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   5522篇
  免费   244篇
  国内免费   52篇
化学   4124篇
晶体学   40篇
力学   216篇
综合类   2篇
数学   777篇
物理学   659篇
  2024年   9篇
  2023年   43篇
  2022年   79篇
  2021年   306篇
  2020年   207篇
  2019年   230篇
  2018年   218篇
  2017年   168篇
  2016年   292篇
  2015年   202篇
  2014年   210篇
  2013年   533篇
  2012年   359篇
  2011年   384篇
  2010年   238篇
  2009年   204篇
  2008年   258篇
  2007年   259篇
  2006年   207篇
  2005年   181篇
  2004年   164篇
  2003年   141篇
  2002年   144篇
  2001年   54篇
  2000年   63篇
  1999年   44篇
  1998年   30篇
  1997年   44篇
  1996年   40篇
  1995年   32篇
  1994年   39篇
  1993年   31篇
  1992年   32篇
  1991年   27篇
  1990年   41篇
  1989年   25篇
  1988年   22篇
  1987年   25篇
  1986年   28篇
  1985年   34篇
  1984年   20篇
  1983年   17篇
  1982年   25篇
  1981年   20篇
  1980年   13篇
  1979年   16篇
  1978年   11篇
  1977年   12篇
  1976年   9篇
  1975年   6篇
排序方式: 共有5818条查询结果,搜索用时 156 毫秒
991.
In this paper, we report an efficient coupling scheme with relaxed misalignment tolerances. The proposed coupling scheme consists of two ball lenses of same diameter (1 mm) and different refractive indices. The second ball lens which is facing the fiber tip has a higher refractive index (1.833), whereas the first one which faces the laser diode has a refractive index of 1.5. Employing Gaussian and ABCD ray tracing optics, the theoretically obtained coupling efficiency can reach a unity with relaxed working distance (separation of the coupling system from the fiber tip) in the range between 1 and 4 mm at some optimum positions of the coupling lenses with regard to each other and to the facet of the laser diode. It has been found that if the distance between the first ball lens and the laser diode (d1) is fixed at 1.1 mm, which is twice its focal length, the coupling efficiency and the working distance as well as the misalignment tolerances are greatly affected by variation of the separation between the two ball lenses (s), and for this proposed coupling scheme the highest coupling efficiency and largest working distance are obtained when s is in the range of 0.3-0.35 mm. Above and below this range there is a significant reduction in the values of the above-mentioned parameters. Experimentally, the Nd:YAG laser welding system has been used for the alignment and welding of the coupling components in a butterfly configuration; the experimentally obtained coupling efficiency of the proposed coupling system was around 75% with relaxed working distance. From the effect of lateral and angular offsets on coupling efficiency, it is clearly noticed that the mode field of laser diode is transformed from elliptical into circular and hence effectively matched with that of the single-mode fiber.  相似文献   
992.
Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N3) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N3 substrate was obtained by nucleophilic attack of NaN3 on gold substrates modified by the electrochemical reduction of the , +N2–C6H4–CH2Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C6H4–CH2Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N3 by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF2)7- chain and terminal CF3. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N3 to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm−1); CF2 (1000–1100 cm−1) and CF3 (1100–1350 cm−1) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.  相似文献   
993.
The presence of organic dyes from industrial wastewater can cause pollution and exacerbate environmental problems; therefore, in the present work, activated carbon was synthesized from locally available oil palm trunk (OPT) biomass as a low-cost adsorbent to remove synthetic dye from aqueous media. The physical properties of the synthesized oil palm trunk activated carbon (OPTAC) were analyzed by SEM, FTIR-ATR, and XRD. The concurrent effects of the process variables (adsorbent dosage (g), methylene blue (MB) concentration (mg/L), and contact time (h)) on the MB removal percentage from aqueous solution were studied using a three-factor three-level Box–Behnken design (BBD) of response surface methodology (RSM), followed by the optimization of MB adsorption using OPTAC as the adsorbent. Based on the results of the analysis of variance (ANOVA) for the three parameters considered, adsorbent dosage (X1) is the most crucial parameter, with an F-value of 1857.43, followed by MB concentration (X2) and contact time (X3) with the F-values of 95.60 and 29.48, respectively. Furthermore, the highest MB removal efficiency of 97.9% was achieved at the optimum X1, X2, and X3 of 1.5 g, 200 mg/L, and 2 h, respectively.  相似文献   
994.
A capillary zone electrophoretic method has been developed and validated for the determination of the impurity quinocide (QC) in the antimalarial drug primaquine (PQ). Different buffer additives such as native cyclodextrins and crown ethers were evaluated. Promising results were obtained when either β‐cyclodextrin (β‐CD) or 18‐crown‐6 ether (18C6) were used. Their separation conditions such as type of buffer and its pH, buffer additive concentration, applied voltage capillary temperature and injection time were optimized. The use of 18C6 offers slight advantages over β‐CD such as faster elution times and improved resolution. Nevertheless, migration times of less than 5 min and resolution factors (Rs) in the range of 2–4 were obtained when both additives were used. The method was validated with respect to selectivity, linearity, limits of detection and quantitation, analytical precision (intra‐ and inter‐day variability) and repeatability. Concentrations of 2.12 and 2.71% (w/w) of QC were found in pharmaceutical preparations of PQ from two different manufacturers. A possible mechanism for the successful separation of the isomers is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   
995.
