全文获取类型
收费全文 | 3364篇 |
免费 | 101篇 |
国内免费 | 16篇 |
专业分类
化学 | 2451篇 |
晶体学 | 36篇 |
力学 | 31篇 |
数学 | 126篇 |
物理学 | 837篇 |
出版年
2022年 | 24篇 |
2021年 | 23篇 |
2020年 | 35篇 |
2019年 | 54篇 |
2018年 | 23篇 |
2017年 | 25篇 |
2016年 | 57篇 |
2015年 | 58篇 |
2014年 | 65篇 |
2013年 | 144篇 |
2012年 | 171篇 |
2011年 | 168篇 |
2010年 | 105篇 |
2009年 | 100篇 |
2008年 | 180篇 |
2007年 | 162篇 |
2006年 | 183篇 |
2005年 | 147篇 |
2004年 | 168篇 |
2003年 | 137篇 |
2002年 | 114篇 |
2001年 | 86篇 |
2000年 | 67篇 |
1999年 | 45篇 |
1998年 | 30篇 |
1997年 | 34篇 |
1996年 | 54篇 |
1995年 | 51篇 |
1994年 | 35篇 |
1993年 | 46篇 |
1992年 | 55篇 |
1991年 | 41篇 |
1990年 | 31篇 |
1989年 | 37篇 |
1988年 | 42篇 |
1987年 | 36篇 |
1986年 | 24篇 |
1985年 | 72篇 |
1984年 | 61篇 |
1983年 | 41篇 |
1982年 | 49篇 |
1981年 | 42篇 |
1980年 | 37篇 |
1979年 | 36篇 |
1978年 | 38篇 |
1977年 | 38篇 |
1976年 | 33篇 |
1975年 | 31篇 |
1973年 | 29篇 |
1966年 | 17篇 |
排序方式: 共有3481条查询结果,搜索用时 0 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.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
3.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
4.
A pressure sensitive paint (PSP) measurement has been known as a pressure field measurement technique based on the oxygen quenching phenomenon of luminescence of specific luminophores. A PSP measurement was applied for pressure field measurement in a low-solidity circular cascade diffuser of a single-stage transonic centrifugal compressor with 5 in pressure ratio for HFC134a gas. The oxygen concentration was about 500 ppm. Ru (bath-phen) was adsorbed on a silica-gel thinlayer chromatography sheet, and the sheet was pasted onto the side-wall between the cascade vanes. A drastic change in luminescent intensity was recognized during a surge condition. Also the pressure variations based on luminescent intensity agreed well with the pressure fluctuations measured using a semiconductor pressure sensor with high-frequency-response. It was shown that a PSP measurement worked well to investigate the unsteady pressure fields in a circular cascade diffuser of a transonic centrifugal compressor. Moreover, the time response of PSP becomes clear as a problem to be overcome for the present. 相似文献
5.
6.
Takahiro Harada Per B. Zetterlund Bunichiro Yamada 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):597-607
The unsaturated dimer of methyl acrylate [CH2C(CO2CH3)CH2CH2CO2CH3, or MAD] was copolymerized with various monomers to prepare copolymers bearing the ω-unsaturated end group [CH2C(CO2CH3)CH2 ] arising from β fragmentation of the MAD propagating radical. Copolymerizations of MAD with cyclohexyl and n-butyl acrylate resulted in copolymers with ω-unsaturated end groups, and increasing the temperature up to 180 °C resulted in an increase in the rate of β fragmentation of MAD radicals relative to propagation. Only a small amount of unsaturated end groups was introduced by copolymerization with ethyl methacrylate (EMA), and the EMA content in the copolymer increased with temperature. These findings could be explained by the reversible addition of the poly(EMA) radical to MAD. The copolymerization with ethyl α-ethyl acrylate (EEA) did yield a copolymer containing unsaturated end groups with MAD units as part of the main chain, although the steric hindrance of the ethyl group suppressed homopropagation and crosspropagation of EEA, resulting in low polymerization rates. Therefore, the copolymerization of MAD with acrylic esters at high temperatures was noted as a convenient route for obtaining acrylate–MAD copolymers bearing unsaturated end groups at the ω end (macromonomer). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 597–607, 2004 相似文献
7.
Per B. Zetterlund Kazuki Miyake Kunihiro Goto Bunichiro Yamada 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2640-2650
A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (kadd) over 60–120 °C resulted in Eadd = 21.7 kJ mol?1 and Aadd = 2.18 × 106 M?1 s?1 and a very weak temperature dependence of the chain‐transfer constant (Eadd ≈ Ep). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as kf ≈ 39 s?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004 相似文献
8.
Yasumitsu Matsuo Takehiko Ijichi Hironori Yamada Junko Hatori Seiichiro Ikehata 《Central European Journal of Physics》2004,2(2):357-366
We have fabricated a field effect transistor (FET) based on an organic ferroelectric insulator and molecular conductor, and
investigated the electrical properties and memory effects on the PEN-FET. We have observed a drastic change in the drain current
at around the coercive electric fieldE
c
of the organic ferroelectric insulator in not only a FET (PEN-FET) based on a pentacene (PEN) film but also a FET (IPEN-FET)
based on an iodine doped PEN film. The magnitude of the change of the drain current for the IPEN-FET is 200 times larger than
that for the PEN-FET. It is expected from these results that the PEN-FET (especially the IPEN-FET) is an improvement in such
devices, since it operates at a low gate electric field accompanied by the appearance of the spontaneous polarization in the
organic ferroelectric insulator. In addition, we have found that the drain current for the PEN-FET does not return to the
initial drain current ofE
G
=0 V/cm for more than one week, even if the gate electric field is changed to 0 V/cm from 500 V/cm(>E
c
). From these results, it is suggested that the PEN-FET becomes a memory device. 相似文献
9.
10.
Hiroyasu Nishiguchi Hiroshi Yamada Masaru Ogura Tatsumi Ishihara Yusaku Takita 《Research on Chemical Intermediates》2003,29(7-9):755-760
The oxygen storage capacity of CeO2, Ce0.9Pr0.1O2, Pt?Rh/CeO2 and Pt?Rh/Ce0.9Pr0.1O2 was investigated by conventional GC pulse method and transient pulse techniques. It is shown that incorporation of PrOy into CeO2 matrix strongly promotes oxygen storage capacity (OSC) measured using the transient pulse technique. The improvement of OSC at low temperature is observed in Pt?Rh loaded onto CeO2 and Ce?Pr catalysts. 相似文献