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1.
Biofabrication ; 16(3)2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38604157

RESUMEN

Scaffolds play a pivotal role in tissue engineering and serve as vital biological substitutes, providing structural support for cell adhesion and subsequent tissue development. An ideal scaffold must possess mechanical properties suitable for tissue function and exhibit biodegradability. Although synthetic polymer scaffolds offer high rigidity and elasticity owing to their reactive side groups, which facilitate tailored mechanical and rheological properties, they may lack biological cues and cause persistent side effects during degradation. To address these challenges, natural polymers have garnered attention owing to their inherent bioactivity and biocompatibility. However, natural polymers such as silk fibroin (SF) and tyramine-modified alginate (AT) have limitations, including uncontrolled mechanical properties and weak structural integrity. In this study, we developed a blend of SF and AT as a printable biomaterial for extrusion-based 3D printing. Using photocrosslinkable SF/AT inks facilitated the fabrication of complex scaffolds with high printability, thereby enhancing their structural stability. The incorporation of silver nitrate facilitated the tunability of mechanical and rheological behaviors. SF/AT scaffolds with varying stiffness in the physiologically relevant range for soft tissues (51-246 kPa) exhibited excellent biocompatibility, indicating their promising potential for diverse applications in tissue engineering.


Asunto(s)
Alginatos , Fibroínas , Impresión Tridimensional , Nitrato de Plata , Andamios del Tejido , Fibroínas/química , Alginatos/química , Andamios del Tejido/química , Nitrato de Plata/química , Animales , Reactivos de Enlaces Cruzados/química , Ingeniería de Tejidos , Materiales Biocompatibles/química , Materiales Biocompatibles/farmacología , Reología , Humanos , Ratones , Procesos Fotoquímicos , Tiramina/química
2.
J Hazard Mater ; 470: 134198, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38608582

RESUMEN

A novel Ag3PO4/ZnWO4-modified graphite felt electrode (AZW@GF) was prepared by drop coating method and applied to photoelectrocatalytic removal of harmful algae. Results showed that approximately 99.21% of chlorophyll a and 91.57% of Microcystin-LR (MCLR) were degraded by the AZW@GF-Pt photoelectrocatalytic system under the optimal operating conditions with a rate constant of 0.02617 min-1 and 0.01416 min-1, respectively. The calculated synergistic coefficient of photoelectrocatalytic algal removal and MC-LR degradation by the AZW@GF-Pt system was both larger than 1.9. In addition, the experiments of quenching experiments and electron spin resonance (ESR) revealed that the photoelectrocatalytic reaction mainly generated •OH and •O2- for algal removal and MC-LR degradation. Furthermore, the potential pathway for photoelectrocatalytic degradation of MC-LR was proposed. Finally, the photoelectrocatalytic cycle algae removal experiments were carried out on AZW@GF electrode, which was found to maintain the algae removal efficiency at about 91% after three cycles of use, indicating that the photoelectrocatalysis of AZW@GF electrode is an effective emergency algae removal technology.


Asunto(s)
Electrodos , Grafito , Toxinas Marinas , Microcistinas , Compuestos de Plata , Grafito/química , Grafito/efectos de la radiación , Microcistinas/química , Microcistinas/aislamiento & purificación , Catálisis , Compuestos de Plata/química , Fosfatos/química , Óxidos/química , Técnicas Electroquímicas , Tungsteno/química , Clorofila A/química , Zinc/química , Purificación del Agua/métodos , Clorofila/química , Procesos Fotoquímicos , Floraciones de Algas Nocivas
3.
J Hazard Mater ; 470: 134258, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38608588

