全文获取类型
收费全文 | 29384篇 |
免费 | 3790篇 |
国内免费 | 3146篇 |
专业分类
化学 | 21686篇 |
晶体学 | 621篇 |
力学 | 870篇 |
综合类 | 187篇 |
数学 | 731篇 |
物理学 | 12225篇 |
出版年
2024年 | 60篇 |
2023年 | 281篇 |
2022年 | 540篇 |
2021年 | 812篇 |
2020年 | 1047篇 |
2019年 | 1044篇 |
2018年 | 920篇 |
2017年 | 1141篇 |
2016年 | 1522篇 |
2015年 | 1378篇 |
2014年 | 1626篇 |
2013年 | 2915篇 |
2012年 | 2148篇 |
2011年 | 2205篇 |
2010年 | 1781篇 |
2009年 | 2026篇 |
2008年 | 1907篇 |
2007年 | 2031篇 |
2006年 | 1742篇 |
2005年 | 1426篇 |
2004年 | 1297篇 |
2003年 | 1112篇 |
2002年 | 1120篇 |
2001年 | 607篇 |
2000年 | 534篇 |
1999年 | 432篇 |
1998年 | 400篇 |
1997年 | 313篇 |
1996年 | 272篇 |
1995年 | 297篇 |
1994年 | 258篇 |
1993年 | 200篇 |
1992年 | 197篇 |
1991年 | 123篇 |
1990年 | 86篇 |
1989年 | 70篇 |
1988年 | 79篇 |
1987年 | 72篇 |
1986年 | 46篇 |
1985年 | 40篇 |
1984年 | 44篇 |
1983年 | 21篇 |
1982年 | 34篇 |
1981年 | 24篇 |
1980年 | 16篇 |
1979年 | 23篇 |
1978年 | 12篇 |
1977年 | 10篇 |
1974年 | 7篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
High‐Energy Long‐Lived Mixed Frenkel–Charge‐Transfer Excitons: From Double Stranded (AT)n to Natural DNA 下载免费PDF全文
Dr. Ignacio Vayá Dr. Johanna Brazard Dr. Miquel Huix‐Rotllant Dr. Arun K. Thazhathveetil Prof. Frederick D. Lewis Dr. Thomas Gustavsson Prof. Dr. Irene Burghardt Dr. Roberto Improta Dr. Dimitra Markovitsi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4904-4914
The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV‐induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine–thymine double‐stranded structures (AT)n. Fluorescence measurements on (AT)n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale. Time‐dependent (TD)‐DFT calculations, performed for two base pairs and exploring various relaxation pathways, allow the assignment of this emission band to excited states resulting from mixing between Frenkel excitons and adenine‐to‐thymine charge‐transfer states. Emission from such high‐energy long‐lived mixed (HELM) states is in agreement with their fluorescence anisotropy (0.03), which is lower than that expected for π–π* states (≥0.1). An increase in the size of the system quenches π–π* fluorescence while enhancing HELM fluorescence. The latter process varies linearly with the hypochromism of the absorption spectra, both depending on the coupling between π–π* and charge‐transfer states. Subsequently, we identify the common features between the HELM states of (AT)n structures with those reported previously for alternating (GC)n: high emission energy, low fluorescence anisotropy, nanosecond lifetimes, and sensitivity to conformational disorder. These features are also detected for calf thymus DNA in which HELM states could evolve toward reactive π–π* states, giving rise to delayed fluorescence. 相似文献
72.
Ao‐kai Zhang Jun Ling Kewen Li Guo‐dong Fu Tasuku Nakajima Takayuki Nonoyama Takayuki Kurokawa Jian Ping Gong 《Journal of Polymer Science.Polymer Physics》2016,54(13):1227-1236
In this study, controlled amount of dangling ends is introduced to the two series of poly(ethylene glycol)‐based hydrogel networks with three and four crosslinking functionality by using click chemistry. The structure of the gels with regulated defect percentage is confirmed by comparing the results of low‐field NMR characterization and Monte Carlo simulation. The mechanical properties of these gels were characterized by tensile stress–strain behaviors of the gels, and the results are analyzed by Gent model and Mooney–Rivlin model. The shear modulus of the swollen gels is found to be dependent on the functionality of the network, and decreases with the defect percentage. Furthermore, the value of shear modulus well obeys the Phantom model for all the gels with varied percentage of the defects. The maximum extension ratio, obtained from the fitting of Gent model, is also found to be dependent on the functionality of the network, and does not change with the defect percentage, except at very high defect percentage. The value of the maximum extension ratio is between that predicted from Phantom model and the Affine model. This indicates that at the large deformation, the fluctuation of the crosslinking points is suppressed for some extend but still exists. Polymer volume fractions at various defect percentages obtained from prediction of Flory–Rehner model are found to be in well agreement with the swelling experiment. All these results indicate that click chemistry is a powerful method to regulate the network structure and mechanical properties of the gels. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1227–1236 相似文献
73.
