全文获取类型
收费全文 | 1917篇 |
免费 | 57篇 |
国内免费 | 10篇 |
专业分类
化学 | 1459篇 |
晶体学 | 14篇 |
力学 | 31篇 |
数学 | 116篇 |
物理学 | 364篇 |
出版年
2023年 | 8篇 |
2022年 | 8篇 |
2021年 | 20篇 |
2020年 | 40篇 |
2019年 | 22篇 |
2018年 | 17篇 |
2017年 | 22篇 |
2016年 | 40篇 |
2015年 | 27篇 |
2014年 | 43篇 |
2013年 | 83篇 |
2012年 | 105篇 |
2011年 | 115篇 |
2010年 | 67篇 |
2009年 | 70篇 |
2008年 | 113篇 |
2007年 | 115篇 |
2006年 | 111篇 |
2005年 | 112篇 |
2004年 | 110篇 |
2003年 | 78篇 |
2002年 | 80篇 |
2001年 | 48篇 |
2000年 | 39篇 |
1999年 | 29篇 |
1998年 | 28篇 |
1997年 | 31篇 |
1996年 | 28篇 |
1995年 | 16篇 |
1994年 | 13篇 |
1993年 | 20篇 |
1992年 | 15篇 |
1991年 | 11篇 |
1990年 | 16篇 |
1989年 | 16篇 |
1987年 | 12篇 |
1986年 | 16篇 |
1985年 | 32篇 |
1984年 | 24篇 |
1983年 | 13篇 |
1982年 | 28篇 |
1981年 | 22篇 |
1980年 | 26篇 |
1979年 | 18篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 12篇 |
1975年 | 10篇 |
1974年 | 7篇 |
1973年 | 9篇 |
排序方式: 共有1984条查询结果,搜索用时 15 毫秒
51.
52.
The solubilities of o-, m- and p-xylene in water were measured at 25.0°C up to 250, 385, and 50 MPa, respectively. The solubility increased with increasing pressure up to 120 MPa (50 MPa for p-xylene) and then decreased. The reaction volumes, Vo accompanying the dissolution at 0.1 MPa were estimated as –3.6±0.5, –3.4±0.5, and –4.1±0.5 cm3-mol–1 for o-, m-, and p-xylene, respectively, from the pressure dependences of the solubilities. The limiting partial molar volumes, of p- and o-xylene in water under high pressure were estimated from Vo and the molar volume of the xylene. The partial molar volumes decreased with increasing pressure. The reaction volume for the formation of intra-molecular pairwise hydrophobic interaction between the methyl groups, as proposed by Ben-Naim, is discussed for the Vo of p- and o-xylene at 0.1 MPa. 相似文献
53.
Sontaya Limmatvapirat Etsuo Yonemochi Toshio Oguchi Keiji Yamamoto 《Journal of inclusion phenomena and macrocyclic chemistry》1998,31(4):367-379
A complex between deoxycholic acid (DCA) and salicylic acid (SA) was prepared by grinding and coprecipitation methods. The resultant complex was characterized by means of powder X-ray diffractometry, IR spectroscopy and thermal analysis. The stoichiometry (DCA : SA 1 : 1) of the complex obtained by grinding was identical to that obtained by coprecipitation. The powder X-ray diffraction pattern of the DCA–SA complex differed from the typical pattern of DCA–guest complexes such as DCA–camphor and DCA–phenanthrene complexes. IR spectra suggested that a different kind of hydrogen bonding was formed in the crystal of the DCA–SA complex, compared with the other DCA–guest complexes. This was in good agreement with data from the crystal structure. 相似文献
54.
Oxime-based salen-type tetradentate ligands with high stability against imine metathesis reaction 总被引:2,自引:0,他引:2
Akine S Taniguchi T Dong W Masubuchi S Nabeshima T 《The Journal of organic chemistry》2005,70(5):1704-1711
Although salen and its analogues are versatile chelate ligands in inorganic and organometallic chemistry, synthesis of unsymmetrical salen derivatives consisting of two different salicylideneimine moieties is difficult because of the C=N bond recombination. To develop stable analogues of salen-type ligands, we synthesized a series of new ligands salamo (=1,2-bis(salicylideneaminooxy)ethane) on the basis of O-alkyl oxime instead of the imine moiety. Eight salamo ligands 1a-h were prepared in 64-88% yields as colorless crystals from the corresponding salicylaldehydes 2a-h. The crystal structure of 1a-c suggests that the oxime-OH form is more predominant than the keto-NH form. The reaction of 2a-e with excess 1,2-bis(aminooxy)ethane gave monooximes 3a-e in 59-86%, which further reacted with a different salicylaldehyde to afford unsymmetrical salamo ligands 4-8 as stable crystals in 51-70%. No reaction took place when a mixture of salamo derivatives 1a and 1b was treated at 40 degrees C in H2O/MeCN (5:95). However, the metathesis reaction of salen derivatives 9a and 9b completed in 2 h to give a statistical mixture. Monooxime 3b was much more stable than monoimine 11 which is difficult to be isolated. These results indicate the extremely high stability of the salamo derivatives 1 and precursors 3. 相似文献
55.