RESUMEN

Photochemical active species generated from photosensitizers, e.g., dissolved organic matter (DOM), play vital roles in the transformation of micropollutants in water. Here, butanedione (BD), a redox-active moiety in DOM and widely found in nature, was employed to photo-transform naproxen (NPX) with peracetic acid (PAA) and H2O2 as contrasts. The results obtained showed that the BD exhibited more applicable on NPX degradation. It works in the lake or river water under UV and solar irradiation, and its NPX degradation efficiency was 10-30 times faster than that of PAA and H2O2. The reason for the efficient transformation of pollutants is that the BD system was proved to be a non-free radical dominated mechanism. The quantum yield of BD (Ф254 nm) was calculated to be 0.064, which indicates that photophysical process is the dominant mode of BD conversion. By adding trapping agents, direct energy transfer from 3BD* to NPX (in anoxic environment) or dissolved oxygen (in aerobic environment) was proved to play a major role (> 91 %). Additionally, the BD process reduces the toxicity of NPX and promotes microbial growth after irradiation. Overall, this study significantly deepened the understanding of the transformation between BD and micropollutants, and provided a potential BD-based process for micropollutants removal under solar irradiation.


Asunto(s)
Naproxeno , Fotólisis , Rayos Ultravioleta , Contaminantes Químicos del Agua , Naproxeno/química , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/efectos de la radiación , Transferencia de Energía , Peróxido de Hidrógeno/química , Ácido Peracético/química , Procesos Fotoquímicos
4.
J Mater Chem B ; 12(16): 3881-3907, 2024 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-38572601

RESUMEN

Water splitting is promising, especially for energy and environmental applications; however, there are limited studies on the link between water splitting and cancer treatment. Upconversion nanoparticles (UCNPs) can be used to convert near-infrared (NIR) light to ultraviolet (UV) or visible (Vis) light and have great potential for biomedical applications because of their profound penetration ability, theranostic approaches, low self-fluorescence background, reduced damage to biological tissue, and low toxicity. UCNPs with photocatalytic materials can enhance the photocatalytic activities that generate a shorter wavelength to increase the tissue penetration depth in the biological microenvironment under NIR light irradiation. Moreover, UCNPs with a photosensitizer can absorb NIR light and convert it into UV/vis light and emit upconverted photons, which excite the photoinitiator to create H2, O2, and/or OH˙ via water splitting processes when exposed to NIR irradiation. Therefore, combining UCNPs with intensified photocatalytic and photoinitiator materials may be a promising therapeutic approach for cancer treatment. This review provides a novel strategy for explaining the principles and mechanisms of UCNPs and NIR-driven UCNPs with photocatalytic materials through water splitting to achieve therapeutic outcomes for clinical applications. Moreover, the challenges and future perspectives of UCNP-based photocatalytic materials for water splitting for cancer treatment are discussed in this review.


Asunto(s)
Rayos Infrarrojos , Nanopartículas , Neoplasias , Agua , Humanos , Nanopartículas/química , Catálisis , Agua/química , Neoplasias/tratamiento farmacológico , Antineoplásicos/química , Antineoplásicos/farmacología , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Animales , Procesos Fotoquímicos
5.
Chem Commun (Camb) ; 60(34): 4581-4584, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38576349

RESUMEN

A study of an integrated OPECT biosensor gate and the EC color-changing region on the same chip was carried out, achieving sensitive detection through bioetching-induced signal changes. Enzymatic bioetching enables specific alkaline phosphatase (ALP) detection by catalyzing the production of CdS, which modulates the channel current and generates a visual signal.


Asunto(s)
Fosfatasa Alcalina , Técnicas Biosensibles , Técnicas Electroquímicas , Fosfatasa Alcalina/metabolismo , Fosfatasa Alcalina/análisis , Transistores Electrónicos , Compuestos de Cadmio/química , Sulfuros/química , Procesos Fotoquímicos
6.
Environ Int ; 186: 108629, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38582060

