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1.
J Photochem Photobiol B ; 257: 112965, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38955078

RESUMO

This research aimed to develop natural plant systems to serve as biological sentinels for the detection of organophosphate pesticides in the environment. The working hypothesis was that the presence of the pesticide in the environment caused changes in the content of pigments and in the photosynthetic functioning of the plant, which could be evaluated non-destructively through the analysis of reflected light and emitted fluorescence. The objective of the research was to furnish in vivo indicators derived from spectroscopic parameters, serving as early alert signals for the presence of organophosphates in the environment. In this context, the effects of two pesticides, Chlorpyrifos and Dimethoate, on the spectroscopic properties of aquatic plants (Vallisneria nana and Spathyfillum wallisii) were studied. Chlorophyll-a variable fluorescence allowed monitoring both pesticides' presence before any damage was observed at the naked eye, with the analysis of the fast transient (OJIP curve) proving more responsive than Kautsky kinetics, steady-state fluorescence, or reflectance measurements. Pesticides produced a decrease in the maximum quantum yield of PSII photochemistry, in the proportion of PSII photochemical deexcitation relative to PSII non photochemical decay and in the probability that trapped excitons moved electrons into the photosynthetic transport chain beyond QA-. Additionally, an increase in the proportion of absorbed energy being dissipated as heat rather than being utilized in the photosynthetic process, was notorious. The pesticides induced a higher deactivation of chlorophyll excited states by photophysical pathways (including fluorescence) with a decrease in the quantum yields of photosystem II and heat dissipation by non-photochemical quenching. The investigated aquatic plants served as sentinels for the presence of pesticides in the environment, with the alert signal starting within the first milliseconds of electronic transport in the photosynthetic chain. Organophosphates damage animals' central nervous systems similarly to certain compounds found in chemical weapons, thus raising the possibility that sentinel plants could potentially signal the presence of such weapons.


Assuntos
Clorofila , Clorpirifos , Clorofila/metabolismo , Clorofila/química , Clorpirifos/metabolismo , Clorpirifos/toxicidade , Fluorescência , Praguicidas/toxicidade , Praguicidas/metabolismo , Fotossíntese/efeitos dos fármacos , Dimetoato/toxicidade , Dimetoato/metabolismo , Espectrometria de Fluorescência , Complexo de Proteína do Fotossistema II/metabolismo , Complexo de Proteína do Fotossistema II/química , Monitoramento Ambiental/métodos , Clorofila A/metabolismo , Clorofila A/química , Cinética , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/metabolismo
2.
Chemosphere ; 363: 142923, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39059642

RESUMO

Biobeds are presented as an alternative for good pesticide wastewater management on farms. This work proposes a new test for in-situ biomonitoring of pesticide detoxification in biobeds. It is based on the assessment of visually appreciable injuries to Eisenia fetida. The severity of the injury to each exposed individual is assessed from the morphological changes observed in comparison with the patterns established in seven categories and, an injury index is calculated. A linear relationship between the proposed injury index and the pesticide concentration was determined for each pesticide sprayed individually in the biomixture. The five pesticides used were atrazine, prometryn, clethodim, haloxyfop-P-methyl and dicamba. In addition, a multiple linear regression model (i.e., a multivariate response surface) was fitted, which showed a good generalization capacity. The sensitivity range of the injury test was tested from 0.01 to 630 mg kg-1 as the total pesticide concentration. This index is then used to monitor the detoxification of these pesticides in a biomixture (composed of wheat stubble, river waste, and soil, 50:25:25% by volume) over 210 days. The results are compared with standardized tests (Eisenia fetida avoidance test and Lactuca sativa seed germination test) carried out on the same biomixture. The results are also compared with data on the removal of pesticides. The injury test showed a better correlation with the removal of pesticides than the avoidance test and seed germination test. This simple and inexpensive test has proved to be useful for decontamination in-situ monitoring in biobeds.


Assuntos
Monitoramento Biológico , Oligoquetos , Praguicidas , Praguicidas/análise , Praguicidas/metabolismo , Oligoquetos/metabolismo , Monitoramento Biológico/métodos , Animais , Atrazina/toxicidade , Atrazina/análise , Poluentes do Solo/análise , Poluentes do Solo/toxicidade , Monitoramento Ambiental/métodos , Águas Residuárias/química , Prometrina/toxicidade , Dicamba
3.
Chemphyschem ; 25(14): e202400246, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38656666

RESUMO

In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2'-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.

4.
Entropy (Basel) ; 26(3)2024 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-38539771

RESUMO

The Kardar-Parisi-Zhang (KPZ) equation describes a wide range of growth-like phenomena, with applications in physics, chemistry and biology. There are three central questions in the study of KPZ growth: the determination of height probability distributions; the search for ever more precise universal growth exponents; and the apparent absence of a fluctuation-dissipation theorem (FDT) for spatial dimension d>1. Notably, these questions were answered exactly only for 1+1 dimensions. In this work, we propose a new FDT valid for the KPZ problem in d+1 dimensions. This is achieved by rearranging terms and identifying a new correlated noise which we argue to be characterized by a fractal dimension dn. We present relations between the KPZ exponents and two emergent fractal dimensions, namely df, of the rough interface, and dn. Also, we simulate KPZ growth to obtain values for transient versions of the roughness exponent α, the surface fractal dimension df and, through our relations, the noise fractal dimension dn. Our results indicate that KPZ may have at least two fractal dimensions and that, within this proposal, an FDT is restored. Finally, we provide new insights into the old question about the upper critical dimension of the KPZ universality class.

