全文获取类型
收费全文 | 14212篇 |
免费 | 1090篇 |
国内免费 | 923篇 |
专业分类
化学 | 12905篇 |
晶体学 | 104篇 |
力学 | 55篇 |
综合类 | 11篇 |
数学 | 69篇 |
物理学 | 3081篇 |
出版年
2023年 | 117篇 |
2022年 | 145篇 |
2021年 | 277篇 |
2020年 | 364篇 |
2019年 | 347篇 |
2018年 | 201篇 |
2017年 | 255篇 |
2016年 | 465篇 |
2015年 | 526篇 |
2014年 | 508篇 |
2013年 | 1195篇 |
2012年 | 669篇 |
2011年 | 705篇 |
2010年 | 645篇 |
2009年 | 777篇 |
2008年 | 906篇 |
2007年 | 964篇 |
2006年 | 884篇 |
2005年 | 750篇 |
2004年 | 782篇 |
2003年 | 697篇 |
2002年 | 536篇 |
2001年 | 351篇 |
2000年 | 418篇 |
1999年 | 336篇 |
1998年 | 327篇 |
1997年 | 288篇 |
1996年 | 267篇 |
1995年 | 281篇 |
1994年 | 216篇 |
1993年 | 181篇 |
1992年 | 194篇 |
1991年 | 116篇 |
1990年 | 93篇 |
1989年 | 93篇 |
1988年 | 78篇 |
1987年 | 64篇 |
1986年 | 44篇 |
1985年 | 30篇 |
1984年 | 34篇 |
1983年 | 14篇 |
1982年 | 22篇 |
1981年 | 7篇 |
1980年 | 10篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1972年 | 5篇 |
1970年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
《Magnetic resonance in chemistry : MRC》2003,41(8):626-628
15N isotopic enrichment was necessary for the unequivocal assignment of the 1H NMR lines to the protons in the NH–OH fragment of benzohydroxamic acid, BHXA, C6H5CONHOH, in dry dimethyl sulfoxide solutions. The assignment [δ(NH) = 11.21, δ(OH) = 9.01, 1J(15N,1H) = 102.2 Hz, 2J(15N,1H) <1.5 Hz], which is opposite to that used by other authors, confirms the assignment extended to BHXA by Brown and co‐workers from the spectra of acetohydroxamic acid. The enrichment allowed also assignment of the 29Si lines in the spectra of disilylated benzohydroxamic acid, (Z)‐tert‐butyldimethylsilyl N‐tert‐butyldimethylsilyloxybenzoimidate (2) and (Z)‐tert‐butyldiphenylsilyl N‐tert‐butyldiphenylsilyloxybenzoimidate (3), and confirmed structure of the monosilylated products, N‐tert‐butyldiphenylsilyloxybenzamide (4) and N‐tert‐butyldiphenylsilyloxy benzoimidic acid (5). Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
102.
Berit OlofssonPeter Somfai 《Tetrahedron letters》2003,44(6):1279-1281
A large set of syn- and anti-1,2-amino alcohols has been synthesized. Upon comparison of the CH?O and CH?N 1H NMR shifts a general trend has been observed, making it possible to determine the relative configuration of 1,2-amino alcohols without derivatization or shift reagents. 相似文献
103.
《Magnetic resonance in chemistry : MRC》2003,41(1):61-64
Palladium(II) dichloride reacts with 1,10‐bis(2‐pyrrolyl)‐2,5,9‐triaza‐1,9‐decadiene to give a [Pd(C15H20N5)]Cl complex in which the ligand is four‐coordinated, leaving one pyrrole group dangling. By using COSY, gHSQC, gHMBC connectivities and NOE experiments it has been concluded that one linkage isomer exists in DMSO solution, in spite of the fact that different sets of N atoms of potentially pentadentate ligand might be involved in coordination, and that the three chelate rings in the complex cation are arranged in a sequence: five‐membered, six‐membered, five‐membered which is different from that (5–5–6) found by x‐ray studies on the related [Ni(C15H20N5)]Cl compound. NMR studies allowed an unambiguous assignment of all 1H and 13C NMR resonances for the complex. Results of x‐ray structural analysis of [Pd(C15H20N5)](CH3COO)H2O supported the five‐membered, six‐membered, five‐membered ring sequence in the [Pd(C15H20N5)]+ complex cation and show an E (trans) orientation of the dangling pyrrole group with respect to the metal center. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
104.
