Development of electrochemical methods for determination of tramadol - analytical application to pharmaceutical dosage forms

A square-wave voltammetric (SWV) method and a flow injection analysis system with amperometric detection were developed for the determination of tramadol hydrochloride. The SWV method enables the determination of tramadol over the concentration range of 15-75 µM with a detection limit of 2.2 µM. Tramadol could be determined in concentrations between 9 and 50 µM at a sampling rate of 90 h-1, with a detection limit of 1.7 µM using the flow injection system. The electrochemical methods developed were successfully applied to the determination of tramadol in pharmaceutical dosage forms, without any pre-treatment of the samples. Recovery trials were performed to assess the accuracy of the results; the values were between 97 and 102% for both methods

Host-Guest interaction between herbicide oxadiargyl and hydroxypropyl-β-cyclodextrin

In the face of a growing human population and increased urbanization, the demand for pesticides will simply rise. Farmers must escalate yields on increasingly fewer farm acres. However, the risks of pesticides, whether real or perceived, may force changes in the way these chemicals are used. Scientists are working toward pest control plans that are environmentally sound, effective, and profitable. In this context the development of new pesticide formulations which may improve application effectiveness, safety, handling, and storage can be pointed out as a solution. As a contribution to the area, the microencapsulation of the herbicide oxadiargyl (OXA) in (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was performed. The study was conducted in different aqueous media (ultrapure water and in different pH buffer solutions). In all cases an increment of the oxadiargyl solubility as a function of the HP-β-CD concentration that has been related to the formation of an inclusion complex was verified. UV-Vis and NMR experiments allowed concluding that the stoichiometry of the OXA/HP-β-CD complex formed is 1 : 1. The gathered results can be regarded as an important step for its removal from industrial effluents and/or to increase the stabilizing action, encapsulation, and adsorption in water treatment plants

Microencapsulation of herbicide MCPA with native β-cyclodextrin and its methyl and hydroxypropyl derivatives : an experimental and theoretical investigation

When a pesticide is released into the environment, most of it is lost before it reaches its target. An effective way to reduce environmental losses of pesticides is by using controlled release technology. Microencapsulation becomes a promising technique for the production of controlled release agricultural formulations. In this work, the microencapsulation of chlorophenoxy herbicide MCPA with native β-cyclodextrin and its methyl and hydroxypropyl derivatives was investigated. The phase solubility study showed that both native and β-CD derivatives increased the water solubility of the herbicide and inclusion complexes are formed in a stoichiometric ratio of 1:1. The stability constants describing the extent of formation of the complexes have been determined by phase solubility studies. 1H NMR experiments were also accomplished for the prepared solid systems and the data gathered confirm the formation of the inclusion complexes. 1H NMR data obtained for the MCPA/CDs complexes disclosed noticeable proton shift displacements for OCH2 group and H6 aromatic proton of MCPA provided clear evidence of inclusion complexation process, suggesting that the phenyl moiety of the herbicide was included in the hydrophobic cavity of CDs. Free energy molecular mechanics calculations confirm all these findings. The gathered results can be regarded as an essential step to the development of controlled release agricultural formulations containing herbicide MCPA.Fundação para a Ciência e a Tecnologia (FCT

Voltammetric quantification of fluoxetine: application to quality control and quality assurance processes

The oxidative behaviour of fluoxetine was studied at a glassy carbon electrode in various buffer systems and at different pH using cyclic, differential pulse and square wave voltammetry. A new square wave voltammetric method suitable for the quality control of fluoxetine in commercial formulations has been developed using a borate pH 9 buffer solution as supporting electrolyte. Under optimized conditions, a linear response was obtained in the range 10 to 16 μM with a detection limit of 1.0 μM. Validation parameters such as sensitivity, precision and accuracy were evaluated. The proposed method was successfully applied to the determination of fluoxetine in pharmaceutical formulations. The results were statistically compared with those obtained by the reference high-performance liquid chromatographic method. No significant differences were found between the methods

Isothiazolinone Biocides: Chemistry, Biological, and Toxicity Profiles

The importance of isothiazole and of compounds containing the isothiazole nucleus has been growing over the last few years. Isothiazolinones are used in cosmetic and as chemical additives for occupational and industrial usage due to their bacteriostatic and fungiostatic activity. Despite their effectiveness as biocides, isothiazolinones are strong sensitizers, producing skin irritations and allergies and may pose ecotoxicological hazards. Therefore, their use is restricted by EU legislation. Considering the relevance and importance of isothiazolinone biocides, the present review describes the state-of-the-art knowledge regarding their synthesis, antibacterial components, toxicity (including structure-activity-toxicity relationships) outlines, and (photo)chemical stability. Due to the increasing prevalence and impact of isothiazolinones in consumer's health, analytical methods for the identification and determination of this type of biocides were also discussed.The authors would like to acknowledge ANI for the support of the Project FAMEST 24529 by Portugal 2020 Programme. This project was supported by FEDER funds through COMPETE2020—Programa Operacional Competitividade e Internacionalização (POCI) and by national funds through Foundation for Science and Technology (FCT) (Projects UID/QUI/00081/2019 and POCI-01-0145-FEDER-030219).info:eu-repo/semantics/publishedVersio

