全文获取类型
收费全文 | 5836篇 |
免费 | 940篇 |
国内免费 | 801篇 |
专业分类
化学 | 4690篇 |
晶体学 | 88篇 |
力学 | 303篇 |
综合类 | 90篇 |
数学 | 620篇 |
物理学 | 1786篇 |
出版年
2024年 | 31篇 |
2023年 | 138篇 |
2022年 | 205篇 |
2021年 | 256篇 |
2020年 | 328篇 |
2019年 | 301篇 |
2018年 | 257篇 |
2017年 | 236篇 |
2016年 | 336篇 |
2015年 | 341篇 |
2014年 | 394篇 |
2013年 | 493篇 |
2012年 | 524篇 |
2011年 | 549篇 |
2010年 | 411篇 |
2009年 | 378篇 |
2008年 | 385篇 |
2007年 | 341篇 |
2006年 | 252篇 |
2005年 | 208篇 |
2004年 | 150篇 |
2003年 | 144篇 |
2002年 | 149篇 |
2001年 | 132篇 |
2000年 | 97篇 |
1999年 | 92篇 |
1998年 | 47篇 |
1997年 | 43篇 |
1996年 | 30篇 |
1995年 | 34篇 |
1994年 | 31篇 |
1993年 | 31篇 |
1992年 | 29篇 |
1991年 | 13篇 |
1990年 | 25篇 |
1989年 | 10篇 |
1988年 | 16篇 |
1987年 | 13篇 |
1986年 | 6篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 7篇 |
1982年 | 9篇 |
1977年 | 7篇 |
1975年 | 10篇 |
1974年 | 8篇 |
1972年 | 11篇 |
1971年 | 6篇 |
1970年 | 5篇 |
1969年 | 5篇 |
排序方式: 共有7577条查询结果,搜索用时 15 毫秒
101.
Hankun Zhou Si Chen Ning Gan Tianhua Li Yuting Cao Qianli Jiang 《Electroanalysis》2013,25(10):2384-2393
A novel sandwich‐type electrochemiluminescence (ECL) immunosensor was developed to enable the sensitive detection of HIV‐1 antibodies. This system incorporated mesoporous silica (mSiO2) complexed with quantum dots (QDs) and nano‐gold particles, which were assembled to enhance signal detection. Magnetic beads were used by immobilizing the secondary anti‐IgG antibody. This was first employed to capture HIV‐1 antibody (Ab) to form a Fe3O4/anti‐IgG/Ab complex. A high loading and signal‐enhanced nanocomposite (hereafter referred to as Au‐mSiO2‐CdTe) was used as a HIV‐1 antigen label. The Au‐mSiO2‐CdTe nanocomposite was conjugated with the Fe3O4/anti‐IgG/Ab complex to form an immunocomplex (hereafter referred to as Fe3O4/anti‐IgG/Ab/HIV‐1/CdTe‐mSiO2‐Au). This complex could be further separated by an external magnetic field to produce ECL signals. Due to the large specific surface area and pore volume of mSiO2, the loading of the CdTe QDs was markedly increased. Thus, the loaded QDs released a powerful chemiluminescent signal with a concordantly increased sensitivity of the immunosensor. The immunosensor was highly sensitive, and displayed a linear range of responses for HIV‐1 antibody across a dilution range of 1 : 1500 through 1 : 50 with the detection limit of 1 : 4500. The immunoassay can be a promising candidate in early diagnosis of HIV infection. 相似文献
102.
Shi Qiao Xiaowei Shi Rui Shi Man Liu Ting Liu Kerong Zhang Qiao Wang Meicun Yao Lantong Zhang 《Analytical and bioanalytical chemistry》2013,405(21):6721-6738
The detection of drug metabolites, especially for minor metabolites, continues to be a challenge because of the complexity of biological samples. Imperatorin (IMP) is an active natural furocoumarin component originating from many traditional Chinese herbal medicines and is expected to be pursued as a new vasorelaxant agent. In the present study, a generic and efficient approach was developed for the in vivo screening and identification of IMP metabolites using liquid chromatography-Triple TOF mass spectrometry. In this approach, a novel on-line data acquisition method mutiple mass defect filter (MMDF) combined with dynamic background subtraction was developed to trace all probable urinary metabolites of IMP. Comparing with the traditionally intensity-dependent data acquisition method, MMDF method could give the information of low-level metabolites masked by background noise and endogenous components. Thus, the minor metabolites in complex biological matrices could be detected. Then, the sensitive and specific multiple data-mining techniques extracted ion chromatography, mass defect filter, product ion filter, and neutral loss filter were used for the discovery of IMP metabolites. Based on the proposed strategy, 44 phase I and 7 phase II metabolites were identified in rat urine after oral administration of IMP. The results indicated that oxidization was the main metabolic pathway and that different oxidized substituent positions had a significant influence on the fragmentation of the metabolites. Two types of characteristic ions at m/z 203 and 219 can be observed in the MS/MS spectra. This is the first study of IMP metabolism in vivo. The interpretation of the MS/MS spectra of these metabolites and the proposed metabolite pathway provide essential data for further pharmacological studies of other linear-type furocoumarins. 相似文献
103.
