Aromatic protonation—4: On the 1H-2H exchange of three 9-n-alkylanthracenes on reaction with CF3CO2[2H] and FSO3[2H]

The reactions of 9-methyl-, 9-ethyl- and 9-propyl-anthracene with CF₃CO₂[²H] in C[²H]Cl₃ and with FSO₃[²H] in SO₂ClF have been investigated. Using 4 equivalents of CF₃CO₂[²H] at 50° ¹H-²H exchange was observed only for the 10-H and the side-chain α-hydrogens, and on using 8 and 12 equivalents at 50° also for the aromatic α-hydrogens. Treatment of the substrates with FSO₃[²H] at -60° leads to the stable 9-alkyl-[10-²H]-10-anthracenium ions. On warming up to ?25° a slow ¹H-²H exchange of only the 10-¹H of these anthracenium ions is observed. A mechanism for the ¹H-²H exchange of the aromatic and the side-chain α-hydrogens of the 9-alkylanthracenes is presented.     

Sequential energy and electron transfer in aggregates of tetrakis[oligo(p-phenylene vinylene)] porphyrins and C60 in water

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.     

Flavonoids in Leguminosae: analysis of extracts of T. pratense L., T. dubium L., T. repens L., and L. corniculatus L. leaves using liquid chromatography with UV, mass spectrometric and fluorescence detection

Reversed-phase LC on C-18 bonded silica with a methanol–ammonium formate gradient was used to determine the main flavonoids in leaves of four species of the Leguminosae family. The detection modes were diode-array UV absorbance, fluorescence, and (tandem) mass spectrometry. LC–UV was used for a general screening, sub-classification, and the calculation of total flavonoid contents. LC–FLU was included to identify isoflavones on the basis of their native fluorescence. Most structural information regarding aglycons, sugar moieties, and acidic groups was derived from LC–MS in both the full-scan and extracted-ion mode, using negative-ion atmospheric pressure chemical ionization. MS/MS did not provide much additional information, because the same fragments were observed as in full-scan MS.In T. pratense and T. repens, the main constituents were flavonoid glucoside–(di)malonates, while T. dubium and L. corniculatus mainly contained flavonoid (di)glycosides. Satellite sets comprising an aglycon, the glucoside and glucoside–malonates or –acetates, were abundantly present only in T. pratense. Generally speaking, the main aglycons and sugars in the four plant species are surprisingly different. In addition, while the results for T. pratense are similar to those reported in the literature, there is little agreement in the case of the other species. Finally, total flavonoid contents ranged from 50–65 mg/g for L. corniculatus and T. dubium, to 15 mg/g for T. pratense and only 1 mg/g for T. repens.     

Hyphenation of column liquid chromatography and Raman spectroscopy via a liquid-core waveguide: chemometrical elimination of spectral eluent background

In column liquid chromatography (LC) coupled to conventional Raman spectroscopy (RS) removal of the spectral background of the eluent is often demanding, because of the strong signals of the organic modifier. A new chemometrical method is proposed, called the eluent background subtraction (EBS) method, which can correct for small shape and intensity differences of the eluent spectra. The variations in the eluent spectra are modelled using principal component analysis (PCA). The PCA loading vectors are subsequently used for eluent background correction of the elution spectra of the analyte. The loading vectors are fitted under these spectra by an asymmetric least-squares method. This method was successfully applied under various experimental conditions and performed much better than conventional background correction methods. Analyte detectability was improved by (weighted) averaging of all elution spectra and smoothing via a p-spline function.     

