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   36949篇
  免费   3332篇
  国内免费   1747篇
电工技术   1730篇
综合类   2399篇
化学工业   11497篇
金属工艺   4933篇
机械仪表   1034篇
建筑科学   2054篇
矿业工程   754篇
能源动力   3720篇
轻工业   3118篇
水利工程   484篇
石油天然气   1876篇
武器工业   175篇
无线电   1137篇
一般工业技术   3934篇
冶金工业   1532篇
原子能技术   585篇
自动化技术   1066篇
  2024年   68篇
  2023年   685篇
  2022年   982篇
  2021年   1297篇
  2020年   1308篇
  2019年   1239篇
  2018年   1134篇
  2017年   1277篇
  2016年   1293篇
  2015年   1219篇
  2014年   1939篇
  2013年   2182篇
  2012年   2223篇
  2011年   2798篇
  2010年   1981篇
  2009年   2226篇
  2008年   1932篇
  2007年   2319篇
  2006年   2098篇
  2005年   1811篇
  2004年   1544篇
  2003年   1329篇
  2002年   1135篇
  2001年   994篇
  2000年   826篇
  1999年   605篇
  1998年   525篇
  1997年   426篇
  1996年   432篇
  1995年   311篇
  1994年   285篇
  1993年   254篇
  1992年   228篇
  1991年   201篇
  1990年   177篇
  1989年   107篇
  1988年   78篇
  1987年   77篇
  1986年   67篇
  1985年   62篇
  1984年   66篇
  1983年   27篇
  1982年   53篇
  1981年   39篇
  1980年   37篇
  1979年   26篇
  1978年   25篇
  1977年   18篇
  1976年   18篇
  1975年   21篇
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
1.
Semi-synthetic triterpenoids, holding an amino substituted seven-membered A-ring (azepano-ring), which could be synthesized from triterpenic oximes through a Beckmann type rearrangement followed by a reduction of lactame fragment, are considered to be novel promising agents exhibiting anti-microbial, alpha-glucosidase, and butyrylcholinesterase inhibitory activities. In this study, in an attempt to develop new antitumor candidates, a series of A-ring azepano- and 3-amino-3,4-seco-derivatives of betulin, oleanolic, ursolic, and glycyrrhetinic acids were evaluated for their cytotoxic activity against five human cancer cell lines and non-malignant mouse fibroblasts by means of a colorimetric sulforhodamine assay. Azepanoallobetulinic acid amide derivative 11 was the most cytotoxic compound of this series but showed little selectivity between the different human tumor cell lines. Flow cytometry experiments showed compound 11 to act mainly by apoptosis (44.3%) and late apoptosis (21.4%). The compounds were further screened at the National Cancer Institute towards a panel of 60 cancer cell lines. It was found that compounds 3, 4, 7, 8, 9, 11, 15, 16, 19, and 20 showed growth inhibitory (GI50) against the most sensitive cell lines at submicromolar concentrations (0.20–0.94 μM), and their cytotoxic activity (LC50) was also high (1–6 μM). Derivatives 3, 8, 11, 15, and 16 demonstrated a certain selectivity profile at GI50 level from 5.16 to 9.56 towards K-562, CCRF-CEM, HL-60(TB), and RPMI-8226 (Leukemia), HT29 (Colon cancer), and OVCAR-4 (Ovarian cancer) cell lines. Selectivity indexes of azepanoerythrodiol 3 at TGI level ranged from 5.93 (CNS cancer cell lines SF-539, SNB-19 and SNB-75) to 14.89 for HCT-116 (colon cancer) with SI 9.56 at GI50 level for the leukemia cell line K-562. The present study highlighted the importance of A-azepano-ring in the triterpenic core for the development of novel antitumor agents, and a future aim to increase the selectivity profile will thus lie in the area of modifications of azepano-triterpenic acids at their carboxyl group.  相似文献   
2.
Electroreduction of small molecules such as H2O, CO2, and N2 for producing clean fuels or valuable chemicals provides a sustainable approach to meet the increasing global energy demands and to alleviate the concern on climate change resulting from fossil fuel consumption. On the path to implement this purpose, however, several scientific hurdles remain, one of which is the low energy efficiency due to the sluggish kinetics of the paired oxygen evolution reaction (OER). In response, it is highly desirable to synthesize high-performance and cost-effective OER electrocatalysts. Recent advances have witnessed surface reconstruction engineering as a salient tool to significantly improve the catalytic performance of OER electrocatalysts. In this review, recent progress on the reconstructed OER electrocatalysts and future opportunities are discussed. A brief introduction of the fundamentals of OER and the experimental approaches for generating and characterizing the reconstructed active sites in OER nanocatalysts are given first, followed by an expanded discussion of recent advances on the reconstructed OER electrocatalysts with improved activities, with a particular emphasis on understanding the correlation between surface dynamics and activities. Finally, a prospect for clean future energy communities harnessing surface reconstruction-promoted electrochemical water oxidation will be provided.  相似文献   
3.
Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.  相似文献   
4.
The aim of this exploratory study has been to investigate the fire properties and environmental aspects of different upholstery material combinations, mainly for domestic applications. An analysis of the sustainability and circularity of selected textiles, along with lifecycle assessment, is used to qualitatively evaluate materials from an environmental perspective. The cone calorimeter was the primary tool used to screen 20 different material combinations from a fire performance perspective. It was found that textile covers of conventional fibres such as wool, cotton and polyester, can be improved by blending them with fire resistant speciality fibres. A new three‐dimensional web structure has been examined as an alternative padding material, showing preliminary promising fire properties with regard to ignition time, heat release rates and smoke production.  相似文献   
5.
