全文获取类型
收费全文 | 1303篇 |
免费 | 22篇 |
国内免费 | 1篇 |
专业分类
化学 | 902篇 |
晶体学 | 11篇 |
力学 | 29篇 |
数学 | 56篇 |
物理学 | 240篇 |
无线电 | 88篇 |
出版年
2022年 | 8篇 |
2021年 | 8篇 |
2020年 | 15篇 |
2019年 | 19篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 17篇 |
2015年 | 21篇 |
2014年 | 20篇 |
2013年 | 54篇 |
2012年 | 57篇 |
2011年 | 71篇 |
2010年 | 53篇 |
2009年 | 50篇 |
2008年 | 62篇 |
2007年 | 72篇 |
2006年 | 75篇 |
2005年 | 77篇 |
2004年 | 63篇 |
2003年 | 57篇 |
2002年 | 62篇 |
2001年 | 19篇 |
2000年 | 23篇 |
1999年 | 22篇 |
1998年 | 18篇 |
1997年 | 17篇 |
1996年 | 25篇 |
1995年 | 15篇 |
1994年 | 22篇 |
1993年 | 13篇 |
1992年 | 20篇 |
1991年 | 12篇 |
1990年 | 14篇 |
1989年 | 17篇 |
1988年 | 14篇 |
1987年 | 14篇 |
1986年 | 14篇 |
1985年 | 29篇 |
1984年 | 12篇 |
1983年 | 15篇 |
1982年 | 7篇 |
1981年 | 18篇 |
1980年 | 6篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 9篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1967年 | 5篇 |
排序方式: 共有1326条查询结果,搜索用时 19 毫秒
91.
Caffeine (1,3,7-trimethylxanthine) is a chemical substance associated with everyday human life. In order to recognize caffeine in water, six water-soluble acyclic phane compounds composed of three aromatic rings were examined as artificial receptors. 1H NMR titration experiments revealed that 6,6′-[1,3-phenylenebis(carbonylimino)]bis-1,3-naphthalenedisulfonate had the highest binding ability for caffeine, with a binding constant (Kb) of 127±5 M−1 at 300 K. While this phane compound also formed a complex with theophylline (1,3-dimethylxanthine) at around half the value of the binding constant for caffeine (Kb=64±4 M−1), it showed weak or little complexation for adenosine, guanosine, inosine, and their 5′-phosphates (sodium salts of adenylic acid, guanylic acid, and inosinic acid). 相似文献
92.
Naokazu Kano Hideaki Miyake Keishi Sasaki Takayuki Kawashima 《Heteroatom Chemistry》2015,26(2):183-186
The Si Si bond of a pentacoordinated disilicate was readily cleaved by treatment with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone in the presence of sodium carbonate under mild conditions. The bond cleavage did not proceed under the same conditions after conversion of the disilicate into the corresponding monoanionic silylsilicate and neutral disilane by protonation. The difference in the charges of the Si Si bond compounds affects the reactivity toward an oxidant, resulting in the Si Si bond cleavage, considering that all of these compounds have a bond between pentacoordinated silicon atoms. 相似文献
93.
Rate constant measurements for initial addition reactions of radicals at the propagation step of photo‐polymerization as studied by pulsed EPR spectroscopy
下载免费PDF全文
![点击此处可从《Journal of Physical Organic Chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yusuke Miyake Yutaka Marushima Hirona Takahashi Nobuyuki Akai Kazuhiko Shibuya Akio Kawai 《Journal of Physical Organic Chemistry》2016,29(9):468-475
Pulsed EPR spectroscopy was employed to determine reaction rate constants at an early stage of addition reactions in radical polymerizations triggered by four initiator radicals, which were generated by photodissociation of four parent molecules. Two monomers (tert‐butylacrylate and tert‐butylmethacrylate) were examined as reactant. Stern–Volmer analysis on the measured decay time of electron spin echo intensity of reacting radicals provides rate constants for addition reactions. We focused on rate constants for the second step reaction between monomer and adduct radical that is produced by the first step addition reaction between initiator radical and monomer. The rate constant measured by pulsed EPR was evaluated by theoretical calculations in the light of (1) enthalpy difference between product radical and reactants and (2) charge transfer interaction between reacting radical and monomer. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
94.
We propose an efficient quantum key distribution protocol based on the photon-pair generation from parametric down-conversion (PDC). It uses the same experimental setup as the conventional protocol, but a refined data analysis enables detection of photon-number splitting attacks by utilizing information from a built-in decoy state. Assuming the use of practical detectors, we analyze the unconditional security of the new scheme and show that it improves the secure key generation rate by several orders of magnitude at long distances, using a high intensity PDC source. 相似文献
95.
