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   9101篇
  免费   1657篇
  国内免费   841篇
化学   9178篇
晶体学   70篇
力学   87篇
综合类   25篇
数学   9篇
物理学   2230篇
  2024年   3篇
  2023年   152篇
  2022年   227篇
  2021年   455篇
  2020年   670篇
  2019年   531篇
  2018年   468篇
  2017年   539篇
  2016年   741篇
  2015年   720篇
  2014年   801篇
  2013年   924篇
  2012年   830篇
  2011年   818篇
  2010年   632篇
  2009年   623篇
  2008年   538篇
  2007年   488篇
  2006年   377篇
  2005年   273篇
  2004年   181篇
  2003年   170篇
  2002年   121篇
  2001年   114篇
  2000年   74篇
  1999年   54篇
  1998年   27篇
  1997年   14篇
  1996年   8篇
  1995年   8篇
  1994年   2篇
  1992年   1篇
  1991年   2篇
  1990年   7篇
  1985年   2篇
  1983年   3篇
  1979年   1篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
A facile biosynthesis route was followed to prepare zinc oxide nanoparticles (ZnO NPs) using Euphorbia milii (E. milii) leaf constituents. The SEM images exhibited presence of spherical ZnO NPs and the corresponding TEM images disclosed monodisperse nature of the ZnO NPs with diameter ranges between 12 and 20 nm. The Brunauer–Emmett–Teller (BET) analysis revealed that the ZnO NPs have specific surface area of 20.46 m2/g with pore diameter of 2 nm–10 nm and pore volume of 0.908 cm3/g. The EDAX spectrum exemplified the existence of Zn and O elements and non-appearance of impurities that confirmed pristine nature of the ZnO NPs. The XRD pattern indicated crystalline peaks corresponding to hexagonal wurtzite structured ZnO with an average crystallite size of 16.11 nm. The FTIR spectrum displayed strong absorption bands at 512 and 534 cm?1 related to ZnO. The photocatalytic action of ZnO NPs exhibited noteworthy degradation of methylene blue dye under natural sunlight illumination. The maximum degradation efficiency achieved was 98.17% at an illumination period of 50 min. The reusability study proved considerable photostability of the ZnO NPs during photocatalytic experiments. These findings suggest that the E. milii leaf constituents can be utilized as suitable biological source to synthesis ZnO NPs for photocatalytic applications.  相似文献   
2.
《Mendeleev Communications》2022,32(2):234-237
Starting from the functional cyclotriphosphazene, polysiloxane and nano-SiO2 precursors, three new hybrid nanocomposites with reinforced mechanical properties were prepared. Young’s modulus values for all the composite samples are similar in the range of 7–11 MPa, stress at fracture increases with the nano-SiO2 content increase in the material and reaches a maximum value of 36 MPa for the composite with 20% nano-SiO2. The nanocomposites investigated are elastic and demonstrate the ability to be deformed without failure up to 54% strain.  相似文献   
3.
Herein, we report a Mott-Schottky catalyst by entrapping cobalt nanoparticles inside the N-doped graphene shell (Co@NC). The Co@NC delivered excellent oxygen evolution activity with an overpotential of merely 248 mV at a current density of 10 mA cm–2 with promising long-term stability. The importance of Co encapsulated in NC has further been demonstrated by synthesizing Co nanoparticles without NC shell. The synergy between the hexagonal close-packed (hcp) and face-centered cubic (fcc) Co plays a major role to improve the OER activity, whereas the NC shell optimizes the electronic structure, improves the electron conductivity, and offers a large number of active sites in Co@NC. The density functional theory calculations have revealed that the hcp Co has a dominant role in the surface reaction of electrocatalytic oxygen evolution, whereas the fcc phase induces the built-in electric field at the interfaces with N-doped graphene to accelerate the H+ ion transport.  相似文献   
4.
The sonocatalytic degradation of EDTA (C0 = 5 10−3 M) in aqueous solutions was studied under 345 kHz (Pac = 0.25 W mL−1) ultrasound at 22–51 °C, Ar/20%O2, Ar or air, and in the presence of metallic titanium (Ti0) or core-shell Ti@TiO2 nanoparticles (NPs). Ti@TiO2 NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti0 NPs in pure water. Ti0 is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti3O. SHT treatment at 150–214 °C leads to the oxidation of Ti3O and partial oxidation of Ti0 and formation of nanocrystalline shell (10–20 nm) composed of TiO2 anatase. It was found that Ti0 NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti0 NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti0 NPs and Ar/20%O2 gas mixture. Coating of Ti0 with TiO2 nanocrystalline shell reduces sonocatalytic activity. Pristine TiO2 anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO2 radicals in solution and (ii) EDTA oxidation at the surface of Ti0 NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti0/O2 species at cavitation bubble/solution interface.  相似文献   
5.
