Synthesis and evaluation of octocrylene-inspired compounds for UV-filter activity

Octocrylene (2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate) is present in several sunscreens and is known to work synergistically with UV filters. We prepared eight octocrylene-related compounds to test their photoprotective activities by measuring diffuse transmittance. The compounds had varied photoprotection profiles, with Sun Protection Factors (SPF) ranging from 1 to 5 and UVA Protection Factors (UVAPF) ranging from 1 to 8. Compounds 4, 5, and 7 showed the best protection against UVB sunrays, while compounds 5, 6, and 7 presented the best results for protection from UVA, so compound 7 had the most balanced protection overall. Results for compounds 4, 8, and 9 are reported for the first time in the literature.

UV determination of epinephrine, uric acid, and acetaminophen in pharmaceutical formulations and some human body fluids using multivariate calibration

In this work, a spectrophotometric methodology was applied in order to determine epinephrine (EP), uric acid (UA), and acetaminophen (AC) in pharmaceutical formulations and spiked human serum, plasma, and urine by using a multivariate approach. Multivariate calibration methods such as partial least squares (PLS) methods and its derivates were used to obtain a model for simultaneous determination of EP, UA and AC with good figures of merit and mixture design was in the range of 1.8 - 35.3, 1.7 - 16.8, and 1.5 - 12.1 µg mL-1. The 2nd derivate PLS showed recoveries of 95.3 - 103.3, 93.3 - 104.0, and 94.0 - 105.5 µg mL-1 for EP, UA, and AC, respectively.

Simultaneous determination of four phenolic compounds in extracts of aerial parts of Ipomoea pes-caprae (L.) R. Br. (Convolvulaceae) by HPLC-UV

Among other applications, Ipomoea pes-caprae is popularly used to treat jellyfish stings, supporting the development of a product for dermatological use. Hydroethanolic spray-dried extract was chosen for the further development of phytomedicines, and a stability-indicative HPLC-UV method was developed and validated for the determination of isoquercitrin and isochlorogenic acids A, B and C. The method was developed using a C18 column (250 x 4.6 mm, 5 µm) with an acetonitrile:water mobile phase at pH 3.0 in a gradient run. The four constituents and other unidentified components of the extract were appropriately resolved without interference of degradation products after stress tests (acid, alkali, neutral, oxidant, photolysis). The method showed linearity in the isoquercitrin concentration range from 5.0-50.0 µg mL-1, with adequate precision (RSD% < 2.5% for the intra- and inter-day studies), accuracy (recovery of 100.0 ± 2.0%), and robustness. Both the herbal drug and spray-dried extract of I. pes-caprae were subjected to stability studies in accelerated and long-term conditions over four months. The samples maintained their characteristics and marker contents (< 10% of variation).

Estudo do teste de Scott via técnicas espectroscópicas: um método alternativo para diferenciar cloridrato de cocaína e seus adulterantes

Cocaine is usually seized mixed with a wide variety of adulterants such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these street drug mixtures is normally performed using colorimetric testing kits, but these tests may suffer from interferences, producing false-positive results. Here, we describe the use of analytical techniques including attenuated total reflection Fourier transform infrared (ATR-FTIR) and ultraviolet-visible (UV-VIS) spectroscopies to distinguish between cocaine and other adulterants (lidocaine, promethazine, powdered milk and yeast) that yield positive results on the Scott test using the thiocyanate cobalt reagent. A further 13 substances were also analyzed using the Scott test.