5.
Pflugers Arch ; 476(3): 365-377, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38308122

RESUMO

To assess the influence of physical training on neuronal activation and hypothalamic expression of vasopressin and oxytocin in spontaneously hypertensive rats (SHR), untrained and trained normotensive rats and SHR were submitted to running until fatigue while internal body and tail temperatures were recorded. Hypothalamic c-Fos expression was evaluated in thermoregulatory centers such as the median preoptic nucleus (MnPO), medial preoptic nucleus (mPOA), paraventricular nucleus of the hypothalamus (PVN), and supraoptic nucleus (SON). The PVN and the SON were also investigated for vasopressin and oxytocin expressions. Although exercise training improved the workload performed by the animals, it was reduced in SHR and followed by increased internal body temperature due to tail vasodilation deficit. Physical training enhanced c-Fos expression in the MnPO, mPOA, and PVN of both strains, and these responses were attenuated in SHR. Vasopressin immunoreactivity in the PVN was also increased by physical training to a lesser extent in SHR. The already-reduced oxytocin expression in the PVN of SHR was increased in response to physical training. Within the SON, neuronal activation and the expressions of vasopressin and oxytocin were reduced by hypertension and unaffected by physical training. The data indicate that physical training counterbalances in part the negative effect of hypertension on hypothalamic neuronal activation elicited by exercise, as well as on the expression of vasopressin and oxytocin. These hypertension features seem to negatively influence the workload performed by SHR due to the hyperthermia derived from the inability of physical training to improve heat dissipation through skin vasodilation.


Assuntos
Hipertensão , Corrida , Ratos , Animais , Ratos Endogâmicos SHR , Ocitocina/metabolismo , Ocitocina/farmacologia , Hipotálamo/metabolismo , Núcleo Hipotalâmico Paraventricular/metabolismo , Vasopressinas/metabolismo , Hipertensão/metabolismo , Fadiga
6.
Chemosphere ; 346: 140569, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37918533

RESUMO

2,4-D and fipronil are among Brazil's most used pesticides. The presence of these substances in surface waters is a concern for the aquatic ecosystem health. Thus, understanding the behavior of these substances under environmentally relevant conditions is essential for an effective risk assessment. This study aimed to determine the degradation profiles of 2,4-D and fipronil after controlled application in aquatic mesocosm systems under influencing factors such as environmental aspects and vinasse application, evaluate pesticide dissipation at the water-sediment interface, and perform an environmental risk assessment in water and sediment compartments. Mesocosm systems were divided into six different treatments, namely: control (C), vinasse application (V), 2,4-D application (D), fipronil application (F), mixture of 2,4-D and fipronil application (M), and mixture of 2,4-D and fipronil with vinasse application (MV). Pesticide application was performed according to typical Brazilian sugarcane management procedures, and the experimental systems were monitored for 150 days. Pesticide dissipation kinetics was modeled using first-order reaction models. The estimated half-life times of 2,4-D were 18.2 days for individual application, 50.2 days for combined application, and 9.6 days for combined application with vinasse. For fipronil, the respective half-life times were 11.7, 13.8, and 24.5 days. The dynamics of pesticides in surface waters resulted in the deposition of these compounds in the sediment. Also, fipronil transformation products fipronil-sulfide and fipronil-sulfone were quantified in water 21 days after pesticide application. Finally, performed risk assessments showed significant potential risk to environmental health, with RQ values for 2,4-D up to 1359 in freshwater and 98 in sediment, and RQ values for fipronil up to 22,078 in freshwater and 2582 in sediment.


Assuntos
Praguicidas , Poluentes Químicos da Água , Ecossistema , Poluentes Químicos da Água/análise , Praguicidas/toxicidade , Praguicidas/análise , Água , Ácido 2,4-Diclorofenoxiacético/toxicidade
7.
Medicina (Kaunas) ; 59(7)2023 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-37512000

