全文获取类型
收费全文 | 22578篇 |
免费 | 3788篇 |
国内免费 | 3611篇 |
专业分类
化学 | 16876篇 |
晶体学 | 444篇 |
力学 | 1283篇 |
综合类 | 321篇 |
数学 | 2722篇 |
物理学 | 8331篇 |
出版年
2024年 | 40篇 |
2023年 | 311篇 |
2022年 | 531篇 |
2021年 | 698篇 |
2020年 | 783篇 |
2019年 | 927篇 |
2018年 | 754篇 |
2017年 | 786篇 |
2016年 | 1041篇 |
2015年 | 1159篇 |
2014年 | 1345篇 |
2013年 | 1714篇 |
2012年 | 2056篇 |
2011年 | 2098篇 |
2010年 | 1590篇 |
2009年 | 1637篇 |
2008年 | 1782篇 |
2007年 | 1608篇 |
2006年 | 1496篇 |
2005年 | 1156篇 |
2004年 | 1044篇 |
2003年 | 843篇 |
2002年 | 929篇 |
2001年 | 793篇 |
2000年 | 540篇 |
1999年 | 462篇 |
1998年 | 318篇 |
1997年 | 220篇 |
1996年 | 231篇 |
1995年 | 201篇 |
1994年 | 161篇 |
1993年 | 152篇 |
1992年 | 107篇 |
1991年 | 86篇 |
1990年 | 80篇 |
1989年 | 63篇 |
1988年 | 56篇 |
1987年 | 41篇 |
1986年 | 38篇 |
1985年 | 40篇 |
1984年 | 15篇 |
1983年 | 13篇 |
1982年 | 5篇 |
1981年 | 8篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1975年 | 1篇 |
1959年 | 1篇 |
1957年 | 2篇 |
1936年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
991.
992.
993.
Zhifu Jiang Jian Zhao Beibei Gao Shuo Chen Wenyan Qu Xiangdong Mei 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1026-1037
Abstract A series of novel (4′-tosyl) piperidin-4-yl containing α-aminophosphonates were synthesized by a one-pot reaction, efficiently catalyzed by magnesium perchlorate, under solvent-free conditions from 1-tosylpiperidin-4-one, substituted aromatic amines, and diethyl phosphite (DEP). The synthesized compounds were characterized by IR, 1H NMR, 13C NMR, 31P NMR, and HRMS spectroscopy. A single-crystal X-ray structure of diethyl 4-(2-chlorophenyl) amino-1-(4’-methylbezenesulfonyl) piperidin-4-yl-phosphonate (2a) was obtained, and some of the title compounds displayed insecticidal activities against Plutella xylostella. Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables. 相似文献
994.
Synthesis and characterization of poly(2‐methacryloyloxyethyl phosphorylcholine) onto graphene oxide
The polyzwitterionic brushes comprised of poly(2‐methacryloyloxyethyl phosphorylcholine) (pMPC) segments, which are used for surface modification of polymers and biocompatible coatings, were investigated. In this work, reverse surface‐initiated atom transfer radical polymerization (RATRP) of zwitterionic 2‐methacryloyloxyethyl phosphorylcholine (MPC) is employed to tailor the functionality of graphene oxide (GeneO) in a well‐controlled manner and produce a series of well‐defined hemocompatible hybrids (termed as GeneO‐g‐pMPC). The complexes were characterized by FT‐IR, XRD, and Raman. Results show that MPC has been coordinated on the graphene oxide sheet. Thermal stability of the nanocomposites in comparison with the neat copolymer is revealed by thermogravimetric analysis and differential thermal analysis. Scanning electron microscopy and transmission electron microscope images of the nanoconposite displays pMPC chains were capable of existing on GeneO sheet by RATRP. The biocompatibility properties were measured by plasma recalcification profile tests, hemolysis test, and MTT assays, respectively. The results confirm that the pMPC grafting can substantially enhance the hemocompatibility of the GeneO particles, and the GeneO‐g‐pMPC hybrids can be used as biomaterials without causing any hemolysis. With the versatility of RATRP and the excellent hemocompatibility of zwitterionic polymer chains, the GeneO‐g‐pMPC nanoparticles with desirable blood properties can be readily tailored to cater to various biomedical applications. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
995.
