全文获取类型
收费全文 | 1858篇 |
免费 | 39篇 |
国内免费 | 23篇 |
专业分类
化学 | 1492篇 |
晶体学 | 16篇 |
力学 | 15篇 |
数学 | 79篇 |
物理学 | 318篇 |
出版年
2023年 | 6篇 |
2021年 | 23篇 |
2020年 | 23篇 |
2019年 | 19篇 |
2018年 | 17篇 |
2017年 | 12篇 |
2016年 | 25篇 |
2015年 | 14篇 |
2014年 | 35篇 |
2013年 | 70篇 |
2012年 | 97篇 |
2011年 | 100篇 |
2010年 | 64篇 |
2009年 | 81篇 |
2008年 | 113篇 |
2007年 | 112篇 |
2006年 | 117篇 |
2005年 | 130篇 |
2004年 | 116篇 |
2003年 | 99篇 |
2002年 | 88篇 |
2001年 | 33篇 |
2000年 | 26篇 |
1999年 | 34篇 |
1998年 | 33篇 |
1997年 | 21篇 |
1996年 | 35篇 |
1995年 | 20篇 |
1994年 | 11篇 |
1993年 | 10篇 |
1992年 | 14篇 |
1991年 | 13篇 |
1989年 | 13篇 |
1988年 | 14篇 |
1987年 | 14篇 |
1986年 | 5篇 |
1985年 | 17篇 |
1984年 | 25篇 |
1983年 | 10篇 |
1982年 | 24篇 |
1981年 | 21篇 |
1980年 | 14篇 |
1979年 | 22篇 |
1978年 | 18篇 |
1977年 | 24篇 |
1976年 | 14篇 |
1975年 | 14篇 |
1974年 | 13篇 |
1973年 | 14篇 |
1971年 | 5篇 |
排序方式: 共有1920条查询结果,搜索用时 31 毫秒
101.
Tsuda O Ishihara M Koga Y Fujiwara S Setsuhara Y Sato N 《The journal of physical chemistry. B》2005,109(11):4917-4922
Three-dimensional plasma enhanced chemical vapor deposition (CVD) of hydrogenated amorphous carbon (a-C:H) has been demonstrated using a new type high-density volumetric plasma source with multiple low-inductance antenna system. The plasma density in the volume of phi 200 mm x 100 mm is 5.1 x 10(10) cm(-3) within +/-5% in the lateral directions and 5.2 x 10(10)cm(-3) within +/-10% in the axial direction for argon plasma under the pressure of 0.1 Pa and the total power as low as 400 W. The uniformity of the thickness and refractive index is within +/-3.5% and +/-1%, respectively, for the a-C:H films deposited on the substrates placed on the six side walls, the top of the phi 60 mm x 80 mm hexagonal substrate holder in the pure toluene plasma under the pressure is as low as 0.04 Pa, and the total power is as low as 300 W. It is also found that precisely controlled ion bombardment by pulse biasing led to the explicit observation in Raman and IR spectra of the transition from polymer-like structure to diamond-like structure accompanied by dehydrogenation due to ion bombardment. Moreover, it is also concluded that the pulse biasing technique is effective for stress reduction without a significant degradation of hardness. The stress of 0.6 GPa and the hardness of 15 GPa have been obtained for 2.0 microm thick films deposited with the optimized deposition conditions. The films are durable for the tribology test with a high load of 20 N up to more than 20,000 cycles, showing the specific wear rate and the friction coefficient were 1.2 x 10(-7) mm3/Nm and 0.04, respectively. 相似文献
102.
Yoshikuni Uchida Masao Yoshida Osamu Nishiara Kazunori Matsui 《Journal of Sol-Gel Science and Technology》2003,26(1-3):177-180
Silica gels doped with Cu2+ ions were prepared from the (3-aminopropyl) trimethoxysilane (APTMOS)/tetraethoxysilane (TEOS) systems. Sols showed a broad absorption peak at 640 nm, suggesting 3–5 coordination of the aminopropyl groups to Cu2+. For gels prepared from APTMOS and dried at room temperature, the 640 nm peak decreased and a red-shifted absorption appeared below 400 nm within a few months. The luminescence spectra of the xerogels showed emission bands at 430–470 and 510 nm. The former and latter bands are ascribed to Cu+ monomer and dimer emissions, respectively. These results indicate that Cu2+ ions are reduced to Cu+. When xerogels were prepared from APTMOS/TEOS = 1 (vol/vol), the color of xerogels was blue with an absorption peak at around 670 nm, indicating no reduction of Cu2+ ions. 相似文献
103.
Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)5]) was selected as a mediator for amperometric creatinine determination based on the reductive H2O2 detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)5] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O2. It is revealed that PVI[Fe(CN)5] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)5] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)5], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R2 = 0.993), respectively, and the sensitivity was 11 mA cm−2 M−1, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results. 相似文献
104.
105.
Isao Takahashi Fumika Morita Shunsuke Kusagaya Haruhiko Fukaya Osamu Kitagawa 《Tetrahedron: Asymmetry》2012,23(24):1657-1662
In the presence of an (R)-MOP-Pd2(dba)3 catalyst, the reaction of ortho-tert-butylaniline with 2-bromophenyl arylethynyl ketone proceeded via a tandem amination (1,4-addition of aniline to an ynone and subsequent intramolecular Buchwald–Hartwig amination) to afford axially chiral N-(2-tert-butylphenyl)-2-aryl-4-quinolinone derivatives with moderate enantioselectivity (up to 72% ee). 相似文献
106.
Asymmetric synthesis is one of the most important and valuable research fields in modern organic chemistry. Since the use of electricity as a traceless oxidant or reductant under electrochemical conditions, highly reactive intermediates can selectively generate under mild reaction conditions through more environmentally benign conditions compared with the reactions using common chemical oxidants or reductants. Thus, the merging electrochemistry with asymmetric catalysis would provide a unique and powerful approach for the synthesis of optically active compounds under oxidative or reductive conditions. Selected recent (2018–2020) examples of enantioselective electro-organic synthesis using transition metal catalysts or organocatalysts are summarized in this short review. These examples are divided to oxidative and reductive transformations and described together with brief reaction mechanisms. 相似文献
107.
Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes 下载免费PDF全文
Guo‐Ling Li Dr. Shinji Kanegawa Dr. Zi‐Shuo Yao Dr. Sheng‐Qun Su Shu‐Qi Wu Dr. You‐Gui Huang Dr. Soonchul Kang Prof. Dr. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17130-17135
Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π???π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π???π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B? 2H2O has a higher thermal relaxation temperature than that of 1A? 3H2O. 相似文献
108.
Nallusamy Venkatachalam Eva Hemmer Tomoyoshi Yamano Hiroshi Hyodo Hidehiro Kishimoto Kohei Soga 《Progress in Crystal Growth and Characterization of Materials》2012,58(2-3):121-134
Yttrium hydroxyl carbonate (Y(OH)CO3) precursors were synthesized by the homogeneous co-precipitation method in the presence of polyacrylic acid (PAAc). Resultant precursor particle size is about 15–20 nm with narrow size distribution whereas the particle size is smaller than those acquired by the conventional homogeneous precipitation method. Effective decrease of Y(OH)CO3 particle size was found to be higher for the presence of weak polyanionic ionomer such as PAAc than the presence of strong polyanionic ionomer such as sodium polystyrene sulfonate (PSS). It was observed that the morphology and size of the precursors are almost unchanged after the calcination process. Er3+ doped Y2O3 nanoparticles were synthesized by PAAc assisted homogeneous co-precipitation method showed bright green (550 nm) and red (660 nm) upconversion (UC) as well as near-infrared (NIR) fluorescence (1550 nm) under 980-nm excitation. UC and NIR fluorescence bioimaging and in-vitro cytotoxicity assay of Er3+ doped Y2O3 nanoparticles were successfully attempted with commercially available macrophages and B-cell hybridomas. Cellular uptake of nanoparticles is evidenced from bright field, UC and NIR fluorescence images of macrophages. 相似文献
109.
Masami Kuriyama Satoko Tanigawa Yuki Kubo Yosuke Demizu Osamu Onomura 《Tetrahedron: Asymmetry》2010,21(11-12):1370-1373
A facile synthetic method toward optically active 3,3-disubstituted oxindoles with excellent enantioselectivity was achieved using chiral copper-catalyzed desymmetrization of prochiral 1,3-diols. The monotosylated product was transformed into oxindole derivatives efficiently. 相似文献
110.
Yusuke Fukahori Yohei Takayama Takuya Imaoka Dr. Osamu Iwamoto Prof. Dr. Kazuo Nagasawa 《化学:亚洲杂志》2013,8(1):244-250
We present a diastereoselective synthesis of disubstituted cyclopentane 8 having a nitrogen‐containing quaternary carbon center, which is found in axinellamine A ( 5 ) and related compounds. During this work, we found that the 1,3‐dipolar cycloaddition product 24 immediately underwent intramolecular redox reaction at the newly formed morpholin‐2‐one moiety, thus affording disubstituted cyclopentane containing a tertiary amine ( 9 ) stereoselectively in good yield. The amine 9 was successfully converted into guanidine 31 , which corresponds to 8 , through iminium cation–enamine isomerization. 相似文献