Yoshiki K Kanamaru R Ryosuke K Hashimoto M Hashimoto N Araki T 《Optics letters》2007,32(12):1680-1682
We developed a compact polarization-mode converter for microscopy to control three-dimensional polarization at the focus. The converter consisted of two homogeneously aligned liquid-crystal spatial light modulators with eight independently controllable electrodes (segments), and a quarter-waveplate. The converter converted a linearly polarized beam to three polarization modes: two orthogonal linear polarizations and a pseudo-radial polarization. We applied the converter to second-harmonic-generation microscopy and demonstrated the detection of three-dimensional molecular orientation. 相似文献
96.
Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C60 to Afford Efficient Photodriven Charge Separation
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Mustafa Supur Yuki Kawashima Dr. Karina R. Larsen Dr. Kei Ohkubo Prof. Jan O. Jeppesen Prof. Shunichi Fukuzumi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):13976-13983
Inclusion complexes of benzo‐ and dithiabenzo‐crown ether functionalized monopyrrolotetrathiafulvalene (MPTTF) molecules were formed with Li+@C60 ( 1? Li+@C60 and 2? Li+@C60). The strong complexation has been quantified by high binding constants that exceed 106 M ?1 obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6‐311G(d,p) level, the orbital interactions between the crown ether moieties and the π surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation. Interestingly, complexation of Li+@C60 with crown ethers accelerates the intersystem crossing upon photoexcitation of the complex, thereby yielding 3(Li+@C60)*, when no charge separation by means of 1Li+@C60* occurs. Photoinduced charge separation by means of 3Li+@C60* with lifetimes of 135 and 120 μs for 1? Li+@C60 and 2? Li+@C60, respectively, and quantum yields of 0.82 in PhCN have been observed by utilizing time‐resolved transient absorption spectroscopy and then confirmed by electron paramagnetic resonance measurements at 4 K. The difference in crown ether structures affects the binding constant and the rates of photoinduced electron‐transfer events in the corresponding complex. 相似文献
97.
Kei Fujise Eiji Tsurumaki Gaku Fukuhara Nobuyuki Hara Yoshitane Imai Shinji Toyota 《化学:亚洲杂志》2020,15(16):2456-2461
Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol?1 cm?1) and CPL (|glum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations. 相似文献
98.
Nobuyuki Tanaka 《Macromolecular Symposia》1996,102(1):429-431
The possibility of porosity control in N6/N66 membranes prepared from N6/N66 blend solutions of calcium chloride – methanol mixture was investigated. For N6/N66 blend solutions at 10 °C and 20 °C, the four-phase structure of solid, gel 1, gel 2 and solution was observed clearly in the pore formation process after adding water on a solution surface. In the boundary part between gel 1 and gel 2, the phase separation of N6 and N66 was predicted. The macroscopic pores of blend membranes prepared at 10°C and 20 °C were almost spherical. 相似文献
99.
Jun Koyanagi Keita Takeguchi Kazuki Murai Hirokazu Furue Nobuyuki Masuda 《Molecular Crystals and Liquid Crystals》2017,656(1):54-65
Blue-phase liquid crystals form three-dimensional structures in a self-organizing manner and are similar to living tissue structures such as the teeth of mice and collagen tissues. This study presents numerical results regarding the conditions under which blue-phase liquid crystals occur. The Monte Carlo simulations are performed by employing an improved Lennard–Jones potential that considers anisotropy and chirality. The conditions for the formation of the blue phase, which vary with respect to the chirality, are examined first. The relationship between the anisotropic parameters and the chiral parameter for the formation of the blue phase is discussed. Identical blue-phase structures are obtained, even when the cell size and molecular number are varied drastically. This discussion is useful for considering the scale-up problem, which is almost always a difficult issue for molecular-scale simulations. 相似文献
100.
J. Kawanaka Y. Takeuchi A. Yoshida S. J. Pearce R. Yasuhara T. Kawashima H. Kan 《Laser Physics》2010,20(5):1079-1084
A MOPA laser system for high pulse energy and high average power has been developed by using a cryogenic Yb:YAG. In the regenerative
amplifier with our original TRAM architecture, the high pulse energies of 6.5 and 1.5 mJ were obtained at the repetition rate
of 200 Hz and 1 kHz, respectively. An optical efficiency was as high as ηo-o = 9.3% with an excellent beam quality of M
2 < 1.1, which ensured that a cryogenic Yb:YAG TRAM had a high thermal strength. The following four pass power amplifier with
a cryogenic Yb:YAG rod showed 140 mJ at 100 Hz. Both a high optical efficiency of ηo-o = 30% and a high slope efficiency of ηs = 44% showed that an efficient laser operation could be realized for a power amplification with both a high pulse energy
and a high average power by using a cryogenic Yb:YAG. 相似文献