Quality control of Metamitron in agrochemicals using Fourier transform infrared spectroscopy in the middle and near range

Two vibrational spectrometry-based methodologies were developed for Metamitron determination in pesticide formulations. Fourier transform-middle infrared (FT-MIR) procedure was based on the extraction of Metamitron by CHCl₃ and latter determination by peak area measurement between 1556 and 1533 cm⁻¹, corrected with a two points baseline established from 1572 to 1514 cm⁻¹. Fourier transform-near infrared (FT-NIR) determination was made after the extraction of Metamitron in acetonitrile and measuring the peak area between 6434 and 6394 cm⁻¹ corrected using a two points baseline defined between 6555 and 6228 cm⁻¹. Repeatability, as relative standard deviation, of 5 independent measurements at mg g⁻¹ concentration level, of 0.16% and 0.07% for MIR and NIR and a limit of detection of 0.03 and 0.004 mg g⁻¹ were obtained for MIR and NIR, respectively.NIR determination provides a sample frequency of 120 h⁻¹, higher than that found by MIR and liquid chromatographic methods (60 and 15 h⁻¹, respectively). On the other hand, the NIR method reduces the solvent consumption and waste generation, to only 1 ml acetonitrile per sample as compared with 3.4 ml chloroform required for the MIR determination and 60 ml acetonitrile used in the chromatographic reference procedure. So, vibrational procedures can be considered serious alternatives to long and time consuming chromatographic methods usually recommended for quality control of commercially available pesticide formulations.     

Cyclopentathiadiazines, new heterocyclic materials from cyclic enaminonitriles

Indene and cyclopentene enaminonitriles were reacted with SCl2, iBu3N and NCS to give the first cyclopenta[1,2,6]thiadiazines that showed unusual characteristics, one as a NIR dye and another as a liquid crystal.     

Dynamic contact angle and spreading rate measurements for the characterization of the effect of dentin surface treatments

A new methodology capable of providing reliable and reproducible contact angle (theta) data has been employed to study the effect of clinical treatments grinding, acid etching, and deproteinization on medial dentin tissue. It is based on the application of the ADSA-CD algorithm to the determination of low-rate dynamic contact angles, obtained from slowly growing drops, and on contact angle measurement, as well as spreading behavior analysis, during the relaxation of the system (water on treated dentin) after initial drop growth. The theta data obtained were substantially more reproducible than those obtained with classical methods. A net effect of the treatment on theta was found, increasing dentin wettability: theta (polished) >theta (etched) >theta (deproteinized). The spreading rates correlate with the angles and are adequate for the dentin surface characterization. ANOVA and SNK tests show that for advancing contact angles the means corresponding to all treatments are significantly different. In the relaxing phase, mean angle and spreading rates on polished dentin differ significantly from those on etched and deproteinized dentin, but the latter do not differ significantly from each other.     

Assessment of Four Inter-Comparison Exercises in Organic Elemental Analysis

 Four inter-comparison exercises on organic elemental analysis were carried out between 1997 and 2001 by the Department of Analytical Chemistry of the University of Barcelona, together with the Microanalysis Service and the Institute of the Marine Sciences, which both belong to the CSIC in Barcelona, and the University of A Coru?a. More than sixty laboratories participated in these exercises. Here we describe the design and characteristics of the trials, the samples and the homogeneity tests applied. We report the results obtained for the analysis of carbon, hydrogen, nitrogen, sulphur and oxygen, their statistical analysis, and the most relevant aspects of the technical discussion meetings. Received December 20, 2001; accepted March 18, 2002; published online July 22, 2002     

Self-assembly of nonionic surfactants into lyotropic liquid crystals in ethylammonium nitrate, a room-temperature ionic liquid

The stability of a variety of lyotropic liquid crystals formed by a number of polyoxyethylene nonionic surfactants in the room-temperature ionic liquid ethylammonium nitrate (EAN) is surveyed and reported. The pattern of self-assembly behaviour and mesophase formation is strikingly similar to that observed in water, even including the existence of a lower consolute boundary or cloud point. The only quantitative difference from water is that longer alkyl chains are necessary to drive the formation of liquid crystalline mesophases in EAN, suggesting that a rich pattern of "solvophobic" self-assembly should exist in this solvent.     

Study of the ESI-mass spectrometry ionization mechanism of Fischer carbene complexes

By means of deuterium-labeling experiments, we have carried out a systematic ESI-MS study to determine the mechanism of ESI ionization of alkenyl and alkynyl group 6 Fischer carbene complexes. These compounds can be ionized under ESI conditions only in the presence of additives such as hydroquinone (HQ) or tetrathiafulvalene (TTF). Our results demonstrate that in the ESI source an anion-radical is formed after the initial HQ- or TTF-mediated electron transfer to the metallic carbene complex. For alkenyl carbene complexes, this species evolves by extrusion of a hydrogen radical to form an allenylchromium anion that is detected as the [M - H](-) ion in the mass spectrum. The preference for this mechanistic pathway could be rationalized by DFT calculations. In the case of alkynyl carbene complexes, experiments combining deuterated substrate, additive, and solvent demonstrate that the previously proposed allene-anion carbene complex is not formed. Instead, the H transfer from the ethoxy group in the anion radical, followed by extrusion of a hydrogen radical, leads to an allenyl anion that is detected in the ESI-MS as [M - H - CO](-).     

Stepwise cycloreversion of oxetane radical cations with initial C-O bond cleavage

2,4,6-Triaryl(thia)pyrylium salts have been used as electron-transfer photosensitizers for the cycloreversion of the oxetane ring system. The radical cation of 2,3-diphenyl-4-hydroxymethyloxetane (1) undergoes stepwise splitting via initial O-C2 cleavage. Spin and charge in the resulting intermediate are located in the oxygen and carbon atoms, respectively. Subsequent intramolecular nucleophilic attack produces 2,3-diphenyl-4-hydroxytetrahydrofuran (4a). Formation of this product occurs in the submicrosecond time scale, competing with C3-C4 cleavage to the detectable (lambdamax = 470 nm) trans-stilbene radical cation.     

Effect of the carbon burn-off on the performance of activated carbon as a support for hydrogenation catalysts

The hydrogenation activity of Pt supported on activated carbon would depend on both the Pt dispersity (which can be modified by a partial carbon burn-off in air) and the impurities concentration.     

Reductive PET cycloreversion of oxetanes: singlet multiplicity, regioselectivity, and detection of olefin radical anion

Cycloreversion of 2-(p-cyanophenyl)-4-methyl-3-phenyloxetane (1) is achieved using 1-methoxynaphthalene (2) as electron-transfer photosensitizer. The experimental results are consistent with the reaction taking place from the singlet excited state of the sensitizer. Ring splitting of the radical anion 1*- occurs with cleavage of O-C2 and C3-C4 bonds, leading to products (acetaldehyde and p-cyanostilbene) different from the reagents used in the Paterno-Büchi synthesis of 1. The olefin radical anion involved in the electron-transfer process has been detected by means of laser flash photolysis.