全文获取类型
收费全文 | 70372篇 |
免费 | 9863篇 |
国内免费 | 6642篇 |
专业分类
化学 | 46984篇 |
晶体学 | 659篇 |
力学 | 4661篇 |
综合类 | 515篇 |
数学 | 8449篇 |
物理学 | 25609篇 |
出版年
2024年 | 228篇 |
2023年 | 1399篇 |
2022年 | 2280篇 |
2021年 | 2468篇 |
2020年 | 2522篇 |
2019年 | 2422篇 |
2018年 | 2188篇 |
2017年 | 1939篇 |
2016年 | 2964篇 |
2015年 | 3078篇 |
2014年 | 3650篇 |
2013年 | 4843篇 |
2012年 | 5889篇 |
2011年 | 6014篇 |
2010年 | 4079篇 |
2009年 | 4018篇 |
2008年 | 4187篇 |
2007年 | 3788篇 |
2006年 | 3567篇 |
2005年 | 3092篇 |
2004年 | 2478篇 |
2003年 | 1895篇 |
2002年 | 1682篇 |
2001年 | 1520篇 |
2000年 | 1418篇 |
1999年 | 1563篇 |
1998年 | 1330篇 |
1997年 | 1169篇 |
1996年 | 1227篇 |
1995年 | 1071篇 |
1994年 | 1007篇 |
1993年 | 865篇 |
1992年 | 768篇 |
1991年 | 664篇 |
1990年 | 555篇 |
1989年 | 481篇 |
1988年 | 366篇 |
1987年 | 349篇 |
1986年 | 297篇 |
1985年 | 300篇 |
1984年 | 202篇 |
1983年 | 176篇 |
1982年 | 145篇 |
1981年 | 112篇 |
1980年 | 82篇 |
1978年 | 56篇 |
1977年 | 52篇 |
1976年 | 50篇 |
1975年 | 57篇 |
1973年 | 57篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A quantification method for imatinib (IM), its major metabolite N-desmethyl imatinib (NDI), and a degradation by-product was developed using CE–MS combined with an online concentration technique. The use of multiple reaction monitoring (MRM)–MS/MS further improved the sensitivity of this technology. Liquid–liquid extraction (LLE) using tertiary butyl methyl ether yielded high recovery and reproducibility for the pretreatment of serum samples. The recovery rate exceeded 83% for all three analytes, and was 90% for IM. To improve quantification results, a conductivity-induced online analyte concentration technique, field-amplified sample stacking (FASS), was used. The S/N ratios were improved at least 10-fold when compared with conventional capillary zone electrophoresis. The detection limits were 0.2 ng/mL for IM, 0.4 ng/mL for NDI, and 4 ng/mL for the degradation by-product. These results are superior to those previously obtained by other reported methods. The new method was validated in terms of its selectivity, intra- and interday repeatability and accuracy, and sample storage stability, following the guidelines issued by the European Medicines Agency. Considering the convenient pretreatment procedure (LLE), superior sensitivity, and fast analysis speed (<15 min), this method can be useful in the determination of imatinib levels in blood. 相似文献
992.
Chun-Dong Xue Zhong-Ping Sun Yong-Jiang Li Jian-Feng Chen Bo Liu Kai-Rong Qin 《Electrophoresis》2020,41(10-11):909-916
In the present study, we numerically demonstrate an approach for separation of micro and sub-micro diamagnetic particles in dual ferrofluid streams based on negative magnetophoresis. The dual streams are constructed by an intermediate sheath flow, after which the negative magnetophoretic force induced by an array of permanent magnets dominates the separation of diamagnetic particles. A simple and efficient numerical model is developed to calculate the motions of particles under the action of magnetic field and flow field. Effects of the average flow velocity, the ratio of sheath fluid flow to sample fluid flow, the number of the magnet pair as well as the position of magnet pair are investigated. The optimal parametric condition for complete separation is obtained through the parametric analysis, and the separation principle is further elucidated by the force analysis. The separation of smaller micro and sub-micro diamagnetic particles is finally demonstrated. This study provides an insight into the negative magnetophoretic phenomenon and guides the fabrication of feasible, low-cost diagnostic devices for sub-micro particle separation. 相似文献
993.
Shushi Chen 《中国化学会会志》2020,67(9):1661-1667
Three selected flavonoids, commonly found in spices, red-purple fruits, and vegetables, were adsorbed on humic fraction-modified silica gel in hexane. The percentage of adsorption in hexane for all examined analytes was nearly 100% after 1 hr, as a result of the strong dipole–dipole interaction. The increasing amount of adsorbent involved in the process improved the percentage of adsorption, which in turn shortened the time needed to reach the maximum by providing more binding sites. However, adsorption was not observed in other liquid phases under the same conditions, such as acetonitrile and ethyl ether. The mechanism leading to the adsorption was explored chromatographically, as well as by fourier transform infrared spectroscopy (FTIR) and theoretical simulations. 相似文献
994.
