全文获取类型
收费全文 | 416篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 297篇 |
晶体学 | 3篇 |
力学 | 13篇 |
数学 | 46篇 |
物理学 | 78篇 |
出版年
2023年 | 6篇 |
2022年 | 3篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 11篇 |
2018年 | 14篇 |
2017年 | 4篇 |
2016年 | 21篇 |
2015年 | 7篇 |
2014年 | 19篇 |
2013年 | 25篇 |
2012年 | 28篇 |
2011年 | 38篇 |
2010年 | 21篇 |
2009年 | 25篇 |
2008年 | 40篇 |
2007年 | 22篇 |
2006年 | 22篇 |
2005年 | 21篇 |
2004年 | 25篇 |
2003年 | 9篇 |
2002年 | 15篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有437条查询结果,搜索用时 15 毫秒
1.
2.
Ya-Xin Li Fang-Fang Fan Jie Wang Dr. Liliana Cseh Dr. Min Xue Dr. Xiang-Bing Zeng Prof. Goran Ungar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13739-13747
Wedge-shaped molecules, such as dendrons, are among the most important building blocks for directed supramolecular self-assembly. Here we present a new approach aimed at widening the range and complexity of potential mesophases by introducing double-tapered mesogens. Two series of compounds are presented, both alkali metal salts (Li, Na, Cs) of 3,4,5-tris-alkoxybenzoic acid with a second tapered tris-alkoxyaryl group attached at the end of an alkoxy chain. The double-tapered compounds all display an unusual hexagonal columnar phase consisting of one ionic and three non-ionic columns per unit cell. The cation size has an unexpectedly drastic effect on unit cell size. Unlike most columnar phases, the current phases show unusually high dimensional stability on heating, and high stiffness in spite of being 80–85 % aliphatic, attributed to their molecular topology. The described approach may lead to co-assemblies of multifunctional materials, for example, parallel p- and n-semiconducting nanowires or parallel ionic and electronic conductors. 相似文献
3.
Vladimir Piterbarg Goran Popivoda Siniša Stamatović 《Lithuanian Mathematical Journal》2017,57(1):128-141
Let ξ(t), t ∈ [0, T],T > 0, be a Gaussian stationary process with expectation 0 and variance 1, and let η(t) and μ(t) be other sufficiently smooth random processes independent of ξ(t). In this paper, we obtain an asymptotic exact result for P(sup t∈[0,T](η(t)ξ(t) + μ(t)) > u) as u→∞. 相似文献
4.
Sren Arlt Vladana Petkovi Gerd Ludwig Thomas Eichhorn Heinrich Lang Tobias Rüffer Sanja Mijatovi Danijela Maksimovi-Ivani Goran N. Kaluerovi 《Molecules (Basel, Switzerland)》2021,26(7)
Neutral [Ru(η6-arene)Cl2{Ph2P(CH2)3SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η6-arene)Cl(Ph2P(CH2)3SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF6: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, 1H, 13C and 31P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation. 相似文献
5.
Neboja . Panteli Bojan Boi Bojana B. Zmejkovski Neboja R. Banjac Biljana Doj
inovi Ludger A. Wessjohann Goran N. Kaluerovi 《Molecules (Basel, Switzerland)》2021,26(11)
The synthesis of novel triphenyltin(IV) compounds, Ph3SnLn (n = 1–3), with oxaprozin (3-(4,5-diphenyloxazol-2-yl)propanoic acid), HL1, and the new propanoic acid derivatives 3-(4,5-bis(4-methoxylphenyl)oxazol-2-yl)propanoic acid, HL2, and 3-(2,5-dioxo-4,4-diphenylimidazolidin-1-yl)propanoic acid, HL3, has been performed. The ligands represent commercial drugs or their derivatives and the tin complexes have been characterized by standard analytical methods. The in vitro antiproliferative activity of both ligands and organotin(IV) compounds has been evaluated on the following tumour cell lines: human prostate cancer (PC-3), human colorectal adenocarcinoma (HT-29), breast cancer (MCF-7), and hepatocellular cancer (HepG2), as well as on normal mouse embryonic fibroblast cells (NIH3T3) with the aid of MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-12 diphenyltetrazolium bromide) and CV (crystal violet) assays. Contrary to the inactive ligand precursors, all organotin(IV) carboxylates showed very good activity with IC50 values ranging from 0.100 to 0.758 µM. According to the CV assay (IC50 = 0.218 ± 0.025 µM), complex Ph3SnL1 demonstrated the highest cytotoxicity against the caspase 3 deficient MCF-7 cell line. Inductively coupled plasma mass spectrometry (ICP-MS) analysis indicated a two-fold lower concentration of tin in MCF-7 cells in comparison to platinum. To investigate the mechanism of action of the compound Ph3SnL1 on MCF-7 cells, morphological, autophagy and cell cycle analysis, as well as the activation of caspase and ROS/RNS and NO production, has been performed. Results suggest that Ph3SnL1 induces caspase-independent apoptosis in MCF-7 cells. 相似文献
6.
