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1.
CNS Neurol Disord Drug Targets ; 23(3): 402-410, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-36797610

RESUMO

BACKGROUND: Postsynaptic density (PSD) is an electron-dense structure that contains various scaffolding and signaling proteins. Shank1 is a master regulator of the synaptic scaffold located at glutamatergic synapses, and has been proposed to be involved in multiple neurological disorders. METHODS: In this study, we investigated the role of shank1 in an in vitro Parkinson's disease (PD) model mimicked by 6-OHDA treatment in neuronal SN4741 cells. The expression of related molecules was detected by western blot and immunostaining. RESULTS: We found that 6-OHDA significantly increased the mRNA and protein levels of shank1 in SN4741 cells, but the subcellular distribution was not altered. Knockdown of shank1 via small interfering RNA (siRNA) protected against 6-OHDA treatment, as evidenced by reduced lactate dehydrogenase (LDH) release and decreased apoptosis. The results of RT-PCR and western blot showed that knockdown of shank1 markedly inhibited the activation of endoplasmic reticulum (ER) stress associated factors after 6-OHDA exposure. In addition, the downregulation of shank1 obviously increased the expression of PRDX3, which was accompanied by the preservation of mitochondrial function. Mechanically, downregulation of PRDX3 via siRNA partially prevented the shank1 knockdowninduced protection against 6-OHDA in SN4741 cells. CONCLUSION: In summary, the present study has provided the first evidence that the knockdown of shank1 protects against 6-OHDA-induced ER stress and mitochondrial dysfunction through activating the PRDX3 pathway.


Assuntos
Doença de Parkinson , Humanos , Oxidopamina/toxicidade , Apoptose , Proteínas , RNA Interferente Pequeno/metabolismo , Peroxirredoxina III
2.
Brain Res Bull ; 203: 110780, 2023 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-37820952

RESUMO

Aneurysmal subarachnoid hemorrhage (aSAH) accounts for only 5 % of all stroke cases, but carries a heavy burden of morbidity and mortality. Activity regulated cytoskeleton associated protein (Arc) is an immediate early gene (IEG)-coded postsynaptic protein that is involved in synaptic plasticity. Increasing evidence and our previous studies have shown that Arc might be involved in the pathological mechanism of various neurological diseases, such as traumatic brain injury (TBI). In this study, we investigated the level of Arc in cerebrospinal fluids (CSF) of aSAH patients and its potential role in brain damage following experimental SAH model. We found that the levels of Arc in aSAH patients' CSF positively correlated with Hunt-Hess (H&H) grades. Knockdown of endogenous Arc expression by small interfere RNA (siRNA) significantly increased brain edema and oxidative stress following SAH. The results of immunostaining in brain sections showed that knockdown of Arc enhanced activation of microglia and astrocytes. In congruent, generation of inflammatory cytokines following SAH was increased by Si-Arc transfection. The results of western blot analysis showed that knockdown of Arc inhibited the expression of Sirt1 and Nrf2, which was accompanied by decreased enzymatic activities of superoxide dismutase (SOD) and glutathione peroxidase (GSH-px). In addition, activation of sirtuin 1 (Sirt1) via agonist SRT2104 markedly decreased the brain damage and neuroinflammation induced by Arc knockdown. In conclusion, knockdown of endogenous Arc could aggravate brain damage and neuroinflammation following experimental SAH, and Arc levels in aSAH patients' CSF might be a potential indicator of brain damage and prognosis.


Assuntos
Lesões Encefálicas , Hemorragia Subaracnóidea , Ratos , Animais , Humanos , Hemorragia Subaracnóidea/metabolismo , Sirtuína 1/metabolismo , Ratos Sprague-Dawley , Doenças Neuroinflamatórias , Encéfalo/metabolismo , Lesões Encefálicas/metabolismo
3.
Health Inf Sci Syst ; 11(1): 23, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37151917

