全文获取类型
收费全文 | 1307篇 |
免费 | 47篇 |
国内免费 | 12篇 |
专业分类
化学 | 1020篇 |
晶体学 | 26篇 |
力学 | 9篇 |
数学 | 67篇 |
物理学 | 244篇 |
出版年
2023年 | 6篇 |
2022年 | 9篇 |
2021年 | 14篇 |
2020年 | 22篇 |
2019年 | 25篇 |
2018年 | 20篇 |
2017年 | 8篇 |
2016年 | 37篇 |
2015年 | 35篇 |
2014年 | 29篇 |
2013年 | 53篇 |
2012年 | 61篇 |
2011年 | 93篇 |
2010年 | 42篇 |
2009年 | 40篇 |
2008年 | 75篇 |
2007年 | 73篇 |
2006年 | 77篇 |
2005年 | 61篇 |
2004年 | 69篇 |
2003年 | 49篇 |
2002年 | 43篇 |
2001年 | 49篇 |
2000年 | 28篇 |
1999年 | 30篇 |
1998年 | 19篇 |
1997年 | 13篇 |
1996年 | 18篇 |
1995年 | 10篇 |
1994年 | 8篇 |
1993年 | 11篇 |
1992年 | 12篇 |
1991年 | 14篇 |
1990年 | 15篇 |
1989年 | 10篇 |
1988年 | 13篇 |
1987年 | 19篇 |
1986年 | 12篇 |
1985年 | 22篇 |
1984年 | 13篇 |
1983年 | 14篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 9篇 |
1972年 | 5篇 |
1967年 | 5篇 |
排序方式: 共有1366条查询结果,搜索用时 0 毫秒
51.
Xuan B. Nguyen Yuji Nakano Nisharnthi M. Duggan Lydia Scott Martin Breugst David W. Lupton 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(33):11607-11614
Direct polarity inversion of conjugate acceptors provides a valuable entry to homoenolates. N‐heterocyclic carbene (NHC) catalyzed reactions, in which β‐unsubstituted conjugate acceptors undergo homoenolate formation and C?C bond formation twice, have been developed. Specifically, the all‐carbon (5+1) annulations give a range of mono‐ and bicyclic cyclohexanones (31 examples). In the first family of annulations, β‐unsubstituted acrylates tethered to a divinyl ketone undergo cycloisomerization, providing hexahydroindenes and tetralins. In the second, partially untethered substrates undergo an intermolecular (5+1) annulation involving dimerization followed by cycloisomerization. While enantioselectivity was not possible with the former, the latter proved viable, allowing cyclohexanones to be produced with high levels of enantiopurity (most >95:5 e.r.) and exclusive diastereoselectivity (>20:1 d.r.). Derivatizations and mechanistic studies are also reported. 相似文献
52.
Nickel‐Catalyzed Dimerization and Alkylarylation of 1,3‐Dienes with Alkyl Fluorides and Aryl Grignard Reagents 下载免费PDF全文
Dr. Takanori Iwasaki Xin Min Asuka Fukuoka Prof. Dr. Hitoshi Kuniyasu Prof. Dr. Nobuaki Kambe 《Angewandte Chemie (International ed. in English)》2016,55(18):5550-5554
In the presence of a nickel catalyst, 1,3‐butadiene undergoes selective dimerization and alkylarylation with alkyl fluorides and aryl Grignard reagents to give 1,6‐octadienes with alkyl and aryl groups at the 3‐ and 8‐positions, respectively, by the consecutive formation of three carbon–carbon bonds. The formation of an anionic nickel complex plays an important role in forming C?C bonds with alkyl fluorides. 相似文献
53.
Nakayama T Kurosawa Y Furui S Kerman K Kobayashi M Rao SR Yonezawa Y Nakano K Hino A Yamamura S Takamura Y Tamiya E 《Analytical and bioanalytical chemistry》2006,386(5):1327-1333
Polymerase chain reaction (PCR) is an essential part of research based on genomics or cell analysis. The development of a
microfluidic device that would be suitable for high-temperature-based reactions therefore becomes an important contribution
towards the integration of micro-total analysis systems (μTAS). However, problems associated with the generation of air bubbles
in the microchannels before the introduction of the assay liquid, which we call the “initial start-up” in this study, made
the flow irregular and unstable. In this report, we have tried to address these problems by adapting a novel liquid-flow method
for high-temperature-based reactions. A PDMS-based microfluidic device was fabricated by soft-lithography techniques and placed
on a cartridge heater. The generation of the air bubbles was prevented by introducing the fluorinated oil, an inert and highly
viscous liquid, as the cap just before the introduction of the sample solutions into the microchannels. The technique was
applied for continuous-flow PCR, which could perform PCR on-chip in a microfluidic system. For the evaluation of practical
accuracy, plasmid DNA that serves as a reference molecule for the quantification of genetically modified (GM) maize was used
as the template DNA for continuous-flow PCR. After PCR, the products were collected in a vial and analyzed by gel electrophoresis
to confirm the accuracy of the results. Additionally, quantitative continuous-flow PCR was performed using TaqMan technology
on our PCR device. A laser detection system was also used for the quantitative PCR method. We observed a linear relationship
between the threshold cycle (Ct) and the initial DNA concentration. These results showed that it would be possible to quantify
the initial copies of the template DNA on our microfluidic device. Accurate quantitative DNA analysis in microfluidic systems
is required for the integration of PCR with μTAS, thus we anticipate that our device would have promising potential for applications
in a wide range of research. 相似文献
54.
55.
