全文获取类型
收费全文 | 2660篇 |
免费 | 62篇 |
国内免费 | 20篇 |
专业分类
化学 | 2092篇 |
晶体学 | 29篇 |
力学 | 21篇 |
数学 | 95篇 |
物理学 | 505篇 |
出版年
2022年 | 20篇 |
2021年 | 25篇 |
2020年 | 22篇 |
2019年 | 33篇 |
2018年 | 33篇 |
2017年 | 17篇 |
2016年 | 32篇 |
2015年 | 36篇 |
2014年 | 49篇 |
2013年 | 142篇 |
2012年 | 113篇 |
2011年 | 150篇 |
2010年 | 71篇 |
2009年 | 72篇 |
2008年 | 157篇 |
2007年 | 148篇 |
2006年 | 139篇 |
2005年 | 151篇 |
2004年 | 118篇 |
2003年 | 106篇 |
2002年 | 105篇 |
2001年 | 62篇 |
2000年 | 57篇 |
1999年 | 48篇 |
1998年 | 28篇 |
1997年 | 24篇 |
1996年 | 38篇 |
1995年 | 40篇 |
1994年 | 32篇 |
1993年 | 19篇 |
1992年 | 40篇 |
1991年 | 36篇 |
1990年 | 30篇 |
1989年 | 30篇 |
1988年 | 29篇 |
1987年 | 38篇 |
1986年 | 28篇 |
1985年 | 54篇 |
1984年 | 54篇 |
1983年 | 26篇 |
1982年 | 34篇 |
1980年 | 27篇 |
1979年 | 33篇 |
1978年 | 31篇 |
1977年 | 24篇 |
1976年 | 20篇 |
1975年 | 22篇 |
1974年 | 18篇 |
1973年 | 11篇 |
1971年 | 17篇 |
排序方式: 共有2742条查询结果,搜索用时 46 毫秒
141.
Motoko S. Asano Sho Hashimoto Takuya Shinozuka Yasutaka Fushimi 《Molecular physics》2019,117(19):2664-2672
ABSTRACTInteraction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent. 相似文献
142.
Synthesis,Properties, and Redox Behavior of 1,1,4,4‐Tetracyano‐2‐ferrocenyl‐1,3‐butadienes Connected by Aryl,Biaryl, and Teraryl Spacers
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)
Dr. Taku Shoji Akifumi Maruyama Chisa Yaku Natsumi Kamata Prof. Dr. Shunji Ito Dr. Tetsuo Okujima Prof. Dr. Kozo Toyota 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):402-409
Aryl‐substituted 1,1,4,4‐tetracyano‐1,3‐butadienes (FcTCBDs) and bis(1,1,4,4‐tetracyanobutadiene)s (bis‐FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro‐electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis‐FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi‐electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 相似文献
143.
Hong Xia Yoshio Hashimoto Toru Morita Toshihiro Hirai 《Journal of Polymer Science.Polymer Physics》2014,52(13):887-892
Few solvents are capable of dissolving polyketones (PKs). 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (hexafluoroisopropanol, HFIP) is a better solvent than trifluoroethanol and m‐cresol. When HFIP was evaporated from a PK/HFIP solution, a porous cast‐film with a microparticle structure was formed because the isotactic PKs adopted a helical conformation, and convection during evaporation of the high polarity and low‐boiling‐point HFIP caused aggregation and rolling of the polymer molecules. The addition of plasticizer suppressed particle formation, improving the surface structure and mechanical properties of the film. In particular, the dielectric properties of the film improved significantly. This will enable PKs, which are rigid insulating materials, to be used as dielectric materials, broadening their range of applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 887–892 相似文献
144.
Yoshio Aso Shoji Nishiguchi Tetsuya Jigami Tetsuo Otsubo Fumio Ogura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):417-418
Several well-defined 3,4-thienylene-ethynylene oligomers with different chain lengths have been synthesized and characterized. X-Ray crystallographic analyses proved their unique, totally helical conformations. 相似文献
145.
Type I (α-) and II cleavages are two of the best known photochemical processes of alkanone.2 Extensive and intensive investigations have been done on both types of reactions in order to clarify the influence of structural changes on the reactivity, specificity, and efficiency of photoreactions of alkanones.3 The type I cleavage of medium-ring alkanones is believed to produce a radical pair, the fate of which will be determined by the ready formation of transition states for transfer of Ha, Hb, and recyclization. We now wish to report 相似文献
146.
Kisuke Tabata Naoya Jinno Keiichi Noda Masahiko Hashimoto Kazuhiko Tsukagoshi 《Chromatographia》2012,75(7-8):423-428
Tube radical distribution chromatography (TRDC) uses an untreated open tubular capillary tube and a ternary mixture of solvents (water and hydrophilic/hydrophobic organic solvents) as a carrier solution. A model analyte mixture comprising 1-naphthol, 1-naphthoic acid, 1-naphthalenesulfonic acid, 2,6-naphthalenedisulfonic acid, and 1,3,6-naphthalenetrisulfonic acid was examined by the TRDC and capillary zone electrophoresis (CZE) systems that comprised mainly a capillary tube and a detector. In the TRDC system the elution order of analytes could be changed by altering the component ratios of the solvents, whereas in the CZE system the elution order was changed by altering the electroosmotic flow direction. The experimental data obtained provide clues about the features and utility of TRDC as a new separation method. 相似文献
147.
148.
Sun-Chan Jeong Ichiro Katayama Hirokane Kawakami Yutaka Watanabe Hironobu Ishiyama Nobuaki Imai Yoshikazu Hirayama Hiroari Miyatake Masao Sataka Hiroyuki Sugai Satoru Okayasu Shin-Ichi Ichikawa Katsuhisa Nishio Shinichi Mitsuoka Takamitsu Nakanoya Takashi Hashimoto Takanori Hashimoto Masahito Yahagi 《Solid State Ionics》2009,180(6-8):626-630
The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of 8Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects. 相似文献
149.
K. Hirose M. Ejima T. Fujibayashi Y. Fujii K. Futatsukawa O. Hashimoto T. Ishikawa S. Kameoka H. Kanda F. Kato S. Kinoshita T. Kinoshita T. Kon O. Konno K. Maeda A. Matsumura Y. Miura F. Miyahara H. Miyase T. Nakabayashi S.N. Nakamura H. Nomura K. Nonaka A. Ohtani Y. Okayasu M. Oyamada A. Sasaki H. Shimizu T. Takahashi T. Tamae H. Tamura T. Terasawa H. Tsubota K. Tsukada D. Uchida M. Ukai M. Wakamatsu T. Watanabe H. Yamauchi H. Yamazaki K. Yawata 《Physics letters. [Part B]》2009
150.
Toyoji Kakuchi Toshifumi Satoh Junji Mata Satoshi Umeda Hisaho Hashimoto Kazuaki Yokota 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):325-336
Abstract The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF3OEt2 and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF3O-decyl2 comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl3, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs+ > Rb+ > K+ ? Na+ > Li+. The ratio of K+ and Na+, K+/Na+, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c. 相似文献