RESUMO

Background: Prognostic models of glioma have been the focus of many studies. However, most of them are based on Western populations. Additionally, because of the complexity of healthcare data in China, it is important to select a suitable model based on existing clinical data. This study aimed to develop and independently validate a nomogram for predicting the overall survival (OS) with newly diagnosed grade II/III astrocytoma after surgery. Methods: Data of 472 patients with astrocytoma (grades II-III) were collected from Qilu Hospital as training cohort while data of 250 participants from Linyi People's Hospital were collected as validation cohort. Cox proportional hazards model was used to construct the nomogram and individually predicted 1-, 3-, and 5-year survival probabilities. Calibration ability, and discrimination ability were analyzed in both training and validation cohort. Results: Overall survival was negatively associated with histopathology, age, subtotal resection, multiple tumors, lower KPS and midline tumors. Internal validation and external validation showed good discrimination (The C-index for 1-, 3-, and 5-year survival were 0.791, 0.748, 0.733 in internal validation and 0.754, 0.735, 0.730 in external validation, respectively). The calibration curves showed good agreement between the predicted and actual 1-, 3-, and 5-year OS rates. Conclusion: This is the first nomogram study that integrates common clinicopathological factors to provide an individual probabilistic prognosis prediction for Chinese Han patients with astrocytoma (grades II-III). This model can serve as an easy-to-use tool to advise patients and establish optimized surveillance approaches after surgery. Supplementary Information: The online version contains supplementary material available at 10.1007/s13755-023-00223-0.

4.
Acta Cir Bras ; 36(10): e361002, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34817023

RESUMO

PURPOSE: Spontaneous intracerebral hemorrhage (ICH) is a major cause of death and disability with a huge economic burden worldwide. Cerebrolysin (CBL) has been previously used as a nootropic drug. Necroptosis is a programmed cell death mechanism that plays a vital role in neuronal cell death after ICH. However, the precise role of necroptosis in CBL neuroprotection following ICH has not been confirmed. METHODS: In the present study, we aimed to investigate the neuroprotective effects and potential molecular mechanisms of CBL in ICH-induced early brain injury (EBI) by regulating neural necroptosis in the C57BL/6 mice model. Mortality, neurological score, brain water content, and neuronal death were evaluated by terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) staining, Evans blue extravasation, Western blotting, and quantitative real-time polymerase chain reaction (PCR). RESULTS: The results show that CBL treatment markedly increased the survival rate, neurological score, and neuron survival, and downregulated the protein expression of RIP1 and RIP3, which indicated that CBL-mediated inhibition of necroptosis, and ameliorated neuronal death after ICH. The neuroprotective capacity of CBL is partly dependent on the Akt/GSK3ß signaling pathway. CONCLUSIONS: CBL improves neurological outcomes in mice and reduces neuronal death by protecting against neural necroptosis.


Assuntos
Necroptose , Fármacos Neuroprotetores , Aminoácidos , Animais , Apoptose , Hemorragia Cerebral/tratamento farmacológico , Glicogênio Sintase Quinase 3 beta/farmacologia , Camundongos , Camundongos Endogâmicos C57BL , Neurônios/metabolismo , Neuroproteção , Fármacos Neuroprotetores/farmacologia , Proteínas Proto-Oncogênicas c-akt/metabolismo , Transdução de Sinais
5.
Aging (Albany NY) ; 13(2): 3101-3111, 2021 01 21.
Artigo em Inglês | MEDLINE | ID: mdl-33479186

RESUMO

Subarachnoid hemorrhage (SAH) is a life-threatening cerebrovascular disease, and most of the SAH patients experience sleep deprivation during their hospital stay. It is well-known that sleep deprivation is one of the key components of developing several neurological disorders, but its effect on brain damage after SAH has not been determined. Therefore, this study was designed to evaluate the effect of sleep deprivation using an experimental SAH model in rats. Induction of sleep deprivation for 24 h aggravated the SAH-induced brain damage, as evidenced by brain edema, neuronal apoptosis and activation of caspase-3. Sleep deprivation also worsened the neurological impairment and cognitive deficits after SAH. The results of immunostaining and western blot showed that sleep deprivation increased the activation of microglial cells. In addition, sleep deprivation differently regulated the expression of anti-inflammatory and pro-inflammatory cytokines. The results of immunofluorescence staining and western blot showed that sleep deprivation markedly increased the activation of Toll-like receptor 4 (TLR4) and myeloid differentiation primary response protein 88 (MyD88). Mechanically, treatment with the TLR4 inhibitor TAK-242 or the MyD88 inhibitor ST2825 significantly attenuated the brain damage and neuroinflammation induced by sleep deprivation after SAH. In conclusion, our results indicate that sleep deprivation aggravates brain damage and neurological dysfunction following experimental SAH in rats. These effects were mediated by the activation of the TLR4-MyD88 cascades and regulation of neuroinflammation.