RESUMEN

Recently, extreme wildfires occur frequently around the world and emit substantial brown carbon (BrC) into the atmosphere, whereas the molecular compositions and photochemical evolution of BrC remain poorly understood. In this work, primary smoke aerosols were generated from wood smoldering, and secondary smoke aerosols were formed by the OH radical photooxidation in an oxidation flow reactor, where both primary and secondary smoke samples were collected on filters. After solvent extraction of filter samples, the molecular composition of dissolved organic carbon (DOC) was determined by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). The molecular composition of dissolved BrC was obtained based on the constraints of DOC formulae. The proportion of dissolved BrC fractions accounted for approximately 1/3-1/2 molecular formulae of DOC. The molecular characteristics of dissolved BrC showed higher levels of carbon oxidation state, double bond equivalents, and modified aromaticity index than those of DOC, indicating that dissolved BrC fractions were a class of organic structures with relatively higher oxidation state, unsaturated and aromatic degree in DOC fractions. The comparative analysis suggested that aliphatic and olefinic structures dominated DOC fractions (contributing to 70.1%-76.9%), while olefinic, aromatic, and condensed aromatic structures dominated dissolved BrC fractions (contributing to 97.5%-99.9%). It is worth noting that dissolved BrC fractions only contained carboxylic-rich alicyclic molecules (CRAMs)-like structures, unsaturated hydrocarbons, aromatic structures, and highly oxygenated compounds. CRAMs-like structures were the most abundant species in both DOC and dissolved BrC fractions. Nevertheless, the specific molecular characteristics for DOC and dissolved BrC fractions varied with subgroups after aging. The results highlight the similarities and differences in the molecular compositions and characteristics of DOC and dissolved BrC fractions with aging. This work will provide insights into understanding the molecular composition of DOC and dissolved BrC in smoke.


Asunto(s)
Aerosoles , Carbono , Humo , Madera , Carbono/análisis , Carbono/química , Humo/análisis , Madera/química , Aerosoles/análisis , Aerosoles/química , Oxidación-Reducción , Incendios Forestales , Contaminantes Atmosféricos/análisis , Contaminantes Atmosféricos/química , Procesos Fotoquímicos
7.
Inorg Chem ; 63(16): 7493-7503, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38578920

RESUMEN

The relentless increase in drug resistance of platinum-based chemotherapeutics has opened the scope for other new cancer therapies with novel mechanisms of action (MoA). Recently, photocatalytic cancer therapy, an intrusive catalytic treatment, is receiving significant interest due to its multitargeting cell death mechanism with high selectivity. Here, we report the synthesis and characterization of three photoresponsive Ru(II) complexes, viz., [Ru(ph-tpy)(bpy)Cl]PF6 (Ru1), [Ru(ph-tpy)(phen)Cl]PF6 (Ru2), and [Ru(ph-tpy)(aip)Cl]PF6 (Ru3), where, ph-tpy = 4'-phenyl-2,2':6',2″-terpyridine, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and aip = 2-(anthracen-9-yl)-1H-imidazo[4,5-f][1,10] phenanthroline, showing photocatalytic anticancer activity. The X-ray crystal structures of Ru1 and Ru2 revealed a distorted octahedral geometry with a RuN5Cl core. The complexes showed an intense absorption band in the 440-600 nm range corresponding to the metal-to-ligand charge transfer (MLCT) that was further used to achieve the green light-induced photocatalytic anticancer effect. The mitochondria-targeting photostable complex Ru3 induced phototoxicity with IC50 and PI values of ca. 0.7 µM and 88, respectively, under white light irradiation and ca. 1.9 µM and 35 under green light irradiation against HeLa cells. The complexes (Ru1-Ru3) showed negligible dark cytotoxicity toward normal splenocytes (IC50s > 50 µM). The cell death mechanistic study revealed that Ru3 induced ROS-mediated apoptosis in HeLa cells via mitochondrial depolarization under white or green light exposure. Interestingly, Ru3 also acted as a highly potent catalyst for NADH photo-oxidation under green light. This NADH photo-oxidation process also contributed to the photocytotoxicity of the complexes. Overall, Ru3 presented multitargeting synergistic type I and type II photochemotherapeutic effects.


