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1.
Front Immunol ; 15: 1350837, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38745654

RESUMO

Introduction: Anti-NMDA receptor encephalitis is an autoimmune disorder caused by autoantibodies (abs) against the conformational epitope on GluN1 subunits. GluN1-abs have been determined with cell-based assay (CBA) co-expressing GluN1/GluN2 subunits. However, commercial fixed CBA expressing only GluN1 subunit has increasingly been used in clinical practice. The ab titers can be determined with serial dilutions, but its clinical significance remains unclear. We aimed to develop an H-intensity scale (HIS) score to estimate GluN1-ab titers in cerebrospinal fluid (CSF) with one-time immunostaining using both commercial CBA and immunohistochemistry and report its usefulness. "H" is the initial of a patient with high CSF GluN1-ab titers (1:2,048). Methods: We first determined the reliability of CBA in 370 patients with suspected autoimmune encephalitis by comparing the results between commercial CBA and established assay in Dalmau's Lab. Then, we made positive control panels using the patient H's CSF diluted in a fourfold serial dilution method (1:2, 1:8, 1:32, 1:128, 1:512, and 1:2,048). Based on the panels, we scored the intensity of ab reactivity of 79 GluN1-ab-positive patients' CSF (diluted at 1:2) on a scale from 0 to 6 (with ≥1 considered positive). To assess inter-assay reliability, we performed immunostaining twice in 21 patients' CSF. We investigated an association between the score of CSF obtained at diagnosis and the clinical/paraclinical features. Results: The sensitivity and specificity of CBA were 93.7% (95% CI: 86.0-97.3) and 98.6% (95% CI: 96.5-99.5), respectively. Linear regression analysis showed a good agreement between the scores of the first and second assays. Patients with a typical spectrum, need for mechanical ventilation support, autonomic symptoms/central hypoventilation, dyskinesias, speech dysfunction, decreased level of consciousness, preceding headache, ovarian teratoma, and CSF leukocyte count >20 cells/µL had a higher median HIS score than those without, but HIS score was not associated with sex, age at onset, or seizure. HIS score at diagnosis had a significant effect on 1-year functional status. Discussion: The severity of disease and four of the six core symptoms were associated with higher GluN1-ab titers in CSF at diagnosis, which may play a role in poor 1-year functional status. An incomplete phenotype can be attributed to low CSF GluN1-ab titers.


Assuntos
Encefalite Antirreceptor de N-Metil-D-Aspartato , Autoanticorpos , Receptores de N-Metil-D-Aspartato , Humanos , Feminino , Autoanticorpos/líquido cefalorraquidiano , Autoanticorpos/imunologia , Pessoa de Meia-Idade , Adulto , Masculino , Receptores de N-Metil-D-Aspartato/imunologia , Idoso , Encefalite Antirreceptor de N-Metil-D-Aspartato/diagnóstico , Encefalite Antirreceptor de N-Metil-D-Aspartato/líquido cefalorraquidiano , Encefalite Antirreceptor de N-Metil-D-Aspartato/imunologia , Adulto Jovem , Adolescente , Criança , Imuno-Histoquímica , Pré-Escolar , Proteínas do Tecido Nervoso/imunologia , Reprodutibilidade dos Testes , Biomarcadores/líquido cefalorraquidiano , Idoso de 80 Anos ou mais
2.
Environ Res ; 235: 116688, 2023 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-37467938

RESUMO

The most severe effects of methylmercury (MeHg) exposure during child development are thought to result from exposure during fetal life and childhood. However, comparing the neurodevelopmental effects of prenatal and postnatal MeHg exposure (PreMeHg and PostMeHg, respectively) remains unclear. We aimed to investigate the associations between neurodevelopmental indicators and PreMeHg or PostMeHg. The participants were 134 children in the first grade of elementary schools aged 7-8 years from the Kinan region, an area with high consumption of MeHg-rich whales and tunas in Japan. We measured MeHg levels in preserved umbilical cord tissues and total mercury (T-Hg) levels in children's hair to estimate PreMeHg and PostMeHg levels, respectively. Neuropsychological (intelligence quotient testing and Boston Naming Test) and neurophysiological (brainstem auditory evoked potential [BAEP], visual evoked potential [VEP], and color vision tests) studies were performed to evaluate the neurodevelopmental status. Multiple regression analyses were conducted according to sex. The geometric mean MeHg levels in preserved umbilical cord tissues and T-Hg levels in children's hair were 0.11 µg/g and 2.94 µg/g, respectively. Neither PreMeHg nor PostMeHg was related to neuropsychological indicators. Some associations between MeHg exposure and neurophysiological results were observed only in boys. N145 latency in VEPs was significantly prolonged with increasing PreMeHg (ß: 12.01, 95% confidence interval [CI]: 0.648, 23.38). The III-V interpeak intervals in BAEP were significantly prolonged with increasing PreMeHg or PostMeHg (ß [95% CI]: 0.142 [0.041, 0.243] and 0.159 [0.052, 0.265], respectively). After adjusting for PreMeHg, the association between PostMeHg and BAEP latencies disappeared. In conclusion, the latency in the auditory and visual pathways was significantly prolonged with increasing PreMeHg in boys. These findings suggest that male fetuses may be more susceptible to MeHg exposure.


