全文获取类型
收费全文 | 930篇 |
免费 | 36篇 |
国内免费 | 4篇 |
专业分类
化学 | 742篇 |
晶体学 | 11篇 |
力学 | 20篇 |
数学 | 44篇 |
物理学 | 153篇 |
出版年
2023年 | 12篇 |
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 13篇 |
2019年 | 13篇 |
2018年 | 13篇 |
2017年 | 12篇 |
2016年 | 25篇 |
2015年 | 18篇 |
2014年 | 14篇 |
2013年 | 43篇 |
2012年 | 58篇 |
2011年 | 55篇 |
2010年 | 46篇 |
2009年 | 32篇 |
2008年 | 54篇 |
2007年 | 76篇 |
2006年 | 69篇 |
2005年 | 43篇 |
2004年 | 65篇 |
2003年 | 48篇 |
2002年 | 38篇 |
2001年 | 12篇 |
2000年 | 9篇 |
1999年 | 10篇 |
1998年 | 12篇 |
1997年 | 6篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1987年 | 3篇 |
1985年 | 15篇 |
1984年 | 18篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1972年 | 2篇 |
1966年 | 2篇 |
排序方式: 共有970条查询结果,搜索用时 31 毫秒
41.
42.
Incubation of diosgenone (1, 25D-spirost-4-en-3-one) with Verticillium theobromae (Turconi) Mason et Hughes (CBS) afforded 20α-hydroxypregn-4<ne-3,16-dione (3) and 3α,11β,20α-trihydroxy-5α-pregnan-16-one (4). The same transformation products were also obtained by the use of Stachylidium bicolor Link (IFO 6647). Isolation and identification processes of the products are discussed. 相似文献
43.
Fabrication of mesoporous ZnO nanosheets from precursor templates grown in aqueous solutions 总被引:1,自引:0,他引:1
Keita Kakiuchi Eiji Hosono Toshio Kimura Hiroaki Imai Shinobu Fujihara 《Journal of Sol-Gel Science and Technology》2006,39(1):63-72
Mesoporous ZnO nanosheets were successfully prepared by pyrolytic transformation of zinc carbonate hydroxide hydrate, Zn4CO3(OH)6·H2O. The nanosheets were initially formed as assemblies on glass substrates during chemical bath deposition (CBD) in aqueous
solutions of urea and zinc acetate dihydrate, zinc chloride, zinc nitrate hexahydrate, or zinc sulfate heptahydrate at 80°C.
It was key to induce heterogeneous nucleation of Zn4CO3(OH)6·H2O by promoting a gradual hydrolysis reaction of urea and controlling the degree of supersaturation of zinc hydroxide species.
Morphology of Zn4CO3(OH)6·H2O was largely influenced by the anions present in the CBD solutions. The Zn4CO3(OH)6·H2O nanosheets were transformed into wurtzite ZnO by heating at 300°C in air without losing the microstructural feature. 相似文献
44.
Ooi T Takahashi M Yamada M Tayama E Omoto K Maruoka K 《Journal of the American Chemical Society》2004,126(4):1150-1160
A series of (2,7-disubstituted-1,8-biphenylenedioxy)bis(dimethylaluminum) (2) has been readily prepared in situ by treatment of the requisite 2,7-disubstituted-1,8-biphenylenediol (1) with Me3Al (2 equiv) in CH2Cl2 at room temperature; this primarily relies on the successful establishment of a new synthetic procedure of 1 starting from inexpensive m-anisidine. Evaluation of 2 as a bidentate organoaluminum Lewis acid has been performed by the reduction of ketonic substrates using Bu3SnH as a hydride source in comparison to the conventional monodentate Lewis acid dimethylaluminum 2,6-xylenoxide (11), uncovering the significantly high activation ability of 2 toward carbonyl. Particularly, (2,7-dimethyl-1,8-biphenylenedioxy)bis(dimethylaluminum) (2a) exerted the highest reactivity, which has also been emphasized in the Mukaiyama aldol reaction. The structure of the bidentate Lewis acid 2 was unambiguously determined by single-crystal X-ray diffraction analysis of 2g possessing a bulky 3,5-di-tert-butylphenyl substituent, revealing the rigid dimeric assembly in the solid state. The double electrophilic activation of carbonyl substrate by 2a has been supported by low-temperature 13C NMR analysis as well as theoretical study using the Gaussian 98 program. Moreover, unique stereoselectivity has been observed in the 2a-promoted Mukaiyama Michael addition, and highly chemoselective functionalization of carbonyl compounds in the presence of their acetal counterparts has been realized using 2a. Finally, the effectiveness of 2a for the activation of ether functionality has been demonstrated in the Claisen rearrangement of allyl vinyl ethers. 相似文献
45.
