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1.
Nat Commun ; 15(1): 1141, 2024 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-38326323

RESUMEN

The catalytic valorisation of biomass to afford synthetically useful small molecules is essential for sustainable biorefinery processes. Herein, we present a mild cascaded electrochemical protocol for converting furoic acid, a common biomass-derived feedstock, into a versatile platform chemical, gamma-butyrolactone. In the platinum(+)|nickel(-) electrode paired undivided cell, furoic acid is electrochemically oxidised with 84.2% selectivity to 2(5H)-furanone, the olefin of which is then hydrogenated to yield gamma-butyrolactone with 98.5% selectivity. The final gamma-butyrolactone yield is 69.1% with 38.3% Faradaic efficiency and 80.1% carbon balance when the reaction is performed with 100 mM furoic acid at 80 °C at +2.0 VAg/AgCl. Mechanistic investigation revealed the critical temperature and electrolyte pH conditions that maximise the production and protection of the key intermediate, furan radical, promoting its transition to 2(5H)-furanone rather than self-polymerising. The reaction is scalable, as 2.1 g of 98.1% pure gamma-butyrolactone is isolated through a simple solvent extraction.

2.
J Org Chem ; 89(5): 3226-3237, 2024 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-38361498

RESUMEN

Dehydrogenative aromatization (DA) of cyclic ketones is central to the development of functionalized aromatic precursors and hydrogen transfer-related technologies. Traditional DA strategies require precious metals with oxidants and are typically performed at high temperatures (100-150 °C) to overcome the high energy barrier of aliphatic C-H bond activation. Recently, a mild alternative approach based on I2 has been proposed to realize DA on substituted unsaturated cyclic ketones under ambient conditions. However, depending on the solvent, the product selectivity may vary between phenol ether and phenol, and the reaction mechanisms remain unclear. Herein, based on time-resolved proton nuclear magnetic resonance, DFT calculation, and mass spectrometric analyses, we established a unified mechanism to account for the product distribution. Through substrate scope and desorption electrospray ionization-mass spectrometry, we discovered the formation of a carbocation, which has been overlooked in previous studies. An expanded substrate scope study coupled with spectroscopic observation provided strong evidence to elucidate the formation mechanism and the location of the carbocation. With a renewed understanding of the mechanism, we achieved a phenolic product yield of 17-96% while controlling the selectivity. Moreover, some reactants could undergo DA in H2O, achieving 95-96% yield at below water-boiling temperature.

3.
Chemosphere ; 349: 140967, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38122939

RESUMEN

Developing electroactive membranes for filtration has gained importance owing to their effectiveness in mitigating the long-lasting issue of fouling faced with traditional membranes. Here, we developed thin electroactive metallic films on to stainless steel mesh (SSM) using electrodeposition method and evaluated their performance for microalgae harvesting via electro filtration. The effect of electrodeposition parameters on membrane formulation and operating parameters for electro filtration, both in continuous and intermittent modes, were evaluated and optimum values were obtained using response surface methodology (RSM). The optimal combination of electrodeposition parameters is 1000 µA/cm2 and 5 min for deposition current density and time, respectively. Whereas the electric field strength of 20 V/mm with an application time of 1 min is suggested to be the optimal combination of electro filtration parameters for maximized flux recovery and corresponding experimental rejection efficiency of more than 90%. Overall, this research contributes to a better understanding of the parameters governing electro-filtration and offers insights for improving the performance of membrane-based microalgae harvesting systems.


Asunto(s)
Microalgas , Membranas Artificiales , Filtración , Electricidad , Membranas
4.
J Hazard Mater ; 463: 132822, 2024 02 05.
Artículo en Inglés | MEDLINE | ID: mdl-37898090

RESUMEN

Organic ultraviolet filters (OUVFs) have been used globally for the past 20 years. Given that OUVFs can be quickly released from sunscreens applied on human skins, they have been frequently detected in aquatic environments and organisms. Some byproducts of OUVFs might be more recalcitrant and toxic than their parent compounds. To further assess the toxicity and potential risk of OUVFs' byproducts, it is necessary to determine the fate of OUVFs and identify their transformation products. This review summarizes and analyzes pertinent literature and reports in the field of OUVFs research. These published research works majorly focus on the degradation mechanisms of OUVFs in aquatic environments, their intermediates/byproducts, and chlorination reaction. Photodegradation (direct photolysis, self-sensitive photolysis and indirect photolysis) and biodegradation are the main transformation pathways of OUVFs through natural degradation. To remove residual OUVFs' pollutants from aqueous environments, novel physicochemical and biological approaches have been developed in recent years. Advanced oxidation, ultrasound, and bio-based technologies have been proven to eliminate OUVFs from wastewaters. In addition, the disinfection mechanism and the byproducts (DBPs) of various OUVFs in swimming pools are discussed in this review. Besides, knowledge gaps and future research directions in this field of study are also mentioned.


