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BACKGROUND: On June 30, 2021, China received certification from the World Health Organization for malaria elimination. However, this certification does not signify the absence of malaria within China. Due to the increasing frequency of international exchanges and collaborations, the threat of imported malaria persists in China. Consequently, the prevention and control of imported malaria have become a primary focus for our country to maintain its malaria elimination status. CASE SUMMARY: Herein, we present a case report of a 53-year-old Chinese man who worked in Africa for nearly two years. He was diagnosed with malaria in the Democratic Republic of the Congo between November 19 and November 23, 2022. After receiving effective treatment with oral antimalarial drugs, his condition improved, allowing him to return to China. He was later admitted to our hospital on January 12, 2023, during the coronavirus disease 2019 pandemic in Huangshi, China. Through a thorough evaluation of the patient's symptoms, clinical signs, imaging and laboratory test results, and epidemiological data, he was rapidly diagnosed with severe cerebral malaria. The patient underwent successful treatment through a series of intensive care unit interventions. CONCLUSION: The successful treatment of this imported case of severe cerebral malaria provides a valuable reference for managing patients with similar malaria infections and has significant clinical implications.
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Zn-I2 flow batteries, with a standard voltage of 1.29 V based on the redox potential gap between the Zn2+-negolyte (-0.76 vs. SHE) and I2-posolyte (0.53 vs. SHE), are gaining attention for their safety, sustainability, and environmental-friendliness. However, the significant growth of Zn dendrites and the formation of dead Zn generally prevent them from being cycled at high current density (>80 mA cm-2). In addition, the crossover of Zn2+ across cation-exchange-membrane also limits their cycle stability. Herein, we propose a chelated Zn(P2O7)26- (donated as Zn(PPi)26-) negolyte, which facilitates dendrite-free Zn plating and effectively prevents Zn2+ crossover. Remarkably, the utilization of chelated Zn(PPi)26- as a negolyte shifts the Zn2+/Zn plating/stripping potential to -1.08 V (vs. SHE), increasing cell voltage to 1.61 V. Such high voltage Zn-I2 flow battery shows a promising stability over 250 cycles at a high current density of 200 mA cm-2, and a high power density up to 606.5 mW cm-2.
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OBJECTIVES: The objective of this study was to assess the effect of repetitive transcranial magnetic stimulation (rTMS) on the supplementary motor area (SMA) in motor function in Parkinson's disease (PD) patients. METHOD: Databases searched included 5 databases from October 7,2022 to January 4, 2023. The Cochrane Bias Risk Assessment Tool was used for quality assessment. Standardized mean differences (SMDs) were calculated using a random-effects model. Outcome measure is the motor function examination of the motor part of Unified Parkinson's Disease Rating Scale (UPDRS-III). RESULTS: Seven studies totaling 374 patients were included. Meta-analysis showed that stimulation of SMA significantly improved motor function in PD patients compared with sham stimulation (SMD = -1.24; 95% CI, -2.24 to -0.24; P = 0.02; I 2 = 93%). Stimulation of the same target (SMA), subgroup analysis showed that high-frequency rTMS (HF-rTMS) is more effective than low-frequency rTMS (LF-rTMS) in improving motor function in PD (SMD = -1.39; 95% CI, -2.21 to -0.57; P = 0.04; I 2 = 77.2%). CONCLUSIONS: Overall, rTMS over SMA had a statistically significant improvement in motor function in PD patients, and HF-rTMS is statistically significantly more effective than LF-rTMS.
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Metal-organic frameworks (MOFs) are considered as a promising candidate for advancing energy storage owing to their intrinsic multi-channel architecture, high theoretical capacity, and precise adjustability. However, the low conductivity and poor structural stability lead to unsatisfactory rate and cycling performance, greatly hindering their practical application. Herein, we propose a sea urchin-like Co-ZIF-L superstructure using molecular template to induce self-assembly followed by ion exchange method, which shows improved conductivity, successive channels, and high stability. The ion exchange can gradually etch the superstructure, leading to the reconstruction of Co-ZIF-L with three-dimensional (3D) cross-linked ultrathin porous nanosheets. Moreover, the precise control of Co to Ni ratios can construct effective micro-electric field and synergistically enhance the rapid transfer of electrons and electrolyte ions, improving the conductivity and stability of CoNi-ZIF-L. The Co6.53Ni-ZIF-L electrode exhibits a high specific capacity (602â F g-1 at 1â A g-1) and long cycling stability (95.3 % retention after 4,000 cycles at 5â A g-1). The Co6.53Ni-ZIF-L//AC asymmetric flexible supercapacitor employing gel electrolyte also exhibits excellent cycling stability (93.3 % retention after 4000 cycles at 5â A g-1). This discovery provides valuable insights for electrode material selection and energy storage efficiency improvement.
