Chemical modification and doping of poly(p-phenylenes): A theoretical study.

CONTEXT: Conjugated polymers (CPs) have been recognized as promising materials for the manufacture of electronic devices. However, further studies are still needed to enhance the electrical conductivity of these type of organic materials. The two main strategies for achieving this improvement are the doping process and chemical modification of the polymer chain. Therefore, in this article, we conduct a theoretical investigation, employing DFT calculations to evaluate the structural, energetic, and electronic properties of pristine and push-pull-derived poly(p-phenylene) oligomers (PPPs), as well as the analysis at the molecular level of the polymer doping process. As a primary conclusion, we determined that the PPP oligomer substituted with the push-pull group 4-EtN/CNPhNO2 exhibited the smallest HOMO-LUMO gap (Eg) among the studied oligomers. Moreover, we observed that the doping process, whether through electron removal or the introduction of the dopant anion ClO4-, led to a substantial reduction in the Eg of the PPP, indicating an enhancement in the polymer's electrical conductivity. METHODS: DFT calculations were conducted using the PBE0 functional along with the Pople's split valence 6-31G(d,p) basis set, which includes polarization functions on all atoms (B97D/6-31G(d,p)).

Investigation of antimicrobial susceptibility and genetic diversity among Staphylococcus pseudintermedius isolated from dogs in Rio de Janeiro.

Staphylococcus pseudintermedius is an opportunistic pathogen causing a variety of infections that are difficult to treat, especially because of the development of antimicrobial resistance. It has a clonal distribution around the world. To have a better understanding of the MRSP population, we search the presence of MRSP in colonized or infected dogs. Samples from 99 dogs with infections and 35 from asymptomatic dogs were collected. Isolates were identified by mass spectrometry and Multiplex-PCR. The mecA gene was confirmed by conventional PCR. MRSP strains were analyzed by whole-genome sequencing. 75 S. pseudintermedius were identified, most from infection cases. The species were isolated from 70 out of the 135 dogs. Penicillin and Trimethoprim/Sulfamethoxazole presented higher resistance rates. Forty-seven strains were classified as multi-drug resistant (MDR), and were more isolated from dogs with infection (P < 0.05). Eighteen samples were classified as MRSP, representing 24.0% of the population. Six of 16 MRSP sequenced samples belonged to the world spread clone ST71; others belonged to unknown clones. Most samples carried the SCCmec type IIIA. Twenty-one different genetic resistance determinants were found among MRPS strains. MRSP is circulating among infected and colonized dogs in Rio de Janeiro, Brazil.

Epidemiologic case investigation on the zoonotic transmission of Methicillin-resistant Staphylococcus pseudintermedius among dogs and their owners.

Dogs often carry methicillin-resistant Staphylococci asymptomatically. These bacteria are frequently linked to conditions such as canine pyoderma and otitis. Close interaction between dogs and humans can facilitate the exchange of resistant strains, particularly Methicillin-resistant Staphylococcus pseudintermedius (MRSP). This represents a public health issue, since these strains, in addition to occasionally causing infections in humans, can also serve as a source of resistance and virulence genes for strains of greater importance in human medicine, such as Staphylococcus aureus. Furthermore, MRSP strains are often multidrug resistant, which ends up compromising the treatment of infections. This study aimed to assess the potential transmission of Staphylococcus pseudintermedius among dogs and their owners. We examined a total of one hundred canine samples collected from cases of pyoderma and otitis to detect the presence of staphylococci. Simultaneously, we conducted evaluations on all dog owners. Staphylococci strains were identified using MALDI-TOF MS and PCR targeting the nuc gene. Methicillin resistance screening was also performed by detecting the mecA gene using PCR. Among the sampled dogs, 64 carried S. pseudintermedius. Nine were identified as MRSP. In six instances, dogs and their owners exhibited S. pseudintermedius. These samples underwent genome sequencing and were screened for antimicrobial resistance genes, SCCmec typing, MLST characterization, and Single Nucleotide Polymorphisms (SNP) analyses. The results of the phylogenetic analysis revealed that in three cases, dogs and owners had closely related isolates, suggesting interspecies transmission. Two of these cases involved MRSP and one MSSP. Moreover, in the two MRSP cases, the same SCCmec type (type V) was detected. Additionally, the sequence type was consistent across all three cases involving dogs and owners (MSSP ST2277, MRSP ST2282, and ST2286). These findings strongly indicate a transmission event. Since Staphylococcus pseudintermedius is primarily isolated from canine samples, it is plausible that dogs may have acted as a potential source. In the remaining three cases, despite identifying the same species in both samples, they had notable phylogenetic differences.