Multiwalled carbon nanotubes were modified by carboxy groups. Four independent methods for the determination of the degree
of functionalization of the surface were proposed: 13C NMR spectroscopy, thermogravimetry, titrimetry, and fluorimetry. The first two methods show the total content of carboxy
groups in the sample, and the latter two methods give information about the content of the surface groups only.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 291–295, February, 2008. 相似文献
105.
Mohamed Haouas Amine Harrane Mohamed Belbachir Francis Taulelle 《Journal of Polymer Science.Polymer Physics》2007,45(22):3060-3068
Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. 1H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. 27Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the 29Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007 相似文献
106.
Casey Chun Zhou Eric J. Stoner Kent D. Stewart L. Steven Hollis Edmund D. Matayoshi Gregory M. Brill 《Tetrahedron》2004,60(47):10611-10618
Oritavancin is a semi-synthetic glycopeptide antibiotic which is structurally related to vancomycin. When oritavancin bisphosphate is dried in vacuo with heat, a new compound forms. This new compound is stable only in the solid state and reverts to oritavancin in solution. Highly enriched samples of this compound were obtained by preparative HPLC and the structure of this compound was elucidated by using one and two-dimensional (1H and 13C) NMR spectroscopy in conjunction with computer-assisted molecular modeling. It has been determined that oritavancin adopts a conformation similar to that of vancomycin in solution, while the new compound is the unnatural R-AB-biaryl atropisomer of oritavancin. This is the first observation and isolation of an AB-biaryl atropisomer in an intact member of the vancomycin family of glycopeptide antibiotics. 相似文献
107.
108.
Akira Shimazu Tukasa Miyazaki Shigeru Katayama Yasuo Ito 《Journal of Polymer Science.Polymer Physics》2003,41(3):308-318
The ortho‐positronium (o‐Ps) lifetime τ3 and its intensity I3 in various fluorinated polyimides were determined by the positron annihilation technique and were studied with the spin–lattice relaxation time T1 and the propylene permeability, solubility, diffusivity, and permselectivity for propylene/propane in them. τ3, I3, and the distribution of τ3 changed when the bulky moieties in the polyimides were changed. The polyimides, having both large τ3 and I3 values, exhibited a short T1 and a high permeability with a low permselectivity. The propylene permeability and diffusivity were exponentially correlated with the product of I3 and the average free‐volume hole size estimated from τ3. In highly plasticized states induced by the sorption of propylene, the permeability increased with the propylene pressure in excellent agreement with the change in the free‐volume hole properties probed by o‐Ps. The large and broad distribution of the free‐volume holes and increased local chain mobility for the 2,2‐bis(3,4‐decarboxyphenyl) hexafluoropropane dianhydride‐based polyimides are thought to be important physical properties for promoting penetrant‐induced plasticization. These results suggest that o‐Ps is a powerful probe of not only the free‐volume holes but also the corresponding permeation mechanism and penetrant‐induced plasticization phenomenon. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 308–318, 2003 相似文献
109.
《Magnetic resonance in chemistry : MRC》2003,41(1):77-79
The complete assignment of the 1H and 13C NMR spectra of the title enediones, bearing as substituents N‐aziridinyl (a novel compound), methoxy, chloro and methylsulfanyl, is reported. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
110.
Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re2(CO)9NCCH3 was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re2(CO)9PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re2(CO)9PH3 led to the new bi- and trinuclear complexes Re2(μ-H)(μ3-PHRe(CO)5)(CO)8, Re2(μ-PH2)2(CO)8 and Re2(μ-H) · (μ-PH2)(CO)8, which were characterized by IR-, 1H- and 31P-NMR spectroscopy. The structures of ax-Re2(CO)9PH3, Re2(μ-H)(μ3-PHRe(CO)5)(CO)8 and Re2(μ-PH2)2(CO)8 were confirmed by single-crystal X-ray analysis. ax-Re2(CO)9PH3 has a very short Re? P bond length of 228(2) pm. 相似文献