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   30110篇
  免费   4055篇
  国内免费   2712篇
化学   20477篇
晶体学   284篇
力学   1944篇
综合类   273篇
数学   3279篇
物理学   10620篇
  2024年   105篇
  2023年   589篇
  2022年   907篇
  2021年   987篇
  2020年   1112篇
  2019年   1081篇
  2018年   911篇
  2017年   814篇
  2016年   1279篇
  2015年   1268篇
  2014年   1536篇
  2013年   2049篇
  2012年   2629篇
  2011年   2657篇
  2010年   1646篇
  2009年   1632篇
  2008年   1736篇
  2007年   1659篇
  2006年   1489篇
  2005年   1227篇
  2004年   940篇
  2003年   789篇
  2002年   751篇
  2001年   561篇
  2000年   558篇
  1999年   651篇
  1998年   578篇
  1997年   574篇
  1996年   659篇
  1995年   506篇
  1994年   464篇
  1993年   388篇
  1992年   371篇
  1991年   322篇
  1990年   255篇
  1989年   202篇
  1988年   157篇
  1987年   136篇
  1986年   127篇
  1985年   118篇
  1984年   88篇
  1983年   61篇
  1982年   41篇
  1981年   36篇
  1980年   18篇
  1978年   19篇
  1977年   23篇
  1976年   20篇
  1975年   28篇
  1974年   27篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Aluminosilicate boggsite (Si/Al-BOG) has been hydrothermally synthesized without adding organic structure-directing agents (OSDAs) in the synthesis gel using the borosilicogermanium ITQ-47 (Si/B-ITQ-47) zeolite as seeds. The introduction of the costly and environmentally less benign phosphazene organic structure-directing agent is not required to grow the zeolite. Physicochemical characterization experiments show that Si/Al-BOG has good crystallinity, high surface area, tetrahedral Al3+ species, and acid sites. In order to test the catalytic performance of the zeolite, the synthesis of l,l-lactide from l-lactic acid was performed. Si/Al-BOG exhibits 88.2% conversion of l-lactic acid and 83.8% l,l-lactide selectivity, which are better than those of other zeolites studied up to now.

Aluminosilicate boggsite (Si/Al-BOG) has been hydrothermally synthesized without adding organic structure-directing agents (OSDAs) in the synthesis gel using the borosilicogermanium ITQ-47 (Si/B-ITQ-47) zeolite as seeds.  相似文献   
992.
在选定毛细管柱温,载气流量、分流比、注入口和FID的温度等色谱条件下,分析了对环芳烷(PCP)二氯化产物的组成。定性分析结果表明,PCP二氯化产物除主要组分是二氯对环芳烷(DCPCP)外,还含少量的一氯对环芳烷(MCPCP)和三氯对环芳烷(TCPCP);DCPCP的色谱图上出现了3个明显的色谱峰,证明3种异构体相对含量较高。用丙酮-石油醚混合溶剂分离去除 物得到了纯度为99.1%的DCPCP。以邻苯二甲酸二丁酯为内标物,测定了DCPCP对内标物的相对质量校正因子。按内标法定量分析了PCP二氯化产物各组分的含量,对DCPCP分析的相对标准偏差小于3%。  相似文献   
993.
化学镀镍磷合金镀层孔隙率的电化学评价   总被引:4,自引:0,他引:4  
本文通过研究镍磷合金、镍磷合金镀层和碳钢在不同浓度硝酸溶液中的动电位极化曲线 ,选择了能够快速检测镍磷合金镀层孔隙率的硝酸浓度 ,并对不同厚度的镍磷合金镀层试样进行评价 .结果表明 :镍磷合金镀层在 1 0 %硝酸溶液中的动电位极化曲线能准确地反映镀层的孔隙率 ,该硝酸溶液最适合作为应用电化学方法检测镀层孔隙率的检测溶液 ,其变化规律是随着镀层孔隙率的减少 ,镀层的腐蚀电位逐渐正移 .应用常规的孔隙率检测方法只能检测较大的孔隙 .  相似文献   
994.
铝壶煮沸的饮用水中铝的形态分析   总被引:1,自引:0,他引:1  
用过滤、离子交换和光解氧化分离自来水和经铝壶煮沸的饮用水中铝的形态,以石墨炉原子吸收光谱法测定铝的浓度,采用化学平衡模式计算铝的形态分布。实验结果表明:经铝壶煮沸1min的饮用水中颗凿态铝量比自来水降低了3.3倍,可交换态、不可交换有机态、不可交换无机态铝量分别2增加了1.4、0.5和1.28倍,可交换态和不可交换无机态是铝的主要存在形态。随着煮沸时间的增加,可交换态、不可交换有机态、不可交换无机  相似文献   
995.
Fifteen novel furoxan-based nitric oxide (NO) releasing hybrids of estradiol derivatives were synthesized and evaluated in vitro anti-proliferative activity in MDA-MB-231, A2780, Hela and HUVEC cell lines. Most of them displayed potent anti-proliferative effects. Among the compounds, 4-bromo-3-((phenylsulfonyl)-1,2,5-oxadiazole 2-oxide)-oxy-propoxy-estradiol ( 11 b ) exhibited the best activity with IC50 values of 3.58–0.0008 μM. Preliminary pharmacological studies showed that 11 b induced apoptosis and hardly affected the cell cycle of MDA-MB-231 cell line. NO-releasing capacity and inhibition of ERK/MAPK pathway signaling might explain the potent antineoplastic activity of these compounds. The preliminary structure-activity relationship (SAR) showed that steroidal scaffolds with a linker in 3-position were favorable moieties to evidently increase the bioactivities of these hybrids. Overall, these results implied that 11 b merited to be further investigated as a promising anti-cancer candidate.  相似文献   
996.
