全文获取类型
收费全文 | 2320篇 |
免费 | 104篇 |
国内免费 | 9篇 |
专业分类
化学 | 1946篇 |
晶体学 | 12篇 |
力学 | 25篇 |
数学 | 221篇 |
物理学 | 229篇 |
出版年
2023年 | 24篇 |
2022年 | 31篇 |
2021年 | 68篇 |
2020年 | 48篇 |
2019年 | 59篇 |
2018年 | 40篇 |
2017年 | 37篇 |
2016年 | 82篇 |
2015年 | 85篇 |
2014年 | 82篇 |
2013年 | 117篇 |
2012年 | 150篇 |
2011年 | 201篇 |
2010年 | 119篇 |
2009年 | 109篇 |
2008年 | 152篇 |
2007年 | 153篇 |
2006年 | 114篇 |
2005年 | 121篇 |
2004年 | 100篇 |
2003年 | 93篇 |
2002年 | 74篇 |
2001年 | 37篇 |
2000年 | 20篇 |
1999年 | 34篇 |
1998年 | 17篇 |
1997年 | 13篇 |
1996年 | 23篇 |
1995年 | 23篇 |
1994年 | 21篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 19篇 |
1989年 | 15篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 15篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 12篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1970年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有2433条查询结果,搜索用时 15 毫秒
341.
Noury F Mispelter J Szeremeta F Même S Doan BT Beloeil JC 《Magnetic resonance imaging》2008,26(10):1421-1432
Intervertebral disc (IVD) degeneration is a complex process characterized by biochemical and structural changes in both the nucleus pulposus and the anulus fibrosus. In this study, we were able to obtain in vivo magnetic resonance (MR) images of the rabbit spine, with several MR imaging (MRI) contrasts (ρ, T1 and T2). We quantified several parameters (T2, apparent diffusion coefficient, disc height and area) to differentiate between healthy and degenerative IVDs and to characterize the degeneration process. To our knowledge, there has not been any previous in vivo study of rabbit IVDs at high-field MRI (9.4 T).A custom radio frequency (RF) coil for 9.4 T was designed to match rabbit IVD morphology, to study the degeneration in vivo on a model of human lumbar disease. Our new probe, a custom half-birdcage-type coil, obtains the necessary exploration depth while meeting the requirements for signal homogeneity and sensitivity of the study. This design addresses some of the difficulties with constructing RF coils at high field strengths. 相似文献
342.
Anna Peterson Mari-Liis Ludvig Jevgenija Martõnova Sandra Kaabel Paul Kerner Merle Uudsemaa 《Supramolecular chemistry》2020,32(5):313-319
ABSTRACT We demonstrate that Ullman fragment-coupling can be used to synthesise an oxacalix[4]arene monocarboxylic acid, which provides easy access to its water-soluble carboxylato derivatives. Crystallographic and computational data suggest that the new carboxyl-substituted oxacalix[4]arene adopts a 1,3-alternate conformation both in the solid-state and in methanol solution. Its water-soluble tetrabutylammonium derivate can detect the herbicide paraquat at neutral pH in aqueous media (K a = 111 ± 3 M–1) and in methanol (K a = 2020 ± 70 M–1). 相似文献
343.
Ana Diniz Dr. Helena Coelho Dr. Jorge S. Dias Dr. Sandra J. van Vliet Prof. Dr. Jesús Jiménez-Barbero Prof. Dr. Francisco Corzana Prof. Dr. Eurico J. Cabrita Dr. Filipa Marcelo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(61):13945-13955
The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy. 相似文献
344.
