全文获取类型
收费全文 | 12379篇 |
免费 | 2411篇 |
国内免费 | 1671篇 |
专业分类
化学 | 9208篇 |
晶体学 | 239篇 |
力学 | 892篇 |
综合类 | 178篇 |
数学 | 1232篇 |
物理学 | 4712篇 |
出版年
2024年 | 37篇 |
2023年 | 278篇 |
2022年 | 449篇 |
2021年 | 533篇 |
2020年 | 694篇 |
2019年 | 612篇 |
2018年 | 510篇 |
2017年 | 517篇 |
2016年 | 728篇 |
2015年 | 775篇 |
2014年 | 884篇 |
2013年 | 1086篇 |
2012年 | 1213篇 |
2011年 | 1238篇 |
2010年 | 856篇 |
2009年 | 765篇 |
2008年 | 751篇 |
2007年 | 650篇 |
2006年 | 541篇 |
2005年 | 518篇 |
2004年 | 419篇 |
2003年 | 347篇 |
2002年 | 360篇 |
2001年 | 318篇 |
2000年 | 189篇 |
1999年 | 182篇 |
1998年 | 145篇 |
1997年 | 104篇 |
1996年 | 120篇 |
1995年 | 65篇 |
1994年 | 88篇 |
1993年 | 58篇 |
1992年 | 51篇 |
1991年 | 42篇 |
1990年 | 43篇 |
1989年 | 29篇 |
1988年 | 32篇 |
1987年 | 20篇 |
1986年 | 26篇 |
1985年 | 22篇 |
1984年 | 16篇 |
1983年 | 22篇 |
1982年 | 20篇 |
1981年 | 18篇 |
1980年 | 15篇 |
1979年 | 15篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1975年 | 6篇 |
1974年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
301.
Hui Yang Xing Chen Guoxiang Hu Wan-Ting Chen Siobhan J. Bradley Weijie Zhang Gaurav Verma Thomas Nann De-en Jiang Paul E. Kruger Xiangke Wang He Tian Geoffrey I. N. Waterhouse Shane G. Telfer Shengqian Ma 《Chemical science》2020,11(13):3523
Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine β-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (β-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo–O surface layer, thus producing intimate O–Mo–C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O–Mo–C interfaces for these surface-engineered ultrafine nanostructures. The β-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O–Mo–C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of β-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.Ultrafine β-Mo2C nanostructures encapsulated in N-doped carbon capsules featuring O–Mo–C interfaces as the active sites for HER have been unveiled. 相似文献
302.
Zilu Chen Huihui Xing Fupei Liang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(12):m576-m578
In the title compound, [Mn(C5H2N2O4)(H2O)2]n, the MnII ion has a distorted octahedral geometry and the 4‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (Hiso2−) anion acts as a μ3:η4‐bridging ligand. Two oxo O atoms from different Hiso2− ligands bridge two MnII ions, forming centrosymmetric dinuclear building blocks. Each dinuclear building block interacts with another four by the coordination of the oxide groups and carboxylate O atoms, producing a two‐dimensional framework in the ab plane. Hydrogen bonds further extend the two‐dimensional sheets into a three‐dimensional supramolecular framework. 相似文献
303.
Chao Song Dan Gao Tianying Yuan Yongli Chen Liping Liu Xiaowu Chen Yuyang Jiang 《中国化学快报》2019,30(5):1038-1042
Cell migration and invasion are critical steps in cancer metastasis, which are the major cause of death in cancer patients. Tumor-associated macrophages(TAMs) and interstitial flow(IF) are two important biochemical and biomechanical cues in tumor microenvironment, play essential roles in tumor progression. However, their combined effects on tumor cell migration and invasion as well as molecular mechanism remains largely unknown. In this work, we developed a microfluidic-based 3 D breast cancer model by co-culturing tumor aggregates, macrophages, monocytes and endothelial cells within 3 D extracellular matrix in the presence of IF to study tumor cell migration and invasion. On the established platform, we can precisely control the parameters related to tumor microenvironment and observe cellular responses and interactions in real-time. When co-culture of U937 with human umbilical vein endothelial cells(HUVECs) or MDA-MB-231 cells and tri-culture of U937 with HUVECs and MDA-MB-231 cells, we found that mesenchymal-like MDA-MB-231 aggregates activated the monocytes to TAM-like phenotype macrophages. MDA-MB-231 cells and IF simultaneously enhanced the macrophages activation by the stimulation of colony-stimulating factor 1(CSF-1). The activated macrophages and IF further promoted vascular sprouting via vascular endothelial growth factor(VEGFα) signal and tumor cell invasion. This is the first attempt to study the interaction between macrophages and breast cancer cells under IF condition. Taken together, our results provide a new insight to reveal the important physiological and pathological processes of macrophages-tumor communication. Moreover, our established platform with a more mimetic 3 D breast cancer model has the potential for drug screening with more accurate results. 相似文献
304.
A series of new, 2‐substituted 3‐aryl‐8,9,10,11‐tetrahydro‐5‐methyl[1]benzothieno[3′,2′ : 5,6]pyrido[4,3‐d]pyrimidin‐4(3H)‐ones, compounds 5a – q , were designed and synthesized via the aza‐Wittig reaction as the key step. The iminophosphorane 1 reacted with phenyl isocyanate (or 4‐chlorophenyl isocyanate) to the carbodiimide 4 , which was cyclized to 5 upon addition of different amines, EtOH, or phenols in the presence of a catalytic amount of EtONa or K2CO3 (Schemes 1 and 2). The structures of compounds 5 were confirmed by IR, 1H‐ and 13C‐NMR, EI‐MS, elemental analyses, and, in the case of 5l , by single‐crystal X‐ray diffraction (Figure). 相似文献
305.
