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   23714篇
  免费   3023篇
  国内免费   2395篇
化学   11168篇
晶体学   227篇
力学   837篇
综合类   130篇
数学   1605篇
物理学   5546篇
综合类   9619篇
  2024年   93篇
  2023年   399篇
  2022年   642篇
  2021年   752篇
  2020年   719篇
  2019年   732篇
  2018年   595篇
  2017年   623篇
  2016年   853篇
  2015年   974篇
  2014年   1306篇
  2013年   1625篇
  2012年   1885篇
  2011年   2008篇
  2010年   1529篇
  2009年   1500篇
  2008年   1567篇
  2007年   1530篇
  2006年   1236篇
  2005年   1060篇
  2004年   863篇
  2003年   669篇
  2002年   675篇
  2001年   593篇
  2000年   542篇
  1999年   518篇
  1998年   466篇
  1997年   426篇
  1996年   422篇
  1995年   379篇
  1994年   348篇
  1993年   296篇
  1992年   240篇
  1991年   217篇
  1990年   185篇
  1989年   169篇
  1988年   137篇
  1987年   92篇
  1986年   76篇
  1985年   57篇
  1984年   32篇
  1983年   16篇
  1982年   6篇
  1981年   10篇
  1980年   10篇
  1979年   11篇
  1977年   6篇
  1976年   8篇
  1975年   6篇
  1957年   5篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
851.
The BiCl3‐catalyzed reaction of pyrroles with electron‐deficient olefins generated the corresponding Michael adducts in high yields.  相似文献   
852.
We present here a practical stereoselective synthetic method to produce enantiopure isomers of a new muscarinic receptor antagonist, HL‐031120 (3‐quinuclidinyl‐2′‐cyclopentyl‐2′‐hydroxy‐2′‐phenylacetate, I). Four optical isomers were effectively by stereoselective synthesized using pivaldehyde as steric hindrance agent from the chiral starting material, (S) or (R)‐mandelic acid. The isomers were obtained with 70–76% yields in 98–99% e.e.  相似文献   
853.
Ethynylferrocene was prepared in satisfactory yield by reaction of formylferrocene with triphenylphosphine and carbon tetrachloride followed by dehydrohalogenation in presence of n-butyllithum. The reaction condition is mild and the reaction time is much shorter. The method is convenient and economical.  相似文献   
854.
We report on a multiplex bead-based competitive immunoassay using suspension array technology for the simultaneous detection of the pesticides triazophos, carbofuran and chlorpyrifos. Three hapten-protein conjugates were covalently bound to carboxylated fluorescent microspheres to serve as probes. The amount of conjugates and antibodies were optimized. The new multi-analyte assay has dynamic ranges of 0.02–50 ng?mL?1, 0.5–500 ng?mL?1 and 1.0–1000 ng?mL?1 for triazophos, carbofuran and chlorpyrifos, respectively, and the detection limits are 0.024, 0.93 and 1.68 ng?mL?1. This new multiplex assay is superior to the traditional ELISA in possessing a wider detection range, better reproducibility and the feature of multi-target detection. Cross-reactivity studies indicated that the bead-array method is highly selective for the three target pesticides, and that individual analyses have no significant influence between each other, also without cross-reactions from other structurally related pesticides. The method was applied to analyze vegetables spiked with the three pesticides, and the recoveries were in ranges of 78.5–112.1 %, 72.2–120.2 % and 70.2–112.8 %, respectively, with mean coefficients of variation of <15 %.
Figure
Schematic illustration of the multiplex bead-based competitive immunoassay  相似文献   
855.