RESUMO

Background: The objective of this study was to evaluate the load transmitted to the peri-implant bone by seven different restorative materials in single-unit rehabilitations with morse taper implants using a strain gauge. Materials: In a polyurethane block that simulated type III bone, a morse taper platform implant was installed (3.5 × 11 mm) in the center and 1 mm below the test base surface, and four strain gauges were installed around the implant, simulating the mesial, distal, buccal and lingual positions. Seven similar hybrid abutment crowns were crafted to simulate a lower premolar using different materials: 1-PMMA; 2-glass ceramic over resin matrix; 3-PEEK + lithium disilicate; 4-metal-ceramic; 5-lithium disilicate; 6-zirconia + feldspathic; 7-monolithic zirconia. All groups underwent axial and oblique loads (45 degrees) of 150 N from a universal testing machine. Five measurements (n = 5) were performed with each material and for each load type; the microdeformation data underwent statistical analysis. The data were obtained in microdeformation (µÎµ), and the significance level was set at p ≤ 0.05. Results: There was no statistically significant difference in the evaluation among the materials under either the axial load or the oblique load at 45 degrees. In turn, in the comparison between axial load and oblique load, there was a difference in load for all materials. Conclusion: The restorative material did not influence the load transmitted to the bone. Furthermore, the load transmitted to the bone was greater when it occurred obliquely at 45° regardless of the material used. In conclusion, it appeared that the different elastic modulus of each material did not influence the load transmission to the peri-implant bone.


Assuntos
Coroas , Zircônio , Humanos
8.
HardwareX ; 14: e00416, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37090786

RESUMO

Advances in sensors have revolutionized the biomedical engineering field, having an extreme affinity for specific analytes also providing an effective, real-time, point-of-care testing for an accurate diagnosis. Quartz Crystal Microbalance (QCM) is a well-established sensor that has been successfully applied in a broad range of applications to monitor and explore various surface interactions, in situ thin-film formations, and layer properties. This technology has gained interest in biomedical applications since novel QCM systems are able to work in liquid media. QCM with dissipation monitoring (QCM-D) is an expanded version of a QCM that measures changes in damping properties of adsorbed layers thus providing information on its viscoelastic nature. In this article, an open source and low cost QCM-D prototype for biomedical applications was developed. In addition, the system was validated using different Polyethylene Glycol (PEG) concentrations due to its importance for many medical applications. The statistics show a bigger dissipation of the system as the fluid becomes more viscous, also having a very acceptable sensibility when temperature is controlled.

9.
Int J Biometeorol ; 67(3): 517-526, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36723757

RESUMO

Surface temperature can be used as a tool for calculating sensible heat transfer. However, it needs to be associated with air temperature to identify the direction of heat flow (gain or loss). This study quantified sensible heat transfer in Japanese quail as a function of operative temperature. The meteorological variables were air temperature, relative humidity, and black globe temperature. Quail surface temperature was measured on 50 adult Coturnix coturnix japonica individuals 270 days old during 8 days by using a thermographic camera. The data were analyzed by the least-squares method to assess the effects of sex (male and female), period of the day (morning and afternoon), and body region (head, body, and feet). Quail surface temperature was strongly correlated with operative temperature. The total sensible heat flow was 64.02 W m-2. The morning period had a mean operative temperature of 22.48 °C, providing a higher gradient between air and quail temperature and thereby producing a higher heat flow (82.19 W m-2). In the afternoon, the heat transfer was lower (45.70 W m-2) because the operative temperature was higher (30.84 °C). Comparison between sexes showed that heat transfer was higher in females (67.37 W m-2) than in males (60.53 W m-2). The head served as an important thermal window, with a heat transfer of 78.24 W m-2, whereas the body and feet had a transfer of 56.80 W m-2. Heat transfer by sensible mechanisms was quantified in Japanese quail. Heat transfer depended greatly on ambient temperature. When the operative temperature was below 28 °C, sensible mechanisms were efficient in dissipating heat to the environment. When the ambient temperature exceeded 29 °C, quail could not effectively dissipate heat to the environment through sensible mechanisms. At 30 °C and above, heat loss shifted to heat gain, causing thermal stress in Japanese quail.


Assuntos
Coturnix , Temperatura Alta , Humanos , Animais , Masculino , Feminino , Regulação da Temperatura Corporal , Temperatura
10.
Environ Pollut ; 324: 121283, 2023 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-36804884

RESUMO

Recently, Comte et al. (2022) re-examined the natural degradation of chlordecone (CLD) in the soils of the French West Indies (FWI) by introducing an additional 'dissipation parameter' into the WISORCH model developed by Cabidoche et al. (2009). Recent data sets of CLD concentrations in FWI soils obtained by Comte et al. enabled them optimizing the model parameters, resulting in significantly shorter estimates of pollution persistence than in the original model. Their conclusions jeopardize the paradigm of a very limited degradation of CLD in FWI soils, which may lead to an entire revision of the management of CLD contamination. However, we believe that their study is questionable on several important aspects. This includes potential biases in the data sets and in the modeling approach. It results in an inconsistency between the estimated dissipation half-life time (DT50) of five years that the authors determined for CLD and the fate of CLD in soil from the application period 1972-1993 until nowadays. Most importantly, a rapid dissipation of CLD in the field as proposed by Comte et al. is not sufficiently supported by data and estimates. Hence, the paradigm of long-term persistence of CLD in FWI soils is still to be considered.


Assuntos
Clordecona , Inseticidas , Poluentes do Solo , Clordecona/análise , Clordecona/metabolismo , Inseticidas/análise , Solo , Meia-Vida , Poluentes do Solo/análise , Índias Ocidentais
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