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   26919篇
  免费   4283篇
  国内免费   4029篇
化学   20602篇
晶体学   424篇
力学   1316篇
综合类   296篇
数学   2951篇
物理学   9642篇
  2024年   94篇
  2023年   489篇
  2022年   929篇
  2021年   1016篇
  2020年   1063篇
  2019年   1126篇
  2018年   947篇
  2017年   988篇
  2016年   1289篇
  2015年   1333篇
  2014年   1669篇
  2013年   2072篇
  2012年   2483篇
  2011年   2540篇
  2010年   1946篇
  2009年   1836篇
  2008年   1947篇
  2007年   1802篇
  2006年   1684篇
  2005年   1345篇
  2004年   987篇
  2003年   783篇
  2002年   740篇
  2001年   652篇
  2000年   574篇
  1999年   481篇
  1998年   354篇
  1997年   312篇
  1996年   266篇
  1995年   254篇
  1994年   233篇
  1993年   168篇
  1992年   146篇
  1991年   135篇
  1990年   121篇
  1989年   89篇
  1988年   73篇
  1987年   53篇
  1986年   61篇
  1985年   49篇
  1984年   19篇
  1983年   18篇
  1982年   19篇
  1981年   6篇
  1980年   7篇
  1979年   8篇
  1978年   3篇
  1971年   4篇
  1957年   4篇
  1936年   4篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
An investigation aimed at checking the integration of cathodic pyrrhotite Fenton's reaction with anodic microbial respiration for the enhancement of MFC performance and treatment of a real landfill leachate was carried out. The MFC equipped with a pyrrhotite-coated graphite-cathode generated the maximum power density of 4.2 W/m3 that was 133% higher than graphite-cathode. Concomitantly, electrochemical impedance spectroscopy (EIS) showed that the polarization resistance of pyrrhotite-cathode (92 Ω) was much lower than the graphite-cathode (1057 Ω), indicating that the cathodic overpotential was significantly lowered, probably due to the occurrence of pyrrhotite Fenton's reaction. The in situ generation of Fenton's reagents (Fe2+ and H2O2) at the pyrrhotite-cathode was demonstrated by the cyclic voltammetry measurement. Besides, reactive oxygen species produced from the pyrrhotite Fenton's reaction were detected and demonstrated to be vital to the enhancement of MFC power output. Further, the effectiveness of this system was examined by treating an old-aged landfill leachate. 77% of color and 78% of COD were removed from the original leachate, indicating that the pyrrhotite not only acted as a cost-effective cathodic catalyst for MFCs in power generation, but also extended the practical merits of traditional MFCs towards advanced oxidation of biorefractory pollutants.  相似文献   
992.
Two new ent‐kaurane diterpenoids, taihangexcisoidesin C (1) and its acetonide, taihangexcisoidesin D (2), along with 9 known compounds were isolated from the leaves of Isodon excisoides. The structures of the new compounds were elucidated using 1D and 2D NMR spectroscopy analysis. Compounds 3‐6 and 8‐9 were tested for their antibacterial activity against Escherichia coli, Staphylococcus aureus, S. epidermidis and S. saprophyticus. Compound 6 showed inhibitory effects on Staphylococcus aureus, S. epidermidis and S. saprophyticus MIC values 32, 16 and 16 μg/mL, respectively. All of the compounds didn't show effects on Escherichia coli (MIC > 10 mg/mL).  相似文献   
993.
Dihydroxyurea (DHU) was synthesized using tri-associated solid phosgene [bis(trichloromethyl) carbonate] dissolved in dioxane and hydroxylamine hydrochloride dissolved in potassium acetate solution. The reduction of Pu(IV) by DHU was investigated using UV-Vis spectrophotometry. The reduction back-extraction behavior of Pu(IV) in 30% tri-butyl phosphate/kerosene was firstly investigated under conditions of various temperature, various DHU and HNO3 concentrations and various phase contact times. The results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by DHU. Simulating the 1B contactor of the PUREX process using a 0.1 M DHU in 0.36M nitric acid solution as the stripping agent, the separation factors of uranium/plutonium can reach 2.1·104. This indicates that DHU is a promising salt free agent for uranium/plutonium separation.  相似文献   
994.
Research on aggregation-induced emission (AIE) has been a hot topic. Due to enthusiastic efforts by many researchers, hundreds of AIE luminogens (AIEgens) have been generated which were mainly based on archetypal silole, tetraphenylethene, distyrylanthracene, triphenylethene, and tetraphenyl-1,4-butadiene, etc. To enlarge the family of AIEgens and to enrich their functions, new AIEgens are in high demand. In this work, we report a new kind of AIEgen based on tetraphenylpyrazine (TPP), which could be readily prepared under mild reaction conditions. Furthermore, we show that the TPP derivatives possess a good thermal stability and their emission could be fine-tuned by varying the substituents on their phenyl rings. It is anticipated that TPP derivatives could serve as a new type of widely utilized AIEgen, based on their facile preparation, good thermo-, photo- and chemostabilities, and efficient emission.  相似文献   
995.
