Distribution Of Photoproducts Research Articles

Photochemical Oxidation of Polyethylene Terephthalate Microplastics Adsorbed on Sand and Silica Surfaces.

The environmental contamination by plastics, microplastics, and related compounds is a major concern. While the detection and release of micro- and nanoparticles from these materials have been widely studied, the formation and release of molecules resulting from their degradation in the environment have been overlooked. This work presents a study of the products released from poly(ethylene terephthalate) (PET) irradiated as pure particles and adsorbed on silica and sand surfaces under different irradiation conditions. The role of oxygen was also evaluated. The products were identified by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-high resolution mass spectrometry (LC-HRMS). The main released molecules can be accounted for by considering the cleavage of α- and β-bonds next to the ester moiety of the polymer chain. Volatile products such as benzene as well as monomer units of the polymer and related products were identified. In the presence of oxygen, acetic acid and products resulting from hydroxylation at the benzenic ring or at the ethyl moiety were detected. Adsorption on silica and sand has little effect on the photoproduct distributions. The irradiation at 360 nm leads to distributions similar to the ones observed at 257 nm, but the reaction rate is lower. The identified product ethylene terephthalate is a marker of PET plastics and particles and can therefore be used to evaluate the environmental contamination by this polymer material.

Fourier-Hankel-Abel Nyquist-limited tomography: A spherical harmonic basis function approach to tomographic velocity-map image reconstruction.

A new method for the fully generalized reconstruction of three-dimensional (3D) photoproduct distributions from velocity-map imaging (VMI) projection data is presented. This approach, dubbed Fourier-Hankel-Abel Nyquist-limited TOMography (FHANTOM), builds on recent previous work in tomographic image reconstruction [C. Sparling and D. Townsend, J. Chem. Phys. 157, 114201 (2022)] and takes advantage of the fact that the distributions produced in typical VMI experiments can be simply described as a sum over a small number of spherical harmonic functions. Knowing the solution is constrained in this way dramatically simplifies the reconstruction process and leads to a considerable reduction in the number of projections required for robust tomographic analysis. Our new method significantly extends basis set expansion approaches previously developed for the reconstruction of photoproduct distributions possessing an axis of cylindrical symmetry. FHANTOM, however, can be applied generally to any distribution-cylindrically symmetric or otherwise-that can be suitably described by an expansion in spherical harmonics. Using both simulated and real experimental data, this new approach is tested and benchmarked against other tomographic reconstruction strategies. In particular, the reconstruction of photoelectron angular distributions recorded in a strong-field ionization regime-marked by their extensive expansion in terms of spherical harmonics-serves as a key test of the FHANTOM methodology. With the increasing use of exotic optical polarization geometries in photoionization experiments, it is anticipated that FHANTOM and related reconstruction techniques will provide an easily accessible and relatively low-cost alternative to more advanced 3D-VMI spectrometers.

Accessing chiral-even quark generalised parton distributions in the exclusive photoproduction of a γπ± pair with large invariant mass in both fixed-target and collider experiments

We compute the exclusive photoproduction of a γπ± pair using the collinear factorisation framework, in the kinematic regime where the pair has a large invariant mass and the meson has a sufficiently large transverse momentum to not resonate with the outgoing nucleon. This exclusive channel presents a new avenue for the investigation of GPDs. It is particularly interesting as the high centre of mass energies available at future experiments will allow the study of GPDs at small skewness ξ. We compute the scattering amplitude of the process, at leading twist and leading order in αs, which is used to estimate its cross-section and linear polarisation asymmetries with respect to the incoming photon, for JLab 12-GeV, COMPASS, future EIC and LHC (in ultra-peripheral collisions) kinematics. We find that the order of magnitude of estimates are sufficiently large for a dedicated experimental analysis to be performed, especially at JLab. We also compare the results from an asymptotic distribution amplitude (DA) to those using a recently proposed holographic DA.

