全文获取类型
收费全文 | 2909篇 |
免费 | 307篇 |
国内免费 | 416篇 |
专业分类
化学 | 3213篇 |
晶体学 | 13篇 |
力学 | 11篇 |
综合类 | 38篇 |
数学 | 84篇 |
物理学 | 273篇 |
出版年
2024年 | 13篇 |
2023年 | 66篇 |
2022年 | 221篇 |
2021年 | 188篇 |
2020年 | 167篇 |
2019年 | 134篇 |
2018年 | 139篇 |
2017年 | 128篇 |
2016年 | 151篇 |
2015年 | 107篇 |
2014年 | 140篇 |
2013年 | 339篇 |
2012年 | 151篇 |
2011年 | 130篇 |
2010年 | 138篇 |
2009年 | 115篇 |
2008年 | 140篇 |
2007年 | 164篇 |
2006年 | 147篇 |
2005年 | 141篇 |
2004年 | 101篇 |
2003年 | 111篇 |
2002年 | 76篇 |
2001年 | 66篇 |
2000年 | 46篇 |
1999年 | 40篇 |
1998年 | 46篇 |
1997年 | 33篇 |
1996年 | 31篇 |
1995年 | 22篇 |
1994年 | 25篇 |
1993年 | 26篇 |
1992年 | 22篇 |
1991年 | 19篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有3632条查询结果,搜索用时 31 毫秒
1.
Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones
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)
Behrooz Maleki Samaneh Barat Nam Chalaki Samaneh Sedigh Ashrafi Esmail Rezaee Seresht Farid Moeinpour Amir Khojastehnezhad Reza Tayebee 《应用有机金属化学》2015,29(5):290-295
A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni0.5Zn0.5Fe2O4 magnetic nanoparticles (Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3 could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
2.
Recyclable and reusable Pd(OAc)2/PPh3/PEG‐2000 system for homocoupling reaction of arylboronic acids under air without base
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)
A stable and efficient Pd(OAc)2/PPh3/PEG‐2000 catalytic system for homocoupling of arylboronic acids has been developed. In the presence of Pd(OAc)2 and PPh3, the homocoupling reaction of arylboronic acids was carried out smoothly in PEG‐2000 at 70 °C under air without base to afford a variety of symmetric biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with diethyl ether, and the Pd(OAc)2/PPh3/PEG‐2000 system could be easily recycled and reused six times without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
3.
Dr. Wan‐Ling Liu Ni‐Shin Yang Ya‐Ting Chen Stephen Lirio Cheng‐You Wu Prof. Chia‐Her Lin Prof. Hsi‐Ya Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):115-119
A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors. 相似文献
4.
Levoglucosenone reacts with α-aminoazoles to yield azolo[1,5-a]pyrimidine systems fused with a carbohydrate fragment. The reaction oocurs much more smoothly than in the case of other α,β-unsaturated
ketones. The reactions of levoglucosenone with β-dicarbonyl compounds (dimedone, barbituric acid) in the presence of a base
results in the pyran ring closure, which has never been observed earlier in reactions of β-dicarbonyl compounds with α,β-unsaturated
ketones under the conditions of basic catalysis. The structures of products were established by IR and NMR spectroscopy.
For Part 3, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 553–558, March, 1997. 相似文献
5.
Anuj Mittal Swaminathan Sivaram 《Journal of polymer science. Part A, Polymer chemistry》2005,43(21):4996-5008
A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, CuIBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities Mw/Mn ≤ 1.23. The rate of polymerization follows first‐order kinetics, kapp = 3.4 × 10?5 s?1, indicating the presence of low radical concentration ([P*] ≤ 10?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (Mn,SEC) increased linearly with conversion and were found to be higher than predicted molecular (Mn,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (Mn = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (Mn = 10,300), which is achieved in 23 h. The plot of lnkapp versus 1/T gave an apparent activation energy of polymerization as (ΔE≠app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH0eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005 相似文献
6.
S. V. Semikolenov K. A. Dubkov E. V. Starokon' D. E. Babushkin G. I. Panov 《Russian Chemical Bulletin》2005,54(4):948-956
The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene
solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation
energies and have the first orders with respect to the alkene and N2O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal
and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene
proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation
of terminal and internal alkenes C2—C8 with nitrous oxide were analyzed using the previously published data.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005. 相似文献
7.
Zavarzin I. V. Smirnova N. G. Chernoburova E. I. Yarovenko V. N. Krayushkin M. M. 《Russian Chemical Bulletin》2004,53(6):1257-1260
A method for syntheses of previously unknown derivatives of thieno[2,3-d]pyrimidines and quinazolines from monothiooxamides was proposed. 相似文献
8.
Xiao Qi ZHENG Yong Hui WANG Qing Xiang GUO* Li YANG You Cheng LIU Department of Chemistry University of Science Technology of China Hefei National Laboratory of Applied Organic Chemistry Lanzhou University Lanzhou 《中国化学快报》2003,(8)
As artificial enzymes, the binding constants of cyclodextrins (CDs) and their substrates are expected to be high1. For this purpose, many kinds of bridged cyclodextrin dimers2 whose two cyclodextrins are linked by various spacers have been constructed. It was of interest to make the dimers, whose binding constants would exceed 108dm3/mol3. Up to date, the bridged cyclodextrin dimers have been extensively studied as enzyme models and as molecular receptors4-6. Recently, we synthesized a brid… 相似文献
9.
Xanthenediones derivatives have attracted considerable interests in recent times because they constitute a structural unit in a number of natural products1 and have been used as versatile synthons due to the inherent reactivity of the inbuilt pyran ring2. The conventional syntheses of xanthenediones were acid or base catalyzed condensation of appropriate active methylene carbonyl compounds with aldehydes3. However, many of these procedures involved longer reaction times,low yields and side reactions of aldehydes. In recent years, room temperature ionic liquids (RTILs) have been used as novel green reaction media4. Considering that InCl3 is an efficient Lewis acid catalyst used in promoting many organic reactions, especially in several condensation processes, we herein wish to report a very simple and green method for the preparation of poly-hydrogenated xanthenediones through InCl3·4H2O promoted cascade reaction of aldehydes and 5,5-dimethyl-l,3-cyclohexanedione in ionic liquid,1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]). The preparative process presented here is operationally simple, environmentally benign and has the advantage of enhanced atom utilization. Furthermore, the solvent and the catalyst used can be recovered easily and reused efficiently. 相似文献
10.
Leong‐Huat Gan Palaniswamy Ravi Bao Wei Mao Kam‐Chiu Tam 《Journal of polymer science. Part A, Polymer chemistry》2003,41(17):2688-2695
Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003 相似文献