全文获取类型
收费全文 | 1372篇 |
免费 | 282篇 |
国内免费 | 113篇 |
专业分类
化学 | 581篇 |
晶体学 | 22篇 |
力学 | 302篇 |
综合类 | 13篇 |
数学 | 490篇 |
物理学 | 359篇 |
出版年
2024年 | 1篇 |
2023年 | 3篇 |
2022年 | 4篇 |
2021年 | 10篇 |
2020年 | 13篇 |
2019年 | 62篇 |
2018年 | 47篇 |
2017年 | 85篇 |
2016年 | 89篇 |
2015年 | 105篇 |
2014年 | 72篇 |
2013年 | 131篇 |
2012年 | 69篇 |
2011年 | 83篇 |
2010年 | 66篇 |
2009年 | 68篇 |
2008年 | 65篇 |
2007年 | 74篇 |
2006年 | 79篇 |
2005年 | 88篇 |
2004年 | 76篇 |
2003年 | 79篇 |
2002年 | 70篇 |
2001年 | 73篇 |
2000年 | 64篇 |
1999年 | 79篇 |
1998年 | 35篇 |
1997年 | 31篇 |
1996年 | 13篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 5篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
排序方式: 共有1767条查询结果,搜索用时 15 毫秒
81.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes 下载免费PDF全文
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献
82.
Shivanand M. Pudakalakatti Kousik Chandra Ravula Thirupathi Hanudatta S. Atreya 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(48):15719-15722
An NMR‐based approach for rapid characterization of translational diffusion of molecules has been developed. Unlike the conventional method of acquiring a series of 2D 13C and 1H spectra, the proposed approach involves a single 2D NMR spectrum, which can be acquired in minutes. Using this method, it was possible to detect the presence of intermediate oligomeric species of diphenylalanine in solution during the process of its self‐assembly to form nanotubular structures. 相似文献
83.
Dr. Yann Gloaguen Christophe Rebreyend Dr. Martin Lutz Pravin Kumar Dr. Martina Huber Dr. Ir. Jarl Ivar van der Vlugt Prof. Dr. Sven Schneider Prof. Dr. Bas de Bruin 《Angewandte Chemie (International ed. in English)》2014,53(26):6814-6818
Photochemical activation of [(PNNH)Rh(N3)] (PNNH=6‐di‐(tert‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)Rh?N.‐Rh(PNN)] complex 3 (PNN?=methylene‐deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical (.N2?) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)RhI(CO)] complex 4 , presumably by nitridyl radical N,N‐coupling. 相似文献
84.
Gayan Heruka De Zoysa Kelvin Wang Jun Lu Yacine Hemar Vijayalekshmi Sarojini 《Molecules (Basel, Switzerland)》2020,25(24)
Novel antibiotic treatments are in increasing demand to tackle life-threatening infections from bacterial pathogens. In this study, we report the use of a potent battacin lipopeptide as an antimicrobial gel to inhibit planktonic and mature biofilms of S. aureus and P. aeruginosa. The antimicrobial gels were made by covalently linking the N-terminal cysteine containing lipopeptide (GZ3.163) onto the polyethylene glycol polymer matrix and initiating gelation using thiol-ene click chemistry. The gels were prepared both in methanol and in water and were characterised using rheology, Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). Antibacterial and antibiofilm analyses revealed that the gels prepared in methanol have better antibacterial and antibiofilm activity. Additionally, a minimum peptide content of 0.5 wt% (relative to polymer content) is required to successfully inhibit the planktonic bacterial growth and disperse mature biofilms of P. aeruginosa and S. aureus. The antibacterial activity of these lipopeptide gels is mediated by a contact kill mechanism of action. The gels are non-haemolytic against mouse red blood cells and are non-cytotoxic against human dermal fibroblasts. Findings from this study show that battacin lipopeptide gels have the potential to be developed as novel topical antibacterial agents to combat skin infections, particularly caused by S. aureus. 相似文献
85.
新鲜苹果汁可溶性固形物含量的傅里叶变换近红外光谱检测 总被引:6,自引:6,他引:0
用傅里叶变换近红外(FTNIR)光谱透射方式对新鲜苹果汁溶性固形物含量(SSC)进行了快速定量分析。实验共测定了60个果汁样品的SSC,并采集了样品的近红外光谱数据。42个样品用来建模,剩下的18个用来验证模型的性能。对实验室测得的SSC与FTNIR光谱数据进行相关性分析,以TQ 6.2.1定量分析软件中集成的主成分回归法(PCR)和偏最小二乘回归法(PLS)建立了检测模型。该研究对比了不同光谱范围内建立的检测模型的性能。根据预测平方根误差(RMSEP)和相关系数(r2)进行不同模型的预测性能,最好的新鲜苹果汁SSC预测模型的RMSEP=0.603 0Brix,r2=0.997。结果表明FT-NIR可以作为一种可靠、准确、快速的无损检测方法来评价新鲜果汁的可溶性固形物含量。 相似文献
86.
