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   9930篇
  免费   1667篇
  国内免费   870篇
化学   9956篇
晶体学   74篇
力学   88篇
综合类   26篇
数学   9篇
物理学   2314篇
  2024年   23篇
  2023年   174篇
  2022年   456篇
  2021年   505篇
  2020年   678篇
  2019年   540篇
  2018年   473篇
  2017年   555篇
  2016年   745篇
  2015年   731篇
  2014年   820篇
  2013年   956篇
  2012年   847篇
  2011年   853篇
  2010年   661篇
  2009年   672篇
  2008年   555篇
  2007年   526篇
  2006年   406篇
  2005年   322篇
  2004年   224篇
  2003年   197篇
  2002年   146篇
  2001年   126篇
  2000年   85篇
  1999年   71篇
  1998年   35篇
  1997年   19篇
  1996年   12篇
  1995年   14篇
  1994年   5篇
  1993年   4篇
  1992年   3篇
  1991年   2篇
  1990年   13篇
  1989年   2篇
  1988年   3篇
  1987年   1篇
  1985年   2篇
  1984年   1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 31 毫秒
151.
A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Aunano-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10 nm. Electrochemical behavior of the PAT-Aunano-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Aunano-ME exhibits two well defined anodic peaks at the potential of 75 and 400 mV for the oxidation of AA and DA, respectively with a potential difference of 325 mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Aunano-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Aunano-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.  相似文献   
152.
The unique binding event between Escherichia coli single-stranded DNA binding protein (SSB) and single-stranded oligonucleotides conjugated to gold (Au) nanoparticles is utilized for the electrochemical detection of DNA hybridization. SSB was attached onto a self-assembled monolayer (SAM) of single-stranded oligonucleotide modified Au nanoparticle, and the resulting Au-tagged SSB was used as the hybridization label. Changes in the Au oxidation signal was monitored upon binding of Au tagged SSB to probe and hybrid on the electrode surface. The amplified oxidation signal of Au nanoparticles provided a detection limit of 2.17 pM target DNA, which can be applied to genetic diagnosis applications. This work presented here has important implications with regard to combining a biological binding event between a protein and DNA with a solid transducer and metal nanoparticles.  相似文献   
153.
Fibers and films prepared from blends of poly(vinyl alcohol) and poly(acrylic acid) were found to be suitable matrices for the solid-state photoreduction of silver ions in the presence of air. Fast generation of nanometer-sized silver crystallites was observed when fibers of polymer blends crosslinked with dimethyl sulfoxide were irradiated with 350nm light. Optical determinations of the formation kinetics were carried out using thin films of noncrosslinked as well as lightly and heavily crosslinked polymer blends. Small Ag clusters were detected initially, which were stable in the dark but transformed into larger metal particles upon further illumination. Both formation processes occurred only under high light intensity illumination and the kinetic data were inconsistent with monophotonic mechanisms.  相似文献   
154.
With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm−2 toward hydrogen evolution in 1.0 mol∙L−1 KOH aqueous solution with 0.5 mol∙L−1 methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm−2 at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation.  相似文献   
155.
A chemiluminescence signal at 425 nm was observed when ferric state myoglobin was mixed with luminol in alkaline medium. Because the signal was remarkably enhanced in the presence of Fe(CN)6 4–, analytical applications were investigated in a flow-injection system. The increase in chemiluminescence was linearly dependent on myoglobin concentration in the range 0.1 to 100 nmol L–1, and the limit of detection was 0.04 nmol L–1 with relative standard deviation 3.2% (3). It was also found that binding of Mb with the ligands CN, SCN, and F significantly inhibited the chemiluminescence reaction. The linear dynamic ranges for the ligands were 1.0–300.0, 0.1–3.0, and 0.5–100.0 nmol L–1, and the limits of detection (S/N=3) 0.4, 0.04, and 0.2 nmol L–1, for F, CN, and SCN, respectively. The relative standard deviations were 5.32%, 6.13%, and 3.38% for 0.1 nmol L–1 CN, 0.5 nmol L–1 SCN, and 1.0 nmol L–1 F, respectively. At a flow rate of 2.0 mL min–1 the assay could be accomplished in 1 min, including sampling and washing. The method has been successfully applied to the determination of myoglobin in human urine and F in water samples. A possible mechanism of chemiluminescence production by myoglobin and luminol is presented.  相似文献   
156.