Solid phase microextraction (SPME) then capillary gas chromatography with mass spectrometric detection have been used for determination of nine phenyl compounds in snow water in Beijing City. Headspace extraction with a fiber coated with 100 µm PDMS was used to extract the compounds. Extraction and desorption times were optimized at 8 and 2 min, respectively. Relative standard deviation (RSD) of the analytical method was found to be less than 5%. The linear range was wide and limits of detection were less than 5 ng mL−1 for the nine target analytes. Several phenyl compounds at ng mL−1 levels were detected in snow samples in Beijing, indicating the corresponding air pollution. 相似文献
306.
HZSM-5分子筛焙烧脱铝的27Al MQMAS NMR研究 总被引:1,自引:0,他引:1
用29Si、27Al魔角旋转固体核磁共振(MAS NMR)结合二维多量子魔角旋转(2D MQMAS)技术对焙烧脱铝的HZSM-5分子筛中铝的配位状态进行了研究.结果表明,HZSM-5分子筛经焙烧后,在化学位移(δ)45处出现一宽峰信号,其主要来自扭曲四配位铝.通过二维三量子铝谱计算出扭曲四配位铝的四极作用常数约为5.2 MHz.对700和750 ℃焙烧样品的铝谱进行分峰拟合,发现在δ 30处又出现一个小峰,归属为非骨架五配位铝.同时,在750 ℃焙烧样品的二维多量子铝谱中直接观察到非骨架五配位铝的信号.焙烧温度低于700 ℃,脱铝不明显;高于700 ℃,引起分子筛骨架的显著脱铝.焙烧还造成部分骨架铝的信号变得“不可观测”. 相似文献
307.
通过在聚氨酯泡沫模板中沉积多壁碳纳米管,用炭的预制体酚醛树酯将碳纳米管粘接固定在一起,经过高温碳化过程制备了碳纳米管-炭复合泡沫材料。红外光谱结果表明利用浓硫酸和浓硝酸的混合溶液处理可以使复合泡沫表面活化形成羧基和羟基,从而使复合泡沫具备较强的分子吸附能力。扫描电镜和氮吸附实验表明这种复合泡沫同时具备大孔和介孔,大孔能够满足流体自由流动的通畅性,介孔可以满足中分子的吸附需要。对标定物维生素B12的吸附实验证明这种复合泡沫对中分子量的生化分子具有有效的吸附能力。这种宏观尺寸的泡沫材料与传统的颗粒状活性炭相比具有简化工艺,提高吸附效率的应用潜力。 相似文献
308.
A series of Al=-(Alq3)l-x granular films is prepared on Si wafer with native oxide layer using co-evaporation technique. Large lateral photovoltaic effect (LPE) is observed, with an optimal LPV sensitivity of 75 mV/mm in x=0.35 sample. The dependence of LPE on temperature and A1 composition is investigated, and the possible mechanism is discussed. 相似文献
309.
Seed‐Mediated Synthesis of Gold Tetrahedra in High Purity and with Tunable,Well‐Controlled Sizes 下载免费PDF全文
Yiqun Zheng Wenying Liu Tian Lv Ming Luo Dr. Hefei Hu Dr. Ping Lu Dr. Sang‐Il Choi Chao Zhang Dr. Jing Tao Prof. Yimei Zhu Prof. Zhi‐Yuan Li Prof. Younan Xia 《化学:亚洲杂志》2014,9(9):2635-2640
We report a facile synthesis of Au tetrahedra in high purity and with tunable, well‐controlled sizes via seed‐mediated growth. The success of this synthesis relies on the use of single‐crystal, spherical Au nanocrystals as the seeds and manipulation of the reaction kinetics to induce an unsymmetrical growth pattern for the seeds. In particular, the dropwise addition of a precursor solution with a syringe pump, assisted by cetyltrimethylammonium chloride and bromide at appropriate concentrations, was found to be critical to the formation of Au tetrahedra in high purity. Their sizes could be readily tuned in the range of 30–60 nm by simply varying the amount of precursor added to the reaction solution. The current strategy not only enables the synthesis of Au tetrahedra with tunable and controlled sizes but also provides a facile and versatile approach to reducing the symmetry of nanocrystals made of a face‐centered cubic lattice. 相似文献
310.
建立了中空纤维脂质体微筛选(Hollow fiber liposome microscreening,HFLMS)研究中药透膜化合物的方法。以中空纤维为脂质体载体,在模拟人体自然吸收的条件下,对中药提取液中可透膜化合物进行了筛选,并用HPLC进行分析。本研究在对空白和脂质体中空纤维表面性质表征的基础上,对中空纤维活性中心与目标物的非特异性结合和HFLMS方法的重现性进行了考察;将HFLMS与HPLC结合,分别对中药材蛇床子、补骨脂、羌活、独活提取液中透过脂质体的香豆素类成分群和五味子提取液中透过脂质体的木脂素类成分群进行了筛选和捕获;通过与对照品的色谱保留时间比对,对筛选出的与脂质体结合的部分化合物进行了结构鉴别。 相似文献