全文获取类型
收费全文 | 1130篇 |
免费 | 56篇 |
国内免费 | 491篇 |
专业分类
化学 | 1611篇 |
晶体学 | 8篇 |
综合类 | 4篇 |
数学 | 1篇 |
物理学 | 53篇 |
出版年
2024年 | 2篇 |
2023年 | 5篇 |
2022年 | 23篇 |
2021年 | 28篇 |
2020年 | 33篇 |
2019年 | 35篇 |
2018年 | 40篇 |
2017年 | 39篇 |
2016年 | 38篇 |
2015年 | 41篇 |
2014年 | 61篇 |
2013年 | 149篇 |
2012年 | 73篇 |
2011年 | 79篇 |
2010年 | 59篇 |
2009年 | 82篇 |
2008年 | 81篇 |
2007年 | 94篇 |
2006年 | 77篇 |
2005年 | 82篇 |
2004年 | 81篇 |
2003年 | 73篇 |
2002年 | 48篇 |
2001年 | 41篇 |
2000年 | 52篇 |
1999年 | 32篇 |
1998年 | 31篇 |
1997年 | 29篇 |
1996年 | 37篇 |
1995年 | 23篇 |
1994年 | 31篇 |
1993年 | 23篇 |
1992年 | 11篇 |
1991年 | 9篇 |
1990年 | 15篇 |
1989年 | 1篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1982年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有1677条查询结果,搜索用时 15 毫秒
31.
Prasain JK Moore R Hurst JS Barnes S van Kuijk FJ 《Journal of mass spectrometry : JMS》2005,40(7):916-923
Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample. 相似文献
32.
采用溶液缩聚法由酰氯端基聚醚酮酮(PEKK)齐聚物和4,4′-二苯氧基二苯砜(DPODPS)制备了PEKK/DPODPS多嵌段共聚物,用DSC、TGA等方法对共聚物进行了表征和性能测试。结果表明,随着共聚物中DPODPS含量的增加,共聚物的熔融温度逐渐降低,而其玻璃化转变温度则逐渐升高。当DPODPS质量分数在32.63%~40.73%范围内时,所得共聚物的Tg为185~193℃,比纯PEKK的Tg高出20~28℃;其Tm为322~346℃,比纯PEKK的Tm降低35~59℃,这既保持了纯PEKK的耐热性,又改善了熔融加工性能。该组成范围内的共聚物的拉伸强度(σi)为86.6~84.2MPa,拉伸模量(M)为3.1~3.4GPa,断裂伸长率(ε)为18.5%~20.3%。 相似文献
33.
34.
Density functional (BLYP, B3LYP and BHLYP) and highly correlated MP2 and CCSD(T) calculations have been performed to investigate conformers, energy barriers, intramolecular H-bond strength, gas-phase basicity and deprotonation energies of glyoxilic acid oxime (gao) and related ions in gas phase and in aqueous solution (SCRF-PCM method). BHLYP/6-311G(d,p) and B3LYP/6-31++G(d) predictions for the global minimum conformer of gao were consistent with experiment. BLYP level overestimated the H-bond and stabilized incorrectly the H-bonded conformer. The calculations in solution indicated destabilization of H-bonded conformers due to the small polarizability and weaken of the H-bond. The same global minimum structures in gas phase and aqueous solution were found for gao-neutral (ectt) and gao-dianion (e−2), whereas they were different for gao-anion because of the strong decrease of the conformational energies in solution. The global minimum structures of the neutral, anion and dianion of gao, obtained in solution, are in agreement with experiment. The gas-phase basicity (GB) and molecular electrostatic potential (MEP) calculations revealed the same sites for electrophilic attack, supported by the nature of HOMO: the carbonylic oxygen for the neutral, the carboxylic oxygen for the anion and the oxime nitrogen for the dianion. MEP results in gas phase and in solution suggested a region between the two atoms, but not on one atom in accordance with bidentate binding of gao ions to a metal. The BHLYP/6-31++G(d,p) molecular properties of gao were in best consistent with CCSD(T) results. The thermodynamical properties (GB and bond deprotonation energy) of gao were better estimated at B3LYP level. 相似文献
35.
36.
Shou‐Ri Sheng Xiao‐Ling Liu Yong‐Fen Tong Lie Chen Hong‐Li Wen Cai‐Sheng Song 《中国化学会会志》2005,52(5):943-946
Several new methyl substituted poly(aryl ether ketone)s containing sulfone linkage with inherent viscosities of 0.62–0.84 dL/g have been prepared from 4,4′‐bis(2‐methylphenoxy)diphenylsulfone and 4,4′‐bis(3‐methylphenoxy)diphenylsulfone with terephthaloyl chloride and isophthaloyl chloride by electrophilic Friedel‐Crafts acylation in the presence of DMF with anhydrous AlCl3 as a catalyst in 1,2‐dichloroethane, respectively. These polymers having weight‐average molecular weight in the range of 71,000–49,000 are all amorphous and show high glass transition temperatures ranging from 167 °C to 191 °C, excellent thermal stability at temperatures over 400 °C in air or nitrogen, high char yields of 51–58% in nitrogen and good solubility in CHCl3 and polar solvents such as DMF, DMSO and NMP at room temperature. 相似文献
37.