Wei  Xiang  CHEN  Xiao  Chun  MA 《中国化学快报》2003,14(3):312-315
Non-carbon inorganic fullerene-like(IF) nanoscale materials have recently attracted intense interest due to their nested hollow and nanotube structures,In this letter,IF-WS2 nanoparticles prepared by solid-gas reaction were characterized by X-ray diffraction,Scanning electron microscopy and transmission electron microscopy.The results show that the IF-WS2 nanoparticles have a nested hollow closed spherical structure with diameter of 100-150mm.  相似文献   
157.
Ba3Cu2Al2F16 is monoclinic: a = 7.334(1)Å, b = 5.320(2)Å, c = 16.022(1)Å, β = 96.34(1)°, Z = 2. Its crystal structure was solved in the space group P21 (No. 4) from synchrotron X‐ray single crystal data using 2685 unique reflections (2639 with Fo/σ(Fo) > 4). The final R factor is 0.044. The structure consists of a succession along the c‐axis of the cell of three layers of two different kinds of sheets developing in the (a, b) plane. The first one, formulated [(AlF5)2]4— and hereafter named A, is built up from infinite cis‐chains of aluminium‐fluorine octahedra [AlF6], linked by two vertices and distanced by a. The second one, formulated [Cu2AlF11]4— and named B, is bidimensional. It is constituted of distorted copper‐fluorine octahedra [CuF6], linked by edges, which form infinite chains interconnected by three vertices of isolated [AlF6] octahedra. The stacking sequence of the sheets is (A, B, B). The barium ions, 12‐coordinated, are inserted between the sheets. The crystal structure of Ba3Cu2Al2F16 is closely related to that of Ba4Cu2Al3F21. Only the proportion and the stacking sequence of the two kinds of sheets in the c‐direction differ, according to two different compositions and two different symmetries.  相似文献   
158.
唐志诚  吕功煊 《化学进展》2007,19(9):1301-1312
直接甲醇燃料电池作为未来清洁的动力能源,由于具有下列优点:操作温度低(<100℃)、燃料易储存和运输、能量效率高、污染低和燃料启动快而受到人们广泛的关注。阳极电催化剂是直接甲醇燃料电池最重要的组成部分。本文综述了近三年来直接甲醇燃料电池阳极电催化剂最新的研究进展,主要对催化剂制备方法、新型碳载体材料、催化剂类型作了详细的评述,展望了未来甲醇电催化氧化催化剂的发展,指出了电催化剂面临的问题。  相似文献   
159.
Bis(dimethylamino)trifluoro sulfonium Salts: [CF3S(NMe2)2]+[Me3SiF2], [CF3S(NMe2)2]+ [HF2] and [CF3S(NMe2)2]+[CF3S] From the reaction of CF3SF3 with an excess of Me2NSiMe3 [CF3(NMe2)2]+[Me3SiF2] (CF3‐BAS‐fluoride) ( 5 ), from CF3SF3/CF3SSCF3 and Me2NSiMe3 [CF3S(NMe2)2]+‐ [CF3S] ( 7 ) are isolated. Thermal decomposition of 5 gives [CF3S(NMe2)2]+ [HF2] ( 6 ). Reaction pathways are discussed, the structures of 5 ‐ 7 are reported.  相似文献   
160.
In order to quantitatively predict nano- as well as other particle-size distributions, one needs to have both a mathematical model and estimates of the parameters that appear in these models. Here, we show how one can use Bayesian inversion to obtain statistical estimates for the parameters that appear in recently derived mechanism-enabled population balance models (ME-PBM) of nanoparticle growth. The Bayesian approach addresses the question of “how well do we know our parameters, along with their uncertainties?.” The results reveal that Bayesian inversion statistical analysis on an example, prototype nanoparticle formation system allows one to estimate not just the most likely rate constants and other parameter values, but also their SDs, confidence intervals, and other statistical information. Moreover, knowing the reliability of the mechanistic model's parameters in turn helps inform one about the reliability of the proposed mechanism, as well as the reliability of its predictions. The paper can also be seen as a tutorial with the additional goal of achieving a “Gold Standard” Bayesian inversion ME-PBM benchmark that others can use as a control to check their own use of this methodology for other systems of interest throughout nature. Overall, the results provide strong support for the hypothesis that there is substantial value in using a Bayesian inversion methodology for parameter estimation in particle formation systems.  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