全文获取类型
收费全文 | 609篇 |
免费 | 13篇 |
国内免费 | 3篇 |
专业分类
化学 | 424篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 63篇 |
物理学 | 121篇 |
出版年
2023年 | 5篇 |
2022年 | 9篇 |
2021年 | 8篇 |
2020年 | 13篇 |
2019年 | 9篇 |
2018年 | 14篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 9篇 |
2014年 | 12篇 |
2013年 | 31篇 |
2012年 | 32篇 |
2011年 | 54篇 |
2010年 | 35篇 |
2009年 | 30篇 |
2008年 | 36篇 |
2007年 | 48篇 |
2006年 | 34篇 |
2005年 | 29篇 |
2004年 | 33篇 |
2003年 | 26篇 |
2002年 | 21篇 |
2001年 | 13篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有625条查询结果,搜索用时 140 毫秒
91.
CE was coupled to inductively coupled plasma MS (ICP-MS) and ESI-MS to identify and quantify the arsenic species arsenobetaine (AsB), arsenite (As(III)), arsenate (As(V)), and dimethylarsinic acid (DMA). A GC-flame ionization detector (FID)-based German standard method and ICP-MS were used for validation of the data obtained for arsenobetaine and total arsenic, respectively. LODs obtained with the CE-ESI-TOF-MS method were 1.0x10(-7) M for AsB, 5.0x10(-7) M for DMA, and 1.0x10(-6) M for As(III) and As(V). For the CE-ICP-MS method, LODs were 8.5x10(-8) M for AsB, 9.5x10(-8) M for DMA, 9.3x10(-8) M for As(III), and 6.2x10(-8) M for As(V). While CE-ICP-MS provided high sensitivity and better reproducibility for quantitative measurements, CE-ESI-MS with a TOF mass analyzer proved to be valuable for species identification. With this setup, fish samples were prepared and analyzed and the obtained data were successfully validated with the independent methods. 相似文献
92.
A novel algorithmic scheme for numerical solution of the 3D Poisson-Nernst-Planck model is proposed. The algorithmic improvements are universal and independent of the detailed physical model. They include three major steps: an adjustable gradient-based step value, an adjustable relaxation coefficient, and an optimized segmentation of the modeled space. The enhanced algorithm significantly accelerates the speed of computation and reduces the computational demands. The theoretical model was tested on a regular artificial channel and validated on a real protein channel-alpha-hemolysin, proving its efficiency. 相似文献
93.
Kian Eang Neo Han Vinh Huynh Lip Lin Koh William Henderson T.S. Andy Hor 《Journal of organometallic chemistry》2008,693(8-9):1628-1635
Pincer PCP-Pd(II) complex [PdCl(PCP)] (1) (PCP = ?CH(CH2CH2PPh2)2) reacts with AgNO3 to give [Pd(NO3)(PCP)] (2). Similar reaction with AgBF4 gives the aqua complex [Pd(OH2)(PCP)][BF4] (3) and the dinuclear complex [{Pd(PCP)}2(μ-Cl)][BF4] (4) with singly bridging chloro ligand. All new complexes were characterized by NMR spectroscopy, ESI-MS and single-crystal X-ray diffraction. Complex 1 and the triflate complex [Pd(OTf)(PCP)] (5) are active towards Suzuki–Miyaura coupling between aryl bromides and phenyl boronic acid. 相似文献
94.
An efficient and facile procedure for the preparation of 1-[2-(6,7-dimethyl-3,4-dihydronaphthalen-2-yl)ethyl]pyrrolidine hydrochloride
from 6,7-dimethyl-1,2,3,4-tetrahydronaphtalen-1-one in four steps is proposed. It includes one-step synthesis of 1-(6,7-dimethyl-1,2,3,4-tetrahydronaphthalen-2-yl)acetic
acid as key intermediate and subsequent transformations of functional groups therein.
Published in Russian in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 3, pp. 449–453.
The text was submitted by the authors in English. 相似文献
95.
96.
Benjamin A. Chalmers Hui Xing Sevan Houston Charlotte Clark Sussan Ghassabian Andy Kuo Benjamin Cao Andrea Reitsma Cody‐Ellen P. Murray Jeanette E. Stok Glen M. Boyle Carly J. Pierce Stuart W. Littler David A. Winkler Paul V. Bernhardt Cielo Pasay James J. DeVoss James McCarthy Peter G. Parsons Gimme H. Walter Maree T. Smith Helen M. Cooper Susan K. Nilsson John Tsanaktsidis G. Paul Savage Craig M. Williams 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(11)
97.
