全文获取类型
收费全文 | 5491篇 |
免费 | 1167篇 |
国内免费 | 2021篇 |
专业分类
化学 | 3980篇 |
晶体学 | 359篇 |
力学 | 400篇 |
综合类 | 156篇 |
数学 | 902篇 |
物理学 | 2882篇 |
出版年
2024年 | 17篇 |
2023年 | 46篇 |
2022年 | 213篇 |
2021年 | 207篇 |
2020年 | 188篇 |
2019年 | 187篇 |
2018年 | 181篇 |
2017年 | 269篇 |
2016年 | 190篇 |
2015年 | 298篇 |
2014年 | 353篇 |
2013年 | 453篇 |
2012年 | 476篇 |
2011年 | 472篇 |
2010年 | 489篇 |
2009年 | 506篇 |
2008年 | 615篇 |
2007年 | 517篇 |
2006年 | 527篇 |
2005年 | 431篇 |
2004年 | 319篇 |
2003年 | 258篇 |
2002年 | 202篇 |
2001年 | 279篇 |
2000年 | 249篇 |
1999年 | 125篇 |
1998年 | 68篇 |
1997年 | 68篇 |
1996年 | 59篇 |
1995年 | 54篇 |
1994年 | 67篇 |
1993年 | 31篇 |
1992年 | 38篇 |
1991年 | 34篇 |
1990年 | 26篇 |
1989年 | 40篇 |
1988年 | 23篇 |
1987年 | 17篇 |
1986年 | 19篇 |
1985年 | 10篇 |
1984年 | 14篇 |
1983年 | 10篇 |
1982年 | 3篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1964年 | 2篇 |
1957年 | 1篇 |
1954年 | 1篇 |
排序方式: 共有8679条查询结果,搜索用时 15 毫秒
991.
Theoretical study about the magnetic properties of conjugated organic molecules containing borepin with π current density was carried out. 1-(2,4,6-Trimethylphenyl)borepin moiety is the center and other different groups are situated on the both β sides, which are named molecules 1-12 as theoretical model in order to establish the relationship between aromaticity and geometry variation of borepin. The optimized molecular structures of molecules 1-12 are almost keeping planar and the C2-C3 bond length of borepin turns longer from molecule 1 to molecule 12. Different borepin-annulated ring could change the conjugated effect of π-electron between borepin and these borepin-annulated rings. Moreover, the molecule presents antiaromaticity, in other words, the molecule became unstable when the C2-C3 bond length of borepin extended more than ca. 0.1417 nm. But the β position fragment and substituent groups of borepin are not affected in this case, they are still steady. However, the central borepin ring current is counteracted by symmetrical overlap of it with affiliated borepin-annulated ring current. Hence, the central borepin ring breaking would be liable to occur. These molecules have higher vertical ionization potentials(VIPs) and lower vertical electron affinities(VEAs), which suggests that these molecules could easily exist in anionic form. 相似文献
992.
研究了钛酸钡和钛酸钙担载的Ag和Pt纳米催化剂的表面结构随氧化-还原处理过程的动态变化及其对CO完全氧化反应性能的影响.发现氧化物担载的Ag催化剂在氧化处理后其催化活性较还原处理的高; X射线衍射(XRD)和X射线光电子能谱(XPS)表征结果表明,氧化处理能够提高载体表面Ag颗粒的分散度,而还原处理导致Ag颗粒的聚集,从而降低了催化氧化CO反应的活性.氧化-还原处理改变了担载Ag纳米粒子的尺寸并影响其CO氧化反应活性.与此相反,氧化物担载的Pt催化剂在还原处理后所表现出的CO氧化反应活性较氧化处理的高; 对比研究发现,氧化和还原处理后Pt纳米粒子的尺寸基本相同,但是氧化处理的样品中Pt表面物种以氧化态为主,而还原处理后Pt表面物种主要为金属态.Pt纳米粒子表面化学状态随氧化-还原处理的调变是导致表面催化活性差异的主要原因. 相似文献
993.
Acylthiourea derivatives are useful as pesticides, herbicides, fungicides and regulator for plant growth, and also as important intermediates in the organic synthesis. In recent years, phase transfer catalysis reaction technique has been widely recognized as an efficient synthetic tool and attracted much attention. In view of these observations, a series of 5-aryl-2-furoyl thioureas containing substituted pyrimidine ring were synthesized using PEG-400 as solid-liquid phase transfer catalyst under ultrasonic irradiation. All of the new compounds have been exactly determined by IR, 1H NMRand elemental analysis. 相似文献
994.
995.
996.
