全文获取类型
收费全文 | 504篇 |
免费 | 20篇 |
专业分类
化学 | 478篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 9篇 |
物理学 | 34篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2016年 | 10篇 |
2015年 | 10篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 32篇 |
2011年 | 42篇 |
2010年 | 13篇 |
2009年 | 16篇 |
2008年 | 31篇 |
2007年 | 38篇 |
2006年 | 36篇 |
2005年 | 29篇 |
2004年 | 36篇 |
2003年 | 21篇 |
2002年 | 30篇 |
2001年 | 8篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 7篇 |
1983年 | 2篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有524条查询结果,搜索用时 15 毫秒
511.
512.
Shimoyama A Saeki A Tanimura N Tsutsui H Miyake K Suda Y Fujimoto Y Fukase K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(51):14464-14474
Helicobacter pylori is a common cause of gastroduodenal inflammatory diseases such as chronic gastritis and peptic ulcers and also an important factor in gastric carcinogenesis. Recent reports have demonstrated that bacterial inflammatory processes, such as stimulation with H. pylori lipopolysaccharide (LPS), initiate atherosclerosis. To establish the structures responsible for the inflammatory response of H. pylori LPS, we synthesized various kinds of lipid A structures (i.e., triacylated lipid A and Kdo‐lipid A compounds), with or without the ethanolamine group at the 1‐phosphate moiety, by a new divergent synthetic route. Stereoselective α‐glycosylation of Kdo N‐phenyltrifluoroacetimidate was achieved by use of microfluidic methods. None of the lipid A and Kdo‐lipid A compounds were a strong inducer of IL‐1β, IL‐6, or IL‐8, suggesting that H. pylori LPS is unable to induce acute inflammation. In fact, the lipid A and Kdo‐lipid A compounds showed antagonistic activity against cytokine induction by E. coli LPS, except for the lipid A compound with the ethanolamine group, which showed very weak agonistic activity. On the other hand, these H. pylori LPS partial structures showed potent IL‐18‐ and IL‐12‐inducing activities. IL‐18 has been shown to correlate with chronic inflammation, so H. pylori LPS might be implicated in the chronic inflammatory responses induced by H. pylori. These results also indicated that H. pylori LPS can modulate the immune response: NF‐κB activation through hTLR4/MD‐2 was suppressed, whereas production of IL‐18 and IL‐12 was promoted. 相似文献
513.
Kondo A Kajiro H Noguchi H Carlucci L Proserpio DM Ciani G Kato K Takata M Seki H Sakamoto M Hattori Y Okino F Maeda K Ohba T Kaneko K Kanoh H 《Journal of the American Chemical Society》2011,133(27):10512-10522
Selective synthetic routes to coordination polymers [Cu(bpy)(2)(OTf)(2)](n) (bpy = 4,4'-bipyridine, OTf = trifluoromethanesulfonate) with 2- and 3-dimensionalities of the frameworks were established by properly choosing each different solvent-solution system. They show a quite similar local coordination environment around the Cu(II) centers, but these assemble in a different way leading to the 2D and 3D building-up structures. Although the two kinds of porous coordination polymers (PCPs) both have flexible frameworks, the 2D shows more marked flexibility than the 3D, giving rise to different flexibility-associated gas adsorption behaviors. All adsorption isotherms for N(2), CO(2), and Ar on the 3D PCP are of type I, whereas the 2D PCP has stepwise gas adsorption isotherms, also for CH(4) and water, in addition to these gases. The 3D structure, having hydrophilic and hydrophobic pores, shows the size-selective and quadrupole-surface electrical field interaction dependent adsorption. Remarkably, the 2D structure can accommodate greater amounts of gas molecules than that corresponding to the inherent crystallographic void volume through framework structural changes. In alcohol adsorption isotherms, however, the 2D PCP changes its framework structure through the guest accommodation, leading to no stepwise adsorption isotherms. The structural diversity of the 2D PCP stems from the breathing phenomenon and expansion/shrinkage modulation. 相似文献
514.
515.
Mitsuaki Yamauchi Kosuke Yokoyama Naoki Aratani Hiroko Yamada Sadahiro Masuo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14311-14316
Most azobenzene derivatives are utilized as well‐defined photoresponsive materials, but their emission properties have not been of great interest as they are relatively poor. Here, we report crystallization‐induced emission (CIE) based on the suppression of the photoisomerization of azobenzene derivatives. Although these molecules show negligible emission in solution, their microcrystals exhibit intense emission from the azobenzene moieties as a result of CIE. Upon rapid precipitation, fine particles with low crystallinity were kinetically formed and underwent CIE over time with a concomitant increase in crystallinity. Furthermore, we demonstrated “photocutting” of an emissive single crystal using a strong laser by a combination of CIE behavior and photomelting based on the photoisomerization of the azobenzene moiety. Our results regarding the CIE behavior of azobenzene derivatives in addition to their photoisomerization can provide a new platform for developing photoresponsive luminescent materials. 相似文献
516.
Nuida T Matsuda T Tokoro H Sakurai S Hashimoto K Ohkoshi S 《Journal of the American Chemical Society》2005,127(33):11604-11605
The second harmonic generation (SHG) and magnetization-induced SHG (MSHG) of AMA[MB(CN)6]-type (F3m) Prussian blue analogues (i.e., CsCo[Cr(CN)6].0.5H2O and RbMn[Fe(CN)6]) were observed. A large interaction between the nonlinear optical response and magnetic spins was observed in CsCo[Cr(CN)6].0.5H2O. These observations of SHG and MSHG imply that AMA[MB(CN)6]-type Prussian blue analogues are piezoelectric above the Curie temperature (TC) and piezoelectric ferromagnet below TC. 相似文献
517.
