全文获取类型
收费全文 | 3013篇 |
免费 | 255篇 |
国内免费 | 247篇 |
专业分类
化学 | 1798篇 |
晶体学 | 6篇 |
力学 | 110篇 |
综合类 | 94篇 |
数学 | 609篇 |
物理学 | 898篇 |
出版年
2024年 | 5篇 |
2023年 | 27篇 |
2022年 | 105篇 |
2021年 | 87篇 |
2020年 | 92篇 |
2019年 | 102篇 |
2018年 | 111篇 |
2017年 | 138篇 |
2016年 | 153篇 |
2015年 | 141篇 |
2014年 | 159篇 |
2013年 | 247篇 |
2012年 | 177篇 |
2011年 | 165篇 |
2010年 | 138篇 |
2009年 | 178篇 |
2008年 | 176篇 |
2007年 | 189篇 |
2006年 | 158篇 |
2005年 | 122篇 |
2004年 | 124篇 |
2003年 | 107篇 |
2002年 | 132篇 |
2001年 | 51篇 |
2000年 | 80篇 |
1999年 | 54篇 |
1998年 | 44篇 |
1997年 | 42篇 |
1996年 | 45篇 |
1995年 | 27篇 |
1994年 | 13篇 |
1993年 | 19篇 |
1992年 | 22篇 |
1991年 | 14篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 8篇 |
1987年 | 3篇 |
1986年 | 14篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1959年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有3515条查询结果,搜索用时 0 毫秒
91.
Serum pharmacochemistry combined with multiple data processing approach to screen the bioactive components and their metabolites in Mutan Cortex by ultra‐performance liquid chromatography tandem mass spectrometry
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Jian‐hua Liu Hui Sun Ai‐hua Zhang Guang‐li Yan Ying Han Chang‐song Xue Xiao‐hang Zhou Hui Shi Xi‐jun Wang 《Biomedical chromatography : BMC》2014,28(4):500-510
Root cortex of Paeonia suffruticosa Andrews (Paeoniaceae), known as Moutan Cortex (MC), is known to have anti‐allergic and anti‐inflammatory properties. However, the constituents absorbed into blood after oral administration of MC remain unknown. A sensitive and rapid method by ultra‐high‐pressure liquid chromatography–electrospray ionization–quadrupole‐time‐of‐flight mass spectrometry (UPLC‐ESI‐Q‐TOF‐MS) technology and the MetaboLynxTM software combined with multiple data processing approach (Mdpa) was established to investigate the absorbed constituents in rats after oral administration of MC, providing unique high‐throughput capabilities for drug metabolism study. A hyphenated electrospray ionization and quadrupole‐time‐of‐flight analyzer was used for the determination of accurate mass of the fragment ion in negative mode, with excellent MS mass accuracy and enhanced data acquisition. This rapid automated analysis method was successfully applied for screening and identification of the constituents absorbed and metabolized studies of MC after oral administration to rats. A total of 46 peaks were obtained from MC, 41 of which were tentatively characterized. In the VIP‐plot of orthogonal partial least‐squares discriminant analysis, 23 interesting ions in serum samples were extracted, and 16 parent components and seven metabolites were detected in vivo. The integrative serum pharmacochemistry technique, UPLC‐ESI‐Q‐TOF‐MS, and Mdpa method were successfully applied for rapid discovery of multiple components from MC. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
92.
建立了离子色谱法分析火灾烟气成分的方法。样品用去离子水和氢氧化钠溶液配制,采用0.45μm的滤膜过滤2~3次后,配制成样品溶液,稀释适当倍数后进样分析,采用电导检测器进行检测。各阴离子在1.0~50.0mg/L范围内与色谱峰面积均呈现良好的线性关系,相关系数均大于0.999,方法的检出限在0.06~0.1 mg/L之间。方法的加标回收率在86.0%~110%之间,测定结果的相对标准偏差为0.5%~9.0%(n=5)。该方法简便快捷,选择性好,灵敏度高,可满足火灾烟气成分的分析要求。 相似文献
93.
HZSM‐5‐supported Brönsted and Lewis acidic ionic solid 1,3‐disulfoimidazolium chlorozincate materials ([dsim]2[ZnCl4]@HZSM‐5) were synthesized with various ratios (3, 6, 9, 17 and 50% w/w). The heterogeneous materials were characterized via a variety of spectroscopic techniques. Dual acidity of these materials was determined using specified techniques. These acidic solids were examined as stable heterogeneous catalysts for the Fischer indole reaction of equimolar amounts of phenylhydrazine hydrochloride and various aliphatic or aromatic ketones at 80–90°C in neat condition to produce substituted indole derivatives. The efficient 17% ionic salt‐loaded HZSM‐5 composite was easily reused for ten consecutive cycles with a slight loss of its activity. The recycled catalyst was further analysed using powder X‐ray diffraction and inductively coupled plasma optical emission spectrometric techniques. 相似文献
94.
