全文获取类型
收费全文 | 1024篇 |
免费 | 106篇 |
国内免费 | 126篇 |
专业分类
化学 | 348篇 |
晶体学 | 2篇 |
力学 | 59篇 |
综合类 | 23篇 |
数学 | 651篇 |
物理学 | 173篇 |
出版年
2023年 | 10篇 |
2022年 | 27篇 |
2021年 | 13篇 |
2020年 | 28篇 |
2019年 | 21篇 |
2018年 | 23篇 |
2017年 | 26篇 |
2016年 | 48篇 |
2015年 | 18篇 |
2014年 | 31篇 |
2013年 | 60篇 |
2012年 | 71篇 |
2011年 | 53篇 |
2010年 | 36篇 |
2009年 | 77篇 |
2008年 | 62篇 |
2007年 | 90篇 |
2006年 | 63篇 |
2005年 | 54篇 |
2004年 | 50篇 |
2003年 | 50篇 |
2002年 | 66篇 |
2001年 | 41篇 |
2000年 | 46篇 |
1999年 | 38篇 |
1998年 | 29篇 |
1997年 | 25篇 |
1996年 | 18篇 |
1995年 | 13篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 6篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有1256条查询结果,搜索用时 15 毫秒
21.
Unimolecular fragmentation patterns of the molecular ions of selected lactams and sultams bearing alkoxymethyl group at the nitrogen atom were studied. The main common fragmentation reaction observed for all compounds studied in this work is the elimination of an aldehyde molecule. This reaction is considered to proceed via two different mechanisms. For lactams, hydrogen rearrangement within an alkoxymethyl group is observed, which leads to the appropriate N-methyl derivatives. For sultams, transfer of the methyl group to the nitrogen and oxygen atoms, proceeding through an ion-neutral complex, dominates. Another important fragmentation channel characteristic exclusively for lactams is the loss of an alkyl radical. This process takes place within the N-alkoxymethyl moiety, yielding the appropriate protonated ion of N-formyllactams. This process is accompanied by relatively high kinetic energy release. 相似文献
22.
D. T. Asilbekova 《Chemistry of Natural Compounds》2003,39(5):442-445
Lipids from fruit pulp of the sweet red pepper (Capsicum annuum, Solanaceae) were characterized. The principal components of the lipids from pepper fruit pulp were neutral lipids with predominance of triacylglycerines (55.8%). The polar lipids contained sulfoquinovosyldiacylglycerines and phosphotidylglycerines. The fatty-acid compositions of the neutral lipids, glycolipids, and phospholipids were determined. 相似文献
23.
2-Arylazo-5,5,10,10,15,15,20,20-octamethylcalix[4]pyrroles (azo-OMCPs) have been synthesised by the reaction of calix[4]pyrrole with aryldiazonium chloride in 15–45% yields. The solution-state binding studies of the synthesised hosts were investigated by absorption spectroscopy and 1H NMR in DMSO and CDCl3, respectively. These receptors, appended with electron-donating and electron-withdrawing groups, displayed enhanced affinity and selectivity for fluoride anion. Well-defined colour change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO solution of azo-OMCPs. Detailed NMR studies in CDCl3 revealed that azo-OMCPs with nitro and chloro groups have higher binding affinity for fluoride ion. 相似文献
24.
Oscillation criteria and asymptotic properties of solutions of third‐order nonlinear neutral differential equations 下载免费PDF全文
T. Candan 《Mathematical Methods in the Applied Sciences》2015,38(7):1379-1392
The main goal of this article is to study the asymptotic properties and oscillation of the third‐order neutral differential equations with discrete and distributed delay. We give several theorems and related examples to illustrate the applicability of these theorems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
25.
Electrochemical derivatization‐capillary electrophoresis‐contactless conductivity detection: A versatile strategy for simultaneous determination of cationic,anionic, and neutral analytes 下载免费PDF全文
Mauro Sérgio Ferreira Santos Fernando Silva Lopes Ivano Gebhardt Rolf Gutz 《Electrophoresis》2014,35(6):864-869
The simultaneous determination of cationic, anionic, and neutral analytes in a real sample was demonstrated by coupling electrochemical (EC) derivatization with counter‐EOF CE‐C4D. An EC flow cell was used to oxidize alcohols from an antiseptic mouthwash sample into carboxylic acids at a platinum electrode in acid medium. The carboxylates formed in the derivatization process and other sample ingredients, such as benzoate, saccharinate, and sodium ions, were separated in counter‐flow mode and detected in one run in Tris‐HCl buffer, pH 8.6. Fewer than 5 min were needed to complete each analysis with the automated flow system comprising solenoid pumps for the management of solutions. Insights into the electrochemistry of benzoic acid, present in the sample matrix, were also gained by EC‐CE‐C4D; more specifically, by applying potentials higher than 1.47 V to the platinum electrode, some formiate and minute amounts of salicylate were detected. 相似文献
26.