ADAPTAÇÃO DA METODOLOGIA DE ANÁLISE DE METEMOGLOBINA COMO BIOMARCADOR DE EFEITO DA EXPOSIÇÃO AO AGROTÓXICO DIFLUBENZURON

This work aimed to adapt the analysis of methemoglobin recommended by Evelyn - Malloy (visible spectrophotometry), in order to facilitate its application in the field, or to analysis in clinical laboratory, of existing sites of diflubenzuron application. The parameters changed included: centrifuge rotation speed; time between the collection of biological sample and analysis, and storage temperature of the samples; and the volume of reagents. The comparison of the rotation speed (rpm) of the reference methodology with the rpm of a "clinical centrifuge" did not reveal a statistically significant difference in the levels of methemoglobin. The time between the collection of biological sample and analysis was extended for a period of up to 48 hours for both conservation by refrigeration and ambient temperature, producing no statistically significant difference when compared to the standard duration of 2 hours. Regarding the reagents, the reference methodology already uses the volume necessary to ensure complete reaction, whereas a wider range from the recommended volume to a 5-fold reduction in comparison to the reference methodology could be used. It was concluded that the proposed changes to the methodology for adapting the analysis are applicable to studies of field / workplace exposure and ensure the reliability of results. The adapted methodology was inter-laboratory validated and the parameters changed can be selected according to the requirements of the laboratory at which the methemoglobin is to be measured.

CHARACTERIZING THE MECHANISM OF QUETIAPINE DISTRIBUTION IN LIPID-CORE NANOCAPSULES PSEUDO-PHASES USING A VALIDATED LC/UV METHOD

Quetiapine is an atypical antipsychotic used to treat schizophrenia. However, despite great interest for its chronic therapeutic use, quetiapine has some important side effects such as weight gain induction. The development of a quetiapine nanocarrier can potentially target the drug into central nervous system, resulting in a reduction of systemic side effects and improved patient treatment. In the present work, a simple liquid chromatography/ultraviolet detection (LC/UV) analytical method was developed and validated for quantification of total quetiapine content in lipid core nanocapsules as well as for determination of incorporation efficiency. An algorithm proposed by Oliveira et al. (2012) was applied to characterize the distribution of quetiapine in the pseudo-phases of the nanocarrier, leading to a better understanding of the quetiapine nanoparticles produced. The analytical methodology developed was specific, linear in the range of 0.5 to 100 µg mL−1 (r2 > 0,99), and accurate and precise (R.S.D < ±5%). The absolute recovery of quetiapine from the nanoparticles was approximately 98% with an incorporation efficiency of approximately 96%. The results indicated that quetiapine was present in a type III distribution according to the algorithm, and was mainly located in the core of the nanoparticle because of its logD in the formulation pH (6.86 ± 0.4).

SISTEMAS ALTERNATIVOS DE CALIBRAÇÃO PARA DETERMINAÇÃO ESPECTROFOTOMÉTRICA SIMULTÂNEA DE ESPÉCIES COM INTERFERÊNCIA ESPECTRAL

Two simple and efficient procedures have been developed for the rapid simultaneous determination of compounds with mutual spectral interference (rifampicin (RIF) and isoniazid (INH)). The first method was based on the UV–Vis spectral signal (190–600 nm) of synthetic RIF and INH aqueous solutions, whereas the second method involved the visible spectral signal registered between 350 and 800 nm after the reaction of INH with a Cu2+/neocuproine complex. Both multivariate spectrophotometric methods show excellent prevision capacity, providing results that are statistically equivalent with those provided by the standard chromatographic procedure. The methods were validated according to criteria established by ANVISA, showing precision, accuracy and robustness compatible with the requirements for new analytical methods, additionally allowing the reduction of waste generation.

MCR-ALS APLICADO NO MONITORAMENTO QUANTITATIVO DO PROCESSO DE ELETRODEGRADAÇÃO DA ATRAZINA USANDO ESPECTROS UV: RESULTADOS COMPARATIVOS COM HPLC-DAD COMO UM MÉTODO DE REFERÊNCIA