Compounds 1a-d react with benzylidenemalononitrile 2 to yield dihydroaminopyridazines 3a-d and, in contrast, compounds 1e,f react with 2 under the same conditions to yield aminobenzenedicarbonitriles 8e,f compound 8e underwent intramolecular cyclization to phthalazine 9e. Compound 10e reacted with 2a to yield 11e.  相似文献   
996.
N-Bromosuccinimide (NBS) is a brominating and oxidizing agent that is used as a source of bromine. The proton affinities, the tautomeric forms and NBr bond dissociation of NBS have been computed using the B3LYP functional as implemented in the density functional approach. The electronic structures of all possible tautomeric forms of NBS have been thoroughly investigated. The keto form of NBS has been shown to be more stable than any other tautomeric forms. The geometries and relative energies for various stationary structures were determined. The results indicate clearly that O-site protonation is strongly favored over N-site protonation for the studied compound in case of mono- and di-protonation. The bond dissociation energies (BDEs), involving the formation of the bromine radical, cation, and anion, of the NBr bond have been investigated. The NBr BDE of the Br radical formation is lower than that of the Br anion or cation. These conclusions are in good agreement with the experimental results.  相似文献   
997.

Abstract  

Two simple, sensitive, and selective spectrophotometric methods were developed for determining amodiaquine (AQ) and chloroquine (CQ) based on their oxidation with potassium iodate and potassium bromate, respectively. The initial rates of oxidation of AQ and CQ were monitored at 342 and 343 nm, the wavelengths of maximum absorptions of the two drugs. The various experimental parameters affecting oxidation reactions were thoroughly studied and optimized. Beer’s law was obeyed for 0.2–4.0 and 0.5–5.0 μg cm−3, with correlation coefficients of 0.9999 and 0.9998 (n = 6) and a detection limit (based on the 3S b -criterion) of 0.04 and 0.06 μg cm−3 for AQ and CQ. The proposed methods were conveniently applied to determining AQ and CQ in pure and dosage forms.  相似文献   
998.
Electrokinetic supercharging (EKS) has been used in the last few years as a powerful tool for separation and on-line preconcentration of different types of analytes. We have developed a valuable modification for EKS system, namely counter-flow EKS (CF-EKS) and applied it for the separation and on-line preconcentration of seven non-steroidal anti-inflammatory drugs (NSAIDs) in water samples. In CF-EKS, a hydrodynamic counter-flow is applied during electrokinetic injection of the analytes within the EKS system. This counter-flow minimises the introduction of the sample matrix into the capillary, allowing longer injections to be performed. Careful choice of the optimum counter-flow as well as the optimum injection voltage allowed the sensitivity to be enhanced by 11,800-fold, giving limits of detection (LODs) of 10.7–47.0 ng/L for the selected NSAIDs. The developed method was validated and then applied for the determination of the studied NSAIDs in drinking water as well as wastewater samples from Hobart city.  相似文献   
999.
The thermal behavior of unsonicated dispersions of a double-chained surfactant, Dioctadecyldimethylammonium bromide (DODAB), has been studied over a wide concentration range using DSC and dynamic rheology. All dispersions are characterized by the pre- and main transition peaks at 35 °C and 43 °C, respectively. But, only above 10 mM DODAB, a third endotherm at 52 °C appears which may correspond to the (ULVs + Lα fragments) → MLVs transition. The thermal-induced MLV’s size is proportionally dependent on the concentration. In addition, and in agreement with DSC data, dynamic rheology has proven to be an indirect way to elucidate the structural transitions in these DODAB vesicular dispersions.  相似文献   
1000.
Biological buffers are of utmost importance for research in biological and clinical chemistry and in oceanography, but they may not be inert enough, thus interfering with the system under study. The N-[Tris(hydroxymethyl)methyl]-3-aminopropanesulfonic acid (TAPS) and N-[Tris(hydroxymethyl)methyl]-3-amino-2-hydroxypropanesulfonic acid (TAPSO) are useful zwitterionic buffers for pH control as standard buffers in the physiological region of pH 7.7 to 9.1 for TAPS and 7.0 to 8.2 for TAPSO, respectively. In this work, interaction between these zwitterionic compounds and electrolytes of potassium acetate (KAc), potassium bromide (KBr), potassium chloride (KCl), and sodium chloride (NaCl) were investigated through measuring the densities of these buffers in aqueous and in aqueous electrolyte solutions by a high precision vibrating tube digital densitometer from T = (298.15 to 328.15) K under atmospheric pressure. In this series of measurements, the aqueous samples were prepared with various concentrations of the zwitterionic buffers, up to saturated conditions, and over salt concentrations from (1 to 4) mol · dm?3. The measured densities served to evaluate the cubic expansion coefficients, α(m, T) and the apparent molar volumes, V?(m, T). An empirical equation was used to correlate quantitatively the experimental densities over the entire concentration ranges.  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