全文获取类型
收费全文 | 1226篇 |
免费 | 44篇 |
国内免费 | 12篇 |
专业分类
化学 | 833篇 |
晶体学 | 4篇 |
力学 | 40篇 |
数学 | 184篇 |
物理学 | 221篇 |
出版年
2023年 | 5篇 |
2022年 | 14篇 |
2021年 | 10篇 |
2020年 | 17篇 |
2019年 | 17篇 |
2018年 | 23篇 |
2017年 | 15篇 |
2016年 | 36篇 |
2015年 | 32篇 |
2014年 | 48篇 |
2013年 | 60篇 |
2012年 | 82篇 |
2011年 | 71篇 |
2010年 | 46篇 |
2009年 | 30篇 |
2008年 | 80篇 |
2007年 | 80篇 |
2006年 | 83篇 |
2005年 | 112篇 |
2004年 | 63篇 |
2003年 | 50篇 |
2002年 | 40篇 |
2001年 | 22篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1998年 | 17篇 |
1997年 | 16篇 |
1996年 | 21篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1987年 | 4篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 10篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 13篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 10篇 |
1973年 | 7篇 |
1970年 | 4篇 |
1969年 | 6篇 |
1881年 | 3篇 |
排序方式: 共有1282条查询结果,搜索用时 62 毫秒
61.
Ketones and aldehydes are conveniently and rapidly reduced to the corresponding alcohols in good yields using sodium borohydride under sealed-tube microwave conditions in either 95% ethanol or water. In purely aqueous systems, highly aliphatic substrates are sluggish, but this can be overcome by introducing sodium dodecyl sulfate (SDS) at the critical micelle concentration. With a 2:1 substrate/borohydride ratio and a reaction temperature of 100 °C, reduction is typically complete within 1 min in 95% ethanol and 5 min in water/SDS. The methodology is well suited for parallel and combinatorial synthetic approaches. 相似文献
62.
A general molecular mechanics (MM) model for treating aqueous Cu2+ and Zn2+ ions was developed based on valence bond (VB) theory and incorporated into the atomic multipole optimized energetics for biomolecular applications (AMOEBA) polarizable force field. Parameters were obtained by fitting MM energies to that computed by ab initio methods for gas‐phase tetra‐ and hexa‐aqua metal complexes. Molecular dynamics (MD) simulations using the proposed AMOEBA‐VB model were performed for each transition metal ion in aqueous solution, and solvent coordination was evaluated. Results show that the AMOEBA‐VB model generates the correct square‐planar geometry for gas‐phase tetra‐aqua Cu2+ complex and improves the accuracy of MM model energetics for a number of ligation geometries when compared to quantum mechanical (QM) computations. On the other hand, both AMOEBA and AMOEBA‐VB generate results for Zn2+–water complexes in good agreement with QM calculations. Analyses of the MD trajectories revealed a six‐coordination first solvation shell for both Cu2+ and Zn2+ ions in aqueous solution, with ligation geometries falling in the range reported by previous studies. © 2012 Wiley Periodicals, Inc. 相似文献
63.
Simin Cao Haoyang Li Zenan Zhao Sanjun Zhang Jinquan Chen Jianhua Xu Jay R. Knutson Ludwig Brand 《Molecules (Basel, Switzerland)》2021,26(1)
In this review, the experimental set-up and functional characteristics of single-wavelength and broad-band femtosecond upconversion spectrophotofluorometers developed in our laboratory are described. We discuss applications of this technique to biophysical problems, such as ultrafast fluorescence quenching and solvation dynamics of tryptophan, peptides, proteins, reduced nicotinamide adenine dinucleotide (NADH), and nucleic acids. In the tryptophan dynamics field, especially for proteins, two types of solvation dynamics on different time scales have been well explored: ~1 ps for bulk water, and tens of picoseconds for “biological water”, a term that combines effects of water and macromolecule dynamics. In addition, some proteins also show quasi-static self-quenching (QSSQ) phenomena. Interestingly, in our more recent work, we also find that similar mixtures of quenching and solvation dynamics occur for the metabolic cofactor NADH. In this review, we add a brief overview of the emerging development of fluorescent RNA aptamers and their potential application to live cell imaging, while noting how ultrafast measurement may speed their optimization. 相似文献
64.
Neel Sisodia Monica Miranda Kay L. McGuinness Jay D. Wadhawan Nathan S. Lawrence 《Electroanalysis》2021,33(3):559-562
This work presents the electrochemical response of a 2-(methylthio)phenol glassy carbon based electrode for a promising voltammetric pH sensor in both buffered and low-buffered solutions. Electropolymerization of the redox species was performed with the resulting polymer presenting a Nernstian response in buffered media, with a sensitivity of 51 mV/pH unit. The effectiveness of the sulfhydryl bond to facilitate proton transfer from the bulk solution to the phenol molecules has been confirmed, providing an accurate pH measurement of 8.28 in sea water media, compared to that measured with a calibrated glass pH probe of 8.30. 相似文献
65.