Assuntos
Mercúrio , Compostos de Metilmercúrio , Efeitos Tardios da Exposição Pré-Natal , Humanos , Gravidez , Feminino , Masculino , Compostos de Metilmercúrio/análise , Japão , Potenciais Evocados Visuais , Mercúrio/análise , Desenvolvimento Infantil , Efeitos Tardios da Exposição Pré-Natal/induzido quimicamente , Efeitos Tardios da Exposição Pré-Natal/epidemiologia
3.
Neuroimage Clin ; 38: 103422, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37163912

RESUMO

Methylmercury pollution is a global problem, and Minamata disease (MD) is a stark reminder that exposure to methylmercury can cause irreversible neurological damage. A "glove and stocking type" sensory disturbance due to injured primary sensory cortex (SI) (central somatosensory disturbance) is the most common neurologic sign in MD. As this sign is also prevalent in those with polyneuropathy, we aimed to develop an objective assessment for detecting central somatosensory disturbances in cases of chronic MD. We selected 289 healthy volunteers and 42 patients with MD. We recorded the sensory nerve action potentials (SNAPs) and somatosensory evoked magnetic fields (SEFs) to median nerve stimulation with magnetoencephalography. Single-trial epochs were classified into three categories (N20m, non-response, and P20m epochs) based on the cross-correlation between averaged sensor SEFs and individual epochs. We assessed SI responses (the appearance rate of P20m [P20m rate] and non-response epochs [non-response rate]) and early somatosensory cortical processing (N20m amplitude, reproducibility of N20m in single-trial responses [cross-correlation value], and induced gamma-band oscillations of the SI [gamma response] of single epochs excluding non-response epochs). Receiver operating characteristic curve analyses were used to examine the diagnostic accuracy of each parameter. We found that SNAPs exerted a marginal effect on the N20m. The N20m amplitude, cross-correlation value, and gamma response were significantly reduced in the MD group on either side (p < 0.0001), suggestive of altered early somatosensory cortical processing. Interestingly, the P20m rate and non-response rate were significantly increased in the MD group on either side (p < 0.0001), thereby suggesting impaired SI responses. Notably, P20m and absent N20m peaks were observed in 6 and 11 patients with MD, respectively, which may be attributed to increased numbers of P20m epochs. The cross-correlation value exhibited the highest correlation with the P20m rate or non-response rate. Thus, reduced reproducibility of N20m may play an important role in chronic MD. The cross-correlation value exhibited the highest correlation with the gamma response for both SI parameters in early somatosensory cortical processing. The area under the curve was > 0.77 (range: 0.77-0.79) for all parameters. Their confidence intervals overlapped with each other; thus, each SEF parameter likely had an approximately equivalent discrimination ability. In conclusion, chronic MD is characterized by impaired SI responses and alterations in early somatosensory cortical processing. Thus, single-trial neuromagnetic analysis of somatosensory function may be useful for detecting central somatosensory disturbance and elucidating the relevant pathophysiological mechanisms even in the context of chronic MD.