High prevalence of Panton-Valentine Leucocidin among Staphylococcus coagulans isolated from dogs in Rio de Janeiro.

AIMS: The purpose of this study was to characterize the capacity for biofilm formation, antimicrobial resistance rates, and search for genetic determinants of resistance and virulence in the species. METHODS AND RESULTS: Strains were collected from asymptomatic and infected dogs. Identification was conducted using matrix-assisted laser desorption ionization-time of flight (MALDI-TOF), antimicrobial susceptibility using disk diffusion and PCR targeting mecA. Biofilm formation was evaluated on a microtiter plate assay. A total of 27 strains were selected for whole-genome sequencing. We identified 111 Staphylococcus coagulans. The highest number was obtained from infected dogs. The highest resistance rates were observed for penicillin, gentamicin, and ciprofloxacin/erythromycin. Twelve strains were characterized as resistant to methicillin. All isolates had the ability to form biofilm and were strong producers. Among Methicillin Resistant Staphylococcus coagulans (MRSC), SCCmec types IIIA, and Vc were identified. Acquired resistance genes, such as aac(6')-aph(2''), tet(K), blaZ, qacG, qacJ, and erm(C) were found. Different virulence genes were identified. Of note, Panton-Valentine Leucocidin was highly prevalent among the isolates. CONCLUSION: Staphylococcus coagulans had a high isolation rate among infected dogs and demonstrated significant resistance to commonly used antibiotics such as penicillin and gentamicin.

Levobunolol-imprinted polymer: a theoretical study.

CONTEXT: Levobunolol is a ß-blocker drug prescribed for the control and prevention of cardiovascular events, such as individuals with cardiac arrhythmia or a history of myocardial infarction. Creating a levobunolol-specific molecularly imprinted polymer (MIP) allows for enhanced selectivity, efficient sample preparation, controlled drug delivery, and improved sensing and detection capabilities. In this sense, the aim of this study was to obtain through DFT calculations the synthesis protocol of a MIP for levobunolol testing different functional monomers (FMs), solvents, and cross-linker agents (CLAs). The analysis of structural and energetic data led to the identification of the optimal MIP synthesis parameters, which involves the use of (trifluoromethyl)-arylic acid (TFMAA) as the functional monomer, toluene and chloroform as the solvents, and pentaerythritol triacrylate (PETRA) as the cross-linking agent. This rational design offers valuable insights for experimentalists seeking to efficiently synthesize a MIP for this important ß-blocker drug. METHODS: DFT calculations were conducted using the B97D functional along with the Pople's split valence 6-31G(d,p) basis set, which includes polarization functions on all atoms (B97D/6-31G(d,p)).

Computational modeling (in silico) methods combined with ecotoxicological experiments (in vivo) to predict the environmental risks of an antihistamine drug (loratadine).

This study employed computational modeling (in silico) methods, combined with ecotoxicological experiments (in vivo) to predict the persistence/biodegradability, bioaccumulation, mobility, and ecological risks of an antihistamine drug (Loratadine: LOR) in the aquatic compartment. To achieve these goals, four endpoints of the LOR were obtained from different open-source computational tools, namely: (i) "STP total removal"; (ii) Predicted ready biodegradability; (iii) Octanol-water partition coefficient (KOW); and (iv) Soil organic adsorption coefficient (KOC). Moreover, acute and chronic, ecotoxicological assays using non-target freshwater organisms of different trophic levels (namely, algae Pseudokirchneriella subcapitata; microcrustaceans Daphnia similis and Ceriodaphnia dubia; and fish Danio rerio), were used to predict the ecological risks of LOR. The main results showed that LOR: (i) is considered persistent (after a weight-of-evidence assessment) and highly resistant to biodegradation; (ii) is hydrophobic (LOG KOW = 5.20), immobile (LOG KOC = 5.63), and thus, it can potentially bioaccumulate and/or can cause numerous deleterious effects in aquatic species; and (iii) after ecotoxicological evaluation is considered "toxic" and/or "highly toxic" to the three trophic levels tested. Moreover, both the ecotoxicological assays and risk assessment (RQ), showed that LOR is more harmful for the crustaceans (RQcrustaceans = moderate to high risks) than for algae and fish. Ultimately, this study reinforces the ecological concern due to the indiscriminate disposal of this antihistamine drug in worldwide aquatic ecosystems.

