全文获取类型
收费全文 | 18113篇 |
免费 | 2564篇 |
国内免费 | 2143篇 |
专业分类
化学 | 12935篇 |
晶体学 | 128篇 |
力学 | 1323篇 |
综合类 | 87篇 |
数学 | 590篇 |
物理学 | 5301篇 |
无线电 | 2456篇 |
出版年
2024年 | 50篇 |
2023年 | 230篇 |
2022年 | 394篇 |
2021年 | 549篇 |
2020年 | 664篇 |
2019年 | 536篇 |
2018年 | 475篇 |
2017年 | 542篇 |
2016年 | 715篇 |
2015年 | 784篇 |
2014年 | 985篇 |
2013年 | 1411篇 |
2012年 | 1125篇 |
2011年 | 1372篇 |
2010年 | 1099篇 |
2009年 | 1141篇 |
2008年 | 1252篇 |
2007年 | 1256篇 |
2006年 | 1204篇 |
2005年 | 1008篇 |
2004年 | 901篇 |
2003年 | 726篇 |
2002年 | 719篇 |
2001年 | 488篇 |
2000年 | 452篇 |
1999年 | 381篇 |
1998年 | 316篇 |
1997年 | 311篇 |
1996年 | 266篇 |
1995年 | 250篇 |
1994年 | 198篇 |
1993年 | 170篇 |
1992年 | 157篇 |
1991年 | 130篇 |
1990年 | 102篇 |
1989年 | 80篇 |
1988年 | 74篇 |
1987年 | 42篇 |
1986年 | 40篇 |
1985年 | 37篇 |
1984年 | 39篇 |
1983年 | 13篇 |
1982年 | 36篇 |
1981年 | 17篇 |
1980年 | 20篇 |
1979年 | 15篇 |
1978年 | 9篇 |
1977年 | 8篇 |
1976年 | 13篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
151.
The addition of the macrocyclic polyether 18-Crown-6 (18C6) increases the selectivity of oxidation of ethylbenzene to -phenylethylhydroperoxide (PEH) in the presence of Ni(acac)2. The initial oxidation rate, selectivity and degree of conversion of ethylbenzene to PEH are greater than those catalyzed by Ni(acac)2 only. The efficiency of the macrocyclic ligand as an activator of Ni(acac)2 exceeds that of monodentate donor ligands. The high selectivity of the process is due to both the primary Ni(acac)2 · 18C6 complexes and the products of their transformation in the course of oxidation. The mechanism of ethylbenzene oxidation catalyzed by Ni(acac)2 · 18C6 complexes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1406–1411, August, 1994. 相似文献
152.
原子转移自由基聚合原位合成温敏性微球 总被引:1,自引:0,他引:1
以过硫酸钾为引发剂、丙酮-水[V(丙酮)∶V(水)=4∶6]的混合溶剂为反应介质, 在少量二乙烯苯存在的条件下使苯乙烯(St)和对氯甲基苯乙烯(CMSt)进行无皂乳液共聚反应, 得到了粒径大小均匀的交联型聚苯乙烯(PSt)微球, 由X射线光电子能谱对表面组分测定发现: CMSt上的氯原子在聚合过程中富集于交联微球的表面. 以此交联型PSt微球为原子转移自由基聚合(ATRP)的引发剂, 在22 ℃下引发N-异丙基丙烯酰胺(NIPAAm)进行原位ATRP反应, 得到了表面原子转移自由基聚合接枝的交联聚苯乙烯(PNIPAAm-g-PSt)温敏性微球. 借助傅立叶变换红外光谱、差示扫描量热仪、扫描电子显微镜及激光光散射仪等对PNIPAAm-g-PSt的结构、相转变温度、形态及不同温度下的粒径变化进行了测定, 结果表明NIPAAm单体成功地原位ATRP接枝在交联PSt微球的表面, 接枝微球的球形更规整, 在水中的相转变温度约为32 ℃, 具有明显的温度敏感性. 相似文献
153.
由环氧乙烷及烯丙基缩水甘油醚合成含双键侧基的聚氧乙烯用苯乙烯接枝共聚,接枝效率可达50%左右.接枝产物经纯化,用IR及~1H NMR表征.该产物与LiClO_4的络合物有较高的室温导电率,其PEO含量在70%及EO/Li=20/1时,25℃的导电率接近10~(-4)S/cm.此外,该接枝共聚物有较高的乳化能力.在Williamson固液反应中具有良好的相转移催化作用. 相似文献
154.
自由基链式亲核取代反应(S_(RN)1)的进展 总被引:1,自引:0,他引:1
本文评述了自由基链式亲核取代反应的最近进展。内容包括:脂肪族化合物和芳香族化合物按S_(RN)l进行的反应及其机理。 相似文献
155.
Modified modeling of the effect of pH and viscosity on the mass transfer in hydrophobic hollow fiber membrane contactors 总被引:3,自引:0,他引:3
This paper studied the effect of pH and the viscosity of feed solution on the mass transfer in two different specifications of hydrophobic hollow fiber membrane contactors. Experimental results showed that the pH of the feed had a significant effect on the rate of mass transfer, the flux and the removal efficiency of easily ionized volatile compounds (VCs), such as ammonia. In unbuffered feed solutions, both the resistance of membrane and the resistance of feed side were affected by the pH of feed and both of them had contributions to the overall mass transfer. A model, , was proposed to predict the effect of pH and gave good agreement with the experimental data for the two contactors. The relationship between viscosities and the mass transfer coefficient could be described by . Based on our experiments, the change of the viscosities in the concentration range of ammonia from 50 to 10,000 mg l−1 caused about 3–4% variation of the mass transfer coefficients. Moreover, it may be more suitable to use the equilibrium concentrations of volatile species instead of the total concentrations of VCs to estimate mass transfer coefficients, removal efficiency and flux. Experimental results also revealed that the choice of the pH of feed might be one of the most crucial factors for removing easily ionized VCs, such as ammonia, from water and wastewater. 相似文献
156.
157.
158.
Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O2) in the oxygenation process. 相似文献
159.
α 羟基 α 甲基苯丙酮 (PHMP)是一种性能优良的新型光引发剂 ,具有引发效率高、热稳定性好、耐黄变、无异味等优点[1,2 ] 。现有合成方法步骤多 ,产率低 ,后处理麻烦 ,操作复杂[3,4] ,且在反应过程中会产生HC1或HBr等有毒副产物。本文研究了在相转移催化剂的作用下[5,6 ] ,CCl4直接氯化水解生成α 羟基 α 甲基苯丙酮的新方法。该方法不仅减少了反应步骤 ,简化了操作 ,而且提高了产品质量。1 实验部分1 .1 仪器与试剂傅立叶红外光谱仪Perkin Elmer 1 71 0 ,WXS 1型阿贝折光仪。异丁酸 ,SOCl2 ,苯 ,四氯化… 相似文献
160.
J. Howard Rytting Danny R. McHan Takeru Higuchi David J. W. Grant 《Journal of solution chemistry》1986,15(8):693-703
Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G
2
0
of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G
2
0
decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G
2
0
against the change in pair potential energy calculated from the classical expressions suggests that G
2
0
seriously underestimates the strength of the Debye interactions in comparison with the London interactions. 相似文献