Reactivity-based fluoride detection: evolving design principles for spring-loaded turn-on fluorescent probes

A covalently triggered fluorescence turn-on detection scheme has been implemented for a tris(N-salicylideneamine)-derived dynamic fluorophore. Selective cleavage of strategically placed Si-O bonds by fluoride ion induces spring-loaded conformational transitions that are tightly coupled to fluorescence enhancement.     

Aminolysis of 2,2-difluoro-4-alkoxy-1,3,2-dioxaborinanes: route to β-keto amides and β-enamino carboxamides

4-Alkoxy substituted 1,3,2-dioxaborinanes 1, readily available from β-keto esters, undergo substitution reactions under mild reaction conditions with primary and secondary amines, deriving the 4-alkylamino analogue 2. Reactions of 1 with substituted phenylhydrazines gave the corresponding hydrazones, or pyrazolones, and 5-alkoxy-1H-pyrazoles as a mixture of products.     

Rotational fluctuations of water confined to layered oxide materials: nonmonotonous temperature dependence of relaxation times

The rotational molecular dynamics of water confined to layered oxide materials with brucite structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(7) Hz and in a broad temperature interval. The layered double hydroxide samples show one relaxation process, which was assigned to fluctuations of water molecules forming a layer, strongly adsorbed to the oxide surface. The temperature dependence of the relaxation rates has an unusual saddlelike shape characterized by a maximum. The model of Ryabov et al. (J. Phys. Chem. B 2001, 105, 1845) recently applied to describe the dynamics of water molecules in porous glasses is employed also for the layered materials. This model assumes two competing effects: rotational fluctuations of water molecules that take place simultaneously with defect formation, allowing the creation of free volume necessary for reorientation. The activation energy of rotational fluctuations, the energy of defect formation, a pre-exponential factor, and the defect concentration are obtained as main parameters from a fit of this model to the data. The values of these parameters were compared with those found for water confined to nanoporous molecular sieves, porous glasses, or bulk ice. Several correlations were discussed in detail, such as the lower the value of the energy of defect formation, the higher the number of defects. The pre-exponential factor increases with increasing activation energy, as an expression of the compensation law, and indicates the cooperative nature of the motional process. The involvement of the surface OH groups and of the oxygen atoms of the interlayer anions in the formation of hydrogen bonds was further discussed. For the birnessite sample, the relaxation processes are probably overlaid by a dominating conductivity contribution, which is analyzed in its frequency and temperature dependence. It is found that the conductivity of birnessite obeys the characteristics of semiconducting disordered materials. Especially the Barton/Nakajima/Namikawa relationship is fulfilled. Analyzing the temperature dependence of the direct current (dc) conductivity sigma0 in detail gives some hint that sigma0(T) has also an unusual saddlelike form.     

Quantum chemical investigation of formation of polychlorodibenzo-p-dioxins and dibenzofurans from oxidation and pyrolysis of 2-chlorophenol

Density functional theory (DFT) calculations have been used to obtain thermochemical parameters for formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) from the oxidation of 2-chlorophenol. Formation mechanisms of PCDD through radical-radical coupling have been investigated in detail. The sequence of 2-chlorophenoxy radical coupling has been studied. The formation of chlorinated bis keto dimers which results from cross coupling of 2-chlorophenoxy at the ortho carbon bearing hydrogen (a known direct route for PCDF formation) passes through a tight transition structure whose barrier is 9.4 kcal/mol (0 K). Three routes for the formation of the most abundant PCDD/PCDF species (viz., 4,6-dichlorodibenzofuran, 4,6-DCDF, and 1-monochlorodibenzo-p-dioxin, 1-MCDD) in oxidation and pyrolysis of 2-chlorophenol are discussed. In the case of 4,6-DCDF, formation through H or HO + keto-keto <==> H2 or H2O + keto-keto* <==> H2 or H2O + enol-keto* <==> H2 or H2O + 4,6-DCDF + HO is shown to be the preferred route. The other two routes proceed via closed shell processes (keto-keto <==> enol-keto <==> enol-enol <==> H2O + 4,6-DCDF) and (keto-keto <==> enol-keto <==> (H-,OH-) 4,6-DCDF <==> H2O + 4,6-DCDF). Results indicate that 1-MCDD should be the favored product in 2-chlorophenol pyrolysis in agreement with experimental findings. According to our results, tautomerization (inter-ring hydrogen transfer) and intra-annular displacement of HCl would not be competitive with paths deriving from H abstraction from the phenolic oxygen and the benzene ring followed by displacement of Cl in the formation of dibenzo-p-dioxin (DD) and 1-MCDD. The results presented here will assist in construction of detailed kinetic models to account for the formation of PCDD/PCDF from chlorophenols.     