Asunto(s)
Contaminantes Químicos del Agua , Purificación del Agua , Humanos , Agua , Contaminantes Químicos del Agua/toxicidad , Contaminantes Químicos del Agua/análisis , Rayos Ultravioleta , Protectores Solares/toxicidad , Desinfección , Fotólisis
5.
Small ; : e2310117, 2023 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-38155494

RESUMEN

Chemical mechanical polishing (CMP) offers a promising pathway to smooth third-generation semiconductors. However, it is still a challenge to reduce the use of additional oxidants or/and energy in current CMP processes. Here, a new and green atomically smoothing method: Piezocatalytic-CMP (Piezo-CMP) is reported. Investigation shows that the Piezo-CMP based on tetragonal BaTiO3 (t-BT) can polish the rough surface of a reaction sintering SiC (RS-SiC) to the ultra-smooth surface with an average surface roughness (Ra) of 0.45 nm and the rough surface of a single-crystal 4H-SiC to the atomic planarization Si and C surfaces with Ra of 0.120 and 0.157 nm, respectively. In these processes, t-BT plays a dual role of piezocatalyst and abrasive. That is, it piezo-catalytically generates in-situ active oxygen species to selectively oxidize protruding sites of SiC surface, yielding soft SiO2 , and subsequently, it acts as a usual abrasive to mechanically remove these SiO2 . This mechanism is further confirmed by density functional theory (DFT) calculation and molecular simulation. In this process, piezocatalytic oxidation is driven only by the original pressure and friction force of a conventional polishing process, thus, the piezo-CMP process do not require any additional oxidant and energy, being a green and effective polishing method.

6.
J Hazard Mater ; 433: 128702, 2022 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-35395522

RESUMEN

The continuous growth of e-waste necessitates an efficient method to recover their metal contents to improve their recycling rate. The successful recovery of the metallic component from Waste Electrical and Electronic Equipment (WEEE) can generate great economic benefits to incentivize the industrial recycling effort. In this study, we report the use of slurry electrolysis (SE) in pH-neutral ethylene glycol (EG) electrolyte to extract and recover the metallic component from waste printed circuit broad (WPCB) powder. The system operates at room temperature and atmospheric pressure, and the electrolyte can be recycled multiple times with no signs of chemical degradation. The EG electrolyte system can oxidize the metallic component without triggering anodic gas evolution, which allowed us to incorporate a reticulated vitreous carbon (RVC) foam anode to maximize the capture and oxidation of the metal content. The system demonstrated up to 99.1% Faraday efficiency for the cathodic metal deposition and could recover Cu from the WPCB powder in a selective manner of 59.7% in the presence of 12 other metals. The SE reaction system was also scalable and displayed no compromises on the Cu recovery selectivity. With the ability to leach and recover metallic content from WPCB in a mild and chemically benign condition, the SE system displayed much promise to be adapted for industrial-scale metal recovery from WPCB.

7.
Int J Ophthalmol ; 10(2): 293-299, 2017.
Artículo en Inglés | MEDLINE | ID: mdl-28251091

RESUMEN

AIM: To estimate the overall drug compliance for local Chinese glaucoma patients on long-term topical treatment. METHODS: This was a retrospective cross-sectional study. Fifty-seven primary glaucoma patients from the subspecialty clinic of a publicly-funded tertiary care hospital in Hong Kong completed a questionnaire on compliance with topical glaucoma medication, attitude towards glaucoma and therapy and vision related quality of life. Noncompliance was defined as reporting missing more than or equal to 10% of the prescribed topical glaucoma medication during the 2wk immediately prior to the consultation. Relationships between noncompliance and demographics, attitude, disease and treatment status was studied. Cost was estimated with quality of life and direct medical cost involved with noncompliance. Multivariable logistic regression on noncompliance was performed on selected factors. RESULTS: Compliance was calculated as 75% (95% CI: 64%-87%) among 57 subjects (mean age 69y, female 51%). No statistical significant relationship was established between noncompliance and any single factors or outcomes. Age (P=0.048) and forgetfulness (P=0.064) were found to be marginally significant predictive factors on noncompliance in multivariable logistic regression. Noncompliance might be related (P=0.130) to poorer self-rated vision-associated quality of life. The societal cost of noncompliance was estimated to be over 2510 life-years and US$ 3.7 million territory-wide. CONCLUSION: The compliance of Chinese glaucoma patients in Hong Kong is comparable to other parts in the world, and carries detrimental impacts on individual and societal levels. Age and forgetfulness are two possible independent predictors for noncompliance.

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