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   2664篇
  免费   117篇
  国内免费   481篇
化学   2931篇
晶体学   57篇
力学   15篇
综合类   68篇
数学   2篇
物理学   189篇
  2024年   2篇
  2023年   43篇
  2022年   117篇
  2021年   116篇
  2020年   89篇
  2019年   80篇
  2018年   68篇
  2017年   94篇
  2016年   76篇
  2015年   122篇
  2014年   119篇
  2013年   227篇
  2012年   130篇
  2011年   137篇
  2010年   134篇
  2009年   150篇
  2008年   175篇
  2007年   164篇
  2006年   160篇
  2005年   182篇
  2004年   145篇
  2003年   147篇
  2002年   87篇
  2001年   84篇
  2000年   78篇
  1999年   68篇
  1998年   54篇
  1997年   41篇
  1996年   34篇
  1995年   21篇
  1994年   28篇
  1993年   19篇
  1992年   12篇
  1991年   9篇
  1990年   6篇
  1989年   7篇
  1988年   10篇
  1987年   6篇
  1986年   2篇
  1985年   5篇
  1984年   2篇
  1983年   1篇
  1982年   1篇
  1981年   2篇
  1979年   1篇
  1977年   1篇
  1976年   4篇
  1975年   1篇
  1972年   1篇
排序方式: 共有3262条查询结果,搜索用时 0 毫秒
991.
Organic–inorganic polymer hybrid films of epoxy polymer were prepared, using Cobaltous sulfate heptahydrate (CoSO4.7H2O) as a filler component, by physical blending method. UV–Vis optical absorption spectra were analyzed to determine optical band gaps (Eg) of the hybrid material. FTIR studies revealed the interaction of inorganic component with molecules of the polymer matrix. Glass transition temperature (Tg) and degradation temperature were determined by DSC. TG analysis showed the improvement in thermal stability of prepared hybrid films. XRD patterns revealed the amorphous nature of the pure epoxy polymer. Additional sharp peaks were seen for higher filler levels (FLs), indicating self formed nanostructures in the material, which was also evident from SEM analysis.  相似文献   
992.
《Electroanalysis》2018,30(3):551-560
The development of a low‐cost and disposable biosensor platform for the sensitive and rapid detection of microRNAs (miRNAs) is of great interest for healthcare, pharmaceuticals, and medical science. We designed an impedimetric biosensing platform using Chitosan (CHIT)/nitrogen doped reduced graphene oxide (NRGO) conductive composite to modify the surface of pencil graphite electrodes (PGE) for the sensitive detection of miRNAs. An initial optimisation protocol involved investigation of the effect of NRGO concentration and miR 660 DNA probe concentration on the response of the modified electrode. After the optimization protocol, the sequence‐selective hybridization between miR 660 DNA probe and its RNA target was evaluated by measuring changes on charge transfer resistance, Rct values. Moreover, the selectivity of impedimetric biosensor was tested in the presence of non‐complementary miRNA (NC) sequences, such as miR 34a and miR 16. The hybridization process was examined both in phosphate buffer (PBS) and in PBS diluted fetal bovine serum (FBS:PBS) solutions. The biosensor demonstrated a detection limit of 1.72 μg/mL in PBS and 1.65 μg/mL in FBS:PBS diluted solution. Given the easy, quick and disposable attributes, the proposed conductive nanocomposite biosensor platform shows great promise as a low‐cost sensor kit for healthcare monitoring, clinical diagnostics, and biomedical devices.  相似文献   
993.
In this work, phosphorylated chitosan‐coated carbon microspheres (PCH@CMS) was successfully synthesized. Obtained PCH@CMS used as flame retardant was added into unsaturated polyester resin (UPR). Fourier infrared spectroscopy (FTIR) and X‐ray electron spectroscopy (XPS) results indicated that C═O, P─O, and P═O appeared on the surface of PCH@CMS. Compared with UPR, the residues of UPR/PCH@CMS‐10 at 800°C under nitrogen and air atmospheres increased by 9.0 and 3.9 wt%, respectively, and the peak heat release rate (pHRR) and the peak smoke release rate (pSPR) of UPR/PCH@CMS‐3 decreased by 18.9% and 23.5%, respectively. Limiting oxygen index (LOI), thermogravimetric analyzer (TG), and cone calorimeter test (CCT) results showed that the addition of PCH@CMS could enhance the flame retardancy and smoke suppression of the UPR composites. Moreover, the residues after CCT were characterized by scanning electron microscopy (SEM), XPS, and laser Raman spectroscopy (LRS). Based on the above results, the flame retardant mechanism of PCH@CMS was proposed. The carbon layer produced by the UPR/PCH@CMS composites was tortuous and could suppress the heat and pyrolysis product exchange with UPR matrix.  相似文献   
994.
本文研究了硫酸根阴离子对1-苯基-3-甲基-4-苯甲酰基吡唑酮-5(HPMBP,HL)及三辛胺(TOA)协同萃取镨(Ⅲ)及钕(Ⅲ)的影响。发现在SO42-体系中协萃机理为: c="http://www.rhhz.net/qikantupian/WJHXXB-19900116-89-2.gif" /> 式中Ln3+=Pr3+或Nd3+,下标“o”指示有机相中物种,无下标指示水相中物种。固体萃合物的红外光谱及元素分析数据确证了上述机理。  相似文献   
995.
