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1.
Clin Gerontol ; : 1-12, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38509684

RESUMO

OBJECTIVES: This research comprises a pilot study of the CAI-Health, a new tool for the evaluation of decision-making capacity in healthcare. It aims to analyze the instrument's indicators of reliability and internal validity to conclude its final version. METHODS: A total of 89 participants were included, of which 22 had Alzheimer's Disease; 32 had mild cognitive impairment, and 35 were controls. Cronbach's alpha and the intercorrelation matrix were used as indicators of reliability and internal validity as well as to identify items for elimination. Repeated-measures ANOVA allowed for the analysis of differences between the vignettes that comprise CAI-Health. RESULTS: The internal consistency results were acceptable, and no items were proposed for elimination. A repeated-measures ANOVA revealed that the vignettes were unexpectedly equivalent. Despite the procedures used to develop clinical vignettes with increased levels of complexity in assessing decision-making capacity, this study showed no differences in the vignettes' level of demand. CONCLUSIONS: The extensive application of CAI-Health compromises its clinical usefulness and viability. To reduce its length while maintaining a thorough assessment of each ability, it was decided to eliminate two vignettes and retain all interview items. The final version of the CAI-Health comprises a clinical vignette and a capacity interview. CLINICAL IMPLICATIONS: CAI-Health was designed for the assessment of medical decision-making capacity in older adults.

2.
Aging Ment Health ; 27(2): 380-388, 2023 02.
Artigo em Inglês | MEDLINE | ID: mdl-35466829

RESUMO

OBJECTIVES: To characterize all hospitalizations held in mainland Portugal (2010-2015) with dementia-related agitation based on International Classification of Diseases, Ninth Revision, Clinical Modification (ICD-9-CM) coding, and to investigate whether there is a relationship between agitation and hospitalization outcomes. METHODS: A retrospective observational study was conducted using an administrative dataset containing data from all mainland Portuguese public hospitals. Only hospitalization episodes for patients aged over 65 years who have received a dementia diagnosis ascertained by an ICD-9-CM code of dementia with behavioral disturbance (294.11 and 294.21) and dementia without behavioral disturbance (294.10 and 294.20) were selected. Episodes were further grouped according to the presence of an agitation code. For each episode, demographic data and hospitalization outcomes, including length of stay (LoS), in-hospital mortality, discharge destination and all-cause hospital readmissions, were sourced from the dataset. Comparative analyses were performed and multivariable logistic methods were used to estimate the adjusted associations between agitation (exposure) and outcomes. RESULTS: Overall, 53,156 episodes were selected, of which 6,586 had an agitation code. These were mostly related to male, younger inpatients (mean 81.19 vs. 83.29 years, p < 0.001), had a higher comorbidity burden, stayed longer at the hospital (median 9.00 vs. 8.00 days, p < 0.001) and frequently ended being transferred to another facility with inpatient care. Agitation was shown to independently increase LoS (aOR = 1.385; 95%CI:1.314-1.461), but not the risk of a fatal outcome (aOR = 0.648; 95%CI:0.600-0.700). CONCLUSION: These results support the importance of detecting and managing agitation early on admission, since its prompt management may prevent lengthy disruptive hospitalizations.


Assuntos
Demência , Hospitalização , Humanos , Masculino , Idoso , Tempo de Internação , Alta do Paciente , Comorbidade , Estudos Retrospectivos , Demência/epidemiologia
3.
Int J Mol Sci ; 24(8)2023 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-37108479

RESUMO

Molecular dynamics simulations employing the all-atom optimized potential for liquid simulations (OPLS-AA) force field were performed for determining self-diffusion coefficients (D11) of ethanol and tracer diffusion coefficients (D12) of solutes in ethanol at several temperature and pressure conditions. For simulations employing the original OPLS-AA diameter of ethanol's oxygen atom (σOH), calculated and experimental diffusivities of protic solutes differed by more than 25%. To correct this behavior, the σOH was reoptimized using the experimental D12 of quercetin and of gallic acid in liquid ethanol as benchmarks. A substantial improvement of the calculated diffusivities was found by changing σOH from its original value (0.312 nm) to 0.306 nm, with average absolute relative deviations (AARD) of 3.71% and 4.59% for quercetin and gallic acid, respectively. The new σOH value was further tested by computing D12 of ibuprofen and butan-1-ol in liquid ethanol with AARDs of 1.55% and 4.81%, respectively. A significant improvement was also obtained for the D11 of ethanol with AARD = 3.51%. It was also demonstrated that in the case of diffusion coefficients of non-polar solutes in ethanol, the original σOH=0.312 nm should be used for better agreement with experiment. If equilibrium properties such as enthalpy of vaporization and density are estimated, the original diameter should be once again adopted.


