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   3305篇
  免费   357篇
  国内免费   236篇
化学   2559篇
晶体学   34篇
力学   137篇
综合类   10篇
数学   325篇
物理学   833篇
  2024年   18篇
  2023年   131篇
  2022年   230篇
  2021年   199篇
  2020年   215篇
  2019年   219篇
  2018年   190篇
  2017年   147篇
  2016年   229篇
  2015年   227篇
  2014年   236篇
  2013年   288篇
  2012年   331篇
  2011年   322篇
  2010年   208篇
  2009年   158篇
  2008年   165篇
  2007年   138篇
  2006年   79篇
  2005年   42篇
  2004年   28篇
  2003年   15篇
  2002年   21篇
  2001年   6篇
  2000年   12篇
  1999年   5篇
  1998年   7篇
  1997年   6篇
  1996年   2篇
  1995年   5篇
  1994年   1篇
  1993年   5篇
  1992年   1篇
  1991年   1篇
  1990年   7篇
  1986年   2篇
  1985年   2篇
排序方式: 共有3898条查询结果,搜索用时 15 毫秒
41.
Rapid and efficient side‐chain functionalization of polypeptide with neighboring carboxylgroups is achieved via the combination of ring‐opening polymerization and subsequent thiol‐yne click chemistry. The spontaneous formation of polymersomes with uniform size is found to occur in aqueous medium via electrostatic interaction between the anionic polypeptide and cationic doxorubicin hydrochloride (DOX·HCl). The polymersomes are taken up by A549 cells via endocytosis, with a slightly lower cytotoxicity compared with free DOX ·HCl. Moreover, the drug‐loaded polymersomes exhibit the enhanced therapeutic efficacy, increase apoptosis in tumor tissues, and reduce systemic toxicity in nude mice bearing A549 lung cancer xenograft, in comparison with free DOX ·HCl.  相似文献   
42.
Graphene-nanosheet-based highly porous magnetite nanocomposites (GN-HPMNs) have been prepared using a simple solvothermal method and used as an immobilization matrix for the fabrication of a solid-state electrochemiluminescence (ECL) sensor on paper-based chips. Highly porous Fe3O4 nanocrystal clusters were coated with acrylate and wrapped tightly on the skeleton of graphene nanosheets. The structures and sizes of the GN-HPMNs could be tuned by varying the proportions of the solvents ethylene glycol and diethylene glycol. Then, the relatively highly porous ones with an average diameter of about 65 nm were combined with Nafion to form composite films on an electrode surface for immobilization of Ru(bpy)3 2+ (bpy is 2,2′-bipyridine). Because of their porosity, negatively charged surface, and cooperative characteristics of magnetic nanomaterials and graphene, under an external magnetic field, the GN-HPMNs ensured effective immobilization, excellent electron transfer, and long-term stability of Ru(bpy)3 2+ in the composite film. The sensor developed exhibited excellent reproducibility with a relative standard deviation of 0.65 % for 30 continuous cycles. It was found to be much more favorable for detecting compounds containing tertiary amino groups and DNAs with guanine and adenine. A detection limit (signal-to-noise ratio of 3) of 5.0 nM was obtained for tripropylamine. As an application example, 0.5 nM single-nucleotide mismatch could be detected. This was the first attempt to introduce magnetic nanomaterials and an external magnetic field into paper-based chips. The sensor developed has the advantages of high sensitivity, good stability, and wide potential applicability as well as simplicity, low cost, and good disposability.
Figure
Schematic diagram of using graphene-nanosheet-based highly porous magnetite nanocomposites for fabrication of a solid-state electrochemiluminescence sensor on paper-based chips and application example of the developed sensor for single-nucleotide mismatch discrimination  相似文献   
43.
This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single‐stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005–5.0 and from 0.02–20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5–109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7–10.5% and from 3.1–13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components.  相似文献   
44.
A nitrite sensor based on Dawson vanodotungstophosphates α2-K7P2VW17O62·18H2O (P2W17V) and carbon nanotubes (CNTs) was prepared by electrostatic layer-by-layer self-assembly technique. The sensor {PEI/PSS/[PDDA/P2W17V-CNTs]n} was characterized by UV–vis spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS). The electron transfer and sensing ability of this sensor were explored using cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) technology. The results show that the incorporation of CNTs and P2W17V into the composite film endowed the modified electrode with fast transfer rate and high electrocatalytic activity towards oxidation of nitrite. This nitrite sensor with 10 bilayers has a broad linear range of 5 × 10−8 to 2.13 × 10−3 M, a low detection limit of 0.0367 μM (S N−1 = 3), a high sensitivity of 0.35 mA mM−1 NO2, an excellent anti-interference property in the presence of other potential interfering species and a good stable. It was successfully employed for determination of nitrite in real towards.  相似文献   
45.
46.
Zhou  Dan-Ling  Zhang  Qian-Li  Lv  Zhang-Ying  Chen  Wan-Yi  Liu  Xiang-Feng  Lu  Ya-Hui  Wang  Ai-Jun  Feng  Jiu-Ju 《Mikrochimica acta》2013,180(15):1495-1500