The asymmetric hydroformylation of 2‐ and 3‐vinylfurans ( 2a and 2b , resp.) was investigated by using [Rh{(R,S)‐binaphos}] complexes as catalysts ((R,S)‐binaphos = (11bS)‐4‐{[1R)‐2′‐phosphino[1,1′‐binaphthalen]‐2‐yl]oxy}dinaphtho[2,1‐d:1′,2′‐f][1,3,2]dioxaphosphepin; 1 ). Hydroformylation of 2 gave isoaldehydes 3 in high regio‐ and enantioselectivities (Scheme 2 and Table). Reduction of the aldehydes 3 with NaBH4 successfully afforded the corresponding alcohols 5 without loss of enantiomeric purity (Scheme 3). 相似文献
56.
[Structure: see text] Beta-isocupreidine (beta-ICD)-catalyzed Baylis-Hillman reaction of chiral N-Boc-alpha-amino aldehydes and 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) takes place without racemization and exhibits the match-mismatch relationship between the substrate and the catalyst. In the case of acyclic amino aldehydes, L-substrates show excellent syn selectivity and high reactivity in contrast to D-substrates. On the other hand, in the case of cyclic amino aldehydes, D-substrates rather than L-substrates show excellent anti selectivity and high reactivity. 相似文献
57.
Hideaki Takahashi Hajime Ohno Ryohei Kishi Masayoshi Nakano Nobuyuki Matubayasi 《Chemical physics letters》2008,456(4-6):176-180
In a recent development we proposed a quantum chemical approach to compute free energy change for chemical reactions in condensed phases by combining the QM/MM method with the theory of energy representation (QM/MM-ER). We extend in this Letter the novel approach to compute reduction free energy of isoalloxazine ring of FAD (flavin adenine dinucleotide) immersed in water within the framework of the QM/MM-ER method. The characteristic feature of our approach is that the excess electron to be attached on the FAD is identified as a solute. The reduction free energy has been obtained as −80.1 kcal/mol in the aqueous solution. 相似文献
58.
Feng PL Beedle CC Koo C Wernsdorfer W Nakano M Hill S Hendrickson DN 《Inorganic chemistry》2008,47(8):3188-3204
A family of distorted heterometallic cubanes, [Mn (III) 3Ni (II)(hmp) 3O(N 3) 3(O 2CR) 3], where O 2CR (-) is benzoate ( 1), 3-phenylpropionate ( 2), 1-adamantanecarboxylate ( 3), or acetate ( 4) and hmp (-) is the anion of 2-pyridinemethanol, was synthesized and structurally as well as magnetically characterized. These complexes have a distorted-cubane core structure similar to that found in the S = 9/2 Mn 4 cubane family of complexes. Complexes 1, 3, and 4 crystallize in rhombohedral, hexagonal, and cubic space groups, respectively, and have C 3 molecular symmetry, while complex 2 crystallizes in the monoclinic space group Cc with local C 1 symmetry. Magnetic susceptibility and magnetization hysteresis measurements and high-frequency electron paramagnetic resonance (HFEPR) spectroscopy established that complexes 1-4 have S = 5 spin ground states with axial zero-field splitting (ZFS) parameters ( D) ranging from -0.20 to -0.33 cm (-1). Magnetization versus direct-current field sweeps below 1.1 K revealed hysteresis loops with magnetization relaxation, definitely indicating that complexes 1-4 are single-molecule magnets that exhibit quantum tunneling of magnetization (QTM) through an anisotropy barrier. Complex 2 exhibits the smallest coercive field and fastest magnetization tunneling rate, suggesting a significant rhombic ZFS parameter ( E), as expected from the low C 1 symmetry. This was confirmed by HFEPR spectroscopy studies on single crystals that gave the following parameter values for complex 2: gz = 1.98, gx = gy = 1.95, D = -0.17 cm (-1), B 4 (0) = -6.68 x 10 (-5) cm (-1), E = 6.68 x 10 (-3) cm (-1), and B 4 (2) = -1.00 x 10 (-4) cm (-1). Single-crystal HFEPR data for complex 1 gave g z = 2.02, gx = gy = 1.95, D = -0.23 cm (-1), and B 4 (0) = -5.68 x 10 (-5) cm (-1), in keeping with the C 3 site symmetry of this Mn 3Ni complex. The combined results highlight the importance of spin-parity effects and molecular symmetry, which determine the QTM rates. 相似文献
59.
Petronela Drambei Yumiko Nakano Yuezhen Bin Tsumuko Okuno Masaru Matsuo 《Macromolecular Symposia》2006,242(1):146-156
Uniplaner orientation of a particular crystal plane along the surface of a film was investigated for poly (vinyl alcohol) (PVA) film prepared by a coagulation bath with concentrated aqueous solution containing 100 ∼ 300g of Na2SO4 against 1 ℓ of water. The orientation distribution functions of the three crystallographic principal axes of the dried films were obtained by the X-ray diffraction technique. The same treatment was carried out for the films prepared by stretching biaxially of the fresh gel and then by drying the resultant fresh gel. The very high preferential orientation of the crystal chain axes and amorphous chain segments could be realized by the biaxially elongation. Accordingly, the techniques were applied to the biaxially stretching of chitosan and PVA blend films with high Young's modulus. The planer orientation of the chain axes of chitosan and PVA crystallites could be confirmed. The morphology of the film surface was estimated by measurements of contact angle and electron spectroscopy for chemical analysis. The results suggested that the admixture of chitosan decreases wet ability of the specimen and this tendency was slightly enhanced by the biaxially elongation. 相似文献
60.
Chiral cationic palladium-phosphinooxazolidine catalysts in ionic liquid afforded excellent enantioselectivity in Diels-Alder reactions and the catalyst was easily recycled eight times without any significant decrease in chemical yields or enantioselectivity (89-99%, 88-99% ee). 相似文献