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51.
The electronic absorption spectrum for the dibiphenylene-ethene radical anion (
), generated electrochemically in dimethylsulfoxide solutions, is reported. Based on calculations by the LCAO-MO method in theHückel approximation and on the analysis of the band positions it is suggested that in the
molecule two planar fluorenylidene fragments are twisted (60°) about the central C=C bond.
Das Elektronenabsorptionsspektrum des Dibiphenylen-Radikalanions (Kurze Mitteilung)
Zusammenfassung Das Dibiphenylenethen-Radikalanion ( ) wurde elektrochemisch hergestellt und das Elektronenabsorptionsspektrum aufgenommen. Auf Grund von LCAO-MO Berechnungen in derHückel-Annäherung und der Analyse der Bandenlagen wird nahegelegt, daß im -Molekül zwei planare Fluorenyliden-Fragmente ca. 60° um die zentrale C=C-Bindung verdrillt angeordnet sind.相似文献
52.
The reaction of spirobisilafluorene (1) with lithium in dimethoxyethane produces lithium 1-methyl-spirobisilafluorenide (2), a stable pentacoordinate silicon compound with five carbon ligands, and lithium 2-methoxyethoxide, which was identified by trapping with Ph3SiCl to give Ph3Si-OCH2CH2OCH3 (4). The X-ray crystal structure of 2 shows that the geometry at silicon is an idealized trigonal bipyramid, slightly distorted toward a square pyramid. Methanolysis of 2 cleaves a Si-aryl bond producing a methyl biphenylsilafluorene, 3. Crystal structures are reported for 3 and 4. 相似文献
53.
T. L. Luke H. Mohan V. M. Manoj P. Manoj J. P. Mittal C. T. Aravindakumar 《Research on Chemical Intermediates》2003,29(4):379-391
Reactions of sulphate radical anion (SO·4
-) with 4,6-dihydroxy-2-methyl pyrimidine (DHMP), 2,4-dimethyl-6-hydroxy pyrimidine (DMHP), 6-methyl uracil (MU) and 5,6-dimethyl uracil (DMU) have been studied by pulse radiolysis at pH 3 and at pH 10. The transient intermediate spectra were compared with those from the reaction of hydroxyl radical (·OH). It is proposed that SO·4
- produces radical cations of these pyrimidines in the initial stage. These radical cations are short-lived except in the case of DMHP where a relatively longer lived radical cation is proposed to be formed. When there is a hydrogen atom attached to the N(1) or N(3) position, a deprotonation from these sites is highly favored. When there is no hydrogen attached to these sites, deprotonation from a substituted methyl group is favored. At acidic pH, deprotonation from nitrogen is observed for DHMP, MU and DMU. At basic pH, the radical cation reacts with OH- leading to the formation of OH adducts. 相似文献
54.
聚合物硼氢阴离子还原剂的制备及其对酯的还原研究 总被引:3,自引:0,他引:3
氯型季我安盐型强碱性阴离子交换树脂711^#与硼氢化钾反应制得聚合物硼氢阴离子还原剂,树脂容量3.2mmol BH4/g。用于不同酯化合物的还原,操作简便,树脂可再生重复使用。 相似文献
55.
Christine Bonal Jean-Pierre Morel Nicole Morel-Desrosiers 《Journal of solution chemistry》1998,27(4):361-372
The apparent equilibrium constants and enthalpies of complexation of Nd3+, Sm3+, Eu3+, and Gd3+ by xylitol in aqueous solutions containing NaNO3 at an ionic strength of 2.0 mol-kg–1 have been determined by microcalorimetry at 25°C. Since nitrate anion weakly complexes the lanthanide cations, these values are analyzed in terms of competition between xylitol and NO
3
-
The method leads to the apparent equilibrium constants and enthalpies of complexation of the lanthanide cations by NO
3
-
at this particular ionic strength. Despite the difficulties encountered in characterizing rather weak associations, the results are, whenever comparison is possible, in good agreement with those obtained by direct microcalorimetry. The advantage of this competition method is that it can be used when the enthalpic effects are too weak and insufficiently concentration dependent for direct microcalorimetric determination. In the present case, it allows us to thermodynamically characterize the formation of SmNO
3
2+
and EuNO
3
2+
, processes we have not been able to study directly. 相似文献
56.