Assuntos
Etanol , Quercetina , Simulação de Dinâmica Molecular , Termodinâmica , Temperatura
4.
Molecules ; 28(18)2023 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-37764459

RESUMO

Diazo compounds are organic substances that are often used as precursors in organic synthesis like cyclization reactions, olefinations, cyclopropanations, cyclopropenations, rearrangements, and carbene or metallocarbene insertions into C-H, N-H, O-H, S-H, and Si-H bonds. Typically, reactions from diazo compounds are catalyzed by transition metals with various ligands that modulate the capacity and selectivity of the catalyst. These ligands can modify and enhance chemoselectivity in the substrate, regioselectivity and enantioselectivity by reflecting these preferences in the products. Porphyrins have been used as catalysts in several important reactions for organic synthesis and also in several medicinal applications. In the chemistry of diazo compounds, porphyrins are very efficient as catalysts when complexed with low-cost metals (e.g., Fe and Co) and, therefore, in recent years, this has been the subject of significant research. This review will summarize the advances in the studies involving the field of diazo compounds catalyzed by metalloporphyrins (M-Porph, M = Fe, Ru, Os, Co, Rh, Ir) in the last five years to provide a clear overview and possible opportunities for future applications. Also, at the end of this review, the properties of artificial metalloenzymes and hemoproteins as biocatalysts for a broad range of applications, namely those concerning carbene-transfer reactions, will be considered.

5.
Molecules ; 28(12)2023 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-37375269

RESUMO

Skin cancer is one of the cancers that registers the highest number of new cases annually. Among all forms of skin cancer, melanoma is the most invasive and deadliest. The resistance of this form of cancer to conventional treatments has led to the employment of alternative/complementary therapeutic approaches. Photodynamic therapy (PDT) appears to be a promising alternative to overcome the resistance of melanoma to conventional therapies. PDT is a non-invasive therapeutic procedure in which highly reactive oxygen species (ROS) are generated upon excitation of a photosensitizer (PS) when subjected to visible light of an adequate wavelength, resulting in the death of cancer cells. In this work, inspired by the efficacy of tetrapyrrolic macrocycles to act as PS against tumor cells, we report the photophysical characterization and biological assays of isobacteriochlorins and their corresponding chlorins and porphyrins against melanoma cancer cells through a photodynamic process. The non-tumoral L929 fibroblast murine cell line was used as the control. The results show that the choice of adequate tetrapyrrolic macrocycle-based PS can be modulated to improve the performance of PDT.


Assuntos
Dermatite Fototóxica , Melanoma , Fotoquimioterapia , Porfirinas , Neoplasias Cutâneas , Humanos , Animais , Camundongos , Fotoquimioterapia/métodos , Porfirinas/farmacologia , Porfirinas/uso terapêutico , Fármacos Fotossensibilizantes/uso terapêutico , Dermatite Fototóxica/tratamento farmacológico , Melanoma/tratamento farmacológico , Melanoma/patologia , Neoplasias Cutâneas/tratamento farmacológico , Linhagem Celular Tumoral
6.
Crim Behav Ment Health ; 33(5): 330-341, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37552612