Ahmad R Deng Y Vikram DS Clymer B Srinivasan P Zweier JL Kuppusamy P 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(2):236-245
In continuous wave (CW) electron paramagnetic resonance imaging (EPRI), high quality of reconstructed image along with fast and reliable data acquisition is highly desirable for many biological applications. An accurate representation of uniform distribution of projection data is necessary to ensure high reconstruction quality. The current techniques for data acquisition suffer from nonuniformities or local anisotropies in the distribution of projection data and present a poor approximation of a true uniform and isotropic distribution. In this work, we have implemented a technique based on Quasi-Monte Carlo method to acquire projections with more uniform and isotropic distribution of data over a 3D acquisition space. The proposed technique exhibits improvements in the reconstruction quality in terms of both mean-square-error and visual judgment. The effectiveness of the suggested technique is demonstrated using computer simulations and 3D EPRI experiments. The technique is robust and exhibits consistent performance for different object configurations and orientations. 相似文献
66.
Jay E. Taylor 《Journal of Physical Organic Chemistry》2007,20(12):1088-1092
Periodate oxidations of ethanediol and pinacol each occur in two phases; these are (1) formation and (2) decomposition of the intermediate complex. In phase (1), an increase in acidity gives . The rate of oxidation of ethanediol decreases with increasing acidity, whereas the rate of oxidation of pinacol maximizes with H5IO6. For both glycols, the activation energy increases and ΔSact decreases with increasing acidity. In phase (2), the energy of activation is essentially constant with pH, whereas the rate decreases, and the entropy of activation decreases modestly as pH decreases. The latter correlates with the nonhomogeniuty of product formation. Rates for 3‐chloro‐1,2‐propanediol are also listed. Pentaerythritol forms an inactive complex with or H5IO6 indicating the importance of chelation in the formation of the intermediate complex. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
67.
Cadars S Sein J Duma L Lesage A Pham TN Baltisberger JH Brown SP Emsley L 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(1):24-34
The robustness of the refocused INADEQUATE MAS NMR pulse sequence for probing through-bond connectivities has been demonstrated in a large range of solid-state applications. This pulse sequence nevertheless suffers from artifacts when applied to multispin systems, e.g. uniformly labeled (13)C solids, which distort the lineshapes and can potentially result in misleading correlation peaks. In this paper, we present a detailed account that combines product-operator analysis, numerical simulations and experiments of the behavior of a three-spin system during the refocused INADEQUATE pulse sequence. The origin of undesired anti-phase contributions to the spectral lineshapes are described, and we show that they do not interfere with the observation of long-range correlations (e.g. two-bond (13)C-(13)C correlations). The suppression of undesired contributions to the refocused INADEQUATE spectra is shown to require the removal of zero-quantum coherences within a z-filter. A method is proposed to eliminate zero-quantum coherences through dephasing by heteronuclear dipolar couplings, which leads to pure in-phase spectra. 相似文献
68.
Dr. Hong‐Jay Lo M. Sc. Chin‐Yin Lin Dr. Mei‐Chun Tseng Prof. Rong‐Jie Chein 《Angewandte Chemie (International ed. in English)》2014,53(34):9026-9029
A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported. 相似文献
69.
Zongchao Jia Ying Liu Maurycy Daroch Shu Geng Jay J. Cheng 《Applied biochemistry and biotechnology》2014,173(7):1667-1679
This article presents a study on screening of microalgal strains from the Peking University Algae Collection and heterotrophic cultivation for biodiesel production of a selected microalgal strain. Among 89 strains, only five were capable of growing under heterotrophic conditions in liquid cultures and Chlorella sp. PKUAC 102 was found the best for the production of heterotrophic algal biodiesel. Composition of the growth medium was optimised using response surface methodology and optimised growth conditions were successfully used for cultivation of the strain in a fermentor. Conversion of algal lipids to fatty acid methyl esters (FAMEs) showed that the lipid profile of the heterotrophically cultivated Chlorella sp. PKUAC 102 contains fatty acids suitable for biodiesel production. 相似文献
70.
David Mouran Jay Reimers F. Joseph Schork 《Journal of polymer science. Part A, Polymer chemistry》1996,34(6):1073-1081
Miniemulsions of methyl methacrylate with sodium lauryl sulfate as the surfactant and dodecyl mercaptan (DDM) as the cosurfactant (or hydrophobe) were prepared and polymerized. The emulsions were of a droplet size range common to miniemulsions and exhibited long-term stability (greater than 3 months). Results indicate that DDM retards Ostwald ripening and allows the production of stable miniemulsions. When these emulsions were initiated, particle formation occurred predominantly by monomer droplet nucleation. The effects of the concentration of surfactant, cosurfactant and initiator were determined. Rates of polymerization, monomer droplet sizes, polymer particle sizes, molecular weights of the polymer, and the effect of initiator concentration on the number of particles vary systematically in ways that indicate predominant droplet nucleation in these systems. © 1996 John Wiley & Sons, Inc. 相似文献