全文获取类型
收费全文 | 6796篇 |
免费 | 208篇 |
国内免费 | 17篇 |
专业分类
化学 | 4180篇 |
晶体学 | 115篇 |
力学 | 234篇 |
数学 | 843篇 |
物理学 | 1649篇 |
出版年
2022年 | 87篇 |
2021年 | 141篇 |
2020年 | 154篇 |
2019年 | 105篇 |
2018年 | 82篇 |
2017年 | 75篇 |
2016年 | 210篇 |
2015年 | 174篇 |
2014年 | 162篇 |
2013年 | 292篇 |
2012年 | 336篇 |
2011年 | 427篇 |
2010年 | 253篇 |
2009年 | 213篇 |
2008年 | 326篇 |
2007年 | 328篇 |
2006年 | 325篇 |
2005年 | 273篇 |
2004年 | 279篇 |
2003年 | 221篇 |
2002年 | 184篇 |
2001年 | 117篇 |
2000年 | 111篇 |
1999年 | 71篇 |
1998年 | 62篇 |
1997年 | 75篇 |
1996年 | 88篇 |
1995年 | 71篇 |
1994年 | 65篇 |
1993年 | 68篇 |
1992年 | 69篇 |
1991年 | 52篇 |
1990年 | 56篇 |
1989年 | 61篇 |
1988年 | 67篇 |
1987年 | 62篇 |
1986年 | 54篇 |
1985年 | 56篇 |
1984年 | 45篇 |
1983年 | 61篇 |
1982年 | 47篇 |
1981年 | 69篇 |
1980年 | 51篇 |
1979年 | 65篇 |
1978年 | 63篇 |
1977年 | 53篇 |
1976年 | 48篇 |
1975年 | 34篇 |
1974年 | 37篇 |
1973年 | 37篇 |
排序方式: 共有7021条查询结果,搜索用时 15 毫秒
71.
Gallo E Caselli A Ragaini F Fantauzzi S Masciocchi N Sironi A Cenini S 《Inorganic chemistry》2005,44(6):2039-2049
A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru(IV)(TPP)(OH)]2O, a reported byproduct in the synthesis of [Ru(VI)(TPP)(O)2], was synthesized in a pure form by oxidation of [Ru(II)(TPP)(CO)L] or by a coproportionation reaction of [Ru(VI)(TPP)(O)2] and [Ru(II)(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru(VI)(TPP)(O)2] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru(II)(TPP)(S-DMSO)2] or [Ru(II)(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis. 相似文献
72.
We present a combined Molecular Dynamics/Quantum Chemical study of the solvent-mediated electronic coupling between an electron donor and acceptor in a C-clamp molecule. We characterize the coupling fluctuations due to the solvent motion for different solvents (acetonitrile, benzene, 1,3-diisopropyl-benzene) for the charge separation and the charge recombination processes. The time scale for solvent-induced coupling fluctuation is approximately 0.1 ps. The effect of these fluctuations on the observed rate is discussed using a recently developed theoretical model. We show that, while the microscopic charge transfer process is very complicated and its computational modeling very subtle, the macroscopic phenomenology can be captured by the standard models. Analyzing the contribution to the coupling given by different solvent orbitals, we find that many solvent orbitals mediate the electron transfer and that paths through different solvent orbitals can interfere constructively or destructively. A relatively small subset of substrate-solvent configurations dominate contributions to solvent-mediated coupling. This subset of configurations is related to the electronic structure of the C-clamp molecule. 相似文献
73.
The tetraphosphides (tBu3Si)3P4M3 (M = Li, Na) and (tBu2PhSi)3P4Na3 have been synthesized in high yield from the reaction of 3 equivalents of the silanides tBu3SiM (M = Li, Na) and tBu2PhSiNa with P4 in benzene. (tBu3Si)3P4M3 (M = Li, Na) are transformed into the unsaturated triphosphides (tBu3Si)2P3M (M = Li, Na) and tBu3SiPM2 in tetrahydrofuran at ambient temperature. 相似文献
74.
For the assignment of the configuration at C(8) and C(15) of the natural oviposition-deterring pheromone 1 in Rhagoletis cerasi L., the four possible stereoisomers of 1 are synthesized. By condensing the C6 building blocks (5R)- 4 and (5S)- 4 with the boron enolates of the C10 building blocks (4S)- 13 and (4R)- 13 , followed by decarboxylative dehydration, all stereoisomers of 16 are available (Scheme 5). Glucosylation of 16 followed by formation of the taurin amide gives, after deprotection, the four stereoisomers (8R,15S)- 1 , (8R,15R)- 1 , (8R,15S) -1 , and (8S,15S)- 1 (Scheme 6). 相似文献
75.
