γ-Irradiation of tris (methylidene)-cyclopropane (‘[3]radialene’) 1 in a rigid electron scavenging matrix (butylchoride/i-pentane, 1:1) at 77 K leads to formation of its molecular cation 1 +. Slight softening of the matrix by a temperature increase of 3–5 K results in formation of a newly absorbing species, tentatively assigned arising from structrral relaxation of 1 + by π-bond rotation: 相似文献
The condensation of ethyl trifluoroacetoacetate with various heterocyclic amines yielded 2-(trifluoromethyl)phenanthrolin-4-ones. The structures of these compounds were established from a study of their infrared and ultraviolet spectra. Substituted phenanthrolines were prepared by nucleophilic attack on a chlorophenanthroline. The oxidation of 5-methoxy-2-trifluoromethyl-1,10-phenanthroline yielded an o-quinone which was treated with typical quinone reagents. A molecular orbital calculation was carried out in an attempt to explain the ease of reduction of the 1,10-phenanthroline system and the colors of the reduced compounds. 相似文献
The design, synthesis and evaluation of a pentacyclic scaffold, CWO-324 to mimic saframycin A is described. CWO-324 is readily synthesized in five steps from 1,4-diacetyl-piperazine-2,5-dione and 2,5-dimethoxybenzaldehyde. CWO-324 was found to scission DNA, binds to bases 69-83(5′-GCAGTCAGG CACCGT-3′) of Hind III/Rsa I from plasmid pBR322 DNA in a foot-printing study and possesses anti-tumor activity. 相似文献
The effects of the medium ionic composition on the apparent equilibrium association constant (K) for the formation of a 1:1 inclusion complex between the guest methyl viologen (MV(2+)) and the host cucurbit[7]uril (CB7) were studied in aqueous solutions. The K values were found to decrease with increasing ionic strength, with more pronounced effects for solutions containing divalent Ca(2+) ions than for solutions containing monovalent Na(+) ions. The competing ion-dipole interactions between Ca(2+) or Na(+) and MV(2+) ions appear to be responsible for the remarkable modulation of the K values observed in this work. 相似文献
Chiral aggregation of oligo(p-phenylene vinylene)-functionalized Zn and free-base porphyrins is observed in water. The formation of mixed assemblies containing both porphyrins results in sequential energy transfer from OPV via zinc porphyrin to free-base porphyrin. Furthermore, the incorporation of C60 as electron acceptor yields a charge separated state by ultimate electron transfer. 相似文献
Photoelectron spectroscopic investigations indicate that (i) monocyclic diaziridines prefer a trans-conformation of the nitrogen-lone pairs, and (ii) the interaction between these is comparable to that exhibited by open-chain analogues, i.e. alkyl-substituted hydrazines. The chemical experience concerning the particular case of ? NH? NH? →? N?N? oxidation of diaziridines can therefore not be accounted for by a prevailing unfavorable ‘lone pair’ interaction. Thermochemical as well as entropy arguments may serve as an explanation. A rather unsatisfactory agreement between predictions from various theoretical procedures and experimental results for the ionization potentials of ‘lone pair’ MO electrons is noted. 相似文献
We report an experimental study of energy pooling collisions involving Cs atoms in the 6P and 5D states. The 5D state was populated by a cw dye-laser tuned to the cesium dipole-forbidden transition 6S → 5D at 685.0 nm. The 6P state was populated by subsequent radiative relaxation of the 5D state. The 6P population density was determined from the absorption of a cw diode-laser probe beam. The population densities of the 5D state and the higher, by energy pooling excited states were determined by measuring the corresponding fluorescence intensities relative to the fluorescence intensity from the optically thin quasi-static wings of the cesium D2 line. The rate coefficient for the process Cs*(6P)+Cs*(6P)→Cs**(6D)+Cs(6S) is found to be (4.2±0.13)×10?10 cm3 s?1 at T=570 K. In addition, estimates of the rate coefficients for the processes Cs*(6P)+Cs*(5D)→Cs**(7D)+Cs(6S) and Cs*(5D)+ Cs*(5D)→Cs**(7F)+Cs(6S) are given. 相似文献
Zusammenfassung Die Reaktion zwischen CaSi2 und JCl liefert in einer Festkörperreaktion unter Aufspaltung des Schichtgitters ein stöchiometrisch und strukturell definiertes (SiCl)n. Eigenschaften und Hydrolyse der Verbindung werden besprochen. Solvolyse mit Alkoholen führt zu entsprechenden Alkoxyderivaten, die Umsetzung mit Lithiummethyl zur methylierten Verbindung.Mit 2 Abbildungen4. Mitt.:E. Hengge undH. Grupe, Chem. Ber.97, 1783 (1964). 相似文献
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects. 相似文献
The study and extension of a simple automated clean-up method for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) to a broad range of polychlorinated biphenyls (PCB) is described. The isolation of seven PCDD, ten PCDF, and three coplanar PCB (cPCB) is extended to eight monoortho substituted PCB and seven so-called "marker PCB" (Aroclor 1260) for fatty food samples. This enables quantification of 35 compounds - including all congeners with a WHO toxic equivalent factor (TEF)--in a single extraction and single purification step. The chromatographic behaviour of mono-ortho PCB and marker PCB on a variety of adsorbents, including basic alumina, has been studied. Partitioning of analytes through multi-column sequences is described and correlated with their structural and electronic properties, by use of molecular modelling calculations. The fractionation process available with the Power-Prep automated clean-up system enables rapid independent analysis of the different groups of compounds. Gas chromatography with high resolution mass spectrometry (GC-HRMS) is used for the PCDD/F and cPCB fraction and quadrupole ion-storage tandem in time mass spectrometry (GC-QISTMS) for analysis of the remaining PCB. A comparison study was performed on quality-control samples and real fatty food samples to evaluate the robustness of the new strategy compared with a reference method. On the basis of this simultaneous clean-up, a rapid simplified strategy for PCDD/F and selected PCB analysis determination is proposed for fatty food samples. 相似文献