Xiang Ting Zhang ZuLei Liu HaiQing Yin ZhengZhi Li Lei Liu XiaoMing 《中国科学:化学(英文版)》2013,56(5):567-575
Science China Chemistry - Nanofiber membranes from the composite of cellulose acetate/polyvinylpyrrolidone were prepared using electrospinning technique. After treated with water and alcoholic KOH... 相似文献
104.
A new bridging ligand, 2,3‐di(2‐pyridyl)‐5‐phenylpyrazine (dpppzH), has been synthesized. This ligand was designed so that it could bind two metals through a NN‐CNN‐type coordination mode. The reaction of dpppzH with cis‐[(bpy)2RuCl2] (bpy=2,2′‐bipyridine) affords monoruthenium complex [(bpy)2Ru(dpppzH)]2+ ( 12+ ) in 64 % yield, in which dpppzH behaves as a NN bidentate ligand. The asymmetric biruthenium complex [(bpy)2Ru(dpppz)Ru(Mebip)]3+ ( 23+ ) was prepared from complex 12+ and [(Mebip)RuCl3] (Mebip=bis(N‐methylbenzimidazolyl)pyridine), in which one hydrogen atom on the phenyl ring of dpppzH is lost and the bridging ligand binds to the second ruthenium atom in a CNN tridentate fashion. In addition, the RuPt heterobimetallic complex [(bpy)2Ru(dpppz)Pt(C?CPh)]2+ ( 42+ ) has been prepared from complex 12+ , in which the bridging ligand binds to the platinum atom through a CNN binding mode. The electronic properties of these complexes have been probed by using electrochemical and spectroscopic techniques and studied by theoretical calculations. Complex 12+ is emissive at room temperature, with an emission λmax=695 nm. No emission was detected for complex 23+ at room temperature in MeCN, whereas complex 42+ displayed an emission at about 750 nm. The emission properties of these complexes are compared to those of previously reported Ru and RuPt bimetallic complexes with a related ligand, 2,3‐di(2‐pyridyl)‐5,6‐diphenylpyrazine. 相似文献
105.
Yi‐Chin Chen Sheng‐Cih Huang Dr. Yu‐Kuo Wang Dr. Yuan‐Ting Liu Prof. Dr. Tung‐Kung Wu Prof. Dr. Teng‐Ming Chen 《化学:亚洲杂志》2013,8(11):2652-2659
In this study, surface‐functionalized, branched polyethylenimine (BPEI)‐modified YVO4:Bi3+,Eu3+ nanocrystals (NCs) were successfully synthesized by a simple, rapid, solvent‐free hydrothermal method. The BPEI‐coated YVO4:Bi3+,Eu3+ NCs with high crystallinity show broad‐band excitation in the λ=250 to 400 nm near‐ultraviolet (NUV) region and exhibit a sharp‐line emission band centered at λ=619 nm under excitation at λ=350 nm. The surface amino groups contributed by the capping agent, BPEI, not only improve the dispersibility and water/buffer stability of the BPEI‐coated YVO4:Bi3+,Eu3+ NCs, but also provide a capability for specifically targeted biomolecule conjugation. Folic acid (FA) and epidermal growth factor (EGF) were further attached to the BPEI‐coated YVO4:Bi3+,Eu3+ NCs and exhibited effective positioning of fluorescent NCs toward the targeted folate receptor overexpressed in HeLa cells or EGFR overexpressed in A431 cells with low cytotoxicity. These results demonstrate that the ligand‐functionalized, BPEI‐coated YVO4:Bi3+, Eu3+ NCs show great potential as a new‐generation biological luminescent bioprobe for bioimaging applications. Moreover, the unique luminescence properties of BPEI‐coated YVO4:Bi3+,Eu3+ NCs show potential to combine with a UVA photosensitizing drug to produce both detective and therapeutic effects for human skin cancer therapy. 相似文献
106.