Assuntos
Compostos de Metilmercúrio , Humanos , Estimulação Elétrica , Potenciais Somatossensoriais Evocados/fisiologia , Magnetoencefalografia , Nervo Mediano/fisiologia , Reprodutibilidade dos Testes , Córtex Somatossensorial
4.
Brain Res ; 1805: 148278, 2023 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-36775085

RESUMO

Exploratory whole-brain studies in patients suffering from methylmercury (MeHg) poisoning have not been conducted. We aimed to evaluate the neuroanatomical differences between patients with chronic MeHg poisoning and healthy volunteers via magnetic resonance (MR) imaging. Patients included in this case-control study were divided into three categories based on whether MeHg exposure occurred in utero, under 15 years of age, or over 15 years of age, as fetal-, pediatric-, and adult-type patients, respectively. This study analyzed MR imaging data from 10 patients each of fetal, pediatric, and adult types of chronic MeHg poisoning in Minamata and corresponding 53, 37, and 15 age- and sex-matched healthy volunteers. Whole-brain voxel-based morphometry (VBM) analysis was used to determine the volumetric gray and white matter (GM and WM) differences in patients with chronic MeHg poisoning. Compared to healthy individuals, VBM revealed a significant reduction in GM in the cerebellar and calcarine areas in pediatric- and adult-type cases and in the thalamus of fetal-type cases. A significant reduction in WM volume was also noted in the cerebral and the cerebellar regions, especially in pediatric-type cases. Patients with chronic MeHg poisoning develop structural differences in the GM of the calcarine, the cerebellum, and the thalamus and in the WM of the cerebrum and cerebellum. These changes can appear, depending on the timing of MeHg exposure.


Assuntos
Compostos de Metilmercúrio , Adulto , Humanos , Criança , Adolescente , Estudos de Casos e Controles , Encéfalo/patologia , Substância Cinzenta/patologia , Córtex Cerebral , Imageamento por Ressonância Magnética/métodos
5.
J Phys Chem A ; 126(47): 8844-8850, 2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-36384267

RESUMO

Photodissociation dynamics of 1-chloro-2-iodo-1,1,2-trifluoroethane (CF2ClCHFI) were investigated at 267 nm by a slice imaging technique combined with an oriented molecular beam. The speed and angular distributions of the spin-orbit-selected I atoms were determined by analyzing the images. The anisotropic parameter was 1.67 ± 0.04 for the ground state of I(2P3/2) and 1.94 ± 0.04 for the excited state of I(2P1/2). A vector correlation study between the laser polarization and the dipole moment of the molecule revealed that the transition dipole moment in photoabsorption was found to be at 90° ± 15 to the molecular dipole moment, suggesting the transition dipole moment was nearly parallel to the C-I bond axis. The quantum yield for the excited state obtained from the observed signal intensities was estimated to more than 0.9 at this wavelength. The analysis of the kinetic energy release for both fragments indicated that a large amount of energy was distributed into the internal energy of the CF2ClCHF· radical, which led to the secondary reaction of the C-Cl bond rupture. The study of the ground state of Cl atom formation via photolysis at 235 nm supported the existence of the secondary reaction. The results of the kinetic energy release of the I photofragments and the analysis of the image for the photofragment of the Cl atom suggested that the ground state of I atom formation mainly led to the secondary reaction of the C-Cl bond rupture through the short-lived CF2ClCHF· radical. However, only part of the excited state of I atom formation involved the Cl atom formation through the long-lived CF2ClCHF· radical.

6.
Phys Chem Chem Phys ; 24(10): 5914-5920, 2022 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-35195628

RESUMO

The photodissociation dynamics of isohaloethane (1-bromo-2-chloro-1,1,2-trifluoroethane) at 234 nm was studied by a sliced imaging technique combined with an oriented molecular beam. The speed and angular distributions of the competitive products of spin-orbit selected Br and Cl atoms were determined by analysis of the obtained images. The anisotropic parameter, ß, was found to be 2.0 ± 0.2 for the excited state of Br(2P1/2) (Br*) and 1.2 ± 0.3 for the ground state of Br(2P3/2) (Br). The speed distributions for both Br and Br* exhibited Gaussian-like characteristics. These results indicate that Br atoms were generated by direct formation after excitation through the nσ*(C-Br) potential energy surfaces. In contrast, the angular distributions for the Cl fragments were almost isotropic, while the speed distributions displayed Boltzmann-like characteristics. This suggests that the Cl atoms may form through long-lived parent molecules after photoexcitation. The branching ratio for Br and Cl atom formation was found to be approximately 1.2, that is, Br atom formation occurred preferentially, in contrast to the case of halothane photodissociation reported in our previous work [Che et al., J. Phys. Chem. A, 2020, 124, 5288]. A vector correlation study between the laser polarization axis and the direction of the dipole moment revealed a similar tendency for all photofragments, suggesting that the fragments were formed through a common excited state of isohaloethane. The vector correlation was also studied theoretically for comparison with the experimental results. The angle between the transition dipole moment in photodissociation and the permanent dipole moment was found to be 42 ± 15°. The obtained results indicate that this vector correlation approach combined with an oriented molecular beam is a powerful tool for determining the transition dipole moments in photodissociation.