Battistina Asproni Gabriele Murineddu Paola Corona Grard A. Pinna 《Molecules (Basel, Switzerland)》2021,26(8)
Cannabinoids comprise different classes of compounds, which aroused interest in recent years because of their several pharmacological properties. Such properties include analgesic activity, bodyweight reduction, the antiemetic effect, the reduction of intraocular pressure and many others, which appear correlated to the affinity of cannabinoids towards CB1 and/or CB2 receptors. Within the search aiming to identify novel chemical scaffolds for cannabinoid receptor interaction, the CB1 antagonist/inverse agonist pyrazole-based derivative rimonabant has been modified, giving rise to several tricyclic pyrazole-based compounds, most of which endowed of high affinity and selectivity for CB1 or CB2 receptors. The aim of this review is to present the synthesis and summarize the SAR study of such tricyclic pyrazole-based compounds, evidencing, for some derivatives, their potential in the treatment of neuropathic pain, obesity or in the management of glaucoma. 相似文献
27.
Wim
Van Uytven Maarten Blommaert Wouter Dekeyser Niels Horsten Martine Baelmans 《等离子体物理论文集》2020,60(5-6):e201900147
In plasma edge transport codes for nuclear fusion devices, fluid-neutral models offer an interesting alternative to the currently used kinetic Monte Carlo simulations, especially for cases of high ion-neutral collisionality. In this paper, we elaborate a separate neutral energy equation in the state-of-the-art SOLPS-ITER code suite, which previously assumed perfect ion-neutral temperature equilibration. Furthermore, we study the coupled plasma-neutral solutions for a range of divertor operating regimes, proving the validity of these fluid-neutral models for high-recycling and detached regimes. 相似文献
28.
TONG Yi-Ping ② 《结构化学》2007,26(2)
The title compound has been synthesized and characterized crystallographically. It is a co-crystal consisting of two different neutral zinc(Ⅱ) complexes with Hbpbm (Hbpbm = 4-bromo-2-(benzimidazol-2-yl)phenol) and Hnpbm (Hnpbm = 2-(1-butylbenzimidazol-2-yl)phenol).One is a monomeric mixed-ligand complex of [Zn(bpbm)(npbm)] 1 and the other a dimer of[Zn2(npbm)4] 2 with their ratio of 2:1. Thus the overall formula for the title compound is 21·2.Adjacent 1 and 2 are connected to each other by intermolecular hydrogen bonding interactions in the lattice. The crystal data: monoclinic, space group P21/c, a= 15.0141(12), b = 20.9941(17), c =18.4686(15) (A), β = 97.445(2)°, V= 5772.4(8) (A)3, Mr= 2429.68, Z = 2, Dc = 1.398 g/cm3,μ = 1.579mm-1, F(000) = 2504, R = 0.0637 and wR = 0.1771 for 6464 observed reflections (I> 2σ(Ⅰ)). The geometrical structure for 1 has also been theoretically optimized and compared with the experimental one. 相似文献
29.
YAO Wen-Zhi WU Hai-Shun 《结构化学》2007,26(8):897-901
The structures, energies and aromaticity (the nuclear-independent chemical shifts, NICS) of AlCO-substituted semibullvalenes were investigated at the B3LYP/6-311+G** level. Similar to BCO-substituted analogues, [2,6]-AlCO-semibullvalene is neutral bishomoaromatic. The NICS values reveal that the aromaticity of AlCO-substituted structures is smaller than that of BCO analogues. 相似文献
30.
聚中性红膜修饰电极测定痕量NO2^—的研究 总被引:4,自引:1,他引:4
研究了聚中性红膜修饰电极对NO-2的催化氧化性能,建立了测定NO-2的新方法。NO-2的浓度在2.0×10-6~5.0×10-3mol/L范围内与催化氧化峰电流呈良好的线性关系,检测限为6.0×10-7mol/L。若利用计时电流法分析,检测限可达8.0×10-8mol/L。 相似文献