Photochem, Volume 2, Issue 3 (September 2022) – 20 articles

Coulomb explosion experiments using linearly polarized intense 60 fs laser pulses were conducted for structural characterization of three dichloroethylene (DCE) isomers, 1,1-DCE, cis-1,2-DCE, and trans-1,2-DCE. Under relatively low laser intensity at 1.8 × 10¹⁴ W/cm², mass-resolved momentum imaging (MRMI) for selected fragment ions of ³⁵Cl⁺ and C²⁺ revealed different patterns for the three isomers. The C²⁺ ion fragmented from multiply charged trans-1,2-DCE was forced to leave perpendicularly to the direction of the laser polarization, due to recoil forces from adjacent cations. In contrast, the fast ions of C²⁺ from cis-1,2-DCE exhibited an isotropic distribution, whereas the fast ions of C²⁺ from 1,1-DCE recoiled along the laser polarization together with the slow C²⁺ ions, and thereby distinction of the three isomers was demonstrated. Coulomb explosion occurs predominantly at specific orientation, which is useful for potential applications of MRMI analysis to molecular structure assays. Full article

Photosystem II (PSII) is the unique pigment–protein complex that is capable of evolving molecular oxygen using solar energy. The activity of PSII determines the overall productivity of all oxygenic photosynthetic organisms. It is well known that the absence of HCO₃⁻ induces a drop in the activity of PSII. However, it is not yet clear what type of photochemical reaction, single turn-over or multiple turn-over, HCO₃⁻ is involved in. Kinetic parameters of this (these) involvement(s) are almost unexplored now. This work addresses these issues. Using the JIP test, being the perspective noninvasive method for measuring PSII activity in plants, this paper describes how HCO₃⁻ deficiency affects the electron transfer on the oxidizing as well as the reducing sides of PSII in thylakoids and in PSII preparations from the leaves of pea plants. HCO₃⁻ was found to be simultaneously involved both in single turn-over and in multiple turn-over events (“dynamical processes”). Moreover, the involvement of HCO₃⁻ in dynamical photochemical processes was revealed to be associated with both sides of PSII, being the rate limiting on the reducing side, which follows from obtained kinetic parameters. The involvement of HCO₃⁻ in dynamical processes as the constant exchangeable ligand is discussed for both the electron donor and acceptor sides of PSII. Full article

In this work, prereactive complexes, reaction products, and conformational preferences derived from the photochemical reaction between CS₂ and ClF were analyzed following the codeposition of the reactants trapped in argon matrices at cryogenic temperatures. After codeposition of CS₂ and ClF diluted in Ar, the formation of van der Waals complexes is observed. When the mixture is subsequently irradiated by means of broad-band UV-visible light (225 ≤ λ ≤ 800 nm), fluorothiocarbonylsulfenyl chloride (FC(S)SCl) and chlorothiocarbonylsulfenyl fluoride (ClC(S)SF) are produced. These species exist as two stable planar anti- and syn-conformers (anti- and syn- of the C=S double bond with respect to the S–Cl or S–F single bond, respectively). For both novel molecules, anti-FC(S)SCl and anti-ClC(S)SF are the lowest-energy computed rotamers. As expected due to the photochemical activity of these species, additional reaction products due to alternative or subsequent photochannels are formed during this process. Full article

Presented study included human blood from healthy people and patients with BReast CAncer gene (BRCA) mutation. We used Raman spectroscopy for BRCA mutation detection and the bioanalytical characterization of pathologically changed samples. The aim of this study is to evaluate the Raman biomarkers to distinguish blood samples from healthy people and patients with BRCA mutation. We demonstrated that Raman spectroscopy is a powerful technique to distinguish between healthy blood and blood with BRCA mutation and to characterize the biochemical composition of samples. We applied partial least squares discriminant analysis (PLS-DA) to discriminate BRCA1/2 mutations and control samples without the mutations based on vibrational features. The sensitivity and specificity for calibration obtained directly from PLS-DA are equal to 94.2% and 97.6% and for cross-validation are equal to 93.3% and 97%. Our combination (Raman spectroscopy and PLS-DA) provides quick methods to reliably visualize the biochemical differences in human blood plasma. We proved that Raman spectroscopy combined with the chemometric method is a promising tool for hunting BRCA mutation in breast cancer. Full article

