Temporal Analysis of Pharmaceuticals as Emerging Contaminants in Surface Water and Wastewater Samples: A Case Study.

Pharmaceuticals in the environment are a global concern, with studies in all continents highlighting their widespread occurrence and potential ecological impacts, revealing their presence, fate, and associated risks in aquatic ecosystems. Despite typically occurring at low concentrations (ranging from ng/L to µg/L), advancements in analytical methods and more sensitive equipment have enabled the detection of a higher number of pharmaceuticals. In this study, surface and wastewater samples were extracted using solid phase extraction and analyzed using ultra-high-performance liquid chromatography with tandem mass spectrometry. Among the therapeutic classes investigated, nonsteroidal anti-inflammatory drugs/analgesics, antibiotics, and psychiatric drugs showed a higher number of detected pharmaceuticals. Concentrations ranged from below method detection limit (

Adulteration of Brain Health (Cognitive, Mood, and Sleep Enhancement) Food Supplements by the Addition of Pharmaceutical Drugs: A Comprehensive Review of Analytical Approaches and Trends.

In recent years, the consumption of dietary supplements has grown worldwide, particularly in developed regions. However, this growing market has also become a prime target for adulteration practices, with some manufacturers illegally adding pharmaceuticals into plant-based food supplements (PFS) to enhance their effects. While extensive research has focused on detecting adulterant drugs in PFS tailored for improving sexual performance, weight loss, and muscle building, less attention has been given to supplements intended for mood enhancement, sleep aid, and cognitive function (nootropics). Nonetheless, recent reports indicate an increasing level of adulteration within this group of PFS. Therefore, this review aims at providing a comprehensive overview on the adulteration of PFS tailored for brain health, with a focus on the analytical techniques utilized for detection while also presenting data on consumption patterns and the prevalence of reported adulterants. Considering that the detection of such fraudulent practices primarily relies on chromatographic techniques coupled with mass spectrometry (MS), the developments in this field comprising either targeted or untargeted analysis of pharmaceutical adulterants are discussed.

Health Management: Evaluating the Relationship between Organizational Factors, Psychosocial Risks at Work, Performance Management, and Hospital Outcomes.

Introduction-Health system (HS) health organizations are complex and are in constant dynamic interaction with multiple elements, including political, environmental, societal, legal, and organizational factors, along with human components, such as human resources, patients, and other stakeholders. Objective-This research aimed to study three HS organizations, identifying and characterizing the elements of health organizations and the factors related to professionals, determining their influence on economic and financial performance results, as well as results related to the professionals and to the patients comprising the institutions. Method-A quantitative study was conducted in which data were collected through questionnaires from various sources to better understand and characterize the factors related to organizations, professionals, and patients (470 health professionals and 768 patients). To test the integrated evaluation model for health organizations, path analysis was used. Results-The results reveal that the organizational culture (OC) presents a positive relationship between the professional's quality of life (QL) and the performance management (PM) of the professionals, along with a negative relationship with the psychosocial work risks (PWR). There is also a relationship between the OC and patient satisfaction (PS), professional job satisfaction (PJS), and economic and financial results (EFR). In the relationship between the processes and the results, there are significant relationships between PM and PJS and PWR and PJS. In terms of the results, there is a significant relationship between the EFR and the PS. Conclusions-This study contributes to a deeper knowledge of the factors that influence the quality of health organizations and their results and produces recommendations for health organizations to address the current challenges.

Assessment of the Antioxidant Capacity of Commercial Coffee Using Conventional Optical and Chromatographic Methods and an Innovative Electrochemical DNA-Based Biosensor.

As one of the most popular beverages in the world, coffee is a rich source of non-enzymatic bioactive compounds with antioxidant capacity. In this study, twelve commercial coffee beverages found in local Portuguese markets were assessed to determine their total phenolic and flavonoid contents, as well as their antioxidant capacity, by conventional optical procedures, namely, ferric reducing antioxidant power and DPPH-radical scavenging assay, and non-conventional procedures such as a homemade DNA-based biosensor against two reactive radicals: HO• and H2O2. The innovative DNA-based biosensor comprised an adenine-rich oligonucleotide adsorbed onto a carbon paste electrode. This method detects the different peak intensities generated by square-wave voltammetry based on the partial damage to the adenine layer adsorbed on the electrode surface by the free radicals in the presence/absence of antioxidants. The DNA-based biosensor against H2O2 presented a higher DNA layer protection compared with HO• in the presence of the reference gallic acid. Additionally, the phenolic profiles of the twelve coffee samples were assessed by HPLC-DAD, and the main contributors to the exhibited antioxidant capacity properties were caffeine, and chlorogenic, protocatechuic, neochlorogenic and gallic acids. The DNA-based sensor used provides reliable and fast measurements of antioxidant capacity, and is also cheap and easy to construct.

