全文获取类型
收费全文 | 885篇 |
免费 | 46篇 |
国内免费 | 2篇 |
专业分类
化学 | 750篇 |
晶体学 | 6篇 |
力学 | 10篇 |
数学 | 51篇 |
物理学 | 116篇 |
出版年
2023年 | 7篇 |
2021年 | 9篇 |
2020年 | 5篇 |
2019年 | 17篇 |
2018年 | 10篇 |
2017年 | 5篇 |
2016年 | 16篇 |
2015年 | 15篇 |
2014年 | 23篇 |
2013年 | 36篇 |
2012年 | 41篇 |
2011年 | 42篇 |
2010年 | 28篇 |
2009年 | 13篇 |
2008年 | 38篇 |
2007年 | 36篇 |
2006年 | 37篇 |
2005年 | 46篇 |
2004年 | 35篇 |
2003年 | 46篇 |
2002年 | 40篇 |
2001年 | 9篇 |
2000年 | 17篇 |
1999年 | 15篇 |
1998年 | 11篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 13篇 |
1994年 | 18篇 |
1993年 | 15篇 |
1992年 | 18篇 |
1991年 | 13篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 23篇 |
1984年 | 18篇 |
1983年 | 11篇 |
1982年 | 11篇 |
1981年 | 19篇 |
1980年 | 13篇 |
1979年 | 23篇 |
1978年 | 11篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1974年 | 10篇 |
1972年 | 5篇 |
排序方式: 共有933条查询结果,搜索用时 15 毫秒
61.
Reaction of 1-trimethylsilyloxybenzocyclobutene(1) with carbonyl compounds catalyzed by tris(dimethylamino)sulfur (trimethylsilyl)difluoride (TASF) at room temperature gave 1-isochromanol derivatives as corresponding hetero Diels-Alder adducts in good yields. 相似文献
62.
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
63.
Quantitative Detection for Porphyromonas gingivalis in Tooth Pocket and Saliva by Portable Electrochemical DNA Sensor Linked with PCR
下载免费PDF全文
![点击此处可从《Electroanalysis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Keiichiro Yamanaka Shinichi Sekine Takahiro Uenoyama Masahiro Wada Tomohiko Ikeuchi Masato Saito Yoshinori Yamaguchi Eiichi Tamiya 《Electroanalysis》2014,26(12):2686-2692
Here, a quantitative electrochemical analysis of periodontal bacteria in gingival crevicular fluid (GCF) and saliva by direct polymerase chain reaction (PCR) is presented. The electrochemical measurement was performed by mixing with PCR products and electrochemical indicator (bisbenzimidazole trihydrochloride). The peak current of indicator is reduced due to slower diffusion when the dye intercalates into the amplified DNA, and the degree of reduction in the peak current is correlates with the quantity of amplified DNA. Therefore, a quantitative analysis is possible by using our electrochemical method at the end point of PCR. In the GCF testing, The number of Porphyromonas gingivalis (Pg) detected by our electrochemical method at the end point of PCR were almost same compared with that were calculated by the conventional method of quantitative real? time PCR. In the saliva testing, the relationship between number of Pg in saliva and average pocket depth, and age‐dependence were also clearly observed. Since the saliva sample is obtained in a non‐invasive manner, this method is useful for the primary screening of periodontal disease. Moreover, our detection method is simple and uses a hand‐held potentiostat making it suitable for development of an on‐site periodontal diagnosis system. 相似文献
64.
Ewelina Lipiec Dr. Ryo Sekine Dr. Jakub Bielecki Prof. Dr. Wojciech M. Kwiatek Assoc. Prof. Bayden R. Wood 《Angewandte Chemie (International ed. in English)》2014,53(1):169-172
DNA double strand breaks (DSBs) are deadly lesions that can lead to genetic defects and cell apoptosis. Techniques that directly detect DNA DSBs include scanning electron microscopy, atomic force microscopy (AFM), and fluorescence based approaches. While these techniques can be used to identify DSBs they provide no information on the molecular events occurring at the break. Tip‐enhanced Raman scattering (TERS) can provide molecular information from DNA at the nanoscale and in combination with AFM provides a new way to visualize and characterize the molecular structure of DSBs. DSBs result from cleavage at the 3’‐ and 5’‐bonds of deoxyribose upon exposure to UVC radiation based on the observation of P? O? H and methyl/methylene deformation modes enhanced in the TERS spectra. It is hypothesized that strand fragments are hydrogen‐terminated at the lesion, indicating the action of free radicals during photon exposure. 相似文献
65.
