全文获取类型
收费全文 | 437篇 |
免费 | 59篇 |
国内免费 | 9篇 |
专业分类
化学 | 363篇 |
晶体学 | 6篇 |
力学 | 2篇 |
数学 | 11篇 |
物理学 | 123篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2022年 | 11篇 |
2021年 | 17篇 |
2020年 | 13篇 |
2019年 | 20篇 |
2018年 | 19篇 |
2017年 | 19篇 |
2016年 | 26篇 |
2015年 | 20篇 |
2014年 | 33篇 |
2013年 | 16篇 |
2012年 | 41篇 |
2011年 | 39篇 |
2010年 | 21篇 |
2009年 | 21篇 |
2008年 | 37篇 |
2007年 | 18篇 |
2006年 | 14篇 |
2005年 | 14篇 |
2004年 | 12篇 |
2003年 | 14篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 9篇 |
1994年 | 6篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1973年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有505条查询结果,搜索用时 15 毫秒
1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity
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)
Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
2.
Yuta Yamamoto Shogo Nakano Fumio Seki Yasuteru Shigeta Sohei Ito Hiroaki Tokiwa Makoto Takeda 《Molecules (Basel, Switzerland)》2021,26(5)
Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility. 相似文献
3.
T.R. Saitoh N. Hashimoto G. Sletten R.A. Bark S. Törmänen M. Bergström K. Furuno K. Furutaka G.B. Hagemann T. Hayakawa T. Komatsubara A. Maj S. Mitarai M. Oshima J. Sampson T. Shizuma P.G. Varmette 《The European Physical Journal A - Hadrons and Nuclei》1998,3(3):197-199
High-spin states in 181Ta have been studied via the 176Yb(11B,α2n) reaction at 52 MeV using the PEX array and at 57 MeV using the NORDBALL array, with α-particle detection. The previously
known, Kπ=(7/2)+ ground state band and Kπ=(9/2)− band have been extended to spins (29/2)+ and (31/2)−, respectively. Two new one-quasiparticle bands, the Kπ=(5/2)+ band built on the known (5/2)+ isomer and a Kπ=((1/2)−) band have been observed. Two other rotational bands with three-quasiparticle structure, Kπ=(15/2)− and ((19/2)+ with π(7/2)[404]ν2(1/2)[510](9/2)[624] and π(9/2)[514]ν2(1/2)[510](9/2)[624] configurations, respectively, have been newly observed. The half-life of the Kπ=((19/2)+) bandhead which decays to the head of the (15/2)− band has been measured to be 140(36) ns. However, transitions from the ((19/2)+) state to the (15/2)− band have not been observed.
Received: 26 August 1998 相似文献
4.
Diamond-like carbon films prepared by pulsed-laser evaporation 总被引:1,自引:0,他引:1
T. Sato S. Furuno S. Iguchi M. Hanabusa 《Applied Physics A: Materials Science & Processing》1988,45(4):355-360
Diamond-like carbon thin films were prepared by pulsed-laser evaporation. In this method a carbon target was irradiated by a XeCl laser with a power density of 3×108 W/cm2 and carbon atoms, together with a small number of ions, were produced. Deposition rates and film properties changed sensitively with substrate temperature. The films deposited at 50°C were diamond-like, having reasonable hardness, high refractive index (2.1–2.2 at 633 nm), optical transparency in the infrared, electrical resistivity of 108 cm and chemical inertness (no dissolution in a HFHNO3 solution). The band gap measured from optical absorption was 1.4 eV. Raman spectrum and infrared absorption, whose features varied with the substrate temperature, were also measured. The films were amorphous and no crystallinity was observed, as confirmed by x-ray diffraction, transmission electron diffraction and Raman spectroscopy. Hydrogen atoms were incorporated in the films with a typical H/C ratio of 0.3. The application of a negative bias to the substrate modified the deposition due to the presence of ions. 相似文献
5.
6.
Abe K Abt I Ahn CJ Akagi T Ash WW Aston D Bacchetta N Baird KG Baltay C Band HR Barakat MB Baranko G Bardon O Barklow T Bazarko AO Ben-David R Benvenuti AC Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Cassell R Castaldi R Castro A Cavalli-Sforza M Church E Cohn HO Coller JA Cook V Cotton R Cowan RF Coyne DG D'Oliveira A Damerell CJ Dasu S 《Physical review letters》1995,74(9):1512-1516
7.
Abe K Abt I Ahn CJ Akagi T Allen NJ Ash WW Aston D Baird KG Baltay C Band HR Barakat MB Baranko G Bardon O Barklow T Bazarko AO Ben-David R Benvenuti AC Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Cassell R Castaldi R Castro A Cavalli-Sforza M Church E Cohn HO Coller JA Cook V Cotton R Cowan RF Coyne DG D'Oliveira A Damerell CJ Daoudi M 《Physical review D: Particles and fields》1995,52(7):4240-4244
8.
Abe K Abt I Ash WW Aston D Bacchetta N Baird KG Baltay C Band HR Barakat MB Baranko G Bardon O Barklow T Bazarko AO Ben-David R Benvenuti AC Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Cassell R Castaldi R Castro A Cavalli-Sforza M Church E Cohn HO Coller JA Cook V Cotton R Cowan RF Coyne DG D'Oliveira A Damerell CJ Dasu S De Sangro R De Simone P 《Physical review D: Particles and fields》1994,50(9):5580-5590
9.
Yukihiro Shintani Keiji Hirako Masanori Motokawa Yoshihiko Takano Masahiro Furuno Hiroyoshi Minakuchi Mitsuyoshi Ueda 《Analytical sciences》2004,20(12):1721-1723
An interconnecting technique, the "PDMS connection method", for quartz microchips in a high-pressure system is presented. The connection between quartz microchips is an essential technology for modular microfluidic devices, such as microchip-HPLC. PDMS was applied to the seal material, being spread on the seal side of the chips, and set into the metal housing. The characteristics of the PDMS connection method concerning pressure resistance and the extension of the peak were examined. The experimental results showed a good seal at 5 MPa, which seem to be sufficient for realizing microchip-HPLC utilizing a monolithic silica capillary column as a separation medium. The influence of the extra column effect on chromatographic separation was almost the same as in the case using a commercial union fitting. In addition, the PDMS connection enabled the detachability of chip-based modules with user-friendliness. Our experimental findings suggest that the novel PDMS connection method can possibly be applied as a generic technology in high-pressure microTAS. 相似文献
10.
Optically active sulfinylaziridines having a 4-methoxyphenyl group on their nitrogen atom were synthesized from optically active 1-chloroalkyl p-tolyl sulfoxide and an imine derived from benzaldehyde and p-anisidine stereoselectively in good overall yields. The sulfinylaziridines were treated with ethylmagnesium bromide or tert-butyllithium to afford aziridinylmagnesiums or aziridinyllithiums, respectively, in quantitative yields. Cross-coupling of the aziridinylmagnesiums with iodoalkanes in the presence of Cu(I) iodide gave tri-substituted aziridines in high yields from which enantiomerically pure β,β-disubstituted β-amino acid derivatives were synthesized. A β-amino acid derivative having deuterium at the stereogenic center was also realized by this method. On the other hand, from the aziridinyllithium, enantiomerically pure quaternary phenylalanine and quaternary aspartic acid derivatives were synthesized. 相似文献