7.
Environ Res ; 208: 112772, 2022 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-35063428

RESUMO

The developing perinatal brain is vulnerable to methylmercury (MeHg) exposure. The contribution of breast milk to tissue MeHg levels in offspring is a significant public health concern because breast milk contains a certain amount of MeHg. Here, the contribution of MeHg transferred via breast milk to the Hg levels in the tissues of pups (Wistar rats) was investigated. Mated maternal rats were fed a MeHg (2 ppm)-supplemented or a control diet during pregnancy. Following parturition, male neonates from each group were cross-fostered between exposed or control dams, and they were further raised by dams fed a MeHg-supplemented diet or a control diet during lactation. Consequently, we evaluated three pup groups, which were raised by dams exposed to MeHg during pregnancy (P pups), lactation (L pups), or pregnancy and lactation (PL pups). Total mercury (THg) concentrations in the tissues of the offspring were measured at birth (postnatal day 0 [PD0]), during lactation (PD6, PD12, and PD19), and after weaning (PD29 and PD36). Blood and brain THg levels in the P and PL pups declined dramatically during lactation, however, there were no considerable differences between the two groups at PD6 and PD12. In contrast, blood and brain THg levels in the L pups increased slightly during lactation. The increase in the THg levels in the blood and brain of L pups at PD12 were approximately 3.3% and 1.5%, respectively, compared to the corresponding THg levels in the neonates in the P and PL groups. Our results suggest that if the MeHg exposure level during pregnancy is not high enough to cause neuronal development defects in the fetus, the exposure via breast milk is not a significant concern.


Assuntos
Mercúrio , Compostos de Metilmercúrio , Animais , Feminino , Humanos , Lactação/fisiologia , Masculino , Glândulas Mamárias Animais , Mercúrio/toxicidade , Compostos de Metilmercúrio/toxicidade , Leite/química , Parto , Gravidez , Ratos , Ratos Wistar
8.
Acta Vet Scand ; 64(1): 1, 2022 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-35086557

RESUMO

Delphinids are top ocean predators and accumulate high concentrations of mercury (Hg) through the food chain, particularly in organs such as liver and kidney, although the proportion of methylmercury (MeHg) is relatively low due to the demethylation process. Total mercury (T-Hg) levels in marine mammals have been shown to correlate with selenium (Se) concentrations, and ingested MeHg that is demethylated may be present in tissues as mercury selenide (HgSe). In this study, we determined T-Hg, MeHg and Se concentrations of three Indo-Pacific bottlenose dolphins (Tursiops aduncus), and we used the individual with the highest Hg concentration for electron probe microanalysis to assess the co-localization of Hg and Se in the tissues. By electron probe microanalysis, we found that Hg and Se were co-localized in large granules in hepatic Kupffer cells and in small granules in hepatocytes. The analysis suggested that MeHg was demethylated in hepatocytes and then phagocytosed by Kupffer cells. In the kidney, Hg and Se were co-localized in the glomerular capillary wall and in interstitial blood vessel walls. Hg and Se were also co-localized in the cytoplasm of large neurons and in glial cells in the cerebrum. Divalent Hg and HgSe cannot cross the blood-brain barrier, suggesting that MeHg is demethylated in the dolphin brain and that binding to Se suppresses Hg toxicity.


Assuntos
Golfinho Nariz-de-Garrafa , Mercúrio , Compostos de Metilmercúrio , Selênio , Poluentes Químicos da Água , Animais , Mercúrio/análise , Poluentes Químicos da Água/análise
9.
Front Immunol ; 13: 1066830, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36726989

