全文获取类型
收费全文 | 40311篇 |
免费 | 3131篇 |
国内免费 | 5125篇 |
专业分类
化学 | 23286篇 |
晶体学 | 1257篇 |
力学 | 2231篇 |
综合类 | 494篇 |
数学 | 14298篇 |
物理学 | 7001篇 |
出版年
2024年 | 54篇 |
2023年 | 363篇 |
2022年 | 1010篇 |
2021年 | 1018篇 |
2020年 | 970篇 |
2019年 | 917篇 |
2018年 | 818篇 |
2017年 | 1028篇 |
2016年 | 1081篇 |
2015年 | 921篇 |
2014年 | 1506篇 |
2013年 | 2935篇 |
2012年 | 2134篇 |
2011年 | 2433篇 |
2010年 | 2370篇 |
2009年 | 2671篇 |
2008年 | 2729篇 |
2007年 | 2809篇 |
2006年 | 2526篇 |
2005年 | 2252篇 |
2004年 | 2109篇 |
2003年 | 1963篇 |
2002年 | 1669篇 |
2001年 | 1323篇 |
2000年 | 1258篇 |
1999年 | 1019篇 |
1998年 | 946篇 |
1997年 | 780篇 |
1996年 | 689篇 |
1995年 | 633篇 |
1994年 | 543篇 |
1993年 | 453篇 |
1992年 | 432篇 |
1991年 | 339篇 |
1990年 | 228篇 |
1989年 | 226篇 |
1988年 | 219篇 |
1987年 | 156篇 |
1986年 | 126篇 |
1985年 | 143篇 |
1984年 | 144篇 |
1983年 | 56篇 |
1982年 | 106篇 |
1981年 | 107篇 |
1980年 | 87篇 |
1979年 | 69篇 |
1978年 | 51篇 |
1977年 | 36篇 |
1976年 | 31篇 |
1974年 | 17篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
992.
Vilsmeier–Haack‐type cyclization of 1H‐indole‐4‐propanoic acid derivatives was examined as model construction for the A–B–C ring system of lysergic acid ( 1 ). Smooth cyclization from the 4 position of 1H‐indole to the 3 position was achieved by Vilsmeier–Haack reaction in the presence of K2CO3 in MeCN, and the best substrate was found to be the N,N‐dimethylcarboxamide 9 (Table 1). The modified method can be successfully applied to an α‐amino acid derivative protected with an N‐acetyl function, i.e., to 27 (Table 2); however, loss of optical purity was observed in the cyclization when a chiral substrate (S)‐ 27 was used (Scheme 5). On the other hand, the intramolecular Pummerer reaction of the corresponding sulfoxide 20 afforded an S‐containing tricyclic system 22 , which was formed by a cyclization to the 5 position (Scheme 3). 相似文献
993.
994.
Bis(cyclodisilazane-1-yl) dimethylsilanes — Synthesis and Reactions The monolithium derivate of trisilazan-1-yl-cyclodisilazane 1 reacts with F3SiN (SiMe3)2 with substitution. The silyl-bridged cyclodisilazanes 3–6 are formed in the reaction of the dilithium derivate of 1 with fluoro- and chlorosilanes. Using lithiumamide and lithiummethanolate a controlled exchange of one fluoro atom of 4 occurs ( 7,8 ). 9 and 10 are formed by hydrolysis of 4 . The aminofunctional compounds 11 und 12 are obtained in the reaction of 5 and 6 with NH3. The dispirocyclus 13 is formed in the reaction of 8 with tert.-butyllithium. The reaction of dilithiated 1 with 4 gives the spirocyclus 14 . The crystal structure of 14 is discussed. 相似文献
995.
Reinvestigation of the acid-catalyzed cyclization of 1-(3-hydroxypropynyl)cyclododecan-1-ol under the conditions of the Nazarov
reaction demonstrated that this conversion yields two isomeric bicyclic ketones, namely, bicyclo[10.3.0]pentadec-1(12)-en-13-one
and bicyclo[10.3.0]pentadec-1-en-3-one. The latter compound is thermodynamically less stable.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1325–1327, July, 1997. 相似文献
996.