Electrodegradation of atrazine in water was performed using homemade (PA and PB) and purchased (PC) boron-doped diamond anodes. The degradation was monitored off-line by analyzing total organic carbon and high performance liquid chromatography with diode array detector (HPLC-DAD) and at-line by UV spectroscopy. The spectra were recorded every 2 min. The rank deficiency problem was resolved by assembling an augmented column-wise matrix. HPLC was employed to separate the original and byproducts degradation components. Aiming the same goal, multivariate curve resolution - alternating least squares (MCR-ALS) was applied to resolve the UV spectroscopic data. Comparison between HPLC and MCR-ALS separations is presented. By using MCR-ALS the spectra of atrazine and two byproducts were successfully resolved and the resulted concentration profiles properly represented the system studied. The ALS explained variance (R2) for PA, PB and PC was equal to 99.99% for all of them and the lack of fit for PA, PB and PC were 0.39, 0.34 and 0.54 respectively. The correlation (R) between the recovered and pure spectra were calculate for each electrodegradation, validating the MCR-ALS results. The average R was equal to 0.997. The spectral and concentration profiles described with this new approach are in agreement with HPLC-DAD results. The proposed method is an alternative to classical analyses for monitoring of the degradation process, mainly due to the simplicity, fast results and economy.

2-(4-IODO-2,5-DIMETOXIFENIL)-N-[(2-METOXIFENIL)METIL]ETAMINA OU 25I-NBOME: CARACTERIZAÇÃO QUÍMICA DE UMA DESIGNER DRUG

Drug trafficking and the introduction of new drugs onto the illicit market are one of the main challenges of the forensic community. In this study, the chemical profile of a new designer drug, 2-(4-iodine-2,5-dimethoxyphenyl)-n-[(2-methoxyphenyl)methyl]etamine or 25I-NBOMe was explored using thin layer chromatography (TLC), ultraviolet-visible spectrophotometry (UV-Vis), attenuated total reflection with Fourier transform infrared spectroscopy(ATR-FTIR), gas chromatography mass spectrometry (GC-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). First, the TLC technique was effective for identifying spots related to 25C-, 25B- and 25I-NBOMe compounds, all with the same retention factor, Rf ≈ 0.50. No spot was detected for 2,5-dimethoxy-4-bromoamphetamine, 2,5-Dimethoxy-4-chloroamphetamine or lysergic acid diethylamide compounds. ATR-FTIR preserved the physical-chemical properties of the material, whereas GC-MS and ESI-MS showed better analytical selectivity. ESI(+)FT-ICR MS was used to identify the exact mass (m/z428.1706 for the [M + H]+ ion), molecular formula (M = C18H22INO3), degree of unsaturation (DBE = 8) and the chemical structure (from collision induced dissociation, CID, experiments) of the 25I-NBOMe compound. Furthermore, the ATR-FTIR and CID results suggested the presence of isomers, where a second structure is proposed as an isomer of the 25I-NBOMe molecule.

PROPOSTA EXPERIMENTAL DIDÁTICA PARA O ENSINO DE ANÁLISE DE COMPONENTES PRINCIPAIS

Principal component analysis (PCA) is a chemometric method that allows for the extraction of chemical information that would otherwise be impossible to determine. Teaching chemometrics to undergraduates can contribute to the overall professional development and training of new teachers, whose profiles have been gaining attention due to the current demand for data interpretation. In this study, a didactic experiment involving PCA is proposed. Spectrophotometry was used in the ultraviolet-visible (UV-Vis) region to assess the behavior of anthocyanins extracted from red cabbage at different pH values. The results suggest the possible separation of anthocyanin structures into three distinct groups, according to their chemical characteristics displayed in acid, neutral, and basic media. The objective is to develop educational materials targeted to undergraduate courses, which encompass a larger number of concepts and introduce instrumental techniques currently being employed in both academic research and the industrial sector. Specifically, the proposed experiment introduces concepts related to spectrophotometry in the UV-Vis range and the PCA chemometric method. The materials used are easily accessible, and UV-Vis spectroscopy equipment is less expensive in comparison with other spectroscopy methods.