CBCT study on the prevalence, morphology and position of the mandibular incisive canal in a North-Brazilian population.

Background: The mandibular incisive canal (MIC) is an anatomic structure to be considered in treatment planning for surgeries in the anterior region of the mandible. Awareness of the MIC increased with the use of 3D imaging for treatment planning, such as cone beam computed tomography (CBCT). This study aimed to use CBCT to assess the prevalence, morphology and position of the MIC among North-Brazilians. Material and Methods: The sample consisted of CBCT scans of 100 hemi-mandibles (50 individuals) that were assessed for the absolute (n) and relative frequency of the MIC. The morphological component of this study was the diameter (mm) of the detected MIC in five anatomic sites between the mental foramen and the midline. Within the interformainal region, the position of the MIC was assessed by measuring (mm) the distances between the MIC and the basal, vestibular and lingual cortical bone surfaces. Results: The prevalence of the MIC was >76% considering the different anatomic regions screened in CBCT. The mean diameter of the MIC progressively reduced from 1.29 mm to 0.86 throughout the five anatomic regions measured. The position of the MIC showed a downward trajectory away from the lingual cortical bone surface. Conclusions: MIC was a highly prevalent anatomic structure in the studied sample. The funnel-shaped outline of the MIC and its trajectory into the interforaminal region highlighted a major risk of damage to the neurovascular bundle in surgeries (e.g. implant placement) that are close to the mental foramen and the vestibular cortical bone. Key words:Anatomy, cone beam computed tomography, imaging, mandibular incisive canal, oral radiology.

Occurrence, ecological risk assessment and prioritization of pharmaceuticals and abuse drugs in estuarine waters along the São Paulo coast, Brazil.

The pollution of the surface waters by pharmaceuticals and personal care products (PPCPs) has attracted worldwide attention, but data regarding their occurrence and potential risks for the aquatic biota on tropical coastal rivers of South America are still scarce. In this context, the occurrence and the preliminary ecological risk assessment of eleven pharmaceuticals of various therapeutic classes (including cocaine and its primary metabolite, benzoylecgonine) were investigated, for the first time, in five rivers of São Paulo, southeast Brazil, covering a coastline of about 140 km, namely Perequê River, Itinga River, Mongaguá River, Itanhaém River and Guaraú River. Although these five rivers are born in well-preserved areas of the Atlantic rainforest biome, on its way to sea and when they cross the urban perimeter, they receive untreated sewage discharges containing a complex mixture of contaminants. In addition, a "persistence, bioaccumulation and toxicity" (PBT) approach allowed to pre-select the priority PPCPs to be monitored in this coastline. Identification of several PPCPs in the samples was done using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Ten PPCPs were successfully quantified in all five rivers, namely caffeine (9.00-560.00 ng/L), acetaminophen (

First report on the occurrence of pharmaceuticals and cocaine in the coastal waters of Santa Catarina, Brazil, and its related ecological risk assessment.