Flow-injection determination of total organic fluorine with off-line defluorination reaction on a solid sorbent bed

Considering recent reports on widespread occurrence and concerns about perfluoroalkyl substances (PFAS) in environmental and biological systems, analysis of these compounds have gained much attention in recent years. Majority of analyte-specific methods are based on a LC/MS/MS or a GC/MS detection, however many environmental or biological studies would benefit from a total organic fluorine (TOF) determination. Presented work was aimed at developing a method for TOF determination. TOF is determined as an amount of inorganic fluoride obtained after defluorination reaction conducted off-line using sodium biphenyl reagent directly on the sorbent without elution of retained analytes. Recovered fluoride was analyzed using flow-injection system with either fluorimetric or potentiometric detection. The TOF method was tested using perfluorocarboxylic acids (PFCA), including perfluorooctanoic acid (PFOA), as model compounds. Considering low concentrations of PFAS in natural samples, solid-phase extraction as a preconcentration procedure was evaluated. Several carbon-based sorbents were tested, namely multi-wall carbon nanotubes, carbon nanofibres and activated carbon. Good sorption of all analytes was achieved and defluorination reaction was possible to carry out directly on a sorbent bed. Recoveries obtained for PFCAs, adsorbed on an activated carbon sorbent, and measured as TOF, were 99.5 ± 1.7, 110 ± 9.4, 95 ± 26, 120 ± 32, 110 ± 12 for C4, C6, C8, C10 and C12-PFCA, respectively. Two flow systems that would enable the defluorination reaction and fluoride determination in a single system were designed and tested.     

Efficient peptide coupling involving sterically hindered amino acids

Hindered amino acids have been introduced into peptide chains by coupling N-(Cbz- and Fmoc-alpha-aminoacyl)benzotriazoles with amino acids, wherein at least one of the components was sterically hindered, to provide compounds 3a-e, (3c +3 c'), 5a-d, (5a + 5a'), 6a-c, (6b + 6b'), 8a-c, 9a-e, 10a-d, and (10a + 10a') in isolated yields of 41-95% with complete retention of chirality as evidenced by NMR and HPLC analysis. The benzotriazole activation methodology is a new route for the synthesis of sterically hindered peptides. (Note: compound numbers written within brackets represent diastereomeric mixtures or racemates; compound numbers without brackets represent enantiomers.).     

Factors affecting the stability of foamed concentrated emulsions

This paper attempts to quantify the stability of three-phase systems generated by aerating concentrated water-in-oil emulsions. In such materials, which we call foamed emulsions, the continuous phase is itself a two-phase system. In this work, we modify and extend the method originally proposed by Iglesias et al. (Colloids and Surfaces A, 98 (1995) 167–174) to viscous three-phase foams. The modified method involves imparting a destabilising force to the sample to make the foam short-lived and measuring the change in height as a function of decay time. The change of height during decay represents the rate at which gas is evolved from the foamed emulsion and is logarithmic with time. The data treatment yields two values, the decay constant and half-life, which are used as a means of measuring and comparing stability. Two distinct decay mechanisms (smooth decay and catastrophic collapse) operate in foamed emulsions that are subjected to oscillations. For a given decay mechanism, the decay constant is an intrinsic property of the foamed emulsion and is independent of the imposed oscillations. Experimental results indicate that different bubble stabilising surfactants and emulsion morphology significantly affect the foam stability, and that the stability is inversely related to the initial expansion. Examination of the gas–emulsion interface shows a segregation of droplets, with smaller droplets found preferentially at the gas–emulsion interface.     

An end theorem for stratified spaces

We show that a manifold-stratified space X is the interior of a compact manifold-stratified space with boundary if and only if X is tame-ended and a K-theoretic obstruction γ_*(X) vanishes. The obstruction γ_*(X) is a localization of Quinn's mapping cylinder neighborhood obstruction. The main results are Theorem 1.6 and Theorem 1.7 below. In particular, this explains when a G-manifold is the interior of a compact G-manifold with boundary. One of our methods is a new transversality theorem, Theorem 1.16. Oblatum 30-VI-1996 & 21-X-1997 / Published online: 14 January 1999     

Application of solid-phase microextraction to monitoring indoor air quality

Practical application of Solid-Phase Microextraction (SPME) for the assessment of the quality of indoor air is presented. SPME was used to sample selected organic pollutants (carbon tetrachloride, benzene, toluene, chlorobenzene, p-xylene and n-decane). An SPME fiber was coated with a 100 μm film of polydimethylsiloxane. The analytes extracted were analysed with a gas chromatograph directly coupled with a mass spectrometer (GC-MS). The method was used to assess the indoor air quality in a few selected flats. The concentrations ranged from below detection limits to 6.9 mg/m³ for benzene depending on the flat; they were relatively high for newly built or freshly renovated flats. Received: 14 July 1998 / Revised: 17 November 1998 / Accepted: 21 November 1998