Xiao-Ying Yu Jennifer Yao Edgar C. Buck Zihua Zhu 《Surface and interface analysis : SIA》2020,52(7):454-459
Trace analysis of nuclear materials in solid particles collected in the environment or particles in liquid slurry generated in nuclear material manufacturing processes can pinpoint elemental, organic, and isotopic signatures of nuclear fuel cycle activities and processes. Such information can support nuclear safeguards programs by increasing our ability to detect undeclared nuclear materials, routine activities for safeguarding at declared facilities, and illicit activities. However, trace radioactive material analysis in liquids and slurries is challenging using bulk approaches. For example, one drawback of sensitive analysis such as inductively coupled plasma mass spectrometry (ICP-MS) is that sample is consumed or destroyed as a result of the technical approach. We developed a vacuum compatible microfluidic interface to enable surface analysis of liquids and solid–liquid interactions using time-of-flight secondary ion mass spectrometry (ToF-SIMS). In this work, we illustrate the initial results from the analysis of liquid uranium oxide standard solutions using in situ liquid SIMS. Because the liquid SIMS analysis is almost nondestructive, the same sample can then be analyzed by other analytical techniques or saved for future reference. Consequently, multimodal analysis is possible. Our results demonstrate that in situ liquid SIMS can be used as a new approach to analyze radioactive materials in liquid and slurry forms of relevance to diverse applications. 相似文献
95.
Nanomagnetically modified vitamin B3 (Fe3O4@Niacin): An efficient and reusable green biocatalyst for microwave‐assisted rapid synthesis of 2‐amino‐3‐cyanopyridines in aqueous medium
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Superparamagnetic nanoparticles of modified vitamin B3 (Fe3O4@Niacin) represent a new, efficient and green biocatalyst for the one‐pot synthesis of 2‐amino‐3‐cyanopyridine derivatives via four‐component condensation reaction between aldehydes, ketones, malononitrile, and ammonium acetate under microwave irradiation in water. This new magnetic organocatalyst was easily isolated from the reaction mixture by magnetic decantation using an external magnet and reused at least six times without significant degradation in the activity. The catalyst was fully characterized by FT‐IR, XRD, SEM, VSM, UV–Vis, DLS and EDS. Excellent yield, very short reaction time (7–10 min), operational simplicity, easy work‐up procedure, avoidance of hazardous or toxic catalysts and organic solvents are the main advantages of this green methodology which makes it more economic than the other conventional methods. 相似文献
96.
Pd nanoparticles immobilized on PNIPAM–halloysite: highly active and reusable catalyst for Suzuki–Miyaura coupling reactions in water
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Myeng Chan Hong Hyunseok Ahn Myung Chan Choi Yongwoo Lee Jongsik Kim Hakjune Rhee 《应用有机金属化学》2014,28(3):156-161
Poly(N‐isopropylacrylamide)–halloysite (PNIPAM‐HNT) nanocomposites exhibited inverse temperature solubility with a lower critical solution temperature (LCST) in water. Palladium (Pd) nanoparticles were anchored on PNIPAM‐HNT nanocomposites with various amounts of HNT from 5 to 30 wt%. These Pd catalysts exhibited excellent reactivities for Suzuki–Miyaura coupling reactions at 50–70 °C in water. In particular, Pd anchored PNIPAM/HNT (95:5 w/w ratio) nanocomposites showed excellent recyclability up to 10 times in 96% average yield by simple filtration. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
97.