RESUMO

BACKGROUND: There are numerous scales for screening cognitive performance and thus identification of any potential deficits, but in spite of the vulnerability of the prison population to such problems, there has been no adequate validation of screening tools specifically for use with prisoners or others in the criminal justice system. AIM: To validate the Montreal Cognitive Assessment (MoCA) for use with prisoners. METHODS: 100 adult prisoners in one Portuguese prison were randomly invited by clinicians to take part in this study. A same size sample of community-living adult non-offenders of similar age was selected from the MoCA's normative study database in Portugal. For both groups, the key inclusion criterion was fluency in the Portuguese language. All participants completed the Mini Mental State Examination (MMSE) and the MoCA, both in Portuguese translation. Cronbach's alpha coefficient was calculated as an index of internal consistency and Pearson's r correlations calculated. Group performances were compared using independent samples t-test. Covariance analysis (ANCOVA) was computed with level of education as covariate. To measure the magnitude of the effect, η p 2 ${\eta }_{p}^{2}$ was used. A receiver operating characteristics curve analysis was computed to evaluate the discriminatory accuracy of MoCA and MMSE. RESULTS: The MoCA showed a 'reasonable' internal consistency index (α = 0.75) as well as positive and significant correlations with the MMSE. As a cognitive measure, however, the MoCA showed consistently superior psychometric properties and higher discriminatory accuracy (MoCA = 89%) than the MMSE (65%). According to the Youden index, the optimal cut-off point for the MoCA is below 24 points, whereas for the MMSE, it is below 27. CONCLUSIONS: The MoCA is a valid cognitive screening tool for use with prisoners. Further validations against detailed cognitive evaluation would be a useful next step.


Assuntos
Disfunção Cognitiva , Criminosos , Prisioneiros , Adulto , Humanos , Disfunção Cognitiva/diagnóstico , Disfunção Cognitiva/psicologia , Testes de Estado Mental e Demência , Psicometria , Testes Neuropsicológicos
7.
Psychiatr Q ; 93(1): 35-53, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-33387258

RESUMO

The prevalence of neurodegenerative diseases has been significantly increasing in the last decades, and it is expected to continue to grow. These health disorders can impair patients' decision-making capacity in healthcare. The capacity to make healthcare decisions is a fundamental pillar of informed consent, therefore, it should be carefully assessed. Clinicians' assessment, when not supported by a standardized tool, has revealed to be unreliable, so the recourse to an instrument of capacity assessment is crucial. The present paper aims to identify and summarize published instruments of healthcare decision-making capacity. To do so, a search of peer-reviewed articles in English, Portuguese and Spanish was conducted. A total of eighteen articles, detailing seventeen assessment instruments were selected. Instruments differ on format, structure, assessed abilities and psychometric properties. Likewise, instruments' targeted population also varies, with a few being specifically developed for patients with dementia. Although a high number of instruments were found, there is still no gold standard for healthcare decision-making capacity assessment. The lack of a gold standard highlights the need for more research in this field, as well as an effort to develop guidelines and normative data, in order to improve clinical practices.


Assuntos
Disfunção Cognitiva , Demência , Idoso , Disfunção Cognitiva/diagnóstico , Tomada de Decisões , Demência/psicologia , Necessidades e Demandas de Serviços de Saúde , Humanos , Competência Mental/psicologia
8.
Clin Gerontol ; 45(3): 591-605, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-33491599

RESUMO

OBJECTIVES: This study aims to report on the development and psychometric properties of the Portuguese-language Abe's BPSD score (ABS) to screen for neuropsychiatric symptoms (NPS). METHODS: ISPOR and COSMIN recommendations were followed to translate and culturally adapt the ABS. A validation study was conducted to assess the psychometric properties of the newly-translated instrument. Outpatients attending a psychogeriatric consultation were included by consecutive referrals and were assessed with the ABS, the Neuropsychiatric Inventory (NPI) and NPI Caregiver Distress scale (NPI-D), and the Mini-Mental State Examination (MMSE). The ABS reliability (internal consistency, item-total correlations, inter-rater and test-retest reliability), validity (concurrent and convergent), feasibility and diagnostic accuracy were examined. RESULTS: Overall, 107 participants were included. The ABS Cronbach alpha was 0.672, and item-total correlations ranged from -0.056 to 0.546. Strong inter-rater (ICC 0.997; 95%CI: 0.995-0.999) and test-retest reliability (ICC 0.976; 95%CI: 0.958-0.986) were found. Concurrent validity with NPI was high (rs = 0.847, p < .001), and correlations with MMSE and NPI-D were also significant. An exploratory threshold score ≥2 is proposed to identify clinically relevant NPS. CONCLUSIONS: Data provide satisfactory proof of ABS psychometric characteristics. Nevertheless, some items exhibited less optimal properties. CLINICAL IMPLICATIONS: The newly-translated instrument proved to be relevant, valid and easy to use in a real geriatric clinical setting.