Asunto(s)
Antineoplásicos , Complejos de Coordinación , Luz , Piridinas , Rutenio , Humanos , Rutenio/química , Rutenio/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Piridinas/química , Piridinas/farmacología , Catálisis , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Complejos de Coordinación/efectos de la radiación , Ensayos de Selección de Medicamentos Antitumorales , Procesos Fotoquímicos , Proliferación Celular/efectos de los fármacos , Estructura Molecular , Células HeLa , Especies Reactivas de Oxígeno/metabolismo , Apoptosis/efectos de los fármacos , Supervivencia Celular/efectos de los fármacos , 60495
8.
Astrobiology ; 24(4): 407-422, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38603526

RESUMEN

Recent ground-based observations of Venus have detected a single spectral feature consistent with phosphine (PH3) in the middle atmosphere, a gas which has been suggested as a biosignature on rocky planets. The presence of PH3 in the oxidized atmosphere of Venus has not yet been explained by any abiotic process. However, state-of-the-art experimental and theoretical research published in previous works demonstrated a photochemical origin of another potential biosignature-the hydride methane-from carbon dioxide over acidic mineral surfaces on Mars. The production of methane includes formation of the HC · O radical. Our density functional theory (DFT) calculations predict an energetically plausible reaction network leading to PH3, involving either HC · O or H· radicals. We suggest that, similarly to the photochemical formation of methane over acidic minerals already discussed for Mars, the origin of PH3 in Venus' atmosphere could be explained by radical chemistry starting with the reaction of ·PO with HC·O, the latter being produced by reduction of CO2 over acidic dust in upper atmospheric layers of Venus by ultraviolet radiation. HPO, H2P·O, and H3P·OH have been identified as key intermediate species in our model pathway for phosphine synthesis.


Asunto(s)
Fosfinas , Venus , Medio Ambiente Extraterrestre , Rayos Ultravioleta , Procesos Fotoquímicos , Atmósfera , Metano
9.
J Chem Inf Model ; 64(8): 3205-3212, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38544337

RESUMEN

Language models trained on domain-specific corpora have been employed to increase the performance in specialized tasks. However, little previous work has been reported on how specific a "domain-specific" corpus should be. Here, we test a number of language models trained on varyingly specific corpora by employing them in the task of extracting information from photocatalytic water splitting. We find that more specific corpora can benefit performance on downstream tasks. Furthermore, PhotocatalysisBERT, a pretrained model from scratch on scientific papers on photocatalytic water splitting, demonstrates improved performance over previous work in associating the correct photocatalyst with the correct photocatalytic activity during information extraction, achieving a precision of 60.8(+11.5)% and a recall of 37.2(+4.5)%.


Asunto(s)
Procesos Fotoquímicos , Agua , Agua/química , Catálisis
10.
Langmuir ; 40(13): 7021-7028, 2024 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-38501919

RESUMEN

Photodynamic therapy (PDT) stands as an efficacious modality for the treatment of cancer and various diseases, in which optimization of the electron transfer and augmentation of the production of lethal reactive oxygen species (ROS) represent pivotal challenges to enhance its therapeutic efficacy. Empirical investigations have established that the spontaneous initiation of redox reactions associated with electron transfer is feasible and is located in the gas-liquid interfaces. Meanwhile, nanobubbles (NBs) are emerging as entities capable of furnishing a plethora of such interfaces, attributed to their stability and large surface/volume ratio in bulk water. Thus, NBs provide a chance to expedite the electron-transfer kinetics within the context of PDT in an ambient environment. In this paper, we present a pioneering exploration into the impact of nitrogen nanobubbles (N2-NBs) on the electron transfer of the photosensitizer levofloxacin (LEV). Transient absorption spectra and time-resolved decay spectra, as determined through laser flash photolysis, unequivocally reveal that N2-NBs exhibit a mitigating effect on the decay of the LEV excitation triplet state, thereby facilitating subsequent processes. Of paramount significance is the observation that the presence of N2-NBs markedly accelerates the electron transfer of LEV, albeit with a marginal inhibitory influence on its energy-transfer reaction. This observation is corroborated through absorbance measurements and offers compelling evidence substantiating the role of NBs in expediting electron transfer within the ambit of PDT. The mechanism elucidated herein sheds light on how N2-NBs intricately influence both electron-transfer and energy-transfer reactions in the photosensitizer LEV. These findings not only contribute to a nuanced understanding of the underlying processes but also furnish novel insights that may inform the application of NBs in the realm of photodynamic therapy.