Impact of COVID-19 on Management, Quality and Satisfaction of Health Organizations: A Case Study in a Portuguese Hospital.

The hospital health care professionals are the front-line fighting COVID-19 considering they are responsible for all the care provided to patients. The purpose of this study was to determine the impact of COVID-19 at the hospital management level and, also, to understand how psychosocial environment, and satisfaction of Health Professionals were affected. A case study was performed in a Portuguese Hospital. Data were collected at one hospital under study at two different occasions: the first before the pandemic (November 2019) and the second almost two years after the pandemic started (November 2021). Regarding data collection, 37.0% of participants responded in the occasion 1 (n = 296) and 63.0% responded in the occasion 2 (n = 503). The instrument for the Assessment of Global Management of Health Organizations (AGMHO) consists of 39 items organized into six dimensions (Gaspar et al. in J Occup Environ Med 63: 581-587, 2021). Comparing timings pre and during pandemic COVID-19, it was found that the participants in the pre-COVID-19 era showed stronger organizational culture, higher quality of life, better psychosocial environment regarding content/leadership and higher job satisfaction when compared to the participants during pandemic COVID-19. On the other hand, participants in the second occasion were found to have higher psychosocial risks related to mental health when compared to participants in the pre-COVID-19 phase. We conclude that the professionals' perception of the different dimensions of the health organization worsened after 2 years of the pandemic. With special focus on psychosocial risks at work and relationship with leadership.

Bioactive Lipids of Seaweeds from the Portuguese North Coast: Health Benefits versus Potential Contamination.

The total lipid content and lipidic profile of seaweeds harvested in the North Coast and purchased in Portugal were determined in this paper. The amount of total lipids in the different species of seaweeds varied between 0.7 ± 0.1% (Chondrus crispus) and 3.8 ± 0.6% (Ulva spp.). Regarding the fatty acid content, polyunsaturated fatty acids (PUFA) ranged between 0-35%, with Ulva spp. presenting the highest amount; monounsaturated fatty acids (MUFA) varied between 19 and 67%; and saturated fatty acids (SFA) were predominant in C. crispus (45-78%) and Gracilaria spp. (36-79%). Concerning the nutritional indices, the atherogenicity index (AI) was between 0.4-3.2, the thrombogenicity index (TI) ranged from 0.04 to 1.95, except for Gracilaria spp., which had a TI of 7.6, and the hypocholesterolemic/hypercholesterolemic ratio (HH) values ranged between 0.88-4.21, except for Gracilaria spp., which exhibited values between 0.22-9.26. The n6/n3 ratio was below 1 for most of the species evaluated, except for Ascophyllum nodosum, which presented a higher value, although below 2. Considering the PUFA/SFA ratio, seaweeds presented values between 0.11-1.02. The polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHCs) contamination of seaweeds under study was also quantified, the values found being much lower than the maximum levels recommended for foodstuff.

Multi-residue analysis of fifty pesticides in river waters and in wastewaters.

Three sampling campaigns were performed in the Lis River (Leiria, Portugal) in February of 2018, November of 2018, and May of 2019. River water and wastewater (influent and effluent) samples of two wastewater treatment plants were target of the study. A total of 25 samples were collected and 50 pesticides were monitored, including organochlorines, triazines, pyrethroids, and organophosphorus, among others. Most of the detected pesticides were insecticides and mainly organochlorines. Concentrations between 1.29 and 2134 ng/L were found. Aldrin, γ-HCH, and cypermethrin were detected in some samples in µg/L, being γ-HCH the pesticide most frequently detected with concentration in µg/L level. The pesticides with the highest detection frequency were (i) cypermethrin, HCB, methoxychlor, and ζ-HCH in river waters; (ii) isoproturon, cypermethrin, methoxychlor, pyrimethanil, γ-HCH, dieldrin, diuron, α-HCH, and α-endosulfan in effluents; and (iii) diuron and isoproturon in influents. The detection of the organochlorides and their degradation products is a consequence of their persistence in the environment, as their usage has long been prohibited in the European Union. Pesticides were grouped by their types in herbicides, insecticides, or fungicides and the detection and concentration for each type were discussed with the climatic conditions. Pesticide toxicity index was determined in the samples collected in the river.

Development of New Canned Chub Mackerel Products Incorporating Edible Seaweeds-Influence on the Minerals and Trace Elements Composition.

