全文获取类型
收费全文 | 489篇 |
免费 | 11篇 |
国内免费 | 82篇 |
专业分类
化学 | 497篇 |
晶体学 | 3篇 |
力学 | 1篇 |
综合类 | 1篇 |
数学 | 1篇 |
物理学 | 79篇 |
出版年
2023年 | 17篇 |
2022年 | 13篇 |
2021年 | 15篇 |
2020年 | 18篇 |
2019年 | 10篇 |
2018年 | 8篇 |
2017年 | 13篇 |
2016年 | 15篇 |
2015年 | 8篇 |
2014年 | 18篇 |
2013年 | 35篇 |
2012年 | 32篇 |
2011年 | 24篇 |
2010年 | 22篇 |
2009年 | 27篇 |
2008年 | 28篇 |
2007年 | 24篇 |
2006年 | 28篇 |
2005年 | 32篇 |
2004年 | 29篇 |
2003年 | 16篇 |
2002年 | 26篇 |
2001年 | 19篇 |
2000年 | 9篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 13篇 |
1995年 | 9篇 |
1994年 | 4篇 |
1993年 | 11篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1982年 | 1篇 |
排序方式: 共有582条查询结果,搜索用时 31 毫秒
11.
12.
J. Aupiais 《Chromatographia》1997,44(5-6):303-312
Summary The indirect UV detection of cations by capillary zone electrophoresis gives peaks of very different height or area between
cations. We show that the height depends on the electrophoretic mobility of the cation compared with the electrophoretic mobility
of the chromophore used. Moreover, the limit of detection can be easily improved by about 4-fold by adjusting the concentration
of complexing agent or by using a chromophore with the same velocity as the studied cation. Using a new parameter termedsensitization power we can optimize the limit of detection and have determined the best chromophores for each family of cations.Sensitization power is a maximum for: alkali metals and alkali earths with imidazole and UV Cat 2?, for transition metal with pyridine, for light rare earth with ephedrine and UV Cat 1?, for heavy lanthanides with 1-naphthylamine and phenyl-trimethyl-ammonium bromide. Corrected areas of all cations studied
have normal distributions directly proportional to their ionic charge. Certain behaviour can be predicted for elements such
as actinides. Detection can also be enhanced because the relation of proportionality between ionic charge and corrected area
allows comparison of the performance of all chromophores. 相似文献
13.
The effect of process variables on uronic acids (UAs) and hexenuronic acids (HexAs) in the annual crop Arundo donax L. during ethanol–alkali pulping has been examined. A substantial loss of UA moieties (up to 90%) was observed by the end of pulping (target kappa number 18) performed with 25% NaOH and 40% EtOH (by volume) within the temperature range of 130–150 °C. At the same time, the progressive formation of HexA in pulp was detected from the early phases of delignification. The proportion of HexA in the residual UA of the final pulp was found to be 84%, indicating almost complete conversion of 4-O-methylglucuronic acid side groups (MeGlcA) of heteroxylan into HexA. The kinetics of UA degradation and HexA formation has been described in terms of three consecutive first-order reaction stages. The overall rate of UA degradation was one order higher than the rate of UA conversion into HexA. The values of apparent activation energy were estimated as 68.6 and 94.7 kJ mol–1, respectively. The reaction medium alkalinity was shown to be the controlling factor for UA and HexA stability during ethanol–alkali pulping. An increase in alkali charge from 5% to 35% (as NaOH) led to UA loss of 40%, but promoted HexA formation from 11.8 to 20.1 mol g–1. The addition of organic solvent to the alkaline pulping solution had a similar effect, and about 10% of UA was lost and the content of HexA increased from 6.9 to 10.9 mol g–1 with an increase in ethanol proportion in the liquor from 20% to 60%. 相似文献
14.
High-resolution neutron and synchrotron X-ray powder diffraction studies are reported for the six oxides AB2O4 (A=Ca2+, Sr2+ and Ba2+ and B=Al3+ and Ga3+). These oxides all adopt a stuffed tridymite type structure, the precise nature of which depends on both the A- and B-type cations. Bond valence calculations reveal a range of values for the various A-type cations, in all cases at least one site is significantly underbonded. Conversely the tetrahedral B-type sites invariably exhibit unexceptional bond valencies. Attempts to dope the oxides with various lanthanides to the 1% level invariably resulted in some segregation into alternate phases located at the grain boundaries. The identity of the impurity phases is presented and the importance of bond valencies in understanding this segregation is highlighted. 相似文献
15.