SULFONATION OF 9-ALKYLANTHRACENES

Abstract

The reaction of anthracene, 9-phenylanthracene and some 9-alkylanthracenes with dioxan-SO₃ has been studied. Anthracene yields the 1-, 2- and 9-sulfonic acid in a ratio of 24 : 6 : 70. 9-Phenyl- and 9-neopentyl-anthracene both yield a mixture of the 4- and 10-sulfonic acids in a ratio of 33 : 67 and 15 : 85 respectively. Unexpectedly, 9-methylanthracene yields, in a more rapid reaction, exclusively 9-anthrylmethanesulfonic acid (1, R[dbnd]H) 9-Alkylanthracenes of which the alkyl group contains at least one α-H yield as main product (s) the α-sulfonic acids 1 and/or (depending on the further structure of the alkyl group) the sulfonic acids 2–4.     

Structural Effects in Visible‐Light‐Responsive Metal–Organic Frameworks Incorporating ortho‐Fluoroazobenzenes

The ability to control the interplay of materials with low‐energy photons is important as visible light offers several appealing features compared to ultraviolet radiation (less damaging, more selective, predominant in the solar spectrum, possibility to increase the penetration depth). Two different metal–organic frameworks (MOFs) were synthesized from the same linker bearing all‐visible ortho‐fluoroazobenzene photoswitches as pendant groups. The MOFs exhibit different architectures that strongly influence the ability of the azobenzenes to isomerize inside the voids. The framework built with Al‐based nodes has congested 1D channels that preclude efficient isomerization. As a result, local light–heat conversion can be used to alter the CO₂ adsorption capacity of the material on exposure to green light. The second framework, built with Zr nodes, provides enough room for the photoswitches to isomerize, which leads to a unique bistable photochromic MOF that readily responds to blue and green light. The superiority of green over UV irradiation was additionally demonstrated by reflectance spectroscopy and analysis of digested samples. This material offers promising perspectives for liquid‐phase applications such as light‐controlled catalysis and adsorptive separation.     

Ethane/ethene separation turned on its head: selective ethane adsorption on the metal-organic framework ZIF-7 through a gate-opening mechanism

Ethane is selectively adsorbed over ethylene in their mixtures on the zeolite imidazolate framework ZIF-7. In packed columns, this results in the direct production of pure ethylene. This gas-phase separation is attributed to a gate-opening effect in which specific threshold pressures control the uptake and release of individual molecules. These threshold pressures differ for the different molecules, leaving a window of selective uptake operation. This phenomenon makes ZIF-7 a perfect candidate for the separation of olefins from paraffins, since in contrast to most microporous materials, the paraffin is selectively adsorbed. Mixture adsorption, as studied by breakthrough experiments, demonstrates that gate-opening effects can be effectively used to separate molecules of very similar size.     

Laser-induced quenched phosphorescence detection in capillary electrophoresis.

The feasibility of laser-based excitation for quenched phosphorescence detection in capillary electrophoresis (CE) was explored for the first time by using a small-size, quadrupled Nd-YAG laser emitting 266 nm pulses (duration, 0.4 ns) at a repetition rate of 7.8 kHz. To provide a continuous phosphorescence background, the phosphorophore 1-bromo-4-naphthalene sulfonic acid (BrNS) was added to the separation buffer. Both experiments and theory show that in laser-induced phosphorescence (LIP) - in contrast with lamp-excited phosphorescence - one normally deals with such high triplet-state phosphorophore concentrations that triplet-triplet annihilation is the major deactivation pathway. This results in a lower quantum yield of the analyte-induced bimolecular quenching interaction and, thus, the observed quenching signal. The situation can be improved by using a cylindrical lens for excitation in order to reduce the irradiance. In this case limits of detection (LODs) similar to those obtained using lamp excitation (1x10(-8) M) were achieved, while the width of the detection window was reduced from about 4 mm to 1 mm. Even under exclusion of triplet-triplet annihilation, i.e., under conditions of low irradiance, for our setup the quenching yields in LIP were smaller than in lamp-based phosphorescence detection. This is due to the repetition rate of the laser (7.8 kHz), which is too high in view of the phosphorescence lifetime (ca. 300 micros at low irradiance). Theory shows that this disadvantageous effect will be fully eliminated if the repetition rate is decreased to 1 kHz.