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Current Advances in Photochemistry
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Current Advances in Photochemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Photochemistry".

Deadline for manuscript submissions: 30 June 2024 | Viewed by 6008

Special Issue Editors

Dr. Giuseppina La Ganga

E-Mail Website
Guest Editor
Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, and Interuniversitary Research Center for Artificial Photosynthesis (SOLAR-CHEM), Università degli Studi di Messina, Via F. Stagno d’Alcontres 31, 98166 Messina, Italy
Interests: artificial photosynthesis; supramolecular photochemistry; photophysics and photochemistry of coordination compounds/photocatalysis; photoinduced electron and energy transfer
Dr. Serena Berardi

E-Mail Website
Guest Editor
Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, Ferrara, Italy
Interests: photoelectrochemistry; semiconductor; catalysis

Special Issue Information

Dear Colleagues,

In recent years, photochemistry has undergone considerable development in various fields of science, as well as influenced several aspects of our life. The study of photochemical systems can exploit sunlight in order to drive chemical reactions or to generate electricity, which is of great practical significance for the production of sustainable energy vectors.

This Special Issue aims to provide an overview on the latest achievements in photochemistry, highlighting new molecular, supramolecular, and/or material-based systems, as well as their use in applications such as (but not limited to) bioimaging, functional devices, and catalysis. Particular attention can be given to the artificial photosynthesis approach, i.e., to the design of new molecular chromophores, redox catalysts, and electron donors/acceptors for solar energy conversion into value-added products or fuels. Studies of the dynamics of energy/charge transfer processes, also by means of ultrafast techniques, will also be welcomed.

Dr. Giuseppina La Ganga
Dr. Serena Berardi
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • supramolecular photochemistry
  • photocatalysis
  • new luminescent material
  • artificial photosynthesis
  • photochemistry and photophysics of coordination compounds
  • environmental photocatalysis
  • photoinduced electron and energy transfer
  • photoelectrocatalysis

Published Papers (6 papers)

