全文获取类型
收费全文 | 3332篇 |
免费 | 693篇 |
国内免费 | 852篇 |
专业分类
化学 | 2616篇 |
晶体学 | 108篇 |
力学 | 253篇 |
综合类 | 70篇 |
数学 | 406篇 |
物理学 | 1424篇 |
出版年
2024年 | 25篇 |
2023年 | 62篇 |
2022年 | 150篇 |
2021年 | 150篇 |
2020年 | 169篇 |
2019年 | 163篇 |
2018年 | 162篇 |
2017年 | 156篇 |
2016年 | 171篇 |
2015年 | 188篇 |
2014年 | 242篇 |
2013年 | 303篇 |
2012年 | 321篇 |
2011年 | 325篇 |
2010年 | 262篇 |
2009年 | 231篇 |
2008年 | 232篇 |
2007年 | 191篇 |
2006年 | 172篇 |
2005年 | 180篇 |
2004年 | 128篇 |
2003年 | 105篇 |
2002年 | 117篇 |
2001年 | 119篇 |
2000年 | 107篇 |
1999年 | 90篇 |
1998年 | 42篇 |
1997年 | 42篇 |
1996年 | 32篇 |
1995年 | 26篇 |
1994年 | 28篇 |
1993年 | 19篇 |
1992年 | 25篇 |
1991年 | 23篇 |
1990年 | 15篇 |
1989年 | 17篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 12篇 |
1981年 | 7篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1977年 | 3篇 |
1974年 | 2篇 |
1965年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有4877条查询结果,搜索用时 15 毫秒
31.
32.
The structural and thermodynamic properties of the donor-acceptor (DA) complexes of Group 13 metal halides (MX3) with ethylenediamine and their decomposition products have been studied theoretically at the B3LYP/LANL2DZ(d,p) level of theory. Gas-phase dissociation into various components and HX elimination reactions are considered. Both processes are endothermic but favored by entropy. Complexes of 2:1 composition are predicted to be stable in the gas phase up to 640-1000 K. It is found that complexation with the second acceptor molecule lowers the HX elimination enthalpy; in turn, HX elimination increases DA bonding with a second MX3 molecule. Exceptionally high values of the dissociation enthalpies (310-390 kJ mol(-1)) and HX elimination reactions (360-420 kJ mol(-1)) of the amido compounds MX2NHC2H4NH2 and MX2NHC2H4NHMX2 make them important intermediates in the decomposition processes. Dissociation reactions of the complexes are more favorable than HX elimination reactions; however, the subsequent oligomerization and cyclization processes of coordinationally unsaturated amido and imido compounds may facilitate HX elimination. Since HI elimination reactions are predicted to be the least endothermic, and aluminum-containing compounds have the strongest M-N dissociation enthalpies, it is expected that compounds based on aluminum iodide are promising objects for experimental studies. 相似文献
33.
热解-还原法制备单分散Fe3O4亚微空心球 总被引:3,自引:0,他引:3
在用模板法水解FeCl3制备单分散聚(苯乙烯-共-丙烯酸)/Fe2O3[P(St-co-AA)/Fe2O3]核壳粒子的基础上, 于N2环境下热解内核直接得到了单分散的磁性Fe3O4亚微空心球. 用透射电镜(TEM)、场发射扫描电镜(FESEM)、X射线衍射(XRD)、振动样品磁强计(VSM)表征并测试了空心微球的结构形貌、成分以及静磁性能. 结果表明, P(St-co-AA)/Fe2O3核壳粒子在热处理过程中, 由于内核热解生成的有机小分子将Fe2O3 壳层同时还原为Fe3O4, 从而生成了粒径和壁厚均匀的单分散Fe3O4亚微空心球. 该空心微球在室温下的饱和磁化强度、剩余磁化强度和矫顽力分别为50.91 A·m2·kg-1、3.97 A·m2·kg-1和2.33 kA·m-1. 相似文献
34.
用内径为0.53mm的填充毛细管正相液相色谱为第一维,用4.6mm(i.d.)×50mmRP-18e整体柱反相色谱为第二维,建立了定量环一阀切换接口的全二维液相色谱系统(NPLC×RPLC).第一维色谱分离洗脱出的组分交替存储在十通阀上的两个定量环中,同时定量环中前一个组分被转移到第二维进行反相分离.因为第一维的流动相流量仅是第二维的1/500,自然解决了流动相兼容问题.采用芳香族化合物的混合物和中药丹参正己烷提取液对该全二维液相系统的分离能力进行了评价. 相似文献
35.