G.B. Song C.Q. Han J.K. Liang Q.L. Liu F.S. Liu G.H. Rao 《Journal of solid state chemistry》2004,177(7):2394-2403
The subsolidus phase relations of the PrOx-CaO-CuO pseudo-ternary system sintered at 950-1000°C have been investigated by X-ray powder diffraction. In this system, there exist one compound Ca10Pr4Cu24O41, one Ca2Pr2Cu5O10-based solid solution, seven three-phase regions and two two-phase regions. The crystal structures of Ca10Pr4Cu24O41 and Ca2Pr2Cu5O10-based solid solution have been determined. Compound Ca10Pr4Cu24O41 crystallizes in an orthorhombic cell with space group D2h20−Cccm, Z=4. Its lattice parameters are a=11.278(2) Å, b=12.448(3) Å and c=27.486(8) Å. The crystal structure of Ca2Pr2Cu5O10-based solid solution is an incommensurate phase based on the orthorhombic NaCuO2 type subcell. The lattice parameters of the subcell of the Ca2.4Pr1.6Cu5O10 are a0=2.8246(7) Å, b0=6.3693(5) Å, c0=10.679(1) Å, and those of the orthorhombic superstructure are with a=5a0, b=b0, c=5c0. The Ca2.4Pr1.6Cu5O10 structure can also be determined by using a monoclinic supercell with space group C2h5−P21/c, Z=4, a=5a0, b=b0, and β=104.79(1)° or 136.60(1)°, V=5a0b0c0. 相似文献
997.
Martina Gudelj Paola urina Lucija Jurko Ante Prki Perica Bokovi 《Molecules (Basel, Switzerland)》2021,26(12)
Micellar systems are colloids with significant properties for pharmaceutical and food applications. They can be used to formulate thermodynamically stable mixtures to solubilize hydrophobic food-related substances. Furthermore, micellar formation is a complex process in which a variety of intermolecular interactions determine the course of formation and most important are the hydrophobic and hydrophilic interactions between surfactant–solvent and solvent–solvent. Glycols are organic compounds that belong to the group of alcohols. Among them, propane-1,2-diol (PG) is a substance commonly used as a food additive or ingredient in many cosmetic and hygiene products. The nature of the additive influences the micellar structure and properties of sodium dodecyl sulfate (SDS). When increasing the mass fraction of propane-1,2-diol in binary mixtures, the c.m.c. values decrease because propane-1,2-diol is a polar solvent, which gives it the ability to form hydrogen bonds, decreasing the cohesivity of water and reducing the dielectric constant of the aqueous phase. The values of are negative in all mixed solvents according to the reduction in solvophobic interactions and increase in electrostatic interaction. With the rising concentration of cosolvent, the equilibrium between cosolvent in bulk solution and in the formed micelles is on the side of micelles, leading to the formation of micelles at a lower concentration with a small change in micellar size. According to the 1H NMR, with the addition of propylene glycol, there is a slight shift of SDS peaks towards lower ppm regions in comparison to the D2O peak. The shift is more evident with the increase in the amount of added propane-1,2-diol in comparison to the NMR spectra of pure SDS. Addition of propane-1,2-diol causes the upfield shift of the protons associated with hydrophilic groups, causing the shielding effect. This signifies that the alcohol is linked with the polar head groups of SDS due to its proximity to the SDS molecules. 相似文献
998.
Imre T Schlosser G Pocsfalvi G Siciliano R Molnár-Szöllosi E Kremmer T Malorni A Vékey K 《Journal of mass spectrometry : JMS》2005,40(11):1472-1483
A new anionic surfactant (RapiGest SF) was successfully used for site-specific analysis of glycosylation in human alpha-1-acid glycoprotein (AGP). By means of this analytical approach combined with capillary HPLC-mass spectrometry (and tandem mass spectrometry), the N-linked glycosylation pattern of AGP was explored. On the basis of mass matching and MS/MS experiments ca 80 different AGP-derived glycopeptides were identified. Glycosylation shows a markedly different pattern for the various glycosylation sites. At sites I and II, triantennary complex-type oligosaccharides predominate and at sites III, IV and V, tetra-antennary complex-type oligosaccharides predominate. Sites IV and V show the presence of additional N-acetyl lactosamine (Gal-GlcNAc) units (even higher degree of branching and/or longer antennae are also present). 相似文献
999.
The relation between thermochromism and thermal motion of aromatic rings on model bithiophene and 3-butylbithiophene molecules was studied by molecular dynamics (MD) simulations based on semiempirical AM1 hamiltonian. Theoretical optical spectra at various temperatures are generated from the conformations obtained from MD calculations. Alkyl chains have a tendency to tilt bithiophene fragments from co-planarity (connected with blue shift) whereas the unsubstituted systems prefer the higher degree of planarity (connected with red shift) upon the temperature increase. The slope of the linear temperature dependence of the reciprocal maximal wavelengths consists of the above electronic and of the vibrational contribution that (according to Wien’s displacement law) causes always the increase of the above mentioned slope by reciprocal Wien’s constant. This model explains the temperature dependence of experimental UV–vis spectra for dibutylheptathiophene and 3′,3,4′,4-tetrahexylhexathiophene. 相似文献
1000.