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Research

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14 pages, 4493 KiB  
Article
Visible Light-Promoted Oxidative Cross-Coupling of Alcohols to Esters
by Andrea Dellisanti, Elisa Chessa, Andrea Porcheddu, Massimo Carraro, Luisa Pisano, Lidia De Luca and Silvia Gaspa
Molecules 2024, 29(3), 570; https://doi.org/10.3390/molecules29030570 - 23 Jan 2024
Viewed by 911
Abstract
Ester is one of the most significant functional groups in organic chemistry and is enclosed in several valued molecules. Usually, esters are prepared through the acid-catalyzed esterification reaction of carboxylic acids with alcohols, transesterification of esters with alcohols, or via activation of carboxylic [...] Read more.
Ester is one of the most significant functional groups in organic chemistry and is enclosed in several valued molecules. Usually, esters are prepared through the acid-catalyzed esterification reaction of carboxylic acids with alcohols, transesterification of esters with alcohols, or via activation of carboxylic acids followed by the addition of alcohols. However, these procedures typically imply the excess use of reactants and harsh reaction conditions. Visible light-mediated photoreactions have been disclosed to display a safe, sustainable, and accessible alternative to traditional methods, and to lead new reactivity modes in organic procedures. In this context, we propose a transition metal-based and organic-based photocatalyst-free synthesis of esters from alcohols induced by visible light. The methodology can be carried out using sunlight or artificial visible light as a solar simulator or a blue LED source. Full article
(This article belongs to the Special Issue Current Advances in Photochemistry)
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14 pages, 2295 KiB  
Article
Possible Effects of Changes in Carbonate Concentration and River Flow Rate on Photochemical Reactions in Temperate Aquatic Environments
by Davide Vione, Federica Saglia and Carola Pelazza
Molecules 2023, 28(20), 7072; https://doi.org/10.3390/molecules28207072 - 13 Oct 2023
Cited by 1 | Viewed by 635
Abstract
In temperate environments, climate change could affect water pH by inducing enhanced dissolution of CaSO4 followed by biological sulphate reduction, with the potential to basify water due to H+ consumption. At the same time, increased atmospheric CO2 could enhance weathering [...] Read more.
In temperate environments, climate change could affect water pH by inducing enhanced dissolution of CaSO4 followed by biological sulphate reduction, with the potential to basify water due to H+ consumption. At the same time, increased atmospheric CO2 could enhance weathering of carbonate rocks (e.g., dolomite) and increase the total concentration of dissolved carbonate species. Both processes enhance phototransformation by the carbonate radical (CO3•−), as shown for the non-steroidal anti-inflammatory drug paracetamol, provided that the dissolved organic carbon of water does not undergo important fluctuations. Climate change could also affect hydrology, and prolonged drought periods might considerably decrease flow rates in rivers. This is a substantial problem because wastewater pollutants become less diluted and, as a result, can exert more harmful effects due to increased concentrations. At the same time, in low-flow conditions, water is also shallower and its flow velocity is decreased. Photochemical reactions become faster because shallow water is efficiently illuminated by sunlight, and they also have more time to occur because water takes longer to cover the same river stretch. As a result, photodegradation of contaminants is enhanced, which offsets lower dilution but only at a sufficient distance from the wastewater outlet; this is because photoreactions need time (which translates into space for a flowing river) to attenuate pollution. Full article
(This article belongs to the Special Issue Current Advances in Photochemistry)
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18 pages, 4098 KiB  
Article
Excited-State Dynamics Leading Either to Triplet Formation or Coordinative Expansion following Photolysis of Cu(II)-Porphyrins: A DFT, TD-DFT, Luminescence and Femtosecond Time-Resolved Absorbance Study
by Ross J. McGarry, Lazaros Varvarezos, Mary T. Pryce and Conor Long
Molecules 2023, 28(17), 6310; https://doi.org/10.3390/molecules28176310 - 29 Aug 2023
Viewed by 1035
Abstract
The photophysical properties of Cu(II) complexes with 5,10,15,20-meso-tetrakis(phenyl)porphyrin and 5,10,15,20-meso-tetrakis(N-methylpyridium-4-yl)porphyrin are examined via the luminescence and femtosecond time-resolved absorbance methods, respectively. These studies are supported by DFT and TD-DFT calculations, which highlight the [...] Read more.
The photophysical properties of Cu(II) complexes with 5,10,15,20-meso-tetrakis(phenyl)porphyrin and 5,10,15,20-meso-tetrakis(N-methylpyridium-4-yl)porphyrin are examined via the luminescence and femtosecond time-resolved absorbance methods, respectively. These studies are supported by DFT and TD-DFT calculations, which highlight the important role played by ligand-to-metal charge-transfer states in directing the system toward either intersystem crossing to the triplet hypersurface or coordinative expansion to a five-coordinate quasi-stable intermediate. The latter processes occur when the porphyrin is photolyzed in the presence of suitably located Lewis bases. Femtosecond time-resolved absorbance measurements of Cu(II)-5,10,15,20-meso-tetrakis(N-methylpyridium-4-yl)porphyrin confirm that the coordinative expansion in water occurs in approximately 700 fs, while crossing to the triplet hypersurface takes approximately 140 fs in the same solvent. These processes are mutually exclusive, although both can occur simultaneously depending on the environment of the porphyrin. The ratio of the two processes depends on the relative orientation of the Lewis base with respect to the copper atom at the time of excitation. As a consequence, copper porphyrins such as these are excellent probes in the environment of the porphyrin and can be used to identify the location of the porphyrin when interacting with DNA fragments. Full article
(This article belongs to the Special Issue Current Advances in Photochemistry)
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16 pages, 5261 KiB  
Article
Effect of the Synthetic Parameters over ZnO in the CO2 Photoreduction
by Danny Zanardo, Giulia Forghieri, Elena Ghedini, Federica Menegazzo, Alessia Giordana, Giuseppina Cerrato, Elti Cattaruzza, Alessandro Di Michele, Giuseppe Cruciani and Michela Signoretto
Molecules 2023, 28(12), 4798; https://doi.org/10.3390/molecules28124798 - 16 Jun 2023
Cited by 1 | Viewed by 899
Abstract
Zinc oxide (ZnO) is an attractive semiconductor material for photocatalytic applications, owing to its opto-electronic properties. Its performances are, however, strongly affected by the surface and opto-electronic properties (i.e., surface composition, facets and defects), in turn related to the synthesis conditions. The knowledge [...] Read more.
Zinc oxide (ZnO) is an attractive semiconductor material for photocatalytic applications, owing to its opto-electronic properties. Its performances are, however, strongly affected by the surface and opto-electronic properties (i.e., surface composition, facets and defects), in turn related to the synthesis conditions. The knowledge on how these properties can be tuned and how they are reflected on the photocatalytic performances (activity and stability) is thus essential to achieve an active and stable material. In this work, we studied how the annealing temperature (400 °C vs. 600 °C) and the addition of a promoter (titanium dioxide, TiO2) can affect the physico-chemical properties of ZnO materials, in particular surface and opto-electronic ones, prepared through a wet-chemistry method. Then, we explored the application of ZnO as a photocatalyst in CO2 photoreduction, an appealing light-to-fuel conversion process, with the aim to understand how the above-mentioned properties can affect the photocatalytic activity and selectivity. We eventually assessed the capability of ZnO to act as both photocatalyst and CO2 adsorber, thus allowing the exploitation of diluted CO2 sources as a carbon source. Full article
(This article belongs to the Special Issue Current Advances in Photochemistry)
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11 pages, 1805 KiB  
Article
Photochemical Implications of Changes in the Spectral Properties of Chromophoric Dissolved Organic Matter: A Model Assessment for Surface Waters
by Nicole Altare and Davide Vione
Molecules 2023, 28(6), 2664; https://doi.org/10.3390/molecules28062664 - 15 Mar 2023
Viewed by 993
Abstract
Chromophoric dissolved organic matter (CDOM) is the main sunlight absorber in surface waters and a very important photosensitiser towards the generation of photochemically produced reactive intermediates (PPRIs), which take part in pollutant degradation. The absorption spectrum of CDOM (ACDOM(λ), unitless) [...] Read more.
Chromophoric dissolved organic matter (CDOM) is the main sunlight absorber in surface waters and a very important photosensitiser towards the generation of photochemically produced reactive intermediates (PPRIs), which take part in pollutant degradation. The absorption spectrum of CDOM (ACDOM(λ), unitless) can be described by an exponential function that decays with increasing wavelength: ACDOM(λ) = 100 d DOC Ao e− Sλ, where d [m] is water depth, DOC [mgC L−1] is dissolved organic carbon, Ao [L mgC−1 cm−1] is a pre-exponential factor, and S [nm−1] is the spectral slope. Sunlight absorption by CDOM is higher when Ao and DOC are higher and S is lower, and vice versa. By the use of models, here we investigate the impact of changes in CDOM spectral parameters (Ao and S) on the steady-state concentrations of three PPRIs: the hydroxyl radical (•OH), the carbonate radical (CO3•−), and CDOM excited triplet states (3CDOM*). A first finding is that variations in both Ao and S have impacts comparable to DOC variations on the photochemistry of CDOM, when reasonable parameter values are considered. Therefore, natural variability of the spectral parameters or their modifications cannot be neglected. In the natural environment, spectral parameters could, for instance, change because of photobleaching (prolonged exposure of CDOM to sunlight, which decreases Ao and increases S) or of the complex and still poorly predictable effects of climate change. A second finding is that, while the steady-state [3CDOM*] would increase with increasing ACDOM (increasing Ao, decreasing S), the effect of spectral parameters on [•OH] and [CO3•−] depends on the relative roles of CDOM vs. NO3− and NO2− as photochemical •OH sources. Full article
(This article belongs to the Special Issue Current Advances in Photochemistry)
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Review