Assuntos
Encéfalo/patologia , Fator 88 de Diferenciação Mieloide/metabolismo , Transdução de Sinais/fisiologia , Privação do Sono/complicações , Hemorragia Subaracnóidea/complicações , Receptor 4 Toll-Like/metabolismo , Animais , Apoptose/fisiologia , Encéfalo/metabolismo , Inflamação/metabolismo , Inflamação/patologia , Masculino , Microglia/metabolismo , Microglia/patologia , Ratos , Ratos Sprague-Dawley , Privação do Sono/metabolismo , Privação do Sono/patologia , Hemorragia Subaracnóidea/metabolismo , Hemorragia Subaracnóidea/patologia
6.
Acta cir. bras ; 36(10): e361002, 2021. graf
Artigo em Inglês | LILACS, VETINDEX | ID: biblio-1349867

RESUMO

ABSTRACT Purpose: Spontaneous intracerebral hemorrhage (ICH) is a major cause of death and disability with a huge economic burden worldwide. Cerebrolysin (CBL) has been previously used as a nootropic drug. Necroptosis is a programmed cell death mechanism that plays a vital role in neuronal cell death after ICH. However, the precise role of necroptosis in CBL neuroprotection following ICH has not been confirmed. Methods: In the present study, we aimed to investigate the neuroprotective effects and potential molecular mechanisms of CBL in ICH-induced early brain injury (EBI) by regulating neural necroptosis in the C57BL/6 mice model. Mortality, neurological score, brain water content, and neuronal death were evaluated by terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) staining, Evans blue extravasation, Western blotting, and quantitative real-time polymerase chain reaction (PCR). Results: The results show that CBL treatment markedly increased the survival rate, neurological score, and neuron survival, and downregulated the protein expression of RIP1 and RIP3, which indicated that CBL-mediated inhibition of necroptosis, and ameliorated neuronal death after ICH. The neuroprotective capacity of CBL is partly dependent on the Akt/GSK3β signaling pathway. Conclusions: CBL improves neurological outcomes in mice and reduces neuronal death by protecting against neural necroptosis.


Assuntos
Animais , Camundongos , Fármacos Neuroprotetores/farmacologia , Necroptose , Transdução de Sinais , Hemorragia Cerebral/tratamento farmacológico , Apoptose , Proteínas Proto-Oncogênicas c-akt/metabolismo , Neuroproteção , Glicogênio Sintase Quinase 3 beta/farmacologia , Aminoácidos , Camundongos Endogâmicos C57BL , Neurônios/metabolismo
7.
Ann Palliat Med ; 9(5): 3643-3650, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-33065803

RESUMO

Intracranial inflammatory granuloma is a common intracranial occupying lesion. Common postoperative complications include intracranial edema, intracranial infection, hydrocephalus, epilepsy, and cerebrospinal fluid leakage. This report aims to summarize the nursing care of a patient with right frontoparietal inflammatory granuloma complicated with acute pulmonary embolism (APE). Acute pulmonary embolism is a clinical syndrome in which endogenous or exogenous emboli block the main trunk or branches of the pulmonary artery, resulting in disorders of pulmonary and respiratory circulation that seriously threatening the lives of patients. The occurrence and report of pulmonary embolism caused by intracranial inflammatory granuloma are rare. The patient had rapid onset, atypical clinical manifestations, and was in critical condition. Pulmonary embolism can easily lead to death. Nursing care after rapid thrombolysis included observation of coagulation function, prevention of complication, control of infection, improvement of intestinal dysfunction, maintenance and monitoring of sedation, prevention and observation of epilepsy, and prevention of the recurrence of embolism. After early intervention, active treatment and meticulous care, the patient's condition improved, mechanical ventilation was successfully withdrawn, and the patient was ultimately discharged and walked out on his own.