We have developed a stable and sensitive nonenzymatic glucose sensor by modifying a glassy carbon electrode (GCE) with a composite incorporating nickel(II) oxides and reduced graphene. The oxides were generated by directly electrodepositing nickel on the GCE with a graphene modifier using a multi-potential pulse process, and then oxidizing nickel to nickel(II) oxides by potential cycling. In comparison to the conventional nickel(II) oxides-modified GCE, this new nickel(II) oxides-graphene modified GCE (NiO-GR/GCE) has an about 1.5 times larger current response toward the nonenzymatic oxidation of glucose in alkaline media. The response to glucose is linear in the 20 μM to 4.5 mM concentration range. The limit of detection is 5 μM (at a S/N of 3), and the response time is very short (<3 s). Other beneficial features include selectivity, reproducibility and stability. A comparison was performed on the determination of glucose in commercial red wines by high-performance liquid chromatography (HPLC) and revealed the promising aspects of this sensor with respect to the determination of glucose in real samples.
Figure
A stable and sensitive nonenzymatic glucose sensor is developed by preparing the nickel(II) oxides-reduced graphene nanocomposite modified glassy carbon electrode (NiO-GR/GCE), and then used to detect the glucose contents in the commercial red wines. This NiO-GR/GCE also has a high selectivity  相似文献   
856.
The C1–8 fragment of autolytimycin was synthesized via a reliable 10-step route capable of delivering 41% overall yield at multi-gram scale. As a key step, a chelation-controlled isopropenylation of α-oxygenated aldehydes was established with a reagent combination of diisopropenylzinc, magnesium halide, and a dichloromethane/toluene mixed solvent. Cram-chelate isopropenylation products dominated for aldehydes with a small α-substituents, such as –OMe and –OBn groups, while the Felkin product could be obtained with a bulky –OTBS group.  相似文献   
857.
Two indole-containing fullerene derivatives, N-hydrogen-2-[3-(N-2-ethylhexylindolyl)][60]fulleropyrrolidine (EHIHC60P), and N-(2-ethylhexylindolyl))-2-[3-(N-2-ethylhexylindolyl)][60]fulleropyrrolidine (DEHIC60P) were synthesized by the typical Prato reaction. The absorption spectra, electrochemical properties of the two compounds were measured. Inverted solar cells were fabricated with the structure of ITO/ZnO/poly(3-hexylthiophene) (P3HT):fullerene derivatives/MoO3/Ag. The highest power conversion efficiencies (PCEs) of 3.32% and 3.23% were obtained for P3HT/EHIHC60P and P3HT/DEHIC60P based solar cells at the composite ratio of 1:1 after the active layers were annealed at 150 °C under inert atmosphere, with a open-circuit voltage (Voc) of 0.66 V and 0.74 V, respectively. For comparison, the device based on P3HT/PCBM at the same conditions showed the PCE of 3.28%, with a Voc of 0.61 V. The influence on the photovoltaic property of the fullerene derivatives, which was induced by some subtle changes in the chemical structure was compared and discussed.  相似文献   
858.
A transition-metal-free method for the synthesis of indolines has been developed. In the presence of K2CO3, the cyclization reaction of N-(ortho-chloromethyl)aryl amides and iodonium ylides proceeded smoothly at room temperature in moderate to good yields.  相似文献   
859.
Two coordination polymers (CPs), {[Zn2(BMB)(5‐AIPA)2] · 2H2O}n( 1 ) and [Zn(BMB)(5‐NIPA)]n( 2 ) {BMB = 1, 4‐bis[(2‐methyl‐imidazol‐1‐yl)methyl]benzene, 5‐AIPA = 5‐aminoisophthalic acid, 5‐NIPA = 5‐nitroisophthalic acid}, were synthesized under hydrothermal conditions. Compound 1 displays a 2D double‐layer structure, which is packed into a 3D supramolecule by interlayer hydrogen bonds and π–π stacking interactions. Compound 2 displays a threefold interpenetrating 3D network, which is composed of left‐handed helical chains and two types of meso‐helical chains along different directions.  相似文献   
860.
[首页] « 上一页 [81] [82] [83] [84] [85] 86 [87] [88] [89] [90] [91] 下一页 » 末  页»
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