全文获取类型
收费全文 | 363篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 299篇 |
晶体学 | 8篇 |
力学 | 4篇 |
数学 | 16篇 |
物理学 | 57篇 |
出版年
2023年 | 5篇 |
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 13篇 |
2019年 | 10篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 8篇 |
2015年 | 5篇 |
2014年 | 14篇 |
2013年 | 16篇 |
2012年 | 28篇 |
2011年 | 28篇 |
2010年 | 11篇 |
2009年 | 14篇 |
2008年 | 25篇 |
2007年 | 20篇 |
2006年 | 17篇 |
2005年 | 24篇 |
2004年 | 21篇 |
2003年 | 24篇 |
2002年 | 15篇 |
2001年 | 8篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 5篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1973年 | 2篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有384条查询结果,搜索用时 31 毫秒
51.
Ken’ichiro Tanaka Tomoaki Okayama Takayasu Matsuo Masaaki Sugihara 《Numerische Mathematik》2013,125(3):511-543
In this paper, the theoretical convergence rate of the trapezoidal rule combined with the double-exponential (DE) transformation is given for a class of functions for which the single-exponential (SE) transformation is suitable. It is well known that the DE transformation enables the rule to achieve a much higher rate of convergence than the SE transformation, and the convergence rate has been analyzed and justified theoretically under a proper assumption. Here, it should be emphasized that the assumption is more severe than the one for the SE transformation, and there actually exist some examples such that the trapezoidal rule with the SE transformation achieves its usual rate, whereas the rule with DE does not. Such cases have been observed numerically, but no theoretical analysis has been given thus far. This paper reveals the theoretical rate of convergence in such cases, and it turns out that the DE’s rate is almost the same as, but slightly lower than that of the SE. By using the analysis technique developed here, the theoretical convergence rate of the Sinc approximation with the DE transformation is also given for a class of functions for which the SE transformation is suitable. The result is quite similar to above; the convergence rate in the DE case is slightly lower than in the SE case. Numerical examples which support those two theoretical results are also given. 相似文献
52.
Halichonic acid,a new rearranged bisabolene-type sesquiterpene from a marine sponge Halichondria sp.
Kenta Raiju Yuki Hitora Hikaru Kato Yuji Ise Esther D. Angkouw Remy E.P. Mangindaan Sachiko Tsukamoto 《Tetrahedron letters》2019,60(15):1079-1081
A new compound, halichonic acid (1), was isolated from a marine sponge Halichondria sp., together with (6R,7S)-7-amino-7,8-dihydro-α-bisabolene (2). The structure of 1 was elucidated by spectroscopic analysis and ECD spectrum calculation to be a rearranged bisabolene-type sesquiterpene having a 3-azabicyclo[3.3.1]nonene moiety. Compound 2 was cytotoxic against HeLa cells with an IC50 value of 50?μM, whereas 1 did not show cytotoxicity even at 50?μM. It is possible that 1 is biosynthesized from farnesyl pyrophosphate and glycine, with rearrangement. 相似文献
53.
Tomoaki Miura 《Molecular physics》2020,118(6)
Since 1970s, magnetic field effects (MFEs) on photogenerated radical pairs have been the centre of focus in the field of spin chemistry. The MFE attributes to quantum mechanical interconversion between the singlet and triplet radical pair states and subsequent spin-selective recombination reactions. In this New View article, the author picks up two hot topics studied during the last two decades, which are (i) so-called low field effect (LFE) and (ii) 2J-resonance MFE on fixed distance donor–acceptor linked molecules. In both of the topics, quantum mechanical explanations are given referring to recent reports, and some novel calculations have been carried out for bridging theoretical and experimental data for long-lived radical pairs. For the first topic, time domain calculations of coherent state mixing have been carried out for elucidation of hyperfine (HF) structure dependence of the LFE. For the second topic, Monte Carlo simulations of the torsional motion of polyaromatic linker unit have been carried out for the demonstration of fast decoherence in such rigid molecules. From these considerations, future possibilities of MFE studies on photo-functional materials and biomolecules have been indicated. 相似文献
54.
