全文获取类型
收费全文 | 1448篇 |
免费 | 295篇 |
国内免费 | 168篇 |
专业分类
化学 | 1855篇 |
晶体学 | 11篇 |
力学 | 1篇 |
综合类 | 3篇 |
物理学 | 41篇 |
出版年
2024年 | 2篇 |
2023年 | 24篇 |
2022年 | 59篇 |
2021年 | 94篇 |
2020年 | 126篇 |
2019年 | 80篇 |
2018年 | 68篇 |
2017年 | 61篇 |
2016年 | 115篇 |
2015年 | 107篇 |
2014年 | 100篇 |
2013年 | 142篇 |
2012年 | 128篇 |
2011年 | 89篇 |
2010年 | 64篇 |
2009年 | 63篇 |
2008年 | 77篇 |
2007年 | 61篇 |
2006年 | 68篇 |
2005年 | 54篇 |
2004年 | 54篇 |
2003年 | 44篇 |
2002年 | 31篇 |
2001年 | 20篇 |
2000年 | 26篇 |
1999年 | 19篇 |
1998年 | 17篇 |
1997年 | 26篇 |
1996年 | 22篇 |
1995年 | 18篇 |
1994年 | 12篇 |
1993年 | 5篇 |
1992年 | 16篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有1911条查询结果,搜索用时 78 毫秒
91.
The surface contact disinfecting technique is a newly developed method for water sterilization. In this paper, the grafted quaternary ammonium salts (QAS) antibacterial fibers were prepared and designed to apply for the surface contact disinfecting process in water treatment. The antibacterial fibers were directly prepared by grafting methacryloxylethyl benzyl dimethyl ammonium chloride (DMAE-BC) onto cellulose fiber using thiocarbonate-H2O2 redox system. All kinds of factors in the grafting reactions, such as reaction time, reaction temperature, monomer concentration, initiator concentration, which influence the percentage of grafting, were studied and optimized. The modified cellulose fibers were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope(SEM). The effects of the percentage of grafting of the grafted cellulose fibers on bactericidal activity were also studied. The spread plate method was used to characterize the bactericidal activity. The disinfection process was further investigated by directly observing the morphology of the bacterial cells adsorbed on the antibacterial fibers with SEM and measuring extracelluar total protein concentration in suspension. The poly(DMAE-BC)-grafted cellulose ?ber was found to exhibit particularly high activity against E.coli. 相似文献
92.
Redox initiated free‐radical polymerization of methyl methacrylate (MMA) with allyl alcohol 1,2‐butoxylate‐block‐etoxylate (AABE) was carried out to yield AABE‐b‐PMMA copolymers at elevated temperatures. The composition of the copolymers depending on the polymerization temperature was qualitatively estimated by the dielectric measurements. It has been seen that AABE segment quantity decreased and PMMA segment quantity increased with increasing the polymerization temperature. The dielectric constant and the dissipation factor of the copolymers were investigated as a function of frequency and temperature. The dielectric constant and the dissipation factor were found to be strongly affected by the polymerization temperature. The highest dielectric constant in all studied temperatures and frequencies was obtained in the case of the copolymer which was prepared at 313 K. The dipolar C‐O and OH groups of the AABE segment have the primary effect on the dielectric constant. The copolymer which was prepared at 323 K, showed the highest dissipation factor near the relaxation temperature of PMMA. 相似文献
93.
Yinghai Liu Jianping Zhang Rongyue Zhang Weiqi Zhou Shengxian Li 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1127-1132
In this article, the graft copolymerization of 4‐vinyl pyridine (4VP) onto nylon‐6 (PA6) using potassium diperiodacuprate (III) (DPC)–PA6 redox system as initiator is investigated in an alkaline medium. The structure and the properties of graft copolymer are confirmed by Fourier transfer infrared spectroscopy (IR), X‐ray diffraction and thermogravimetric analysis (TGA). The mechanism is proposed to explain the generation of radicals and the initiation. The effects of reaction variables, such as the initiator concentration, ratio of 4VP to PA6, pH, as well as reaction temperature and time are investigated. Graft copolymers with high grafting efficiency (>95%) were obtained, which indicated that the DPC–PA6 redox system was an efficient initiator for this graft copolymerization. The quaternized PA6‐g‐P4VP (QPAVP) is proven to be an excellent adsorbent to heavy metal ions. 相似文献
94.
95.
Yusuke Fukahori Yohei Takayama Takuya Imaoka Dr. Osamu Iwamoto Prof. Dr. Kazuo Nagasawa 《化学:亚洲杂志》2013,8(1):244-250
We present a diastereoselective synthesis of disubstituted cyclopentane 8 having a nitrogen‐containing quaternary carbon center, which is found in axinellamine A ( 5 ) and related compounds. During this work, we found that the 1,3‐dipolar cycloaddition product 24 immediately underwent intramolecular redox reaction at the newly formed morpholin‐2‐one moiety, thus affording disubstituted cyclopentane containing a tertiary amine ( 9 ) stereoselectively in good yield. The amine 9 was successfully converted into guanidine 31 , which corresponds to 8 , through iminium cation–enamine isomerization. 相似文献
96.
97.
The internal redox esterification of α,β-unsaturated aldehydes and alcohols was carried out using different ionic liquids (ILs) as catalysts and reaction solvents. The basic ionic liquid, 1-butyl-3-methylimidazolium acetate ([bmim]OAc), exhibited the best activity for this reaction. The influences of the amount of ionic liquid catalyst and reaction time on yield of saturated ester have been investigated. The results showed that ionic liquid anions have a crucial effect on the redox esterification of α,β-unsaturated aldehydes and alcohols. The nucleophilic carbenes generated in situ from the ionic liquid cation were believed to be actual active species for this reactions. 相似文献
98.
The redox cycle between alloxan, a mild oxidizing agent, and its reduction partner, dialuric acid, is investigated using density functional theory. It is found that the initial step is the one‐electron reduction of alloxan followed by protonation, yielding a stable neutral radical, AH·. The radical can then accept another electron to form the dialuric acid anion. The formation of this anion is thermodynamically favored in both the gas phase and in solution. The radical may also undergo dimerization to alloxantin, followed by the transfer of a proton from one moiety to another, yielding alloxan and dialuric acid. This reduction is thermodynamically feasible in the gas phase, but not in aqueous solution. In the case of reduction of alloxan by glutathione at the physiological pH, computed redox potentials indicate that a two‐electron reduction is the favored course of reaction, yielding directly the dialuric acid anion, which then undergoes aerial oxidation to yield the superoxide radical. The redox cycling between alloxan and dialuric acid is responsible for the diabetogenic activity of alloxan, producing cytotoxic radicals on reoxidation of dialuric acid. © 2013 Wiley Periodicals, Inc. 相似文献
99.
Dr. Bo Peng Dr. Nuno Maulide 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13274-13287
The direct functionalization of C? H bonds is an attractive strategy in organic synthesis. Although several advances have been made in this area, the selective activation of inert sp3 C? H bonds remains a daunting challenge. Recently, a new type of sp3 C? H activation mode through internal hydride transfer has demonstrated the potential to activate remote sp3 C? H linkages in an atom‐economic manner. This Minireview attempts to classify recent advances in this area including the transition to non‐activated sp3 C? H bonds and asymmetric hydride transfers. 相似文献