Efeito da irradiação UV-C no controle da podridão parda (Monilinia fructicola) e da podridão mole (Rhizopus stolonifer) em pós-colheita de pêssegos

Este trabalho teve por objetivo avaliar o efeito da irradiação UV-C no controle in vitro de Monilinia fructicola e Rhizopus stolonifer e no controle das doenças causadas por estes fungos em pêssegos inoculados com ferimento. No experimento in vitro, avaliou-se o crescimento micelial dos fungos em meio BDA após a exposição nas doses de UV-C de 0, 0,26, 0,52, 1,04, 3,13, 5,22, 10,44, 15,66, e 31,32 kJ.m-2 num equipamento com quatro lâmpadas com taxa de fluência de 1,74 mW.cm-2. Nos experimentos in vivo, os frutos foram tratados com irradiação UV-C de forma protetora e curativa. No tratamento protetor, os frutos foram expostos a 1,04 kJ.m-2 por 1 min. e foram inoculados imediatamente após e 16, 24 e 40 h após. No tratamento curativo, os frutos foram inoculados, incubados e irradiados com doses de UV-C de 0, 1,04, 5,22, 10,44, 15,66 e 31,32 kJ.m². Avaliou-se a incidência das doenças e a severidade da podridão parda. No experimento in vitro, apenas as doses aplicadas durante 1 e 10 min. de exposição reduziram o crescimento micelial de M. fructicola enquanto que a aplicação da luz UV-C entre 10-15 minutos reduziu o crescimento micelial de R. stolonifer e a dose aplicada durante 30 minutos inibiu completamente o crescimento micelial deste fungo. Não houve efeito protetor da luz UV-C no controle das doenças. Não houve controle curativo da podridão parda. A irradiação UV-C foi eficiente no controle curativo da podridão mole e o tempo de exposição de 10 min. foi o que apresentou melhor resultado.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

Puulevystä valmistettujen kalusteosien pintakäsittelyn kehittäminen UV-telalinjalla

Diplomityö tehtiin Kidex Oy:lle, joka on Kiteellä sijaitseva Martela-konsernin tytäryhtiö. Kidex Oy toimii sopimusvalmistajana Martelalle sekä muille valituille levykalusteasiakkaille, ja tuotteet ovat pääasiassa toimisto- ja keittiökalusteita. Kevättalvella 2008 yritykseen siirrettiin Nummelasta pintakäsittelyosasto, jolla on tehty petsaus- ja lakkaustöitä. Näiden lisäksi tehtaalla on pohdittu mahdollisuuksia maalaustöihin, jotta UV-telalinjan kapasiteetti saataisiin paremmin käyttöön Työssä selvitettiin, mitä muutoksia UV-kovettuvilla aineilla maalaaminen vaatii linjaan ja luotiin edellytykset maalaustoiminnan aloittamiselle. Muutokset pyrittiin pitämään niin vähäisinä kuin mahdollista. Lisäksi määritettiin maalattavien tuotteiden laadun kriteerit ja todennusmenetelmät, jotka voidaan viestiä asiakkaille väärinkäsitysten välttämiseksi. Laadun todentamista varten valmistettiin sarja koekappaleita, joista mitattiin asiakkaan kannalta tärkeimmät maalikalvon ominaisuudet. Työssä tarkasteltiin myös pintakäsittelylaitoksia koskevaa VOC-asetusta ja verrattiin liuottimien kulutusta asetuksen määrittämiin rajoihin. Puulevystä valmistettujen kalusteosien pintakäsittely UV-telalinjalla eroaa oleellisesti perinteisistä menetelmistä esimerkiksi tuotantonopeuden osalta, joka johtuu pääasiassa pinnoitekalvon hetkessä tapahtuvasta kovettumisesta UV-valon vaikutuksesta. UV-aineet ovat käytännössä täysin kiinteistä aineista koostuvia, eivätkä näin sisällä vaarallisia haihtuvia liuottimia. UV-kovettuvilla tuotteilla maalaaminen on viime vuosina runsaasti tutkittu alue, joka eroaa tietyiltä osin myös pintakäsittelystä UV-kirkaslakoilla. Pigmentoitujen kalvojen kovettuminen vaatii erilaista UV-säteilyä ja levitysmäärien seuranta on huomattavasti tarkempaa.