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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 325: 125075, 2024 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-39236569

RESUMO

Alzheimer's disease (AD), characterized by its incurable nature and prevalence among the elderly, has remained a focal point in medical research. Increasing evidence suggests that peroxynitrite (ONOO-) serves as a crucial biomarker for the diagnosis of AD. In this study, we present a novel, easily available, high-yield, and cost-effective near-infrared (NIR) fluorescent probe, CDCI-ONOO. This probe utilizes a coumarin-dicyanoisophorone conjugate as the fluorophore and diphenylphosphinic chloride as the recognition site, enabling the detection of ONOO- both in vitro and in vivo. Upon interaction with ONOO-, CDCI-ONOO exhibits a distinct maximum emission peak at 715 nm with a substantial Stokes shift of 184 nm. The probe demonstrates excellent selectivity and sensitivity (LOD = 144 nM), along with noticeable colorimetric and fluorescence changes after the reaction. Comprehensive analyses using high-performance liquid chromatography (HPLC), high-resolution mass spectrometry (HRMS), and density functional theory (DFT) calculations confirm that the reaction with ONOO- restores the initially quenched Intramolecular Charge Transfer (ICT), resulting in the formation of CDCI-OH, a product that emitting fluorescence in the near-infrared region. Furthermore, we demonstrated the successful application of CDCI-ONOO for ONOO- detection in neuronal cells and imaging of ONOO- in the brains of mice. These findings underscore the potential of CDCI-ONOO as a near-infrared fluorescent probe for in vivo ONOO- detection, offering a significant avenue for advancing our understanding of AD pathology and diagnosis.

2.
Chem Sci ; 2024 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-39184295

RESUMO

Transition-metal-catalyzed hydroarylation of unactivated alkenes via metal hydride hydrogen atom transfer (MHAT) is an attractive approach for the construction of C(sp2)-C(sp3) bonds. However, this kind of reaction focuses mainly on using reductive hydrosilane as a hydrogen donor. Here, a novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides using protons as a hydrogen source has been developed. This reaction represents the first example of photoinduced MHAT via a reductive route intercepting an organometallic coreactant. The key to this transformation was that the CoIII-H species was generated from the protonation of the CoI intermediate, and the formed CoIII-C(sp3) intermediate interacted with the organometallic coreactant rather than reacting with nucleophiles, a method which has been well developed in photoinduced Co-catalyzed MHAT reactions. This reaction is characterized by its high catalytic efficiency, construction of quaternary carbons, simple reaction conditions and expansion of the reactive mode of Co-catalyzed MHAT reactions via a reductive route. Moreover, this catalytic system could also be applied to complex substrates derived from glycosides.

3.
J Phys Chem B ; 128(24): 5846-5854, 2024 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-38830814

RESUMO

Hydrogen sulfide (H2S) is an important endogenous gas transmitter that plays a critical role in various physiological and pathological processes and can also cause a negative impact on foodstuffs. In this study, we designed and synthesized a simple, easily available, high-yield, and low-cost near-infrared (λem = 710 nm) fluorescent probe, DEM-H2S, with a substantial Stokes shift (205 nm) for the detection of H2S. DEM-H2S features high selectivity and sensitivity (LOD = 80 nM) toward H2S, accompanied by a noticeable color change. Upon interaction with H2S, DEM-H2S exhibits a restored ICT (Intramolecular Charge Transfer) process, thereby manifesting near-infrared fluorescence. DEM-H2S has been successfully utilized to detect H2S in actual water samples and to monitor the spoilage of food items, such as pork, shrimp, and eggs. Furthermore, DEM-H2S enables the imaging of endogenous and exogenous H2S in living MCF-7 cells and zebrafish. Hence, DEM-H2S provides an attractive method for the detection of H2S in environmental, food, and biological systems, holding potential value in physiological and pathological research.


Assuntos
Corantes Fluorescentes , Sulfeto de Hidrogênio , Peixe-Zebra , Sulfeto de Hidrogênio/análise , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Humanos , Animais , Células MCF-7 , Água/química , Imagem Óptica , Contaminação de Alimentos/análise , Limite de Detecção , Ovos/análise , Espectrometria de Fluorescência , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química
4.
ACS Appl Bio Mater ; 7(6): 4116-4132, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38772009