A dendrimeric trimer undergoes folding and unfolding in response to a chemical stimulus. The trimer of interest contains a central dendrimer with a butadiyne‐linked zinc porphyrin dimer ((ZnP)2) core, in addition to two terminal dendrimers with zinc porphyrin (ZnP) cores. The obtained absorption spectra indicate that the unfolded form is the exclusive conformer in chloroform, while the addition of 1,4‐diazabicyclo[2.2.2]octane (DABCO) in chloroform leads to transformation from the unfolded to the folded structure containing two DABCO units per trimer; the folded structure originates from the cross‐linking of (ZnP)2 and ZnP with DABCO. Moreover, the addition of excess DABCO promotes the generation of the unfolded structure containing four DABCO units. 相似文献
56.
An Efficient Method for the Conjugation of Hydrophilic and Hydrophobic Components by Solid‐Phase‐Assisted Disulfide Ligation 下载免费PDF全文
Kyohei Muguruma Takuya Shirasaka Daichi Akiyama Dr. Kentarou Fukumoto Dr. Akihiro Taguchi Dr. Kentaro Takayama Dr. Atsuhiko Taniguchi Prof. Yoshio Hayashi 《Angewandte Chemie (International ed. in English)》2018,57(8):2170-2173
Chemical conjugation between hydrophilic and hydrophobic components is difficult because of their extremely different solubility. Herein, we report a new versatile method with a solid‐phase‐assisted disulfide ligation to overcome the difficulty of conjugation attributed to solubility. The method involves two steps in a one‐pot process: 1) loading of a hydrophobic molecule onto a resin in an organic solvent, and 2) release of the solid‐supported hydrophobic molecule as a conjugate with a hydrophilic molecule into an aqueous solvent. This strategy allows the use of a suitable solvent system for the substrates in each step. Conjugates of a water‐insoluble drug, plinabulin, with hydrophilic carriers that could not be prepared by solution‐phase reactions were obtained in moderate yields (29–45 %). This strategy is widely applicable to the conjugation of compounds with solubility problems. 相似文献
57.
Papain‐Catalyzed Chemoenzymatic Synthesis of Telechelic Polypeptides Using Bis(Leucine Ethyl Ester) Initiator 下载免费PDF全文
In order to construct unique polypeptide architectures, a novel telechelic‐type initiator with two leucine ethyl ester units is designed for chemoenzymatic polymerization. Glycine or alanine ethyl ester is chemoenzymatically polymerized using papain in the presence of the initiator, and the propagation occurs at each leucine ethyl ester unit to produce the telechelic polypeptide. The formation of the telechelic polypeptides is confirmed by 1H NMR and MALDI‐TOF mass spectroscopies. It is revealed by AFM observation that long nanofibrils are formed from the telechelic polyalanine, whereas a conventional linear polyalanine with a similar degree of polymerization shows granule‐like structures. The telechelic polyglycine and polyalanine show the crystalline structures of Polyglycine II and antiparallel β‐sheet, respectively. It is demonstrated that this method to synthesize telechelic‐type polypeptides potentially opens up a pathway to construct novel hierarchical structures by self‐assembly.
58.
Magnetite particles were synthesized through a process including dissolution of Fe(OH)2 and precipitation of an oxidized phase in aqueous solution. The Fe3+ ion was added at the beginning of the synthesis to accelerate the formation of magnetite, control the particle size and improve the monodispersibility. It was found that the addition of Fe3+ ion affected the nucleation and the formation of magnetite particles significantly. Magnetite nanoparticles with small particle size and narrow size distribution were obtained. Furthermore, high magnetic properties were obtained in small particle size. The particle size and magnetic properties increased through the increase of Fe2+/Fe3+ ratio. 相似文献
59.
60.
Although methanolysis of [α-(trimethylsilyl)benzyl]ferrocene (I) and [p-methyl-α-(trimethylsilyl)benzyl]ferrocene (II) in the presence of anhydrous ferric chloride merely gave α-ferrocenylbenzyl methyl ether (III) and p-methyl-α-ferrocenylbenzyl methyl ether (IV), respectively, acid-catalyzed methanolysis of (I) and (II) in the presence of an equimolar amount of (III) or (IV) afforded 1,2-diferrocenyl-l,2-diarylethanes. It is suggested that one electron oxidation of [α-(trimethylsilyl)benzyl]ferrocene by α-ferrocenylbenzyl cation generated from α-ferrocenylbenzyl methyl ether, and subsequent methanolysis of the resulting substituted ferricenium ion may occur to give the two species of α-ferrocenylbenzyl radical, which in turn undergo an approximately statistical coupling. 相似文献