Flow-through solid-phase based optical sensor for the multisyringe flow injection trace determination of orthophosphate in waters with chemiluminescence detection

In this work, a novel flow-through solid-phase based chemiluminescence (CL) optical sensor is described for the trace determination of orthophosphate in waters exploiting the multisyringe flow injection analysis (MSFIA) concept with multicommutation. The proposed time-based injection flow system relies upon the in-line derivatisation of the analyte with ammonium molybdate in the presence of vanadate, and the transient immobilisation of the resulting heteropolyacid in a N-vinylpyrrolidone/divinylbenzene copolymer packed spiral shape flow-through cell located in front of the window of a photomultiplier tube. The simultaneous injection of well-defined slugs of luminol in alkaline medium and methanol solution towards the packed reactor is afterwards performed by proper switching of the solenoid valves. Then, the light emission from the luminol oxidation by the oxidant species retained onto the sorbent material is readily detected. At the same time, the generated molybdenum-blue compound is eluted by the minute amount of injected methanol, rendering the system prepared for a new measuring cycle. Therefore, the devised sensor enables the integration of the solid-phase CL reaction with elution and detection of the emitted light without the typical drawbacks of the molybdenum-blue based spectrophotometric procedures regarding the excess of molybdate anion, which causes high background signals due to its self-reduction. The noteworthy features of the developed CL-MSFIA system are the feasibility to accommodate reactions with different pH requirements and the ability to determine trace levels of orthophosphate in high silicate content samples (Si/P ratios up to 500). Under the optimised conditions, a dynamic linear range from 5 to 50 μg P l⁻¹ for a 1.8 ml sample, repeatability better than 3.0% and a quantification limit of 4 μg P l⁻¹ were attained. The flowing stream system handles 11 analysis h⁻¹ and has been successfully applied to the determination of trace levels of orthophosphate in environmental samples such as mineral, ground, tap and pond waters as well as samples from a water-steam cycle of an incineration plant. The t-test comparison of the means for the developed optical sensor and the molybdenum-blue spectrophotometric APHA/AWWA/WPCF reference method revealed that there is no evidence of significant differences between the obtained results at the 95% confidence level.     

Infinitary queries and their asymptotic probabilities. II. Properties definable in least fixed point logic

We develop an almost complete theory for existence of asymptotic probabilities of least fixed point and partial fixed pint definable properties, and for the complexity of the associated almost sure theory. Our method works for any randomized class of finite structures. © 1994 John Wiley & Sons, Inc.     

De Sitter Quasigroups

The Cayley–Klein parameters for the de Sitter groups SO(4, 1) and SO(3, 2) are introduced, and in an extension of the earlier investigation of quasigroups connected with Clifford groups, quasigroups connected with the SO(4, 1) and SO(3, 2) groups are determined. It is shown that these quasigroups have eight-dimensional, double-valued irreducible cracovian representations. The covariance of a five-dimensional form of the Dirac equation with respect to the quasi-rotations forming quasigroups connected with the groups SO(4, 1) and SO(3, 2) is demonstrated. An analogy is drawn between Weyl's hidden symmetry group and a quasigroup.     

Past and Present of Sol-Gel Science and Technology

In the last twenty years sol-gel science has undergone a spectacular development. The various stages of the sol-gel process have been scrutinised in considerable detail and a sound basis for future technological developments established. In the beginning the studies centred mainly on silica and silicate glasses and were progressively extended to many ceramics and composites. A turning point was reached with the emergence of ormosils and of organic-inorganic nanocomposites. This opened the gateway to whole classes of new materials. The present studies show a definite tendency towards very specialised high-tech applications.     

Synthesis and 1H NMR characterization of substituted 1-amino-9-imino-4-nitro-9,10-dihydr oacridines as potential antitumor agents

A convenient method for the synthesis of unsubstituted and substituted 1-amino-9-imino-4-nitro-9,10-dihydroacridines, 9 and 10 , respectively, is reported. Their ¹H nmr data are reported and discussed in order to confirm the imino tautomeric structure.     

Distribution of the strength of acid sites in mildly steamed HZSM-5 studied by IR spectroscopy

Steaming resulted in modification of the distribution of acid strength of OH groups. The contribution of less acidic sites increased and new, very strongly acidic hydroxyls characterized by IR band at 3590 cm^-1 appeared.     

Solution differentiability for variational inequalities

In this paper we study solution differentiability properties for variational inequalities. We characterize Fréchet differentiability of perturbed solutions to parametric variational inequality problems defined on polyhedral sets. Our result extends the recent result of Pang and it directly specializes to nonlinear complementarity problems, variational inequality problems defined on perturbed sets and to nonlinear programming problems.