Macrocyclic Gd3+ Complexes with Pendant Crown Ethers Designed for Binding Zwitterionic Neurotransmitters 下载免费PDF全文
Dr. Fatima Oukhatar Hervé Meudal Dr. Céline Landon Prof. Dr. Nikos K. Logothetis Prof. Dr. Carlos Platas‐Iglesias Priv.‐Doz. Dr. Goran Angelovski Dr. Éva Tóth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11226-11237
A series of Gd3+ complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd3+ chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen‐type macrocycle that binds the Ln3+ ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM ?1 s?1 at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by 1H relaxometric titrations of the Gd3+ complexes and by luminescence measurements on the Eu3+ and Tb3+ analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu3+ complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non‐amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved. 相似文献
7.
Najdoski Metodija Oklevski Slobodan Stojković Goran 《Russian Journal of Applied Chemistry》2015,88(11):1896-1901
Russian Journal of Applied Chemistry - This paper presents a new method for chemical development of latent fingerprints on unfired cartridge cases and some metal surfaces. It is based on chemical... 相似文献
8.
Electronic absorption spectroscopy was employed to study the aerial oxidation of catechol (1,2-benzenediol) in alkaline aqueous solution containing an excess of Mg(II) ions. Graphical analysis by the matrix method of UV spectra recorded at regular time intervals gave a good fit for two absorbing species in solution. Based on this result and our earlier ESR spectroscopic investigations we concluded that two main absorbing species in this system are Mg(II)-spin stabilized o-benzosemiquinone anion radical and C-C dimer formed by the nucleophilic attack of catecholate anion on o-benzoquinone. Although the formation of 1,2,4-benzenetriol during the catechol oxidation has been detected in some ESR studies its presence was not indicated by this analysis probably because of the low and/or stable steady state concentration throughout the experiment. 相似文献
9.
Dalibor Stankovic Dragan Manojlovic Goran Roglic Sladjana Kostic‐Rajacic Ivan Andjelkovic Biljana Dojcinovic Jelena Mutic 《Electroanalysis》2011,23(8):1928-1933
The determination of Pb and Cd with a Nafion‐modified glassy carbon electrode and Cu‐DPABA complex (Cu‐DPABA–NA/GCE; DPABA is methyl 3,5‐bis{bis‐[(pyridin‐2‐yl)methyl]amino}methyl‐benzoate) as an alternative electrode for anodic stripping voltammetry was described. Pb and Cd were accumulated in acetate buffer pH 4 at a potential of ?1.4 V (vs. Ag/AgCl electrode) for 120 s followed by a DPASV scan from ?1.2 to ?0.2 V. Under optimum conditions the calibration curves were linear in the range of 4.8×10?9–5.0×10?5 and 5.0×10?9–5×10?5 mol L?1 for Pb and Cd, respectively. Detection limits were 1.8×10?9 and 1.2×10?9 mol L?1 for Pb and Cd, respectively. Different parameters and conditions, such as membrane ingredients, accumulation time, potential and pH value were optimized. A study of interfering substances was also performed. A significant increase in current was achieved at the modified electrode in comparison with the bare glassy carbon electrode. The validation of the proposed method was made by Pb and Cd determination in the certified reference material Groundwater CRM 610 (BCR, Community Bureau of Reference, Brussels, Belgium). The electrode was successfully applied for determination of Pb and Cd in river water with a high content of organic contaminants without any pretreatment. 相似文献