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   10880篇
  免费   3202篇
  国内免费   441篇
化学   11430篇
晶体学   147篇
力学   321篇
综合类   59篇
数学   190篇
物理学   2376篇
  2024年   9篇
  2023年   189篇
  2022年   369篇
  2021年   436篇
  2020年   738篇
  2019年   523篇
  2018年   457篇
  2017年   496篇
  2016年   625篇
  2015年   604篇
  2014年   666篇
  2013年   1220篇
  2012年   837篇
  2011年   834篇
  2010年   657篇
  2009年   688篇
  2008年   696篇
  2007年   657篇
  2006年   578篇
  2005年   520篇
  2004年   521篇
  2003年   422篇
  2002年   300篇
  2001年   260篇
  2000年   199篇
  1999年   172篇
  1998年   157篇
  1997年   120篇
  1996年   97篇
  1995年   106篇
  1994年   79篇
  1993年   81篇
  1992年   31篇
  1991年   33篇
  1990年   25篇
  1989年   15篇
  1988年   17篇
  1987年   13篇
  1986年   10篇
  1985年   10篇
  1984年   11篇
  1983年   9篇
  1982年   9篇
  1981年   7篇
  1980年   6篇
  1979年   8篇
  1977年   1篇
  1976年   2篇
  1972年   1篇
  1971年   1篇
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
1.
A novel technique utilizing the adsorptive potential of immobilized multi‐walled carbon nanotubes (I‐MWCNT) in hollow fiber liquid‐phase microextraction (HF‐LPME) was developed for the determination of diuretics in urine. In this study, the potential of carbon nanotubes as a sorbent for three‐phase liquid‐phase microextraction of diuretics from urine samples was evaluated. Analysis was performed using liquid chromatography‐tandem mass spectrometry (LC‐MS/MS). A novel method was applied to detect acetazolamide (AAA), chlorothiazide (CTA), hydrochlorothiazide (HCT), hydroflumethiazide (HFT), clopamide (CA), trichlormethiazide (TCM), althiazide (AT) and bendroflumethiazide (BFT) in urine. Two‐step extractions using different times and temperatures for each step were adopted. Parameters influencing the extraction efficiency, including the extraction solvent, sample pH, salt concentration, extraction time and extraction temperature were systematically optimized. Under the resulting optimal extraction conditions, this method showed good linearity over an analytes concentration range of 1 to 1000 ng/mL, high extraction repeatability with relative standard deviations of less than 6%, and low detection limits (0.09 to 0.51 ng/mL). The application of the methods to the determination of diuretics in real samples was tested by analyzing urine samples of patient.  相似文献   
2.
The functionalized multi‐wall carbon nanotube with 1,2‐naphthoquinone‐4‐sulfonic acid sodium (Nq‐MWNT) was fabricated by a simple and low‐cost method. Techniques of scanning electron microscope (SEM) with energy dispersive X‐ray (EDX) analysis, fourier transform infrared spectroscopy (FT‐IR), ultraviolet visible spectroscopy (UV‐vis) and cyclic voltammetry (CV) were used to characterize the property of the Nq‐MWNT. The results showed that the MWNT with high functionalization of Nq can be obtained using this simple method. The Nq‐MWNT modified carbon paste electrode (Nq‐MWNT/CPE) was fabricated by drop‐casting technique. The resulted modified electrode was tested successfully to detection D‐penicillamine (D‐PA) and captopril (CAP) in an aqueous solution. It is found that D‐PA and CAP participate in Michael addition reaction with Nq on MWNT to form the corresponding thioquinone derivative. The reoxidation of adducts at a potential of less positive than D‐PA and CAP at the surface of the bare CPE leads to an increase in the oxidative current, which is proportional to the concentration of D‐PA and CAP. The catalytic response showed a wide linear range (3‐200 μM and 1‐130 μM for D‐PA and CAP, respectively) as well as its experimental limit of detection can be achieved 0.8 μM, and 0.4 μM for D‐PA and CAP, respectively. The modified electrode for D‐PA and CAP determination is of the property of simple preparation, good stability and high sensitivity. Furthermore, the fabricated electrode was used to determine the content of D‐PA and CAP in the tablet, suggesting the good accuracy of the method.  相似文献   
3.
Single‐wall carbon nanotubes (SWCNTs) were used as an immobilization matrix to incorporate [Ir(ppy)2(phen‐dione)](PF6) complex onto a glassy carbon electrode for the study of electrocatalytic reduction of periodate ion. Detailed preliminary electrochemical data for the Ir(III)‐complex in acetonitrile solution and for the modified GCE/SWCNTs/[Ir(ppy)2(phen‐dione)](PF6)/CGE are presented. The modified electrode was applied to selective amperometric detection of periodate through its electrocatalytic reduction to iodide at 0.200 V and pH 2.0. The use of amperometry resulted in two calibration plots over the concentration ranges of 1‐20 μM and 20‐450 μM, with a detection limit of 0.6 μM and sensitivity of 198 nA μM?1.  相似文献   
4.