Novel metal oxide/polymer composite photocatalysts prepared by photocuring with common metal oxide particles (ZnO or CeO₂) and acrylic ester monomers have been investigated for the first time. Metal oxide particles were fully integrated with the acrylate polymer network based on the crosslink of poly ethylene glycol diacrylate (noted below as Poly-PEG) by photopolymerization upon mild light source (LED@405 nm) irradiation. The prepared metal/oxide composite showed excellent performance in the photodegradation of Acid Black dye (used as a benchmark pollutant) in an aqueous environment. Indeed, under UV lamp irradiation for 60 min, the degradation of Acid Black reached 59% and 56%, in the presence of 10 wt% ZnO/Poly-PEG and 3 wt% CeO₂/poly PEG, respectively. Markedly, the new reported photocatalysts have offered much better performance over the conventional TiO₂ photocatalytic material used as a control (39% degradation using 1 wt% TiO₂/poly PEG). In turn, the new proposed metal oxide/polymer composites were further characterized by a range of analytical characterization methods, including the swelling test, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), dynamic mechanical analysis (DMA), UV–visible diffuse reflectance spectroscopy, and electron spin resonance analysis. The results showed that the new photocatalysts demonstrated excellent water adsorption properties, high-temperature resistance, and excellent recyclability, which were very suitable for wide application and in line with the concept of green chemistry. Full article

Pyromellitic acid diimides are not as chemically unreactive as conjecturable (and presupposed) from their numerous applications as electron acceptor units or electron carriers in molecular donor–acceptor dyads or triads. Similar to the corresponding phthalimides, electronically excited pyromellitic diimides oxidize alkyl carboxylates in aqueous solution via intermolecular electron transfer (PET) processes, which eventually results in radical–radical combination products, e.g., the benzylation product 6 from N,N′-dimethyl pyromellitic diimide 5. The analogous product 7 was formed with pivalic acid as tert-butyl radical source. One additional product 8 was isolated from alkylation/dearomatization and multiple radical additions, respectively, after prolonged irradiation. In intramolecular versions, from N-carboxyalkylated pyromellitic diimides 9a–e (C₁ to C₅-spaced), degradation processes were detected, e.g., the cyclization products 10 from the GABA substrate 9c. In sharp contrast to phthalimide photochemistry, the green pyromellitic diimide radical anion was detected here by UV-vis absorption (λ_abs = 720 nm), EPR (from 9d), and NMR spectroscopy for several intramolecular electron transfer examples. Only the yellow 1,4-quinodial structure is formed from intermolecular PET, which was deduced from the absorption spectra (λ_abs = 440 nm) and the subsequent chemistry. The pyromellitimide radical anion lives for hours at room temperature in the dark, but is further degraded under photochemical reaction conditions. Full article

The design of molecular solar fuels is challenging because of the long list of requirements these molecules have to fulfil: storage density, solar harvesting capacity, robustness, and heat release ability. All of these features cause a paradoxical design due to the conflicting effects found when trying to improve any of these properties. In this contribution, we will review different types of compounds previously suggested for this application. Each of them present several advantages and disadvantages, and the scientific community is still struggling to find the ideal candidate suitable for practical applications. The most promising results have been found using norbornadiene-based systems, although the use of other alternatives like azobenzene or dihydroazulene cannot be discarded. In this review, we primarily focus on highlighting the optical and photochemical aspects of these three families, discussing the recently proposed systems and recent advances in the field. Full article

Merocyanines with embedded butadiene structure in a cyclohexane scaffold are readily obtained by consecutive three-component alkynylation-addition sequences in moderate to excellent yield. Moreover, employing pyrrolidine as an amine provides a pseudo four-component synthesis of related cyanines by carbonyl condensation of the heterocyclic amine in excellent yield. While the merocyanines are essentially nonluminescent, pentamethine cyanines show luminescence with low quantum yield. TDDFT calculations using various exchange correlation hybrid functionals in the gas phase and explicit continuum of dichloromethane underline that the lowest energy absorption bands are highly solvent dependent for a merocyanine and cyanine model. The blue-shifted deviation from the experimental spectra agrees with related merocyanine and cyanine systems. The lowest energy absorption band of merocyanines contains n-π* character, which rationalizes the absence of luminescence. Full article