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55 pages, 7312 KiB  
Review
Recent Advances in Light-Driven Semiconductor-Based Micro/Nanomotors: Optimization Strategies and Emerging Applications
by Vanessa R. A. Ferreira and Manuel A. Azenha
Molecules 2024, 29(5), 1154; https://doi.org/10.3390/molecules29051154 - 05 Mar 2024
Viewed by 887
Abstract
Micro/nanomotors represent a burgeoning field of research featuring small devices capable of autonomous movement in liquid environments through catalytic reactions and/or external stimuli. This review delves into recent advancements in light-driven semiconductor-based micro/nanomotors (LDSM), focusing on optimized syntheses, enhanced motion mechanisms, and emerging [...] Read more.
Micro/nanomotors represent a burgeoning field of research featuring small devices capable of autonomous movement in liquid environments through catalytic reactions and/or external stimuli. This review delves into recent advancements in light-driven semiconductor-based micro/nanomotors (LDSM), focusing on optimized syntheses, enhanced motion mechanisms, and emerging applications in the environmental and biomedical domains. The survey commences with a theoretical introduction to micromotors and their propulsion mechanisms, followed by an exploration of commonly studied LDSM, emphasizing their advantages. Critical properties affecting propulsion, such as surface features, morphology, and size, are presented alongside discussions on external conditions related to light sources and intensity, which are crucial for optimizing the propulsion speed. Each property is accompanied by a theoretical background and conclusions drawn up to 2018. The review further investigates recent adaptations of LDSM, uncovering underlying mechanisms and associated benefits. A brief discussion is included on potential synergistic effects between different external conditions, aiming to enhance efficiency—a relatively underexplored topic. In conclusion, the review outlines emerging applications in biomedicine and environmental monitoring/remediation resulting from recent LDSM research, highlighting the growing significance of this field. The comprehensive exploration of LDSM advancements provides valuable insights for researchers and practitioners seeking to leverage these innovative micro/nanomotors in diverse applications. Full article
(This article belongs to the Special Issue Current Advances in Photochemistry)
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