The worldwide occurrence of pharmaceuticals and personal care products (PPCPs) in aquatic ecosystems is reason for public concern. These emerging micropollutants include a large and diverse group of organic compounds, with continuous input, high environmental persistence and potential threat to biota and human health. The aim of this study was to evaluate, for the first time, the occurrence of twenty-seven PPCPs of various therapeutic classes (including cocaine and its primary metabolite, benzoylecgonine), in the coastal waters of Santa Catarina, southern Brazil. Water samples were taken in November 2020, during the low tide periods, at eight sampling points located along the coast of Santa Catarina, covering its entire geographical extension. Sampling was carried out in triplicate and at different depths of the water column. Nine compounds were detected through liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS): caffeine (12.58-119.80 ng/L), diclofenac (1.34-7.92 ng/L), atenolol (1.13-2.50 ng/L), losartan (0.43-3.20 ng/L), acetaminophen (0.21-10.04 ng/L), orphenadrine (0.07-0.09 ng/L), cocaine (0.02-0.17 ng/L), benzoylecgonine (0.01-1.1 ng/L) and carbamazepine (0.02-0.27 ng/L). The highest occurrence of these compounds was detected in the northern and central coastal region of Santa Catarina, namely in Penha and Palhoça cities. Moreover, the risk assessment showed that almost compounds (atenolol, benzoylecgonine, carbamazepine, cocaine and orphenadrine) presented no ecological risk in the recorded concentrations. However, a few compounds suggest low (caffeine and diclofenac) to moderate (acetaminophen and losartan) risk taking into consideration the acute and chronic effects for the three trophic levels (algae, crustacean and fish) tested. These compounds are usually found in areas with high population density, aggravated by tourism, because of the sanitary sewage and solid waste. Although in low concentrations, the occurrence of these chemical compounds can imply deleterious effects on the environmental health of Santa Catarina coastal zone, and therefore deserve more attention by the public authorities and environmental agencies.

Occurrence of pharmaceuticals and cocaine in the urban drainage channels located on the outskirts of the São Vicente Island (São Paulo, Brazil) and related ecological risk assessment.

"Wealth by the sea and poverty away from the sea breeze" is a metaphor that mirrors what happens along the Brazilian coastal zone, namely in São Vicente Island, São Paulo, Brazil. Due to the high cost of the properties on this shore, the impoverished population started to migrate to the northern outskirts of the island (away from the tourist beaches), potentiating the emergence of poor housing conditions, namely stilt-house slums. Consequently, the urban drainage channels across these outskirts neighbourhoods are potentially contaminated by human wastes. In this context, the occurrence and preliminary ecological risk assessment of eleven pharmaceuticals of various therapeutic classes (including cocaine and its primary metabolite, benzoylecgonine) were investigated, for the first time, in five urban drainage channels whose diffuse loads flow continuously to the estuarine waters of São Vicente Island. The results showed the widespread presence of these environmental stressors in all urban channels analysed, namely losartan (7.3-2680.0 ng/L), caffeine (314.0-726.0 ng/L), acetaminophen (7.0-78.2 ng/L), atenolol (6.2-23.6 ng/L), benzoylecgonine (10.2-17.2 ng/L), furosemide (1.0-7.2 ng/L), cocaine (2.3-6.7 ng/L), carbamazepine (0.2-2.6 ng/L), diclofenac (1.1-2.5 ng/L), orphenadrine (0.2-1.1 ng/L) and chlortalidone (0.5-1.0 ng/L). The overall total estimated load of pharmaceuticals and personal care products flowing to the estuarine waters of São Vicente Island is on the order of 41.1 g/day. The ecological risk assessment revealed a great environmental concern for São Vicente Island, ranging between low (e.g. carbamazepine and cocaine) and moderate to high (e.g. caffeine, acetaminophen and losartan) threats for the aquatic biota. Therefore, initiatives promoting basic sanitation, land-use regularisation and population awareness are highly recommended.

Occurrence and ecological risk assessment of pharmaceuticals and cocaine in the urban drainage channels of Santos beaches (São Paulo, Brazil): a neglected, but sensitive issue.

In some Brazilian coastal cities, it is common to observe 'black tongues' in beaches, i.e. a mixture of urban runoff and untreated domestic sewage containing pollutants of emerging concern, namely pharmaceutical and personal care products (PPCPs), flowing into the South Atlantic Ocean. Such diffuse loads of pollutants might expose nontarget aquatic organisms to harmful compounds. In this work, the occurrence and preliminary ecological risk of 27 PPCPs of various therapeutic classes (including cocaine and its primary metabolite, benzoylecgonine) were investigated, for the first time, in seven urban drainage channels whose diffuse loads flow continuously to the beaches of Santos Bay, São Paulo, Brazil. Of these, 21 compounds were detected using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS), and nine of them were consistently quantified in all urban channels of Santos, suggesting that those pollutants are ubiquitous in this region: caffeine (143.4-516.0 ng/L), losartan (4.2-21.8 ng/L), atenolol (1.1-18.2 ng/L), acetaminophen (1.5-13.8 ng/L), benzoylecgonine (1.0-4.8 ng/L), carbamazepine (1.1-4.0 ng/L), diclofenac (1.9-3.5 ng/L), cocaine (0.5-1.7 ng/L), and orphenadrine (0.1-0.8 ng/L). Moreover, twelve compounds were found below the limit of quantification (