In this study, we report the green synthesis of nontoxic, stable, and small size gold nanoparticle by using chitosan/sodium lignosulfonate hydrogel with capping/reducing ability for the synthesis of CS/NaLS/Au NPs. The prepared bio-nanocomposite were characterized by advanced physicochemical techniques like Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray spectroscopy (EDX) and X-ray Diffraction (XRD) study. It has been established that CS/NaLS/Au NPs have a spherical shape with a mean diameter from 20 to 30 nm. Diabetes was induced by administration of 60 mg/kg of streptozotocin (STZ) intraperitoneally in 100 mature male mice and they were randomly divided into 5 groups. The negative control group received normal saline and treatment groups received glibenclamide with dose 0.5 mg/kg and 10 and 40 μg/kg of CS/NaLS/Au NPs through gavage for 50 days. In addition, one group considered as positive control (in treated-diabetic). On the last day, serum levels of samples blood glucose, urea and creatinine were measured. After tissue processing, 5 μm sections of the kidneys were prepared and they were stained by periodic acid Schiff (PAS) and used for stereological analysis. In the antioxidant test, the IC50 of CS/NaLS/Au NPs and BHT against DPPH free radicals were 117 and 86 µg/mL, respectively. In the cellular and molecular part of the recent study, the treated cells with CS/NaLS/Au NPs were assessed by MTT assay for 48 h about the cytotoxicity properties on normal (HUVEC) cell line. The increased levels of blood glucose and urea were decreased (p < 0.05) significantly in CS/NaLS/Au NPs-treated groups as compared to the untreated diabetic. The kidney weight, kidney volume (Volume of cortex, medulla, glomerulus, proximal and distal tubules, collecting ducts, loop of Henle, interstitial tissues, and vessels) and kidney structures length (length of proximal and distal tubules, collecting ducts, loop of Henle, and vessels) decreased significantly (p < 0.05) after treatment with high dose of CS/NaLS/Au NPs (p < 0.05). According to the obtained results, CS/NaLS/Au NPs can regulates the levels of blood glucose and urea and inhibits from kidney damages in STZ-induced diabetic mice. This study suggested CS/NaLS/Au NPs as an antidiabetic and nephroprotective drug in the developing countries.  相似文献   
6.
Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface-regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighted.  相似文献   
7.
Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent.  相似文献   
8.
A fast and accurate experimental method is demonstrated to assess the fraction of exsolved metallic nanoparticles using magnetic measurements. As a benchmark, nanometric metallic nickel exsolved from (La1−xSrx)(Cr1−yNiy)O3−δ is used for its high relevance as a solid oxide fuel cell component. The method is based on the difference in the magnetic response of the exsolved metallic nickel (ferromagnetic) and Sr-doped lanthanum chromite ceramic matrix (paramagnetic). The exsolved nickel results in coherent nanoparticles pinned on the surface of the Sr-doped lanthanum chromite ceramic matrix, as evidenced by electron microscopy analyses. The results obtained indicate the procedure as a fast and sensitive method to study the exsolution of ferromagnetic nanoparticles.  相似文献   
9.
Sample preparation methods used for genetically modified organisms (GMOs) analysis are often time consuming, require extensive manual manipulation, and result in limited amounts of purified protein, which may complicate the detection of low‐abundance GM protein. A robust sample pretreatment method prior to mass spectrometry (MS) detection of the transgenic protein (5‐enolpyruvylshikimate‐3‐phosphate synthase [CP4 EPSPS]) present in Roundup Ready soya is investigated. Liquid chromatography‐multiple reaction monitoring tandem MS (nano LC‐MS/MS‐MRM) was used for the detection and quantification of CP4 EPSPS. Gold nanoparticles (AuNPs) and concanavalin A (Con A)‐immobilized Sepharose 4B were used as selective probes for the separation of the major storage proteins in soybeans. AuNPs that enable the capture of cysteine‐containing proteins were used to reduce the complexity of the crude extract of GM soya. Con A‐sepharose was used for the affinity capture of β‐conglycinin and other glycoproteins of soya prior to enzymatic digestion. The methods enabled the detection of unique peptides of CP4 EPSPS at a level as low as 0.5% of GM soya in MRM mode. Stable‐isotope dimethyl labeling was further applied to the quantification of GM soya. Both probes exhibited high selectivity and efficiency for the affinity capture of storage proteins, leading to the quantitative detection at 0.5% GM soya, which is a level below the current European Union's threshold for food labeling. The square correlation coefficients were greater than 0.99. The approach for sample preparation is very simple without the need for time‐consuming protein prefractionation or separation procedures and thus presents a significant improvement over existing methods for the analysis of the GM soya protein.  相似文献   
10.
Abstract

In this study, the Pt nanoparticles/over-oxidized polypyrrole nanofiber/reduced graphene oxide (Pt NPs/OPPy/RGO) nanocomposite was electrochemically synthesized and used to modify a glassy carbon electrode. To confirm the Surface morphology and characterization of the nanocomposite, field emission scanning microscopy (FE-SEM), X-ray diffraction (XRD), Raman, FT-IR, and X-ray photoelectron spectroscopy (XPS) were used. Simultaneous determination of these species showed one linear response 0.1–250.0?μM and two linear responses 0.5–10.0?μM and 10.0–470.0?μM, with detection limits 42?nM and 106?nM (S/N?=?3) for DA and 5-HT, respectively. Finally, the analytical application of this modified electrode was investigated in the human blood plasma.  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