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BACKGROUND: Recently, a growing number of adolescents have been afflicted with mental disorders, with annual morbidity rates on the rise. This trend has been exacerbated by the global coronavirus disease 2019 (COVID-19) pandemic, leading to a surge in suicide and self-harm rates among this demographic. AIM: To investigate the impact of the COVID-19 pandemic on adolescent bipolar disorder (BD), along with the underlying factors contributing to heightened rates of suicide and self-harm among adolescents. METHODS: A comprehensive statistical analysis was conducted utilizing clinical interviews and self-reports obtained from patients or their guardians. Diagnostic criteria for BDs were based on the Diagnostic and statistical manual of mental disorders, international classification of diseases-11, and the National institute of mental health research domain criteria. Statistical analyses were performed using SPSS 26.0 software, with significance set at P < 0.05. RESULTS: A cohort of 171 adolescents diagnosed with BD between January 1, 2018, and December 31, 2022, was included in the analysis. The gender distribution was 2.8:1 (female to male), with ages ranging from 11 to 18 years old. Major factors contributing to adolescent BDs included familial influences, academic stress, genetic predisposition and exposure to school-related violence. Notably, a significant increase in suicide attempts and self-harm incidents was observed among adolescents with BD during the COVID-19 pandemic. Statistical analysis indicated that the pandemic exacerbated familial discord and heightened academic stress, thereby amplifying the prevalence of suicidal behavior and self-harm among adolescents. CONCLUSION: The COVID-19 pandemic has exacerbated familial tensions and intensified the incidence of suicide and self-harm among adolescents diagnosed with BD. This study underscores the urgent need for societal, familial and educational support systems to prioritize the well-being of adolescents and offers valuable insights and guidelines for the prevention, diagnosis and treatment of adolescent BDs.
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Aqueous two-phase systems (ATPS) are considered a new type of green separation system, but their low selectivity to target molecules limits their practical application. In this study, we used surfactant@MWCNT as an adjuvant to improve the selectivity of PEG/(NH4)2SO4 ATPS. The surfactants used include Triton X-100 (TX-100), Tween 80, sodium dodecyl sulfate (SDS), sodium dodecyl benzenesulfonate (SDBS), and bis(2-ethylhexyl)sulfosuccinate sodium salt (AOT). Nine aromatic compounds, including syringic acid, vanillin, tryptophan, phenylalanine, tyrosine, mandelic acid, theophylline, theobromine, and cephalexin, were selected as model extracts. The results showed that the use of the surfactant@MWCNT composite as an adjuvant significantly improved the selectivity of the ATPS toward syringic acid among the nine extracts. Moreover, the selectivity of the ATPS for syringic acid with the TX-100/MWCNT composite as the adjuvant is better than that with the Tween 80/MWCNT composite as the adjuvant, followed by that with the anionic surfactant/MWCNT composite as the adjuvant. The enhanced selectivity of ATPS by the surfactant/MWCNT composite is ascribed to the spatial effect and the electrostatic and hydrophobic interactions between the extract and the surfactant adsorbed on the MWCNT.
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Degradation of polysaccharides based on lytic polysaccharide monooxygenases (LPMOs) has received considerably interest in the environment and energy fields since 2010. With the rapid development of nanozymes in various fields, it is highly desirable but challenging to develop LPMO-like nanozymes with high specificity and satisfied activity. Here, a defective copper-cobalt binuclear Prussian blue analogue (CuCoPBA) nanozyme was developed via a facile and ingenious methodology based on single histidine (His). For the first time, His-CuCoPBA nanozyme was found to exhibit LPMO-like activity with H2O2 as a cosubstrate at room temperature and neutral pH, which can efficiently catalyze the degradation of galactomannans selectively. Significantly, the high degradation activity at pH 10 expands the application of Fenton-like nanozymes in alkaline condition. Singlet oxygen (1O2), as a main reactive intermediate, plays a crucial role in the galactomannan degradation catalyzed by His-CuCoPBA nanozyme. Both control experimental and density functional theory (DFT) results indicate Cu-NxHis contributes to the efficiently and selectively catalytic activity of His-CuCoPBA nanozymes by emulating the binding and catalytic sites of LPMOs. The present work not only represents a fundamental breakthrough toward degradation of polysaccharide based on nanozyme, but also contributes to understanding the catalytic mechanism of natural Cu-dependent LPMOs.