Edge‐to‐Center Propagation of Photochemical Reaction during Single‐Crystal‐to‐Single‐Crystal Photomechanical Transformation of 2,5‐Distyrylpyrazine Crystals**

AbstractPhotomechanical molecular crystals are promising materials for photon‐powered artificial actuators. To interpret the photomechanical responses, the spatiotemporal distribution of photoproducts in crystals could be an important role in addition to molecular structures, molecular packings, illumination conditions, crystal morphology, crystal size, and so on. In this study, we have found that single crystals of 2,5‐distyrylpyrazine show a smooth single‐crystal‐to‐single‐crystal photomechanical expansion, and the photochemical reaction propagates from the edge to the center of the single crystal. We revealed that the surface effect (special reactivity at the crystal surface) in addition to the cooperative effect (the reaction is facilitated by neighboring molecules) is essential for the edge‐to‐center propagation of the photochemical reaction. Our results would provide a foundation for future studies of the photochemical reaction dynamics in photomechanical molecular crystals.

Edge-to-Center Propagation of Photochemical Reaction during Single-Crystal-to-Single-Crystal Photomechanical Transformation of 2,5-Distyrylpyrazine Crystals.

Photomechanical molecular crystals are promising materials for photon-powered artificial actuators. To interpret the photomechanical responses, the spatiotemporal distribution of photoproducts in crystals could be an important role in addition to molecular structures, molecular packings, illumination conditions, crystal morphology, crystal size, and so on. In this study, we have found that single crystals of 2,5-distyrylpyrazine show a smooth single-crystal-to-single-crystal photomechanical expansion, and the photochemical reaction propagates from the edge to the center of the single crystal. We revealed that the surface effect (special reactivity at the crystal surface) in addition to the cooperative effect (the reaction is facilitated by neighboring molecules) is essential for the edge-to-center propagation of the photochemical reaction. Our results would provide a foundation for future studies of the photochemical reaction dynamics in photomechanical molecular crystals.

Role of supramolecular steric compression during photoinduced intramolecular hydrogen abstraction reactions of ketones and thioketones

Excited state behavior of molecules is influenced by the environment in which they are present. The influence of solvents on reactions is understood in terms of the bulk properties of the solvent such as polarity, polarizability, hydrogen bonding, solvophobic interactions etc. Under these conditions, the ‘space’ surrounding the guest does not play any role in influencing the fate of an excited molecule. The current study focusses on understanding the factors that control the excited state reactivity of molecules within a confined space. In this context organic capsules assembled from two molecules of octa acid serves as the host and aryl alkyl ketones and aryl alkyl thioketones as reactive guests. One obvious prediction has been when the product is larger in size than the host capsule it would not be formed within the confined space although this may be the predominant product in solution. The authors demonstrate below that even if the product fits well within the capsule it may not be formed if the intermediate structures that connects the reactant to product does not fit within the capsule. The above hidden factor that controls photoproduct distribution has been investigated employing several aryl alkyl ketones that undergo γ-hydrogen abstraction as guests. In some of the examples investigated here, the Yang cyclization product, cyclobutanol, is suppressed within OA capsule even though it fits well within the capsule. Another factor that has come to light is ‘time’. Aryl alkyl thioketones that react from short lived second excited state (S2) fail to undergo δ-hydrogen abstraction within OA capsule although this is the only photoreaction in solution. MD simulations of the thioketones suggest that within the capsule the relevant hydrogens are not within the ideal geometry required for abstraction. Lack of reactivity is attributed to the insufficient time for the excited molecule to achieve the required conformation within the narrow space. Longer lived aryl alkyl ketones had no such problems in adopting a conformation required for hydrogen abstraction. Obviously, time becomes critical when the space is narrow. The results reported here brings out that one could consider ‘free space’ and ‘time’ as valuable tools to control product distribution while performing photochemistry in supramolecular assemblies.

Tomographic reconstruction techniques optimized for velocity-map imaging applications.

