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   11613篇
  免费   1107篇
  国内免费   848篇
化学   7989篇
晶体学   486篇
力学   104篇
综合类   74篇
数学   2420篇
物理学   2495篇
  2024年   13篇
  2023年   72篇
  2022年   92篇
  2021年   133篇
  2020年   176篇
  2019年   259篇
  2018年   211篇
  2017年   239篇
  2016年   261篇
  2015年   449篇
  2014年   486篇
  2013年   1042篇
  2012年   835篇
  2011年   935篇
  2010年   874篇
  2009年   1003篇
  2008年   900篇
  2007年   805篇
  2006年   666篇
  2005年   510篇
  2004年   495篇
  2003年   449篇
  2002年   490篇
  2001年   290篇
  2000年   268篇
  1999年   245篇
  1998年   200篇
  1997年   161篇
  1996年   150篇
  1995年   112篇
  1994年   107篇
  1993年   79篇
  1992年   64篇
  1991年   46篇
  1990年   25篇
  1989年   17篇
  1988年   14篇
  1985年   41篇
  1984年   20篇
  1983年   22篇
  1982年   25篇
  1981年   48篇
  1980年   32篇
  1979年   17篇
  1978年   26篇
  1977年   33篇
  1976年   28篇
  1975年   23篇
  1974年   24篇
  1973年   24篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
151.
152.
A pressure‐controlled procedure for the SN1 reaction of rac‐1‐[(dimethylamino)methyl]‐2‐(tributylstannyl)ferrocene ( 1 ) to rac‐1‐(phthalimidomethyl)‐2‐(tributylstannyl)ferrocene ( 2 ) was developed. Pd0‐Catalyzed Stille coupling of 2 with iodobenzene afforded rac‐1‐phenyl‐2‐(N‐phthalimidomethyl)ferrocene ( 5 ) in 74% yield; after trace enrichment by crystallization of the combined mother liquors, one single crystal of each, 5 , catalysis intermediate trans‐iodo(σ‐phenyl)bis(triphenylarsino)palladium(II) ( 7 ), trans‐diiodobis(triphenylarsino)palladium(II) ( 8 ), and rac‐2,2′‐bis(phthalimidomethyl)‐1,1′‐biferrocene ( 9 ) could be isolated by crystal sorting under a microscope and characterized by X‐ray crystal structure analysis. Furthermore, 5 was deprotected to amine ( 11 ), which does even survive the Birch reduction to rac‐1‐(aminomethyl)‐2‐(cyclohexa‐2,5‐dienyl)ferrocene ( 12 ).  相似文献   
153.
Using high‐resolution transmission electronic micrograph (HR‐TEM) observation, one can clearly see the pore geometry of the MCM‐41 and SBA‐15 mesoporous silicas to determine that their pore shapes are hexagonal and round, respectively. With the perpendicular orientations of the nanochannels to the electron beam, parallel line images of the (100) and (110) repeating spacings were observed. In the SBA‐15 mesoporous silicas, there are byproducts of the granular silica and disordered mesostructures, attributed to the weak hydrogen interactions between Pluronic 123 blockcopolymer and the silica species. There are also many different and significant +π disclination defects in SBA‐15 and MCM‐41 surfactant‐silica composites. The SBA‐15 with a thicker silica wall is more stable under irradiation by high‐energy electron beams compared to MCM‐41, which has thinner wall thickness. Some carbon nanostructure impurities were found in some carbon films on the metal grids.  相似文献   
154.
Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by 1H, 13C, and 31P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the 2JP? N? P coupling constants were determined by 13C{1H, 31P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.  相似文献   
155.
南桐煤镜质组非晶结构的X射线衍射研究   总被引:7,自引:1,他引:7  
本文对经典煤核结构模型评述后,提出了多元非晶煤结构概念。用X射线衍射方法研究了南桐煤镜质组的原子径各分布,论证了煤大分子中同时存在芳香结构单元和脂环结构单元,它们对X射线射射强度均有贡献,非晶煤结构的有序性不在于1nm。  相似文献   
156.
Maher WA 《Talanta》1983,30(7):534-536
The use of wet and dry ashing procedures to decompose marine biological tissues and to degrade organoarsenic compounds to inorganic arsenic for analysis by zinc-column arsine generation and atomic-absorption spectrophotometry was investigated. Wet ashing with nitric, sulphuric and perchloric acids (10:2:3 v/v) released the largest percentage of arsenic from fish tissue and quantitatively degraded methylated and other organoarsenic compounds to inorganic arsenic. The arsenic concentrations found when standard reference materials were ashed with this acid mixture were in agreement with the certified values.  相似文献   
157.