Assuntos
Comparação Transcultural , Idioma , Idoso , Cuidadores/psicologia , Humanos , Portugal/epidemiologia , Reprodutibilidade dos Testes
9.
Curr Psychol ; 41(10): 7383-7392, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-33897227

RESUMO

The COVID-19 pandemic has prompted all countries to adopt restraining measures to mitigate the spread of the disease. Usually, large-scale disasters tend to be accompanied by significant increases of psychological distress, depression and anxiety. Confinement measures imposed during the COVID-19 pandemic are likely to have similar consequences. In the present study we aim to evaluate how COVID-19 affected the overall psychological functioning of Portuguese individuals by providing a comparison of current data with status prior to the COVID-19 pandemic. The study sample was composed of 150 cognitively healthy participants. Results show an overall maintenance of cognitive capacities, although subjective cognitive decline complaints significantly increased during the pandemic. Regarding mental health, restraining measures culminated in an aggravation of depressive and decrease of the perceived quality of life, associated with feelings of loneliness and perceived social isolation. Finally, higher levels of pre-COVID-19 quality of life seem to play a protective role against depression and anxiety and predict less difficulties in emotion regulation, feelings of solitude and cognitive complaints. In sum, confinement due to COVID-19 implied an aggravation of the mental health of the Portuguese population, which appears to have been attenuated in those with higher pre-pandemic levels of perceived quality of life.

10.
Psychol Health Med ; 26(1): 44-55, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-32809853

RESUMO

Like previous pandemics, the coronavirus disease 2019 (COVID-19) has direct and indirect effects, including in mental health. To evaluate the immediate psychological impact of COVID-19, we conducted an online survey in Portugal (24-27 March 2020), using the Impact of Event Scale-Revised (IES-R) and the Depression, Anxiety and Stress Scale (DASS-21). From the 10,529 participants (M = 31.33; SD = 9.73), 83.4% were women, had a mean age of 31.2 years, and 70.9% were active workers. Depression, anxiety, and stress were rated as moderate to severe in 11.7%, 16.9%, and 5.6% of the sample, respectively. Moreover, 49.2% of participants reported a moderate or severe psychological impact of the outbreak. Women, the unemployed, those with lower education, living in rural areas, and with flu-like symptoms or chronic disorders were risk factors. Further research is needed to identify vulnerable groups to better inform and adapt mental health policies and interventions.


Assuntos
Ansiedade/epidemiologia , COVID-19 , Depressão/epidemiologia , Estresse Psicológico/epidemiologia , Adulto , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Portugal/epidemiologia , Fatores de Risco
11.
Psychiatr Q ; 92(1): 1-14, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-32430698

RESUMO

Antipsychotic polypharmacy (APP) is a psychopharmacological practice in which two or more antipsychotics are prescribed simultaneously. Despite the absence of evidence to support it, it is highly prevalent in clinical settings. Another recurrent practice strongly associated with APP is the prescription of high-dose antipsychotics (HDAs). Compulsory treatment is a legal means to impose treatment on an individual suffering from mental illness who refuses therapeutic intervention. Compulsory treatment has been associated with APP and HDAs and rates of both have been proposed to represent indicators of the quality of prescribing. We aimed to perform an antipsychotic prescription audit in a vulnerable psychiatric population, at the psychiatry department of a district hospital in Portugal, across 7 years. We evaluated APP and HDAs in 403 compulsorily admitted patients by reviewing their files at discharge. We used logistic regression to search for factors associated with APP and HDAs. APP was found in 70.5% of individuals, whereas HDAs were found in 51.4%. After adjustment, APP was significantly associated with male gender (Odds Ratio[OR] = 1.85 [1.04; 3.30] 95% Confidence Interval [CI]), involuntary outpatient treatment (OR = .40 [.18; .82] 95% CI), activation of the hospital social services (OR = 1.91 [1.08; 3.38] 95%CI), prescription of antidepressants (OR = .43 [.22; .82] 95%CI) and long-acting injectables (LAI) (OR = 28.29 [13.13; 60.97] 95%CI). HDAs were associated with male gender (OR = 1.76 [1.06; 2.94] 95%CI), the prescription of LAI (OR = 12.92 [6.93; 24.09] 95%CI) and oral first-generation antipsychotics (OR = 2.90 [1.51; 5.60] 95%CI).


