全文获取类型
收费全文 | 611篇 |
免费 | 100篇 |
国内免费 | 38篇 |
专业分类
化学 | 467篇 |
力学 | 2篇 |
综合类 | 2篇 |
数学 | 53篇 |
物理学 | 225篇 |
出版年
2024年 | 2篇 |
2023年 | 6篇 |
2022年 | 10篇 |
2021年 | 27篇 |
2020年 | 37篇 |
2019年 | 10篇 |
2018年 | 21篇 |
2017年 | 14篇 |
2016年 | 19篇 |
2015年 | 32篇 |
2014年 | 34篇 |
2013年 | 127篇 |
2012年 | 52篇 |
2011年 | 32篇 |
2010年 | 30篇 |
2009年 | 37篇 |
2008年 | 27篇 |
2007年 | 33篇 |
2006年 | 26篇 |
2005年 | 25篇 |
2004年 | 20篇 |
2003年 | 16篇 |
2002年 | 15篇 |
2001年 | 11篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 7篇 |
1997年 | 10篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1982年 | 1篇 |
1979年 | 3篇 |
1977年 | 1篇 |
排序方式: 共有749条查询结果,搜索用时 437 毫秒
101.
Wei-Xiu Pang Hong-Ye Wu Jian-Jun Zhao 《Phosphorus, sulfur, and silicon and the related elements》2019,194(1-2):69-75
The anharmonic force field and spectroscopy constants for CH2PCl are determined using CCSD(T), VPT2, and density functional theory employing cc-pVQZ basis sets. The molecule structure, rotational spectroscopic constants, and vibrational wave numbers are compared with the available experimental data. Anharmonicity constants, vibration-rotation interaction constants and cubic force constants are predicted. Vibrational wave numbers and rotational constants for CD2PCl are also determined using the same levels. The isotopic shifts of vibrational wave numbers are remarkable by D atom substitution for 1-chlorophosphaethene. 相似文献
102.
Dr. Rainer Müller Dr. Mevlut Citir Dr. Sebastian Hauke Prof. Dr. Carsten Schultz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(2):384-389
Phosphatidylinositol (PI) is the biosynthetic precursor for seven phosphoinositides, important signaling lipids in cells. A membrane-permeant caged PI derivative featuring a photo-removable coumarinyl group masking the negative charge of the phosphate, as well as two enzymatically removable butyrate esters for increased lipophilicity and for preventing phosphate migration, were synthesized. Rapid cell entry and cellular labeling in fixed cells was demonstrated by a photo-cross-linkable diazirine followed by attachment of a fluorophore through click chemistry. Using this technique, we found that the multifunctional caged PI derivative resided predominantly at internal membranes but rapidly changed to the plasma membrane after uncaging. Accordingly, a preliminary proteomic analysis of the lipid–protein conjugates revealed that the two major PI transport proteins PITPα and β were prime targets of the photo-cross-linked PI derivative. 相似文献
103.
Dr. David Scheerer Prof. Dr. Heng Chi Dr. Dan McElheny Prof. Dr. Timothy A. Keiderling Prof. Dr. Karin Hauser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3524-3534
Site-specific isotopic labeling of molecules is a widely used approach in IR spectroscopy to resolve local contributions to vibrational modes. The induced frequency shift of the corresponding IR band depends on the substituted masses, as well as on hydrogen bonding and vibrational coupling. The impact of these different factors was analyzed with a designed three-stranded β-sheet peptide and by use of selected 13C isotope substitutions at multiple positions in the peptide backbone. Single-strand labels give rise to isotopically shifted bands at different frequencies, depending on the specific sites; this demonstrates sensitivity to the local environment. Cross-strand double- and triple-labeled peptides exhibited two resolved bands that could be uniquely assigned to specific residues, the equilibrium IR spectra of which indicated only weak local-mode coupling. Temperature-jump IR laser spectroscopy was applied to monitor structural dynamics and revealed an impressive enhancement of the isotope sensitivity to both local positions and coupling between them, relative to that of equilibrium FTIR spectroscopy. Site-specific relaxation rates were altered upon the introduction of additional cross-strand isotopes. Likewise, the rates for the global β-sheet dynamics were affected in a manner dependent on the distinct relaxation behavior of the labeled oscillator. This study reveals that isotope labels provide not only local structural probes, but rather sense the dynamic complexity of the molecular environment. 相似文献
104.
Dr. Marion Daniel-Bertrand Sébastien Garcia-Argote Dr. Alberto Palazzolo Dr. Irene Mustieles Marin Dr. Pier-Francesco Fazzini Dr. Simon Tricard Dr. Bruno Chaudret Dr. Volker Derdau Dr. Sophie Feuillastre Dr. Grégory Pieters 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21300-21306
Radiolabelling is fundamental in drug discovery and development as it is mandatory for preclinical ADME studies and late-stage human clinical trials. Herein, a general, effective, and easy to implement method for the multiple site incorporation of deuterium and tritium atoms using the commercially available and air-stable iridium precatalyst [Ir(COD)(OMe)]2 is described. A large scope of pharmaceutically relevant substructures can be labelled using this method including pyridine, pyrazine, indole, carbazole, aniline, oxa-/thia-zoles, thiophene, but also electron-rich phenyl groups. The high functional group tolerance of the reaction is highlighted by the labelling of a wide range of complex pharmaceuticals, containing notably halogen or sulfur atoms and nitrile groups. The multiple site hydrogen isotope incorporation has been explained by the in situ formation of complementary catalytically active species: monometallic iridium complexes and iridium nanoparticles. 相似文献
105.