RESUMO

The management of multibacterial infections remains clinically challenging in the care and treatment of chronic diabetic wounds. Photodynamic therapy (PDT) offers a promising approach to addressing bacterial infections. However, the limited target specificity and internalization properties of traditional photosensitizers (PSs) toward Gram-negative bacteria pose significant challenges to their antibacterial efficacy. In this study, we designed an iron heme-mimetic PS (MnO2@Fe-TCPP(Zn)) based on the iron dependence of bacteria that can be assimilated by bacteria and retained in different bacteria strains (Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus) and which shows high PDT antibacterial efficacy. For accelerated wound healing after antibacterial treatment, MnO2@Fe-TCPP(Zn) was loaded into a zwitterionic hydrogel with biocompatibility and antifouling properties to form a nanocomposite antibacterial hydrogel (PSB-MnO2@Fe-TCPP(Zn)). In the multibacterial infectious diabetic mouse wound model, the PSB-MnO2@Fe-TCPP(Zn) hydrogel dressing rapidly promoted skin regeneration by effectively inhibiting bacterial infections, eliminating inflammation, and promoting angiogenesis. This study provides an avenue for developing broad-spectrum antibacterial nanomaterials for combating the antibiotic resistance crisis and promoting the healing of complex bacterially infected wounds.


Assuntos
Antibacterianos , Materiais Biocompatíveis , Testes de Sensibilidade Microbiana , Fotoquimioterapia , Fármacos Fotossensibilizantes , Cicatrização , Cicatrização/efeitos dos fármacos , Animais , Camundongos , Antibacterianos/farmacologia , Antibacterianos/química , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Heme/química , Teste de Materiais , Ferro/química , Escherichia coli/efeitos dos fármacos , Tamanho da Partícula , Diabetes Mellitus Experimental/tratamento farmacológico , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacos , Staphylococcus aureus/efeitos dos fármacos , Compostos de Manganês/química , Compostos de Manganês/farmacologia
6.
Sci Adv ; 10(8): eadj6801, 2024 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-38394192

RESUMO

Tropical precipitation extremes and their changes with surface warming are investigated using global storm resolving simulations and high-resolution observations. The simulations demonstrate that the mesoscale organization of convection, a process that cannot be physically represented by conventional global climate models, is important for the variations of tropical daily accumulated precipitation extremes. In both the simulations and observations, daily precipitation extremes increase in a more organized state, in association with larger, but less frequent, storms. Repeating the simulations for a warmer climate results in a robust increase in monthly-mean daily precipitation extremes. Higher precipitation percentiles have a greater sensitivity to convective organization, which is predicted to increase with warming. Without changes in organization, the strongest daily precipitation extremes over the tropical oceans increase at a rate close to Clausius-Clapeyron (CC) scaling. Thus, in a future warmer state with increased organization, the strongest daily precipitation extremes over oceans increase at a faster rate than CC scaling.

7.
Mater Horiz ; 11(3): 688-699, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-37990914

RESUMO

The development of potent pseudocapacitive charge storage materials has emerged as an effective solution for closing the gap between high-energy density batteries and high-power density and long-lasting electrical double-layer capacitors. Sulfonyl compounds are ideal candidates owing to their rapid and reversible redox reactions. However, structural instability and low electrical conductivity hinder their practical application as electrode materials. This work addresses these challenges using a fast and clean laser process to interconnect sulfonated carbon nanodots into functionalized porous carbon frameworks. In this bottom-up approach, the resulting laser-converted three-dimensional (3D) turbostratic carbon foams serve as high-surface-area, conductive scaffolds for redox-active sulfonyl groups. This design enables efficient faradaic processes using pendant sulfonyl groups, leading to a high specific capacitance of 157.6 F g-1 due to the fast reversible redox reactions of sulfonyl moieties. Even at 20 A g-1, the capacitance remained at 78.4% due to the uniform distribution of redox-active sites on the graphitic domains. Additionally, the 3D-tsSC300 electrode showed remarkable cycling stability of >15 000 cycles. The dominant capacitive processes and kinetics were analysed using extensive electrochemical characterizations. Furthermore, we successfully used 3D-tsSC300 in flexible solid-state supercapacitors, achieving a high specific capacitance of up to 17.4 mF cm-2 and retaining 91.6% of the initial capacitance after 20 000 cycles of charge and discharge coupled with 90° bending tests. Additionally, an as-assembled flexible all-solid-state symmetric supercapacitor exhibits a high energy density of 12.6 mW h cm-3 at a high power density of 766.2 W cm-3, both normalized by the volumes of the full device, which is comparable or better than state-of-the-art commercial pseudocapacitors and hybrid capacitors. The integrated supercapacitor provides a wide potential window of 2.0 V using a serial circuit, showing great promise for metal-free energy storage devices.