Assuntos
Embolia Pulmonar , Doença Aguda , Granuloma , Humanos
8.
Mol Med Rep ; 22(4): 3103-3110, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32945444

RESUMO

Cerebral ischemia results in severe brain damage, and is a leading cause of death and long-term disability. Previous studies have investigated methods to activate astrocytes in order to promote repair in injured brain tissue and inhibit cell death. It has previously been shown that N-myc downstream-regulated gene 2 (NDRG2) was highly expressed in astrocytes and associated with cell activity, but the underlying mechanism is largely unknown. The present study generated NDRG2 conditional knockout (Ndrg2-/-) mice to investigate whether NDRG2 can block ischemia-induced astrocyte necroptosis by suppressing receptor interacting protein kinase 1 (RIPK1) expression. This study investigated astrocyte activity in cerebral ischemia, and identified that ischemic brain injuries could trigger RIP-dependent astrocyte necroptosis. The depletion of NDRG2 was found to accelerate permanent middle cerebral artery occlusion-induced necroptosis in the brain tissue of Ndrg2-/- mice, indicating that NDRG2 may act as a neuroprotector during cerebral ischemic injury. The present study suggested that NDRG2 attenuated astrocytic cell death via the suppression of RIPK1. The pharmacological inhibition of astrocyte necroptosis by necrostatin-1 provided neuroprotection against ischemic brain injuries after NDRG2 knockdown. Therefore, NDRG2 could be considered as a potential target for the treatment of cerebral ischemia.


Assuntos
Proteínas Adaptadoras de Transdução de Sinal/genética , Astrócitos/citologia , Isquemia Encefálica/genética , Proteína Serina-Treonina Quinases de Interação com Receptores/metabolismo , Animais , Astrócitos/efeitos dos fármacos , Astrócitos/metabolismo , Isquemia Encefálica/etiologia , Regulação da Expressão Gênica/efeitos dos fármacos , Técnicas de Inativação de Genes , Imidazóis/farmacologia , Indóis/farmacologia , Masculino , Camundongos , Necroptose/efeitos dos fármacos , Cultura Primária de Células
9.
BMC Med Res Methodol ; 20(1): 195, 2020 07 22.
Artigo em Inglês | MEDLINE | ID: mdl-32698801

RESUMO

BACKGROUND: Controlling unobserved confounding still remains a great challenge in observational studies, and a series of strict assumptions of the existing methods usually may be violated in practice. Therefore, it is urgent to put forward a novel method. METHODS: We are interested in the causal effect of an exposure on the outcome, which is always confounded by unobserved confounding. We show that, the causal effect of an exposure on a continuous or categorical outcome is nonparametrically identified through only two independent or correlated available confounders satisfying a non-linear condition on the exposure. Asymptotic theory and variance estimators are developed for each case. We also discuss an extension for more than two binary confounders. RESULTS: The simulations show better estimation performance by our approach in contrast to the traditional regression approach adjusting for observed confounders. A real application is separately applied to assess the effects of Body Mass Index (BMI) on Systolic Blood Pressure (SBP), Diastolic Blood Pressure (DBP), Fasting Blood Glucose (FBG), Triglyceride (TG), Total Cholesterol (TC), High Density Lipoprotein (HDL) and Low Density Lipoprotein (LDL) with individuals in Shandong Province, China. Our results suggest that SBP increased 1.60 (95% CI: 0.99-2.93) mmol/L with per 1- kg/m2 higher BMI and DBP increased 0.37 (95% CI: 0.03-0.76) mmol/L with per 1- kg/m2 higher BMI. Moreover, 1- kg/m2 increase in BMI was causally associated with a 1.61 (95% CI: 0.96-2.97) mmol/L increase in TC, a 1.66 (95% CI: 0.91-55.30) mmol/L increase in TG and a 2.01 (95% CI: 1.09-4.31) mmol/L increase in LDL. However, BMI was not causally associated with HDL with effect value - 0.20 (95% CI: - 1.71-1.44). And, the effect value of FBG per 1- kg/m2 higher BMI was 0.56 (95% CI: - 0.24-2.18). CONCLUSIONS: We propose a novel method to control unobserved confounders through double binary confounders satisfying a non-linear condition on the exposure which is easy to access.


