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121.
Emilio San-Fabián José Pérez-Jordá Federico Moscardó 《Theoretical chemistry accounts》1990,77(3):207-212
Summary The correlation energy of two- and four-isoelectronic series, a representative example for which the existing spin-density functionals fails, is calculated using the Colle and Salvetti method, considering mono- and multideterminantal wave functions. The results are in agreement with experimental data, and show the potentiality of this method when it is applied to wave functions including the most relevant configurational features. Also, results for the ionization energies and electron affinities of first- and second-row atoms are reported. 相似文献
122.
用CNDO/2(s,p,d)方法研究了类立方烷系列Fe-S簇合物[Fe_4S_4Cl_4(?)(S_2CNEt_2)_n]~(2-)(n=0,1,2,4)的电子结构。得出[S_2CN(Et)_2]-螯合配位Fe_4S_4~(2+)簇合物中存在两类不同价态铁原子的结论;骨架Fe_4S_4~(2+)中μ_3-S电子是非定域化的,同Mssbauer谱测定结果一致。讨论了簇合物Fe—Fe之间的成键作用、螫合配体的作用和氧化还原性质。 相似文献
123.
The perovskite-based rare earth cobaltates (Ln0.33Sr0.67CoO3−δ) (Ln=Y3+, Ho3+ and Dy3+) have been synthesized at 1100°C under 1 atm oxygen. A thermogravimetric study has determined the overall oxygen content in each case while a combined electron diffraction (ED) and synchrotron X-ray diffraction study has revealed the presence of a complex, previously unreported, perovskite-related superstructure phase. ED gave a resultant C1c1 but most probably Cmcm (, , ) perovskite-related superstructure, describable as a modulated I4/mmm intermediate parent structure. Synchrotron X-ray data has been used to refine the intermediate parent structures of all three compounds. Coupled Ln/Sr and O/vacancy ordering and associated structural relaxation is shown to be responsible for the observed superstructure. 相似文献
124.
C. Acero J. M. Ribó R. Solé F. R. Trull 《Monatshefte für Chemie / Chemical Monthly》1993,124(4):401-417
Summary Characteristic oxidation reactions of bilin-1,19-diones (biliverdins) and biladien-ac-1,19-diones (bilirubins) were reinvestigated. These include bromine and iodine oxidation of biliverdin IX, bilirubin IX and their Zn(II) complexes, the reaction described by Siedel (1941) of mesobilirubin XIII dimethyl ester with nitric acid (Gmelin reaction) and Smith's oxidation (1977) of etiobiliverdin IV using Tl triacetate and Pb tetra-acetate. For some of these reaction products new structures were assigned on the basis of their spectrometric data. These structures agreed with the expected reactivity pattern of biliverdins and bilirubins.
Reaktivität von Pyrrolpigmenten, 15 Mitt.: Über die Oxidation von Bilirubinen und Biliverdinen
Zusammenfassung Einige bekannte Oxydationen von Bilin-1,19-dionen (Biliverdinen) und Biladien-ac-dionen (Bilirubinen) wurden neuerlich untersucht, und zwar die Brom- und Jodoxydation von Biliverdin IX und Bilirubin IX sowie der entsprechenden Zn(II)-Komplexe, die Reaktion des Dimethylesters von Mesobilirubin XIII mit HNO3 (Gmelinreaktion; Siedel 1941) und Smith's Oxydation von Etiobiliverdin IV mit Thaliumtriacetat und Bleitetraacetat. Für einige Reaktionsprodukte wurden aufgrund spektroskopischer Daten neue Strukturen-konsistent mit dem bekannten Reaktionsverhalten von Biliverdinen und Bilirubinen-formuliert.相似文献
125.
Alexandra Lieb Juliane A. Kechele Robert Kraut Wolfgang Schnick Prof. Dr. 《无机化学与普通化学杂志》2007,633(1):166-171
The oxonitridoalumosilicates (so‐called sialons) MLn[Si4?xAlxOxN7?x] with M = Eu, Sr, Ba and Ln =Ho, Er, Tm, Yb were obtained by the reaction of the respective lanthanoid metal, the alkaline earth carbonates or europium carbonate, resp., AlN, “Si(NH)2” and MCl2 as a flux in a radiofrequency furnace at temperatures around 2100 °C. The compounds MLn[Si4?xAlxOxN7?x] are relevant for the investigation of substitutional effects on the materials properties due to their ability of tolerating a comparatively large phase width up to x ≈ 2.0(5). The crystal structures of the twelve compounds were refined from X‐ray single crystal data and X‐ray powder data and are found to be isotypic to the MYb[Si4N7] structure type. The compounds crystallize in space group P63mc (no. 186, hexagonal) and are made up of chains of so‐called starlike units [N[4](SiN3)4] or [N[4]((Si,Al)(O,N)3)4], respectively. These units are formed by four (Si,Al)(N/O)4 tetrahedra sharing a common central nitrogen atom. The structure refinement was performed utilizing an O/N‐distribution model according to Paulings rules, i.e. nitrogen was positioned on the four‐fold bridging site and nitrogen and oxygen were distributed equally on both of the two‐fold bridging sites, resulting in charge neutrality of the compound. The Si and Al atoms were distributed equally on their two crystallographic sites, referring to their elemental proportion in the compound, due to being poorly distinguishable by X‐ray methods. The chemical compositions of the compounds were derived from electron probe micro analyses (EPMA). 相似文献
126.