RESUMO

A variety of neuronal surface (NS) antibodies (NS-Ab) have been identified in autoimmune encephalitis (AE). Tissue-based assay (TBA) using a rodent brain immunohistochemistry (IHC) is used to screen NS-Ab, while cell-based assay (CBA) to determine NS antigens. Commercial rat brain IHC is currently available but its clinical relevance remains unclear. Immunostaining patterns of NS antigens have not been extensively studied yet. To address these issues, we assessed a predictive value of "neuropil pattern" and "GFAP pattern" on commercial IHC in 261 patients, and characterized an immunostaining pattern of 7 NS antigens (NMDAR, LGI1, GABAaR, GABAbR, AMPAR, Caspr2, GluK2). Sensitivity and specificity of "neuropil pattern" for predicting NS-Ab were 66.0% (95% CI 55.7-75.3), and 98.2% (95% CI 94.8-99.6), respectively. False-positive rate was 1.8% (3/164) while false-negative rate was 34.0% (33/97). In all 3 false-positive patients, neuropil-like staining was attributed to high titers of GAD65-Ab. In 33 false-negative patients, NMDAR was most frequently identified (n=18 [54.5%], 16/18 [88.9%] had low titers [< 1:32]), followed by GABAaR (n=5). Of 261 patients, 25 (9.6%) had either GFAP (n=21) or GFAP-mimicking pattern (n=4). GFAP-Ab were identified in 21 of 31 patients examined with CBA (20 with GFAP pattern, 1 with GFAP-mimicking pattern). Immunostaining pattern of each NS antigen was as follows: 1) NMDAR revealed homogenous reactivity in the dentate gyrus molecular layer (DG-ML) with less intense dot-like reactivity in the cerebellar granular layer (CB-GL); 2) both GABAaR and GluK2 revealed intense dot-like reactivity in the CB-GL, but GABAaR revealed homogenous reactivity in the DG-ML while GluK2 revealed intense reactivity along the inner layer of the DG-ML; and 3) LGI1, Caspr2, GABAbR, and AMPAR revealed intense reactivity in the cerebellar ML (CB-ML) but LGI1 revealed intense reactivity along the middle layer of the DG-ML. Whereas, Caspr2, GABAbR, and AMPAR revealed similar reactivity in the DG-ML but some difference in other regions. TBA is useful not only for screening NS- or GFAP-Ab but also for estimating NS antigens; however, negative results should be interpreted cautiously because "neuropil pattern" may be missed on commercial IHC when antibody titers are low. Antigen-specific immunoreactivity is a useful biomarker of AE.


Assuntos
Antígenos de Superfície , Doenças Autoimunes do Sistema Nervoso , Ratos , Animais , Imuno-Histoquímica , Receptores de GABA-A , Encéfalo
10.
J Neurol Sci ; 426: 117472, 2021 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-33962325

RESUMO

BACKGROUND: Asymptomatic acute ischemic lesions (AIL) may be coincidentally found on brain magnetic resonance imaging (MRI) obtained during the acute phase of intracerebral hemorrhage, but its clinical significance has yet to be determined. The objective of this study is to determine the frequency of asymptomatic AIL, its characteristic features of brain MRI and risk factors in patients with acute intracerebral hemorrhage. METHODS: We retrospectively reviewed the clinical information of 108 patients with intracerebral hemorrhage who underwent brain MRIs within 30 days of hospitalization between April 2013 and January 2018. We determined the frequency of asymptomatic AIL, its brain MRI features, and risk factors. RESULTS: AIL was found in 26 of 108 patients; symptomatic in 2 and asymptomatic in 24 (22.2%). Asymptomatic AIL were small, multiple, mainly distributed to the white matter in the anterior circulation (22/24, 91.7%), and occasionally seen in deep watershed areas (15/24, 62.5%). Only 2 patients had severe major vessel stenosis. Asymptomatic AIL was associated with high mean blood pressure (BP) on admission (> 145 mmHg), excessive drug-induced reduction in mean BP (≥ 55 mmHg), and large hemorrhage (> 31 mL in volume). CONCLUSIONS: Asymptomatic AIL were found in 22.2% of patients with intracerebral hemorrhage within 30 days of hospitalization. Asymptomatic AIL were often small, multiple and occasionally developed in deep watershed areas despite the absence of major vessel stenosis. High mean BP on admission, excessive drug-induced BP reduction, and larger hemorrhage may be a risk factor for development of asymptomatic AIL.