Assuntos
Modelos Estatísticos , Triglicerídeos , Pressão Sanguínea , Índice de Massa Corporal , China , HDL-Colesterol , Interpretação Estatística de Dados , Humanos , Estudos Observacionais como Assunto
10.
ACS Appl Mater Interfaces ; 9(23): 20169-20178, 2017 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-28530799

RESUMO

The interfacial adhesion design between "mortar" and "bricks" is essential for mechanical and barrier performance of nanocellulose-based nacre-mimetic nanocomposites, especially at high moisture conditions. To address this fundamental challenge, dopamine (DA) has been conjugated to cellulose nanofibrils (CNFs) and subsequently assembled with montmorillonite (MTM) to generate layered nanocomposite films inspired by the strong adhesion of mussel adhesive proteins to inorganic surfaces under water. The selective formation of catechol/metal ion chelation and hydrogen bonding at the interface between MTM platelets and CNFs bearing DA renders transparent films with strong mechanical properties, particularly at high humidity and in wet state. Increasing the amount of conjugated DA on CNFs results in nanocomposites with increased tensile strength and modulus, up to 57.4 MPa and 1.1 GPa, respectively, after the films are swollen in water. The nanocomposites also show excellent gas barrier properties at high relative humidity (95%), complementing the multifunctional property profile.

11.
Chemistry ; 21(35): 12414-20, 2015 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-26179865

RESUMO

Heterogeneous dirhodium(II) catalysts based on environmentally benign and biocompatible cellulose nanocrystals (CNC-Rh2) as support material were obtained by ligand exchange between carboxyl groups on the CNC surface and Rh2(OOCCF3)4, as was confirmed by solid-state (19)F and (13)C NMR spectroscopy. On average, two CF3COO(-) groups are replaced during ligand exchange, which is consistent with quantitative analysis by a combination of (19)F NMR spectroscopy and thermogravimetry. CNC-Rh2 catalysts performed well in a model cyclopropanation reaction, in spite of the low dirhodium(II) content on the CNC surface (0.23 mmol g(-1)). The immobilization through covalent bonding combined with the separate locations of binding positions and active sites of CNC-Rh2 guarantees a high stability against leaching and allows the recovery and reuse of the catalyst during the cyclopropanation reaction.


Assuntos
Celulose/química , Ciclopropanos/química , Ciclopropanos/síntese química , Nanopartículas/química , Espectroscopia de Ressonância Magnética , Técnicas de Síntese em Fase Sólida
12.
Chemistry ; 21(9): 3798-805, 2015 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-25620003

RESUMO

A novel heterogeneous dirhodium catalyst has been synthesized. This stable catalyst is constructed from dirhodium acetate dimer (Rh2(OAc)4) units, which are covalently linked to amine- and carboxyl-bifunctionalized mesoporous silica (SBA-15-NH2-COOH). It shows good efficiency in catalyzing the cyclopropanation reaction of styrene and ethyl diazoacetate (EDA) forming cis- and trans-1-ethoxycarbonyl-2-phenylcyclopropane. To characterize the structure of this catalyst and to confirm the successful immobilization, heteronuclear solid-state NMR experiments have been performed. The high application potential of dynamic nuclear polarization (DNP) NMR for the analysis of binding sites in this novel catalyst is demonstrated. Signal-enhanced (13)C CP MAS and (15)N CP MAS techniques have been employed to detect different carboxyl and amine binding sites in natural abundance on a fast time scale. The interpretation of the experimental chemical shift values for different binding sites has been corroborated by quantum chemical calculations on dirhodium model complexes.

13.
Phys Chem Chem Phys ; 16(47): 26322-9, 2014 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-25367781

RESUMO

Multi-stimuli responsive materials based on cellulose nanocrystals (CNCs), especially using non-conventional stimuli including light, still need more explorations, to fulfill the requirements of complicated application environments. The structure determination of functional groups on the CNC surface constitutes a significant challenge, partially due to their low amounts. In this study, rhodamine spiroamide groups are immobilized onto the surface of CNCs leading to a hybrid compound being responsive to pH-values, heat and UV light. After the treatment with external stimuli, the fluorescent and correlated optical color change can be induced, which refers to a ring opening and closing process. Amine and amide groups in rhodamine spiroamide play the critical role in this switching process. Solid-state NMR spectroscopy coupled with sensitivity-enhanced dynamic nuclear polarization (DNP) was used to measure (13)C and (15)N in natural abundance, allowing the determination of structural changes during the switching process. It is shown that a temporary bond through an electrostatic interaction could be formed within the confined environment on the CNC surface during the heat treatment. The carboxyl groups on the CNC surface play a pivotal role in stabilizing the open status of rhodamine spiroamide groups.