We optimized the hot water extraction of polysaccharides from the root of Henry wood betony (RHWPs) using a uniform test and explored their anti-tumor activities in vitro and in vivo. The optimal extraction conditions were as follows: 40 min extraction time, liquid/solid ratio 30 mL/g, 100 min soaking time, two extraction cycles, 100% ethanol concentration, and extraction temperature of 80 °C. The molecular weight distribution of RHWPs with MWs was 228,600 g/mol and 5001 g/mol. The IR spectrum further indicated that RHWPs are acidic polysaccharides containing pyranose and furan rings. The main monosaccharides found in RHWPs were mannose, ribose, l-rhamnose monohydrate, glucuronic acid, galacturonic acid, glucose, galactose, xylose, arabinose, and fucose. RHWPs inhibited the proliferation of S180 tumor cells and induced apoptosis in vitro. Oral administration of RHWPs to tumor-bearing mice significantly inhibited the growth of the S180 xenografts, accelerated apoptosis in tumor cells, and expanded the necrotic regions. Furthermore, RHWPs also markedly increased the levels of TNF-α, IFN-γ, and IL-2 in the sera of tumor-bearing mice, and activated immune cells such as lymphocytes, NK cells, and macrophages, thereby inducing tumor cell apoptosis. Taken together, RHWPs are a promising anti-tumor agent that ought to be explored further.  相似文献   
158.
The dielectric constant ?' and loss tangent tan δ of chlorobenzene-cis-decalin mixtures have been measured in the temperature range 77 K to 330 K and frequency range 0.1 to 100 kHz. On cooling, ?' increases with decreasing temperature upto about 135 K, after which it drops rapidly with decreasing T followed by a slow decrease. This indicates that the liquid mixture goes to an amorphous phase which transforms to a glass phase of restricted dipole rotation below Tg; however, the peak in ?' is due to relaxation in the amorphous phase (α relaxation) and does not give an exact Tg. On heating, the behaviour of the cooling curve is retraced upto 160 K, after which ?' drops suddenly to a value lower than that at 77 K in the glass phase. This indicates the transition to a crystalline phase in which dipole rotational freedom is completely lost. The crystalline phase changes to a eutectic liquid phase of high ?' at a temperature (200 K) lower than the melting point of chlorobenzene and cis-decalin. Dielectric dispersion is observed only in the glass and amorphous phases. The dielectric relaxation time is independent of the concentration of chlorobenzene.  相似文献   
159.
Toxicity assays applied to wastewater treatment   总被引:1,自引:0,他引:1  
The utility and validity of toxicity tests for monitoring of wastewater treatment have been assessed. The evaluated acute toxicity tests have been Vibrio fischeri, Selenastrum capricornotum and Daphnia magna tests. The validation studies indicated that the acute toxicity tests can be considered as high sensitivity analytical tools to detect common environmental concentrations of the pollutants at concentration levels as low as ng l−1. The toxicity tests showed to have discriminatory ability to distinguish between different degrees of toxicity, and the toxic specificity of the compounds on target organisms. Synergistic, additive or antagonistic effects were evaluated indicating the capacity of the toxicity test to assess the combined effects of chemicals in wastewaters. The reproducibility of these tests, calculated as relative standard deviation, is acceptable in the range of 5-22.3%. The application of multivariate date analysis proved that toxicity and chemical measures are complementary analytical tools for monitoring of wastewaters quality. The toxicity tests are useful analytical tools for screening of chemical analysis and as an early warning system to monitor the treatment of WWTPs. The use of single toxicity test or battery of tests is the best approach to evaluate the risk because they are reliable indices of the toxic impact of effluents in the aquatic environment. The toxicity tests were applied in the quality control of different European WWTPs.  相似文献   
160.
纳米α-FeOOH催化剂一段法脱除COS和H2S性能的研究   总被引:11,自引:1,他引:11  
利用均相沉淀法、氨水滴定法制备纳米α-FeOOH粒子,以该粒子为活性组分制备催化剂,利用微反-色谱联用活性评价技术,在常压、空速10 000 h-1、25 ℃~60 ℃温度范围内考察了纳米α-FeOOH催化剂对COS催化水解的活性。采用热重法对纳米α-FeOOH催化剂脱除H2S的性能进行了研究。结果表明:纳米α-FeOOH催化剂对COS水解在低温度、大空速下具有高的活性,系列Ⅰ和系列Ⅱ催化剂分别在60 ℃和40 ℃~45 ℃时COS转化率达到100%。在60 ℃时各种催化剂吸附H2S的能力最强,最高饱和硫容可达到21.72w%。催化剂表面能量分布不均匀,COS催化水解在低温时存在补偿效应。  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