Examples of extracting meaningful information from image projection data using tomographic reconstruction techniques can be found in many areas of science. Within the photochemical dynamics community, tomography allows for complete three-dimensional (3D) charged particle momentum distributions to be reconstructed following a photodissociation or photoionization event. This permits highly differential velocity- and angle-resolved measurements to be made simultaneously. However, the generalized tomographic reconstruction strategies typically adopted for use with photochemical imaging-based around the Fourier-slice theorem and filtered back-projection algorithms-are not optimized for these specific types of problems. Here, we discuss pre-existing alternative strategies-namely, the simultaneous iterative reconstruction technique and Hankel Transform Reconstruction (HTR)-and introduce them in the context of velocity-map imaging applications. We demonstrate the clear advantages they afford, and how they can perform considerably better than approaches commonly adopted at present. Most notably, with HTR we can set a bound on the minimum number of projections required to reliably reconstruct 3D photoproduct distributions. This bound is significantly lower than what is currently accepted and will help make tomographic imaging far more accessible and efficient for many experimentalists working in the field of photochemical dynamics.

Arbitrary image reinflation: A deep learning technique for recovering 3D photoproduct distributions from a single 2D projection.

Many charged particle imaging measurements rely on the inverse Abel transform (or related methods) to reconstruct three-dimensional (3D) photoproduct distributions from a single two-dimensional (2D) projection image. This technique allows for both energy- and angle-resolved information to be recorded in a relatively inexpensive experimental setup, and its use is now widespread within the field of photochemical dynamics. There are restrictions, however, as cylindrical symmetry constraints on the overall form of the distribution mean that it can only be used with a limited range of laser polarization geometries. The more general problem of reconstructing arbitrary 3D distributions from a single 2D projection remains open. Here, we demonstrate how artificial neural networks can be used as a replacement for the inverse Abel transform and-more importantly-how they can be used to directly "reinflate" 2D projections into their original 3D distributions, even in cases where no cylindrical symmetry is present. This is subject to the simulation of appropriate training data based on known analytical expressions describing the general functional form of the overall anisotropy. Using both simulated and real experimental data, we show how our arbitrary image reinflation (AIR) neural network can be utilized for a range of different examples, potentially offering a simple and flexible alternative to more expensive and complicated 3D imaging techniques.

Simulation and analysis of the relaxation dynamics of a photochromic furylfulgide.

Furylfulgides, a class of photochromic organic compounds, show a complex system of photoinduced reactions. In the present study, the excited-state dynamics of the Eα and Eβ isomers of a representative furylfulgide is modelled with the use of nonadiabatic molecular dynamics simulations. Moreover, a pattern recognition algorithm is employed in order to automatically identify relaxation pathways, and to quantify the photoproduct distributions. The simulation results indicate that, despite differing only in the orientation of the furyl group, the two isomers show markedly different photochemical behaviour. The predominant Eα isomer undergoes photocyclisation with a quantum yield (QY) of 0.27 ± 0.10. For this isomer, the undesired E → Z photoisomerisation around the central double bond represents a minor side reaction, with a QY of 0.09 ± 0.07. In contrast, the minority Eβ isomer, which is incapable of photocyclisation, undergoes efficient E → Z photoisomerisation, with a QY as high as 0.56 ± 0.14. The relaxation kinetics and the photoproduct distributions are interpreted in the light of the available experimental data.

Multiphoton Control of 6π Photocyclization via State-Dependent Reactant-Product Correlations.

Multiphoton excitation promises opportunities for opening new photochemical reaction pathways and controlling photoproduct distributions. We demonstrate photonic control of the 6π photocyclization of ortho-terphenyl to make 4a,4b-dihydrotriphenylene (DHT). Using pump-repump-probe spectroscopy we show that 1 + 1' excitation to a high-lying reactant electronic state generates a metastable species characterized by a red absorption feature that accompanies a repump-induced depletion in the one-photon trans-dihydro product (trans-DHT); signatures of the new photoproduct are clearer for a structural analogue of the reactant that is sterically inhibited against one-photon cyclization. Quantum-chemical computations support assignment of this species to cis-DHT, which is accessible photochemically along a disrotatory coordinate from high-lying electronic states reached by 1 + 1' excitation. We use time-resolved spectroscopy to track photochemical dynamics producing cis-DHT. In total, we demonstrate that selective multiphoton excitation opens a new photoreaction channel in these photocyclizing reactants by taking advantage of state-dependent correlations between reactant and product electronic states.