在pH值约为8.0的BR缓冲介质中,桑色素、槲皮素和芦丁等黄酮类物质能与Fe(phen)2+3反应形成离子缔合物,此时将引起共振瑞利散射(RRS)显著增强,最大RRS波长均位于310 nm. 在一定范围内散射强度(ΔI)与黄酮类物质的浓度成正比,据此可以建立用Fe(phen)2+3测定某些黄酮类物质的新RRS法. 对桑色素、槲皮素和芦丁的检出限(3σ/K)分别为1.25×10-7 mol/L(37.74 μg/L),1.80×10-7 mol/L(54.42 μg/L),2.72×10-7 mol/L(167.30 μg/L). 研究了反应的适宜条件和影响因素,考察了共存物质的影响. 结果表明,方法有较好的选择性.分别以芦丁和桑色素为对照品测定了中药材山楂果和桑枝中的总黄酮含量,对反应机理进行了初步探讨.  相似文献   
996.
High-quality poly(fluorene-9-acetic acid) (PFAA), a new soluble polyfluorene derivative, was synthesized electrochemically by direct anodic oxidation of fluorene-9-acetic acid (FAA) in boron trifluoride diethyl etherate (BFEE) containing a certain amount of trifluoroacetic acid (TFA). This electrolyte enables facile anodic oxidation of FAA monomer at lower potential (1.05 V vs. SCE). PFAA films with conductivity of 0.53 S cm−1 obtained from this medium showed better redox activity and thermal stability in relation to unsoluble poly(fluorene-9-carboxylic acid). Fluorescent spectral studies indicate that PFAA film with high fluorescence quantum yields and photochemical stability is a good blue-light emitter. The structure and morphology of the polymer were studied by UV–vis, FT-IR, 1H NMR spectra and scanning electron microscopy, respectively.  相似文献   
997.
A highly enantioselective organocatalytic protocol for conjugate addition of new nucleophilic carbonylmethyl 2-pyridinylsulfone to enals has been developed in good yields and with high enantioselectivities. The resulting Michael adducts are versatile building blocks for a variety of organic transformations.  相似文献   
998.
Four novel lanthanide coordination polymers [Pr(mal)(OH)(bipy) · 2H2O]n (1), {[Dy1(SBA)3(H2O)2][Dy2(SBA)3(H2O)2] · 4H2O}n (2), {[Tb(OHnic)(Onic)(H2O)5 · (OHnicH)] · H2O}n (3) and {[Sm(OHnic)(Onic)(H2O)5 · (OHnicH)] · H2O}n (4) (Hmal = maleic acid, HSBA = 4-sulfobenzoic acid, OHnicH = 6-hydroxynicotinic acid and bipy = 2,2′-bipyridine) have been synthesized and determined by single crystal X-ray diffraction. Complex 1 is a 1-D helical chain with seven-coordinated praseodymium centers. Complex 2 forms 1-D chain-like molecular structure containing two crystallographically unique dysprosium centers, the Dy1 center is seven-coordinated while Dy2 is eight-coordinated. The isomorphous complexes 3 and 4 exhibit an unprecedented 1-D chain-like polymeric structure through hydroxyl oxygen atoms of bridging Onic2− anions linking up the neighboring central ions, and there exist three types of 6-OHnicH ligands in the structural unit which is rare for lanthanide carboxylate complexes. The photophysical properties of these complexes were studied using ultraviolet absorption spectra, fluorescence excitation and emission spectra.  相似文献   
999.
A simple and efficient synthesis of dihydropyrrolopyrazole boronic acid intermediate (5) has been developed. Utilization of a three-component Suzuki-Miyaura/etherification with microwave heating led to advanced compound 11 in high yield and with easy purification. Reaction of compound 11 with methanesulfonyl chloride at room temperature furnished the 1,3 O-N rearranged product (12), which is postulated to proceed via an intramolecular mechanism. The outlined synthesis provides a highly efficient and high-yielding route that is amenable to rapid analog synthesis.  相似文献   
1000.
A pressurized CEC (pCEC) method with postcolumn detection cell had been developed for quantifying the lignans from Fructus schisandrae extracts. The effects of different experimental conditions, such as the ACN content of the mobile phase, the concentration and pH of the buffer, the applied voltage, and the supplementary pressure were studied. Five lignans (schisandrin, gomisin A, schisantherin C, deoxyschizandrin, schisandrin B) were baseline separated using a mobile phase of ACN-phosphate buffer (pH 5.4; 5 mM) (40:60 v/v) under -4 kV applied voltage. The method showed the satisfactory retention time and peak area repeatability. The calibration curves were linear in the range 50.0-1000.0 microg/mL for schisandrin, 20.0-500.0 microg/mL for gomisin A, 10.0-200.0 microg/mL for schisantherin C, 20.0-500.0 microg/mL for deoxyschizandrin, and 20.0-500.0 microg/mL for schisandrin B. The correlation coefficients were between 0.9978 and 0.9989. With this pCEC system, fingerprints of F. schisandrae were preliminarily established to distinguish two members S. chinensis (Turcz.) Baill. and S. sphenanthera Rehd. Et Wils. of F. schisandrae by characteristic peaks, and evaluate the quality of various sources of raw materials by determining the contents of the five lignans.  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