Assuntos
Antipsicóticos/administração & dosagem , Antipsicóticos/uso terapêutico , Alta do Paciente , Polimedicação , Padrões de Prática Médica , Adulto , Auditoria Clínica , Feminino , Humanos , Masculino
12.
Molecules ; 25(7)2020 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-32290240

RESUMO

The reaction between organic azides and alkyne derivatives via the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) is an efficient strategy to combine phthalocyanines and analogues with different materials. As examples of such materials, it can be considered the following ones: graphene oxide, carbon nanotubes, silica nanoparticles, gold nanoparticles, and quantum dots. This approach is also being relevant to conjugate phthalocyanines with carbohydrates and to obtain new sophisticated molecules; in such way, new systems with significant potential applications become available. This review highlights recent developments on the synthesis of phthalocyanine, subphthalocyanine, and porphyrazine derivatives where CuAAC reactions are the key synthetic step.


Assuntos
Azidas/química , Indóis/química , Azidas/síntese química , Catálise , Técnicas de Química Sintética , Química Click , Eletrodos , Indóis/síntese química , Isoindóis , Estrutura Molecular , Polímeros/química
13.
Molecules ; 25(7)2020 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-32260294

RESUMO

Azides and porphyrinoids (such as porphyrin and corrole macrocycles) can give rise to new derivatives with significant biological properties and as new materials' components. Significant synthetic approaches have been studied. A wide range of products (e.g., microporous organic networks, rotaxane and dendritic motifs, dendrimers as liquid crystals, as blood substitutes for transfusions and many others) can now be available and used for several medicinal and industrial purposes.


Assuntos
Azidas/química , Porfirinas/química , Estrutura Molecular
14.
Int J Mol Sci ; 20(17)2019 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-31480214

RESUMO

Substantial amounts of vine wastes are produced during vineyard management, and the chemical profiling of high-value lipophilic phytochemicals is becoming crucial in order to find a complementary route towards their integrated valorisation. The prospection of bioactive phytochemicals from unripe grape, vine shoot, vine cane, stalk and leaf dichloromethane extracts was carried out by gas chromatography-mass spectrometry (GC-MS), analysing samples from a mixture of four red Vitis vinifera L. varieties (Baga, Aragonez, Água Santa and Shiraz), collected at Bairrada Appellation, as a representative case study of typical multi-variety Portuguese vineyards. Vine wastes showed distinct amounts of lipophilic extract, ranging from 0.68% (vine canes) to 13.35% (vine leaves) at dry weight (dw). Thirty-three components were identified, including fatty acids and alcohols, sterols and triterpenoids accounting for amounts from 118.9 mg/100 g dw to 1512.0 mg/100 g dw. The integrated study revealed that unripe grape, stalk and leaf dichloromethane extracts stood out as possible sources of triterpenic compounds (103.2 to 653.5 mg/100 g dw), with lupeol, ursolic and oleanolic acids prevailing. Leaf extract is also reported as an undervalued source of α-tocopherol, as the major component detected in this matrix (300.5 mg/100 g dw). These exploratory results are a relevant contribution for the exploitation of undervalued vine residues as a source of health-promoting components with the potential to be used as supplements or nutraceutical ingredients.


Assuntos
Lipídeos/química , Compostos Fitoquímicos/farmacologia , Vitis/química , Resíduos/análise , Álcoois/análise , Ácidos Graxos/análise , Extratos Vegetais/química , Esteróis/análise , Triterpenos/análise
15.
Int J Mol Sci ; 20(10)2019 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-31121942