The non-adiabatic nanoreactor: towards the automated discovery of photochemistry.

The ab initio nanoreactor has previously been introduced to automate reaction discovery for ground state chemistry. In this work, we present the nonadiabatic nanoreactor, an analogous framework for excited state reaction discovery. We automate the study of nonadiabatic decay mechanisms of molecules by probing the intersection seam between adiabatic electronic states with hyper-real metadynamics, sampling the branching plane for relevant conical intersections, and performing seam-constrained path searches. We illustrate the effectiveness of the nonadiabatic nanoreactor by applying it to benzene, a molecule with rich photochemistry and a wide array of photochemical products. Our study confirms the existence of several types of S0/S1 and S1/S2 conical intersections which mediate access to a variety of ground state stationary points. We elucidate the connections between conical intersection energy/topography and the resulting photoproduct distribution, which changes smoothly along seam space segments. The exploration is performed with minimal user input, and the protocol requires no previous knowledge of the photochemical behavior of a target molecule. We demonstrate that the nonadiabatic nanoreactor is a valuable tool for the automated exploration of photochemical reactions and their mechanisms.

Enhancing Double-Beam Laser Tweezers Raman Spectroscopy (LTRS) for the Photochemical Study of Individual Airborne Microdroplets.

A new device and methodology for vertically coupling confocal Raman microscopy with optical tweezers for the in situ physico- and photochemical studies of individual microdroplets (Ø ≤ 10 µm) levitated in air is presented. The coupling expands the spectrum of studies performed with individual particles using laser tweezers Raman spectroscopy (LTRS) to photochemical processes and spatially resolved Raman microspectroscopy on airborne aerosols. This is the first study to demonstrate photochemical studies and Raman mapping on optically levitated droplets. By using this configuration, photochemical reactions in aerosols of atmospheric interest can be studied on a laboratory scale under realistic conditions of gas-phase composition and relative humidity. Likewise, the distribution of photoproducts within the drop can also be observed with this setup. The applicability of the coupling system was tested by studying the photochemical behavior of microdroplets (5 µm < Ø < 8 µm) containing an aqueous solution of sodium nitrate levitated in air and exposed to narrowed UV radiation (254 ± 25 nm). Photolysis of the levitated NaNO3 microdroplets presented photochemical kinetic differences in comparison with larger NaNO3 droplets (40 µm < Ø < 80 µm), previously photolyzed using acoustic traps, and heterogeneity in the distribution of the photoproducts within the drop.

Light-induced full aromatization and hydroxylation of 7-methoxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole alkaloid: Oxygen partial pressure as a key modulator of the photoproducts distribution

Full-aromatic and partially hydrogenated β-carboline (βC) derivatives constitute a group of alkaloids widely distributed in a great variety of living systems. In plants and bacteria, tetrahydro-βCs are the primary product of the Pictet-Spengler enzymatically catalyzed condensation. Tetrahydro-βC skeleton is further modified giving rise to the formation of a vast set of derivatives including dihydro- and full-aromatic βCs. However, in most of the cases, the later processes still remain unclear and other sources, such as photo-triggered reactions, deserve to be explored. In this context, the photophysic and photochemistry of 7-methoxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole or harmaline (Hlina) in aqueous solution is reported herein. UV–visible absorption and fluorescence emission spectroscopy coupled with multivariate data analysis (PARAFAC), HPLC and HRESI-MS techniques were used for both quantitative and qualitative analysis. The formation singlet oxygen and hydrogen peroxide reactive oxygen species (ROS) was quantified and their role together with the influence of pH and oxygen partial pressure on the photochemical degradation of HlinaH+ was assessed. We report herein the first study on photochemical full-aromatization of a dihydro-βC derivative. These results can shed some light on the βCs biosynthesis and role in living systems.