Cobalt‐based metal coordination polymers with 4,4′‐bipyridinyl groups: highly efficient catalysis for one‐pot synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Jin‐Hua Wang Gui‐Mei Tang Shi‐Chen Yan Yong‐Tao Wang Shi‐Jie Zhan E Zhang Yu Sun Yuan Jiang Yue‐Zhi Cui 《应用有机金属化学》2016,30(12):1009-1021
Three new metal coordination complexes, namely [Co(BPY)2(H2O)2](BPY)(BS)2(H2O)4 ( 1 ), [Co(BPY)2(H2O)4](ABS)2(H2O)2 ( 2 ) and [Co(BPY)(H2O)4](MBS)2 ( 3 ) (BPY = 4,4′‐bipyridine, BS = phenylsulfonic acid, ABS = p‐aminobenzenesulfonic acid, MBS = p‐methylbenzenesulfonic acid), were obtained under hydrothermal conditions. Complexes 1 , 2 , 3 were structurally characterized using single‐crystal X‐ray diffraction and infrared spectroscopy. All of them display low‐dimensional motifs: complex 1 displays a two‐dimensional structure; and complexes 2 and 3 exhibit a one‐dimensional tape structure. Through strong intermolecular hydrogen bonding interactions and weak packing interactions, all of them further stack to generate a three‐dimensional supramolecular architecture. Catalysts 1 , 2 , 3 were involved in the green synthesis of a variety of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions through Biginelli reactions. The corresponding catalytic product was obtained in quantitative yields (99%) under eco‐friendly synthesis conditions for the variety of reactions. Catalysts 1 , 2 , 3 exhibit excellent efficiency for the desired product, and their catalytic performance shows the following order: 2 > 1 ≈ 3 , which can be ascribed to the hydrophobic interactions of different phenylsulfonate groups. The catalytic performance for the Biginelli reaction is not only dependent on the selected solvents, but also inversely proportional to the polarities of the solvents. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
98.
A new method based upon data driven tool, principal component analysis (PCA), for fingerprint enhancement is proposed in this paper. PCA is a very useful statistical technique that has found application in many different fields like image compression, face recognition and is commonly used for finding patterns in data of high dimension. In the proposed method, the input image is first decomposed into directional images using decimation free Directional Filter Bank (DDFB). Then these directional images are normalized. A data driven technique PCA is applied to these normalized directional fingerprint images, which gives the PCA filtered images. These are basically directional images. Then these directional images are reconstructed into one image which is the enhanced one. Simulation results are included illustrating the capability of the proposed method. 相似文献
99.
Synthesis and characterization of a Ni nanoparticle stabilized on Ionic liquid‐functionalized magnetic Silica nanoparticles for tandem oxidative reaction of primary alcohols
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Rahim Hosseinzadeh‐Khanmiri Yaser Kamel Zahra Keshvari Ahmad Mobaraki Gholam Hossein Shahverdizadeh Esmail Vessally Mirzaagha Babazadeh 《应用有机金属化学》2018,32(9)
In this research, preparation of the magnetic nanoparticle, coating by a silica shell using (3‐aminopropyl) triethoxysilane and synthesis of a novel sulfonic acid‐substituted imidazolium‐based ionic liquid onto the surface of these particles via a multi‐component reaction, is described. The functionalized nanoparticles was loaded by Ni nanoparticles and characterized by means of techniques such as XRD, FTIR, SEM, EDX, TEM, TGA and ICP‐OES. The nanostructures have spherical shapes that ranged in size from 80 to 100 nm. The catalytic activity of these nanoparticles was tested in aerobic oxidation of primary alcohols that showed good performance in the wide range of primary alcohols in water at mild reaction conditions. As a second step of this work, the tandem oxidative synthesis of alkylacrylonitriles and bisindolylmethanes were investigated using primary alcohols under oxidation conditions. This catalyst system can be recovered using external magnet and reused for five consecutive cycles without significantly less of its activity. 相似文献
100.
Near-infrared (NIR) hyperspectral imaging system was used to detect five concentration levels of ochratoxin A (OTA) in contaminated wheat kernels. The wheat kernels artificially inoculated with two different OTA producing Penicillium verrucosum strains, two different non-toxigenic P. verrucosum strains, and sterile control wheat kernels were subjected to NIR hyperspectral imaging. The acquired three-dimensional data were reshaped into readable two-dimensional data. Principal Component Analysis (PCA) was applied to the two dimensional data to identify the key wavelengths which had greater significance in detecting OTA contamination in wheat. Statistical and histogram features extracted at the key wavelengths were used in the linear, quadratic and Mahalanobis statistical discriminant models to differentiate between sterile control, five concentration levels of OTA contamination in wheat kernels, and five infection levels of non-OTA producing P. verrucosum inoculated wheat kernels. The classification models differentiated sterile control samples from OTA contaminated wheat kernels and non-OTA producing P. verrucosum inoculated wheat kernels with a 100% accuracy. The classification models also differentiated between five concentration levels of OTA contaminated wheat kernels and between five infection levels of non-OTA producing P. verrucosum inoculated wheat kernels with a correct classification of more than 98%. The non-OTA producing P. verrucosum inoculated wheat kernels and OTA contaminated wheat kernels subjected to hyperspectral imaging provided different spectral patterns. 相似文献