Asunto(s)
Levofloxacino , Fármacos Fotosensibilizantes , Fármacos Fotosensibilizantes/farmacología , Levofloxacino/farmacología , Procesos Fotoquímicos , Oxidación-Reducción , Transporte de Electrón
11.
Environ Sci Technol ; 58(13): 5856-5865, 2024 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-38516968

RESUMEN

Measuring the quantum yield and reactivity of triplet-state dissolved organic matter (3DOM*) is essential for assessing the impact of DOM on aquatic photochemical processes. However, current 3DOM* quantification methods require multiple fitting steps and rely on steady-state approximations under stringent application criteria, which may introduce certain inaccuracies in the estimation of DOM photoreactivity parameters. Here, we developed a global kinetic model to simulate the reaction kinetics of the hv/DOM system using four DOM types and 2,4,6-trimethylphenol as the probe for 3DOM*. Analyses of residuals and the root-mean-square error validated the exceptional precision of the new model compared to conventional methods. 3DOM* in the global kinetic model consistently displayed a lower quantum yield and higher reactivity than those in local regression models, indicating that the generation and reactivity of 3DOM* have often been overestimated and underestimated, respectively. The global kinetic model derives parameters by simultaneously fitting probe degradation kinetics under different conditions and considers the temporally increasing concentrations of the involved reactive species. It minimizes error propagation and offers insights into the interactions of different species, thereby providing advantages in accuracy, robustness, and interpretability. This study significantly advances the understanding of 3DOM* behavior and provides a valuable kinetic model for aquatic photochemistry research.


Asunto(s)
Materia Orgánica Disuelta , Procesos Fotoquímicos , Fotoquímica , Fotólisis
13.
Anal Chim Acta ; 1299: 342449, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38499430

RESUMEN

Antifouling biosensors capable of preventing protein nonspecific adhesion in real human bodily fluids are highly sought-after for precise disease diagnosis and treatment. In this context, an enhanced split-type photoelectrochemical (PEC) aptasensor was developed incorporating a four-armed polyethylene glycol (4A-PEG) to construct a robust antifouling coating, enabling accurate and sensitive bioanalysis. The split-type PEC system involved the photoelectrode and the biocathode, effectively separating signal converter with biorecogniton events. Specifically, the TiO2 electrode underwent sequential modification with ZnIn2S4 (ZIS) and polydopamine (PDA) to form the PDA/ZIS/TiO2 photoelectrode. The cathode substrate was synthesized as a hybrid of N-doped graphene loaded with Pt nanoparticles (NG-Pt), and subsequently modified with 4A-PEG to establish a robust antifouling coating. Following the anchoring of probe DNA (pDNA) on the 4A-PEG-grafted antifouling coating, the biocathode for model target of cancer antigen 125 (CA125) was obtained. Leveraging pronounced photocurrent output of the photoelectrode and commendable antifouling characteristics of the biocathode, the split-type PEC aptasensor showcased exceptional detection performances with high sensitivity, good selectivity, antifouling ability, and potential feasibility.


