全文获取类型
收费全文 | 670篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 582篇 |
晶体学 | 6篇 |
力学 | 4篇 |
数学 | 18篇 |
物理学 | 86篇 |
出版年
2023年 | 3篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 22篇 |
2019年 | 12篇 |
2018年 | 10篇 |
2017年 | 4篇 |
2016年 | 16篇 |
2015年 | 9篇 |
2014年 | 17篇 |
2013年 | 38篇 |
2012年 | 45篇 |
2011年 | 45篇 |
2010年 | 24篇 |
2009年 | 28篇 |
2008年 | 46篇 |
2007年 | 43篇 |
2006年 | 45篇 |
2005年 | 46篇 |
2004年 | 49篇 |
2003年 | 45篇 |
2002年 | 25篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 8篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 7篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1973年 | 1篇 |
1967年 | 2篇 |
排序方式: 共有696条查询结果,搜索用时 31 毫秒
41.
Abstract In this study, the formation of polyion complex micelles from a pair of poly(L-lysine) homopolymers (P(Lys)) and poly(ethylene glycol)-poly(aspartic acid) block copolymers (PEG-P(Asp)) with varying chain length was demonstrated in aqueous medium. There exists the lower critical chain length in the charged segments of both P(Lys) and PEG-P(Asp) to form stable polyion complex micelles in nanometric scale. The scaled average characteristic line width (ΓTK2) was independent on the detection angles for all combinations, suggesting that the formed polyion complex micelles may have a spherical shape. Furthermore, the transitional diffusion coefficient (DT) had no concentration dependence, indicating the micelle system was free from secondary aggregates (the cluster of micelles). It is of interest that the micellar size was almost constant (ca. 50 nm) regardless of the change in the chain length of the charged segments. Size distribution was extremely narrow, and the values of variance μ2/Γ 2) were always less than 0.1. Laser-Doppler electrophoresis measurements revealed that the polyion complex micelles were electrically neutral, suggesting that the PEG corona surrounding the polyion complex core may contribute to their stable dispersion in an aqueous medium through steric repulsion of the tethered hydrophilic chain, in this case, PEG. This system was considerably stable against the change in ionic strength, and it maintained a constant diameter in the region below 0.4 M NaCl. However, they dissociated under high ionic strength condition as 0.6 M NaCl. The system may have potential utility to include charged peptides and nucleotides in the core, delivering these biologically useful substances into a target site in the body. 相似文献
42.
An intramolecular aromatic oxidation of a phenolic compound with a hypervalent iodine reagent afforded the coupling product, in which the coupling took place at the para-position of the methoxy goup of the starting material instead of the desired para-position of the isopropenyl group, unfortunately. 相似文献
43.
Takayama K Arakida Y Dixit T Iwashita T Kono T Nakamura E Otsuka K Shimosaki Y Torikai K Wake M 《Physical review letters》2007,98(5):054801
We report an experimental demonstration of the induction synchrotron, the concept of which has been proposed as a future accelerator for the second generation of neutrino factory or hadron collider. The induction synchrotron supports a superbunch and a superbunch permits more charge to be accelerated while observing the constraints of the transverse space-charge limit. By using a newly developed induction acceleration system instead of radio-wave acceleration devices, a single proton bunch injected from the 500 MeV booster ring and captured by the barrier bucket created by the induction step voltages was accelerated to 6 GeV in the KEK proton synchrotron. 相似文献
44.
Frontispiece: Picket‐Fence Polythiophene and its Diblock Copolymers that Afford Microphase Separations Comprising a Stacked and an Isolated Polythiophene Ensemble 下载免费PDF全文
45.