This study aimed to develop new canned chub mackerel products incorporating edible seaweeds (Ascophyllum nodosum, Fucus spiralis, Saccorhiza polyschides, Chondrus crispus, Porphyra sp. and Ulva sp.) harvested in the Portuguese North-Central coast, with simultaneous sensory improvement and minerals enrichment. Two processes were compared, namely the addition of seaweeds in i) the canning step and ii) in the brining step (as the replacement for salt). The concentrations of four macrominerals (Na, K, Ca and Mg), chloride, and twelve trace elements (Co, Cu, Fe, I, Li, Mn, Mo, Rb, Se, Sr, V and Zn) were determined by high-resolution continuum source flame atomic absorption spectrometry (HR-CS-FAAS) and inductively coupled plasma mass spectrometry (ICP-MS), respectively. Results showed that canned chub mackerel incorporating C. crispus and F. spiralis was found to be the preferred sensory option, also exhibiting contents enriched with Cl, Co, Cu, Fe, I, Li, Mg, Mn, Mo, Na, Rb, Se, and Sr. This effect was more pronounced when both seaweed species were added to replace the salt added in the brining step.

Assessment of 83 pharmaceuticals in WWTP influent and effluent samples by UHPLC-MS/MS: Hourly variation.

The removal efficiency of pharmaceuticals in wastewater treatment plants (WWTPs) is variable and some of these compounds pass these plants almost intact and others presenting a removal efficiency close to 100%. Their incomplete removal results in a continuous discharge of pharmaceuticals into the environment. To assess the profile of contamination of influents and effluents over a day, a set of 83 pharmaceuticals were evaluated hourly in a WWTP in Leiria, Portugal. The composite samples of the influent and effluent were also collected. Concentrations varied from 1 in WWTP influents, and carbamazepine, fluoxetine, sertraline the pharmaceuticals with an RQ > 1 in WWTP effluents.

Seaweeds from the Portuguese coast as a source of proteinaceous material: Total and free amino acid composition profile.

The total protein content and the (total and free) amino acid composition of nine edible species of red, brown and green seaweeds collected in the Portuguese North-Central coast were quantified to assess their potential contribution to the recommended dietary intake. Whenever possible, the protein and amino acid composition was compared with that of commercial European seaweeds. The protein content was the highest (P < 0.05) in red species (19.1-28.2 g/100 g dw), followed by the green seaweed Ulva spp. (20.5-23.3 g/100 g dw), with the lowest content found in brown seaweeds (6.90-19.5 g/100 g dw). Brown seaweeds presented the lowest mean contents of essential amino acids (EAAs) (41.0% protein) but significantly (P < 0.05) higher concentrations of non-essential amino acids (36.1% protein) and free amino acids (6.47-24.0% protein). Tryptophan, methionine and leucine were the limiting EAAs in all species. In contrast, lysine was found in high concentrations, especially in red (2.71-3.85% protein) and green (2.84-4.24% protein) seaweeds.

Anthelmintic, Antibacterial and Cytotoxicity Activity of Imidazole Alkaloids from Pilocarpus microphyllus Leaves.

Pilocarpus microphyllus Stapf ex Wardlew (Rutaceae), popularly known as jaborandi, is a plant native to the northern and northeastern macroregions of Brazil. Several alkaloids from this species have been isolated. There are few reports of antibacterial and anthelmintic activities for these compounds. In this work, we report the antibacterial and anthelmintic activity of five alkaloids found in P. microphyllus leaves, namely, pilosine, epiisopilosine, isopilosine, epiisopiloturine and macaubine. Of these, only anthelmintic activity of one of the compounds has been previously reported. Nuclear magnetic resonance, HPLC and mass spectrometry were combined and used to identify and confirm the structure of the five compounds. As regards the anthelmintic activity, the alkaloids were studied using in vitro assays to evaluate survival time and damaged teguments for Schistosoma mansoni adult worms. We found epiisopilosine to have anthelmintic activity at very low concentrations (3.125 µg mL-1 ); at this concentration, it prevented mating, oviposition, reducing motor activity and altered the tegument of these worms. In contrast, none of the alkaloids showed antibacterial activity. Additionally, alkaloids displayed no cytotoxic effect on vero cells. The potent anthelmintic activity of epiisopilosine indicates the potential of this natural compound as an antiparasitic agent. Copyright © 2017 John Wiley & Sons, Ltd.

Analysis of pharmaceutical adulterants in plant food supplements by UHPLC-MS/MS.