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Cobre , Oxigenases de Função Mista , Histidina , Peróxido de Hidrogênio/metabolismo , Polissacarídeos/metabolismo , CobaltoRESUMO
Despite the widespread use in industrial production, benzene derivatives are harmful to both human beings and the environment. The control of these substances has become an important subject of scientific research. This study introduces a new approach for adsorption and separation of benzene derivatives utilizing pagoda[n]arene based supramolecular materials. Density functional theory calculations were employed to investigate the molecular recognition mechanism of benzene derivatives by pagoda[4]arenes and pagoda[5]arenes (Pa[4]As and Pa[5]As). Results indicate that Pa[4]As and Pa[5]As can effectively accommodate benzene derivatives through non-covalent interactions, leading to the formation of stable host-guest complexes. Additionally, molecular dynamics simulations revealed that both crystalline and non-crystalline supramolecular aggregates of Pa[4]As and Pa[5]As possess the ability to adsorb benzene derivatives and maintain the stability of the adsorption. Moreover, increasing the temperature causes benzene derivatives to desorb from the adsorbing aggregates, and thus the material can be reutilized.
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In this work, sixteen typical chlorinated and brominated aromatic disinfection by-products (DBPs) were selected as examples to investigate their different degradation mechanisms initiated by HO⢠and SO4â¢-. Addition reactions were the main mode of degradation of DBPs by HOâ¢, while SO4â¢- dominated H-abstraction reactions and single electron transfer reactions. Chlorinated compounds had higher reactivity than brominated compounds. Furthermore, substituents with stronger electron-donating effects promoted the electrophilic reaction of DBPs with the two radicals. In addition, we developed a model based on the chemical properties LUMO, fmax-, and hardness for predicting the average reaction energy barriers for the initial reactions of DBPs with HO⢠and SO4â¢-. The model had good predictive performance for the difficulty of degradation of different DPBs by HO⢠and SO4â¢-, with R2 values of 0.85 and 0.87, respectively. Through the degradation efficiency simulation, we found that longer reaction times, higher oxidant concentrations and lower pollutant concentrations were more favorable for the removal of DBPs. The UV/PDS process showed better degradation of DBPs than the UV/H2O2 process. In addition, most degradation products of DBPs exhibited less toxicity to aquatic organisms than their parent compounds. This study provided theoretical guidance for the degradation and removal of other aromatic DBPs at the molecular level.
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Poluentes Químicos da Água , Purificação da Água , Peróxido de Hidrogênio , Desinfecção , Poluentes Químicos da Água/análise , Raios Ultravioleta , Cinética , Halogenação , Cloro/química , OxirreduçãoRESUMO
The reactions between chlorobenzene(CB) and ozone have been studied comprehensively in this paper. Chlorobenzene is a commonly found chlorinated aromatic volatile organic compound(VOC), and its emission into the atmosphere can cause harm to the ecosystem and human health. The frequent occurrence of mineral particles from sandstorms exerts a significant influence on the atmospheric chemistry of the troposphere. Mineral particles are abundant in SiO2 and Al2O3 content. Therefore, we investigated the homogeneous and heterogeneous reaction processes of CB and ozone in the atmosphere by using density functional theory (DFT) method at the M06-2X/6-311++g(3df,2p)//M06-2X/6-31+g(d,p) level. The atmospheric fate, reaction rate and toxicity evaluation of CB ozonation were studied in the gas-phase section. Toxicity evaluation results showed that ozonation of CB could effectively reduce its toxicity. For the heterogeneous process, we simulated three types of SiO2 clusters and nine types of (Al2O3)n clusters, and studied the configurations of CB adsorbed on the cluster surfaces. We found that adsorption of CB on the SiO2 clusters was achieved through hydrogen bonding, while adsorption of CB on the Al2O3 clusters was achieved through both hydrogen bonding and metal bonding. The energy for CB adsorption on the (Al2O3)n cluster surface was higher than that for the SixOy(OH)z cluster surface, and both types of clusters exhibited efficient adsorption of CB. As the SixOy(OH)z clusters grew larger, the rates for the reactions between O3 and CB increased. CB travelled long distances along the Al2O3 clusters, leading to an extended influence range.