A highly efficient and versatile method for the synthesis of various sphingolipids, such as sphingomyelin, ceramide, sphingosine, sphingosine 1-phosphate, and functionalized sphingosine derivatives, was established by two types of combinations of the olefin cross metathesis reaction. One reaction was between the same olefin part and appropriate amino alcohols, which were prepared starting from N-Boc-L-serine, and the other was between appropriate olefins and the same amino alcohol. [reaction: see text]. 相似文献
518.
Syntheses,X‐ray crystal structures,and emission properties of protonated tripyridyltriazines and their ruthenium(II) complexes 下载免费PDF全文
Naokazu Yoshikawa Shoko Yamazaki Hiroko Kimura Nobuko Kanehisa Tsuyoshi Inoue Hiroshi Takashima 《Journal of Physical Organic Chemistry》2018,31(3)
A series of metal‐free compounds, ie, planar triprotonated triazine, triazineH3Cl(PF6)2 ( 1 ), planar triprotonated triazineH3Br(PF6)2 ( 2 ), and nonplanar monoprotonated triazineHPF6 ( 3 ), were prepared. Abbreviations used are triazine = tri‐2‐pyridyltriazine. Ruthenium complexes [RuCl(bpy)(L)](PF6), [RuCl(bpy)(L)](PF6)2, and [Ru(L)2](PF6)2 were also prepared, where bpy is 2,2′‐bipyridine and L's are triazine ( 4 ) and monoprotonated triazine ( 5 ), respectively. Ruthenium complexes [Ru(triazine)2](PF6)2 ( 6 ) were also prepared and crystallized. The X‐ray crystal structures of the 3 compounds 1 , 2 , and 3 and the complex 6 were determined. They were also characterized by electrospray ionization mass spectrometry, UV‐vis spectroscopy, and density functional theory calculations. 相似文献
519.
Maroua Ait Tastift Rachida Makbal Thouria Bourhim Zineb Omari Hiroko Isoda Chemseddoha Gadhi 《Molecules (Basel, Switzerland)》2022,27(10)
Saffron is the most expensive spice in the world. In addition to its culinary utilization, this spice is used for medicinal purposes such as in pain management. In this study, the analgesic activity of Crocus sativus stigma extract (CSSE) was evaluated in rodents and its possible physiological mechanism was elucidated. The anti-nociceptive effect of CSSE was evaluated using three animal models (hot plate, writhing, and formalin tests). The analgesic pathways involved were assessed using various analgesia-mediating receptors antagonists. The oral administration of CSSE, up to 2000 mg/kg, caused no death or changes in the behavior or in the hematological and biochemical blood parameters of treated animals nor in the histological architecture of the animals’ livers and kidneys. CSSE showed a central, dose-dependent, anti-nociceptive effect in response to thermal stimuli; and a peripheral analgesic effect in the test of contortions induced by acetic acid. The dual (central and peripheral) analgesic effect was confirmed by the formalin test. The anti-nociceptive activity of CSSE was totally or partially reversed by the co-administration of receptor antagonists, naloxone, atropine, haloperidol, yohimbine, and glibenclamide. CSSE influenced signal processing, by the modulation of the opioidergic, adrenergic, and muscarinic systems at the peripheral and central levels; and by regulation of the dopaminergic system and control of the opening of the ATP-sensitive K+ channels at the spinal level. The obtained data point to a multimodal mechanism of action for CSSE: An anti-inflammatory effect and a modulation, through different physiological pathways, of the electrical signal generated by the nociceptors. Further clinical trials are required to endorse the potential utilization of Moroccan saffron as a natural painkiller. 相似文献
520.
Xue ZL Mack J Lu H Zhang L You XZ Kuzuhara D Stillman M Yamada H Yamauchi S Kobayashi N Shen Z 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(16):4396-4407
The synthesis of [14]triphyrin(2.1.1) compounds is described. In contrast with conventional subporphyrins, which consistently contain a central boron atom, free-base heteroaromatic compounds can be formed. A modified Lindsey method was used to prepare a range of different [14]triphyrins(2.1.1) in yields of up to 35% based on the reaction of diethylpyrrole (1a) and fused pyrroles of bicyclo[2.2.2]octadiene (BCOD) (2a-e) and dihydroethanonaphthalene (4a) with various aryl aldehydes. The concentration of BF(3)·OEt(2) catalyst plays the key role in determining the yield of the [14]triphyrin(2.1.1) macrocycle relative to the conventional tetrapyrrole porphyrin product. Retro-Diels-Alder reactions of 2a-e and 4a result in the formation of [14]tribenzotriphyrin (2.1.1) (3a-e) and [14]trinaphthotriphyrin(2.1.1) (5a). The effects of exocyclic ring annulation on the electronic structure are examined in detail based on optical spectroscopy, theoretical calculations, and electrochemical measurements. The availability of free-base compounds enables the formation of [Re(I)(CO)(3)(triphyrin)] (6a) and [Ru(II)(CO)(2)Cl(triphyrin)] (7a) complexes based on a modified retro-Diels-Alder reaction. X-ray structures are reported for 4a and 6a. 相似文献