A new composite electrode has been fabricated based on coating multi‐walled carbon nanotubes (MWCNTs) and n‐octylpyridinum hexafluorophosphate (OPPF6) ionic liquid composite on a glassy carbon (GC) electrode (OPPF6‐MWCNTs/GCE). This electrode shows very attractive electrochemical performances for electrooxidation of risperidone (RIS) compared to conventional electrodes using carbon and mineral oil, notably improved sensitivity and stability. The oxidation peak potentials in cyclic voltammogram of RIS on the OPPF6‐MWCNTs/GCE was occurred around 230 mV vs. SCE at Britton–Robinson (B–R) buffer (pH 4.0) at scan rate of 100 mV s?1. The electrochemical parameters such as diffusion coefficient (D), charge transfer coefficient (α) and the electron transfer rate constant (k/s) were determined using cyclic voltammetry. Under the optimized conditions, the peak current was linear to risperidone concentration over the concentration range of 10–200 nM with sensitivity of 0.016 μA/nM?1 using differential pulse voltammetry. The detection limit was 6.54 nM (S/N = 3). The electrode also displayed good selectivity and repeatability. In the presence of clozapine (CLZ) the response of RIS kept almost unchanged. Thus this electrode could find application in the determination of RIS in some real samples. The analytical performance of the OPPF6‐MWCNTs/GCE was demonstrated for the determination of RIS in human serum and pharmaceutical samples.  相似文献   
5.
The traditional method for opening the electron shells of noble gas atoms involves a strong electronegative atom or group. However, this approach is limited to only heavy noble‐gas atoms, such as Kr and Xe. In this paper, we performed accurate calculations of He@C8H8 and He@C10H16 and showed the possibility of opening the electron shell of a light noble‐gas atom. © 2012 Wiley Periodicals, Inc.  相似文献   
6.
Fluorine‐doped hydrogenated carbon film was grown by chemical vapor deposition technique using CH4 and CF4 as feedstock, with a pulse DC‐bias power supply. The structure of as‐deposited film was characterized by transmission electron microscopy and Raman spectra. The results suggested that the film could be considered as composite thin film with curved graphitic structures embedded in amorphous carbon matrix. The mechanical properties and friction coefficient were tested by TI 950 TriboIndenter and UMT‐2 at humidity of 30%, respectively. The results showed that the film exhibited high hardness (~11.04 GPa), good elasticity recovery(~83%) and ultra‐low coefficient of friction (~0.01). Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
7.
In this study, 4‐thiophenol modified glassy carbon electrode was prepared by the reduction of 4‐diazothiophenol tetrafluoroborate salt. Silver nanoparticles were attached to the thiophenol modified surface to prepare a thiophenol‐silver nanoparticle composite film. 4‐Aminothiopenol molecules were deposited by self‐assembling technique to form multi‐layered nanofilms of TP/SNP/PhNH2 on glassy carbon substrate. These surfaces were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy, reflectance‐absorption infrared spectroscopy, and ellipsometry at each multilayer film growth process. Atomic force microscopic images of GC/TP/SNP/PhNH2 surfaces were also acquired. The characterization methods show that the amine group containing surface permits the subsequent modification by a variety of coupling reactions for the immobilization of more complex systems. An application of the electrode modification for the determination of uric acid with a significantly lower detection limit is described. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
8.
Surface treatment (ST) of carbon fibers (CF) leads to an enhancement in fiber‐matrix adhesion. However, it deteriorates the strength of a fiber which makes its reinforcing action less effective in a composite. These effects in opposite directions control the net strength of a composite, and hence, the treatment has to be judiciously applied, which would enhance the first factor and minimize the second one. Authors have recently reported on four effective techniques (using various doses) such as treatments with nanoparticles of Ytterbium fluoride (YbF3), cold remote nitrogen–oxygen plasma (CRNOP), γ‐ray irradiation and nitric acid oxidation. Amongst these methods, nitric acid oxidation is studied in depth in the literature, and γ‐ray irradiation is sparingly studied. However, nano‐YbF3 and CRNOP were first time reported in the literature by the authors. However, comparative aspects of all these methods were not addressed. In this paper, these aspects in details are discussed to lay down the right criteria for selection of a ST technique of CF to design the desired performance of a composite. The composites with polyetherimide and treated CF (including untreated) were developed and evaluated for various properties including tribological one. Treated CF based composites exhibited excellent mechanical and tribological properties (under harsh operative conditions with wear rates ≈ 1 × 10?15 m3/Nm and μ ≈ 0.09). It was concluded that for strength and tribo‐performance, different treatments and doses are to be employed. Overall nanosized‐YbF3 treatment of CF proved to be the most promising ST method. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
9.
Polyacrylonitrile‐based carbon fibers with different graphite degrees were oxidative ablated at 500 and 600 °C in air. By Thermal gravimetric (TG), Raman spectroscopy, X‐ray diffraction, and SEM, the mass loss, microstructure, and surface morphology of carbon fibers were investigated. The mass loss of carbon fiber increases linearly with increasing oxidative ablated time under 500 and 600 °C. The carbon fiber with higher graphite degree shows higher oxidative resistance, and the surface roughness increases gradually because of chemical ablation during the whole oxidation. A gloss morphology appears on the surface primarily because of physical denudation for carbon fibers with lower graphite degree and then burn off according to carbon and oxygen reaction. The crystallite size (La) decreases significantly, while interlayer spacing(d002) remains nearly unchanged. SEM observation suggests the two kinds of ablation mechanisms for carbon fibers with different graphite degrees indicating that CC band in sp3 hybridization prefers to be attacked by oxygen molecule more than that in sp2 hybridization during oxidation ablation in air. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   
10.
Interaction‐induced static electric properties, that is, dipole moment, polarizability, and first hyperpolarizability, of the CO? (HF)n and N2? (HF)n, n = 1–9 hydrogen‐bonded complexes are evaluated within the finite field approach using the Hartree–Fock, density functional theory, Møller–Plesset second‐order perturbation theory, and coupled cluster methods, and the LPol‐n (n = ds, dl, fs, fl) basis sets. To compare the performance of the different methods with respect to the increase of the complex size, we consider as model systems linear chains of the complexes. We analyze the results in terms of the many‐body and cooperative effects. © 2012 Wiley Periodicals, Inc.  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