Dean C. Luehrs Richard E. Brown Kalpana A. Godbole 《Journal of solution chemistry》1989,18(5):463-469
A linear free energy relationship was found betweenv
max, the energy of the absorption maximum of chloride, bromide, or iodide ion in various solvents, and the solvatochromic parameter which is a measure of the hydrogen bond donor ability of the solvent. The relationships are: for chloride,v
max=6.99+50.16 kK; for bromide,v
max=5.52+45.20 kK; for iodide,v
max=5.02+40.33 kK. The correlation ofv
max for iodide ion with gave a larger correlation coefficient and smaller standard deviation than a correlation with the E
T
(30) parameter of Dimroth. From the values ofv
max for iodide ion and the solvated electron in liquid ammonia at 25°C, these correlations indicate a preliminary value of 0.00 for the parameter of liquid ammonia. This had not been reported before and is lower than expected from a general knowledge of the physical and chemical properties of liquid ammonia but is consistent with a more detailed consideration and recent gas phase measurements of hydrogen bond donor strength. 相似文献
57.
Suyao?Xiao Xuanming?LiuEmail author Chunyi?Tong Jun?Liu Dongying?Tang Lijian?Zhao 《中国科学B辑(英文版)》2005,48(2):162-166
Anion starch nanoparticle (StNP) with a diameter of 50 nm was prepared in water-in-oil microemulsion, with soluble starch
as raw materials and POCl3 as crosslinking agent. PLL-StNP was prepared by linking poly-L-lysine (PLL) on the surface of StNP. At the same time, the
size of PLL-StNP and its stability in aqueous solution were checked by AFM. The analysis of plasmid DNA binding, DNase I enzymatic
degradation, toxicity and transfection were done. We discovered that PLL-StNP may be used as non-virus nanoparticle gene carrier.
And we developed the method of preparing PLL-StNP gene carrier and used it in cell transfection. As non-virus gene carrier,
PLL-StNP has some advantages, such as large load of DNA, high transfection efficiency, low cell toxicity and biodegradability. 相似文献
58.
O. B. Ryabova E. Yu. Khmel’nitskaya V. A. Makarov L. M. Alekseeva N. B. Grigor’ev V. G. Granik 《Russian Chemical Bulletin》2005,54(12):2873-2879
On heating at pH 6.86, 4-(N,N-dialkylthiocarbamoylthio)-5-nitropyrimidines are transformed into dithiolopyrimidines, which are either oxidized to bis(4-dialkylthiocarbamoylpyrimidin-5-yl)
disulfides or converted into 4,6-diamino-5-nitropyrimidine derivatives with carbon disulfide elimination. The direction of
the reaction is determined by the nature of a substituent in position 2 of pyrimidine and the bulk of the thiocarbamate substituent.
Mechanistic schemes for these processes were proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2777–2783, December, 2005. 相似文献
59.
Summary The dependence of the chloride distribution coefficient on the co-ion of solutions of different alkali fluorides, MF, up to 11M is tested on the strongly basic anion-exchange resin AG1-X10. Under the same experimental conditions the distribution coefficient decreases in the following order for M+: Na+>K+>Rb+>Cs+. This can be explained by the different co-ion-chloride interactions. The consequence of this interaction for a chromatographic separation of chloride is shown with 5M KF and CsF solutions, used as eluants. Depending on the fluoride concentration, the distribution coefficient passes through a minimum value to increase again at higher electrolyte concentration. The non-exchange electrolyte in the resin phase is responsible for this effect. In addition, the bromide and the iodide distribution coefficients up to 10M KF solutions are determined. One results is that the selectivity coefficient between halide ions increases at higher electrolyte concentrations. 相似文献
60.
The paper presents a comparative analysis of the possibilities and characteristic features of the application of various polyhedral boron compounds, viz., the closo-decaborate anion [B10H10]2–, the closo-dodecaborate anion [B12H12]2–, the carba-closo-dodecaborate anion [CB11H12]–, carboranes C2B10H12, and the bis(dicarbollide) complexes [M(C2B9H11)2]– (M = Fe, Co, or Ni), in boron neutron capture therapy (BNCT) for cancer. The requirements on compounds used in BNCT are formulated and the advantages of the application of the closo-dodecaborate anion are considered. The data on the synthesis of various derivatives of the closo-dodecaborate anion, which either already found use in BNCT or are most promising in this field, are summarized. The possibilities of the application of agents derived from the closo-dodecaborate anion in medical diagnostics are discussed. 相似文献