Du YZ Hiratsuka Y Taira S Eguchi M Uyeda TQ Yumoto N Kodaka M 《Chemical communications (Cambridge, England)》2005,(16):2080-2082
A new nano-biomachine has been created from microtubules (MTs) and hetero-bifunctional polymer particles bearing pyruvate kinase, which is propelled on glass surfaces coated with kinesin by use of self-supplying ATP. 相似文献
46.
Mitsuko Asai Eiji Mizuta Motowo Izawa Konomi Haibara Toyokazu Kishi 《Tetrahedron》1979,35(9):1079-1085
In this paper we report the isolation, chemical characterization and structural elucidation of Ansamitocin, a new antitumor antibiotic obtained from Nocardia No. C-15003 (N-1). Ansamitocin P-3, P-3' and P-4 with molecular formulae C32H43ClN2O9, C32H43ClN2O9 and C33H45ClN2O9, respectively, were identified as novel antibiotics. Their UV spectra resemble that of maytansine obtained from a plant source. Analysis of the PMR spectrum and spin-decoup studies of P-3 demonstrated that its skeletal structure was the same as that of maytansine. Reductive cleavage of each antibiotic gave maytansinol (P-0). Alkali hydrolysis of P-3, P-3' and P-4 gave isobutyric, butyric and isovaleric acids, respectively. P-3, P-3' and P-4 were concluded to be the isobutyrate, butyrate and isovalerate ester of maytansinol at C-3, respectively. An antitumor plant product, maytanacine, and its semisynthetic derivative, maytansinol propionate, were also produced by the same strain. 相似文献
47.
Wang CR Kai T Tomiyama T Yoshida T Kobayashi Y Nishibori E Takata M Sakata M Shinohara H 《Angewandte Chemie (International ed. in English)》2001,40(2):265
The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff. 相似文献
48.
Alexei A. Belik Shinya Uji Eiji Takayama-Muromachi 《Journal of solid state chemistry》2005,178(11):3461-3463
Magnetic properties of quasi-one-dimensional S=1/2 Heisenberg antiferromagnet Sr2Cu(PO4)2 were investigated by temperature and field dependence of AC susceptibility down to 0.03 K. A sharp peak was observed at on the temperature dependence of AC susceptibility indicating long-range magnetic ordering. Taking into account the exchange constant, (Hamiltonian =J∑SiSi+1), the ratio kBTN/J is 0.06%. Sr2Cu(PO4)2 is, therefore, one of the best one-dimensional Heisenberg antiferromagnet known so far. 相似文献
49.
Chiral polythiophenes (PTs), in sharp contrast to other optically active polymers, exhibit optical activity in the pi-pi* transition region which is derived from the chirality of the main chain when they self-assemble to form a supramolecular pi-stacked aggregate with intermolecular interactions in a poor solvent or in a film. We now report that the regioregular, optically active PT poly[(R)-3-[4-(4-ethyl-2-oxazolin-2-yl)phenyl]thiophene] (poly-1) exhibits unique split-type induced circular dichroism (ICD) in the pi-pi* transition region of the main chain upon complexation with various metal salts such as trifluoromethanesulfonates of copper(I), copper(II), silver(I), and zinc(II), and iron(II) perchlorate in chloroform, which is a good solvent for poly-1. The appearance of ICD and slight changes in the UV/Vis spectra (no color change), except for the zinc salts, indicated that the chirality may not be induced by chiral pi-stacked aggregates of poly-1, but by the chirality of the main chain, for example, a predominantly one-handed helical structure induced by intermolecular coordination of the oxazoline groups to metal ions. The sign of the Cotton effect depends on the metal salt; most metal salts induced ICDs with similar Cotton-effect patterns, while zinc salts caused an inversion of the signs of the Cotton effect of poly-1 accompanied by a gradual red shift in the absorption of up to 125 nm. The changes in the conformation and the size of the poly-1 aggregates induced by different metal salts were also investigated by (1)H NMR titrations, static light scattering (SLS), atomic force microscopy (AFM), and membrane filtration. On the basis of these results, we propose a possible model for the chiral supramolecular aggregates of poly-1 with metal salts. 相似文献
50.
Eiji Takahashi Fumio Sanda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1037-1046
Novel pyridinium salts [N‐(α‐phenylbenzyl)‐, N‐(1‐naphthylmethyl)‐, or N‐cinnamyl p‐ or o‐cyanopyridinium hexafluoroantimonates] were synthesized by the reaction of p‐ or o‐cyanopyridine and the corresponding bromides followed by anion exchange with KSbF6. These pyridinium salts polymerized epoxy monomers at lower temperatures than previously reported for N‐benzyl‐2‐cyanopyridinium hexafluoroantimonate. The o‐substituted pyridinium salts showed higher activity than the p‐substituted ones, and the crosslinked epoxy polymers cured with these initiators showed higher glass‐transition temperatures. These pyridinium salts photoinitiated radical polymerization as well as cationic polymerization. The photopolymerization was accelerated by the addition of aromatic ketones as photosensitizers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1037–1046, 2002 相似文献