全文获取类型
收费全文 | 1272篇 |
免费 | 42篇 |
国内免费 | 12篇 |
专业分类
化学 | 916篇 |
晶体学 | 12篇 |
力学 | 12篇 |
数学 | 75篇 |
物理学 | 311篇 |
出版年
2022年 | 5篇 |
2021年 | 14篇 |
2020年 | 15篇 |
2019年 | 21篇 |
2018年 | 12篇 |
2017年 | 10篇 |
2016年 | 24篇 |
2015年 | 17篇 |
2014年 | 43篇 |
2013年 | 62篇 |
2012年 | 61篇 |
2011年 | 73篇 |
2010年 | 47篇 |
2009年 | 47篇 |
2008年 | 71篇 |
2007年 | 78篇 |
2006年 | 56篇 |
2005年 | 60篇 |
2004年 | 62篇 |
2003年 | 61篇 |
2002年 | 38篇 |
2001年 | 29篇 |
2000年 | 32篇 |
1999年 | 16篇 |
1998年 | 11篇 |
1997年 | 14篇 |
1996年 | 20篇 |
1995年 | 5篇 |
1994年 | 25篇 |
1993年 | 19篇 |
1992年 | 26篇 |
1991年 | 14篇 |
1990年 | 17篇 |
1989年 | 18篇 |
1988年 | 10篇 |
1987年 | 19篇 |
1986年 | 12篇 |
1985年 | 17篇 |
1984年 | 12篇 |
1983年 | 7篇 |
1982年 | 12篇 |
1981年 | 20篇 |
1980年 | 10篇 |
1979年 | 14篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 12篇 |
1975年 | 6篇 |
1974年 | 8篇 |
1972年 | 4篇 |
排序方式: 共有1326条查询结果,搜索用时 71 毫秒
81.
Dr. Kazukuni Tahara Yuki Yamamoto Dr. Dustin E. Gross Hiroyoshi Kozuma Yoko Arikuma Dr. Koji Ohta Dr. Yoshiko Koizumi Yuan Gao Dr. Yo Shimizu Prof. Shu Seki Dr. Kenji Kamada Prof. Jeffrey S. Moore Prof. Yoshito Tobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11251-11260
We present herein the synthesis and properties of the largest hitherto unknown graphyne fragment, namely trigonally expanded tetrakis(dehydrobenzo[12]annulene)s (tetrakis‐DBAs). Intramolecular three‐fold alkyne metathesis reactions of hexakis(arylethynyl)DBAs 9 a and 9 b using Fürstner’s Mo catalyst furnished tetrakis‐DBAs 8 a and 8 b substituted with tert‐butyl or branched alkyl ester groups in moderate and fair yields, respectively, demonstrating that the metathesis reaction of this protocol is a powerful tool for the construction of graphyne fragment backbones. For comparison, hexakis(arylethynyl)DBAs 9 c – g have also been prepared. The one‐photon absorption spectrum of tetrakis‐DBA 8 a bearing tert‐butyl groups revealed a remarkable bathochromic shift of the absorption cut‐off (λcutoff) compared with those of previously reported graphyne fragments due to extended π‐conjugation. Moreover, in the two‐photon absorption spectrum, 8 a showed a large cross‐section for a pure hydrocarbon because of the planar para‐phenylene‐ethynylene conjugation pathways. Hexakis(arylethynyl)‐DBAs 9 c – e and 9 g and tetrakis‐DBA 8 b bearing electron‐withdrawing groups aggregated in chloroform solutions. Comparison between the free energies of 9 e and 8 b bearing the same substituents revealed the more favorable association of the latter due to stronger π–π interactions between the extended π‐cores. Polarized optical microscopy observations, DSC, and XRD measurements showed that 8 b and 9 e with branched alkyl ester groups displayed columnar rectangular mesophases. By the time‐resolved microwave conductivity method, the columnar rectangular phase of 8 b was shown to exhibit a moderate charge‐carrier mobility of 0.12 cm2 V?1 s?1. These results indicate that large graphyne fragments can serve as good organic semiconductors. 相似文献
82.
Prof. Takanori Suzuki Yuto Sakano Dr. Tomohiro Iwai Dr. Shinichi Iwashita Dr. Youhei Miura Dr. Ryo Katoono Prof. Hidetoshi Kawai Prof. Kenshu Fujiwara Prof. Yasushi Tsuji Prof. Takanori Fukushima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):117-123
When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 2+, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b 2+ and 2 c 2+, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 2+ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response. 相似文献
83.