Chisuzu Tokoh Keiji Takabe Junji Sugiyama Minoru Fujita 《Cellulose (London, England)》2002,9(3-4):351-360
Acetobacter
xylinum was cultured in Schramm–Hestrin medium containing pectin (pectin medium), xylan (xylan medium), or glucomannan (mannan medium). X-ray diffractometry revealed that xylan and glucomannan affected the size of the cellulose crystals and their d-spacing values. Solid-state cross polarization magic angle spinning carbon-13 nuclear magnetic resonance spectroscopy indicated that the ratio of cellulose I was reduced by the addition of polysaccharides. These effects were more remarkable on the cellulose in the mannan medium than that in the xylan medium, and were scarcely observed in the pectin medium. Electron diffraction analysis revealed that these effects on hemicelluloses along cellulose microfibrils are continuous in the mannan medium and discontinuous in the xylan medium. These findings suggest that the uronic acid in the polysaccharides prevents interactions with cellulose leading to alterations of the structure of the cellulose crystal. 相似文献
127.
Craviso GL Chatterjee I Publicover NG 《Bioelectrochemistry (Amsterdam, Netherlands)》2003,60(1-2):57-64
Effects of powerline frequency (50/60 Hz) electric and magnetic fields on the central nervous system may involve altered neurotransmitter release. This possibility was addressed by determining whether 60-Hz linearly polarized sinusoidal magnetic fields (MFs) alter the release of catecholamines from cultured bovine adrenal chromaffin cells, a well-characterized model of neural-type cells. Dishes of cells were placed in the center of each of two four-coil Merritt exposure systems that were enclosed within mu-metal chambers in matched incubators for simultaneous sham and MF exposure. Following 15-min MF exposure of the cells to flux densities of 0.01, 0.1, 1.0 or 2 mT, norepinephrine and epinephrine release were quantified by high-performance liquid chromatography (HPLC) coupled with electrochemical detection. No significant differences in the release of either norepinephrine or epinephrine were detected between sham-exposed cells and cells exposed to MFs in either the absence or presence of Bay K-8644 (2 microM) or dimethylphenylpiperazinium (DMPP, 10 microM). Consistent with these null findings is the lack of effect of MF exposure on calcium influx. We conclude that catecholamine release from chromaffin cells is not sensitive to 60-Hz MFs at magnetic flux densities in the 0.01-2 mT range. 相似文献
128.
粉煤灰与几种酸固相反应特性的表面分析 总被引:1,自引:0,他引:1
用扫描电镜.能量色散谱研究了粉煤灰与酸的固相反应过程中表面形貌和化学组成变化特性。室温下粉煤灰分别与HCI、HNO3、H2SO4、HCIO4固相反应后,表面产生直径20—200nm的结晶颗粒或晶柱。反应生成的水溶物结晶体的扫描电镜图像分别呈手指状、龟背形、蛛蛛状、蝙蝠态,分别为氯化铝铁混晶、硝酸铝铁混晶、硫酸铝铁混晶和高氯酸铝铁混晶。粉煤灰是硅、铝、铁等元素的氧化物聚集体,铁铝等氧化物主要分布在颗粒表面,氧化硅主要分布在颗粒内层。用少量酸进行固相反应这些氧化物聚集体可相互剥离,用H2SO4处理粉煤灰优先将铁铝氧化物转化成可溶性硫酸盐。 相似文献
129.
HeinzD. Roth 《Helvetica chimica acta》2006,89(12):2847-2860
Chemically induced dynamic nuclear polarization (CIDNP) observed during electron transfer (ET) reactions of tertiary amines such as DABCO ( 1 ) or Et3N ( 2 ) with a wide range of electron acceptors support the involvement of amine radical‐cations (e.g., 1. + or 2. + ) as key intermediates. Radical ions such as 2. + may be deprotonated, generating neutral aminoalkyl radicals (e.g., 2. ). When generated by reaction with an electron acceptor of energetically low triplet state such as naphthalene (1Naph*), the resulting pair 2. + /Naph.? reacts mostly by reverse electron transfer (RET) from triplet pairs populating the naphthalene triplet state. 相似文献
130.
Juan Jos Berzas Nevado Rosa Carmen Rodríguez Martín-Doimeadis Francisco Javier Guzmn Bernardo Nuria Rodríguez Farias 《Microchemical Journal》2007,86(2):183-188
An analytical methodology was proposed and validated to be applied to the determination of p,p′-DDT and its metabolites p,p′-DDE and p,p′-DDD in fish oil. The analytical procedure presented in this paper involves a single-step clean up process prior to the analysis. A solution of 1,2,3,4-tetrachloronaphtalene was used as internal standard.The analytical technique used was gas chromatography coupled to an electron capture detector. Details on the validation process are provided.The limits of detection ranged from 2.6 to 4.7 pg μL− 1. The BCR 598 standard reference material (cod liver oil) was used to evaluate the performance of the methodology with satisfactory recoveries for all the compounds.The analytes were determined in three different fish oil pills sold in Spain as a supplementary vitamin support. The sum of p,p′-DDT and metabolites was from 13.2 to 51.3 ng g− 1, the dominant compound being p,p′-DDE. 相似文献