全文获取类型
收费全文 | 2356篇 |
免费 | 128篇 |
国内免费 | 326篇 |
专业分类
化学 | 2185篇 |
晶体学 | 22篇 |
力学 | 98篇 |
数学 | 73篇 |
物理学 | 432篇 |
出版年
2024年 | 1篇 |
2023年 | 277篇 |
2022年 | 66篇 |
2021年 | 65篇 |
2020年 | 140篇 |
2019年 | 80篇 |
2018年 | 86篇 |
2017年 | 105篇 |
2016年 | 113篇 |
2015年 | 119篇 |
2014年 | 140篇 |
2013年 | 158篇 |
2012年 | 168篇 |
2011年 | 134篇 |
2010年 | 111篇 |
2009年 | 120篇 |
2008年 | 115篇 |
2007年 | 139篇 |
2006年 | 126篇 |
2005年 | 74篇 |
2004年 | 44篇 |
2003年 | 63篇 |
2002年 | 49篇 |
2001年 | 97篇 |
2000年 | 30篇 |
1999年 | 76篇 |
1998年 | 50篇 |
1997年 | 23篇 |
1996年 | 13篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
排序方式: 共有2810条查询结果,搜索用时 15 毫秒
31.
《Tetrahedron: Asymmetry》2005,16(3):615-622
Fatty acid esters of cyclodextrins (CDs) were synthesised in a one-step reaction with native CDs as acyl acceptors and vinyl-activated fatty acid esters as acyl donors. Immobilised preparations of thermolysin, subtilisin, the alkaline protease AL-89 and Candida antarctica lipase B were investigated for their catalytic properties regarding transesterification in solvents of increasing hydrophilicity. The synthesis of cyclodextrin fatty acid esters was proved to be catalysed enzymatically by thermolysin in DMSO. The obtained products were analysed by TLC and their structures characterised by NMR, MS and FTIR spectroscopy. With vinyl decanoate as acyl donor β-CD was esterified at all seven glucose C-2 positions resulting in heptakis(2-O-decanoyl)-β-cyclodextrin as the major product. With vinyl butyrate, substitution occurred at all the C-2 and partially at the C-3 or C-6 positions resulting in an average degree of substitution of nine. Between 20% and 25% (w/w) of the acyl donor was converted to esters in 20 h corresponding to an estimated total conversion of the acyl acceptor in the case of maltosyl-β-CD. In the subtilisin and AL-89 catalysed reactions, product formation was simultaneously catalysed non-enzymatically by inorganic buffer salts in aprotic, hydrophilic solvents and with the lipase no products were formed in any of the solvents investigated. 相似文献
32.
《Radiation Physics and Chemistry》2007,76(8-9):1463-1465
Ionizing radiation is widely used as treatment technique for food preservation. It involves among others reduction of microbial contamination, disinfestations, sprout inhibition and extension of shelf life of food. However, the commercialization of irradiated food requires the availability of reliable methods to identify irradiated foodstuffs. In this paper, we present results on the application to irradiated chicken of this method, based on the detection, in muscle and skin samples, of the peaks of ions 98 Da and 112 Da, in a ratio approximately 4:1, typical of radiation induced 2-dodecylcyclobutanones (2-DCB). Aim of the work was also to study the time stability of the measured parameters in samples irradiated at 3 and 5 kGy, and to verify the efficacy of the treatment from a microbiological point of view. Our results show that, one month after irradiation at 3 kGy, the method is suitable using the skin but not the muscle, while the measured parameters are detectable in both samples irradiated at 5 kGy. The microbial population was substantially reduced even at 3 kGy. 相似文献
33.
Jun Zhou Jie Yang Li Qi Xuan Shen Dunru Zhu Yan Xu You Song 《Transition Metal Chemistry》2007,32(6):711-715
A novel dinuclear nickel(II) complex, [Ni2(MOBPT)2Cl2(H2O)2]Cl2 · 7H2O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray
diffraction methods. The crystal structure determination shows that the dinuclear Ni2N8 unit is almost planer in which each NiII ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted
octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex. 相似文献
34.
Zou Jianzhong Wu Yong Duan Chunyin Liu Yongjiang Xu Zheng 《Transition Metal Chemistry》1998,23(3):305-308
Three binuclear copper(II) complexes bridged by three different bridging ligands: μ-TPHA (terephthalato), μ-PHTA (phthalato)
and μ-TCB (tetracarboxylatobenzene) have been synthesized. The crystal structure of [{Cu(dipn)}2(μ-TPHA)](ClO4)2 where dipn = N-(3-aminopropyl)-1,3-propanediamine was solved at room temperature. The [{Cudipn}2(μ-TPHA)](ClO4)2 complex consists of a μ-terephthalato bridging binuclear copper(II) cationic unit and two non-coordinated perchlorate anions.
