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921.
F Lu J Wang M Lang M Toulemonde F Namavar C Trautmann J Zhang RC Ewing J Lian 《Physical chemistry chemical physics : PCCP》2012,14(35):12295-12300
Bulk ZrO(2) polymorphs generally have an extremely high amorphization tolerance upon low energy ion and swift heavy ion irradiation in which ballistic interaction and ionization radiation dominate the ion-solid interaction, respectively. However, under very high-energy irradiation by 1.33 GeV U-238, nanocrystalline (40-50 nm) monoclinic ZrO(2) can be amorphized. A computational simulation based on a thermal spike model reveals that the strong ionizing radiation from swift heavy ions with a very high electronic energy loss of 52.2 keV nm(-1) can induce transient zones with temperatures well above the ZrO(2) melting point. The extreme electronic energy loss, coupled with the high energy state of the nanostructured materials and a high thermal confinement due to the less effective heat transport within the transient hot zone, may eventually be responsible for the ionizing radiation-induced amorphization without transforming to the tetragonal polymorph. The amorphization of nanocrystalline zirconia was also confirmed by 1.69 GeV Au ion irradiation with the electronic energy loss of 40 keV nm(-1). These results suggest that highly radiation tolerant materials in bulk forms, such as ZrO(2), may be radiation sensitive with the reduced length scale down to the nano-metered regime upon irradiation above a threshold value of electronic energy loss. 相似文献
922.
The gas phase reactions of carbon monoxide with small mass-selected clusters of palladium, Pd(x)(+) (x = 2-7), and their oxides, Pd(x)O(+) (x = 2-7) and Pd(x)O(2)(+) (x = 4-6), have been investigated in a radio frequency ion trap operated under multi-collision conditions. The bare palladium clusters were found to readily adsorb CO yielding a highly size dependent product pattern. Most interestingly, the reactions of the pre-oxidized palladium clusters with CO lead to very similar product distributions of Pd(x)(CO)(z)(+) complexes as in the case of the corresponding pure Pd(x)(+) clusters. Consequently, it has been concluded that the investigated palladium oxide clusters efficiently oxidize CO under formation of the bare clusters, which further adsorb CO molecules yielding the previously observed Pd(x)(CO)(z)(+) product complex distributions. This CO combustion reaction has been observed even at temperatures as low as 100 K. However, for Pd(2)O(+), Pd(6)O(+), Pd(6)O(2)(+), and Pd(7)O(+) a competing reaction channel yielding palladium oxide carbonyls Pd(x)O(CO)(z)(+) could be detected. The latter adsorption reaction may even hamper the CO combustion under certain reaction conditions and indicates enhanced activation barriers involved in the CO oxidation and/or the CO(2) elimination process on these clusters. 相似文献
923.
基于丙酮酸/还原型辅酶I/乳酸脱氢酶(LDH)/乳酸/氧化型辅酶I荧光猝灭体系和荧光毛细管分析技术,建立了可用于微量样品中LDH酶活性测定的方法。优化的测定条件为:激发及发射波长分别为350和460nm;测定温度为25℃;酸度为pH 6.5;NADH浓度为300μmol/L;丙酮酸浓度为1.2mmol/L。本方法的测定范围为50~1500IU/L,检出限为30IU/L,相对标准偏差2.1%~2.2%(n=10),回收率在96.4%~105%范围内。本方法操作简单,每次测定仅需样品2.0μL、试剂18.0μL,分析速度约为30样/h,利用本方法测定了微量血清中LDH的活性。 相似文献
924.
925.
Katarzyna Wójcik Petra Ecorchard Dieter Schaarschmidt Tobias Rüffer Heinrich Lang Prof. Dr. Michael Mehring 《无机化学与普通化学杂志》2012,638(11):1723-1730
Abstract. The cyclopentadienyl‐substituted iron‐bismuth complexes [{Cp(CO)2Fe}BiCl2] ( 1 ), [{Cp(CO)2Fe}BiBr2] ( 2 ), [{Cp′′(CO)2Fe}BiBr2] ( 3 ) and [{Cp*(CO)2Fe}BiBr2] ( 4 ) were prepared with high yields starting from [Cpx(CO)2Fe]2 [Cpx = C5H5 (Cp), C5H3‐1, 3‐tBu2 (Cp′′), C5Me5 (Cp*)] and the corresponding bismuth halides. The single crystal X‐ray structure analyses of compounds 2 – 4 are reported. Comparison of their solubility demonstrates that the steric hindrance in this type of compounds is only slightly higher for compound 3 compared with compound 2 but significantly lower compared with the Cp* derivative 4 . Compounds 1 – 4 react with nucleophililic reagents such as KOtBu, NaOCH2CH2OCH3, and NaOSiMe3 as well as with water in the presence of an amine to give a mixture of [{Cpx(CO)2Fe}BiX] (X = Cl, Br) and [{Cpx(CO)2Fe}3Bi]. In case of a reaction with nBu4NCl and DMAP (dimethylaminopyridine) no such dismutation is observed. Instead the complexes [{Cp(CO)2Fe}BiBr2(DMAP)2] ( 5 ), [NnBu4]2[{{Cp(CO)2Fe}BiBr3}2] ( 6 ) and [NnBu4]2[{{Cp(CO)2Fe}BiCl3}2] ( 7 ) were isolated and characterized by single‐crystal X‐ray diffraction. 相似文献
926.
