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   13248篇
  免费   2377篇
  国内免费   2764篇
化学   9733篇
晶体学   272篇
力学   746篇
综合类   289篇
数学   1603篇
物理学   5746篇
  2024年   35篇
  2023年   232篇
  2022年   479篇
  2021年   451篇
  2020年   518篇
  2019年   497篇
  2018年   428篇
  2017年   486篇
  2016年   576篇
  2015年   661篇
  2014年   844篇
  2013年   1000篇
  2012年   1125篇
  2011年   1144篇
  2010年   888篇
  2009年   873篇
  2008年   993篇
  2007年   912篇
  2006年   875篇
  2005年   772篇
  2004年   593篇
  2003年   439篇
  2002年   421篇
  2001年   438篇
  2000年   462篇
  1999年   322篇
  1998年   236篇
  1997年   195篇
  1996年   217篇
  1995年   194篇
  1994年   166篇
  1993年   140篇
  1992年   135篇
  1991年   93篇
  1990年   103篇
  1989年   67篇
  1988年   78篇
  1987年   61篇
  1986年   42篇
  1985年   55篇
  1984年   25篇
  1983年   27篇
  1982年   24篇
  1981年   18篇
  1980年   10篇
  1979年   12篇
  1977年   4篇
  1976年   6篇
  1965年   3篇
  1959年   4篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
931.
The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long-term effectiveness at high rates is still challenged. Herein, to achieve superior long-life and high-rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn2+-conductive SEI and to dynamically patrol its cycling-initiated defects. Profiting from the as-constructed real-time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800 h at an ultrahigh current density of 50 mA cm−2, presenting a record-high cumulative capacity up to 45 Ah cm−2. The superiority of the formulated electrolyte is further demonstrated in the Zn||MnO2 and Zn||NaV3O8 full batteries, even when tested under harsh conditions (limited Zn supply (N/P≈3), 2500 cycles). This work brings inspiration for developing fast-charging Zn batteries toward grid-scale storage of renewable energy sources.  相似文献   
932.
杨文雯  张小平  张兴磊  丁健桦 《化学通报》2023,86(11):1324-1332
脂质在能量贮存和信号传递方面发挥着巨大作用,同时还是生物膜的主要组成成分。不饱和脂质双键位置不同,生理学意义和生物学功能会有很大差异,因此脂质双键位置的识别至关重要。质谱具有灵敏快速、准确度高等优势,已成为脂质结构研究的重要方法。近年来,不同原理的电离技术与选择性衍生反应迅速发展起来,与质谱相结合已广泛应用于多种脂质双键位置的识别。本文主要对这些新型质谱技术进行总结,并展望了其未来发展趋势。  相似文献   
933.
Competition from hydrogen/oxygen evolution reactions and low solubility of N2 in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe3C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe3C/Fe@PCNF-F away from water infiltration and endow a N2 molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust “quasi-solid–gas” state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe3C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH3 yield rate up to 29.2 μg h−1 mg−1cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO3 yield rate up to 15.7 μg h−1 mg−1cat. and FE up to 3.4 % in nitrogen oxidation reaction).  相似文献   
934.
Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO2 reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni−N4 and Fe−N4 pair sites is designed for boosting gas-solid CO2 reduction with H2O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO2 reduction to CO (86.16 μmol g−1 h−1), CH4 (135.35 μmol g−1 h−1) and CH3OH (59.81 μmol g−1 h−1), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO3 dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO3 pathways) for solar-driven photothermal CO2 reduction to initial CO production.  相似文献   
935.
界面微环境是影响酶催化反应及酶传感性能的关键因素. 本研究基于三维微纳米结构多孔金基底, 通过调控电极表面的亲水和疏水浸润性, 制备了具有固-液-气三相界面微环境的氧化酶电极, 并研究了界面微环境对酶催化反应动力学的影响规律. 基于所制备的三相界面多孔金结构酶电极, 反应物氧气能够从气相直接快速地传输到酶催化反应界面, 极大地提升了界面氧气浓度及其稳定性, 从而大幅度提高了氧化酶活性及酶电极响应的稳定性. 以葡萄糖为模型待测物, 基于该三相界面酶电极的电化学酶生物传感器拥有宽的线性范围、 高的灵敏度、 低的检出限以及良好的稳定性. 这类独特的三相反应界面设计为高效酶生物传感器的建构以及生物分子的精准检测提供了新思路.  相似文献   
936.
刘芳  龚芳  清江  杨楚悦  孟桃于  丁利 《分析测试学报》2021,40(12):1765-1771
建立了QuEChERS/高效液相色谱-串联质谱(QuEChERS/HPLC-MS/MS)同时检测柑橘中7种酚类环境激素的分析方法。柑橘样品均质粉碎后采用乙腈(含0.1%甲酸)超声提取,氯化钠盐析,经N-丙基乙二胺(PSA)+C18粉末吸附剂净化,目标化合物经Waters ACQUITY UPLC BEH C18柱(50 mm × 2.1 mm,1.7 μm)分离,以水(含0.5 mmol/L乙酸铵)和甲醇为流动相进行梯度洗脱。考察了不同提取溶剂、提取时间、提取溶剂体积、吸附剂种类和用量对目标化合物回收率的影响。结果表明:在最佳条件下,双酚A(BPA)、壬基酚(NP)、双酚F(BPF)在0.5~100 μg/L范围内线性关系良好,双酚B(BPB)、双酚S(BPS)、4-n-壬基酚(4-n-NP)、4-n-辛基酚(4-n-OP)在0.2~100 μg/L范围内线性关系良好,相关系数(r2)均不小于0.994 1,检出限(LOD)为0.2~0.5 μg/L,定量下限(LOQ)为0.5~1.5 μg/L。在10、250、500 μg/kg 3个加标水平下,目标化合物的回收率为88.5%~109%,相对标准偏差(RSD)为1.2%~9.0%。应用该方法对市售的8种柑橘样品进行检测,BPA在7种柑橘中均检出,4-n-OP在5种柑橘中检出,NP和4-n-NP在3种柑橘中检出,BPB在1种柑橘中检出,BPF、BPS在所有样品中均未检出。该方法操作简单、快速灵敏、定量准确、精密度高,适用于柑橘中7种酚类环境激素的测定。  相似文献   
937.