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Limited by preparation time and ligand solubility, synthetic protocols for cyclodextrin-based metal-organic framework (CD-MOF), as well as subsequent derived materials with improved stability and properties, still remains a challenge. Herein, an ultrafast, environmentally friendly, and cost-effective microwave method is proposed, which is induced by graphene oxide (GO) to design CD-MOF/GOs. This applicable technique can control the crystal size of CD-MOFs from macro- to nanocrystals. CD-MOF/GOs are investigated as a new type of supramolecular adsorbent. It can selectively adsorb the dye molecule methylene green (MG) owing to the synergistic effect between the hydrophobic nanocavity of CDs, and the abundant O-containing functional groups of GO in the composites. Following high temperature calcination, the resulting N, S co-doped porous carbons derived from CD-MOF/GOs exhibit a high capacitance of 501 F g-1 at 0.5 A g-1 , as well as stable cycling stability with 90.1% capacity retention after 5000 cycles. The porous carbon exhibits good electrochemical performance due to its porous surface containing numerous electrochemically active sites after dye adsorption and carbonization. The design strategy by supramolecular incorporating a variety of active molecules into CD-MOFs optimizes the properties of their derived materials, furthering development toward the fabrication of zeitgeisty and high-performance energy storage devices.
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Fraxini Cortex is a traditional Chinese herbal medicine that has been used for thousands of years to treat dampness-heat diarrhea, dysentery, red or white vaginal discharge, painful swelling or redness of the eyes, and nebula. It contains various chemical components, including coumarins, iridoids, phenolic acids, and flavonoids. Coumarins are important active ingredients in Fraxini Cortex and have antibacterial, anti-inflammatory, antioxidant, antitumor, and antiviral activities. Aesculin and aesculetin are two major coumarin components of Fraxini Cortex that are widely used in its quality evaluation. Previous HPLC methods for determination of aesculin and aesculetin present several limitations, such as long analysis times and high solvent and reference compound consumption. In this study, a rapid, eco-friendly and cost saving HPLC method for the determination of aesculin and aesculetin in Fraxini Cortex was established by using the core-shell column and equal absorption wavelength (EAW). Different factors influencing the extraction process, such as the extraction solvent, temperature, and time, were assessed to obtain the optimal extraction conditions. The results showed that Fraxini Cortex samples could be well extracted by ultrasonic extraction for 5 min with a 25% ethanol aqueous solution. A core-shell column was used, and different mobile phases and flow rates were investigated to obtain the best rapid-HPLC separation conditions. The optimized HPLC conditions were as follows: a Poroshell 120 EC-C18 column (50 mm×4.6 mm, 2.7 µm), acetonitrile-0.1% formic acid aqueous solution (6â¶94, v/v) as the eluent, a flow rate of 1.5 mL/min, and a column temperature of 25 â. The EAW of aesculin and aesculetin was a key factor in their determination using a single reference compound. EAW selection was performed in two steps. First, the UV spectra of two equimolar concentrations of the reference compounds (aesculin and aesculetin) were compared to determine the EAW of the two analytes. The EAW results were then verified by the HPLC analysis of the reference compound solutions. The final EAW of aesculin and aesculetin was 341 nm. The determination of aesculin and aesculetin using only one reference compound (i. e., aesculin) was achieved by HPLC-UV at this EAW. The newly developed HPLC method revealed a good linear relationship between the two target analytes (r=1.0000). The limits of detection (LODs) and limits of quantification (LOQs) were 1.5 µmol/L and 3.0 µmol/L, respectively, and the average recoveries of aesculin and aesculetin were 99.0% and 97.5%. The stabilities of the sample solutions were examined, and the two analytes demonstrated good stability for 24 h. The contents of the target analytes in 10 batches of Fraxini Cortex were determined using the proposed EAW method and the classic external standard method (ESM), and comparable concentrations were obtained. The contents of aesculin and aesculetin in the 10 batches of Fraxini Cortex were 0.26%-2.80% and 0.11%-1.47%, respectively. A t-test was conducted to compare the results of the proposed EAW technique with those obtained via the method reported in the Chinese Pharmacopoeia, and no significant difference between the two assay methods was noted (P>0.05). Comparison of the newly established EAW method with those reported in the literature revealed that our method required only 10 min to complete and used as little as 0.5 mL of the solvent and only one standard. Therefore, the developed EAW method is a rapid, simple, eco-friendly, and cost-effective analytical method that is suitable for the determination of aesculin and aesculetin in Fraxini Cortex and its related products. The proposed technique is an improved method for determining aesculin and aesculetin and contributes to the enhancement of the quality evaluation of Fraxini Cortex.