Photocatalysis is a promising route to utilize sunlight, which has been potentially used to solve energy as well as environmental problems with an emphasis on fundamental understanding and technological applications in society. Semiconductors are excellent photocatalysts but often show less efficient activities due to the fast recombination of photogenerated charge carriers and very slow kinetics of surface photochemical reactions. However, recent advancements show promising strategies to improve their photocatalytic activities, including surface modifications using suitable co-catalysts and the development of novel efficient photocatalysts. Graphene oxide (GO) is one of such nanomaterials which shows multifarious roles in photocatalysis with a great potential to act as an independent solar-driven sole photocatalyst. In this minireview, the photochemistry of GO has been discussed in view of its multifarious roles/mechanisms in improving the photocatalytic activity of metal oxide semiconductors, plasmonic nanomaterials, and also their nanocomposites. In addition, recent advancements and applications of such GO-based photocatalysts in photocatalytic degradation of organic dye pollutants, including engineering of GO as the sole photocatalyst, have been discussed. Furthermore, the challenges and future prospects for the development of GO-based photocatalysts are discussed. Full article

Molybdenum disulfide (MoS₂) is a transition metal dichalcogenide (TMDCs) having versatile properties and plays a great role in the photodegradation of organic dyes. MoS₂ also finds applications in diverse fields such as catalysis, electronics, and nanomedicine transportation. MoS₂ can be prepared by using chemical and physical methods such as hydrothermal, solvothermal, and chemical vapour deposition methods. The preparation method employed can produce subtle but significant changes in the morphology. To increase the efficiency of MoS₂, it can be combined with different materials to produce composites that improve the photodegradation efficiency of MoS₂. The various methods of preparation, the morphology of MoS₂, and photodegradation activity of the MoS₂-based nanocomposites are briefly discussed in this review. Full article

Most dyes used in various industries are toxic and carcinogenic, thus posing a serious hazard to humans as well as to the marine ecosystem. Therefore, the impact of dyes released into the environment has been studied extensively in the last few years. Heterogeneous photocatalysis has proved to be an efficient tool for degrading both atmospheric and aquatic organic contaminants. It uses the sunlight in the presence of a semiconductor photocatalyst to accelerate the remediation of environmental contaminants and the destruction of highly toxic molecules. To date, photocatalysis has been considered one of the most appealing options for wastewater treatment due to its great potential and high efficiency by using sunlight to remove organic pollutants and harmful bacteria with the aid of a solid photocatalyst. Among the photocatalysts currently used, nanostructured metal oxide semiconductors have been among the most effective. This review paper presents an overview of the recent research improvements on the degradation of dyes by using nanostructured metal oxide semiconductors obtained by a solid-state method. Metal oxides obtained by this method exhibited better photocatalytic efficiency than nanostructured metal oxides obtained using other solution methods in several cases. The present review discusses examples of various nanostructured transition metal oxides—such as TiO₂, Fe₂O₃, NiO, ReO₃, IrO₂, Rh₂O₃, Rh/RhO₂, and the actinide ThO₂—used as photocatalysts on methylene blue. It was found that photocatalytic efficiency depends not only on the bandgap of the metal oxide but also on its morphology. Porous nanostructured metal oxides tend to present higher photocatalytic efficiency than metal oxides with a similar band gap. Full article

Photoreforming is a process that connects the redox capability of photocatalysts upon light illumination to simultaneously drive the reduction of protons into hydrogen and the oxidation of organic substrates. Over the past few decades, researchers have devoted substantial efforts to enhancing the photocatalytic activity of the catalyst in hydrogen production. Currently, the realization of the potential of photocatalysts for simultaneous hydrogen production with value-added organics has motivated the research field to use the photo-oxidation path. As a distinct benefit, the less energetically demanding organic reforming is highly favorable compared to the slow kinetics of oxygen evolution, negating the need for expensive and/or harmful hole scavengers. Photocatalyst modifications, such as secondary component deposition, doping, defect, phase and morphology engineering, have been the main strategies adopted to tune the photo-oxidation pathways and oxidation products. The effect of the reaction parameters, including temperature, pH, reactant concentration and promising reactor strategies, can further enhance selectivity toward desired outcomes. This review provides a critical overview of photocatalysts in hydrogen production, including chemical reactions occurring with semiconductors and co-catalysts. The use of various oxygenates as sacrificial agents for hydrogen production is outlined in view of the transition of fossil fuels to clean energy. This review mainly focuses on recent development in the photoreforming of carboxylic acids, produced from the primary source, lignocellulose, through pyrolysis. The photo-oxidation of different carboxylic acids, e.g., formic acid, acetic acid and lactic acid, over different photocatalysts for hydrogen production is reviewed. Full article

