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   3186篇
  免费   603篇
  国内免费   519篇
化学   2457篇
晶体学   34篇
力学   144篇
综合类   29篇
数学   395篇
物理学   1249篇
  2024年   8篇
  2023年   82篇
  2022年   90篇
  2021年   128篇
  2020年   155篇
  2019年   161篇
  2018年   142篇
  2017年   132篇
  2016年   175篇
  2015年   200篇
  2014年   198篇
  2013年   243篇
  2012年   287篇
  2011年   304篇
  2010年   234篇
  2009年   224篇
  2008年   241篇
  2007年   182篇
  2006年   175篇
  2005年   153篇
  2004年   98篇
  2003年   62篇
  2002年   79篇
  2001年   47篇
  2000年   55篇
  1999年   60篇
  1998年   31篇
  1997年   51篇
  1996年   63篇
  1995年   59篇
  1994年   45篇
  1993年   40篇
  1992年   19篇
  1991年   27篇
  1990年   15篇
  1989年   13篇
  1988年   10篇
  1987年   3篇
  1986年   6篇
  1985年   3篇
  1984年   1篇
  1983年   1篇
  1982年   1篇
  1980年   1篇
  1965年   3篇
  1936年   1篇
排序方式: 共有4308条查询结果,搜索用时 15 毫秒
11.
Motivated by the quasi-local mass problem in general relativity, we study the rigidity of isometric immersions with the same mean curvature into a warped product space. As a corollary of our main result, two star-shaped hypersurfaces in a spatial Schwarzschild or AdS-Schwarzschild manifold with nonzero mass differ only by a rotation if they are isometric and have the same mean curvature. We also prove similar results if the mean curvature condition is replaced by an σ2-curvature condition.  相似文献   
12.
Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non-solvent to its dilute solution is reported. A three-dimensional network of tangled and snake-like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non-solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application.  相似文献   
13.
Herein, we report two novel derivatives of hexabenzoperylene (HBP) that are functionalized with ester groups. Methyl acetate functionalized HBP ( 1 ) in single crystals self‐assembles into a supramolecular nanosheet, which has a two‐dimensional π‐stack of HBP sandwiched between two layers of ester groups. With the same self‐assembly motif, active ester‐functionalized HBP ( 2 ) in field effect transistors has enabled differentiation of tertiary amines from primary and secondary amines, in agreement with the fact that active ester reacts with primary and secondary amines but not with tertiary amines to form amides.  相似文献   
14.
To expand the library of pyrrole‐containing flavor precursors, two new flavor precursors—methyl N‐benzyl‐2‐methyl‐5‐formylpyrrole‐3‐carboxylate (NBMF) and methyl N‐butyl‐2‐methyl‐5‐formylpyrrole‐3‐carboxylate (NUMF)—were synthesized by cyclization, oxidation, and alkylation reactions. Thermogravimetry (TG), differential scanning calorimeter, and pyrolysis–gas chromatography/mass spectrometry were utilized to analyze the thermal degradation behavior and thermal degradation products of NBMF and NUMF. The TG‐DTG curve indicated that the maximum mass loss rates of NBMF and NUMF appear at 310 and 268°C, respectively. The largest peaks of NBMF and NUMF showed by the differential scanning calorimeter curve were 315 and 274°C, respectively. Pyrolysis–gas chromatography/mass spectrometry detected small molecule fragrance compounds appeared during thermal degradation, such as 2‐methylpyrrole, 1‐methylpyrrole‐2‐carboxylic acid methyl ester, limonene, and methyl formate. Finally, the thermal degradation mechanism of NBMF and NUMF was discussed, which provided a theoretical basis for their application in tobacco flavoring additives.  相似文献   
15.
In the present research, field-amplified sample injection–CZE (FASI–CZE) coupled with a diode array detector was established to determine trace level sulfa antibiotic. Sulfathiazole, sulfadiazine, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfisoxazole were selected as analytes for the experiments. The background electrolyte solution consisted of 70.0 mmol/L borax and 60.0 mmol/L boric acid (including 10% methanol, pH 9.1). The plug was 2.5 mmol/L borax, which was injected into the capillary at a pressure of 0.5 psi for 5 s. Then the sample was injected into the capillary at an injection voltage of –10 kV for 20 s. The electrophoretic separation was carried out under a voltage of +19 kV. The capillary temperature was maintained at 20˚C throughout the analysis, and six sulfonamides were completely separated within 35 min. Compared with pressure injection-CZE, the sensitivity of FASI-CZE was increased by 6.25–10.0 times, and the LODs were reduced from 0.2–0.5 to 0.02–0.05 μg/mL. The method was applied to the determination of sulfonamides in river water and particulate matter samples. The recoveries were 78.59–106.59%. The intraday and interday precisions were 2.89–7.35% and 2.77–7.09%, respectively. This provides a simpler and faster method for the analysis of sulfa antibiotic residues in environmental samples.  相似文献   
16.
17.
18.
Duzhong Jiangya Tablet (DJT) composed of Eucommia ulmoides Oliv. and several other traditional Chinese medicines is a Chinese herbal compound, which is clinically used to treat hypertension. The aim of this study was to evaluate the antihypertensive effect of DJT and amlodipine besylate (AB) on the synergistic treatment of spontaneously hypertensive rats (SHRs), and to explore its antihypertensive mechanism. The synergistic therapeutic effect of DJT in combination with AB on SHR was studied using two metabolomics methods based on mass spectrum (MS) and nuclear magnetic resonance. Metabolomics analysis of plasma, urine, liver, and kidney and the combination of orthogonal partial least squares discriminant analysis was performed to expose potential biomarkers. Then, the overall metabolic characteristics and related abnormal metabolic pathways in hypertensive rats were constructed. Blood pressure measurements showed that DJT combined with AB has better effects in treating hypertension than it being alone. A total of 30 biomarkers were identified, indicating that hypertension disrupted the balance of multiple metabolic pathways in the body, and that combined administration restored metabolite levels better than their administration alone. The changes of biomarkers revealed the synergistic therapeutic mechanism of DJT combined with AB, which provided a reference for the combination of Chinese and Western medicines.  相似文献   
19.
As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)2) clusters based on coinage metals, [(PPh3)2AgO2CFcCO2Ag(PPh3)2]2 ⋅ 7 CH3OH (SC1: super capacitor) and [(PPh3)3CuO2CFcCO2Cu(PPh3)3] ⋅ 3 CH3OH (SC2), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g−1 and 210 F g−1 specific capacitance at 1.5 A g−1 in Na2SO4 electrolyte, respectively. The obtained results show that the presence of CuI instead of AgI improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC2 ([(PPh3)2CuO2CFcCO2]), a polymeric structure of SC2, was synthesized and used as an energy storage electrode. PSC2 displays high conductivity and gives 455 F g−1 capacitance at 3 A g−1. The PSC2 as a supercapacitor electrode presents a high power density (2416 W kg−1), high energy density (161 Wh kg−1), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.  相似文献   
20.
Enantioselective total syntheses of pseudopteroxazole ( 1 ) and ileabethoxazole ( 2 ) are presented. The two original stereocenters were constructed in excellent enantioselectivity and good diastereoselectivity through Carreira's asymmetric dual catalytic allylation, which shows potential for accessing diastereoisomers at C2 and C3 of 1 and 2 . Cationic cyclizations of 13 and 24 demonstrated an effective pathway for the construction of the opposite configurations at C1 in 1 and 2 . Additionally, an approach for the introduction of methyl at C4 is a feasible solution for structural modifications at C4 in 1 and 2 .  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