Phosgene has attracted wide attention because of its important applications and value in modern industry, agriculture, and other fields, though it easily leaks and is difficult to detect. In this work, we designed and synthesized a naphthalimide-based fluorescent probe, which is easy to prepare, stable, and able to discriminate between phosgene, acetyl chloride, oxalyl chloride, thionyl chloride, phosphorus oxychloride, and tosyl chloride. Our results indicate that the probe can react with phosgene selectively and sensitively, showing remarkable ratiometric fluorescence changes. Furthermore, the probe can be made into test strips, which can determine phosgene in air effectively. The present work provides a novel class of naphthalimide-based derivatives with potential application in phosgene sensing in real time simply and safely with further optimization. 相似文献
995.
Shan Jin Manman Zhou Xi Kang Xiaowu Li Wenjun Du Xiao Wei Shuang Chen Dr. Shuxin Wang Prof. Manzhou Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):3919-3923
The high-dimensional (that is, three-dimensional (3D)) assembly of nanomaterials is an effective means of improving their properties; however, achieving this assembly at the atomic level remains challenging. Herein, we obtained a novel nanocluster, [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl (Dppp=1,3-bis(diphenylphosphino)propane) showing a 3D octameric assembly mode involving the kernel penetration of eight complete icosahedral Au@Ag10Au2 units for the first time. The atomically precise structure was determined by single-crystal X-ray diffraction, and further confirmed by thermogravimetric analysis, X-ray photoelectron spectroscopy, and electrospray ionization mass spectrometry measurements. Furthermore, ligand-induced transformation prompted the conversion of [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl, with complete octameric fusion into [Au8Ag55(Dppp)4(C6H11S)34][BPh4]2, with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M13 nanobuilding blocks. 相似文献
996.
Yuesu Chen Gabriel Glotz Dr. David Cantillo Prof. Dr. C. Oliver Kappe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(13):2973-2979
N-Demethylation of oxycodone is one of the key steps in the synthesis of important opioid antagonists like naloxone or analgesics like nalbuphine. The reaction is typically carried out using stoichiometric amounts of toxic and corrosive reagents. Herein, we present a green and scalable organophotocatalytic procedure that accomplishes the N-demethylation step using molecular oxygen as the terminal oxidant and an organic dye (rose bengal) as an effective photocatalyst. Optimization of the reaction conditions under continuous flow conditions using visible-light irradiation led to an efficient, reliable, and scalable process, producing noroxycodone hydrochloride in high isolated yield and purity after a simple workup. 相似文献
997.
In this study,the poly(D-lactide)-block-poly(butylene succinate)-block-poly(D-lactide)(PDLA-b-PBS-b-PDLA)triblock copolymers with a fixed length of PBS and various lengths of PDLA are synthesized,and the crystallization behaviors of the PDLA and PBS blocks are investigated.Although both the crystallization behaviors of PBS and PDLA blocks depend on composition,they exhibit different variations.For the PDLA block,its crystallization behaviors are mainly influenced by temperature and block length.The crystallization signals of PDLA block appear in the B-D 2-2 specimen,and these signals get enhanced with PDLA block length.The crystallization rates tend to decrease with increasing PDLA block lendth during crystallizing at 90 and 100°C.Crystallizing at higher temperature,the crystallization rates increase at first and then decrease with block length.The crystallization rates decrease as elevating the crystallization temperature.The melting temperatures of PDLA blocks increase with block lengths and crystallization temperatures.For the PBS block,its crystallization behaviors are mainly controlled by the nucleation and confinement from PDLA block.The crystallization and melting enthalpies as well as the crystallization and melting temperatures of PBS block reduce as a longer PDLA block has been copolymerized,while the crystallization rates of the PBS block exhibit unique component dependence,and the highest rate is observed in the B-D 2-2 specimen.The Avrami exponent of PBS crystallites is reduced as a longer PDLA block is incorporated or the sample is crystallized at higher temperature.This investigation provides a convenient route to tune the crystallization behavior of PBS and PLA. 相似文献
998.
Here we described the design and synthesis of a discrete 3D amphiphilic metallacage 4,in which the tetragonal prismatic frameworks act as the hydrophobic cores and the poly(ethylene glycol)(PEG)chains as the hydrophilic tails.The structure of 4 was characterized by 1H NMR,31P NMR and electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS).Notably,4 with its Iong PEG tails was subsequently ordered into micelles at a low concentration(1.20×10^-6 mol/L)in water.As the concentration and cultivation time increased,the micelles can further self-assembly into nanofibers and nanoribbons.Considering the dynamic property of the coordination bond,these structures show reversible transformation under external stimuli. 相似文献
999.
1000.
Wang Shuo-Lin Chen Liu-Yi Zhang Ben-Xi Yang Yan-Ru Wang Xiao-Dong 《Journal of Thermal Analysis and Calorimetry》2020,141(1):547-558
Journal of Thermal Analysis and Calorimetry - A new design of double-layered microchannel heat sinks, which combines wavy microchannels with porous vertical ribs, is proposed in this work. The flow... 相似文献