Theoretical and electrochemical studies on organometallic symmetrical schiff base complexes of Zn(II), Cu(II), Ni(II) and Co(II)

The electronic communication between two redox centres through a Schiff base complex has been investigated in a series of ethylenediimine-bis(1-ferrocenyl-1,3-butanedionate) complexes of Zn(II) 1, Cu(II) 2, Ni(II) 3 and Co(II) 4. Cyclic voltammetry experiments of 1 and 2 exhibit a unique two-electron reversible oxidation wave, whereas in the case of 3 and 4 two and three one-electron oxidation processes are, respectively, observed. These results suggest some electronic interaction between the iron atoms of the ferrocenyl groups. DFT calculations carried out on model complexes show that for all the studied compounds the removal of the first two electrons corresponds to the oxidation processes of the iron centres in the weakly coupled ferrocenyl termini. The electronic communication between the two iron centres increases on going from 1 to 4. Finally, a re-indexation of the bands observed in the UV-Visible spectra has been carried out using TDDFT calculations.     

Separation and determination of <Superscript>90</Superscript>Sr in low- and intermediate-level radioactive wastes using extraction chromatography and LSC

A methodology for the determination of ⁹⁰Sr in low- and intermediate-level radioactive wastes from nuclear power plants is presented in this work. It is a part of a methodology developed for the sequential radiochemical separation of radionuclides difficult-to-measure directly by gamma spectrometry in these radioactive wastes. The separation procedure was carried out using precipitation and extraction chromatography with Sr Resin, from Eichrom and the ⁹⁰Sr was measured by liquid scintillation counting (LSC). Optimum conditions for the pretreatment, separation and LSC measurements were determined using simulated samples, which were prepared using standard solutions and carriers. The procedure showed to be rapid and achieved a good chemical yield, in the range 60–90%, and a detection limit of 6.0 × 10⁻⁴ Bq g⁻¹. The method was also tested by participation in a national intercomparison program, with aqueous samples, with good agreement of results.     

Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

Abstract

The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25 ≤ Si/Mn ≤ 48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2 nm), ordered intraparticle mesoporosity (ca. 2.63 nm; after template removal), and well-dispersed microporosity (< 2 nm; as consequence of the lixiviation of the Mn-rich domains). The good dispersion of the guest element (Mn) in the silica intermediate provided by the atrane route is responsible for the disordered but regular microporosity achieved.     

Immunosensor for Detection of the Textile Dye Disperse Orange 1 Based on Non‐conventional Competitive Assay

Textile dyes appear as an important class of compounds that has become a matter of public concern and a serious challenge for scientists and environmentalists due to their large‐scale production and extensive application. In this work, a non‐conventional competitive‐type amperometric immunosensor was successfully developed for detection of the textile dye Disperse Orange 1 (DO1). The DO1 was magnetically captured and separated from the sample solution using magnetic particles (MP) functionalized with the antibody anti‐DO1 and with HRP and gold electrodes were modified with the conjugate DO1‐BSA. Molecules of DO1 immobilized on the electrode surface and DO1 captured by MP compete for antibody binding sites. As a result, the amperometric signal decreases with increasing target DO1 concentration at the capture step, because this decreases, the attachment between the HRP coated MP and the electrode. This strategy allowed us to determine DO1 at the low detection limit of 0.87 ng mL^?1 with great specificity. Also, there were good recoveries for detection of the textile dye in river water samples without the need of sample pre‐treatment. The competitive amperometric immunosensor shows applicability for the determination of small molecules that cannot be determined by conventional competitive or sandwich immunosensors.     

A Theoretical Exploration of the Potential of ICAR ATRP for One‐ and Two‐Pot Synthesis of Well‐Defined Diblock Copolymers

Kinetic Monte Carlo simulations are performed to investigate the capability of ICAR ATRP for the synthesis of well‐defined poly(isobornyl acrylate‐b‐styrene) block(‐like) copolymers using one‐pot semi‐batch and two‐pot batch procedures. The block copolymer quality is quantified via a block deviation (〈BD〉) value. For 〈BD〉 values lower than 0.30, the quality is defined as good and for well‐chosen polymerization conditions the formation of homopolymer chains upon addition of the second monomer can be suppressed. A better block quality is obtained when isobornyl acrylate is polymerized first. For lower Cu levels a one‐pot semi‐batch procedure allows a much faster ATRP and better control over the polymer properties than a two‐pot batch procedure.