We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of −0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N = 3) and a repeatability of 3.4 % (n = 5).

A facile method was developed for in situ construction of a porous network-like Ag film on a glassy carbon electrode by a galvanic replacement reaction, where a layer of Cu nanoparticles previously electrodeposited as a sacrificial template. Thus-formed Ag film displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward nitrate reduction.

  相似文献   
47.
The β-mannanase gene (1,029 nucleotide) from Bacillus subtilis MAFIC-S11, encoding a polypeptide of 342 amino acids, was cloned and expressed in Pichia pastoris. To increase its expression, the β-mannanase gene was optimized for codon usage (mannS) and fused downstream to a sequence-encoding modified α-factor signal peptide. The expression level was improved by 2-fold. This recombinant enzyme (mannS) showed its highest activity of 24,600 U/mL after 144-h fermentation. The optimal temperature and pH of mannS were 50 °C and 6.0, respectively, and its specific activity was 3,706 U/mg. The kinetic parameters V max and K m were determined as 20,000 U/mg and 8 mg/mL, respectively, representing the highest ever expression level of β-mannanase reported in P. pastoris. In addition, the enzyme exhibited much higher binding activity to chitin, chitosan, Avicel, and mannan. The superior catalytic properties of mannS suggested great potential as an effective additive in animal feed industry.  相似文献   
48.
A series of 3,3′-(4-arylpyridine-2,6-diyl)bis(2H-chromen-2-one) derivatives have been synthesized by the one-pot, three-component reaction of 3-acetylcoumarin, an aromatic aldehyde, and ammonium acetate in acetic acid under microwave irradiation. This procedure has the major advantages of short reaction time, good yields, low energy consumption, easy operation, and environmental friendliness. All of the products were characterized by IR and NMR spectroscopy, MS, and elemental analysis.  相似文献   
49.
China becomes the largest energy consumer in 2010 but its energy productivity is well below the world average. To meet China’s fast growing energy using, energy efficiency should be especially emphasized under China’s energy policy. This paper focuses on the regional level of energy efficiency change in China. And we analyze total factor energy efficiency for 30 Chinese provinces over the period 1998–2009 using Malmquist index method and Tobit analysis. The Malmquist estimation results suggest there is a dropping change trend of energy productivity growth. Chinese energy efficiency still faces with huge regional disparity, but the energy technical efficiency reflects convergence in the nationwide and west region. As a result of Tobit regression, we find that industrial structure, energy consumption structure and institutional factor have different influences on energy efficiency.  相似文献   
50.
Current research on pedestrian dynamics mainly focuses on the interactions among isolated individuals, the impact of the presence of groups is not fully considered. In recent 5 years, researchers have started to investigate pedestrian group movement. The aim of this work is to explore the local behavior of pedestrian groups by questionnaires and field observation. Survey study focused on pedestrians' psychology when walking in groups, which included five parts: group size, interpersonal distance, spatial relationship among group members, speed adjustment of group members, information transmission, and acid action among group members. Meantime a field observation was carried out to study group movement characteristics, which contained speed, step frequency, offset angle and interpersonal distance. The survey results show that group members have a closer interpersonal distance, faster information transmission and plenty of acid action. Conversely, group walking has a negative influence on pedestrian's speed, step frequency by comparing with the way isolated pedestrian walks. In addition, it is found that for a certain group, the group members are able to keep movement consistent. Also there exists obvious movement diversity among different group types (male dyads, female dyads, couple groups, and ordinary‐friend groups) because of different gender and social relationship. Ultimately the results will be more promising for helping to model the movement of pedestrian groups. © 2014 Wiley Periodicals, Inc. Complexity 20: 87–97, 2015  相似文献   
[首页] « 上一页 [1] [2] [3] [4] 5 [6] [7] [8] [9] [10] [11] 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