The internal redox esterification of α,β-unsaturated aldehydes and alcohols was carried out using different ionic liquids (ILs) as catalysts and reaction solvents. The basic ionic liquid, 1-butyl-3-methylimidazolium acetate ([bmim]OAc), exhibited the best activity for this reaction. The influences of the amount of ionic liquid catalyst and reaction time on yield of saturated ester have been investigated. The results showed that ionic liquid anions have a crucial effect on the redox esterification of α,β-unsaturated aldehydes and alcohols. The nucleophilic carbenes generated in situ from the ionic liquid cation were believed to be actual active species for this reactions. 相似文献
107.
Ting‐Ting Zhang Xiao‐Xia Qi Jianfeng Jia Hai‐Shun Wu 《International journal of quantum chemistry》2013,113(7):1010-1017
Quantum chemistry methods are applied to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of Iridium (III) complexes [Ir(C∧N)2(L)2]+ (L = 4‐pyCO2Et; C∧N = 2‐phenylpyridine, 1 ; 2‐(4‐tolyl)pyridine, 2 ; 2‐(4,6‐difluorophenyl)pyridimato, 3 ; benzoquinoline, 4 ), which may be used as emitters on organic light emitting diodes (OLEDs). Calculations of ionization potentials and electron affinities are used to evaluate the injection abilities of holes and electrons into these complexes. The reorganization energy (λ) calculations show that the four complexes are suitable as emitters in OLEDs. The absorptions and emissions can be tuned by adding substituent to the ppy ligand or extending the π‐conjugation effect of the C∧N ligand, and quantum yields of 1 – 4 are investigated. In addition, no solvent effect is observed in the absorption and emission spectra. © 2012 Wiley Periodicals, Inc. 相似文献
108.
We have developed a simple and efficient method for dispersive liquid-liquid microextraction of 4-nitrophenol, 2-naphthol and bisphenol A in real water samples. It is making use of solidified floating organic droplets of 1-dodecanol which has low density and a proper melting point. The type and volume of extraction solvent and dispersive solvent, the effect of salts, pH value and extraction time were optimized and resulted in enrichment factors of 84 for 4-nitrophenol, 123 for 2-naphthol, and 97 for bisphenol A. The limits of detection by HPLC are 1.50, 0.10 and 1.02 ng · mL?1, respectively. Excellent linearity is observed in the concentration range from 10 to 800 ng · mL?1, with coefficients of correlation ranging from 0.9988 to 0.9999. The relative standard deviations (for n?=?5) are from 3.2 to 5.3 %, and relative recoveries for the three phenols in tap, river and spring water range from 85.0 to 105.0 %, 98.3 to 110.0 %, and 98.6 to 109.0 %, respectively. Figure
Chromatograms of river water blank (b) and spiked river water (a, 500 ng ? mL?1) analyzed with DLLME-SFO-HPLC. Peak identification: (1) p-nitrophenol; (2) 2-naphthol; (3) bisphenol A. Liquid-liquid microextraction method based on solidification of floating organic droplet (DLLME-SFO) has a high enrichment factor (84, 123and 97), acceptable relative recovery (85.0 %–110.0 %), good repeatability (5.27 %, 3.54 % and 3.16 %) and a wide linear range (10–800 ng · mL?1) for the determination of p-nitrophenol, 2-naphthol and bisphenol A. 相似文献
109.
Shanshan Zhu Ning Gan Daodong Pan Yi Li Ting Yang Futao Hu Yuting Cao Dazhen Wu 《Mikrochimica acta》2013,180(7-8):545-553
We have prepared core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT). The use of particles strongly improves the imprinting effect and leads to fast adsorption kinetics and high adsorption capacities. The functional monomer acrylamide was grafted to the surface of Fe3O4 nanospheres in two steps, and MIP layers were then formed on the surface by creating a MIP layer on the surface consisting of poly(ethyleneglycol dimethacrylate) with a TBT template. The particles were characterized in terms of morphological, magnetic, adsorption, and recognition properties. We then have developed a method for the extraction of TBT from spiked mussel (Mytilidae), and its determination by liquid chromatography-tandem mass spectrometry. The method has a limit of detection of 1.0 ng?g?1 (n?=?5) of TBT, with a linear response between 5.0 and 1,000 ng?g?1. The proposed method was successfully applied to the determination of trace TBT in marine food samples with recoveries in the range of 78.3–95.6 %. Figure
The preparation procedures of core-shell magnetic molecularly imprinted polymer nanoparticles for recognition and extraction of tributyl tin (TBT) in seafood 相似文献
110.
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