A method based on the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was successfully developed and validated for the analysis of 26 pharmaceutical compounds belonging to different therapeutic classes (anorexics, stimulants, anxiolytics, antidepressants and laxatives), which are all prone to be illegally added into weight-loss plant food supplements (PFS) for their pharmacological activity. Internal standard calibration with six isotopically labelled compounds rendered good linearity in the range of 5 to 1000µg/l, depending on the compound, and good sensitivity with limits of quantification in the range of 0.02-9.80µg/l. Recoveries were assessed for all the 16 samples analysed and were found between 70% and 120% for over 90% of the analytes. The average recovery value was 90.8%, for the different studied matrices (liquids, liquid ampoules, tablets and capsules), with RSD values lower than 10% for all forms. The changes introduced to the QuEChERS procedure maintained the good performance characteristics of the extraction method while preserving the chromatographic system for the introduction of unwanted matrix compounds. Synephrine was the only compound detected and quantified in one sample, but at a very low concentration (768µg/l) and its presence may be due to the plant extracts used in the formulation, as synephrine is known to be a natural constituent of Citrus aurantium amara. Despite none of the 16 evaluated samples were found to be adulterated by the illegal addition of the drugs included in this work, the developed methodology can be very useful for monitoring the adulteration of weight-loss PFS.

Development of a SPE-UHPLC-MS/MS methodology for the determination of non-steroidal anti-inflammatory and analgesic pharmaceuticals in seawater.

An analytical methodology for the simultaneous determination of seven pharmaceuticals and two metabolites belonging to the non-steroidal anti-inflammatory drugs (NSAIDs) and analgesics therapeutic groups was developed based on off-line solid-phase extraction and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (SPE-UHPLC-MS/MS). Extraction conditions were optimized taking into account parameters like sorbent material, sample volume and sample pH. Method detection limits (MDLs) ranging from 0.02 to 8.18 ng/L were obtained. This methodology was successfully applied to the determination of the selected pharmaceuticals in seawater samples of Atlantic Ocean in the Northern Portuguese coast. All the pharmaceuticals have been detected in the seawater samples, with pharmaceuticals like ibuprofen, acetaminophen, ketoprofen and the metabolite hydroxyibuprofen being the most frequently detected at concentrations that can reach some hundreds of ng/L.

Assessment of non-steroidal anti-inflammatory and analgesic pharmaceuticals in seawaters of North of Portugal: occurrence and environmental risk.

The occurrence of seven pharmaceuticals and two metabolites belonging to non-steroidal anti-inflammatory drugs and analgesics therapeutic classes was studied in seawaters. A total of 101 samples covering fourteen beaches and five cities were evaluated in order to assess the spatial distribution of pharmaceuticals among north Portuguese coast. Seawaters were selected in order to embrace different bathing water quality (excellent, good and sufficient). Acetaminophen, ketoprofen and the metabolite hydroxyibuprofen were detected in all the seawater samples at maximum concentrations of 584, 89.7 and 287 ng L(-1), respectively. Carboxyibuprofen had the highest seawater concentration (1227 ng L(-1)). The temporal distribution of the selected pharmaceuticals during the bathing season showed that, in general, higher concentrations were detected in August and September. The environmental risk posed by the pharmaceuticals detected in seawaters towards different trophic levels (fish, daphnids and algae) was also assessed. Only diclofenac showed hazard quotients above one for fish, representing a potential risk for aquatic organisms. These results were observed in seawaters classified as excellent bathing water. Additional data is needed in order to support the identification and prioritization of risks posed by pharmaceuticals in marine environment.

Genetic risk assessment for cardiovascular disease in Azoreans (Portugal): a general population-based study.

The identification of clinically validated genetic variants contributing to complex disorders raise the possibility to investigate individuals' risk. In this line of research, the present work aimed to assess the genetic risk for cardiovascular disease (CVD) in Azoreans. Genotyping of 19 SNPs - 9 on 9p21, 5 on LDLR and 5 on USF1 - was performed by TaqMan assays on 170 healthy Azorean individuals. Results demonstrate that the most frequent haplotype in 9p21, with a frequency of 41.4%, is TGGGCGCGC, which harbors all risk alleles. Considering haplotype homozygosity data show that females present higher value of homozygosity for both LDLR (13.5%) and USF1 (15.3%), whereas males present higher value for the 9p21 region (8.2%). Interestingly, genetic profile analysis revealed differences in terms of geographic and gender distribution. The Azorean Central group presented a higher risk for atherosclerosis, 2.7 times higher when compared to the Eastern group, while the Eastern group shows 1.5 times higher risk for dyslipidemias. Moreover, Azorean females demonstrated a 4 times higher risk for dyslipidemias when compared to males, whereas males have an increased risk for atherosclerosis. Although allele frequencies in Azoreans were similar to those reported for the HapMap CEU population, the differences in terms of haplotype and genetic profile distribution must be taken in consideration when assessing genetic risk. Taken together, the data here presented evidence for the need to perform biomedical research and epidemiologic analysis in Azoreans with the aim of developing strategies to CVD prevention, health promotion and population education.