Mutagenic and ecotoxicological assessment of urban surface runoff flowing to the beaches of Guarujá, State of São Paulo, Brazil.

Along the coast of the State of São Paulo, Brazil, urban drainage channels introduce a complex mixture of pollutants into the South Atlantic Ocean, that may cause deleterious effects to the aquatic biota. The objective of this study was to analyse, for the first time, the mutagenicity (Ames Salmonella/microsome test) and ecotoxicity (acute and chronic tests, with Daphnia simillis and Ceriodaphnia dubia, respectively) exerted by the diffuse loads discharged in Guarujá, São Paulo coast, Brazil. Water sampling occurred bimonthly between January and July 2018 (rainy season: January through March; dry season: May through July) at four beaches with different profiles of use and land occupation: Tombo (Blue Flag certification), Enseada (high use by tourists), Perequê (fishing community) and Iporanga (conservation unit). No mutagenic potential was detected in the complex mixtures flowing to the study beaches. However, 30 and 80% of the analyses showed acute and chronic toxicities, respectively, mainly in the Enseada and Perequê channels during the rainy season. To improve the environmental quality of these coastal waters and to reduce the ecological risks posed to the aquatic organisms and public health, several actions are imperative, such as the amelioration of the basic sanitation facilities and land regularisation actions.

Occurrence and risk assessment of pharmaceuticals and cocaine around the coastal submarine sewage outfall in Guarujá, São Paulo State, Brazil.

The aim of this study was to screen and quantify 23 pharmaceutical compounds (including illicit drugs), at two sampling points near the diffusers of the Guarujá submarine outfall, State of São Paulo, Brazil. Samples were collected in triplicate during the high (January 2018) and low (April 2018) seasons at two different water column depths (surface and bottom). A total of 10 compounds were detected using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Caffeine (42.3-141.0 ng/L), diclofenac (3.6-85.7 ng/L), valsartan (4.7-14.3 ng/L), benzoylecgonine (0.3-1.7 ng/L), and cocaine (0.3-0.6 ng/L) were frequently detected (75% occurrence). Orphenadrine (0.6-3.0 ng/L) and atenolol (0.1-0.3 ng/L), and acetaminophen (1.2-1.4 ng/L) and losartan (0.7-3.4 ng/L), were detected in 50% and 25% of the samples, respectively. Only one sample (12.5%) detected the presence of carbamazepine (< 0.001-0.1 ng/L). Unexpectedly a lower frequency of occurrence and concentration of these compounds occurred during the summer season, suggesting that other factors, such as the oceanographic and hydrodynamic regimes of the study area, besides the population rise, should be taken into account. Caffeine presented concentrations above the surface water safety limits (0.01 µg/L). For almost all compounds, the observed concentrations indicate nonenvironmental risk for the aquatic biota, except for caffeine, diclofenac, and acetaminophen that showed low to moderate ecological risk for the three trophic levels tested.

Occurrence and ecological risk assessment of pharmaceuticals and cocaine in a beach area of Guarujá, São Paulo State, Brazil, under the influence of urban surface runoff.