Poly(p‐benzamide) having isopropyl‐substituted chiral tri(ethylene glycol) side Chain: Synthesis and helical conformation 下载免费PDF全文
Akihiro Yokoyama Suguru Nakano Tomoaki Saiki Tsutomu Yokozawa 《Journal of polymer science. Part A, Polymer chemistry》2015,53(13):1623-1628
Isopropyl‐substituted tri(ethylene glycol) is used as a chiral side chain of N‐substituted poly(p‐benzamide) in order to increase the difference of stability between the right‐ and left‐handed helical structures of the polymer. The target polymer is synthesized by the chain‐growth condensation polymerization of the corresponding monomer with an initiator using lithium 1,1,1,3,3,3‐hexamethyldisilazide as a base. A circular dichroism (CD) study of the polymer reveals that the CD signal is due to an excess of a thermodynamically controlled right‐handed helical structure of the polymer, and that the replacement of the methyl group with a bulkier isopropyl group at the side chain of poly(p‐benzamide) increases the abundance of right‐handed helical structure in chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1623–1628 相似文献
55.
Shohei Nakamukai Kentaro Takada Kazuo Furihata Yuji Ise Shigeru Okada Yasuhiro Morii Nobuhiro Yamawaki Tomohiro Takatani Osamu Arakawa Kirk R. Gustafson Shigeki Matsunaga 《Tetrahedron letters》2018,59(26):2532-2536
Stellatolide H (1) was isolated from a deep-sea sponge Discodermia sp. as the cytotoxic constituent. The planar structure of 1 was elucidated on the basis of the NMR spectroscopic and mass spectrometric data. The absolute configurations of the constituent amino acid residues were determined by the Marfey’s method. Stellatolide H (1) is a peptide lactone of the callipeltin class with its N-terminus blocked by 3-hydroxy-6,8-dimethyldeca-(4Z,6E)-dienoic acid (Hdda). 相似文献
56.
Small-angle X-ray scattering (SAXS) measurements on V2O5·nH2O sols and gels, prepared by dissolving V2O5 glass into water at room temperature, show that there are V2O5 polymeric fibers entangled like random coils in the sol of n 5000, while the deviation from the random coil behavior occurs in the dilute sol of n 6000.
A Bragg peak appears at the scattering vector h 0.02 Å−1 to be superimposed on an asymptotic h−2-course in the SAXS curve of the concentrated sol of n 680. This means that the spatial correlation between V2O5 polymeric fibers takes place even in the fluid state.
V2O5·nH2O sols completely lose fluidity at n 250 to transfer to the gel state, where V2O5 polymeric fibers begin to pile up in the parallel with a substrate surface. Such a layer structure is preserved up to the gel of n 4. However, V2O5 polymeric fibers are randomly oriented within each layer. 相似文献
57.
Hamasaki A Yago T Takamasu T Kido G Wakasa M 《The journal of physical chemistry. B》2008,112(11):3375-3379
The magnetic field effects (MFEs) on photoinduced hydrogen abstraction reactions between benzophenone and thiophenol in an ionic liquid, N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl) imide (TMPA TFSI), were studied by a nanosecond laser flash photolysis technique under ultrahigh fields of up to 28 T. Extremely large and anomalous stepwise MFEs were observed for the first time. The escape yield of benzophenone ketyl radical decreased with increasing magnetic field strength (B) at 0 T相似文献
58.
This critical review highlights the "ligand oriented catalyst design concept", a new catalyst design concept for olefin polymerization that has led to the development of high-activity catalysts. The concept has created a series of highly active ethylene polymerization catalysts, many of which show high activities comparable to those of group 4 metallocene catalysts. Moreover, these catalysts display unique polymerization catalysis to produce a wide variety of polymers that possess unprecedented molecular architectures that are either difficult or impossible to achieve using conventional catalysts (98 references). 相似文献
59.