Arseniyadis S Subhash PV Valleix A Wagner A Mioskowski C 《Chemical communications (Cambridge, England)》2005,(26):3310-3312
The high-yielding synthesis and application of the first polymer supported reagent for the kinetic resolution (KR) of amines through enantioselective acetylation is described; this new supported chiral reagent allows the KR of primary amines with excellent selectivities at room temperature; moreover, this supported approach is highly efficient as the Merrifield-supported chiral scaffold can be quantitatively recovered and recycled. 相似文献
76.
Extremely localized molecular orbitals (ELMOs), namely orbitals strictly localized on molecular fragments, are easily transferable from one molecule to another one. Hence, they provide a natural way to set up the electronic structure of large molecules using a data base of orbitals obtained from model molecules. However, this procedure obviously increases the energy with respect to a traditional MO calculation. To gain accuracy, it is important to introduce a partial electron delocalization. This can be carried out by defining proper optimal virtual orbitals that supply an efficient set for nonorthogonal configurations to be employed in VB-like expansions. 相似文献
77.
Manetta AC Di Giuseppe L Giammarco M Fusaro I Simonella A Gramenzi A Formigoni A 《Journal of chromatography. A》2005,1083(1-2):219-222
A new HPLC method with fluorescence detection using pyridinium hydrobromide perbromide as a post-column derivatising agent has been developed to determine aflatoxin M1 in milk and cheese. The detection limits were 1 ng/kg for milk and 5 ng/kg for cheese. The calibration curve was linear from 0.001 to 0.1 ng injected. The method includes a preliminary C18-SPE clean-up and the average recoveries of Aflatoxin M1 from milk and cheese, spiked at levels of 25-75 ng/kg and 100-300 ng/kg, respectively, were 90 and 76%; the precision (RSDr) ranged from 1.7 to 2.6% for milk and from 3.5 to 6.5% for cheese. The method is rapid, easily automatable and therefore useful for accurate and precise screening of aflatoxin M1 in milk and cheese. 相似文献
78.
Abstract— Escherichia coli cells treated with sublethal doses of acridine plus near-UV light exhibit an effective split-dose recovery response that requires an incubation period of about 30–45 min. Studies of the metabolic requirements for split-dose recovery revealed the following: (a) DNA synthesis is not required for split-dose recovery; (b) inhibition of electron transport or protein synthesis reduces the efficiency of split-dose recovery by about one-half; (c) inhibition of phospholipid synthesis or cell wall synthesis completely eliminates the split-dose recovery response. These results suggest an involvement of membrane repair mechanisms in response to damage by acridine plus near-UV light. Additional evidence for such a process was provided by more direct assays for membrane recovery. It was found that cells treated with sublethal doses of acridine plus near-UV light are sensitive to low concentrations of detergents, and lose that sensitivity upon incubation. Likewise, treated cells are susceptible to lethal osmotic shock, but can recover from this susceptibility if incubated after treatment but prior to exposure to low osmotic conditions. Based on accumulating evidence, we propose that E. coli cells are capable of repairing membrane damage resulting from exposure to acridine plus near-UV light. 相似文献
79.
Substituierte 2-(Thiazol-4-yl)-phenole als Liganden und potentielle Extraktionsmittel für Kupfer(II)
Substituted 2-(Thiazol-4-yl)-phenols as Ligands and Potential Extractants for Copper (II) Substituted 2-(thiazol-4-yl)-phenols are obtained by the HANTZSCH synthesis. Their solubility in toluene is higher than in n-octane depending on the position, the chain length, and the polarity of the substituents. From alcoholic solutions complexes of the type CuL2n are precipitated. According to the substituents their structure is distorted octahedral (CuL22, CuL23) or distorted tetrahedral (CuL28, CuL29). The new complexes are nearly insoluble in toluene and aliphatic hydrocarbons, but CuL28 and CuL29 are soluble in chloroform. Therefore copper(II) may be extracted by HL8 and HL9 using chloroform as a diluent. 相似文献
80.
Crovella S Antcheva N Zelezetsky I Boniotto M Pacor S Verga Falzacappa MV Tossi A 《Current protein & peptide science》2005,6(1):7-21
Host defense peptides (HDPs) are endogenous antibiotics that play a multifunctional role in the innate immunity of mammals. Among these, beta-defensins contribute to mucosal and epithelial defense, also acting as signal molecules for cellular components of innate and adaptive immunity. Numerous members of this family have been identified in mammalian and avian species, and genomic studies in human and mouse indicate a considerable complexity in their gene organization. Recent reports on the evolution of primate and rodent members of this family indicate quite a complex pattern of variation. In this review we briefly discuss the evolution of mammalian beta-defensins in relation to other types of defensins, and then concentrate on the evolution of beta-defensins 1 to 4 in primates. In particular, the surprisingly varied patterns of evolution, which range from neutral or weakly purifying, to positive selection to a high level of conservation are analyzed in terms of possible genetics, structural or functional implications, as well as to observed variations on the antimicrobial activity in vitro. The role of polymorphisms in the genes encoding for these host defense peptides in determining susceptibility to human diseases are also briefly considered. 相似文献