Lin SY Zhao L Ke H Guo YN Tang J Guo Y Dou J 《Dalton transactions (Cambridge, England : 2003)》2012,41(11):3248-3252
Two linear tetranuclear lanthanide complexes of general formula [Ln(4)(L)(2)(C(6)H(5)COO)(12)(MeOH)(4)], where HL = 2,6-bis((furan-2-ylmethylimino)methyl)-4-methylphenol, () and Ln(III) = Dy(III) (1) and Gd(III) (2), have been synthesized and characterized. The crystal structural analysis demonstrates that two Schiff-base ligands inhibit the growth of benzoate bridged 1D chains, leading to the isolation of discrete tetranuclear complexes due to their steric hindrances. Every Ln(III) ion is coordinated by eight donor atoms in a distorted bicapped trigonal-prismatic arrangement. Alternating current (ac) susceptibility measurements of complex 1 reveal a frequency- and temperature-dependent out-of-phase signal under zero dc field, typical of single-molecule magnet (SMM) behaviour with an anisotropic barrier Δ(eff) = 17.2 K. 相似文献
927.
Wang Y Shao L Li Y Li X Li J Yu J Xu R 《Dalton transactions (Cambridge, England : 2003)》2012,41(22):6855-6860
By using two different organic amines, n-methylpiperidine and 1,2-diaminocyclohexane (DACH), as the structure-directing agents (SDAs), two magnesium aluminophosphate molecular sieves |(C(6)H(14)N)(2)|[Mg(2)Al(7)(PO(4))(9)] and |(C(6)H(14)N(2))(1.4)(H(2)O)(2)H(2)|[Mg(2)Al(5)(PO(4))(7)], denoted as MgAPO-CJ67(a) and MgAPO-CJ67(b), have been synthesized under hydrothermal conditions. They are the first example of Mg incorporated aluminophosphates with the LEV-zeotype structure. The magnesium and aluminum atoms co-occupy the same crystallographic positions in the frameworks of MgAPO-CJ67(a) and MgAPO-CJ67(b), but with different Mg/Al ratios of 1 : 3.5 and 1 : 2.5, respectively. MgAPO-CJ67(a) exhibits higher thermal stability upon calcination than MgAPO-CJ67(b), and its framework keeps intact after the removal of occluded organic SDAs. The N(2) adsorption on the calcined MgAPO-CJ67(a) sample gives the BET surface area of 386 m(2) g(-1). NH(3)-temperature programmed desorption (NH(3)-TPD) analysis shows that MgAPO-CJ67(a) has a medium acidity. 相似文献
928.