杨乾  范存斐  王毅  任亚琳  毕阳 《食品科学》2021,42(1):243-249
目的:研究抗坏血酸(ascorbic acid,AsA)-还原型谷胱甘肽(reduced glutathione,GSH)循环代谢在水杨酸处理采后甜瓜诱导的过量H2O2清除过程中的作用。方法:用4 mmol/L水杨酸浸泡‘玉金香’厚皮甜瓜10 min,测定处理后果实常温贮藏过程中丙二醛(malondialdehyde,MDA)含量,分析活性氧的积累水平、超氧化物歧化酶(superoxide dismutase,SOD)和过氧化氢酶(catalase,CAT)活力,以及AsA-GSH循环过程相关酶活力及产物和底物含量。结果:水杨酸处理降低了果实MDA含量,第10天处理组MDA含量较对照组降低14.6%;显著提高了果实O2-·的产生速率和H2O2含量(P<0.05),其中处理后第2天O2-·的产生速率高出同期对照组的1.9 倍,第6天H2O2含量高出对照组果实29.7%;提高了果实SOD活力,但抑制了CAT活力,说明H2O2的清除可能是依赖于除酶促系统外的其他系统。此外,水杨酸处理提高了果实抗坏血酸过氧化物酶、单脱氢抗坏血酸过氧化物酶、脱氢抗坏血酸还原酶和谷胱甘肽还原酶的活力,增加了AsA和氧化型谷胱甘肽的含量,降低了脱氢抗坏血酸和GSH的含量。结论:水杨酸处理诱导了厚皮甜瓜果实的氧爆,抑制了MDA产生,由水杨酸诱导产生的过量H2O2主要依靠AsA-GSH循环系统清除。  相似文献   
6.
Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH2-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH2-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.  相似文献   
7.
Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni3S2 nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni3S2 material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.  相似文献   
8.
The durability of metal plate proton exchange membrane fuel cell (PEMFC) stack is still an important factor that hinders its large-scale commercial application. In this paper, we have conducted a 1000 h durability test on a 1 kW metal plate PEMFC stack, and explored the degradation of the core components. After 1000 h of dynamic load cycles, the voltage decay percentage of the stack under the current densities of 1000 mA cm?2 is 5.67%. By analyzing the scanning electron microscopy (SEM) images, the surfaces of the metal plates are contaminated locally by organic matter precipitated from the membrane electrode assembly (MEA). The SEM images of the catalyst coated membrane (CCM) cross section indicate that the MEA has undergone severe degradation, including the agglomeration of the catalyst layer, and the thinning and perforation of the PEM. These are the main factors that cause the rapid increase in hydrogen crossover flow rate and performance decay of the PEMFC stack.  相似文献   
9.
Effects of different drying methods and different addition levels of eggplant (EP) on product quality of low-fat patties (LFPs) were investigated during storage. EP was dried in an oven dryer at 60 °C or a freeze dryer at −50 °C. LFPs were prepared by replacing with 1.5% soy protein isolate (SPI). Six treatments were used in this study: (1) control (CTL), without addition of EP; (2) reference (REF), 0.1% ascorbic acid; (3) O1, 0.25% oven-dried (OD) EP; (4) O2, 0.5% ODEP; (5) F1, 0.25% freeze-dried (FD) EP; and (6) F2, 0.5% FDEP. Redness (a*) and lightness (L*) values in LFPs added with EP were lower than those of others (p < 0.05) and decreased with increasing storage time. Yellowness (b*) values of cooked patties were increased during storage time (p < 0.05), with control having the highest value. The addition of EP or ascorbic acid into LFPs lowered microbial counts than control (p < 0.05). Thiobarbituric acid reactive substances (TBARS) was increased during storage, with REF having the lowest value, and patties added with EP had lower TBARS values than control during storage. Volatile basic nitrogen (VBN, mg%) contents of all patties also increased during storage time with O2 and F2 having lower values than control. Therefore, EP might have potential as a natural antioxidant in meat products during storage.  相似文献   
10.
《Ceramics International》2022,48(11):15252-15260
The Co3O4, as a potential anode of lithium-ion batteries, has gained considerable attention because of high theoretical capacity. However, the Co3O4 is suffering from serious structure deterioration and rapid capacity fading due to its bulky volume change during cyclic charge/discharge process. Herein, to stabilize the lithium storage performance of the Co3O4 nanoparticles, a characteristic carbon scaffold (HPC) integrating hollow and porous structures has been fabricated by a well-designed method for the first time. The ultrafine Co3O4 nanoparticles are cleverly anchored on the HPC (HPC@Co3O4) and hence achieve significantly improved electrochemical properties including high capacity, improved reaction kinetics and outstanding cycle stability, showing high capacity of 1084.7 mAh g-1 after 200 cycles at 200 mA g-1 as well as 681.4 mAh g-1 after 300 cycles at 1000 mA g-1. The HPC@Co3O4 therefore shows good promising for application in advanced lithium-ion battery anodes. The results of the systematically material and electrochemical characterizations indicate that the synergistic effects of ultrafine Co3O4 nanoparticles and well-designed HPC scaffolds are responsible for the outstand performance of the HPC@Co3O4 anode. Moreover, this work can enrich the understanding and development of stable and high-performance metal oxide-based lithium-ion battery anodes for advanced lithium storage.  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