Asunto(s)
Incrustaciones Biológicas , Técnicas Biosensibles , Humanos , Polietilenglicoles , Incrustaciones Biológicas/prevención & control , Técnicas Electroquímicas , Procesos Fotoquímicos
14.
Angew Chem Int Ed Engl ; 63(19): e202403271, 2024 May 06.
Artículo en Inglés | MEDLINE | ID: mdl-38497510

RESUMEN

Unnatural amino acids, and their synthesis by the late-stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design and discovery. Historically, the LSF of biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, such as cysteine, lysine or tyrosine. Herein, we present a photocatalytic hydroarylation process targeting the electrophilic residue dehydroalanine (Dha). This residue possesses an α,ß-unsaturated moiety and can be combined with various arylthianthrenium salts, both in batch and flow reactors. Notably, the flow setup proved instrumental for efficient scale-up, paving the way for the synthesis of unnatural amino acids and peptides in substantial quantities. Our photocatalytic approach, being inherently mild, permits the diversification of peptides even when they contain sensitive functional groups. The readily available arylthianthrenium salts facilitate the seamless integration of Dha-containing peptides with a wide range of arenes, drug blueprints, and natural products, culminating in the creation of unconventional phenylalanine derivatives. The synergistic effect of the high functional group tolerance and the modular characteristic of the aryl electrophile enables efficient peptide conjugation and ligation in both batch and flow conditions.


Asunto(s)
Alanina , Alanina/análogos & derivados , Péptidos , Péptidos/química , Péptidos/síntesis química , Catálisis , Alanina/química , Procesos Fotoquímicos , Estructura Molecular
15.
Mol Pharm ; 21(3): 1233-1245, 2024 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-38350108

RESUMEN

Carbon dioxide radical anion (•CO2-) is a powerful reducing agent that can reduce protein disulfide bonds and convert molecular oxygen to superoxide. Therefore, the generation of •CO2- can be detrimental to pharmaceutical formulations. Iron is among the most prevalent impurities in formulations, where Fe(III) chelates of histidine (His) can produce •CO2- upon exposure to near-UV light (Zhang and Schöneich, Eur. J. Pharm. Biopharm. 2023, 190, 231-241). Here, we monitor by spin-trapping in combination with electron paramagnetic resonance spectroscopy and/or high-performance liquid chromatography-mass spectrometry analysis the photochemical formation of •CO2- for a series of common amino acid excipients, including arginine (Arg), methionine (Met), proline (Pro), glutamic acid (Glu), glycine (Gly), aspartic acid (Asp), and lysine (Lys). Our results indicate that in the presence of Fe(III), Asp, and Glu produce significant yields of •CO2- under photoirradiation with near-UV light. Notably, Asp demonstrates the highest efficiency of •CO2- generation compared with that of the other amino acid excipients. Stable isotope labeling indicates that •CO2- exclusively originates from the α-carboxyl group of Asp. Mechanistic studies reveal two possible pathways for •CO2- formation, which involve either a ß-carboxyl radical or an amino radical cation intermediate.


Asunto(s)
Aminoácidos , Ácido Aspártico , Rayos Ultravioleta , Dióxido de Carbono/química , Excipientes , Compuestos Férricos , Fotólisis , Procesos Fotoquímicos , Ácido Glutámico , Superóxidos
16.
Sci Total Environ ; 919: 170836, 2024 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-38346658