14.
Nanoscale ; 6(22): 13678-89, 2014 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-25278173

RESUMO

A novel single-source precursor was synthesized by the reaction of an allyl hydrido polycarbosilane (SMP10) and tetrakis(dimethylamido)hafnium(iv) (TDMAH) for the purpose of preparing dense monolithic SiC/HfC(x)N(1-x)-based ultrahigh temperature ceramic nanocomposites. The materials obtained at different stages of the synthesis process were characterized via Fourier transform infrared (FT-IR) as well as nuclear magnetic resonance (NMR) spectroscopy. The polymer-to-ceramic transformation was investigated by means of MAS NMR and FT-IR spectroscopy as well as thermogravimetric analysis (TGA) coupled with in situ mass spectrometry. Moreover, the microstructural evolution of the synthesized SiHfCN-based ceramics annealed at different temperatures ranging from 1300 °C to 1800 °C was characterized by elemental analysis, X-ray diffraction, Raman spectroscopy and transmission electron microscopy (TEM). Based on its high temperature behavior, the amorphous SiHfCN-based ceramic powder was used to prepare monolithic SiC/HfC(x)N(1-x)-based nanocomposites using the spark plasma sintering (SPS) technique. The results showed that dense monolithic SiC/HfC(x)N(1-x)-based nanocomposites with low open porosity (0.74 vol%) can be prepared successfully from single-source precursors. The average grain size of both HfC0.83N0.17 and SiC phases was found to be less than 100 nm after SPS processing owing to a unique microstructure: HfC0.83N0.17 grains were embedded homogeneously in a ß-SiC matrix and encapsulated by in situ formed carbon layers which acted as a diffusion barrier to suppress grain growth. The segregated Hf-carbonitride grains significantly influenced the electrical conductivity of the SPS processed monolithic samples. While Hf-free polymer-derived SiC showed an electrical conductivity of ca. 1.8 S cm(-1), the electrical conductivity of the Hf-containing material was analyzed to be ca. 136.2 S cm(-1).

15.
Inorg Chem ; 53(19): 10443-55, 2014 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-25231931

RESUMO

Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300-1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.

16.
Artigo em Inglês | MEDLINE | ID: mdl-24761936

RESUMO

A reliable and selective method was developed for the determination of bisphenol A (BPA) in drinks and fruit using dummy surface molecularly imprinted polymer (DSMIP) as a solid-phase extraction (SPE)-enrichment and separation sorbent coupled with high-performance liquid chromatography (HPLC). Tetrabromobisphenol A (TBBPA), whose structure is similar to BPA, was selected as a dummy template molecule. DSMIP has a higher selectivity for BPA than surface non-imprinted polymer (SNIP) when used as sorbents for SPE. Potential factors affecting the extraction efficiency, including conditioning, sample loading, washing and elution, and the breakthrough volume were optimised. Under the optimum experimental conditions, the recoveries of BPA in drinks and fruit were in the range from 98% to 105% with relative standard deviations (RSDs) below 7%, and a limit of detection (LOD) of 3 ng ml(-1). The developed extraction protocol eliminated the effect of template leakage on quantitative analysis and could be applied to the trace determination of BPA in complicated functional samples.


Assuntos
Compostos Benzidrílicos/análise , Compostos Benzidrílicos/toxicidade , Contaminação de Alimentos/análise , Fenóis/análise , Fenóis/toxicidade , Extração em Fase Sólida/métodos , Bebidas/análise , Bebidas/toxicidade , Cromatografia Líquida de Alta Pressão , Frutas/química , Frutas/toxicidade , Humanos , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Impressão Molecular , Nanosferas/química , Nanosferas/ultraestrutura , Bifenil Polibromatos/análise , Polímeros/química , Dióxido de Silício
17.
Phys Chem Chem Phys ; 16(20): 9327-36, 2014 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-24715202