Izuho Itoh Yoko Matsusaki Akitoshi Fujiya Norihiro Tada Tsuyoshi Miura Akichika Itoh 《Tetrahedron letters》2014
In this Letter, we report the aerobic photo-oxidative synthesis of diacylamines from benzylamides in the presence of molecular oxygen and catalytic amounts of 2-chloroanthraquinones under visible light irradiation from a fluorescent lamp. 相似文献
84.
Yoshiyuki Uchiyama Takahiro Hayasaka Noritaka Masaki Yoshiko Watanabe Kazuma Masumoto Tetsuji Nagata Fuminori Katou Mitsutoshi Setou 《Analytical and bioanalytical chemistry》2014,406(5):1307-1316
Most oral cancers are oral squamous cell carcinoma (OSCC). The anatomical features of OSCC have been histochemically evaluated with hematoxylin and eosin. However, the border between the cancer and stromal regions is unclear and large portions of the cancer and stromal regions are resected in surgery. To reduce the resected area and maintain oral function, a new method of diagnosis is needed. In this study, we tried to clearly distinguish the border on the basis of biomolecule distributions visualized by imaging mass spectrometry (IMS). In the IMS dataset, eleven signals were significantly different in intensity (p?<?0.01) between the cancer and stromal regions. Two signals at m/z 770.5 and m/z 846.6 were distributed in each region, and a clear border was revealed. Tandem mass spectrometric (MS/MS) analysis identified these signals as phosphatidylcholine (PC) (16:0/16:1) at m/z 770.5 in the cancer region and PC (18:1/20:4) at m/z 846.6 in the stromal region. Moreover, the distribution of PC species containing arachidonic acid in the stromal region suggests that lymphocytes accumulated in response to the inflammation caused by cancer invasion. In conclusion, the cancer and stromal regions of OSCCs were clearly distinguished by use of these PC species and IMS analysis, and this molecular identification can provide important information to elucidate the mechanism of cancer invasion. 相似文献
85.
One‐Pot Synthesis of 2,5‐Dihydropyrroles from Terminal Alkynes,Azides, and Propargylic Alcohols by Relay Actions of Copper,Rhodium, and Gold
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)
Prof. Dr. Tomoya Miura Takamasa Tanaka Kohei Matsumoto Prof. Dr. Masahiro Murakami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(49):16078-16082
Relay actions of copper, rhodium, and gold formulate a one‐pot multistep pathway, which directly gives 2,5‐dihydropyrroles starting from terminal alkynes, sulfonyl azides, and propargylic alcohols. Initially, copper‐catalyzed 1,3‐dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1‐sulfonyl‐1,2,3‐triazoles, which then react with propargylic alcohols under the catalysis of rhodium. The resulting alkenyl propargyl ethers subsequently undergo the thermal Claisen rearrangement to give α‐allenyl‐α‐amino ketones. Finally, a gold catalyst prompts 5‐endo cyclization to produce 2,5‐dihydropyrroles. 相似文献
86.
Yu Hoshino Shohei Taniguchi Hinata Takimoto Sotaro Akashi Sho Katakami Yusuke Yonamine Yoshiko Miura 《Angewandte Chemie (International ed. in English)》2020,59(2):679-683
Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences. 相似文献
87.
88.
Masanori Miura Takanori Koike Tsukasa Ishihara Fukushi Hirayama Shuichi Sakamoto Minoru Okada 《合成通讯》2013,43(24):3809-3820
A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na2CO3–toluene/H2O combination gave the highest yields. 相似文献
89.
90.
Hidenori Kinoshita Kazuki Yaguchi Takayuki Tohjima Katsukiyo Miura 《Tetrahedron letters》2017,58(16):1607-1610
The diisobutylaluminum hydride (DIBAL-H)-promoted benzocyclization, recently developed by this group, was adopted for the synthesis of a natural product containing a 9,10-dihydrophenanthrene skeleton to demonstrate its synthetic utility. One of the extracts from the roots of Salvia hydrangea DC. ex Bentham (Lamiaceae), a 20-norabietane derivative, was selected as the target molecule. The key step forming the 9,10-dihydrophenanthrene skeleton was achieved by the DIBAL-H-promoted cyclization of a silylated 1,3-dien-5-yne easily accessible from a substituted α-tetralone. 相似文献