Assuntos
Hemorragia Cerebral , Imageamento por Ressonância Magnética , Encéfalo/diagnóstico por imagem , Hemorragia Cerebral/diagnóstico por imagem , Hemorragia Cerebral/epidemiologia , Humanos , Estudos Retrospectivos , Fatores de Risco
11.
Dalton Trans ; 50(22): 7843-7853, 2021 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-34008663

RESUMO

The magnetic properties and structural aspects of the 1-D cobalt(ii) complexes, [Co(pyterpy)Cl2]·2H2O (1·2H2O; pyterpy = 4'-(4'''-pyridyl)-2,2':6',2''-terpyridine) and [Co(pyethyterpy)Cl2]·2H2O (2·2H2O; pyethyterpy = 4'-((4'''-pyridyl)ethynyl)-2,2':6',2''-terpyridine) are reported. In each complex the central cobalt(ii) ion displays an octahedral coordination environment composed of three nitrogen donors from the terpyridine moiety, a nitrogen donor from a pyridyl group and two chloride ligands which occupy the axial sites. 1·2H2O exhibits abrupt spin-crossover (SCO) behaviour (T1/2↓ = 218 K; T1/2↑ = 227 K) along with a thermal hysteresis loop, while 2·2H2O and the dehydrated species 1 and 2 exhibit high-spin (HS) states at 2-300 K as well as field-induced single-molecule magnet (SMM) behaviour attributed to the presence of magnetic anisotropic HS cobalt(ii) species (S = 3/2). 1·2H2O exhibited reversible desorption/resorption of its two water molecules, revealing reversible switching between SCO and SMM behaviour triggered by the dehydration/rehydration processes. Single crystal X-ray structural analyses revealed that 1·2H2O crystalizes in the orthorhombic space group Pcca while 2 and 2·2H2O crystallize in the monoclinic space group P2/n. Each of the 1-D chains formed by 1·2H2O in the solid state are bridged by hydrogen bonds between water molecules and chloride groups to form a 2-D layered structure. The water molecules bridging 1-D chains in 1·2H2O interact with the chloride ligands occupying the axial positions, complementing the effect of Jahn-Teller distortion and contributing to the abrupt SCO behaviour and associated stabilization of the LS state.

12.
Dalton Trans ; 50(16): 5428-5432, 2021 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-33908958

RESUMO

Mn(iii) complexes with achiral ligands, (E)-N-(2-((2-aminobenzylidene)amino)-2-methylpropyl)-5-X-2-hydroxybenzamide (HLX, X = H, Cl, Br, and I), crystallise as chiral conglomerates containing amide oxygen-bridged one-dimensional coordination polymers that exhibit weak ferromagnetism. The bulk products exhibit symmetry breaking in that they do not contain equal amounts of enantiomers, though which is the dominant species depends on the substituent X.

13.
Angew Chem Int Ed Engl ; 60(24): 13603-13608, 2021 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-33723910

RESUMO

We demonstrate a fluid-fluid phase separation in 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) membranes using a metal complex lipid of type [Mn(L1)] (1; HL1=1-(2-hydroxybenzamide)-2-(2-hydroxy-3-formyl-5-hexadecyloxybenzylideneamino)ethane). Small amount of 1 produces two separated domains in DMPC, whose phase transition temperatures of lipids (Tc ) are both lower than that of the pristine DMPC. Variable temperature fluorescent microscopy for giant-unilamellar vesicles of DMPC/1 hybrids demonstrates that visible phase separations remain in fluid phases up to 37 °C, which is clearly over the Tc of DMPC. This provides a new dimension for the application of metal complex lipids toward controlling lipid distributions in fluid membranes.

14.
Environ Res ; 196: 110896, 2021 05.
Artigo em Inglês | MEDLINE | ID: mdl-33640495

RESUMO

Fetuses are a high-risk group for methylmercury (MeHg) exposure. The main objective of this study was to compare the characteristic profiles of total mercury (THg), inorganic mercury (IHg), MeHg, and selenium in plasma and red blood cells (RBCs) between maternal and cord blood at parturition collected from a group of Japanese women. Furthermore, correlations of THg in RBCs, which is a biomarker of MeHg, and THg in plasma, which is an IHg exposure biomarker, were examined in maternal and cord blood. Fifty-five pairs of maternal and cord blood samples obtained at parturition were collected from pregnant women in Fukuoka, Japan. THg in RBCs and plasma were significant correlated between maternal and cord blood. THg in RBCs was 13.9 ng/mL for cord and 9.16 ng/mL for maternal blood, with a cord:maternal RBCs ratio for THg of 1.58, suggesting that MeHg is actively transferred from the mother to the fetus via the placenta. THg in plasma showed a positive correlation with THg in RBCs for maternal and cord blood. This result suggests that measuring THg in plasma can overestimate the exposure level to IHg in fish-eating populations. The percentages of IHg in cord plasma and RBCs were 31% and 1.7%, respectively, and those in maternal plasma and RBCs were 46% and 5.9%, respectively. These results suggest that cord blood is rich in MeHg and can easily transfer to the fetal brain. Selenium in cord plasma was 67 ng/mL and that in maternal plasma was 97 ng/mL, with a cord:maternal plasma ratio for Se of 0.69, suggesting that the protective effects of Se against MeHg toxicity in fetuses may be weaker than those expected in adult mothers.