The electronic and adsorption properties of the pristine, Al-, Ga-, and Ge-doped BN nanotubes interacted with 5-fluorouracil molecule (5-FU) were theoretically investigated in the gas phase using the B3LYP density functional theory (DFT) calculations. It was found that the adsorption behavior of 5FU molecule on the pristine (8, 0) and (5, 5) BNNTs are electrostatic in nature. In contrast, the 5FU molecule (O-side) implies strong adsorption on the metal-doped BNNTs. Our results indicate that the Ga-doped presents high sensitivity and strong adsorption with the 5-FU molecule than the Al- and Ge-doped BNNTs. Therefore, it can be introduced as a carrier for drug delivery applications. 相似文献
74.
Li Zhang Dr. Julie Jung Dr. Peng Zhang Mei Guo Dr. Lang Zhao Prof. Dr. Jinkui Tang Prof. Dr. Boris Le Guennic 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1392-1398
Elaborate chemical design is of utmost importance in order to slow down the relaxation dynamics in single‐molecule magnets (SMMs) and hence improve their potential applications. Much interest was devoted to the study of distinct relaxation processes related to the different crystal fields of crystallographically independent lanthanide ions. However, the assignment of the relaxation processes to specific metal sites remains a challenging task. To address this challenge, a new asymmetric Dy2 SMM displaying a well‐separated two‐step relaxation process with the anisotropic centers in fine‐tuned local environments was elaborately designed. For the first time a one‐to‐one relationship between the metal sites and the relaxation processes was evidenced. This work sheds light on complex multiple relaxation and may direct the rational design of lanthanide SMMs with enhanced magnetic properties. 相似文献
75.
Ultrasmall Superparamagnetic Iron Oxide Nanoparticles with Europium(III) DO3A as a Bimodal Imaging Probe 下载免费PDF全文
Dr. Sophie Carron Dr. Maarten Bloemen Prof. Luce Vander Elst Prof. Sophie Laurent Prof. Thierry Verbiest Prof. Tatjana N. Parac‐Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4521-4527
A new prototype consisting of ultrasmall superparamagnetic iron oxide (USPIO) nanoparticles decorated with europium(III) ions encapsulated in a DO3A organic scaffold was designed as a platform for further development of bimodal contrast agents for MRI and optical imaging. The USPIO nanoparticles act as negative MRI contrast agents, whereas the europium(III) ion is a luminophore that is suitable for use in optical imaging detection. The functionalized USPIO nanoparticles were characterized by TEM, DLS, XRD, FTIR, and TXRF analysis, and a full investigation of the relaxometric and optical properties was conducted. The typical luminescence emission of europium(III) was observed and the main red emission wavelength was found at 614 nm. The relaxometric study of these ultrasmall nanoparticles showed r2 values of 114.8 mm ?1Fes?1 at 60 MHz, which is nearly double the r2 relaxivity of Sinerem®. 相似文献
76.
Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling
下载免费PDF全文
Dr. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
77.
Dr. Christianus M. A. Leenders Gijs Jansen Martijn M. M. Frissen René P. M. Lafleur Dr. Ilja K. Voets Dr. Anja R. A. Palmans Prof. Dr. E. W. Meijer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4608-4615
We introduce monosaccharides as versatile water‐soluble units to compatibilise supramolecular polymers based on the benzene‐1,3,5‐tricarboxamide (BTA) moiety with water. A library of monosaccharide‐based BTAs is evaluated, varying the length of the alkyl chain (hexyl, octyl, decyl and dodecyl) separating the BTA and saccharide units, as well as the saccharide units (α‐glucose, β‐glucose, α‐mannose and α‐galactose). In all cases, the monosaccharides impart excellent water compatibility. The length of the alkyl chain is the determining factor to obtain either long, one‐dimensional supramolecular polymers (dodecyl spacer), small aggregates (decyl spacer) or molecularly dissolved (octyl and hexyl) BTAs in water. For the BTAs comprising a dodecyl spacer, our results suggest that a cooperative self‐assembly process is operative and that the introduction of different monosaccharides does not significantly change the self‐ assembly behaviour. Finally, we investigate the potential of post‐assembly functionalisation of the formed supramolecular polymers by taking advantage of dynamic covalent bond formation between the monosaccharides and benzoxaboroles. We observe that the supramolecular polymers readily react with a fluorescent benzoxaborole derivative permitting imaging of these dynamic complexes by confocal fluorescence microscopy. 相似文献
78.
79.
Readily Accessible and Predictable Naphthalene‐Based Two‐Photon Fluorophore with Full Visible‐Color Coverage 下载免费PDF全文
Ja Young Koo Cheol Ho Heo Dr. Young‐Hee Shin Dahahm Kim Dr. Chang Su Lim Prof. Dr. Bong Rae Cho Prof. Dr. Hwan Myung Kim Prof. Dr. Seung Bum Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14166-14170
Herein we report 22 acedan‐derived, two‐photon fluorophores with synthetic feasibility and full coverage of visible wavelength emission. The emission wavelengths were predicted by computational analysis, which enabled us to visualize multicolor images by two‐photon excitation with single wavelength, and to design a turn‐on, two‐photon fluorescence sensor for endogenous H2O2 in Raw 264.7 macrophage and rat brain hippocampus ex vivo. 相似文献
80.
Inside Back Cover: Weak Ligand‐Field Effect from Ancillary Ligands on Enhancing Single‐Ion Magnet Performance (Chem. Eur. J. 36/2016) 下载免费PDF全文