Dr. Toru Amaya Riyo Suzuki Prof. Dr. Toshikazu Hirao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):653-656
N,N′‐Diphenyl‐p‐benzoquinonediimine, a redox‐active unit of polyaniline, efficiently induced the oxidative homocoupling of various aryl‐ and vinylmagnesium reagents in suppressing the side reactions, such as 1,2‐ or 1,4‐addition reaction. 相似文献
66.
Dr. Masaki Yoshida Dr. Mio Kondo Prof. Toshikazu Nakamura Prof. Ken Sakai Prof. Shigeyuki Masaoka 《Angewandte Chemie (International ed. in English)》2014,53(43):11519-11523
A series of [{(terpy)(bpy)Ru}(μ‐O){Ru(bpy)(terpy)}]n+ ( [RuORu]n+ , terpy=2,2′;6′,2′′‐terpyridine, bpy=2,2′‐bipyridine) was systematically synthesized and characterized in three distinct redox states (n=3, 4, and 5 for RuII,III2 , RuIII,III2 , and RuIII,IV2 , respectively). The crystal structures of [RuORu]n+ (n=3, 4, 5) in all three redox states were successfully determined. X‐ray crystallography showed that the Ru? O distances and the Ru‐O‐Ru angles are mainly regulated by the oxidation states of the ruthenium centers. X‐ray crystallography and ESR spectra clearly revealed the detailed electronic structures of two mixed‐valence complexes, [RuIIIORuIV]5+ and [RuIIORuIII]3+ , in which each unpaired electron is completely delocalized across the oxo‐bridged dinuclear core. These findings allow us to understand the systematic changes in structure and electronic state that accompany the changes in the redox state. 相似文献
67.
Koji Yamamoto Kazuki Higuchi Masahiro Ogawa Hiromitsu Sogawa Shigeki Kuwata Yoshihiro Hayashi Susumu Kawauchi Toshikazu Takata 《化学:亚洲杂志》2020,15(3):356-359
We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes. 相似文献
68.
Kubo K Akemoto M Anderson S Aoki T Araki S Bane KL Blum P Corlett J Dobashi K Emma P Frisch J Fukuda M Guo Z Hasegawa K Hayano H Higo T Higurashi A Honda Y Iimura T Imai T Jobe K Kamada S Karataev P Kashiwagi S Kim E Kobuki T Kotseroglou T Kurihara Y Kuriki M Kuroda R Kuroda S Lee T Luo X McCormick DJ McKee B Mimashi T Minty M Muto T Naito T Naumenko G Nelson J Nguyen MN Oide K Okugi T Omori T Oshima T Pei G Potylitsyn A Qin Q Raubenheimer T Ross M Sakai H Sakai I Schmidt F Slaton T Smith H 《Physical review letters》2002,88(19):194801
Electron beams with the lowest, normalized transverse emittance recorded so far were produced and confirmed in single-bunch-mode operation of the Accelerator Test Facility at KEK. We established a tuning method of the damping ring which achieves a small vertical dispersion and small x-y orbit coupling. The vertical emittance was less than 1% of the horizontal emittance. At the zero-intensity limit, the vertical normalized emittance was less than 2.8 x 10(-8) rad m at beam energy 1.3 GeV. At high intensity, strong effects of intrabeam scattering were observed, which had been expected in view of the extremely high particle density due to the small transverse emittance. 相似文献
69.
The behavior of arsenite, methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, dimethyl-R-arsine oxides, and trimethyl-R-arsonium compounds (R = carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl) toward sodium borohydride and hot aqueous sodium hydroxide was investigated. The arsines obtained by sodium borohydride reduction of the undigested and digested solutions were collected in a liquid-nitrogen cooled trap, separated with a gas chromatograph, and detected with a mass spectrometer in the selected-ion-monitoring mode. The investigated arsenic compounds were stable in hot 2 mol dm?3 sodium hydroxide except arsenobetaine [trimethyl(carboxymethyl)arsonium zwitterion] that was converted to trimethylarsine oxide, and dimethyl(ribosyl)arsine oxides that were decomposed to dimethylarsinic acid. Hydride generation before and after digestion of extracts from marine organisms allowed inorganic arsenic, methylated arsenic, arsenobetaine, and ribosyl arsenic compounds to be identified and quantified. This method was applied to extracts from shellfish, fish, crustaceans, and seaweeds. 相似文献
70.
Shigeyuki Mayama Toshikazu Tani Tamio Ueno Kazumasa Hirabayashi Tadakazu Nakashima Hiroshi Fukami Yukio Mizuno Hiroshi Irie 《Tetrahedron letters》1981,22(22):2103-2106
The major phytoalexin from oat leaves has been identified as 2-[2-(4-hydroxyphenyDethenyl] -6-hydroxy-4H-3,1-benzoxazin-4-one (). 相似文献