Vladimir I. Bakhmutov Aida Contreras-Ramirez Hannah Drake Hong-Cai Zhou 《Magnetic resonance in chemistry : MRC》2022,60(6):541-553
Solid-state NMR experiments on 2H, 31P, 13C, and 1H nuclei, including 31P T1, 1H T1, and 1H T1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D2O and/or CD3OD. The 13C{1H} CP MAS NMR experiment performed for compound 1-CD 3 OD (Zr (HPO4)2 . 0.2CD3OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD3 rotations around the C3-axis. It has been demonstrated that the intercalated species, D2O and CD3OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Thus, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems. 相似文献
106.
The oxygen isotopic exchange technique is a powerful tool to investigate the oxygen transport kinetics in an oxide solid. In a solid oxide fuel cell, isotopic surface exchange and diffusion coefficients are classically determined by using the Isotopic Exchange Depth Profiling method followed by ex situ SIMS characterizations. Despite its relevance, the utilization of in situ or operando techniques to measure the isotopic exchange under an electrical bias remains marginal. We developed here a set-up which enables operando monitoring of oxygen exchange in SOFC type cells under polarization. The system has been used for studying the oxygen mobility dependency upon polarization on a symmetrical Pt/YSZ/Pt cell (YSZ: yttria-stabilized zirconia). Homomolecular and heterolytic exchange reactions were undertaken to investigate the oxygen activation step and discriminate the limiting step among the sequence of elementary steps which constitute the oxygen transport process in the SOFC system. Oxygen ions incorporation into the dense ionic conductor was identified to be the rate determining step, and its first order rate constant dependency on applied potential was established. 相似文献
107.
Lead was applied as an internal standard for the determination of Hg isotopic ratios. Cold vapor generation (CV) coupled with sector field–inductively coupled plasma–mass spectrometry (CV-SF-ICP-MS) was used for determination of Hg. It was effective to avoid interferences of Pb from samples while improving the sensitivity of Hg isotopic analysis by an approximate factor of 45 times higher than the aerosol mode. CV-SF-ICP-MS system was constructed and operational parameters were optimized. Research showed that the long stability of the system was limited by SF-ICP-MS and had no relationship with CV under the optimized conditions. The optimized precision of Hg isotopic ratio analysis was approximately 0.1% during 4?h. Five models were applied for the mass bias correction and the Baxter model obtained the smallest relative difference, 0.52‰. The results showed that the mean value of NIST SRM 3133 Hg isotopic ratios obtained by Pb internal standard was nearly identical with the value for Tl. The same performance was also obtained in two environmental reference materials. The results show that Pb may be used as the internal standard for determination of Hg isotopic ratio instead of Tl. 相似文献
108.
Macarena Eugui Katerine Rasquin Andrés López Radcenco Leopoldo Suescun Guillermo Moyna 《Tetrahedron letters》2018,59(16):1560-1563
We describe a novel pericyclic/anionic cascade reaction on tropolonic substrates that combines a Diels-Alder reaction, an oxa-Michael addition, and an acyloin rearrangement to afford tricyclic α-hydroxy-β-methoxyketones. Spectroscopic, crystallographic, and mechanistic studies indicate that the process requires stabilization of reaction intermediates through intramolecular H-bonding to take place, and suggest that the conjugate addition step involves a catalytic cycle with initial formation of an ammonium enolate and sustained by an alkoxide ion pair. Given the rich functionality and structural complexity generated in a single step, the process could be exploited in the preparation of natural product-like compound libraries. 相似文献
109.
Direct Access to Aryl Bis(trifluoromethyl)carbinols from Aryl Bromides or Fluorosulfates: Palladium‐Catalyzed Carbonylation
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Katrine Domino Cedrick Veryser Benjamin A. Wahlqvist Cecilie Gaardbo Dr. Karoline T. Neumann Prof.Dr. Kim Daasbjerg Prof. Dr. Wim M. De Borggraeve Prof. Dr. Troels Skrydstrup 《Angewandte Chemie (International ed. in English)》2018,57(23):6858-6862
A palladium‐catalyzed carbonylative approach for the direct conversion of (hetero)aryl bromides into their α,α‐bis(trifluoromethyl)carbinols is described, and it employs only stoichiometric amounts of carbon monoxide and trifluoromethyltrimethylsilane. In addition, aryl fluorosulfates proved highly compatible with these reaction conditions. The method is tolerant of a diverse set of functional groups, and it is adaptable to late‐stage carbon‐isotope labeling. 相似文献
110.
C. Michael Hamilton Maurita Hung Gang Chen Zafar Qureshi John R. Thompson Bingyun Sun Christine E. Bear Robert N. Young 《Tetrahedron》2018,74(38):5528-5538
Cystic Fibrosis (CF) is a genetic disorder caused by loss-of-function mutations to the gene encoding the cystic fibrosis transmembrane conductance regulator (CFTR) protein. Ivacaftor (1) was the first therapeutic approved for the treatment of CF that is able to restore gating activity to certain CFTR variants although the mechanism of action is poorly understood. Herein we describe the synthesis of a photoaffinity labelling (PAL) probe (2) based on the structure of ivacaftor incorporating a photoreactive diazirine moiety for use in labelling studies designed to identify the binding site for ivacaftor on mutant CFTR. The PAL probe 2 retained potentiation activity, with a potency similar to 1, using a Fluorescent Imaging Plate Reader (FLIPR®) assay measuring ion conductance potentiation of wild type (Wt)-CFTR. Photolabelling experiments with human serum albumin (HSA) as a model protein have shown that probe 2 can label HSA in a manner consistent with observed and predicted binding. 相似文献