N‐acetylcysteine (NAC) and gentamicin sulfate (GS) are biologically and pharmaceutically relevant thiol‐containing compounds. NAC is well known for its antioxidant properties, whereas GS is an aminoglycoside that is used as a broadband antibiotic. Both pharmaceuticals play a significant role in the treatment of bacterial infections by suppressing the formation of biofilms. According to the European Pharmacopeia protocol, GS is analyzed by high performance liquid chromatography (HPLC) using gold electrodes for electrochemical detection. Here, we report the electrochemical detection of these compounds at NH2‐terminated boron‐doped diamond electrodes, which show significantly reduced electrode passivation, an issue commonly known for gold electrodes. Cyclic voltammetry experiments performed for a period of 70 minutes showed that the peak current decreased only by 1.6 %/7.4 % for the two peak currents recorded for GS, and 6.6 % for the oxidation peak of NAC, whereas at gold electrodes a decrease in peak current of 14.2 % was observed for GS, and of 64 %/30 % for the two peak currents of NAC. For their quantitative determination, differential pulse voltammetry was performed in a concentration range of 2–49 µg/mL of NAC with a limit of detection (LOD) of 1.527 µg/mL, and a limit of quantification (LOQ) of 3.624 µg/mL, respectively. The quantification of GS in a concentration range of 0.2–50 µg/mL resulted in a LOD of 1.714 µg/mL, and a LOQ of 6.420 µg/mL, respectively.  相似文献   
996.
This paper describes an improved liquid chromatography method combined with pulsed electrochemical detection for the analysis of etimicin sulfate. In total, 22 impurities could be separated. A TSK‐GEL C18 column (250 mm × 4.6 mm i.d., 5 μm) is used, and the mobile phase is composed of 40 mL of acetonitrile and 960 mL of an aqueous solution containing trifluoroacetic acid (15 mL/L), pentafluoropropionic acid (500 μL/L), 50% sodium hydroxide (8 mL/L) and sodium sulfate (1.5 g/L). The pH of the aqueous solution is adjusted to 3.5 with 0.8 M sodium hydroxide. The influence of the different chromatographic parameters on the separation was investigated. A quadruple potential‐time waveform was applied to the electrodes of the detection cell. 0.8 M sodium hydroxide was added post column to raise the pH to at least 12 before detection. A central composite experimental design was used to describe the relationship between factors and response values and to establish factorial analysis. Compared to previously published investigations, this improved method shows higher sensitivity, better separation ability and robustness and has been incorporated by the Chinese Pharmacopoeia 2015 for analysis of etimicin sulfate. A number of commercial samples of etimicin sulfate were also analyzed using this method.  相似文献   
997.
In this study, catalytic activity of two different cationic O-Carboxymethyl chitosan Schiff base palladium (II) complexes in Suzuki coupling reactions and synthesis of biarlys having different functional groups, and reusability of the catalysts were tested. Chemical structures of the synthesized biaryls were elucidated by GC-MS and 1H-NMR; and no by-products were observed in the spectra. Cationic palladium (II) catalysts high turnover numbers and selectivity were recorded for the reactions. Mercury test demonstrated that the reaction mechanism proceed a homogeneous route. Reusability tests of cationic biocatalysts showed that their catalytic activity were still highly efficient even after six cycles.  相似文献   
998.
999.
Chitosan‐based molecular imprinted polymer (CS‐MIP) nanogel is prepared in the presence of morphine template, fully characterized and used as a new vehicle to extend duration of morphine analgesic effect in Naval Medical Research Institute mice. The CS‐MIP nanogel with ≈25 nm size range exhibits 98% loading efficiency, and in vitro release studies show an initial burst followed by an extended slow release of morphine. In order to study the feasibility of CS‐MIP nanogel as morphine carrier, 20 mice are divided into two groups randomly and received subcutaneous injection of morphine‐loaded CS‐MIP and morphine (10 mg kg?1) dissolved in physiologic saline. Those received injection of morphine‐loaded CS‐MIP show slower and long lasting release of morphine with 193 min effective time of 50% (ET50) analgesia compared to 120 min ET50 in mice received morphine dissolved in physiologic saline. These results suggest that CS‐MIP nanogel can be a possible strategy as morphine carrier for controlled release and extension of its analgesic efficacy.

  相似文献   

1000.
天然气与硫酸盐热化学还原反应的模拟实验研究   总被引:4,自引:1,他引:4  
为探讨天然气中高含量硫化氢形成的化学机制,利用高温高压反应装置,对天然气与固态硫酸钙反应体系进行了热模拟实验研究。使用气相色谱仪、微库仑仪、傅里叶变换红外光谱仪和X射线衍射仪对产物进行了分析,探讨了硫酸盐热化学还原反应的热力学特征,并进行了反应动力学研究。结果表明,高温下天然气与固态硫酸钙可以发生反应,产物主要为硫化氢、二氧化碳、碳酸钙、水和炭。热力学研究表明,天然气与固态硫酸钙的反应可行,升高温度对反应有利,同一温度下长链烷烃与固态硫酸钙发生反应的可能性要比短链烷烃大。根据动力学模型得到反应活化能为96.824kJ/mol。  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