The TPHA ligand bridges in a bismonodentate fashion. The environment of the copper(II) ion is a distorted plane-square-planar coordination sphere. The magnetic
properties of the three complexes have been investigated in the 75–300 K range, and show that the geometry of the CuII atom is the important factor for magnetic interactions in the terephthalato bridging binuclear copper(II) complexes.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
35.
A novel carrier of ultradispersed diamond black powder (UDDBP) was used to support metallocene catalyst. Al2O3 was also used as carrier in order to compare with UDDBP. Supported catalysts for ethylene polymerization were synthesized by two different reaction methods. One way was direct immobilization of the metallocene on the support, the other was adsorption of MAO onto the support followed by addition of the metallocene. Four supported catalysts Cp2ZrCl2/UDDBP, Cp2ZrCl2/Al2O3, Cp2ZrCl2/MAO/UDDBP and Cp2ZrCl2/Al2O3/MAO were obtained. The content of the zirconium in the supported catalyst was determined by UV spectroscopy. The activity of the ethylene polymerization catalyzed by supported catalyst was investigated. The influence of Al/Zr molar ratio and polymerization temperature on the activity was discussed. The polymerization rate was also observed. 相似文献
36.
《Tetrahedron: Asymmetry》2006,17(6):900-907
Recently prepared chiral amines have been used in the preparation of novel tridentate ligands based on an imidazole ring with an additional (hetero)ring. The synthesis was carried out by the reaction of chiral amines with suitable aldehydes (2-phenylimidazole-4-carbaldehyde, 2-hydroxybenzaldehyde or pyridine-2-carbaldehyde) under reductive conditions (H2/Pd or NaBH4). All ligands prepared showed strong hydrogen bonds in d6-DMSO solution, which resulted in hindered imidazole tautomerism. The observed hindered tautomerism was studied by 1H NMR spectroscopy. The structures of the prepared ligands were also confirmed by APCI mass spectroscopy. Both chiral amines and tridentate compounds have been applied as ligands in copper (II)-catalyzed nitroaldol reactions (Henry reaction). Various reaction conditions for the Henry reaction have been studied (influence of temperature, molar ratio, solvent or copper (II) precursors). The compounds prepared with the two imidazole rings showed fast reaction times and a reversal in enantioselectivity compared to other chiral amines. 相似文献
37.
《Tetrahedron: Asymmetry》2005,16(3):605-608
The addition of organogallium to aldehydes was realized with titanium tetrachloride as a Lewis acid catalyst. For the first time, the catalytic asymmetric addition of organogallium to aldehydes was investigated with chiral titanium complexes, which were formed from titanium tetrachloride and salan ligands, with mediocre to good chemical yields and enantioselectivities. 相似文献
38.
松香的主要成份是枞酸型树脂酸,其因共轭双键的存在而易被氧化,大大降低了其附加值。经氢化后的松香具有抗氧性好、脆性小、热稳定性高、颜色浅等特点,因而广泛应用于胶粘剂、合成橡胶、涂料、油黑、造纸、电子、食品等工业部门[1]。采用催化加氢的方法可使枞酸型树脂酸中的共轭双键消除[2]。以枞酸为代表的反应式为:松香催化加氢主要有熔融法[3]和溶剂法[4],所用催化剂主要是Pd和N i。熔融法制氢化松香,当反应温度低于200℃时,枞酸加氢速度较慢,反应不完全。温度升高,氢化松香中枞酸含量显著地减少,但温度高于250℃时,树脂酸脱羧严重,甚至… 相似文献
39.
The complex [Cd(tren)(meim)](ClO4)2 was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in monoclinic system, space group P21/m with a=0.786 8(2) nm, b=0.834 2(2) nm, c=1.496 2(4) nm, Mr=538.64, Z=2, F(000)=542, Dc=1.822 g·cm-3, T=298(2) K, μ=1.435 mm-1 and λ=0.071 073 nm. The structure was refined to R=0.045 8 and wR=0.123 1 for 1 489 observed reflections with I>2σ(I). The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method. It was found to be active against the four test bacterial organisms. CCDC: 600198. 相似文献
40.
Min-zhi Chen Xiao-liang Wang Fang-fang Tao Qi Xue Ping-chuan 《高分子科学》2007,(1):107-111
The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale (several to tens of nanometer). In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level. 相似文献