全文获取类型
收费全文 | 1368篇 |
免费 | 21篇 |
国内免费 | 6篇 |
专业分类
化学 | 1122篇 |
晶体学 | 3篇 |
力学 | 24篇 |
数学 | 59篇 |
物理学 | 187篇 |
出版年
2023年 | 7篇 |
2022年 | 7篇 |
2021年 | 8篇 |
2020年 | 14篇 |
2019年 | 14篇 |
2017年 | 9篇 |
2016年 | 18篇 |
2015年 | 12篇 |
2014年 | 27篇 |
2013年 | 72篇 |
2012年 | 57篇 |
2011年 | 64篇 |
2010年 | 46篇 |
2009年 | 39篇 |
2008年 | 93篇 |
2007年 | 78篇 |
2006年 | 76篇 |
2005年 | 68篇 |
2004年 | 65篇 |
2003年 | 68篇 |
2002年 | 76篇 |
2001年 | 30篇 |
2000年 | 25篇 |
1999年 | 15篇 |
1998年 | 17篇 |
1997年 | 28篇 |
1996年 | 24篇 |
1995年 | 20篇 |
1994年 | 19篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 14篇 |
1990年 | 11篇 |
1989年 | 11篇 |
1988年 | 17篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 11篇 |
1984年 | 15篇 |
1983年 | 11篇 |
1982年 | 21篇 |
1981年 | 21篇 |
1980年 | 15篇 |
1979年 | 10篇 |
1978年 | 9篇 |
1977年 | 13篇 |
1976年 | 10篇 |
1975年 | 11篇 |
1974年 | 9篇 |
1968年 | 6篇 |
排序方式: 共有1395条查询结果,搜索用时 125 毫秒
101.
NMR and DFT studies on persistent carbocations derived from benzo[kl]xanthene,dibenzo[d,d′]benzo[1,2‐b:4,3‐b′]difuran,and dibenzo[d,d′]benzo[1,2‐b:4,5‐b′]difuran in superacidic media
下载免费PDF全文
![点击此处可从《Journal of Physical Organic Chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Takao Okazaki Madoka Nakagawa Takeshi Futemma Toshikazu Kitagawa 《Journal of Physical Organic Chemistry》2016,29(2):107-111
Persistent carbocations generated by the protonation of hetero‐polycyclic aromatic compounds with oxygen atom(s) were studied by experimental NMR and density function theory calculations. Benzo[kl]xanthene ( 1 ), dibenzo[d,d′]benzo[1,2‐b:4,3‐b′]difuran ( 2 ), and dibenzo[d,d′]benzo[1,2‐b:4,5‐b′]difuran ( 3 ) were synthesized by the annulation of arenediazonium salts. Compound 1 in FSO3H‐SbF5 (4:1)/SO2ClF and 3 in FSO3H‐SbF5 (1:1)/SO2ClF ionized to 1aH+ with protonation at C(4) and to 3aH+ with protonation at C(6), and these cations were successfully observed by NMR at low temperatures. The density function theory calculations indicated that 1aH+ and 3aH+ were the most stable protonated carbocations and that 2 should ionize to 2aH+ with protonation at C(6). According to the changes in 13C chemical shifts (Δδ13C), the positive charge was delocalized into the naphthalene unit for 1aH+ , into one benzo[b,d]furan unit for 2aH+ , and into one benzo[b,d]furan unit for 3aH+ . Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
102.
Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4+1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4+1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl- or methyl-substituted indolines. The synthesis of 3-trifluoromethyl indoles was also achieved described under stoichiometric conditions. 相似文献
103.
Noriyuki Yoshii Yoshimichi Andoh Susumu Okazaki 《Journal of computational chemistry》2020,41(9):940-948
We derived a new expression for the electrostatic interaction of three-dimensional charge-neutral systems with two-dimensional periodic boundary conditions (slab geometry) using a fast multipole method (FMM). Contributions from all the image cells are expressed as a sum of real and reciprocal space terms, and a self-interaction term. The reciprocal space contribution consists of two parts: zero and nonzero terms of the absolute value of the reciprocal lattice vector. To test the new expressions, electrostatic interactions were calculated for a randomly placed charge distribution in a cubic box and liquid water produced by molecular dynamics calculation. The accuracy could be controlled by the degree of expansion of the FMM. In the present expression, the computational complexity of the electrostatic interaction of N-particle systems is order N, which is superior to that of the conventional two-dimensional periodic Ewald method for a slab geometry and the particle mesh Ewald method with a large empty space at an interface of the unit cell. © 2020 Wiley Periodicals, Inc. 相似文献
104.
