全文获取类型
收费全文 | 925篇 |
免费 | 35篇 |
专业分类
化学 | 672篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 29篇 |
物理学 | 234篇 |
出版年
2021年 | 15篇 |
2019年 | 11篇 |
2018年 | 8篇 |
2016年 | 23篇 |
2015年 | 28篇 |
2014年 | 15篇 |
2013年 | 44篇 |
2012年 | 45篇 |
2011年 | 62篇 |
2010年 | 29篇 |
2009年 | 34篇 |
2008年 | 62篇 |
2007年 | 41篇 |
2006年 | 42篇 |
2005年 | 41篇 |
2004年 | 37篇 |
2003年 | 45篇 |
2002年 | 31篇 |
2001年 | 22篇 |
2000年 | 18篇 |
1999年 | 12篇 |
1998年 | 5篇 |
1997年 | 11篇 |
1996年 | 9篇 |
1995年 | 12篇 |
1994年 | 15篇 |
1993年 | 12篇 |
1992年 | 16篇 |
1991年 | 8篇 |
1990年 | 12篇 |
1989年 | 7篇 |
1988年 | 8篇 |
1987年 | 10篇 |
1986年 | 4篇 |
1985年 | 14篇 |
1984年 | 9篇 |
1983年 | 14篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 12篇 |
1979年 | 13篇 |
1978年 | 12篇 |
1977年 | 8篇 |
1976年 | 13篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 7篇 |
1970年 | 4篇 |
1968年 | 5篇 |
1964年 | 4篇 |
排序方式: 共有960条查询结果,搜索用时 26 毫秒
1.
Meccanica - The static deformation of symmetric bow limbs has been widely studied in the last century. However, asymmetries in shape and length which correspond to a more realistic situation, have... 相似文献
2.
Emiko Igarashi Kenta Sakamoto Tomoyuki Yoshimura Jun-ichi Matsuo 《Tetrahedron letters》2019,60(1):13-15
Various 3-phenylcyclobutanones reacted with aliphatic and aromatic nitriles in the presence of Me3SiOTf to afford dihydropyridones by formal [4+2] cycloaddition. 相似文献
3.
Dr. Motoki Toganoh Hideaki Matsuo Ayumi Sato Prof. Hiroyuki Furuta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8316-8322
Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp2] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles. 相似文献
4.
Dr. Neil J. Stewart Hitomi Nakano Shuto Sugai Mitsushi Tomohiro Yuki Kase Yoshiki Uchio Dr. Toru Yamaguchi Yujirou Matsuo Dr. Tatsuya Naganuma Dr. Norihiko Takeda Dr. Ikuya Nishimura Dr. Hiroshi Hirata Dr. Takuya Hashimoto Dr. Shingo Matsumoto 《Chemphyschem》2021,22(10):915-923
Hyperpolarized [1-13C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-13C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-13C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-13C]fumarate at sufficient 13C polarization for ex vivo detection of hyperpolarized 13C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo 13C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis. 相似文献
5.
The present numerical study has dealt with the enhancement of latent heat Release by using plate type fins mounted on the vertical cooling surface in the rectangular vessel packed with molten salt as a latent heat storage material. It was found that the fin thickness and pitch exerted an influence on solidification heat transfer in a liquid layer of a nitric molten salt. The numerical results elucidated the flow pattern, velocity profile and heat transfer rate in the melted liquid layer. 相似文献
6.
7.
A great number of experimental data indicating shock wave/boundary layer interactions in internal or external supersonic flows
were reviewed to make clear the mechanism of the interaction and to decide the onset of shock-induced separation. The interesting
conclusions were obtained for the considerably wide range of flow geometries that the onset of separation is independent of
the flow geometries and the boundary layer Reynolds number. It is found that the pressure rise necessary to separate the boundary
layer in supersonic external flows could be applied to such internal flows as overexpanded nozzles or diffusers. This is due
to the fact that the separation phenomenon caused by shock wave/boundary layer interactions is processed through a supersonic
deceleration. The shock-induced separation in almost all of interacting flow fields is governed by the concept of free interaction,
and the onset of shock-induced separation is only a function of the Mach number just upstream of shock wave. However, physical
scales of the produced separation are not independent of the downstream flow fields. 相似文献
8.
Takashi Yoshimoto Prof. Dr. Hisako Hashimoto Dr. Nozomi Takagi Prof. Dr. Shigeyoshi Sakaki Naoki Hayakawa Dr. Tsukasa Matsuo Prof. Dr. Hiromi Tobita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3795-3798
A tungsten silylyne complex having a W≡Si triple bond reacted with two molecules of aldehydes at room temperature to give W−Si−O−C four-membered metallacycles by [2+2] cycloaddition and subsequent formyl hydrogen transfer from one aldehyde molecule to another. Upon heating to 70 °C, the four-membered metallacycles underwent metathesis-like fragmentation cleanly to afford carbyne complexes and “silanoic esters,” in a manner similar to that of metallacyclobutadiene, an intermediate of alkyne metathesis reactions, and dimerization of the latter products gave 1,3-cyclodisiloxanes. The “silanoic ester” was also trapped by pivalaldehyde to give a [2+2] cycloaddition product in high yield. 相似文献
9.
Proton Order–Disorder Phenomena in a Hydrogen‐Bonded Rhodium–η5‐Semiquinone Complex: A Possible Dielectric Response Mechanism 下载免费PDF全文
Dr. Minoru Mitsumi Kazunari Ezaki Yuuki Komatsu Prof. Dr. Koshiro Toriumi Dr. Tatsuya Miyatou Prof. Dr. Motohiro Mizuno Nobuaki Azuma Prof. Dr. Yuji Miyazaki Prof. Dr. Motohiro Nakano Prof. Dr. Yasutaka Kitagawa Dr. Takayasu Hanashima Dr. Ryoji Kiyanagi Dr. Takashi Ohhara Prof. Dr. Kazuhiro Nakasuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9682-9696
A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η5‐semiquinone complex, [Cp*Rh(η5‐p‐HSQ‐Me4)]PF6 ([ 1 ]PF6; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6? ion. The relative permittivity εb′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of 13C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10?4–10?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]+ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η6‐hydroquinone complex, [Cp*Rh3+(η6‐p‐H2Q‐Me4)]2+ ([ 2 ]2+), and η4‐benzoquinone complex, [Cp*Rh+(η4‐p‐BQ‐Me4)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]2+ and [ 3 ], which would be generated in the H‐bonded chain. 相似文献
10.