RESUMO

The post-functionalization of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(pentafluorophenyl)porphyrin tri-iodide, known as a highly efficient photosensitizer (PS) for antimicrobial photodynamic therapy (aPDT), in the presence of 3- or 4-mercaptobenzoic acid, afforded two new tricationic porphyrins with adequate carboxylic pending groups to be immobilized on chitosan or titanium oxide. The structural characterization of the newly obtained materials confirmed the success of the porphyrin immobilization on the solid supports. The photophysical properties and the antimicrobial photodynamic efficacy of the non-immobilized porphyrins and of the new conjugates were evaluated. The results showed that the position of the carboxyl group in the mercapto units or the absence of these substituents in the porphyrin core could modulate the action of the photosensitizer towards the bioluminescent Gram-negative Escherichia coli bacterium. The antimicrobial activity was also influenced by the interaction between the photosensitizer and the type of support (chitosan or titanium dioxide). The new cationic porphyrins and some of the materials were shown to be very stable in PBS and effective in the photoinactivation of E. coli bacterium. The physicochemical properties of TiO2 allowed the interaction of the PS with its surface, increasing the absorption profile of TiO2, which enables the use of visible light, inactivating the bacteria more efficiently than the corresponding PS immobilized on chitosan.


Assuntos
Antibacterianos/química , Quitosana/análogos & derivados , Fármacos Fotossensibilizantes/química , Porfirinas/química , Titânio/química , Antibacterianos/síntese química , Antibacterianos/farmacologia , Cátions/síntese química , Cátions/química , Cátions/farmacologia , Quitosana/síntese química , Quitosana/farmacologia , Escherichia coli/efeitos dos fármacos , Infecções por Escherichia coli/tratamento farmacológico , Humanos , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/síntese química , Porfirinas/farmacologia , Titânio/farmacologia
16.
Child Psychiatry Hum Dev ; 50(2): 245-256, 2019 04.
Artigo em Inglês | MEDLINE | ID: mdl-30062495

RESUMO

The primary aim of the present study was to examine the psychometric properties and measurement invariance of the Inventory of Callous-Unemotional Traits (ICU) self-report and its short version (ICU-12) among a mixed-sex normative sample of 782 Portuguese youth (M = 15.87 years; SD = 1.72). Confirmatory factor analysis revealed that the three-factor structure of the ICU obtained the best fit after the removal of two items, and the two-factor structure of the ICU-12 obtained the best fit after the removal of one item. Cross-sex measurement invariance was demonstrated for both versions of the inventory. The 22-item version of the ICU and its 11-item short form (ICU-SF) demonstrated generally adequate psychometric properties of internal consistency, convergent validity, discriminant validity, and criterion-related validity (e.g., with conduct disorder symptoms). In terms of known-groups validity, males scored significantly higher than females. Results suggest that the use of the ICU and ICU-SF among Portuguese-speaking youth is psychometrically justified.


Assuntos
Transtorno da Conduta , Inventário de Personalidade/normas , Psicometria , Adolescente , Transtorno da Conduta/diagnóstico , Transtorno da Conduta/psicologia , Feminino , Humanos , Masculino , Portugal , Psicometria/métodos , Psicometria/normas , Reprodutibilidade dos Testes , Comportamento Social , Traduções , Adulto Jovem
17.
Inorg Chem ; 57(7): 3855-3864, 2018 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-29533608

RESUMO

The use of 5,10,15,20-tetrakis( p-phenylphosphonic acid)porphyrin (H10TPPA) as a linker in the preparation of porphyrin-based metal-organic frameworks (Por-MOFs) through coordination to lanthanides cations is reported. The resulting unprecedented materials, formulated as [M(H9TPPA)(H2O) x]Cl2· yH2O [ x + y = 7; M3+ = La3+ (1), Yb3+ (2), and Y3+ (3)], prepared using hydrothermal synthesis, were extensively characterized in the solid-state, for both their structure and thermal robustness, using a myriad of solid-state advanced techniques. Materials were evaluated as heterogeneous catalysts in the oxidation of thioanisole by H2O2 and as chemosensors for detection of nitroaromatic compounds (NACs). Nano-Por-MOFs 1-3 proved to be effective as heterogeneous catalysts in the sulfoxidation of thioanisole, with Por-MOF 1 exhibiting the best catalytic performance with a conversion of thioanisole of 89% in the first cycle and with a high selectivity for the sulfoxide derivative (90%). The catalyst maintained its activity roughly constant in three consecutive runs. Por-MOFs 1-3 can be employed as chemosensors because of a measured fluorescence quenching up to 70% for nitrobenzene, 1,4-dinitrobenzene, 4-nitrophenol, and phenol, with 2,4,6-trinitrophenol exhibiting a peculiar fluorescence profile.

