全文获取类型
收费全文 | 11062篇 |
免费 | 330篇 |
国内免费 | 50篇 |
专业分类
化学 | 7144篇 |
晶体学 | 82篇 |
力学 | 223篇 |
数学 | 1368篇 |
物理学 | 2625篇 |
出版年
2021年 | 162篇 |
2020年 | 178篇 |
2019年 | 159篇 |
2018年 | 147篇 |
2017年 | 103篇 |
2016年 | 289篇 |
2015年 | 243篇 |
2014年 | 266篇 |
2013年 | 510篇 |
2012年 | 569篇 |
2011年 | 636篇 |
2010年 | 333篇 |
2009年 | 321篇 |
2008年 | 497篇 |
2007年 | 479篇 |
2006年 | 480篇 |
2005年 | 438篇 |
2004年 | 344篇 |
2003年 | 329篇 |
2002年 | 304篇 |
2001年 | 202篇 |
2000年 | 208篇 |
1999年 | 138篇 |
1998年 | 123篇 |
1997年 | 140篇 |
1996年 | 179篇 |
1995年 | 158篇 |
1994年 | 110篇 |
1993年 | 139篇 |
1992年 | 126篇 |
1991年 | 116篇 |
1990年 | 84篇 |
1989年 | 103篇 |
1988年 | 109篇 |
1987年 | 88篇 |
1986年 | 88篇 |
1985年 | 144篇 |
1984年 | 118篇 |
1983年 | 96篇 |
1982年 | 124篇 |
1981年 | 121篇 |
1980年 | 80篇 |
1979年 | 103篇 |
1978年 | 100篇 |
1977年 | 91篇 |
1975年 | 93篇 |
1973年 | 84篇 |
1968年 | 93篇 |
1967年 | 105篇 |
1966年 | 103篇 |
排序方式: 共有10000条查询结果,搜索用时 262 毫秒
101.
Upper rim substituted tetraiodo calix[4]arenes are coupled to a variety of acrylamides using the palladium catalysed Heck reaction. Tetra-acrylamido upper rim substituted calix[4]arenes are obtained in good yields with exceptionally high stereoselectivity, to produce the all-trans isomers. Tetra-acrylamido calix[4]arenes derived from secondary acrylamides are shown to dimerise via eight hydrogen bonds to form dimeric capsules, which are able to include small organic molecules. 相似文献
102.
Single-molecule studies that allow to compute pKa values, proton affinities (gas-phase acidity/basicity) and the electrostatic energy of solvation have been performed for a heterogeneous set of 26 organic compounds. Quantum mechanical density functional theory (DFT) using the Becke-half&half and B3LYP functionals on optimized molecular geometries have been carried out to investigate the energetics of gas-phase protonation. The electrostatic contribution to the solvation energies of protonated and deprotonated compounds were calculated by solving the Poisson equation using atomic charges generated by fitting the electrostatic potential derived from the molecular wave functions in vacuum. The combination of gas-phase and electrostatic solvation energies by means of the thermodynamic cycle enabled us to compute pKa values for the 26 compounds, which cover six distinct chemical groups (carboxylic acids, benzoic acids, phenols, imides, pyridines and imidazoles). The computational procedure for determining pKa values is accurate and transferable with a root-mean-square deviation of 0.53 and 0.57 pKa units and a maximum error of 1.0 pKa and 1.3 pKa units for Becke-half&half and B3LYP DFT functionals, respectively. 相似文献
103.
The method described is based on the extraction of uranium with a chloroform solution of phenylacetic acid from slightly acidic solution containing nitrilotriacetic acid, which masks all interfering metals. After stripping into very dilute hydrochloric acid, uranium is reduced with ascorbic acid and determined complexometrically. The method permits reliable determination of uranium in the presence of all quadri-, ter- and bivalent metals investigated, molybdenum(VI), tungsten(VI), and vanadium(V). 相似文献
104.
