全文获取类型
收费全文 | 1026篇 |
免费 | 70篇 |
国内免费 | 207篇 |
专业分类
化学 | 1225篇 |
晶体学 | 10篇 |
力学 | 4篇 |
综合类 | 5篇 |
数学 | 6篇 |
物理学 | 53篇 |
出版年
2024年 | 1篇 |
2023年 | 17篇 |
2022年 | 29篇 |
2021年 | 46篇 |
2020年 | 35篇 |
2019年 | 30篇 |
2018年 | 38篇 |
2017年 | 34篇 |
2016年 | 43篇 |
2015年 | 42篇 |
2014年 | 58篇 |
2013年 | 114篇 |
2012年 | 45篇 |
2011年 | 57篇 |
2010年 | 44篇 |
2009年 | 52篇 |
2008年 | 62篇 |
2007年 | 60篇 |
2006年 | 51篇 |
2005年 | 67篇 |
2004年 | 52篇 |
2003年 | 62篇 |
2002年 | 65篇 |
2001年 | 22篇 |
2000年 | 33篇 |
1999年 | 19篇 |
1998年 | 18篇 |
1997年 | 20篇 |
1996年 | 6篇 |
1995年 | 17篇 |
1994年 | 17篇 |
1993年 | 10篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有1303条查询结果,搜索用时 15 毫秒
1.
Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed. 相似文献
2.
Christopher J. Nichols 《Tetrahedron letters》2004,45(40):7469-7473
A number of new functionalised bridged indolocarbazole systems have been prepared by ring-opening reactions of a key cyclic sulfate intermediate, prepared from the corresponding diol by the action of sulfuryl diimidazole and DBU. The same cyclic sulfate also undergoes an unprecedented asymmetric rearrangement to a chiral ketone, on treatment with a chiral lithium amide base. 相似文献
3.
K. Y. Sandhya C. K. S. Pillai K. Sree Kumar 《Journal of Polymer Science.Polymer Physics》2004,42(7):1289-1298
New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004 相似文献
4.
The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH2CH2SCH2CH2OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH3CH2SCH2CH2OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results. 相似文献
5.
Shiyue Fang 《Tetrahedron letters》2004,45(43):7987-7990
A reversible biotinylation phosphoramidite was synthesized and incorporated onto the 5′-end of an oligoribonucleotide on a solid phase synthesizer. After cleavage and deprotection, the crude synthetic oligomer mixture was incubated with NeutrAvidin® coated microspheres, and the failure sequences removed by washing with a buffer followed by treating the microspheres with tetrabutylammonium fluoride to give a high quality unmodified full-length oligoribonucleotide. 相似文献
6.
以二(苯腈)-二氯化钯为催化剂,在固液相转移条件下,通过芳卤与N,N-二乙基丙烯酰胺发生偶联反应,生成了E式α,β-不饱和酰胺。碘代芳烃的偶联产率较高,从而建立了简便的2E-不饱和酰胺立体选择合成法。 相似文献
7.
8.
Three new aromatic diester–dicarboxylic acids containing furan rings, namely, benzofuro[2,3-b]benzofuran-2,9-dicarboxyl-bis-phenyl ester-4,4′-dicarboxylic acid, benzofuro[2,3-b]benzofuran-2,9-dicarboxyl-bis-phenyl ester-3,3′-dicarboxylic acid and benzofuro[2,3-b]benzofuran-2,9-dicarboxyl-bis-naphthyl ester-2,2′-dicarboxylic acid were synthesized by the reaction of benzofuro[2,3-b]benzofuran-2,9-dicarbonyl chloride with 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and 3-hydroxy-naphthalene-2-carboxylic acid, respectively. Diester–dicarboxylic acids were characterized by FT-IR and NMR spectroscopy and elemental analyses. Then, these monomers were converted to aromatic copoly(ester–amide)s by their reaction with various aromatic diamines via the direct polycondensation. These polymers were characterized by viscosity measurements, solubility tests, FT-IR, Ultraviolet and 1H-NMR spectroscopy and thermogravimetry. The polymers with inherent viscosities in the range of 0.16–0.37 dl/g in dimethyl sulfoxide at 30 °C were obtained in high yield. Most of them dissolved readily at room temperature in polar solvents. The synthesized copoly(ester–amide)s possessed glass-transition temperatures from 210–255 °C. The copoly(ester–amide)s exhibited excellent thermal stabilities and had 10% weight loss at temperature above 295 °C under nitrogen atmosphere. 相似文献
9.
Yarovenko V. N. Kosarev S. A. Zavarzin I. V. Krayushkin M. M. 《Russian Chemical Bulletin》2002,51(8):1504-1509
Carbamoylformhydroxymoyl chlorides were synthesized by the reactions of carbamoylformamide oximes with sodium nitrite in the presence of hydrochloric acid, and their reactivities were examined. 相似文献
10.
A series of methacrylamide-based C16 monolithic columns were prepared and characterized to determine how their porous structural properties and chromatographic behavior are affected by the percentages of functional monomer, base monomer, and cross-linker in the polymerization solution. Baseline separation of 6 neutral compounds can be readily obtained in an optimized column. Furthermore, the effects of organic additive in the mobile phase, operating voltages, and temperature on retention behaviors and separation efficiencies were also studied. The separation mechanism is also discussed. High column efficiency and good reproducibility indicate that the monolithic columns hold considerable promise. 相似文献