全文获取类型
收费全文 | 1103篇 |
免费 | 23篇 |
国内免费 | 6篇 |
专业分类
化学 | 878篇 |
晶体学 | 13篇 |
力学 | 1篇 |
数学 | 41篇 |
物理学 | 199篇 |
出版年
2023年 | 8篇 |
2020年 | 14篇 |
2019年 | 9篇 |
2018年 | 13篇 |
2017年 | 13篇 |
2016年 | 15篇 |
2015年 | 11篇 |
2014年 | 21篇 |
2013年 | 78篇 |
2012年 | 55篇 |
2011年 | 53篇 |
2010年 | 43篇 |
2009年 | 39篇 |
2008年 | 67篇 |
2007年 | 70篇 |
2006年 | 65篇 |
2005年 | 51篇 |
2004年 | 54篇 |
2003年 | 49篇 |
2002年 | 41篇 |
2001年 | 16篇 |
2000年 | 9篇 |
1999年 | 13篇 |
1998年 | 10篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 10篇 |
1991年 | 10篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 6篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1984年 | 18篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 19篇 |
1979年 | 15篇 |
1978年 | 18篇 |
1977年 | 10篇 |
1976年 | 11篇 |
1975年 | 14篇 |
1974年 | 13篇 |
1973年 | 17篇 |
1971年 | 5篇 |
1968年 | 6篇 |
排序方式: 共有1132条查询结果,搜索用时 125 毫秒
81.
82.
[reaction: see text] [60]Fullerenoacetyl chloride, one of the reactive derivatives of [60]fullerenoacetic acid, was isolated and identified for the first time. This acid chloride was easily synthesized in good yield from tert-butyl [60]fullerenoacetate through two steps. In the presence of 4-(dimethylamino)pyridine as a base, the acid chloride smoothly reacted with various alcohols under mild conditions to give the corresponding esters including [60]fullerene-biomolecule hybrids in moderate to high yields. 相似文献
83.
Recent theoretical advances have identified several computational algorithms that can be implemented utilizing quantum information
processing (QIP), which gives an exponential speedup over the corresponding (known) algorithms on conventional computers.
QIP makes use of the counter-intuitive properties of quantum mechanics, such as entanglement and the superposition principle.
Unfortunately it has so far been impossible to build a practical QIP system that outperforms conventional computers. Atomic
ions confined in an array of interconnected traps represent a potentially scalable approach to QIP. All basic requirements
have been experimentally demonstrated in one and two qubit experiments. The remaining task is to scale the system to many
qubits while minimizing and correcting errors in the system. While this requires extremely challenging technological improvements,
no fundamental roadblocks are currently foreseen. 相似文献
84.
Tetsuo Asaji Janez Seliger Veselko Žagar Hiroyuki Ishida 《Magnetic resonance in chemistry : MRC》2010,48(7):531-536
Proton transfer in hydrogen‐bonded organic co‐crystals of chloranilic acid with some organic bases was investigated by nuclear quadrupole resonance (NQR) spectroscopy. The 35Cl NQR frequencies of chloranilic acid molecule as well as 14N NQR frequencies of the organic base molecule were measured with the conventional pulse methods as well as double‐resonance methods, respectively. The extent of proton transfer in the O···H···N hydrogen bond was estimated from Townes–Dailey analysis of the 14N NQR parameters. The 35Cl NQR frequency and molecular geometry of chloranilic acid are correlated to the extent of proton transfer in the protonation process of the organic base molecule. It is shown that the hydrogen bond affects the π‐electron system of chloranilic acid. Geometry dependence of the O···H···N hydrogen bond, i.e. the H? N valence bond order versus the hydrogen‐bond geometry correlation is also discussed. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
85.
An acoustic field effectively affects chromatographic retention in some separation modes and, thus, can be a novel factor controlling retention. After being transmitted into the column, ultrasound energy is mostly converted into heat as a result of absorption by stationary and mobile phases. Thus, ultrasound brings about temperature increases. However, actual temperature increases measured by thermosensors are smaller than those calculated from chromatographic retention changes. In addition, larger ultrasound effects are observed in chromatographic modes involving ionic interactions. These results possibly imply that ultrasound directly influences ionic interactions involved in retention mechanisms. 相似文献
86.