Hiroyuki Muramatsu Kazunori Fujisawa Yong-Il Ko Kap-Seung Yang Takuya Hayashi Morinobu Endo Cheol-Min Yang Yong Chae Jung Yoong Ahm Kim 《催化学报》2014,35(6):864-868
Nanoscale defects in the outer tube to preserve the electrical and optical features of the inner tube can be engineered to exploit the intrinsic properties of double walled carbon nanotubes (DWCNTs) for various promising applications. We demonstrated a selective way to make defects in the outer tube by the fluorination of DWCNTs followed by the thermal detachment of the F atoms at 1000 °C in argon. Fluorinated DWCNTs with different amounts of F atoms were prepared by reacting with fluorine gas at 25, 200, and 400 °C that gave the stoichiometry of CF0.20, CF0.30, and CF0.43, respectively. At the three different temperatures used, we observed preservation of the coaxial morphology in the fluorinated DWCNTs. For the DWCNTs fluorinated at 25 and 200 °C, the strong radial breathing modes (RBMs) of the inner tube and weakened RBMs of the outer tube indicated selective fluorine attachment onto the outer tube. However, the disappearance of the RBMs in the Raman spectrum of the DWCNTs fluorinated at 400 °C showed the introduction of F atoms onto both inner and outer tubes. There was no significant change in the morphology and optical properties when the DWCNTs fluorinated at 25 and 200 °C were thermally treated at 1000 °C in argon. However, in the case of the DWCNTs fluorinated at 400 °C, the recovery of strong RBMs from the inner tube and weakened RBMs from the outer tube indicated the selective introduction of substantial defects on the outer tube while preserving the original tubular shape. The thermal detachment of F atoms from fluorinated DWCNTs is an efficient way to make highly defective outer tubes for preserving the electrical conduction and optical activity of the inner tubes. 相似文献
46.
Suzuka Kinoshita Ryota Yamano Dr. Yu Shibata Yusuke Tanaka Kyoichi Hanada Dr. Takashi Matsumoto Prof. Dr. Kazunori Miyamoto Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11113-11120
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties. 相似文献
47.
Masaki Kondo Junichiro Kanazawa Tomohiro Ichikawa Takumi Shimokawa Yuki Nagashima Kazunori Miyamoto Masanobu Uchiyama 《Angewandte Chemie (International ed. in English)》2020,59(5):1970-1974
The silaboration of [1.1.1]propellane enables direct introduction of B and Si functional groups onto the bicyclo[1.1.1]pentane (BCP) scaffold in high yield under mild, additive‐free conditions. The silaborated BCP can be obtained on a gram‐scale in a single step without the need for column‐chromatographic purification, and is storable and easy to handle, providing a versatile synthetic intermediate for BCP derivatives. We also describe various conversions of the C?B/C?Si bonds on the BCP scaffold, including development of a modified Suzuki–Miyaura cross‐coupling reaction at the highly sterically hindered bridgehead sp3 carbon center of the BCP skeleton using a combination of highly activated BCP boronic esters, copper(I) oxide, and a PdCl2(dppf) catalyst system. 相似文献
48.
Yulu Jiang Taro Ozaki Mei Harada Tadachika Miyasaka Hajime Sato Kazunori Miyamoto Junichiro Kanazawa Chengwei Liu Jun‐ichi Maruyama Masaatsu Adachi Atsuo Nakazaki Toshio Nishikawa Masanobu Uchiyama Atsushi Minami Hideaki Oikawa 《Angewandte Chemie (International ed. in English)》2020,59(41):17996-18002
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
49.
Yukio Nagasaki Kenji Kazama Eiichi Honzawa Masao Kato Kazunori Kataoka Teiji Tsuruta 《Macromolecular Symposia》1996,109(1):27-40
Reaction between dimethyldivinylsilane and 3,6-diazaoctane in the presence of 3-lithio-3,6-diazaoctane yields a new telechelic oligomer, poly(silamine), which consists of alternating 3,3-dimethyl-3-silapentane and N,N′-diethylethylenediamine units in the main chain. Poly(silamine) shows unique phase transition properties in response to the degree of protonation of amino groups in the polymer. Poly(silamine) also shows a strong interaction with several anions. Due to the interaction between poly(silamine) and anions along with the protonation of amino groups in the poly(silamine), the rubber elasticity of poly(silamine) is drastically changed. A discrete volume change can be observed when the environmental pH of the poly(silamine) gels is varied. This can be explained not only by a change in ionic osmotic pressure but also by a change in the rubber elasticity of the networks in the gel. 相似文献
50.