Prof. Takayuki Nakajima Mizuki Takubo Yurika Komura Yuki Maeda Miwa Sato Maki Zouda Prof. Tomoaki Tanase 《欧洲无机化学杂志》2023,26(9):e202200648
A new series of cationic heterodinuclear complexes, [M1M2Cl2(meso-dpmppp)(RNC)2]PF6 (M1=Ni, M2=Rh, R=tBu ( 1 a ); M1=Pd, M2=Rh, R=tBu ( 2 a ), Xyl ( 2 b ); M1=Pt, M2=Rh, R=tBu ( 3 a ), Xyl ( 3 b ); M1=Pd, M2=Ir, R=tBu ( 4 a )), supported by a tetradentate phosphine ligand, meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), were synthesized by stepwise reactions of meso-dpmppp with NiCl2 ⋅ 6H2O or MCl2(cod) (M=Pd, Pt), forming mononuclear metalloligands of [M1Cl2(meso-dpmppp)], and with [M2Cl(cod)]2 (M2=Rh, Ir) and RNC (R=tBu, Xyl) in the presence of [NH4][PF6]. The related neutral PdRh complex, [PdRhCl3(meso-dpmppp)(XylNC)] ( 5 ), was also prepared. The structures of 1 – 5 were determined by X-ray analyses to contain two square planar d8 metal centers with face-to-face arrangement, where meso-dpmppp supports M1 and M2 metal ions in cis/trans-P,P coordination mode, combining cis-{M1P2Cl2} and trans-{M2P2(CNR)2} units. Complexes 1 – 4 showed an intence characteristic absorption around 422–464 nm derived from RhI→RNC MLCT transition (HOMO→LUMO+1), which are influenced by changing M1 (NiII, PdII, PtII) metal ions since HOMO composed of dσ* orbitals appreciably destabilized by changing M1 from Ni to Pd, and Pt. The electronic structures of 1 a – 4 a were investigated on the basis of DFT calculations and NBO analyses to show weak but noticeable d8–d8 metallophilic interaction as empirical dispersion energy of 0.9–1.5 kcal/mol without M1–M2 covalent bonding interaction. In addition, 1 – 5 were utilized as catalysts for hydrosilylation of styrene, and the NiRh complex 1 a was found to show higher activity and chemo- and regioselectivity compared with 2 – 5 . 相似文献
60.
A series of protonated and methylated Anderson-type molybdoperiodates as well as the unprotonated [IMo6O24]5- have been synthesized and structurally characterized as tetra-n-butylammonium salts: [(n-C4H9)4N]5[IMo6O24] [monoclinic, space group C2/c, a = 33.6101(3) A, b = 15.2575(1) A, c = 24.0294(2) A, beta = 126.9569(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OH)] [monoclinic, space group P21/c, a = 9.5587(1) A, b = 24.1364(2) A, c = 18.2788(2) A, beta = 90.1562(5) degrees , Z = 2], [(n-C4H9)4N]3[IMo6O22(OH)2].2DMF [monoclinic, space group P21/a, a = 17.6105(4) A, b = 15.5432(5) A, c = 29.3316(9) A, beta = 91.475(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OMe)].3H2O [orthorhombic, space group Pbca, a = 17.0679(4) A, b = 25.6998(6) A, c = 20.7428(4) A, Z = 4], [(n-C4H9)4N]3[IMo6O22(OMe)2] [monoclinic, space group P21/n, a = 10.4009(1) A, b = 14.6658(3) A, c = 23.5395(4) A, beta = 100.324(1) degrees , Z = 2]. In all of these compounds, the [IMo6O24]5- anion is protonated or methylated selectively at O atoms shared by two Mo atoms. The results have also revealed that the protonated Anderson-type molybdoperiodates readily react with methanol in a very selective manner, while the unprotonated [IMo6O24]5- anion does not react with methanol under similar conditions. 相似文献