2-氨基-4-氟吡啶是制备酪氨酸激酶抑制剂、PI3K抑制剂和醛固酮合酶抑制剂等酶抑制剂的重要中间体.已报道的制备方法均存在一些缺陷,难以满足工业化生产.本文以4-氯吡啶-2-甲酰胺为原料,经酰胺脱水、卤素交换、氰基水解、霍夫曼降解等反应得到目标化合物.产物结构经1 H NMR和GC-MS确证.本文采用的合成方法简单、反...  相似文献   
938.
A xylanase-producing strain, identified as Streptomyces sp. T7, was isolated from soil by our lab. The endo-β-1,4-xylanase (xynST7) gene was found in the genome sequence of strain T7, which was cloned and expressed in Escherichia coli. XynST7 belonged to the glycoside hydrolase family 10, with a molecular mass of approximately 47 kDa. The optimum pH and temperature of XynST7 were pH 6.0 and 60 °C, respectively, and it showed wide pH and temperature adaptability and stability, retaining more than half of its enzyme activity between pH 5.0 and 11.0 below 80 °C. XynST7 showed only endo-β-1,4-xylanase activity without cellulase- or β-xylosidase activity, and it showed maximal hydrolysis for corncob xylan in all the test substrates. Then, XynST7 was used for the production of xylo-oligosaccharides (XOSs) by hydrolyzing xylan extracted from raw corncobs. The maximum yield of the XOS was 8.61 ± 0.13 mg/mL using 15 U/mL of XynST7 and 1.5% corncob xylan after 10 h of incubation at 60 °C. The resulting hydrolysate products mainly consisted of xylobiose and xylotriose. These data indicated that XynST7 might by a promising tool for various industrial applications.  相似文献   
939.
With the rapid development of communication technology in civil and military fields, the problem of electromagnetic radiation pollution caused by the electromagnetic wave becomes particularly prominent and brings great harm. It is urgent to explore efficient electromagnetic wave absorption materials to solve the problem of electromagnetic radiation pollution. Therefore, various absorbing materials have developed rapidly. Among them, iron (Fe) magnetic absorbent particle material with superior magnetic properties, high Snoek’s cut-off frequency, saturation magnetization and Curie temperature, which shows excellent electromagnetic wave loss ability, are kinds of promising absorbing material. However, ferromagnetic particles have the disadvantages of poor impedance matching, easy oxidation, high density, and strong skin effect. In general, the two strategies of morphological structure design and multi-component material composite are utilized to improve the microwave absorption performance of Fe-based magnetic absorbent. Therefore, Fe-based microwave absorbing materials have been widely studied in microwave absorption. In this review, through the summary of the reports on Fe-based electromagnetic absorbing materials in recent years, the research progress of Fe-based absorbing materials is reviewed, and the preparation methods, absorbing properties and absorbing mechanisms of iron-based absorbing materials are discussed in detail from the aspects of different morphologies of Fe and Fe-based composite absorbers. Meanwhile, the future development direction of Fe-based absorbing materials is also prospected, providing a reference for the research and development of efficient electromagnetic wave absorbing materials with strong absorption performance, frequency bandwidth, light weight and thin thickness.  相似文献   
940.
Surfactants are one of the major pollutants in laundry powder, which have an impact on the environment and human health. Carbon quantum dots (CQDs) are spherical zero-dimensional fluorescent nanoparticles with great potential for fluorescent probing, electrochemical biosensing and ion sensing. Herein, a bottom-up approach was developed for the synthesis of CQDs from biomass to detect laundry detergent and laundry powder. Waste chicken bones were used as carbon precursors after being dried, crushed and reacted with pure water at 180 °C for 4 h to generate CQDs, which exhibited a monodisperse quasi-spherical structure with an average particle size of 3.2 ± 0.2 nm. Functional groups, including -OH, C=O, C=C and C-O, were identified on the surface of the prepared CQDs. The optimal fluorescence excitation wavelength of the yellow-brown CQDs was 380 nm, with a corresponding emission peak at 465 nm. CQDs did not significantly increase cell death in multiple cell lines at concentrations of 200 µg·mL−1. Fluorescence enhancement of CQDs was observed after addition of sodium dodecyl benzene sulphonate, a major anionic surfactant in laundry powder. A linear relationship between fluorescence enhancement CQDs and the concentration of laundry powder was established. Thus, a hydrothermal method was developed to generate CQDs from waste biomass that may be used as a fluorescent probe to detect laundry powder.  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