Lo AY Sudarsan V Sivakumar S van Veggel F Schurko RW 《Journal of the American Chemical Society》2007,129(15):4687-4700
Multinuclear solid-state NMR spectroscopy and powder X-ray diffraction (XRD) experiments are applied to comprehensively characterize a series of pure and lanthanide-doped LaF3 nanoparticles (NPs) that are capped with di-n-octadectyldithiophosphate ligands (Ln3+ = diamagnetic Y3+ and Sc3+ and paramagnetic Yb3+ ions), as well as correlated bulk microcrystalline materials (LaF3, YF3, and ScF3). Solid-state 139La and 19F NMR spectroscopy of bulk LaF3 and the LaF3 NPs reveal that the inorganic core of the NP retains the LaF3 structure at the molecular level; however, inhomogeneous broadening of the NMR powder patterns arises from distributions of 139La and 19F NMR interactions, confirming a gradual change in the La and F site environments from the NP core to the surface. 139La and 19F NMR experiments also indicate that low levels (5 and 10 mol %) of Ln3+ doping do not significantly change the LaF3 structure in the NP core. Similar doping levels of paramagnetic Yb3+ ions severely broaden 19F resonances, but only marginally effect 139La powder patterns, suggesting that the dopant ions are uniformly distributed throughout the NP core and occupy vacant La sites. Measurements of 139La T1 and T2 relaxation constants are seen to vary between the bulk material and NPs and between samples with diamagnetic and paramagnetic dopants. 45Sc NMR experiments confirm that the dopants are integrated into the La sites of the LaF3 core. Solid-state 1H and 31P magic-angle spinning (MAS) NMR spectra aid in probing the nature of the capping ligands and their interactions at the NP surface. 31P cross-polarization (CP)/MAS NMR experiments identify not only the dithiophosphate head groups but also thiophosphate and phosphate species which may form during NP synthesis. Finally, 19F-31P CP/MAS and 1H MAS experiments confirm that ligands are coordinated to the NP surface. 相似文献
98.
Mussone PG Ip AW Schroeder SL Murray BS Miller AF 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3766-3773
The collapse of Langmuir monolayers of poly(vinyl stearate) (PVS) at the air-water interface has been investigated by combined measurements of the surface pressure-area isotherms and Brewster angle microscopy (BAM). Atomic force microscopy (AFM) has been used to gain out-of-plane structural information on collapsed films transferred onto a solid substrate by a modified version of the inverse Langmuir-Schaefer deposition method. At high areas per monomer repeat unit, BAM imaging revealed that the films are heterogeneous, with large solidlike domains (25-200 mum in diameter) coexisting with liquidlike domains. Upon film compression, the domains coalesced to form a homogeneous monolayer before the film collapsed at constant pressure, forming irreversible three-dimensional (3D) structures. BAM images showed that two 3D structures coexisted: buckles of varying width extending across the surface and perpendicular to the direction of the compression and dotted islandlike structures. Upon expansion, the film fractured and both 3D protrusions persisted, explaining the marked hysteresis recorded in the Langmuir isotherms. Experiments with AFM confirmed the 3D nature of both protrusions and revealed that many buckles contain substructures corresponding to narrow buckles whose heights are a multiple of a single bilayer. Additionally, many multilayer islands with diameters spanning from 0.2 mum to over 3.5 mum were characterized by varying heights between 2 nm and up to over 50 nm. The key to the formation of the irreversible 3D structures is the presence of large inhomogeneities in the PVS monolayer, and a generalized phenomenological model is proposed to explain the collapse observed. 相似文献
99.
Kusumo A Bombalski L Lin Q Matyjaszewski K Schneider JW Tilton RD 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4448-4454
Surface plasmon resonance was used to measure binding of proteins from solution to poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes end-grafted from gold surfaces by atom transfer radical polymerization (ATRP). PDMAEMA brushes were prepared with a variety of grafting densities and degrees of polymerization. These brushes displayed charge selective protein uptake. The extent of uptake for net negatively charged bovine serum albumin (BSA) scaled linearly with the surface mass concentration of grafted PDMAEMA, regardless of grafting density. BSA was bound at a constant ratio of 120 DMAEMA monomer units per protein molecule for all brushes examined. The equivalent three-dimensional concentration of BSA bound in the brush (i.e., the bound BSA surface excess concentration divided by the brush thickness) decreased monotonically with decreasing grafting density. The concentration of BSA bound within brushes prepared at higher grafting densities was comparable with the aqueous protein solubility limit. BSA desorption from the brush required changes in solution pH and/or ionic strength to eliminate its net electrostatic attraction to PDMAEMA. Net positively charged lysozyme was completely rejected by the PDMAEMA brushes. 相似文献
100.
Direct conjugation of semiconductor nanocrystals to a globular protein to study protein-folding intermediates 总被引:2,自引:0,他引:2
Sarkar R Narayanan SS Pålsson LO Dias F Monkman A Pal SK 《The journal of physical chemistry. B》2007,111(42):12294-12298
In this Article, we study the development of semiconductor nanocrystals (quantum dots of average diameter less than 2 nm) directly conjugated to a transporter protein human serum albumin (HSA) as fluorescent biological labels. F?rster resonance energy transfer (FRET) from the amino acid tryptophan (Trp214) to quantum dot in HSA is monitored to follow the local and global changes in the protein structure during thermal unfolding and refolding processes. This study is likely to attract widespread attention as a powerful tool for the study of protein folding. 相似文献