Electrochemical oxidation of tamoxifen revisited

Tamoxifen is a selective estrogen receptor modulator that is used as an adjuvant and/or chemotherapeutic agent for the treatment of all stages of hormone-dependent breast cancer. Currently there is a deep interest in the study of tamoxifen biotransformation and identification of metabolites since they can significantly contribute to the overall pharmacological or adverse effects of the drug. Accordingly, the study of the electrochemical behavior of tamoxifen in aqueous solution is reported. To clarify the occurring oxidative process and to assess the influence of the functional groups on the oxidation mechanism, the voltammetric assessment was extended to the study of tamoxifen’s analogues (E)-tamoxifen and dihydrotamoxifen, and to its main phase I oxidative metabolite, N-desmethyl tamoxifen. The data found shows that the oxidative processes occurring in tamoxifen are essentially related with the two chemical moieties present in the molecule: the substituted aromatic nucleus and the tertiary amine group. Moreover, the results obtained suggest that the ethylenic linkage is not critical for tamoxifen’s oxidation although it could play an important role in the course of the oxidation process. These results could contribute to highlight some remaining questions regarding tamoxifen’s metabolic behavior and to the development of new analytical strategies, based on electrochemical approaches

An Electrochemical Outlook on Tamoxifen Biotransformation: Current and Future Prospects

Tamoxifen is a nonsteroidal antiestrogen that is currently and widely used in the treatment of breast cancer in all of its stages, in adjuvant therapy as a long-term suppressant of tumor recurrence and also as a chemopreventive agent in women that are in high risk of developing this type of estrogen-dependent cancer. From a toxicological and (bio)analytical point of view the knowledge of the metabolic pathways of a drug is found to be extremely important. So, in the present work the most important tamoxifen biotransformation steps were reviewed in the light of recent pharmacological data. This overview also includes the current controversy concerning tamoxifen DNA-damaging (genotoxic) versus non-genotoxic mechanisms. A special focus will be given to the putative application of electrochemical methods as a modern and reliable analytical tool for determination of tamoxifen and its metabolites. Moreover, the potential of DNA electrochemical sensors for detection of structural damage to DNA as a basis for toxicity screening is highlighted. Future prospects looking for the importance of developing new analytical methodologies are also discussed.info:eu-repo/semantics/publishedVersio

Design of an Emulgel for Psoriasis Focused on Patient Preferences

Adherence to topical treatments is low and is known to be influenced by the vehicle properties. Betamethasone dipropionate (BD) is an anti-inflammatory steroid, used in psoriasis treatment in the form of an ointment, cream, or solution. The aim of this work was to develop a new vehicle for BD, focusing on the preferences of patients with psoriasis as a strategy to improve treatment adherence. Two vehicles with an aqueous external phase were explored: an emulgel and a hydrogel based on a cyclodextrin inclusion complex used to improve the aqueous solubility of BD. Since BD solubilization was not fully achieved in the hydrogel, only the emulgel was selected for further characterization. This new vehicle (emulgel) is characterized by its white, shiny appearance and good spreading properties. In comparison with petrolatum, a lower residue, higher evaporation rate, lower stickiness, and reduced ability to stain polyester fabric were observed. This vehicle also showed shear thinning behavior. The impact of this new vehicle on adherence to topical treatments should be further confirmed in clinical settings.This work was financed by national funds under the project 47239-Cork2Cosmetic (NORTE-01-0247-FEDER-047239). S. Mota acknowledges the research fellowship (NORTE-01-0247-FEDER-047239), fully supported by national funding from project 47239-Cork2Cosmetic (NORTE-01-0247-FEDER-047239). This work was supported by national funds from FCT-Fundação para a Ciência e a Tecnologia, I.P., in the scope of the project UIDP/04378/2020, UIDB/04378/2020 of the Research Unit on Applied Molecular Biosciences-UCIBIO. The projects UIDB/00081/2020 and I LA/P/0056/2020 were funded by FCT/MCTES (PIDDAC).info:eu-repo/semantics/publishedVersio

Electrochemical methods in pesticides control

The state of the art of voltammetric and amperometric methods used in the study and determination of pesticides in crops, food, phytopharmaceutical products, and environmental samples is reviewed. The main structural groups of pesticides, i.e., triazines, organophosphates, organochlorides, nitrocompounds, carbamates, thiocarbamates, sulfonylureas, and bipyridinium compounds are considered with some degradation products. The advantages, drawbacks, and trends in the development of voltammetric and amperometric methods for study and determination of pesticides in these samples are discussed

Host-guest complexes of phenoxy alkyl acid herbicides and cyclodextrins. MCPA and β-cyclodextrin

The chlorophenoxy herbicideMCPA(4-chloro-2-methylphenoxyacetic acid), widely used for the control of broad-leafweeds primarily in cereal and grass seed crops, still remains one of the most often used herbicides in Portugal. As the formation of inclusion complexes with cyclodextrins can improve its solubility properties, the interaction between the herbicide MCPA and β-cyclodextrin was investigated. The stability constants describing the extent of formation of the complexes have been determined by phase-solubility studies. Different analytical techniques [ultraviolet-visible spectroscopy (UV-Vis), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR)] were employed for a thorough investigation of the structural characteristics of the obtained complexes, which exhibited distinct features and properties from both “guest” and “host” molecules. FTIR and 1H NMR data obtained for the MCPA/β-CD complexes gave information about the interaction between MCPA and the nonpolar cyclodextrin cavity. The dramatic change observed in band frequency and proton displacements of OCH2 group and H6 aromatic proton confirmed the inclusion of MCPA in β-CD. The formation of an inclusion complex between MCPA and β-CD increased the aqueous solubility of this herbicide which could be a particularly advantageous property for some specific applications, namely to improve commercial formulation and for environmental protection.info:eu-repo/semantics/publishedVersio