Hiroki Uoyama Kil Suk Kim Dr. Kenji Kuroki Jae‐Yoon Shin Dr. Toshi Nagata Dr. Tetsuo Okujima Dr. Hiroko Yamada Dr. Noboru Ono Prof. Dongho Kim Prof. Hidemitsu Uno Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(13):4063-4074
Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ(2)) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways. 相似文献
87.
Tsuneyuki Sato Tsuyoshi Yamamoto Tetsuo Ogawa Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1519-1528
Poly[acryloyl-L-valine (ALV)] microspheres containing peroxy ester groups were prepared by radical copolymerization of ALV with a small amount of di-tert-butyl peroxyfumarate. When the microspheres were irradiated in the presence of second vinyl monomers, long-lived propagating radicals of the second monomers were formed in the microspheres by the reaction of microsphere polymer radicals with the monomers. The presence of a minute quantity of ethyl alcohol served to soften the microspheres and made the polymer radicals more mobile in the microspheres. As a result, sharper ESR spectra of the propagating radicals were observed although their lifetimes became shorter. This microsphere method also yielded easily the stable propagating radicals of a-methylstyrene and 1,1-diphenylethylene which have no homopolymerizability in usual radical polymerization. When N-n-propyldimethacroylamide and N,N′-dimethyl-N,N′-dimethacroylhydrazine, which undergo cyclopolymerization, were used as second monomer, uncyclized polymer radicals were only observed. Some discussions were given on the propagation mechanism of the cyclopolymerization. 相似文献
88.
Hiroshi Onizuka Masaki Kato Tetsuo Shimura Wataru Sakamoto Toshinobu Yogo 《Journal of Sol-Gel Science and Technology》2008,46(1):107-115
Proton conductive inorganic–organic hybrid membranes were synthesized from dimethylethoxyvinylsilane (DMEVS), vinylphosphonic
acid (VPA) and 3-glycidoxypropyltrimethoxysilane (GPTMS) through copolymerization followed by sol–gel process. The ratio of
phosphorus to silicon in the copolymer almost corresponded to the charged molar ratio of VPA to DMEVS when the ratio of VPA
to DMEVS was below 1/2. Self-standing, homogeneous, highly transparent membranes were synthesized from DMEVS–VPA copolymer
and GPTMS via sol–gel condensation. Differential thermal analysis-thermogravimetry analyses indicated that these membranes
were thermally stable up to 200 °C. The results of Fourier transform infrared and 13C NMR revealed that phosphonic acid groups of VPA were chemically bound to organosiloxane network. The copolymerization and
condensation of (DMEVS–VPA)/GPTMS were confirmed by 31P and 29Si NMR spectra. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The membrane of (DMEVS–VPA)/GPTMS
showed a remarkable conductivity of 6.3 × 10−2 S cm−1 at 130 °C and 100% relative humidity. 相似文献
89.
Highly regio-selective cyanation of vicinal (Z)-dibromoalkenyl silanes was achieved by a vinylic Rosenmund-von Braun reaction, significantly suppressing side-production of alkyne. The alkyne was generated by a halogen elimination side-reaction that is an intrinsic problem in metal-activation of vicinal dihaloalkenes. We have studied to overcome the problem, and finally found the combination of CuCN and O = PPh3 in toluene solvent effectively controlled the production of byproducts. The resultant single isomer has significance in potentially application as a multi-tunable synthetic scaffold. 相似文献
90.
Hiroaki Aizawa Ken Hatano Hitoshi Saeki Nobuaki Honsho Tetsuo Koyama Koji Matsuoka Daiyo Terunuma 《Tetrahedron letters》2010,51(12):1545-6442
A new compound having a 2,3,4,5-tetraphenylsilole derivative on the center silicon of Dumbbell(1)6Gb3; Silole-Dumbbell(1)6Gb3 (1) was previously reported. It was found that 1 exhibited strongly increased fluorescence both in water and in a 96% acetone/water mixed solvent. The physical behavior of 1 in water and in the 96% acetone/water mixed solvent was investigated, and analyses including fluorescence quantum yields, dynamic-light-scattering (DLS), atomic-force-microscopy (AFM), and fluorescence microscopy were carried out. It was clarified that 1 dynamically formed different types of aggregates in water and in higher acetone concentrations to yield high aggregation-induced emission (AIE) effects due to the formation of micelle-like particles in water and inversion-type micelles in the acetone/water mixed solvent, respectively. 相似文献