在一般情况下,格氏试剂与酰卤偶合反应难以控制在酮阶段,往往得到叔醇。在较低温度下有机铜试剂与酰卤偶合可高产率地得到酮,所以用固体铜盐CuX(X=Cl、Br、I)作为格氏试剂与酰卤偶合的催化剂,可以提高反应的选择性,从而提高酮的产率。但固体铜盐的催化反应仅适合于空间位阻较大的脂肪酮和某些芳香酮的制备,对于直链脂肪酮的制备则产率很低。我们采用可溶性铜络合物Li_2Cucl_4(四氯合铜酸锂)等作催化剂,在均相溶液中反应,有效地提高了催化效果及反应的选择性,从而使格氏试剂与酰卤的偶合反应成功地用于直链脂肪酮的制备,产率良好。 相似文献
38.
用取代的二苄基二茂钛与一氧化碳在正庚烷中反应,生成二羰基二茂钛和二苄基甲酮。通过光谱监测,发现1摩尔一氧化碳插入碳钛键,得到取代的苯乙酰基苄基二茂钛。反应随着取代基给电子能力的增加而加快(Me>t-Bu≈H>F>Cl)。中间体Cp_2Ti[C(O)CH_2Ph]CH_2Ph很活泼,迅速发生分子内消除,消除的苄基和苯乙酰基生成二苄基酮。 相似文献
39.
E. Kavlentis 《Mikrochimica acta》1986,88(3-4):239-243
Mixtures of sulphide-thiocyanate and cyanide-thiocyanate can be analyzed without separation using the Cu(II)-DPGH complex.Sulfide and cyanide cause a decrease in absorption that is a linear function of their concentration in the range 0.06–2 and 0.18–6 ppm, respectively. The Cu(II)-DPGH complex is extractable into chloroform in presence of thiocyanate and this is used for the Spectrophotometric determination of thiocyanate in the range 0.09–3 ppm. 相似文献
40.
合成了3-(水杨酰肼)-丁基-2-酮肟H2L(1,C11H13N3O3)和2个镍的3-(水杨酰肼)-丁基-2-酮肟化合物[Ni(HL)(CH3COO-)(C5H5N)2](2)和[Ni(HL)2]·2C3H7NO(3)。化合物1晶体属单斜晶系,空间群为P21/n,晶体学参数为:a=0.451 87(2) nm,b=2.086 8(1) nm,c=1.224 48(9) nm,β=94.974(3)°,V=1.150 3(1) nm3,Z=4,Dc=1.358 g·cm-3,μ=0.101 mm-1,F(000)=496,R=0.0435,wR=0.142 5。化合物2晶体属单斜晶系,空间群为P21/n,晶体学参数为:a=1.362 39(8) nm,b=1.345 37(6) nm,c=1.438 54(7) nm,β=113.138(3)°,V=2.424 6(2) nm3,Z=4,Dc=1.398 g·cm-3,μ=0.843mm-1,F(000)=1 064,R=0.042 4,wR=0.116 6。化合物3晶体属单斜晶系,空间群为P21/c,晶体学参数为:a=1.104 22(7) nm,b=2.860 1(1) nm,c=1.114 13(7)nm,β=114.589(5)°,V=3.199 5(3) nm3,Z=4,Dc=1.398 g·cm-3,μ=0.667 mm-1,F(000)=1 416,R=0.057 6,wR=0.1535。在化合物1晶体中,酮肟分子之间通过分子间氢键形成二维网状结构。在化合物2中,每个镍(Ⅱ)离子由1个3-(水杨酰肼)-丁基-2-酮肟的2个氮原子和1个氧原子,2个吡啶分子中的2个氮原子和1个乙酸根中的1个氧原子形成畸变的NiN4O2八面体配位构型,存在分子内氢键O-H(肟)…O(乙酸根)和O-H(酚)…N(酰肼)。在化合物3晶体中,每个镍(Ⅱ)离子由2个3-(水杨酰肼)-丁基-2-酮肟的4个氮原子和2个氧原子配位,形成畸变的NiN4O2八面体配位构型。晶体中存在O-H…O和O-H…N两种分子内氢键和O-H…O分子间氢键。 相似文献