Mechanistic Studies of Adamantylacetophenones with Competing Reaction Pathways in Solution and in the Crystalline Solid State.

Photochemical reactions in crystals occur under conditions of highly restricted molecular mobility such that only one product is generally obtained, even when there are many others that can be observed in the gas phase or in solution. A series of 2-(1-adamantyl)-o-alkyl-acetophenones with γ-hydrogen atoms on both the adamantyl and ortho aromatic groups was selected to determine whether one can engineer and observe competing Norrish type II reaction pathways in the crystalline state. It was shown that excited state competition for hydrogen abstraction between secondary adamantyl and benzylic hydrogens is affected not only by the relative bond dissociation energies but also by the molecular conformation in the crystal. The subsequent fate of the resulting biradical species is determined by competition between radical recombination to form the photoproduct and reverse hydrogen atom transfer to regenerate the starting ketone. Crystallographic information, photoproduct distributions in solution and in the solid state, and the results of multiple mechanistic experiments, including transient absorption spectroscopy in acetonitrile and with nanocrystals suspended in water, are reported. The results demonstrate that it is possible to engineer competing reactions in crystals and that consideration of all of the aforementioned factors is necessary to account for the observed photoproduct selectivity.

Photodegradation of ciprofloxacin adsorbed in the intracrystalline space of montmorillonite

Although photolysis of antibiotics in aqueous solution was widely studied for a better understanding of their photolytic behavior in aqueous phase, the knowledge about photodegradation of antibiotics adsorbed on solid surfaces is still very limited. In this study, photodegradation of ciprofloxacin (CIP), a fluoroquinolone antibiotic, adsorbed in the intracrystalline space of montmorillonite (MMT) was examined using a xenon light source (300 W, λ > 320 nm). The gradual decrease of basal spacing of MMT from 1.66 to 1.46 nm with irradiation confirmed CIP decomposition in the intracrystalline space under simulated solar irradiation. Nearly 70 percent of adsorbed CIP was degraded after 5 h irradiation, and the reaction followed the first-order kinetics with a rate constant roughly 3 times than that in aqueous solution, indicating more efficient photodegradation of CIP after being adsorbed in the intracrystalline space of MMT. Spectroscopic analysis revealed that direct photolysis was the main photolytic mechanism. The hydroxyl radical induced by irradiated MMT might play an important role. The major photoproducts were identified with liquid chromatography-tandem mass spectrometry, and the main degradation pathways were proposed. The results demonstrated that the photoproduct distribution and degradation pathways of CIP adsorbed in the intracrystalline space differed from those in aqueous solution.

Tuning the photoreactivity of Z-hexatriene photoswitches by substituents - a non-adiabatic molecular dynamics study.

To understand how substituents can be used to increase the quantum yield of photochemical electrocyclic ring-closing of the Z-hexa-1,3,5-triene (HT) photoswitch forming cyclohexadiene (CHD), we investigate the S1 photo dynamics of HT and its derivatives 2,5-dimethyl-HT (DMHT), 2-isopropyl-5-methyl-HT (2,5-IMHT), 1-isopropyl-4-methyl-HT (1,4-IMHT), and 2,5-diisopropyl-HT (DIHT) using time-dependent density functional theory surface hopping dynamics. We report detailed photoproduct distributions, formation mechanisms, branching ratios, and wavelength-dependent product quantum yields. Most products have been confirmed experimentally and include all-trans HT derivatives, cyclopropanes, cyclobutenes, cyclopentene, cyclohexadienes, and bicyclic compounds. Regarding CHD formation, we find that for the 2,5-substituted derivatives DMHT, 2,5-IMHT, and DIHT, the branching ratios increase with increasing size of the substituents. In contrast the branching ratios of the E/Z-isomerization decrease with increasing size of the substituents. Due to steric interactions, increasing the size of the substituents increases the amount of gZg rotamers in the ground state, which are prone to CHD formation and have lower E/Z-isomerization probability. Furthermore, we find [1,4], [1,5], and [1,6]-sigmatropic hydrogen shift reactions occurring at large percentages (5% to 15%); for sterical reasons these reactions stem from tZg conformers. DIHT shows the lowest percentage of side product formation among the 2,5-substituted molecules and highest CHD branching ratio; its CHD quantum yield can be increased up to more than 64%, by excitation of DIHT on the red tail of its absorption spectrum, whereas the Z/E-isomerization is reduced below 5% and side reactions practically vanish. This makes DIHT the best candidate for applications in molecular switches.