In this study, we demonstrated the formation of gas-phase peptide perthiyl (RSS?) and thiyl (RS?) radical ions besides sulfinyl radical (RSO?) ions from atmospheric pressure (AP) ion/radical reactions of peptides containing inter-chain disulfide bonds. The identity of perthiyl radical was verified from characteristic 65 Da (?SSH) loss in collision-induced dissociation (CID). This signature loss was further used to assess the purity of peptide perthiyl radical ions formed from AP ion/radical reactions. Ion/molecule reactions combined with CID were carried out to confirm the formation of thiyl radical. Transmission mode ion/molecule reactions in collision cell (q2) were developed as a fast means to estimate the population of peptide thiyl radical ions. The reactivity of peptide thiyl, perthiyl, and sulfinyl radical ions was evaluated based on ion/molecule reactions toward organic disulfides, allyl iodide, organic thiol, and oxygen, which followed in order of thiyl (RS?) > perthiyl (RSS?) > sulfinyl (RSO?). The gas-phase reactivity of these three types of sulfur-based radicals is consistent with literature reports from solution studies. 相似文献
996.
997.
Lei Zhang Wei Zhang Nianchen Zhou Jian Zhu Zhengbiao Zhang Zhenping Cheng 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9):876-885
One linear and two miktoarm star side-chain liquid crystalline (LC) block copolymers with p-methoxyazobenzene moieties were prepared by a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) techniques. First, ROPs of ε -caprolactone (ε -CL) were carried out catalyzed by Sn(Oct)2 using three multifunctional initiators, hydroxyethyl 2-bromoisobutyrate (AB type), 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 2-bromo-2-methylpropanoate (A2B type) and 2,2-bis(hydroxymethyl)propane-1,3-diyl bis(2-bromo-2-methylpropanoate) (A2B2 type), at 110°C in toluene, respectively. Second, the previously obtained poly(ε -caprolactone)s (PCLs) with bromines functionalities were used as the macroinitiators to conduct ATRP of 6-(4-methoxy-4-oxy-azobenzene) hexyl methacrylate (MMAZO) with CuBr/PMDETA as the catalyst systems at 85°C in anisole to prepare the linear and miktoarm side-chain LC block copolymers (PCL-b-PMMAZO, (PCL)2-(PMMAZO) and (PCL)2-(PMMAZO)2). The produced polymers were well-controlled with the controlled molecular weights and the relatively narrow molecular weight distributions (M w/M n ≤ 1.35). The structures of the obtained polymers were all characterized by NMR, FT-IR and GPC analysis. Furthermore, the LC properties of the linear and miktoarm star block copolymers were also investigated by differential scanning calorimetry (DSC) and thermal polarized optical microscopy (POM). 相似文献
998.
Experimental data are presented to show the influence of solid particles on demulsification. It was found that the solid particles could effectively resist demulsification. Compared with conventional heating, microwave radiation can enhance the demulsification rate by an order of magnitude and increase the demulsification effectiveness. The demulsification effectiveness of the emulsions stabilized by graphite powder can reach 82%–89% in a very short time under microwave radiation, whilst that of the emulsions stabilized by barium sulfate can attain 100% under similar conditions. 相似文献
999.
Jian Zhang Hui Huang Da-Fu Wei Yong Guan Fu-Zeng Hu Anna Zheng 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):626-632
Sequential anionic copolymerization of styrene and glycidyl methacrylate (GMA) was performed with the protection of argon under normal pressure, where styrene, GMA, toluene, THF, n-butyllithium and a small amount of lithium chloride (LiCl) were used as first monomer, second monomer, solvent, polar reagent, initiator and additive, respectively. Polystyrene-b-poly(glycidyl methacrylate) diblock copolymers (PS-b-PGMA) with well-defined structure and narrow molecular weight distribution were prepared by the copolymerization reaction of poly(styryl)lithium with GMA under certain temperatures. The copolymers were characterized using gel permeation chromatography (GPC), 1H-NMR, 13C-NMR, thin layer chromatography (TLC) and hydrochloric acid-dioxane argentimetric methods. The effects of additives, copolymerization temperature and THF dosage on the copolymerization were studied. No chain transfer reaction of anionic polymerization of styrene in toluene was observed. Slightly broader molecular weight distribution of PS-b-PGMA was observed with the increase the GMA repeat units. Using THF/toluene blend solvent could reduce the polydispersity index (M w /M n ) and dissolve the copolymer better than toluene alone. Lower temperature (< -40°C) and LiCl are required to prepare PS-b-PGMA with narrower molecular weight distribution. 相似文献
1000.
Atom transfer radical polymerization (ATRP) of MMA was conducted using 2‐(4‐chloromethyl‐phenyl)‐benzoxazole as initiator, CuCl as catalyst, and PMDETA as ligand. The results show that the polymerization is a first order reaction with respect to monomer concentration. The polymerization displayed living character as evidenced by a liner increase of monomer weight with conversation and a relatively narrow distribution (Mn/Mw range from 1.30 to 1.45). The structure of PMMA was analyzed by 1H‐NMR and proved the polymerization could be controlled to some degree. The optical property of the initiator was well preserved in the resulting PMMA, and the end‐functionalized PMMA exhibited fluorescent emission at 360 nm whether in DMF solution or in film state. 相似文献