Both vibrational-excitation-induced (by (N)IR laser) and spontaneous (by H atom tunneling) conformational changes are often investigated by matrix-isolation spectroscopy. It is well known that rigid hosts, such as solid noble gases, N₂, or normal-H₂, can largely affect both the quantum efficiency of the (N)IR photon-induced process and the tunneling rate. In the present study, the conformational changes of formic and acetic acids, as well as glycine, were investigated in a soft quantum host, solid para-H₂. It is shown that the tunneling rates in para-H₂ are orders of magnitude larger than those in rigid hosts. Furthermore, our results also suggest that the quantum efficiencies of some (N)IR-light-induced conformational changes are larger than in rigid matrices. These results can open a door for the applications of para-H₂ host in conformational and tunneling studies and can help understand the details of these complex processes. Full article

This review analyzes the photocatalyzed urea syntheses by TiO₂–based materials. The most outstanding works in synthesizing urea from the simultaneous photocatalyzed reduction of carbon dioxide and nitrogen compounds are reviewed and discussed. Urea has been widely used in the agricultural industry as a fertilizer. It represents more than 50% of the nitrogen fertilizer market, and its global demand has increased more than 100 times in the last decades. In energy terms, urea has been considered a hydrogen–storage (6.71 wt.%) and ammonia–storage (56.7 wt.%) compound, giving it fuel potential. Urea properties meet the requirements of the US Department of Energy for hydrogen–storage substances, meanly because urea crystalizes, allowing storage and safe transportation. Conventional industrial urea synthesis is energy–intensive (3.2–5.5 GJ ton⁻¹) since it requires high pressures and temperatures, so developing a photocatalyzed synthesis at ambient temperature and pressure is an attractive alternative to conventional synthesis. Due to the lack of reports for directly catalyzed urea synthesis, this review is based on the most prominent works. We provide details of developed experimental set–ups, amounts of products reported, the advantages and difficulties of the synthesis, and the scope of the technological and energetic challenges faced by TiO₂–based photocatalyst materials used for urea synthesis. The possibility of scaling photocatalysis technology was evaluated as well. We hope this review invites exploring and developing a technology based on clean and renewable energies for industrial urea production. Full article

Aerobic photo-oxidation is a kind of green catalytic process that give valuable chemicals because of its mild reaction conditions and high product selectivity. Recently, small-sized IB metal nanoparticles (NPs; e.g., Cu, Ag, and Au, sized 1–3 nm) upon the surface of titanium oxide show excellent photocatalytic performance. The introduction of IB metal NPs can enhance the separation of photo-generated holes/electrons during photo-oxidations. In this account, we summarize the recent progress of small-sized IB metal NPs catalyzed by aerobic photo-oxidations, including the conversion of methanol, ethanol, sulfide, and benzylamine. More importantly, the structure–property correlations at the atomic level are detailed and discussed, e.g., the insights into the activation of oxygen and the identification of catalytic active sites. Future investigations are needed to carry out and reveal the catalytic mechanisms and conversion pathways. Full article