8.
Front Bioeng Biotechnol ; 11: 1297068, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38249798

RESUMO

Introduction: Falls and fall-related injuries in young male adults with excess weight are closely related to an increased cognitive load. Previous research mainly focuses on analyzing the postural control status of these populations performing cognitive tasks while stabilized walking progress but overlooked a specific period of walking known as gait initiation (GI). It is yet unknown the influences of cognitive load on this population's postural control status during GI. Objective: This study aimed to determine the influences of cognitive load on the center of pressure (CoP) trajectory of young male adults with excess weight during GI. Design: A controlled laboratory study. Methods: Thirty-six male undergraduate students were recruited and divided into normal-weight, overweight, and obese groups based on their body mass index (BMI). Participants' CoP parameters during GI under single and dual-task conditions were collected by two force platforms. A mixed ANOVA was utilized to detect significant differences. Results: Compared with the normal-weight group, the obese group showed significant changes in the duration and CoP parameters during sub-phases of GI, mainly reflecting prolonged duration, increased CoP path length, higher mediolateral CoP displacement amplitude, and decreased velocity of anteroposterior CoP displacement. During GI with 1-back task, significantly increased mediolateral CoP displacement amplitude occurred in the obese group. During GI with 2-back task, the obese group had increased CoP path length, higher mediolateral CoP displacement amplitude, as well as a decreased velocity of CoP displacement. Conclusion: Based on the changes in CoP parameters during GI with cognitive tasks, young male adults with excess weight, mainly obese ones, have compromised postural stability. During GI with a difficult cognitive task, obese young male adults are more susceptible to deterioration in their lateral postural balance. These findings indicate that the increased cognitive load could exacerbate obese young male adults' postural control difficulty during GI under dual-task conditions, putting them at a higher risk of experiencing incidents of falls. Based on these findings, we offer suggestions for therapists to intervene with these young male adults to ensure their safety of GI.

9.
Materials (Basel) ; 13(17)2020 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-32825780

RESUMO

The effect of interlayer materials on the damage of ceramics in the SiC/Al compositestructure was analyzed through experiments and simulation. Using 0.25 mm thermoplasticpolyurethane (TPU) as a reference, a 0.5 mm aramid fabric (AFRP) or a 0.5 mm carbon fiberreinforced epoxy matrix composite (CFRP) was added to the interlayer, respectively. Through theimpact tests, it was discovered that the ceramic damaged area in the TPU composite structure wassevere. With the addition of AFRP, the damaged area of the ceramic layer was reduced by 73%under the same impact conditions. The addition of CFRP also reduced the damage of ceramics. Theevolution process of the tensile stress on the ceramic rear surface was presented by simulation. Thetensile evolution process analysis can explain the experimental phenomenon well and can be usedto predict the damage of the ceramics.

10.
Water Sci Technol ; 80(6): 1196-1204, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31799963

RESUMO

Anaerobic digestion effluent (ADE) from the anaerobic digestion treatment of citric acid wastewater can be reused as a potential substitute for process water in the citric acid fermentation. However, excessive sodium contained in ADE significantly decreases citric acid production. In this paper, the inhibition mechanism of sodium on citric acid fermentation was investigated. We demonstrated that excessive sodium did not increase oxidative stress for Aspergillus niger, but reduced the pH of the medium significantly over the period 4-24 h, which led to lower activities of glucoamylase and isomaltase secreted by A. niger, with a decrease of available sugar concentration and citric acid production. ADE was pretreated by air-stripping prior to recycle and 18 g/L calcium carbonate was added at the start of fermentation to control the pH of the medium. The inhibition caused by ADE was completely alleviated and citric acid production substantially increased from 118.6 g/L to 141.4 g/L, comparable to the fermentation with deionized water (141.2 g/L). This novel process could decrease wastewater discharges and fresh water consumption in the citric acid industry, with benefit to the environment.


Assuntos
Ácido Cítrico , Águas Residuárias , Ar , Anaerobiose , Fermentação , Concentração de Íons de Hidrogênio
11.
Bioresour Technol ; 211: 645-53, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-27054882

RESUMO

In this study, a novel cleaner production process of citric acid was proposed to completely solve the problem of wastewater management in citric acid industry. In the process, wastewater from citric acid fermentation was used to produce methane through anaerobic digestion and then the anaerobic digestion effluent was further treated with air stripping and electrodialysis before recycled as process water for the later citric acid fermentation. This proposed process was performed for 10 batches and the average citric acid production in recycling batches was 142.4±2.1g/L which was comparable to that with tap water (141.6g/L). Anaerobic digestion was also efficient and stable in operation. The average chemical oxygen demand (COD) removal rate was 95.1±1.2% and methane yield approached to 297.7±19.8mL/g TCODremoved. In conclusion, this novel process minimized the wastewater discharge and achieved the cleaner production in citric acid industry.