RESUMEN

Same as other bay areas, the Guangdong-Hong Kong-Macao Greater Bay Area (GBA) is also suffering atmospheric composite pollution. Even a series of atmospheric environment management policies have been conducted to win the "blue sky defense battle", the atmospheric secondary pollutants (e.g., O3) originated from oxygenated volatile organic compounds (OVOCs) still threaten the air quality in GBA. However, there lacks a systematic summary on the emission, formation, pollution and environmental effects of OVOCs in this region for further air quality management. This review focused on the researches related to OVOCs in GBA, including their pollution characteristics, detection methods, source distributions, secondary formations, and impacts on the atmosphere. Pollution profile of OVOCs in GBA revealed that the concentration percentage among total VOCs from Guangzhou and Dongguan cities exceeded 50 %, while methanol, formaldehyde, acetone, and acetaldehyde were the top four highest concentrated OVOCs. The detection technique on regional atmospheric OVOCs (e.g., oxygenated organic molecules (OOMs)) underwent an evolution of off-line derivatization method, on-line spectroscopic method and on-line mass spectrometry method. The OVOCs in GBA were mainly from primary emissions (up to 80 %), including vehicle emissions and biomass combustion. The anthropogenic alkenes and aromatics in urban area, and natural isoprene in rural area also made a significant contribution to the secondary emission (e.g., photochemical formation) of OVOCs. About 20 % in average of ROx radicals was produced from photolysis of formaldehyde in comparison with O3, nitrous acid and rest OVOCs, while the reaction between OVOCs and free radical accelerated the NOx-O3 cycle, contributing to 15 %-60 % cumulative formation of O3 in GBA. Besides, the heterogeneous reactions of dicarbonyls generated 21 %-53 % of SOA. This review also provided suggestions for future research on OVOCs in terms of regional observation, analytical method and mechanistic study to support the development of a control and management strategy on OVOCs in GBA and China.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire , Ozono , Compuestos Orgánicos Volátiles , Hong Kong , Macao , Compuestos Orgánicos Volátiles/análisis , Contaminantes Atmosféricos/análisis , Procesos Fotoquímicos , Monitoreo del Ambiente , Contaminación del Aire/análisis , China , Formaldehído/análisis , Ozono/análisis
17.
Int J Mol Sci ; 24(18)2023 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-37762321

RESUMEN

This paper explores the photochemical synthesis of noble metal nanoparticles, specifically gold (Au) and silver (Ag) nanoparticles, using a one-component photoinitiator system. The synthesis process involves visible light irradiation at a wavelength of 419 nm and an intensity of 250 mW/cm2. The radical-generating capabilities of the photoinitiators were evaluated using electron spin resonance (ESR) spectroscopy. The main objective of this study was to investigate how the concentration of metal salts influences the size and distribution of the nanoparticles. Proposed mechanisms for the photochemical formation of nanoparticles through photoinitiated radicals were validated using cyclic voltammetry. The results showed that the concentration of AgNO3 significantly impacted the size of silver nanoparticles, with diameters ranging from 1 to 5 nm at 1 wt% and 3 wt% concentrations, while increasing the concentration to 5 wt% led to an increase in the diameter of silver nanoparticles to 16 nm. When HAuCl4 was used instead of AgNO3, it was found that the average diameters of gold nanoparticles synthesized using both photoinitiators at different concentrations ranged between 1 and 4 nm. The findings suggest that variations in HAuCl4 concentration have minimal impact on the size of gold nanoparticles. The photoproduction of AuNPs was shown to be thermodynamically favorable, with the reduction of HAuCl4 to Au0 having ∆G values of approximately -3.51 and -2.96 eV for photoinitiators A and B, respectively. Furthermore, the photoreduction of Ag+1 to Ag0 was demonstrated to be thermodynamically feasible, with ∆G values of approximately -3.459 and -2.91 eV for photoinitiators A and B, respectively, confirming the effectiveness of the new photoinitiators on the production of nanoparticles. The synthesis of nanoparticles was monitored using UV-vis absorption spectroscopy, and their sizes were determined through particle size analysis of transmission electron microscopy (TEM) images.


Asunto(s)
Nanopartículas del Metal , Nanopartículas del Metal/química , Oro/química , Plata/química , Procesos Fotoquímicos , Cloruro de Sodio , Cloruro de Sodio Dietético , Tamaño de la Partícula
18.
Macromol Rapid Commun ; 44(21): e2300380, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37595267

RESUMEN

The thermal curing of industrial coatings (e.g., car painting and metal coil coatings) is accompanied by a substantial energy consumption due to the intrinsically high temperatures required during the curing process. Therefore, the development of new photochemical curing processes-preferably using visible light-is in high demand. This work describes new diazo-based cross-linkers that can be used to photocure acrylic coatings using blue light. This work demonstrates that the structure of the tethered diazo compounds influences the cross-linking efficiency, finding that side reactions are suppressed upon engineering greater molecular flexibility. Importantly, this work shows that these diazo compounds can be employed as either thermal or photochemical cross-linkers, exhibiting identical crosslinking performances. The performance of diazo-cross-linked coatings is evaluated to reveal excellent water resistance and demonstrably similar material properties to UV-cured acrylates. These studies pave the way for further usage of diazo-functionalized cross-linkers in the curing of paints and coatings.