Cytokeratin 19, carcinoembryonic antigen, and epithelial cell adhesion molecule detect lung cancer lymph node metastasis in endobronchial ultrasound-guided transbronchial aspiration samples.

INTRODUCTION: Endobronchial ultrasound-guided transbronchial needle aspiration (EBUS-TBNA) holds promise for accurate examination of mediastinal lymph nodes in NSCLC patients. However, it is not always possible to achieve a definitive diagnosis or subtype all cases. We aimed to evaluate the role of EBUS-TBNA combined with quantitative reverse transcription polymerase chain reaction (qRT-PCR) and flow cytometry (FCM) to assess tumor-associated antigens and immune responses to identify metastases and pathological patterns in lymph node aspirates. PATIENTS AND METHODS: EBUS-TBNA samples from patients with NSCLC (n = 33) and nonmalignant diseases (n = 17) were prospectively collected. Cytokeratin 19 (CK-19), carcinoembryonic antigen (CEA), epithelial cell adhesion molecule (EPCAM), sialyl-Lewis(x), CD44, and the immune compartment were analyzed using qRT-PCR and FCM. RESULTS: In the NSCLC patients, the epithelial cell compartment was significantly increased (30.8% vs. 12% CD45⁻ CK-19⁺ cells) and showed brighter CK-19 staining than controls (P = .039) using FCM. Carcinoembryonic antigen was exclusively expressed by the NSCLC epithelial compartment (35% of the cases) and absent in controls. The NSCLC immune compartment showed an increased monocyte population (P = .04), and decreased lymphocyte subpopulations, anticipating a disruption in the distribution of myeloid and lymphoid immune cells. Quantitative reverse transcription polymerase chain reaction showed that CK-19, CEA, and EPCAM transcripts were significantly higher in NSCLC. A positive correlation between the primary tumor lesion size and EPCAM (ρ = 0.476; P = .005), CK-19 (ρ = 0.594; P = .001), and CEA (ρ = 0.394; P = .023) was also found. CONCLUSION: The identification of CK-19, CEA, and EPCAM in EBUS-TBNA samples using FCM and qRT-PCR is feasible and might further aid in the detection of NSCLC lymph node metastasis.

Determination of methiocarb and its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction.

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LC-PAD). Calibration curves were linear in the range of 0.5-10 mg L⁻¹ for all compounds studied. The average recoveries, measured at 0.1 mg kg⁻¹ wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

Extraction of ochratoxin A in bread samples by the QuEChERS methodology.

A QuEChERS method for the extraction of ochratoxin A (OTA) from bread samples was evaluated. A factorial design (2(3)) was used to find the optimal QuEChERS parameters (extraction time, extraction solvent volume and sample mass). Extracts were analysed by LC with fluorescence detection. The optimal extraction conditions were: 5 g of sample, 15 mL of acetonitrile and 3 min of agitation. The extraction procedure was validated by systematic recovery experiments at three levels. The recoveries obtained ranged from 94.8% (at 1.0 µg kg(-1)) to 96.6% (at 3.0 µg kg(-1)). The limit of quantification of the method was 0.05 µg kg(-1). The optimised procedure was applied to 20 samples of different bread types ("Carcaça", "Broa de Milho", and "Broa de Avintes") highly consumed in Portugal. None of the samples exceeded the established European legal limit of 3 µg kg(-1).

A 3-month-old baby with H1N1 and Guillain-Barré syndrome.

Majority of children with pandemic influenza A (H1N1)pdm09 experience mild illness with full recovery without treatment. A previously healthy two and a half month-old girl was admitted to our paediatric intensive care unit because of severe respiratory failure with A (H1N1)pdm09 infection. Despite initial clinical improvement all attempts to extubate to non-invasive ventilation were unsuccessful and 2 to 3 weeks after symptom onset she started periods of cardiovascular instability and a progressive neurological deterioration with distal symmetrical progressive motor weakness and areflexia. All investigations were normal except elevated liver enzymes and cerebrospinal fluid examination that revealed elevated protein without pleocytosis. A possible diagnosis of Guillain-Barré syndrome (GBS) was considered and electromyogram was compatible with axonal form of GBS. To our knowledge this is the youngest case of GBS acquired postnatally and the first in children associated with H1N1 virus.