Ferritins with electrophoretic homogeneity were prepared from the visceral mass of Saccostrea cucullata in batch. The native PAGE approach showed similar electrophoretic mobility among pig pancreatic ferritin, liver ferritin of Dasyatis akajei, and visceral mass ferritin of Saccostrea cucullata. SDS-PAGE indicated that the Saccostrea cucullata visceral ferritin (SCVF) consisted of a single subunit type and had a molecular weight (MW) of approximately 20 kDa, suggesting that the protein shell in SCVF was composed of a single subunit. In addition, peptide mass fingerprinting and transmission electron microscopy were used to identify SCVF further, and to observe its molecular structure. We found that the molecular structure in SCVF was similar to that of most mammalian ferritins, which are composed of a protein shell and an iron core. The results of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry under the assistance of an acidic matrix, sinapic acid, also showed that SCVF was composed of a single subunit type and its subunit MW was calculated to be 19871.042 Da in the absence of heme. Kinetics analysis revealed that the complete process of iron release fitted the law of a first-order reaction, which is similar to that of most ferritins in mammals. Similar to bacterial ferritin, studies indicated that the shell consisted of a single subunit type and showed similar kinetics of iron release, suggesting that this subunit plays two important roles in iron release and storage, and that it shows different stability and intensity of interaction in carrying out its physiological functions in SCVF.  相似文献   
997.
Biotransformation of deoxyandrographolide (1) by Alternaria alternata AS 3.4578 gave five derivatives identified by spectral methods including 2D NMR as the known dehydroandrographolide (2) and 9beta-hydroxy-dehydroandrographolide (3) and the new compounds 9beta-hydroxy-deoxyandrographolide (4), 3alpha,17,19-trihydroxy-8,13-ent-labdadien-15,16-olide (5) and 3-oxo-9beta-hydroxy-deoxyandrographolide (6).  相似文献   
998.
Wei ZH  Wu X  Zhang B  Li R  Huang YP  Liu ZS 《Journal of chromatography. A》2011,1218(37):6498-6504
One monomer molecularly imprinted polymer coatings were first synthesized in fused silica capillary columns with 2-methacrylamidopropyl methacrylate (MAM) as single functional monomer in addition to a cross-linking monomer. Since MAM may generate no or little EOF, a strategy of precursor of polymerization, which does not interfere with the formation of defined imprints, was used to introduce an ionizable functional monomer to generate a stable electroosmotic flow for electrochromatography (CEC) by post-polymerization hydrolization. The resulting MAM-based open-tubular imprinted capillary was able to separate enantiomers by means of CEC. The resolution of enantiomers separation achieved on S-amlodipine-imprinted capillary was up to 16.1. The strong recognition ability (selectivity factor was 3.23) and high column performance (theory plates was 26,053 plates m(-1)) of template were obtained. The MIP coatings were also prepared using either S-naproxen or S-ketoprofen as template molecule. The resolutions of enantiomers separation were 2.20 and 4.56, respectively. The results illustrate that the synthesis of MIP using one monomer is not only an experimental-simplified process, but also an approach to producing chiral stationary phase with high efficiency and selectivity.  相似文献   
999.
The surface of a titanium (Ti) alloy substrate was modified by a simple and quick process using a water-soluble polymer, and the effects of 3,4-dihydroxyphenyl (DHP) groups in the polymer side chain on the modification process were examined. The polymers (PMDP) composed of both 2-methacryloyloxyethyl phosphorylcholine (MPC) unit and 3,4-dihydroxyphenyl methacrylate unit were synthesized for surface anchoring. The Ti alloy substrate was coated with PMDP using an aqueous solution of the polymer. A PMDP layer with a thickness of 20 nm was formed on the Ti alloy substrate simply by dip coating for 10 s without drying. Even when the Ti alloy substrate with PMDP coating was immersed in the aqueous medium for 1 week, no change in the thickness was observed, i.e., the PMDP layer was bound to the surface very stably. Oxidation of the DHP groups reduced the stability of the polymer layer significantly. Thus, the DHP groups play a significant role in achieving stable binding. Protein was adsorbed on the Ti alloy substrate; however, this was not observed for the PMDP-coated Ti alloy substrate. In conclusion, we confirmed the effects of DHP groups in PMDP on the stability of the coating on the Ti alloy substrate. Moreover, we found that surface treatment using PMDP was simple, quick, and reliable, and thus, it has great potential for improving biofouling of Ti alloy substrates used in medical devices.  相似文献   
1000.
Mica supported Pd nanocatalysts were prepared by a two-step approach, in which SnCl(2) was first grafted onto mica via its reaction with hydroxyl groups on mica, followed by the in situ reduction of Pd(2+) by Sn(2+) on the surface of mica. The as-prepared Pd-Sn/mica catalysts were characterized by different techniques including transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and ICP analysis. The loaded Pd particles existed in the form of Pd(0) confirmed by XPS analysis, and distributed uniformly on mica with average size about 2.6 nm, as confirmed by TEM examination. The activities of the resultant catalysts for Heck reactions of iodobenzene and its derivatives with olefins and selective hydrogenation of citral were investigated. It was demonstrated that the as-prepared catalysts exhibited very high efficiency for these reactions.  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