Assuntos
Ácido Cítrico/metabolismo , Águas Residuárias/química , Purificação da Água/métodos , Anaerobiose , Biodegradação Ambiental , Análise da Demanda Biológica de Oxigênio , Fermentação , Metano/biossíntese , Reciclagem
12.
Bioprocess Biosyst Eng ; 39(3): 391-400, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26658985

RESUMO

In this study, an integrated citric acid-methane fermentation process was established to solve the problem of wastewater treatment in citric acid production. Citric acid wastewater was treated through anaerobic digestion and then the anaerobic digestion effluent (ADE) was further treated and recycled for the next batch citric acid fermentation. This process could eliminate wastewater discharge and reduce water resource consumption. Propionic acid was found in the ADE and its concentration continually increased in recycling. Effect of propionic acid on citric acid fermentation was investigated, and results indicated that influence of propionic acid on citric acid fermentation was contributed to the undissociated form. Citric acid fermentation was inhibited when the concentration of propionic acid was above 2, 4, and 6 mM in initial pH 4.0, 4.5 and, 5.0, respectively. However, low concentration of propionic acid could promote isomaltase activity which converted more isomaltose to available sugar, thereby increasing citric acid production. High concentration of propionic acid could influence the vitality of cell and prolong the lag phase, causing large amount of glucose still remaining in medium at the end of fermentation and decreasing citric acid production.


Assuntos
Ácido Cítrico/metabolismo , Metano/metabolismo , Propionatos/metabolismo , Águas Residuárias/microbiologia , Microbiologia da Água , Concentração de Íons de Hidrogênio
13.
Bioresour Technol ; 189: 186-194, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25898079

RESUMO

To solve the pollution problem of extraction wastewater in citric acid production, an integrated citric acid-methane production process was proposed. Extraction wastewater was treated through anaerobic digestion and the anaerobic digestion effluent (ADE) was recycled for the next batch of citric acid fermentation, thus eliminating wastewater discharge and reducing water consumption. Excessive Na(+) contained in ADE could significantly inhibit citric acid fermentation in recycling and was removed by electrodialysis in this paper. Electrodialysis performance was improved after pretreatment of ADE with air stripping and activated carbon adsorption to remove precipitable metal ions and pigments. Moreover, the concentrate water was recycled and mixed with feed to improve the water recovery rate above 95% in electrodialysis treatment, while the dilute water was collected for citric acid fermentation. The removal rate of Na(+) in ADE was above 95% and the citric acid production was even higher than that with tap water.


Assuntos
Ácido Cítrico/metabolismo , Diálise/métodos , Eletricidade , Metano/biossíntese , Reciclagem , Águas Residuárias/química , Purificação da Água/métodos , Anaerobiose , Biodegradação Ambiental , Reatores Biológicos/microbiologia , Fermentação , Troca Iônica , Membranas Artificiais , Sódio/farmacologia
14.
Bioresour Technol ; 176: 121-8, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25460992

RESUMO

To solve the problem of extraction wastewater in citric acid industrial production, an improved integrated citric acid-methane production process was established in this study. Extraction wastewater was treated by anaerobic digestion and then the anaerobic digestion effluent (ADE) was stripped by air to remove ammonia. Followed by solid-liquid separation to remove metal ion precipitation, the supernatant was recycled for the next batch of citric acid fermentation, thus eliminating wastewater discharge and reducing water consumption. 130U/g glucoamylase was added to medium after inoculation and the recycling process performed for 10 batches. Fermentation time decreased by 20% in recycling and the average citric acid production (2nd-10th) was 145.9±3.4g/L, only 2.5% lower than that with tap water (149.6g/L). The average methane production was 292.3±25.1mL/g CODremoved and stable in operation. Excessive Na(+) concentration in ADE was confirmed to be the major challenge for the proposed process.


Assuntos
Bactérias Anaeróbias/metabolismo , Reatores Biológicos , Ácido Cítrico/metabolismo , Metano/biossíntese , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias/química , Purificação da Água/métodos , Amônia/isolamento & purificação , Análise da Demanda Biológica de Oxigênio , Fermentação , Glucana 1,4-alfa-Glucosidase/química , Manihot/química , Metais/isolamento & purificação
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