Assuntos
Mercúrio , Compostos de Metilmercúrio , Selênio , Adulto , Animais , Eritrócitos/química , Feminino , Sangue Fetal/química , Humanos , Japão , Mercúrio/análise , Gravidez
15.
Inorg Chem ; 60(3): 1294-1298, 2021 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-33417440

RESUMO

The generation of elastic crystalline fibers from a nonfibrous crystal of metal complex is demonstrated. Applying mechanical stimuli to a platelike crystal of NiII(salophen) [1; H2salophen = N,N'-bis(salicylidene)-o-phenylenediamine] resulted in this complex being transformed into crystal fibers, which could be bent into a loop and demonstrated its high elasticity. Single-crystal X-ray diffraction analyses revealed that the transformation reflects the presence of molecular strands that are composed of a one-dimensional assembly of the slip-stacked arrangement by nearly planar Ni(salophen) molecules. The fiber flexibility was demonstrated to be lost upon the introduction of chloroform solvent molecules into the crystal lattice by recrystallization.

16.
J Appl Toxicol ; 41(6): 928-940, 2021 06.
Artigo em Inglês | MEDLINE | ID: mdl-33015845

RESUMO

We compared the toxicokinetics of methylmercury (MeHg) in KK-Ay type 2 diabetic mice and C57BL/6J mice to evaluate how metabolic changes associated with diabetes affect MeHg toxicokinetics. A single dose of MeHg (0.2, 1, or 5 mg mercury/kg) was administered orally to 12-week-old KK-Ay and C57BL/6J male mice. Total mercury concentrations in plasma, blood cells, whole blood, and tissues (brain, kidneys, liver, and pancreas) were measured after 4, 7, 11, and 14 days. The volume of distribution/bioavailability and the elimination rate constant per day were higher in KK-Ay mice, while the terminal elimination half-life was lower in almost all samples of KK-Ay mice. The area under the curve was lower in all blood and almost all tissue samples from KK-Ay mice. Total clearance/bioavailability was lower in all blood and tissue samples of KK-Ay mice at all MeHg doses. These results indicate that MeHg is more rapidly absorbed by, and eliminated from, the blood cells, brain, liver, kidney, and pancreas of KK-Ay mice under the experimental conditions. Different patterns of tissue-to-plasma and tissue-to-whole blood partition coefficients suggest that notable differences in MeHg transfer between plasma and blood cells affect its distribution in tissues of the two mouse strains. These findings are useful to understand the selective distribution of MeHg to target organs and the sensitivity to MeHg in pathological states.


Assuntos
Compostos de Metilmercúrio/toxicidade , Animais , Glicemia , Encéfalo , Diabetes Mellitus Experimental/metabolismo , Diabetes Mellitus Tipo 2/metabolismo , Insulina , Rim , Fígado , Masculino , Compostos de Metilmercúrio/farmacocinética , Camundongos , Camundongos Endogâmicos C57BL , Pâncreas , Toxicocinética
17.
Inorg Chem ; 59(23): 16843-16852, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-33001645