18.
Molecules ; 23(4)2018 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-29596367

RESUMO

Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn) as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.


Assuntos
Metaloporfirinas/química , Metano/análogos & derivados , Metano/química
19.
Environ Geochem Health ; 40(5): 1767-1784, 2018 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28281140

RESUMO

New lines of evidence suggest that less than 10% of neurodegenerative diseases have a strict genetic aetiology and other factors may be prevalent. Environmental exposures to potentially toxic elements appear to be a risk factor for Parkinson's, Alzheimer's and sclerosis diseases. This study proposes a multidisciplinary approach combining neurosciences, psychology and environmental sciences while integrating socio-economic, neuropsychological, environmental and health data. We present the preliminary results of a neuropsychological assessment carried out in elderly residents of the industrial city of Estarreja. A battery of cognitive tests and a personal questionnaire were administered to the participants. Multivariate analysis and multiple linear regression analysis were used to identify potential relationships between the cognitive status of the participants and environmental exposure to potentially toxic elements. The results suggest a relationship between urinary PTEs levels and the incidence of cognitive disorders. They also point towards water consumption habits and profession as relevant factors of exposure. Linear regression models show that aluminium (R 2 = 38%), cadmium (R 2 = 11%) and zinc (R 2 = 6%) are good predictors of the scores of the Mini-Mental State Examination cognitive test. Median contents (µg/l) in groundwater are above admissible levels for drinking water for aluminium (371), iron (860), manganese (250), and zinc (305). While the World Health Organization does not provide health-based reference values for aluminium, results obtained from this study suggest that it may have an important role in the cognitive status of the elderly. Urine proved to be a suitable biomarker of exposure both to elements with low and high excretion rates.


Assuntos
Disfunção Cognitiva/induzido quimicamente , Exposição Ambiental , Poluentes Ambientais/toxicidade , Idoso , Disfunção Cognitiva/epidemiologia , Disfunção Cognitiva/psicologia , Feminino , Água Subterrânea/química , Humanos , Incidência , Masculino , Metais Pesados/toxicidade , Testes Neuropsicológicos , Portugal/epidemiologia , Fatores de Risco , Poluentes Químicos da Água/toxicidade
20.
Curr Microbiol ; 74(5): 575-583, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28260118

RESUMO

The aim of this study is to evaluate the effects of the inoculation of the saltmarsh plant (Halimione portulacoides) with Pseudomonas sp. SPN31 nah+ combined with exposure to 2-methylnaphthalene (2-MtN) on the plant rhizosphere and endosphere bacterial communities as well as on plant health. To achieve this goal, microcosm experiments were set up. Denaturing gradient gel electrophoresis (DGGE) profiles and statistical analysis showed that rhizosphere and endosphere bacterial communities had distinct responses to plant inoculation and/or exposure to 2-MtN. PCR-sequencing analysis of nah genes encoding for 2-MtN degrading enzymes suggested the presence of Pseudomonas sp. SPN31 nah+ in the endosphere of H. portulacoides with 2-MtN contamination. Moreover, a significant effect in the photosynthetic performance of inoculated plants was detected. To conclude, despite the potential beneficial effect of plant inoculation with Pseudomonas sp. SPN31 nah+ endophytic bacteria may have on plant health, no significant effect on the removal of MtN was detected for the level of contamination used in the study.


Assuntos
Bactérias , Chenopodiaceae/efeitos dos fármacos , Chenopodiaceae/microbiologia , Naftalenos/efeitos adversos , Pseudomonas/fisiologia , Rizosfera , Poluentes do Solo/efeitos adversos , Bactérias/classificação , Bactérias/genética , Biodegradação Ambiental , Chenopodiaceae/fisiologia , Regulação Bacteriana da Expressão Gênica , Regulação Enzimológica da Expressão Gênica , Genes Bacterianos , Naftalenos/metabolismo , Fotossíntese , Filogenia , Raízes de Plantas/microbiologia , RNA Ribossômico 16S/genética , Microbiologia do Solo , Poluentes do Solo/metabolismo , Compostos Orgânicos Voláteis
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