Paraskevi Tziona Panagiotis Theodosis-Nobelos Georgios Papagiouvannis Anthi Petrou Chryssoula Drouza Eleni A. Rekka 《Molecules (Basel, Switzerland)》2022,27(7)
The synthesis of derivatives of three nonspecific COX-1 and COX-2 inhibitors, ibuprofen, ketoprofen, naproxen is presented. These acids were connected via an amide bond with an amino acid (L-proline, L-tyrosine, and beta-alanine) used as a linker. The amino acid carboxylic group was esterified with 3,4,5 trimethoxybenzyl alcohol. The activity of the novel derivatives was examined in vivo on carrageenan-induced inflammation, and in vitro, as cyclooxygenase and lipoxygenase inhibitors. It was found that the new compounds were more potent anti-inflammatory agents than the parent drugs. Thus, the ibuprofen (21) and ketoprofen (16) derivatives reduced rat paw edema by 67 and 91% (the reduction by the relevant NSAIDs was 36 and 47%, respectively). They inhibited COX-2 more than the starting drugs (21 by 67%, ibuprofen 46%, 19 by 94%, ketoprofen 49%). Docking of compounds on the active sites of COX-1 and COX-2 reflects their in vitro activity. Thus, 19 adopts an unfavorable orientation for COX-1 inhibition, but it binds effectively in the binding pocket of COX-2, in agreement with the absence of activity for COX-1 and the high inhibition of COX-2. In conclusion, the performed structural modifications result in the enhancement of the anti-inflammatory activity, compared with the parent NSAIDs. 相似文献
87.
对蛋白质在离子交换柱上选择民性和非吸附特性进行了研究。蛋白质在有机磷酸锆阳离子色谱柱上,其保留作用随流动相pH值在离子强度的增加而减小;蛋白质在强阳离子和强阴离子色谱柱上的保留作用,即是流动相中的pH值等于蛋白质的等当点,其净电荷为零。不册蛋白质仍有不同程度的保留,这主要是由于蛋白质的三维结构使电荷 密度的大小和分布的不均匀以及离子交换填料表面性质的影响。 相似文献
88.
在轴向应力波传播和反射过程中弹性有限长圆柱壳非对称动态屈曲 总被引:2,自引:0,他引:2
本文讨论弹性有限长圆柱壳端部受冲击载荷作用,在轴向应力波传播和反射过程中的非对称动态屈曲问题。通过建立和求解扰动方程得到了动态屈曲的分叉条件,临界载荷和屈曲模态。数值结果表明:当壳壁厚不很薄时,轴对称屈曲临界载荷比非轴对称临界载荷高;反之,轴对称临界载荷会比非对称临界载荷低;由于应力波的反射,临界载荷降低,因而更容易发生屈曲,屈曲模态也有其不同特点。 相似文献
89.
90.
《中国化学》2017,35(11):1678-1686
Polydiacetylenes (PDAs), an organic layered compound, show a series of intriguing properties, such as thermochromism and fluorescence emission in the red‐phase. However, their irreversible color change, and weak and single‐color fluorescence emitted only from the red‐phase PDAs, have limited their applications. Herein, we report double‐reversible PDA‐Tb3+ nanosheets of which both the color and the fluorescence can be reversibly switched between two colors. PDA‐Tb3+ nanosheets have the nearly defect‐free intercalated structure in which a layer of Tb3+ ions was intercalated in between each two PDA bilayers to tether almost all of the carboxyl groups at the end of the side chains of the PDA. When the PDA is in the blue phase, the PDA‐Tb3+ nanosheets emit the green fluorescence of Tb3+ ions. When the PDA is in the red phase, the Tb3+ fluorescence disappears while the intrinsic red fluorescence of PDA is effectively enhanced through the fluorescence resonance energy transfer (FRET) process; the PDA‐Tb3+ nanosheets emit stronger red fluorescence compared with the PDA in red phase. Moreover, the tethering of almost all of the carboxyl groups at the end of the side chains of the PDA endows the nanosheets with the double reversibility in both the color and fluorescence transitions. 相似文献