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Medicamentos de Ervas Chinesas , Esculina , Feminino , Humanos , Esculina/análise , Cromatografia Líquida de Alta Pressão , Medicamentos de Ervas Chinesas/análise , Cumarínicos , SolventesRESUMO
Developing polyoxometalate-cyclodextrin cluster-organic supramolecular framework (POM-CD-COSF) still remains challenging due to an extremely difficult task in rationally interconnecting two dissimilar building blocks. Here we report an unprecedented POM-CD-COSF crystalline structure produced through the self-assembly process of a Krebs-type POM, [Zn2 (WO2 )2 (SbW9 O33 )2 ]10- , and two ß-CD units. The as-prepared POM-CD-COSF-based battery separator can be applied as a lightweight barrier (approximately 0.3â mg cm-2 ) to mitigate the polysulfide shuttle effect in lithium-sulfur batteries. The designed Li-S batteries equipped with the POM-CD-COSF modified separator exhibit remarkable electrochemical performance, attributed to fast Li+ diffusion through the supramolecular channel of ß-CD, efficient polysulfide-capture ability by the dynamic host-guest interaction of ß-CD, and improved sulfur redox kinetics by the bidirectional catalysis of POM cluster. This research provides a broad perspective for the development of multifunctional supramolecular POM frameworks and their applications in Li-S batteries.
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Degradation of Chlorine-containing disinfection by-products(Cl-DBPs) on surface by electrocatalytic hydrodechlorination (EHDC) is considered a promising advanced water treatment method. Cl-DBPs have ecological toxicity and health risks so that it is urgent to degrade DBPs. We designed and verified the degradation performance of the EHDC of 18 kinds of DBPs (TAAs, TANs, TALs, TNMs, TAcAms, THMs) with different substituents led by the Ti3C2X2(X = O/OH) system by the first-principles. On the surface of Ti3C2(OH)2, DBPs react with atomic hydrogen (*H) by a direct-indirect continuous reduction mechanism to eliminate the Cl atom in turn. Dissociative adsorption of DBPs on the surface of Ti3C2(OH)2 simultaneously realizes the first electron transfer step and forms H vacancy, which makes its electrocatalytic activity superior to that of Ti3C2O2. Removing the six types of DBPs only needs to add -0.1 V of applied potential. In addition, we investigated the impact of substituents and chlorination degree on the reactivity of DBPs removal. The strong electron-withdrawing group is more conducive to the dechlorination reaction. Dehalogenation is much favorable in thermodynamics as the increase in chlorination degree. This study provides important insights and efficient catalysts for the degradation of DBPs and shows the potential of MXenes in eliminating chloride in water.
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Desinfetantes , Poluentes Químicos da Água , Purificação da Água , Cloro/análise , Cloretos , Poluentes Químicos da Água/análise , Titânio , Halogênios , Desinfecção/métodos , Halogenação , Purificação da Água/métodosRESUMO
Organophosphate esters (OPEs) are widely detected in the atmosphere. However, the atmospheric oxidative degradation mechanism of OPEs has not been closely examined. This work took density functional theory (DFT) to investigate the tropospheric ozonolysis of organophosphates, represented by diphenyl phosphate (DPhP), including adsorption mechanisms on the surface of titanium dioxide (TiO2) mineral aerosols and oxidation reaction of hydroxyl groups (·OH) after photolysis. Besides, the reaction mechanism, reaction kinetics, adsorption mechanism, and ecotoxicity evaluation of the transformation products were also studied. At 298 K, the total reaction rate constants kO3, kOH, kTiO2-O3, and kTiO2-OH are 5.72 × 10-15 cm3 molecule-1 s-1, 1.68 × 10-13 cm3 molecule-1 s-1, 1.91 × 10-23 cm3 molecule-1 s-1, and 2.30 × 10-10 cm3 molecule-1 s-1. The atmospheric lifetime of DPhP ozonolysis in the near-surface troposphere is 4 min, much lower than that of hydroxyl radicals (·OH). Besides, the lower the altitude is, the stronger the oxidation is. The TiO2 clusters carry DPhP promoting ·OH oxidation but inhibiting ozonolysis of DPhP. Finally, the main transformation products of this process are glyoxal, malealdehyde, aromatic aldehydes, etc., which are still ecotoxic. The findings shed new light on the atmospheric governance of OPEs.