ChangLuSHAO HongYuGUAN ShangBinWEN BinCHEN XingHuaYANG JianGONG YiChunLIU 《中国化学快报》2004,15(4):492-494
Thin PVA/cobalt acetate composite fibers were prepared by using sol-gel processing and electrospinning technique.After calcination of the above precursor fibers,Co3O4 nanofibers with a diameter of 50-150 nm could be successfully obtained.The fibers were characterized by SEM,FT-IR,WAXD,respectively. 相似文献
36.
JiaChengNING ShuMAO YeDiGUAN 《中国化学快报》2005,16(1):17-19
Eleven (S)-(-)-bishydrocarbyl-(l-alkanoylpyrrolidin-2_yl)_methanol derivatives of three types were synthesized from L-proline.asymmtncally selective alkylation products were obtained oy LDA treatment and alkylation using methyl 2-bromoethyl ether, and three types of chiral α-Substituted-γ-butyrolactones were obtained by hydrolyzing the alkylation products, with %e.e. beijing up to 89 percent. 相似文献
37.
摘要利用改进的可视化装置, 研究了10°锥角的台锥型液相色谱柱内的谱带流型与柱参数变化的关系. 将有机玻璃柱管加工成内圆台外方型的一体结构, 选择折射率一致的色谱固定相硅胶和流动相环己烷, 使整个色谱柱成为高度清晰的透明体, 能直接观察柱中彩色样品谱带的动态三维流型. 研究结果表明, 在实验条件范围内, 流动相流速对谱带流型无影响, 填料的形状和性质对塞子状流型有一定程度的影响. 比较了柱长为5cm和等比例放大后柱长为10cm锥型柱内的流型, 发现放大后的锥型柱内仍然保持塞子状流型, 总柱效等比例增加. 表明继续按比例放大成为工业规模色谱柱后仍能保持塞子状流型. 相似文献
38.
提出了一种动力学李代数方法来研究取代苯体系的非线性光学性质. 对于给定的PPP模型(Pariser-Parr-Pople)哈密顿量, 生成了一个动力学李代数. 依据这些代数元构造出演化算子作为群参数的函数, 通过求解一组非线性微分方程能够得到这些群参数. 再按照统计力学中的密度算子公式给出取代苯分子体系偶极矩的统计平均值. 于是导出二阶极化率的表达式. 与其他量子力学计算结果比较, 表明这种动力学李代数方法在预言有机共轭分子的非线性光学性质上同样有用. 相似文献
39.
Cong Zhang Christian Ludin Marcel K. Eberle Helen Stoeckli-Evans Reinhart Keese 《Helvetica chimica acta》1998,81(1):174-181
(S)-5,5,5,5′,5′,5′-Hexafluoroleucine ((S)- 13 ) of 81 % ee is prepared from hexafluoroacetone ( l ) and ethyl bromopyruvate (= ethyl 2-oxopropanoate) in 7 steps with an overall yield of 18% (Schemes 1 and 2). Key step in this sequence is the highly enantioselective reduction of the carbonyl group in α-keto ester 4 either by bakers' yeast (91 % ee) or by ‘catecholborane’ 6 utilizing an oxazaborolidine catalyst, yielding hydroxy ester (R)- 5 with 99% ee. The absolute configuration was determined by X-ray analysis of the HCl adduct (S,R)- 9b of (2S)-N-[(R)- l-phenylethyl]-5,5,5,5′,5′,5′-hexafluoroleucine ethyl ester. 相似文献
40.
A novel norvancomycin-bonded chiral stationary phase (NVC-CSP) was synthesized by using the chiral selector of norvancomycin. The chiral separation of enantiomers of several dansyl-amino acids by high-performance liquid chromatography (HPLC) in the reversed-phase mode is described. The effects of some parameters, such as organic modifier concentration, column temperature, pH and flow rate of the mobile phase, on the retention and enantioselectivity were investigated. The study showed that ionic, as well as hydrophobic interactions were engaged between the analyte and macrocycle in this chromatographic system. Increasing pH of buffers usually improved the chiral resolution for dansyl--amino-n-butyric acid (Dns-But), dansyl-methionine (Dns-Met) and dansyl-threonine (Dns-Thr), but not for dansyl-glutamic acid (Dns-Glu) which contains two carboxylic groups in its molecular structure. The natural logarithms of selectivity factors (ln ) of all the investigated compounds depended linearly on the reciprocal of temperature (1/T), most processes of enantioseparation were controlled enthalpically. Interestingly, the process of enantioseparaton for dansyl-threonine was enthalpy-controlled at pH of 3.5, while at pH of 7.0, it was entropy-controlled according to thermodynamic parameters ΔR,SΔH° and ΔR,SΔS° afforded by Van’t Hoff plots. In order to get baseline separation for all the solutes researched, norvancomycin was also used as a chiral mobile phase additive. In combination with the NVC-CSP, remarkable increases in enanselectivity were observed for all the compounds, as the result of a “synergistic” effect. 相似文献