RESUMO

Mesoporous carbon materials were synthesized employing polymers and silica gels as structure directing templates. The basic physico-chemical properties of the synthetic mesoporous materials were characterized by (1)H and (13)C MAS solid-state NMR, X-ray diffraction, transmission electron microscopy (TEM) and nitrogen adsorption measurements. The confinement effects on small guest molecules such as water, benzene and pyridine and their interactions with the pore surface were probed by a combination of variable temperature (1)H-MAS NMR and quantum chemical calculations of the magnetic shielding effect of the surface on the solvent molecules. The interactions of the guest molecules depend strongly on the carbonization temperature and the pathway of the synthesis. All the guest-molecules, water, benzene and pyridine, exhibited high-field shifts by the interaction with the surface of carbon materials. The geometric confinement imposed by the surface causes a strong depression of the melting point of the surface phase of water and benzene. The theoretical calculation of (1)H NICS maps shows that the observed proton chemical shifts towards high-field values can be explained as the result of electronic ring currents localized in aromatic groups on the surface. The dependence on the distance between the proton and the aromatic surface can be exploited to estimate the average diameter of the confinement structures.

18.
Talanta ; 117: 281-7, 2013 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-24209342

RESUMO

In this paper, a highly selective sample cleanup procedure combing dummy molecular imprinting and solid-phase extraction (DMIP-SPE) was developed for the isolation and determination of bisphenol A (BPA) in tap water. The novel hollow porous dummy molecularly imprinted polymer (HPDMIP) was prepared adopting a sacrificial support approach, using tetrabromobisphenol A (TBBPA), whose structure was similar to that of BPA, as the dummy template and mesoporous MCM-48 nanospheres as the support. Owing to a very short distance between the binding sites and the surface, a large surface area and a good steric structure to match its imprint molecules, the maximum adsorption capacities (Qmax) of the dummy-imprinted and non-imprinted sorbents for BPA were as high as 445 and 340 µmol g(-1), respectively, and the adsorption reached about 73% of Qmax in 10 min. Meanwhile, a method was developed for the determination of BPA using HPDMIP as a solid-phase extraction enrichment sorbent coupled with HPLC. Under the optimum experimental conditions, HPDMIP exhibited satisfactory results in the enrichment and determination of BPA in tap water with a recovery rate of 95-105%, and relative standard deviations of below 6%, and it can achieve a limit of detection as low as 3 ng mL(-1). The developed extraction protocol eliminated the effect of template leakage on quantitative analysis and could be applied for the determination of BPA in complicated functional samples.


Assuntos
Compostos Benzidrílicos/análise , Água Potável/química , Impressão Molecular/métodos , Fenóis/análise , Bifenil Polibromatos/química , Poluentes Químicos da Água/análise , Adsorção , Cromatografia Líquida de Alta Pressão , Humanos , Limite de Detecção , Metacrilatos/química , Porosidade , Dióxido de Silício/química , Extração em Fase Sólida/métodos
19.
Solid State Nucl Magn Reson ; 55-56: 1-11, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23972428

RESUMO

In recent years, solid-state NMR spectroscopy has evolved into an important characterization tool for the study of solid catalysts and chemical processes on their surface. This interest is mainly triggered by the need of environmentally benign organic transformations ("green chemistry"), which has resulted in a large number of new catalytically active hybrid materials, which are organized on the meso- and nanoscale. Typical examples of these catalysts are supported homogeneous transition metal catalysts or transition metal nanoparticles (MNPs). Solid-state NMR spectroscopy is able to characterize both the structures of these materials and the chemical processes on the catalytic surface. This article presents recent trends both on the characterization of immobilized homogeneous transition metal catalysts and on the characterization of surface species on transition metal surfaces.

20.
Solid State Nucl Magn Reson ; 40(2): 88-90, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21855300

RESUMO

It is shown that the para-hydrogen induced polarization (PHIP) phenomenon in homogenous solution containing the substrate styrene is also observable employing simple inorganic systems of the form MCl(3)·xH(2)O (M=Rh, Ir) as catalyst. Such observation confirms that already very simple metal complexes enable the creation of PHIP signal enhancement in solution. This opens up new pathways to increase the sensitivity of NMR and MRT by PHIP enhancement using cost-effective catalysts and will be essential for further mechanistic studies of simple transition metal systems.


Assuntos
Hidrogênio/química , Irídio/química , Espectroscopia de Ressonância Magnética/métodos , Ródio/química , Derivados de Benzeno/química , Catálise , Solventes/química , Estireno/química , Temperatura
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