RESUMO

The development of molecule-based switchable materials remains an important challenge in the field of molecular science. Achievement of a structural phase transition induced by adsorption/desorption of guest molecules in spin crossover (SCO) Co(II) compounds is of significant interest because of the possibility that the spin state of the magnetic anisotropic high-spin (HS, S = 3/2) and low-spin (LS, S = 1/2) states can be switched via the induced changes in associated intermolecular interactions. In this study, we demonstrated a reversible magnetic switching associated with spin state conversion, along with a single-crystal to single-crystal (SCSC) phase transition induced by dehydration/rehydration. [Co(terpy)2](BF4)2·H2O (1·H2O; terpy = 2,2':6',2''-terpyridine) assembles in the solid state via π-π and CH-π interactions involving adjacent terpyridine cores along the ab direction to form two-dimensional (2D) layered domains. 1·H2O exhibits gradual and incomplete SCO, from fully HS to ca. 0.5 HS, and the field-induced single-molecule magnet (SMM) behavior attributed to the presence of the anisotropic partial high-spin Co(II) species. 1·H2O undergoes a SCSC transformation accompanied by a change from the tetragonal space group I41/a to P42/n via a dehydration process. Dehydrated 1 exhibits a reverse thermal hysteresis behavior (T1/2↑ = 287 K; T1/2↓ = 270 K) in the gradual SCO region from fully HS to ca. 0.5 HS, followed by an ordinary thermal hysteresis (T'1/2↑ = 195 K; T'1/2↓ = 155 K) to fully LS Co(II). A temperature-dependent single-crystal X-ray structural analysis revealed that the reverse hysteresis can be attributed to an order/disorder structural phase transition of the BF4- anions involving a symmetry breaking to yield the monoclinic space group P21/n and orbital (angular momentum) transition (LT). Both the SCSC phase transition and magnetic behavior are switchable by dehydration/rehydration processes; thus 1 again adsorbs water at room temperature to give both the original structure and its magnetic behavior.

18.
Chem Commun (Camb) ; 56(72): 10509-10512, 2020 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-32776059

RESUMO

Vapor-induced crystal to crystal transformation between non-polar [Fe(sap)(acac)(sol)] (H2sap = 2-salicylideneaminophenol, acac = acethylacetate, sol = MeOH, pyridine) and polar [Fe(sap)(acac)(DMSO)] was demonstrated. It provides an example of switchable ferroelectric behaviour attributted to the structural phase transition triggered by solvent vapour.

19.
Environ Res ; 188: 109776, 2020 09.
Artigo em Inglês | MEDLINE | ID: mdl-32592939

RESUMO

The developing brain is known to be sensitive to the toxic effects of methylmercury (MeHg). The effects of toxic levels of MeHg exposure during the most seemingly vulnerable window of the cerebrum are not well studied. In this study, we aimed to examine the specific effects of toxic levels of MeHg on neurobehavior, neurodegeneration, and selenoenzyme activity in the cerebrum of infant rats. Male Wistar rats (n = 8/group) were orally treated with MeHg at an acute toxic dose (8 mg Hg/kg/day) for 10 consecutive days starting on postnatal day 14 (P14). The MeHg-exposed rats showed a significant reduction in body weight after day 8 and severe neurological symptoms similar to dystonia on day 12 (P25). Motor coordination deficits determined using the rotarod performance test and short-term memory impairment determined using the Y-maze task were observed in the MeHg-exposed rats on day 11 (P24). The MeHg-exposed rats sacrificed on day 12 showed severe cerebral neuronal degeneration, reactive astrocytosis, and TUNEL-positive apoptotic nuclei, with the cerebral Hg concentration of 15.0 ± 1.6 µg/g. Furthermore, the activities of glutathione peroxidase and thioredoxin reductase in the cerebrum in MeHg-exposed rats were lower than those in control. These results indicate that MeHg exposure to infant rats will be useful to predict the effects of MeHg at the cerebral growth spurt in humans.


Assuntos
Cérebro , Mercúrio , Compostos de Metilmercúrio , Animais , Encéfalo , Masculino , Compostos de Metilmercúrio/toxicidade , Ratos , Ratos Wistar
20.
Chempluschem ; 85(8): 1692-1696, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32558396

RESUMO

The formation of plastic or brittle organic crystals of salen derivatives that depend on the solvents employed for crystallization is demonstrated. Large yellow crystals (ranging from mm to cm size) of ten different salen derivatives were obtained and investigated. Among them, (bis(2-hydroxyacetophenone)ethylenediimine) 2, which was recrystallized from dichloromethane, tetrahydrofuran or chloroform, exhibited plastic deformation behaviour when mechanical force was applied to the (001) face. In contrast, when 2 was recrystallized from benzene, brittle crystals were obtained. Face indexing confirmed that different crystal faces were obtained by depending on the solvent employed for recrystallization, which leads to either flexible (plastic) or brittle crystals. Photoluminescence with a band maximum at 510 nm and thermochromism related to tautomerism between OH and NH forms were also investigated, and indicate that 2 is a flexible organic single-crystal material with multifunctional properties.

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