Two complexes, [Cu2(Htdb)4(H2O)2] (1) and [Cd(bipy)2(Hmcmbc)2] (2) (H2tdb = 2,2-thiodibenzoic acid, H2mcmbc = m-(carboxyl-methyloxy)-benzenecarboxylic acid, bipy = 4,4'-bipyridine), have been prepared, and were characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structures indicate that complex 1 is a single molecule, and 2 is a one-dimensional chain. Their two-and three-dimensional frameworks are constructed through hydrogen bonding, π…π or C–H…π stacking, and such other weak interactions. The cyclic voltametric behavior of complex 1 and luminescence property of complex 2 were investigated. 1 belongs to the triclinic system, space group P with a = 7.8607(6), b = 11.7619(9), c = 15.3481(12) , α = 109.3670(10), β = 92.4420(10), γ = 92.0450(10)°, V = 1335.65(18) 3, Mr = 1256.26, Dc = 1.5619(2) g/cm3, F(000) = 642, μ = 1.029 mm–1, Z = 1, the final R = 0.0289 and wR = 0.0763 for 5199 observed reflections with I > 2σ(I). Complex 2 crystallizes in triclinic, space group P with a = 9.6378(10), b = 9.7508(10), c = 19.055(2) , α = 88.7020(10), β = 80.5260(10), γ = 69.2000(10)o, V = 1649.9(3) 3, Mr = 815.07, Dc = 1.641 g/cm3, μ = 0.732 mm-1, F(000) = 828, Z = 2, the final R = 0.0511 and wR = 0.1149 for 4729 observed reflections (I > 2σ(I)). 相似文献
997.
规整链球型含C_(60)聚(丙烯酸β-羟乙酯)的合成及其在水中的自组装 总被引:2,自引:0,他引:2
C60 由于其独特的物理化学性质 ,在生命科学中引起了人们的广泛兴趣 .例如 :水溶性C60 的羧酸衍生物 ,羟基取代C60 ,C60 的氨基酸水溶性衍生的合成已有报道[1~ 3] ,并被用来研究C60 的生物化学及医学活性 .Tokuyama[4 ] 等合成了酶功能化C60及与核酸连接的C60 ,研究并证明了它的细胞毒性及G 选择DNA切割能力等生化活性 .Friedman[5]等合成了水溶性C60 的羧酸衍生物 ,研究了它对HIV 1艾滋病毒的抑制作用 ,此外 ,关于不同C60含量的C60 蛋白质衍生物的合成及性质的研究也有报道[6] .C60 是一个直径为 0 71… 相似文献
998.
复方维生素B片中主要成分的高效毛细管电泳电化学法检测 总被引:7,自引:1,他引:7
采用高效毛细管电泳-电化学检测法同时测定复方维生素B片中的主要成分维生素B1,B12,B6和C的含量;研究了电极电位,运行缓冲溶液的浓度和酸度,电泳电压和进样时间等对电泳的影响,以微铂电极为工作电极,检测电位+0.5V(vs SCE),在pH9.0的15mmol/L Tris-1mmol/L H3BO3缓冲溶液中,上述4组分在5min内获得基线分离;维生素B1,B12,B6和C的线性范围分别为2.1mg/L-1.0g/L,6.0mg/L-0.80g/L,1.4mg/L-0.72g/L和0.97mg/L-0.44g/L检出限分别为0.50mg/L,1.0mg/L,,0.65mg/L和0.40mg/L;5次测定峰高的相对标准偏差分别为2.4%,3.0%,3.1%,和2.5%,5次测定的平均回收率分别为99%,102%,98%和100%。 相似文献
999.
1000.
The cyclodextrins(CDs) are a class of cyclic oligosaccharides made up of six(a), seven(a)or more [a-(1,4)-linked] D-glucopyranose units, and shaped like truncated cones with primary and secondary hydroxyl groups crowning the narrower rim and wider rim respectively. As they have a hydrophobic cavity of appropriate dimension, they can bind with various guest moleculars, such as hydrocarbon, cyclohexane, aromatic compounds, to form inclusion complexes. The cyclodextins inclusion complexation has been considered an ideal model mimicking the enzyme-substrate interaction and a lot of effect has been devoted to it. In this paper, we report our investigation on the inclusion complexation behavior of a-cyclodextrin(a-CD) with diphenyl compounds in order to further explore the molecular recongnition mechanism of 2:1 inclusion complexation of a-CD with aromatic compounds.Figure 1: Possible structures of the inclusion compounds.The inclusion complexation behavior of a-CD with sym-diphenyl-urea, sym-diphenyl-thiourea and diphenyl kotone as respective guest moleclars was studied by ultraviolet spectrometric titrations.The absorption spectral changes observed for the compounds in the absence and presence of a-CD are used to draw the corresponding Benesi-Hildebrand plots and caculate the complex stability constant value (Ks) for the inclusion compounds.The 2:1 inclusion complexations show higher binding constants by cooperative binding of one guest molecular in the closely two hydrophobic cyclodextrin cavites as compared with 1:1 inclusion complexations.The highest value observed for sym-diphenyl-urea could be due to the formation of a hydrogen bond between the carbonyl group and the hydrogen in the hydroxyl group of CD and this is not possible with sym-tiphenyl-thiourea. The lowest value observed for diphenyl kotone indicate the hydrophobic interaction is one of the binding force of cyclodextrin inclusion complex. 相似文献