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Retardadores de Chama , Ozônio , Fosfatos , Ésteres , Organofosfatos , AtmosferaRESUMO
Residues in surface water of ribavirin, which used extensively during the COVID-19 pandemic, have become an emerging issue due to its adverse impact on the environment and human health. UV/H2O2 and UV/peroxydisulfate (PDS) have different degradation effects on ribavirin, and the same operational parameter have different effects on the two processes. In this study, the reaction mechanism and degradation efficiency for ribavirin were studied to compare the differences under UV/H2O2 and UV/PDS processes. We calculated the total rate constants of ribavirin with HO⢠and SO4 â¢- in the liquid phase as 2.73 × 108 and 9.39 × 105 M-1s-1. The density functional theory (DFT) calculation results showed that HO⢠and SO4 â¢- react more readily with ribavirin via H-abstraction (HAA). The nitrogen-containing heterocyclic ring is difficult to undergo ring-opening degradation. The UV/PDS process was more stable and performed better than the UV/H2O2 for the ribavirin degradation when the same molar oxidant dosage was applied. HO⢠plays an extremely important role in the degradation of ribavirin by UV/PDS. The reason for this phenomenon is the combination of the higher yield of HO⢠produced in the UV/PDS process and the faster reaction rate of ribavirin with HOâ¢. The UV/H2O2 process is more sensitive to pH than UV/PDS. Alkaline condition can significantly inhibit the ribavirin degradation. The effects of natural organic matter (NOM) and ribavirin concentration were also compared. Eventually, the toxicity prediction of the product showed that the opening-ring products were more toxic than the parent compound.
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OBJECTIVE: The purpose of this review was to systematically assess the effectiveness of 10-Hz repetitive transcranial magnetic stimulation (rTMS) in fibromyalgia. DATA SOURCES: We searched PubMed, Cochrane Library, Embase, Web of Science, and Ovid databases as of November 6, 2021. STUDY SELECTION: The inclusion criteria for this review were randomized controlled trials of 10-Hz rTMS for fibromyalgia, exploring the effects of 10-Hz rTMS on pain, depression, and quality of life in patients with fibromyalgia. DATA EXTRACTION: Data extraction was performed independently by 2 evaluators according to predefined criteria, and the quality of the included literature was assessed using the Cochrane Bias Risk Assessment Tool. The measurement outcomes include visual analog scale, Hamilton Depression Rating Scale, and Fibromyalgia Impact Questionnaire, and so on. DATA SYNTHESIS: A total of 488 articles were screened, and the final 7 selected high-quality articles with 217 patients met our inclusion criteria. Analysis of the results showed that high-frequency transcranial magnetic stimulation at 10 Hz was significantly associated with reduced pain compared with sham stimulation in controls (standardized mean difference [SMD]=-0.72; 95% confidence interval [CI], -1.12 to -0.33; P<.001; I2=46%) and was able to improve quality of life (SMD=-0.70; 95% CI, -1.00 to -0.40; P<.001; I2=15%) but not improve depression (SMD=-0.23; 95% CI, -0.50 to 0.05; P=.11; I2=33%). In addition, a subgroup analysis of pain conducted based on stimulation at the primary motor cortex and dorsolateral prefrontal cortex showed no significant difference (SMD=-0.72; 95% CI, -1.12 to -0.33; P=.10; I2=62%). CONCLUSIONS: Overall, 10-Hz rTMS has a significant effect on analgesia and improved quality of life in patients with FMS but did not improve depression.