Size,Charge, and Stability of Fully Serine‐Based Catanionic Vesicles: Towards Versatile Biocompatible Nanocarriers 下载免费PDF全文
Dr. Sandra G. Silva Prof. M. Luísa C. do Vale Prof. Eduardo F. Marques 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):4092-4101
Vesicles based on mixed cationic and anionic surfactants (catanionic vesicles) offer a number of advantageous colloidal features over conventional lipid‐based vesicles, namely spontaneity in formation, long‐term stability, and easy modulation of size and charge. If biocompatibility is added through rational design of the chemical components, the potential for biorelated applications further emerges. Here, we report for the first time on two catanionic vesicle systems in which both ionic amphiphiles are derivatized from the same amino acid—serine—with the goal of enhancing aggregate biocompatibility. Phase behavior maps for a mixture with chain length symmetry, 12Ser/12‐12Ser, and another with asymmetry, 16Ser/8‐8Ser, are presented, for which regions of vesicles, micelles, and coexisting aggregates are identified. For the asymmetric mixture, detailed phase behavior and microstructure characterization have been carried out based on surface tension, light microscopy, cryo‐SEM, cryo‐TEM, and dynamic light scattering analysis. Vesicles are found with tunable mean size, pH, and zeta potential. Changes in aggregate shape with varying composition and the effect of preparation methods and aging on vesicle features and stability have been investigated in detail. The results are discussed in the light of self‐assembly models and related catanionic systems reported before. A versatile system of robust vesicles is thus presented for potential applications. 相似文献
345.
346.
347.
Gaoxiang Liu Nikita Fedik Chalynette Martinez‐Martinez Sandra M. Ciborowski Xinxing Zhang Alexander I. Boldyrev Kit H. Bowen 《Angewandte Chemie (International ed. in English)》2020,59(23):8760-8764
We reply to the comment by S. Pan and G. Frenking who challenged our interpretation of the Na?:→BH3 dative bond in the recently synthesized NaBH3? cluster. Our conclusion remains the same as that in our original paper ( https://doi.org/10.1002/anie.201907089 and https://doi.org/10.1002/ange.201907089 ). This conclusion is additionally supported by the energetic pathways and NBO charges calculated at UCCSD and CASMP2(4,4) levels of theory. We also discussed the suitability of the Laplacian of electron density (QTAIM) and Adaptive Natural Density Partitioning (AdNDP) method for bond type assignment. It seems that AdNDP yields more sensible results. This discussion reveals that the complex realm of bonding is full of semantic inconsistencies, and we invite experimentalists and theoreticians to elaborate this topic and find solutions incorporating different views on the dative bond. 相似文献
348.
Stefano Federico Tuhina Khan Nicola Relitti Giulia Chemi Margherita Brindisi Simone Brogi Ettore Novellino Daniela M. Zisterer Giuseppe Campiani Sandra Gemma Stefania Butini 《Tetrahedron letters》2018,59(51):4466-4470
We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates. 相似文献
349.
Sreenu Pavurala Krishnaiah Vaarla Rajeshkumar Kesharwani Lieve Naesens Sandra Liekens 《合成通讯》2018,48(12):1494-1503
A series of novel 3,3′-(3,3′-(dihydroxy/hydroxyethane-1,2-diyl)bis(7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine-6,3-diyl))bis(2H-chromen-2-ones) were prepared by the condensation of thiocarbohydrazide with tartaric acid or malic acid followed by various 3-(2-bromoacetyl)-2H-chromen-2-ones in two steps with good yields. All the synthesized compounds were characterized by analytical and spectral (IR, 1H NMR, 13C NMR, and mass) data. These synthesized bis(triazolothiadiazinyl coumarin) compounds were evaluated for broad spectrum of antiviral activity. Among all the tested compounds, compound 5f exhibited antiviral activity against H1N1 virus. The molecular docking studies of these compounds against H1N1 neuraminidase enzyme were performed. The binding affinity and binding values were compared with standard drugs. 相似文献
350.
Hossein Maleki Ahmad K. Karanji Sandra Majuta Megan M. Maurer Stephen J. Valentine 《Journal of the American Society for Mass Spectrometry》2018,29(2):230-241
Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate (in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract. 相似文献