Compounds A3M5 (A = alkaline earth, M = triel/tetrel): A Case Study on Structural and Electronic Factors Stabilizing Polar Intermetallics Starting from the non electron precise binary compounds Ca3Ga5/Sr3In5 (Hf3Ni2Si3 type) and Ba3Al5 at one hand and Ba3Pb5 (Pu3Pd5 type) at the other hand, a series of new ternary intermetallics of the general formula A3M5 (A: alkaline earth, M: triel/tetrel) has been synthesized, structurally characterized and studied by band structure calculations. The chemical substitution of M in A3M5 allows, via the continous variation of the radius ratio (rA:rM) and the valence electron number (VE/M) the detection of the geometrically and electronically determined stability ranges of the three structure types formed by the binary compounds. At values of rA:rM between 1.30 and 1.52 in the triel rich region of A3M′xM″5?x the Hf3Ni2Si3 type (orthorhombic, space group Cmcm) is formed: In Ca3Ga5 up to 1.8 Ga can be substituted by Al, in Sr3In5 similar amount of In can be replaced by either Al or Ga. The mixed trielide Sr3Al2.6Ga2.4 (a = 468.4(1), b = 1132.5(1), c = 1570.0(2) pm, R1 = 0.0261) can be obtained, although both corresponding binary phases are not known. At larger values of the ratio rA/rM as in Ba3Al3Ga2 (Ba3Al5 type, hexagonal, space group P63/mmc, a = 598.9(1), c = 1456.0(3) pm, R1 = 0.0353) layers of condensed M5 building blocks with Al‐Al partial bonds are formed. Substituting one In position in Sr3In5 against Pb results in the isotypic, but electron precise Zintl compound Sr3In4Pb (a = 506.1(1), b = 1191.8(3), c = 1650.2(4) pm, R1 = 0.0286), where the Fermi level in shifted into a distinct minimum of the density of states. Conversely, at the tetrele rich end of the series A3InxPb5?x, characterized by compounds of the Pu3Pd5 type (orthorhombic, space group Cmcm) with almost isolated nido clusters M5, a minimum of the DOS can be reached, if Pb is partially substituted by In (A3InxPb5?x with A = Sr/Ba: x = 0.7/0.6; a = 1084.6(2)/1118.6(2), b = 867.1(2)/904.4(1), c = 1104.8(2)/1133.9(2) pm, R1 = 0.0394/0.0434). 相似文献
16.
Khaja Basheeruddin Vicki Rothman Simeon Margolis 《Applied biochemistry and biotechnology》1985,11(2):133-140
We have immobilized E.coli alkaline phosphatase (EC 3.1.3.1) by linking it covalently to sepharose 4B. This preparation has several advantages over
the soluble enzyme. The immobilized enzyme is easily separable from other constituents in incubation mixtures. The immobilized
enzyme can be reused repeatedly and is more stable than the soluble enzyme to heat treatment in the presence of 10 mM Mg2+. The insoluble and soluble phosphatases removed 75 and77%, respectively, of the inorganic phosphorus from casein. The immobilized enzyme inactivated two enzymes believed to be active
in the phosphorylated state, acyl-CoA : cholesterol acyltransferase (ACAT) by 39% and NADPH-cytochrome P-450 reductase by
89%. The utility of immobilized alkaline phosphatase for studying the phosphorylation and dephosphorylation of soluble or
membrane-bound enzymes and proteins is discussed. 相似文献
17.
