全文获取类型
收费全文 | 5320篇 |
免费 | 662篇 |
国内免费 | 532篇 |
专业分类
化学 | 3801篇 |
晶体学 | 48篇 |
力学 | 258篇 |
综合类 | 42篇 |
数学 | 819篇 |
物理学 | 1546篇 |
出版年
2024年 | 9篇 |
2023年 | 75篇 |
2022年 | 114篇 |
2021年 | 174篇 |
2020年 | 209篇 |
2019年 | 215篇 |
2018年 | 182篇 |
2017年 | 160篇 |
2016年 | 240篇 |
2015年 | 227篇 |
2014年 | 260篇 |
2013年 | 357篇 |
2012年 | 419篇 |
2011年 | 453篇 |
2010年 | 288篇 |
2009年 | 259篇 |
2008年 | 336篇 |
2007年 | 248篇 |
2006年 | 234篇 |
2005年 | 230篇 |
2004年 | 200篇 |
2003年 | 186篇 |
2002年 | 231篇 |
2001年 | 175篇 |
2000年 | 131篇 |
1999年 | 98篇 |
1998年 | 90篇 |
1997年 | 51篇 |
1996年 | 106篇 |
1995年 | 72篇 |
1994年 | 56篇 |
1993年 | 42篇 |
1992年 | 42篇 |
1991年 | 35篇 |
1990年 | 38篇 |
1989年 | 26篇 |
1988年 | 25篇 |
1987年 | 25篇 |
1986年 | 16篇 |
1985年 | 25篇 |
1984年 | 19篇 |
1983年 | 8篇 |
1982年 | 27篇 |
1981年 | 20篇 |
1980年 | 16篇 |
1979年 | 19篇 |
1977年 | 9篇 |
1976年 | 9篇 |
1975年 | 6篇 |
1974年 | 5篇 |
排序方式: 共有6514条查询结果,搜索用时 468 毫秒
71.
The Ullmann-type coupling reaction of vinyl bromides and imidazoles in ILs at 90-110 degrees C gave the corresponding N-vinylimidazoles in good to excellent yields by using L-proline as the ligand; the double bond geometry of the vinyl bromides was retained under the reaction conditions. 相似文献
72.
Ly A Bandong SL Tran NQ Sullivan KJ Milligan JR 《The journal of physical chemistry. B》2005,109(27):13368-13374
Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair. 相似文献
73.
热重分析(TG)和微商热重法(DTG)广泛应用于各个研究领域,用非等温热重法测定固体化合物的热分解动力学参数已有报导.许多作者提出各种不同的数据处理方法.本文用的ρ-CH_3C_6H_4SR 型硫醚对钯的萃取具有选择性好、分配比高、气味较小、易溶于脂肪烃类溶剂、易于合成、是很有发展前途的一类萃取剂.我们合成五种ρ-CH_3C_6H_4SR(R:n-C_4H_9,n-C_6H_(13),n-C_8H_(17),n-C_(10)H_(21),n-C_(12)H_(25))型硫醚与钯(Ⅱ)的配合物,用TG-DTG 法研究它们的热分解过程,用微商法(Freeman-Carroll 方程)及积分法(Coats-Redfern 方程)获得了这些配合物的热分解动力学参数. 相似文献
74.
75.
Dai H Choe WS Thai CK Sarikaya M Traxler BA Baneyx F Schwartz DT 《Journal of the American Chemical Society》2005,127(44):15637-15643
We show that a protein with no intrinsic inorganic synthesis activity can be endowed with the ability to control the formation of inorganic nanostructures under thermodynamically unfavorable (nonequilibrium) conditions, reproducing a key feature of biological hard-tissue growth and assembly. The nonequilibrium synthesis of Cu(2)O nanoparticles is accomplished using an engineered derivative of the DNA-binding protein TraI in a room-temperature precursor electrolyte. The functional TraI derivative (TraIi1753::CN225) is engineered to possess a cysteine-constrained 12-residue Cu(2)O binding sequence, designated CN225, that is inserted into a permissive site in TraI. When TraIi1753::CN225 is included in the precursor electrolyte, stable Cu(2)O nanoparticles form, even though the concentrations of [Cu(+)] and [OH(-)] are at 5% of the solubility product (K(sp,Cu2O)). Negative control experiments verify that Cu(2)O formation is controlled by inclusion of the CN225 binding sequence. Transmission electron microscopy and electron diffraction reveal a core-shell structure for the nonequilibrium nanoparticles: a 2 nm Cu(2)O core is surrounded by an adsorbed protein shell. Quantitative protein adsorption studies show that the unexpected stability of Cu(2)O is imparted by the nanomolar surface binding affinity of TraIi1753::CN225 for Cu(2)O (K(d) = 1.2 x 10(-)(8) M), which provides favorable interfacial energetics (-45 kJ/mol) for the core-shell configuration. The protein shell retains the DNA-binding traits of TraI, as evidenced by the spontaneous organization of nanoparticles onto circular double-stranded DNA. 相似文献
76.
77.
Kang De Yao Tao Peng Han Bao Feng Yu Ying He 《Journal of polymer science. Part A, Polymer chemistry》1994,32(7):1213-1223
The aqueous swelling kinetics of a series of crosslinked chitosan (cr-CS) with glutaraldehyde (GA) interpenetrating polyether hydrogels have been studied as functions of pH, the N-deacetylation degree of chitosan, the amount of crosslinking agent, the electrolyte composition in solution, temperature, and gel composition. Based on these results, the swelling mechanism of the hydrogels was discussed. The release profiles of chlorhexidini acetas from the semi-IPN were also investigated. © 1994 John Wiley & Sons, Inc. 相似文献
78.
氯氧化镁在水中的溶解行为 总被引:3,自引:0,他引:3
用pH法和氯电位法测定氯氧化镁不同温度下在水中的溶解过程。一定间隔时间分析液样中的Mg^2+、Cl^-、OH^-的浓度,用物化方法鉴定固相。得出不同温度下的相转化、溶解的C ̄t曲线及动力学方程。计算了它们的Ksp和热力学函数。 相似文献
79.
Yvette Mettey Jean-Michel Vierfond Claude Thai Marcel Miocque 《Journal of heterocyclic chemistry》1983,20(1):133-137
The action of organolithium reagents such as phenyllithium or n-bulyllithium on 2-methylquinoxaline gave lithiation of the methyl group which upon reaction with electtropholesphiles produce side chain alkenyl derivatives. On the other hand organolithium reagents react with the quinoxaline azomethine bond to give I-lithio-2-alkyl)or ary-1)-3 methylquinoxalines which can be further loithiated on the methyl group to give 2-alkyl(or aryl)-3-alkenylquinoxaline derivatives. The adducts can be condensed with clectrophiles such as benzonitrile or methlyl benzoate but only methyl benzoate leads to N condensed derivatives. Furthermore substituted 1,2,3,4-terahydroqinoxalines are available via the above lithio intermediates. 相似文献
80.
Inrecentyears,thenewsedricrystallinepolymersyndiotacticp0lystyrene(sPS)hasat-ITactedmuchattentionduetoitsg0odchendcalresistanceandenhancedmechanicalperformanceatelevatedtemPeratUre.'H0wever,itexhibitshighbrittlenessandpoorimPact-resistanceandtCar-resistance.2Therefore,itisnecessarytomodifyitwithtougheningpolyIners.AsimPlemeth0dto0verc0methedriscibilityofatwo-phaseblendofsPSandatougheningpolymristotwrovetheinterfacialaffmity,wheretheadditionofablockcoP0lymerisconsideredtobemosteffective.3… 相似文献