The occurrence of pharmaceuticals and illicit drugs in water resources is widely documented in Europe, North America and Asia. However, in South America, these studies are still incipient. The objective of this study was to screen and identify the presence of pharmaceuticals of various therapeutic classes, including illicit drugs such as cocaine and its metabolite benzoylecgonine, in urban drainage channels that flow into the bathing waters of Guarujá city, State of São Paulo, Brazil. Moreover, the ecological potential risks to the aquatic biota were also assessed. The water samples were collected from four beaches of Guarujá in two different points: in the urban drainage channels and in the nearby coast line. A total of 16 compounds were detected using liquid chromatography coupled with tandem mass spectrometry: carbamazepine (0.1-8.0 ng/L), caffeine (33.5-6550.0 ng/L), cocaine (0.2-30.3 ng/L), benzoylecgonine (0.9-278.0 ng/L), citalopram (0.2-0.4 ng/L), acetaminophen (18.3-391.0 ng/L), diclofenac (0.9-79.8 ng/L), orphenadrine (0.2-1.5 ng/L), atenolol (0.1-140.0 ng/L), propranolol (limit of detection: LOD-0.9 ng/L), enalapril (2.2-3.8 ng/L), losartan (3.6-548.0 ng/L), valsartan (19.8-798.0 ng/L), rosuvastatin (2.5-38.5 ng/L), chlortalidone (0.1-0.4 ng/L) and clopidogrel (0.1-0.2 ng/L). The hereby data also showed that five of these compounds, namely caffeine, acetaminophen, diclofenac, losartan and valsartan, could raise moderate to severe risks to aquatic organisms (algae, crustaceans and fishes). This study is the first report of the occurrence of several pharmaceuticals and illicit drugs in urban drainage channels that flow to the bathing waters in South America, and it is the first quantification of rosuvastatin, chlortalidone and clopidogrel in environmental marine waters of Latin America.

Occurrence of human adenoviruses in a beach area of Guarujá, São Paulo, Brazil.

Along the coastal zone of the State of São Paulo, Brazil, diffuse discharges that flow directly to tourist beaches are responsible for introducing various pathogens into recreational waters. The objective of this study was to analyze, for the first time, the presence of protozoa (Cryptosporidium ssp and Giardia ssp), as well as human mastadenoviruses (HAdV-species C and F) and other species of adenoviruses (AdV) in beach drainage channels of Enseada and Perequê, municipality of Guarujá, São Paulo, Brazil. Protozoa were not detected in any sample over the course of the 11-month study. In relation to HAdVs, 100% (n = 22) of the water samples presented contamination by at least one type of virus (C, D, or F species), suggesting potential risks to the public health following recreational exposure of beach users to these waters. PRACTITIONER POINTS: First report on the presence of human adenoviruses in urban drainage channels in the coast of São Paulo State, Brazil. Urban surface water runoff is responsible for introducing human adenoviruses linked to disease outbreaks in areas of intense recreation. Cryptosporidium oocysts and Giardia cysts were below the limit of detection for all analyzed samples. However, all sites were positive for at least one of the viral species (HAdV-C, HAdV-D, or HAdV-F). Viral loads found in the water were similar to those commonly found in the wastewater.

Elucidation of the chromatographic enantiomer elution order for praziquantel: An experimental and theoretical assessment.

In this work, we have studied both experimentally and theoretically the praziquantel (PZQ) chiral discrimination. According to the main results, the enantioseparation of PZQ was efficiently optimized by HPLC on the reverse phase from the Chiralpak IB column, which has cellulose tris (3,5-dimethylphenylcarbamate) (CDMPC) as a chiral selector. The thermodynamic and structural parameters obtained via density functional theory (DFT) calculations pointed out the chiral discrimination as well as the enantiomeric elution order of PZQ, thus elucidating the experimental data and validating our proposed method. Finally, the hydrogen bonds and π-π stacking interactions played a key role in the discrimination between the PZQ diastereomeric complexes formed.

Development and validation of an experimental and theoretical method for the chiral discrimination of dinotefuran.

Dinotefuran is a low-cost agrochemical considered a highly toxic product. In this sense, there is a need for its constant environmental, biological, and food control, aiming to ensure its use to humans as well as to preserve biodiversity and ecosystems. In the present work, we developed an experimental and theoretical method for dinotefuran chiral discrimination. According to the main results, the dinotefuran enantioselective separation was efficiently optimized by high-performance liquid chromatography evaluating the influence of different percentage compositions in the mobile phase to improve the resolution of the peaks in the chromatogram. The novelty of this work was the proposition of a reduced molecular model for the chiral selector amylose-Tris-(3,5-dimethylphenylcarbamate) polysaccharide that was able to adequately describe at the molecular level its interaction with the dinotefuran enantiomers. Besides, the thermodynamic and structural parameters obtained via density functional theory calculations pointed out the chiral discrimination as well as the enantiomeric elution order of the analyte studied, confirming the experimental data, thus validating our proposed method. Finally, hydrogen bonds and repulsive interactions played a key role in the discrimination between the diastereomeric complexes, and consequently, for the dinotefuran enantioselective separation.