D. L. Schmidt H. B. Smith M. Yoshimine M. J. Hatch 《Journal of polymer science. Part A, Polymer chemistry》1972,10(10):2951-2966
A new class of zwitterionic monomers were prepared in which the positive and negative sites are cyclic sulfonium and phenolate. Thermal polymerization occurs by phenolic anionic attack upon the aliphatic carbon α to the sulfonium sulfur. Polymerization proceeds with ring opening and net loss of charge to form nonionic polymers. The monomeric zwitterions are generally hydrated, crystalline solids that are soluble in water or alcohol. Chlorination of the aromatic portion of the molecule yields nonhydrated species. The polymerizations of 1-(4-hydroxy-3-methylphenyl)tetrahydrothiophenium hydroxide inner salt (dihydrate) and 1-(3,5-dichloro-4-hydroxyphenyl)tetrahydrothiophenium hydroxide inner salt were studied. The latter monomer gave a polymer with M?n of 46,000 when a nucleophile was present as an initiator. The physical properties of this polymer were determined. Cyclization appears to be the main mechanism of termination in the polymerization of zwitterions. 相似文献
105.
LiTiCl3 is obtained as one example within an ample solid solution, Li24–2nTinCl24 (?4?n?10), by synpropotionation of TiCl3 and Ti in the presence of LiCl (2:1:3 molar ratio) in sealed tantalum tubes at 750°C. It crystallizes with the inverse spinel-type structure according to (Li0.67)[4](Li0.67Ti1.33)[4]Cl4 with, at 25°C, a = 1048.62(4) pm, space group Fd3m. Thermal expansion is linear with α = 4.85 × 10?5K?1 up to about 300°C and thereafter, when the migration of Li+ from tetrahedral to octahedral interstices becomes increasingly important, it exhibits a relative decrease resulting, finally, in the phase transition to a NaCl-type structure that is observed for the first time at about 575°C. 相似文献
106.
The reactivity of benzo[b]naphtho[2,3-e][1,4]dioxin in the electrophilic aromatic substitution reactions has been studied. Friedel-Crafts acetylation resulted in the formation of three out of the possible five monoacetylated products, with the acetyl group located in positions 8 (major), 7 and 6 (minor) of the heterocycle. In the bromination reaction a higher selectivity was observed with the 6-bromo derivative found as the only monobrominated product and the 6,11-dibromo derivative found as the only polybrominated product. A ratio of unreacted heterocycle:6-bromo:6,11-dibromo derivatives in the bromination reaction has been found to depend strongly on the reaction conditions and on the heterocycle:bromine ratio. 相似文献
107.
Pd/P(t-Bu)(3) serves as an unusually reactive catalyst for Stille reactions of aryl chlorides and bromides, providing solutions to a number of long-standing challenges. An unprecedented array of aryl chlorides can be cross-coupled with a range of organotin reagents, including SnBu(4). Very hindered biaryls (e.g., tetra-ortho-substituted) can be synthesized, and aryl chlorides can be coupled in the presence of aryl triflates. The method is user-friendly, since a commercially available complex, Pd(P(t-Bu)(3))(2), is effective. Pd/P(t-Bu)(3) also functions as an active catalyst for Stille reactions of aryl bromides, furnishing the first general method for room-temperature cross-couplings. 相似文献
108.
Nicholas D. Adams Stanley J. Schmidt Steven D. Knight Dashyant Dhanak 《Tetrahedron letters》2007,48(23):3983-3986
A novel synthesis of 4H-pyrazolo-[3,4-d]pyrimidin-4-ones is described. This approach utilizes an in situ generated iminochloride as a key precursor for amidine formation, with subsequent base-catalyzed ring closure. This method represents a mild and efficient entry into this ring system which is amenable to diversification of the core template. 相似文献
109.
A method for the determination of cadmium microamounts in mixtures with metallic ions withE
1/2 near toE
1/2 of cadmium is discussed. For higher selectivity cadmium was extracted in the form of the pyridin-thiocyanate complexes prior to polarography.
Bestimmung von Cadmium(II) neben anderen Metallionen
Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Cd(II) neben anderen Metallionen mitE 1/2 naheE 1/2(Cd) diskutiert. Zur Erhöhung der Selektivität und Genauigkeit wird eine Pyridin-Thiocyanat-Extraktion vorgeschalten.相似文献
110.
Chloro-dimethylaminosulfonium Salts. Preparation and I. R. Spectra By reaction of bis-dimethylamino-mono- resp. -disulfane with a mixture of chlorine/antimony(V) chloride the chloro dimethylaminosulfonium hexachloroantimonates(V) [(CH3)2N]2SCI⊕SbCl6? (I) and (CH3)2NSCI2⊕SbCl6? (II) are yielded. The i. r. spectra of these compounds were measured and assigned. 相似文献