Photochemical Reactions of Cyclohexanone: Mechanisms and Dynamics.

Photochemistry of carbonyl compounds is of major importance in atmospheric and organic chemistry. The photochemistry of cyclohexanone is studied here using on-the-fly molecular dynamics simulations on a semiempirical multireference configuration interaction potential-energy surface to predict the distribution of photoproducts and time scales for their formation. Rich photochemistry is predicted to occur on a picosecond time scale following the photoexcitation of cyclohexanone to the first singlet excited state. The main findings include: (1) Reaction channels found experimentally are confirmed by the theoretical simulations, and a new reaction channel is predicted. (2) The majority (87%) of the reactive trajectories start with a ring opening via C-Cα bond cleavage, supporting observations of previous studies. (3) Mechanistic details, time scales, and yields are predicted for all reaction channels. These benchmark results shed light on the photochemistry of isolated carbonyl compounds in the atmosphere and can be extended in the future to photochemistry of more complex atmospherically relevant carbonyl compounds in both gaseous and condensed-phase environments.

Proton Inventory and Dynamics in the Nia-S to Nia-C Transition of a [NiFe] Hydrogenase.

Hydrogenases (H2ases) represent one of the most striking examples of biological proton-coupled electron transfer (PCET) chemistry, functioning in facile proton reduction and H2 oxidation involving long-range proton and electron transport. Spectroscopic and electrochemical studies of the [NiFe] H2ases have identified several catalytic intermediates, but the details of their interconversion are still a matter of debate. Here we use steady state and time-resolved infrared spectroscopy, sensitive to the CO ligand of the active site iron, as a probe of the proton inventory as well as electron and proton transfer dynamics in the soluble hydrogenase I from Pyrococcus furiosus. Subtle shifts in infrared signatures associated with the Nia-C and Nia-S states as a function of pH revealed an acid-base equilibrium associated with an ionizable amino acid near the active site. Protonation of this residue was found to correlate with the photoproduct distribution that results from hydride photolysis of the Nia-C state, in which one of the two photoproduct states becomes inaccessible at low pH. Additionally, the ability to generate Nia-S via PCET from Nia-C was weakened at low pH, suggesting prior protonation of the proton acceptor. Kinetic and thermodynamic analysis of electron and proton transfer with respect to the various proton inventories was utilized to develop a chemical model for reversible hydride oxidation involving two intermediates differing in their hydrogen bonding character.

Ultrafast Photogeneration of a Tetrazolinyl Radical.

Radicals in solution are crucial for many chemical processes. In this work, we unveil the photoreaction sequence leading to radical formation from tetrazolium salts, which are extensively used in enzyme assays and also exhibit a rich photochemistry. Upon UV irradiation, the tetrazolium ion turns into the tetrazolinyl radical via two intermediates on a nanosecond timescale. The solvent's polarity governs the rate of formation, but the reaction pathway towards the tetrazolinyl radical is identical for aqueous and alcoholic solutions, although the final photoproduct distribution differs. These observations provide new insight into the versatile reactivity of tetrazolium salts and ultrafast radical formation in the liquid phase.

Solution-phase photochemical transformation of 2-aroylbenzofurans: addition–elimination mechanism

An efficient conversion of 2-aroylbenzofurans into arylbenzofurylmethanols through photoreduction has been described. In these molecules, the photo transformation occurred through the initial addition of solvent followed by elimination involving γ-hydrogen abstraction. The photoproduct distribution markedly depends upon the substituent present on the benzofuran moiety.