Milde B Schaarschmidt D Rüffer T Lang H 《Dalton transactions (Cambridge, England : 2003)》2012,41(17):5377-5390
The consecutive syntheses of imidazoles 1-(4-X-C(6)H(4))-4,5-R(2)-(c)C(3)HN(2) (3a, X = Br, R = H; 3b, X = I, R = Me; 3c, X = H, R = Me; 5, X = Fc, R = H; 7, X = C≡CFc, R = H; 9, X = C(6)H(5), R = Me; Fc = Fe(η(5)-C(5)H(4))(η(5)-C(5)H(5))), phosphino imidazoles 1-(4-X-C(6)H(4))-2-PR'(2)-4,5-R(2)-(c)C(3)N(2) (11a-k; X = Br, I, Fc, FcC≡C, Ph; R = H, Me; R' = Ph, (c)C(6)H(11), (c)C(4)H(3)O), imidazolium salts [1-(4-X-C(6)H(4))-3-R'-4,5-R(2)-(c)C(3)HN(2)]I (16a; X = Br, R = H, R' = n-Bu; 16b, X = Br, R = H, R' = n-C(8)H(17); 16c, X = I, R = Me, R' = n-C(8)H(17), 16d, X = H, R = Me, R' = n-C(8)H(17)) and phosphino imidazolium salts [1-C(6)H(5)-2-PR'(2)-3-n-C(8)H(17)-4,5-Me(2)-(c)C(3)N(2)]PF(6) (17a, R' = C(6)H(5); 17b, R' = (c)C(6)H(11)) or [1-(4-P(C(6)H(5))(2)-C(6)H(4))-3-n-C(8)H(17)-4,5-Me(2)-(c)C(3)HN(2)]PF(6), (20) and their selenium derivatives 1-(4-X-C(6)H(4))-2-P([double bond, length as m-dash]Se)R'(2)-4,5-R(2)-(c)C(3)N(2) (11a-Se-f-Se; X = Br, I; R = H, Me; R' = C(6)H(5), (c)C(6)H(11), (c)C(4)H(3)O) are reported. The structures of 11a-Se and [(1-(4-Br-C(6)H(4))-(c)C(3)H(2)N(2)-3-n-Bu)(2)PdI(2)] (19) in the solid state were determined. Cyclovoltammetric measurements were performed with the ferrocenyl-containing molecules 5 and 7 showing reversible redox events at E(0) = 0.108 V (ΔE(p) = 0.114 V) (5) and E(0) = 0.183 V (ΔE(p) = 0.102 V) (7) indicating that 7 is more difficult to oxidise. Imidazole oxidation does not occur up to 1.3 V in dichloromethane using [(n-Bu)(4)N][B(C(6)F(5))(4)] as supporting electrolyte, whereas an irreversible reduction is observed between -1.2 - -1.5 V. The phosphino imidazoles 11a-k and the imidazolium salts 17a,b and 20, respectively, were applied in the Suzuki C-C cross-coupling of 2-bromo toluene with phenylboronic acid applying [Pd(OAc)(2)] as palladium source. Depending on the electronic character of 11a-k, 17a,b and 20 the catalytic performance of the in situ generated catalytic active species can be predicted. As assumed, more electron-rich phosphines with their higher donor capability show higher activity and productivity. Additionally, 11e was applied in the coupling of 4-chloro toluene with phenylboronic acid showing an excellent catalytic performance when compared to catalysts used by Fu, Beller and Buchwald. Furthermore, 11e is eligible for the synthesis of sterically hindered biaryls under mild reaction conditions. C-C Coupling reactions with the phosphino imidazolium salts 17b and 20 in ionic liquids [BMIM][PF(6)] and [BDMIM][BF(4)] were performed, showing less activity than in common organic solvents. 相似文献
929.
Miao LL Li HX Yu M Zhao W Gong WJ Gao J Ren ZG Wang HF Lang JP 《Dalton transactions (Cambridge, England : 2003)》2012,41(12):3424-3430
Treatment of [CuCl(2)(bppyH(2))] (1, bppyH(2) = 2,6-di(1H-pyrazol-3-yl)pyridine) with 2 equiv. of AgNO(3) in DMF gave rise to a binuclear Cu(II) complex [Cu(2)(bppyH)(2)(NO(3))(2)] (bppyH = 2-(pyrazol-3-yl)-6-(pyrazolate)pyridine) (2). Complex 2 was characterized by elemental analysis, IR and single crystal X-ray diffraction. Complex 2 has a dimeric structure in which the two Cu(ii) centers are bridged by a couple of the in situ-generated bppyH(-) anions. Each Cu(II) center is further coordinated by one O atom of a NO(3)(-) anion and three N atoms of one bppyH(-) anion. Complex 2 exhibited a higher catalytic activity in the polymerization of methyl methacrylate (MMA) than the precursor complex 1. Even though the ratio of catalyst to MMA was raised up to 1 : 1500, the PDI for 2 (reaction time was fixed at 4 h) is 1.63 and the conversion is up to 72%. The effects of solvent, reaction temperature and the ratio of MMA to catalyst were also investigated. 相似文献
930.
ZrW2O8 as the typical negative thermal expansion (NTE) material has attracted much attention for the potential applications in various fields such as tailored coefficient of thermal expansion (CTE) composites. The hexagonal ZrW2O8 (h-ZrW2O8), with the combination of ZrO2 and WO3 in a composite, was synthesized at a pressure of 2 GPa and the temperature between 600°C and 700°C. We found h-ZrW2O8 decomposes to ZrO2+WO3 oxides that start from 500°C and end at 800°C, and determined the CTE of h-ZrW2O8 is?16.3×10?6°C?1 in the temperature range from 150°C to 450°C. The results show that ZrW2O8 with a hexagonal structure is metastable and exhibits high NTE property like its cubic structure. 相似文献