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Fibromialgia , Estimulação Magnética Transcraniana , Humanos , Estimulação Magnética Transcraniana/métodos , Fibromialgia/terapia , Qualidade de Vida , Dor , Manejo da Dor/métodos , Ensaios Clínicos Controlados Aleatórios como AssuntoRESUMO
Recent research revealed inhibition or enhancement of dissolved organic matter (DOM) to the degradation of trace organic contaminants (TrOC) in natural and engineered water systems. Phenols containing acetyl, carboxyl, formyl, hydroxy, and methoxy groups were selected as the model DOM to quantitatively study their roles in the degradation of simple anilines, sulfonamide antibiotics, phenylurea pesticides by sulfate radicals (SO4â¢-). Experimental results found that p-methoxyphenol inhibited aniline and sulfamethoxazole degradation by thermally activated peroxydisulfate (TAP), while p-acetylphenol slightly promoted aniline degradation. Quantum chemical calculations were applied to study the microscopic mechanism and kinetics of phenols affecting the degradation of aniline pollutants (AN) in three ways: competitively reacting with SO4â¢-, repairing aniline cationic radicals (ANâ¢+) and phenylaminyl radicals (AN(-H)â¢), and generating phenoxy radicals to degrade anilines. Generally, the degradation of sulfonamides and phenylureas prefer to be inhibited by hydroxy- and methoxy-phenols with low oxidation potential (Eox), due to their diffusion-limiting reaction with SO4â¢- and rapid back-reduction ANâ¢+ with the calculated rate constants of (0.02 - 6.38) × 109 M-1 s-1. Phenols repairing AN(-H)⢠through H abstraction reaction is speculated to possibly dominate the joint degradation of phenols and anilines by TAP, which has a poor correlation with Eox. This study provides mechanistic insight into the chemical behavior of complex and heterogeneous DOM in complex aqueous environments.
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Sulfatos , Poluentes Químicos da Água , Teoria da Densidade Funcional , Compostos de Anilina , Fenóis , Cinética , OxirreduçãoRESUMO
In lithium-sulfur batteries, a serious obstacle is the dissolution and diffusion of long-chain polysulfides, resulting in rapid capacity decay and low Coulombic efficiency. At present, a common practice is designing cathode materials to solve this problem, but this gives rise to reduced gravimetric and volumetric energy densities. Herein, we present a thiodimolybdate [Mo2S12]2- cluster as sulfur host material that can effectively confine the shuttling of polysulfides and contribute its own capacity in Li-S cells. Moreover, the [Mo2S12]2- cluster as a "bidirectional catalyst" can effectively catalyze polysulfide reduction and lithium sulfide oxidation. We further investigate the catalytic mechanism of [Mo2S12]2- clusters by theoretical calculations, in situ spectroscopic techniques, and electrochemical studies. The (NH4)2Mo2S12/S cathodes show good electrochemical performance under a wide range of temperatures. In addition, a pouch cell fabricated with (NH4)2Mo2S12/S cathodes maintains a stable output for more than 50 cycles.
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Herein, we developed a highly sensitive electrochemical sensor for the trace detection of Sudan I (SDI) dye based on composite molecularly imprinted membranes (MIMs). The pentenyl (lipoic acyl)-isoleucyl-chitosan oligosaccharide (P(L)ICO) and pentenyl-asparaginyl-chitosan oligosaccharide (PASCO) served as bifunctional monomer oligomers. After deposition of gold nanoparticles on a glassy carbon electrode (GCE) surface, a P(L)ICO layer successfully self-assembled on the surface. Subsequently, the primary MIM was polymerised on the electrode surface by using SDI as a template, PASCO as a functional monomer oligomer, and ethylene glycol dimethacrylate as a cross-linking agent. Electrochemical polymerisation was then conducted in an N,N'-methylenebisacrylamide solution. After eluting the SDI molecules from the composite MIMs, the fabricated SDI-MIM(PM)/Fn-Au/GCE demonstrated specific adsorption of SDI. Under optimal conditions, the constructed sensor exhibited a linear relationship between decreasing peak current and SDI concentration from 0.02 to 3.5 µM with a low detection limit of 4 nM (S/N = 3). As a proof of concept, SDI-MIM(PM)/Fn-Au/GCE was also applied to detect SDI in chili powder samples, with recoveries ranging from 96.8 to 106.6%.