     

Improved In vitro and In vivo Cutaneous Delivery of Protoporphyrin IX from PLGA‐based Nanoparticles

We report the development of d , l lactic co‐glycolic acid) (PLGA)‐based nanoparticles (NPs) for topical delivery of protoporphyrin IX (PpIX), a photosensitizer (PS), in treatments like photodynamic therapy (PDT) of skin cancers. PpIX‐NPs were obtained in ~75.0% yield, encapsulation efficiency of 67.7%, drug content of 50.3 μg mg^?1, average diameter of 290 nm maintained up to 30 days and a zeta potential of 32.3 mV. Sustained in vitro release of PpIX through artificial membranes following Higuchi kinetics was kept up to 10 days. In vitro retentions of PpIX both in stratum corneum (SC) and epidermis + dermis ([EP + D]) were higher from NPs (23.0 and 10.0 times, respectively) compared to control solutions at all times. Quantification of PpIX by extraction, after in vivo skin application of NPs‐PpIX on hairless mice, showed higher retention of the PS both in SC and in [EP + D] (3.0 and 2.0 times, respectively) compared to control solutions. Taken together, the results indicate that NPs are suitable for PpIX encapsulation showing minimal permeation through the skin and a localized effect, characteristics of a potential and promising delivery system for PDT‐associated treatments of skin cancers, photodiagnosis and their off‐label uses.     

Aza-analogues of extended tetrathiafulvalenes

The phosphoramidate-like reaction of 1,3-dithiole derived N-(diethoxyphosphinyl)hydrazones with formyl derivatives of 1,3-dithiole affords the longest aza-analogues of extended tetrathiafulvalenes with a polyenic spacer reported to date. Their structural and electrochemical properties are discussed.     

The interaction of an azo compound with a surfactant and ion pair adsorption to solid phases

The adsorption of SPADNS (trisodium salt of 2-(p-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid) onto resins XAD 2, XAD 7 and silica gel was studied in the presence and in the absence of the cationic surfactant CTAB (cetyl trimethylammonium bromide). At a ratio of 2.5 CTAB to 1 SPADNS, the surfactant caused a marked increase in SPADNS adsorption. The experimental results for adsorption versus time were applied on the basis of three kinetic models (pseudo-first-order Lagergren, pseudo-second-order, and intraparticle diffusion). The interaction between CTAB and SPADNS was investigated using spectrophotometric, conductometric, and computational techniques. Theoretical results point to the formation of an ion pair between CTAB and SPADNS that influences the solution spectra, in agreement with conductometric and spectrophotometric data.     

Validation of a high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of tetracyclines residues in bovine milk

A high-performance liquid chromatography-fluorescence detection method was optimized and validated to determine tetracyclines residues in bovine milk. Post-column derivatization using metal complexation in non-aqueous reagent increased the fluorescence of chelates by a factor up to 2.54 compared to water (signal-to-noise ratio enhancement). Overall recoveries ranged from 61 to 115%, with RSD_r from 5 to 15% (n = 54). Detection limits ranged from 5 to 35 μg kg⁻¹. Limits of quantification were established at 50 μg kg⁻¹. Decision limits (CCα) were 109, 108 and 124 μg kg⁻¹ and detection capabilities (CCβ) 119, 117 and 161 μg kg⁻¹ for oxytetracycline, tetracycline and chlortetracycline, respectively. The method was applied successfully in a national monitoring program.     

Improved coupled-column liquid chromatographic method for the determination of glyphosate and aminomethylphosphonic acid residues in environmental waters

An existing method for the determination of glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) in water has been improved. It is based on precolumn derivatization with the fluorescent reagent 9-fluorenylmethylcloroformate (FMOC) followed by large-volume injection in a coupled-column LC system using fluorescence detection (LC-LC-FD). The derivatization step was slightly modified by changing parameters such as volume and/or concentration of sample and reagents to decrease the limits of quantification (LOQ) of glyphosate and AMPA to 0.1 microg/l. Additionally, the use of Amberlite IRA-900 for preconcentration of glyphosate, prior to the derivatization step, was investigated; the LOQ of glyphosate was lowered to 0.02 microg/l. Drinking, surface and ground water spiked with glyphosate and AMPA at 0.1-10 microg/l concentrations were analysed by the improved LC-LC-FD method. Recoveries were 87-106% with relative standard deviations lower than 8%. Drinking and ground water spiked with glyphosate at 0.02 and 0.1 microg/l were analysed after preconcentration on the anion-exchange resin with satisfactory recoveries (94-105%) and precision (better than 8%).