In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C?F bond in acyl fluorides, various transformations are accessible, including C?C, C?H, C?B, and C?F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu. 相似文献
105.
Tadashi Okazaki Fumio Sanda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1996,34(10):2029-2035
Synthesis and radical ring-opening polymerization of vinylcyclopropane bearing six-membered cyclic acetal moiety, 1-vinyl-4,8-dioxaspiro[2.5]octane (1), were carried out. 1 was prepared by the reaction of 1,1-dichloro-2-vinylcyclopropane and 1,3-propanediol in DMF in the presence of a base. Radical polymerization of 1 was carried out in the presence of an appropriate initiator (3 mol % vs. 1) at 60 and 120°C in degassed sealed ampoules for 20 h. A colorless transparent viscous polymer was obtained by the isolation with preparative HPLC. The structure of poly(1) was determined to consist of two 1,5-ring-opened units and a unit bearing no olefinic moiety. The difference of the activation energies for the ring-opening reaction of the cyclopropane ring calculated by the molecular orbital method could explain the selectivity in the direction of the cleavage of the cyclopropane ring. Acid hydrolysis of poly(1) afforded the corresponding polyketone in quantitative conversion. © 1996 John Wiley & Sons, Inc. 相似文献
106.
The relationship between molecular structures and physical properties of linear low density polyethylenes (LLDPEs) produced with single-site catalyst (SSC) was investigated. SSC polymerized LLDPE have excellent physical properties corresponding to its homogeneous molecular structure that had never been achieved by conventional Ziegler-Natta catalysts. It was found that some SSCs have the capability to produce LLDPEs with narrow molecular weight distribution but excellent melt properties. This result suggests that there exist long chain branches in these LLDPEs. 相似文献
107.
Shoichi Maeda Shunta Chikami Glenn Villena Latag Subin Song Norio Iwakiri Tomohiro Hayashi 《Molecules (Basel, Switzerland)》2022,27(7)
In this paper, we propose a new spectroscopic method to explore the behavior of molecules near polymeric molecular networks of water-containing soft materials such as hydrogels. We demonstrate the analysis of hydrogen bonding states of water in the vicinity of hydrogels (soft contact lenses). In this method, we apply force to hydrated contact lenses to deform them and to modulate the ratio between the signals from bulk and vicinal regions. We then collect spectra at different forces. Finally, we extracted the spectra of the vicinal region using the multivariate curve resolution-alternating least square (MCR-ALS) method. We report the hydration states depending on the chemical structures of hydrogels constituting the contact lenses. 相似文献
108.
Dr. Yusuke Sato Yushuang Zhang Dr. Seiichi Nishizawa Dr. Takehiro Seino Kodai Nakamura Dr. Minjie Li Prof. Dr. Norio Teramae 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12719-12724
A fluorescence assay for theophylline, one of the common drugs for acute and chronic asthmatic conditions, has been developed based on an abasic site‐containing DNA duplex aptamer (AP aptamer) in combination with an abasic site‐binding fluorescent ligand, riboflavin. The assay is based on the competitive binding of theophylline and riboflavin at the abasic (AP) site of the AP aptamer. In the absence of theophylline, riboflavin binds to the receptor nucleotide opposite the AP site, which leads to fluorescence quenching of the riboflavin. Upon addition of theophylline, competitive binding occurs between theophylline and riboflavin, which results in an effective fluorescence restoration due to release of riboflavin from the AP site. From an examination of the optimization of the AP aptamers, the complex of riboflavin with a 23‐mer AP aptamer (5′‐TCT GCG TCC AGX GCA ACG CAC AC‐3′/5′‐GTG TGC GTT GCC CTG GAC GCA GA‐3′; X : the AP site (Spacer C3, a propylene residue)) possessing cytosine as a receptor nucleotide was found to show a selective and effective fluorescence response to theophylline; the limit of detection for theophylline was 1.1 μM . Furthermore, fluorescence detection of theophylline was successfully demonstrated with high selectivity in serum samples by using the optimized AP aptamer and riboflavin. 相似文献
109.
Kazuyoshi Kanamori Norio Ishizuka Kazuki Nakanishi Kazuyuki Hirao Hiroshi Jinnai 《Journal of Sol-Gel Science and Technology》2003,26(1-3):157-160
The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels. 相似文献
110.