A.E. Bolzan 《Journal of Electroanalytical Chemistry》1995,380(1-2)
The voltammetric behaviour of smooth palladium electrodes in 1 M NaOH is studied in the potential range related to the thermodynamic stability of water. The electrosorption of H atoms on bulk Pd appears as a reversible reaction coupled to a diffusion process which occurs within bulk Pd. The voltammetric electrodesorption of H from bulk Pd is a process under mixed control, i.e. the diffusion from the bulk and the surface oxidation of H atoms. Fast pseudocapacitive reactions are detected in the range 0.2–0.4 V associated with the adsorption of H atoms at the submonolayer level. The initial stages of Pd oxide layer formation, at ca. 0.68 V, involves two reversible stages. The Pd oxide monolayer formation is achieved at 1.25 V/RHE and is followed by the formation of a third reversible system. This system is enhanced by an excursion in the potential range of the oxygen evolution reaction. This reversible system is probably a redox system involving Pd(II)/Pd(IV) species. The voltammetric electroreduction of the Pd oxide film shows rather irreversible behaviour. Inhibition effects on the reversible adsorption of H atoms due to residual oxide species were observed as well as inhibition on loading the Pd electrode with hydrogen to form the (α + β)-PdH phase. Rotating ring-disc experiments demonstrate that Pd electrodissolution in basic solutions is much smaller than in acid solutions. However, soluble palladium species are detected, especially during the formation of the fast redox systems, in the potential range related to Pd oxide layer growth. 相似文献
18.
Tarun K. Panda 《Journal of organometallic chemistry》2005,690(23):5078-5089
Divalent bis(phosphinimino)methanide lanthanide complexes of composition [{(Me3SiNPPh2)2CH}EuI(THF)]2 and [{(Me3SiNPPh2)2CH}YbI(THF)2] have been prepared by a salt metathesis reactions of K{CH(PPh2NSiMe3)2} and LnI2. Further reactions of these complexes with [K(THF)nN(PPh2)2] led selectively to the heteroleptic amido complexes [{(Me3SiNPPh2)2CH}Ln{(Ph2P)2N}(THF)] (Ln = Eu, Yb). The ytterbium complex can also be obtained by reduction of [{CH(PPh2NSiMe3)2}Yb{(Ph2P)2N}Cl] with elemental potassium. The single crystals of [{(Me3SiNPPh2)2CH}Ln{(Ph2P)2N}(THF)] contain enantiomerically pure complexes. As a result of the similar ionic radii of the divalent lanthanides and the heavier alkaline earth metals some similarities in coordination chemistry of the bis(phosphinimino)methanide ligand were anticipated. Therefore, MI2 (M = Ca, Sr, Ba) was reacted with K{CH(PPh2NSiMe3)2} to give [{(Me3SiNPPh2)2CH}CaI(THF)2], [{(Me3SiNPPh2)2CH}SrI(THF)]2, and [{(Me3SiNPPh2)2CH}BaI(THF)2]2, respectively. As expected the Sr and Eu complexes and the Ca and Yb complexes are very similar, whereas for the Ba compound, as a result of the large ion radius, a different coordination sphere is observed. For all new complexes the solid-state structures were established by single crystal X-ray diffraction. In the solid-state the {CH(PPh2NSiMe3)2}− ligand acts as tridentate donor forming a long methanide carbon metal bond. Thus, all complexes presented can be considered as organometallic compounds. [{(Me3SiNPPh2)2CH}YbI(THF)2] was also used as precatalyst for the intramolecular hydroamination/cyclization reaction of different aminoalkynes and aminoolefines. Good yields but moderate activities were observed. 相似文献
19.
连续一级反应的热动力学研究 总被引:1,自引:0,他引:1
本文把时间比法引入热动力学研究,建立了连续一级反应的热动力学研究法,并用来研究了一个连续反应体系的热动力学,验证了该方法的正确性. 相似文献
20.
ACu9X4 ‐ New Compounds with CeNi8, 5Si4, 5 Structure (A: Sr, Ba; X: Si, Ge) The new compounds SrCu9Si4 (a = 8.146(1), c = 11.629(2)Å), BaCu9Si4 (a = 8.198(2), c = 11.735(2)Å), SrCu9Ge4 (a = 8.273(2), c = 11.909(5)Å), and BaCu9Ge4 (a = 8.338(4), c = 12.011(7)Å) are formed by reaction of the elements at 1000° ‐ 1100 °C. They are isotypic (I4/mcm, Z = 4) and crystallize in an ordered variant of the cubic NaZn13 type structure, also built up by the binary phase BaCu13. In the ternary compounds the positions of Cu2 are orderly occupied by copper and silicon and germanium, respectively. This results in a lowering of symmetry and a distortion of the polyhedra. The metallic conductivity of the compounds was confirmed by measurements on BaCu9Si4. 相似文献