Asunto(s)
Compuestos Azo , Luz , Compuestos Azo/química , Procesos Fotoquímicos
19.
Proc Natl Acad Sci U S A ; 120(28): e2301153120, 2023 07 11.
Artículo en Inglés | MEDLINE | ID: mdl-37399422

RESUMEN

Night-migratory songbirds have a light-dependent magnetic compass sense, the mechanism of which is thought to depend on the photochemical formation of radical pairs in cryptochrome (Cry) proteins located in the retina. The finding that weak radiofrequency (RF) electromagnetic fields can prevent birds from orienting in the Earth's magnetic field has been regarded as a diagnostic test for this mechanism and as a potential source of information on the identities of the radicals. The maximum frequency that could cause such disorientation has been predicted to lie between 120 and 220 MHz for a flavin-tryptophan radical pair in Cry. Here we show that the magnetic orientation capabilities of Eurasian blackcaps (Sylvia atricapilla) are not affected by RF noise in the frequency bands 140 to 150 MHz and 235 to 245 MHz. From a consideration of its internal magnetic interactions, we argue that RF field effects on a flavin-containing radical-pair sensor should be approximately independent of frequency up to 116 MHz and that birds' sensitivity to RF disorientation should fall by about two orders of magnitude when the frequency exceeds 116 MHz. Taken together with our earlier finding that 75 to 85 MHz RF fields disrupt the magnetic orientation of blackcaps, these results provide compelling evidence that the magnetic compass of migratory birds operates by a radical pair mechanism.


Asunto(s)
Pájaros Cantores , Taxia , Animales , Pájaros Cantores/metabolismo , Procesos Fotoquímicos , Migración Animal , Campos Magnéticos , Criptocromos/metabolismo
20.
Environ Sci Process Impacts ; 25(7): 1150-1168, 2023 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-37376782

RESUMEN

Live bacteria in clouds are exposed to free radicals such as the hydroxyl radical (˙OH), which is the main driver of many photochemical processes. While the ˙OH photooxidation of organic matter in clouds has been widely studied, equivalent investigations on the ˙OH photooxidation of bioaerosols are limited. Little is known about the daytime encounters between ˙OH and live bacteria in clouds. Here we investigated the aqueous ˙OH photooxidation of four bacterial strains, B. subtilis, P. putida, E. hormaechei B0910, and E. hormaechei pf0910, in microcosms composed of artificial cloud water that mimicked the chemical composition of cloud water in Hong Kong. The survival rates for the four bacterial strains decreased to zero within 6 hours during exposure to 1 × 10-16 M of ˙OH under artificial sunlight. Bacterial cell damage and lysis released biological and organic compounds, which were subsequently oxidized by ˙OH. The molecular weights of some of these biological and organic compounds were >50 kDa. The O/C, H/C, and N/C ratios increased at the initial onset of photooxidation. As the photooxidation progressed, there were few changes in the H/C and N/C, whereas the O/C continued to increase for hours after all the bacterial cells had died. The increase in the O/C was due to functionalization and fragmentation reactions, which increased the O content and decreased the C content, respectively. In particular, fragmentation reactions played key roles in transforming biological and organic compounds. Fragmentation reactions cleaved the C-C bonds of carbon backbones of higher molecular weight proteinaceous-like matter to form a variety of lower molecular weight compounds, including HULIS of molecular weight <3 kDa and highly oxygenated organic compounds of molecular weight <1.2 kDa. Overall, our results provided new insights at the process level into how daytime reactive interactions between live bacteria and ˙OH in clouds contribute to the formation and transformation of organic matter.


Asunto(s)
Radical Hidroxilo , Agua , Radical Hidroxilo/química , Bacterias , Compuestos Orgánicos , Procesos Fotoquímicos , Oxidación-Reducción
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