Amperometric and spectrophotometric determination of carbaryl in natural waters and commercial formulations

The work presented describes the development and evaluation of two flow-injection analysis (FIA) systems for the automated determination of carbaryl in spiked natural waters and commercial formulations. Samples are injected directly into the system where they are subjected to alkaline hydrolysis thus forming 1-naphthol. This product is readily oxidised at a glassy carbon electrode. The electrochemical behaviour of 1-naphthol allows the development of an FIA system with an amperometric detector in which 1-naphthol determination, and thus measurement of carbaryl concentration, can be performed. Linear response over the range 1.0×10^–7 to 1.0×10^–5 mol L^–1, with a sampling rate of 80 samples h^–1, was recorded. The detection limit was 1.0×10^–8 mol L^–1. Another FIA manifold was constructed but this used a colorimetric detector. The methodology was based on the coupling of 1-naphthol with phenylhydrazine hydrochloride to produce a red complex which has maximum absorbance at 495 nm. The response was linear from 1.0×10^–5 to 1.5×10^–3 mol L^–1 with a detection limit of 1.0×10^–6 mol L^–1. Sample-throughput was about 60 samples h^–1. Validation of the results provided by the two FIA methodologies was performed by comparing them with results from a standard HPLC–UV technique. The relative deviation was <5%. Recovery trials were also carried out and the values obtained ranged from 97.0 to 102.0% for both methods. The repeatability (RSD, %) of 12 consecutive injections of one sample was 0.8% and 1.6% for the amperometric and colorimetric systems, respectively.     

Combination of neutron activation,atomic absorption spectroscopy and conventional methods in the elemental analysis of silicate rocks

Instrumental neutron activation, atomic absorption spectroscopy and conventional methods of analysis were used on eight different silicate rocks and two minerals. Trace elements and major constituents were determined. It was considered that the methods should be regarded as complementary analytical techniques.     

Dead Ends and Detours En Route to Total Syntheses of the 1990s A list of abbreviations can be found at the end of the article

From the very beginning organic chemistry and total synthesis have been intimately joined. In fact, one of the first things that freshmen in organic chemistry learn is how to join two molecules together to obtain a more complex one. Of course they still have a long way to go to become fully mature synthetic chemists, but they must have the primary instinct to build molecules, as synthesis is the essence of organic chemistry. With the different points of view that actually coexist in the chemical community about the maturity of the science (art, or both) of organic synthesis, it is clear that nowadays we know how to make almost all of the most complex molecules ever isolated. The primary question is how easy is it to accomplish? For the readers of papers describing the total synthesis of either simple or complex molecules, it appears that the routes followed are, most of the time, smooth and free of troubles. The synthetic scheme written on paper is, apparently, done in the laboratory with few, if any, modifications and these, essentially, seem to be based on finding the optimal experimental conditions to effect the desired reaction. Failures in the planned synthetic scheme to achieve the goal, detours imposed by unexpected reactivity, or the absence of reactivity are almost never discussed, since they may diminish the value of the work reported. This review attempts to look at total synthesis from a different side; it will focus on troubles found during the synthetic work that cause detours from the original synthetic plan, or on the dead ends that eventually may force redesign. From there, the evolution from the original route to the final successful one that achieves the synthetic target will be presented. The syntheses discussed in this paper have been selected because they contain explicit information about the failures of the original synthetic plan, together with the evolution of the final route to the target molecule. Therefore, they contain a lot of useful negative information that may otherwise be lost.     

Isoniazid-sensing Behavior of a Hybrid Silsesquioxane and Cobalt Pentacyanonitrosylferrate-based Nanocomposite

A novel silsesquioxane and cobalt nitroprusside compound was prepared from octa(aminopropyl)silsesquioxane, resulting in a nanocomposite (ACCoN), which was then characterized by different spectroscopic techniques. The cyclic voltammograms of the ACCoN-modified graphite paste electrode indicated a redox pair with a formal potential (E^θ′)=0.38 V, assigned to the Co^(II)Fe^(II)(CN)₅NO/Co^(II)Fe^(III)(CN)₅NO redox couple. The ACCoN-modified graphite paste electrode was sensitive to isoniazid concentrations, presenting a linear response at a concentration range from 6.0×10⁻⁷ to 1.0×10⁻⁵ mol L⁻¹, with limit of detection and amperometric sensitivity of 5.53×10⁻⁷ mol L⁻¹ and 0.17 A/mol L⁻¹, respectively.     

Applications of counter-current chromatography in organic synthesis purification of heterocyclic derivatives of lapachol

This work describes the application of counter-current chromatography (CCC) as a useful, fast and economic alternative for the isolation and purification of heterocyclic derivatives from lapachol and beta-lapachone, two naturally occurring compounds from Tabebuia species, and nor-beta-lapachone, a synthetic congener of lapachol. The discussed data comprise four examples of purification of synthetic reactions with different solvent systems - the mixture of the oxazole and the imidazole from beta-lapachone; the quinoxaline from nor-beta-lapachone; and the purification of the N-oxides from the quinoxaline and the phenazine from nor-beta-lapachone from their respective not fully reacted substrates by means of aqueous reversed- and normal-phase elution modes and non-aqueous solvent systems. Traditional purification of these reaction products by silica gel column chromatography demanded a large amount of solvent and time and, in some cases, serious degradation of the products occurred, leading to low yield of the reaction. High-speed counter-current chromatography (HSCCC) was used as an alternative to optimize the process and raise the yield of the reactions.     

Flow-induced vibration of a circular cylinder subjected to wake interference at low Reynolds number

Two- and three-dimensional numerical simulations of the flow around two circular cylinders in tandem arrangements are performed. The upstream cylinder is fixed and the downstream cylinder is free to oscillate in the transverse direction, in response to the fluid loads. The Reynolds number is kept constant at 150 for the two-dimensional simulations and at 300 for the three-dimensional simulations, and the reduced velocity is varied by changing the structural stiffness. The in-line centre-to-centre distance is varied from 1.5 to 8.0 diameters, and the results are compared to that of a single isolated flexible cylinder with the same structural characteristics, m^?=2.0 and ζ=0.007. The calculations show that significant changes occur in the dynamic behaviour of the cylinders, when comparing the flow around the tandem arrangements to that around an isolated cylinder: for the tandem arrangements, the lock-in boundaries are wider, the maximum displacement amplitudes are greater and the amplitudes of vibration for high reduced velocities, outside the lock-in, are very significant. The main responsible for these changes appears to be the oscillatory flow in the gap between the cylinders.     

Synthesis and characterisation of a new polycyclic phenazine from 1,4-naphthoquinone

Bioactive naphthoquinone-derived heterocyclic compounds have been prepared. Herein, we describe the semisynthesis of a new phenazine, through modified Hooker’s reaction, using lapachol as a precursor. This compound was characterised by 2D NMR spectroscopy methods and X-ray analysis.