ZnO nanocrystals doped with Nd, Gd, and Er were synthesized using a soft chemical process in ambient atmosphere. Pseudospherical and hexagonal nanocrystals (NC) of the wurtzite phase with a mean size of (7.4 ± 1.7) nm were obtained. The presence of rare earth (RE) dopants was confirmed by X-ray fluorescence (XRF) spectroscopy. The ZnO nanocrystals exhibited simultaneously narrow excitonic- and broad trap/surface-related photoluminescence (PL), both of which were affected by doping with RE atoms. Doping reduced the total PL intensity, suppressing the excitonic emission by a greater extent than the broad band PL. Also, doping resulted in a blue shift of the trap/surface-related emission, while the energy of the excitonic peak remained unchanged. Resonant Raman spectra additionally confirmed the wurtzite phase of ZnO NCs and revealed a shift of the A₁-LO mode towards lower frequency upon doping that could be caused by the mass effect of RE atoms, point defects, and increases in charge carrier concentration. Fitting of the spectra with Voigt profiles showed better results with two surface optical (SO) phonon modes that were previously theoretically predicted for the wurtzite ZnO phase. The influence of RE doping on PL and Raman spectra can be explained by the incorporation of RE ions into the ZnO nanostructures, where the dopants act as non-radiative defects. Full article

The persistence of pharmaceuticals and personal care products (PPCPs) in water has been a cause for concern for several years. Many studies have successfully used TiO₂/UV photocatalysis to remove these compounds from water. In order to optimize these systems for large-scale water treatment, the effects of the reaction matrix, methods to improve energy efficiency, and methods for easy catalyst separation must be considered. The following study examines the photocatalytic degradation of a cocktail of 18 PPCPs using a porous titanium–titanium dioxide membrane and the effect of solution pH on kinetic rate constants. The addition of methanol to the reaction—commonly used as a carrier solvent—had a significant effect on kinetic rate constants even at low concentrations. Solution pH was also found to influence kinetic rate constants. Compounds had higher kinetic rate constants when they were oppositely charged to the membrane at experimental pH as opposed to similarly charged, suggesting that electrostatic forces have a significant effect. The controlled periodic illumination of UV–LEDs was also investigated to increase photonic efficiency. The dual-frequency light cycle used did not cause a decrease in degradation for many compounds, successfully increasing the photonic efficiency without sacrificing performance. Full article

The study of local polarity at the nanoscale is of crucial importance for the development of smart drug delivery systems and photonic materials and is frequently accomplished with the use of luminescent tracer dyes. Nile Red is often used for this purpose, owing to its polarity-sensitive internal charge transfer transition, but its performance is affected by specific solute-solvent interactions that prevent its widespread applicability. Herein, we develop a new 1,8-naphthalimide dye with a strong charge-transfer transition that results in a large dipole moment change upon excitation. This leads to luminescence properties with high sensitivity to solvent polarity, that are independent of specific or inductive interactions. These properties are explored to probe the polarity of biocompatible nanocarriers. This dye was effective in probing the properties of polymeric nanoparticles, allowing the accurate calculation of polarity descriptors and dielectric constants. Full article

Herein we present silver nanoparticles (AgNPs)-doped inorganic–organic hybrid silica films on glass and polypropylene substrates. A hybrid inorganic–organic silica sol in alcoholic medium was prepared at room temperature using TEOS, GLYMO, and APTES. Silver nanoparticles were generated in situ within the hybrid silica sol. AgNPs-SiO₂ film was obtained by dip coating method following drying at 80 °C. FTIR spectra shows several vibrational bands of the hybrid silica network and amine functionalization. AgNPs formation was observed from the XRD spectra of the dried film. UV–Visible spectra show sharp surface plasmon resonance (SPR) band centered at 412 nm arising from the evenly distributed silver nanoparticle inside the silica film that was supported by morphological characterization. Both the coated films showed good antibacterial activity against E. coli bacterial strain by forming a zone of inhibition in the agar diffusion test. The antibacterial efficiency for coated glass and polypropylene was 72.5% and 83.75%. This coating approach provides a straight-forward solution to prepare antibacterial coatings on various substrates especially on plastics, where low temperature processing is necessary. Full article

Acrylamide is a small conjugated organic compound widely used in industrial processes and agriculture, generally in the form of a polymer. It can also be formed from food and tobacco as a result of Maillard reaction from reducing sugars and asparagine during heat treatment. Due to its toxicity and possible carcinogenicity, there is a risk in its release into the environment or human intake. In order to provide molecular and energetic information, we use synchrotron radiation to record the UV and X-ray photoelectron and photoabsorption spectra of acrylamide. The data are rationalized with the support of density functional theory and ab initio calculations, providing precise assignment of the observed features. Full article