Seasonal monitoring of cocaine and benzoylecgonine in a subtropical coastal zone (Santos Bay, Brazil).

Illicit drugs and their metabolites represent a new class of emerging contaminants. These substances are continuously discharged into wastewater which have been detected in the aquatic environment in concentrations ranging from ng.L-1 to µg.L-1. Our study detected the occurrence of cocaine (COC) and benzoylecgonine (BE) in a subtropical coastal zone (Santos Bay, SP, Brazil) within one year. Water samples (surface and bottom) were collected from the Santos Submarine Sewage Outfall (SSOS) area. COC and BE were measured in the samples using ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-ESI-MS/MS). Concentrations ranged from 12.18 to 203.6 ng.L-1 (COC) and 8.20 to 38.59 ng.L-1 (BE). Higher concentrations of COC were observed during the end of spring, following the population increase at summer season. COC and its metabolite occurrence in this coastal zone represent a threat to coastal organisms.

Improvement of antimalarial activity of a 3-alkylpiridine alkaloid analog by replacing the pyridine ring to a thiazole-containing heterocycle: Mode of action, mutagenicity profile, and Caco-2 cell-based permeability.

The development of new antimalarial drugs is urgent to overcome the spread of resistance to the current treatment. Herein we synthesized the compound 3, a hit-to­lead optimization of a thiazole based on the most promising 3-alkylpyridine marine alkaloid analog. Compound 3 was tested against Plasmodium falciparum and has shown to be more potent than its precursor (IC50 values of 1.55 and 14.7 µM, respectively), with higher selectivity index (74.7) for noncancerous human cell line. This compound was not mutagenic and showed genotoxicity only at concentrations four-fold higher than its IC50. Compound 3 was tested in vivo against Plasmodium berghei NK65 strain and inhibited the development of parasite at 50 mg/kg. In silico and UV-vis approaches determined that compound 3 acts impairing hemozoin crystallization and confocal microscopy experiments corroborate these findings as the compound was capable of diminishing food vacuole acidity. The assay of uptake using human intestinal Caco-2 cell line showed that compound 3 is absorbed similarly to chloroquine, a standard antimalarial agent. Therefore, we present here compound 3 as a potent new lead antimalarial compound.

Reliability in Mandibular Movement Evaluation Using Photogrammetry in Patients With Temporomandibular Disorders.

OBJECTIVE: The purpose of this study was to propose a quantitative evaluation for mandibular opening-closing movement asymmetries and to verify the intraexaminer and interexaminer reliability using photogrammetry in individuals with and without myogenic temporomandibular disorders. METHODS: Forty-nine female participants between ages 18 and 40 were enrolled in this study. They were assigned to 2 different groups: a temporomandibular disorder group, (n = 25; 28.1 ± 3.6 years) and an asymptomatic group (n = 24; 25.6 ± 5.1 years). Data were collected through photogrammetry using Corel Draw X3 software (Corel Corp, Ottawa, Ontario, Canada) for angle measurements. Reliability analysis was done on the total sample, and the photographs were obtained by a singular examiner on 2 occasions (intraexaminer) 1 month apart and from measurement made by another examiner (interexaminer) on different days. The intraclass correlation coefficient (ICC) was applied with a significance level of 5%. RESULTS: The photogrammetry had excellent intrarater and inter-rater reliability for the evaluation of opening and closing movements of the jaw (intrarater: opening ICC = 0.99; closing ICC = 0.98; inter-rater: opening ICC = 0.89 and closing ICC = 0.82). Photogrammetry also demonstrated excellent intra- and inter-rater reliability in the evaluation of head posture (intra-rater: head deviation ICC = 0.96; head position ICC = 0.75; inter-rater: head deviation ICC = 0.98; head position ICC = 0.98). CONCLUSION: Under these experimental conditions, most angular values presented excellent intra- and interexaminer reliability.