,forexample,mitochondria,andevenintac…  相似文献   
85.
Equivalence of functional-differential equations of neutral type to well-posed abstract Cauchy problems in the state spaces n }L p ,L p resp.C is investigated. The assumptions allow non-atomic difference operators.This work was supported by the Fonds zur Förderung der wissenschaftlichen Forschung (Austria) under Grant No. P4534.Work done by this author was done during a stay at the University of Graz from October 1981 till April 1984.  相似文献   
86.
1 INTRODUCTION Nonlinear optics (NLO) is at the forefront of cur- rent researches because of its importance in provi- ding the key functions of frequency shifting, optical modulation, optical switching, optical logic and op- tical memory for the emerging …  相似文献   
87.
Loniceroside C,an antiinflammatory saponin from Lonicera japonica   总被引:6,自引:0,他引:6  
A new triterpenoid saponin, loniceroside C was isolated from the aerial parts of Lonicera japonica. Its structure was established to be 3-O-beta-D-glucopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl (1-->2)-[beta-D-xylopyranosyl(1-->6)]-beta-D-glucopyranosyl ester by spectroscopic techniques and chemical transformations. Loniceroside C showed in vivo antiinflammatory activity against mouse ear edema provoked by croton oil.  相似文献   
88.
Two-photon photodynamic therapy (TP-PDT) is a promising approach for the treatment of cancer because of its better penetration depth and superior spatial selectivity. Here, we describe an azo group containing cyclized-cyanine derivatives (ACC1 and ACC2) as a two-photon activated, type I based photosensitizer (PS). These small-molecule and heavy atom-free organic dyes showed marked reactive oxygen species (ROS)-generating ability under physiological conditions, as well as fast loading ability into the cells and negligible dark toxicity. Live cell analyses with one- and two-photon microscopy revealed that these dyes showed higher ROS generation ability upon two-photon excitation than upon one-photon excitation via the type I process. The PSs have superior PDT properties compared to conventional Visudyne and 5-ALA under mild conditions. These characteristics allowed for precise PDT at the target region in mimic tumor spheroids, demonstrating that the developed TP PS could be useful in efficient PDT applications and in designing various PSs.

Azo containing dyes as a two-photon selective and type I based photosensitizers (PSs) were developed that exhibit excellent photodynamic therapy properties under mild condition.  相似文献   
89.
Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH3CH2OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO3, for ethane oxidation into CH3CH2OOH, achieving an impressive yield of 1887 μmol gcat−1 in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH3CH2OOH production by six times to 11 233 μmol gcat−1 at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH3CH2OOH as a potential anticancer drug.

Highly efficient visible-light driven photocatalytic oxidation of ethane into ethyl hydroperoxide was realized for the first time over Au/WO3.  相似文献   
90.
Kim HG  Lee CW  Yun S  Hong BH  Kim YO  Kim D  Ihm H  Lee JW  Lee EC  Tarakeshwar P  Park SM  Kim KS 《Organic letters》2002,4(22):3971-3974
[formula: see text] A new molecular system, 2,11-dithio[4,4]metametaquinocyclophane containing a quinone moiety, was designed and synthesized. As the quinone moiety can readily be converted into an aromatic pi-system (hydroquinone) upon reduction, the nanomechanical molecular cyclophane system exhibits a large flapping motion like a molecular flipper from the electrochemical redox process. The conformational changes upon reduction and oxidation are caused by changes of nonbonding interaction forces (devoid of bond formation/breaking) from the edge-to-face to face-to-face aromatic interactions and vice versa, respectively.  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