The stability constants for the ML+ complex species, where M+ is an alkali metal cation and L is dibenzo-18-crown-6, in nitrobenzene saturated with water were calculated by employing published equilibrium data. The stability is found to increase in the cation order Li+ < Cs+ < Rb+ < K+ < Na+. For the NaL+, KL+, RbL+, and CsL+ complex cations the individual extraction constants in the water-nitrobenzene system were determined; their values increase in the series Na+ < K+ < Rb+ < Cs+.
Pseudomonasfluorescens HK44 is a lux-based bioluminescent bioreporter capable of selective luminescence in the presence of naphthalene and/or salicylic acid intermediate of its metabolism. We attempted to induce bioluminescence (BL) in this strain with 72 compounds, viz. substituted naphthalenes, naphthalene-like compounds (e.g., quinoline), substituted salicylic acids, salicylic acid-like compounds (e.g., 2-anthranilic acid), oligocyclic aromates, and intermediates of naphthalene metabolism to better discriminate response specificity. From them, 42 induced BL significantly lower as compared to naphthalene, three (viz. isoquinoline, o-cresol, and salicylamide) induced BL significantly greater than naphthalene, and 27 yielded no bioluminescent response whatsoever. Strain HK44 is therefore not prone to extensive false-positive signaling and can serve as a fairly specific indicator organism for naphthalene bioavailability. At elevated concentrations, 41 compounds inhibited BL. Thus, the inclusion of constitutive bioreporter controls as indicators of sample toxicity is vital to successful biosensing application.
Seven hypotheses on relationships between the structure of naphthalene analogs and bioluminescence response of bioreporter Pseudomonas fluorescens were formulated using GUHA (General Unary Hypotheses Automaton) on a training set of 37 compounds. Prediction of bioluminescence response of 12 new naphthalene analogs was successful in 69 % cases and resulted in rejection of single hypothesis. The results demonstrate applicability of GUHA in structure-activity research, especially for qualitative data.
The effect of the presence of six different acyclic polyethers (2-glym, 3-glym, 4-glym, PEG 200, PEG 300 and PEG 400), denoted by L, on the distribution of alkali metal dipicrylaminates and ammonium dipicrylaminate (MA) between the aqueous and nitrobenzene phases has been studied. The two-phase system can be quantitatively described by the following five chemical equilibria: Ma+ + Aa- + L0 ↔ MLa+ + Aa-,Ma+ + Aa- ↔ M0+ + A0-, MLA0 ↔ ML0+ + A0-, MA0 ↔ M0+ + A0-, La ↔ L0, for which the respective equilibrium constants Kex(ML+, A-), Kex(M+, A-), Kd0(MLA), Kd0(MA) and KD were determined. The values of Kex(ML+,A-) increase with the increasing crystallographic radius of the M+ ion and with the number of oxyethylene units in the molecule of the ligand, L, in the series 2-glym < 3-glym < 4-glym < PEG 200 < PEG 300 < PEG 400. In addition, it has been demonstrated that the stability of the ML0+ species in the nitrobenzene phase has a maximum value for M+ = Na+ for all the studied ligands. The presence of the polyethers is detrimental to the separation of Cs+ from the other cations, but improves the separation of Na+ from Li+. The extraction selectivities for the K+/NH4+, K+/Li+ and NH4+/Li+ pairs was not significantly affected by the presence of the ligands, except for 2-glym.
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