Photochemical Reaction System Research Articles

Quantification of Synergistic Two-Color Covalent Bond Formation.

The emergence of highly wavelength resolved reactivity information for complex photochemical reaction processes allows the establishment of multi-color reaction modes. One particularly powerful mode is the synergistic two-color reaction, where two colors of light have to be present in the same volume element to either enable or enhance photochemical reactivity that leads to a specific photoproduct. Herein, we introduce a two-color synergistic photochemical reaction system based on a diaryl indenone epoxide (DIO) photoswitch and the cis-to-trans isomerization of a bridged ring-strained azobenzene (SA), which respond to ultraviolet (365 nm) and visible light (430 nm), respectively, with different rates, forming a well-defined heterocyclic photoadduct, DIOSA, that we structurally confirm via single crystal x-ray diffraction (SXRD). To quantitatively capture the effectiveness of the dual-color irradiation as a function of the reaction conditions such as light intensity and starting material ratio as a function of product yield, we introduce a parameter, the photochemical synergistic ratio. A reduced synergistic ratio- that extrapolates to conditions of infinitesimal conversions - allows to compare the efficiency of the synergistic photochemistry at varying reaction conditions.

Quantification of Synergistic Two‐Color Covalent Bond Formation

The emergence of highly wavelength resolved reactivity information for complex photochemical reaction processes allows the establishment of multi‐color reaction modes. One particularly powerful mode is the synergistic two‐color reaction, where two colors of light have to be present in the same volume element to either enable or enhance photochemical reactivity that leads to a specific photoproduct. Herein, we introduce a two‐color synergistic photochemical reaction system based on a diaryl indenone epoxide (DIO) photoswitch and the cis‐to‐trans isomerization of a bridged ring‐strained azobenzene (SA), which respond to ultraviolet (365 nm) and visible light (430 nm), respectively, with different rates, forming a well‐defined heterocyclic photoadduct, DIOSA, that we structurally confirm via single crystal x‐ray diffraction (SXRD). To quantitatively capture the effectiveness of the dual‐color irradiation as a function of the reaction conditions such as light intensity and starting material ratio as a function of product yield, we introduce a parameter, the photochemical synergistic ratio. A reduced synergistic ratio – that extrapolates to conditions of infinitesimal conversions – allows to compare the efficiency of the synergistic photochemistry at varying reaction conditions.

Humic substances mediated superior photochemical pollutant conversion on defective TiO2 in environmentally relevant matrices: The key roles of oxygen vacancy in surface interactions, oxidant activation and radical generation

Ubiquitous humic substances usually exhibit strong interfering effects on target pollutant removal in advanced water purification. This work aims to develop a photochemical conversion system on the nonstoichiometric TiO2 for pollutant removal in environmentally relevant matrices. In this synergistic reaction system, the redox-reactive humic substances and defective oxygen vacancies can serve as the organic electron transfer mediator and the key surface reactive sites, respectively. This system achieves a superior pollutant degradation in real surface water at low oxidant concentrations. Reactive oxygen vacancies on the TiO2 surface and sub-surface are of considerable interest for this photochemical reaction system. By engineering defective oxygen vacancies on high-energy {001} polar facet, the surface and electronic interactions between tailored TiO2 and humic substances are greatly strengthened for the promoted electron transfer and oxidant activation. Rendered by the strong surface affinity and molecular activation, defective oxygen vacancies thermodynamically and dynamically promote reactive chain reactions for free radical formation, including the selective O2 reduction to ·O2− and the H2O2 activation to ·OH. Our findings take new insights into environmental geochemistry, and provide an effective strategy to in-situ boost the humic substances-mediated water purification without secondary pollution. Environmental implicationHumic substances are widely distributed in aquatic environment, thus playing important roles in environmental geochemistry. For example, humic substances can achieve good surface adsorption through electrostatic adsorption, ligand exchange and electronic interactions with typical TiO2 to form reactive ligand-metal charge transfer complexes for pollutant degradation. Inspired by the unique properties of surface and sub-surface oxygen vacancies, the defective TiO2 was designed to refine the humic substances-mediated photochemical reactions. A superior reactivity was measured for pollutant degradation. Our findings provide an effective strategy to boost naturally photochemical decontamination in environmentally relevant matrices.

Development of a flow photochemical process for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence: in situ-generated 2-benzopyrylium as photoredox catalyst and reactive intermediate.

A flow photochemical reaction system for a π-Lewis acidic metal-catalyzed cyclization/radical addition sequence was developed, which utilizes in situ-generated 2-benzopyrylium intermediates as the photoredox catalyst and electrophilic substrates. The key 2-benzopyrylium intermediates were generated in the flow reaction system through the intramolecular cyclization of ortho-carbonyl alkynylbenzene derivatives by the π-Lewis acidic metal catalyst AgNTf2 and the subsequent proto-demetalation with trifluoroacetic acid. The 2-benzopyrylium intermediates underwent further photoreactions with benzyltrimethylsilane derivatives as the donor molecule in the flow photoreactor to provide 1H-isochromene derivatives in higher yields in most cases than the batch reaction system.

Rapid-Scan Resonant Two-Dimensional Impulsive Stimulated Raman Spectroscopy of Excited States.

Photochemical reactions occur in the electronically excited state, which is effectively represented by a multidimensional potential energy surface (PES) with a vast degree of freedom of nuclear coordinates. The elucidation of the intricate shape of the PES constitutes an important topic in the field of photochemistry and has long been studied both experimentally and theoretically. Recently, fully time-domain resonant two-dimensional Raman spectroscopy has emerged as a potentially powerful tool to provide unique information about the coupling between vibrational manifolds in the excited state. However, the wide application of this technique has been significantly hampered by the technical difficulties associated with experimental implementation and remains challenging. Herein, we demonstrate time-domain resonant two-dimensional impulsive stimulated Raman spectroscopy (2D-ISRS) of excited states using sub-10 fs pulses based on the rapid scan of the time delay, which facilitates the efficient collection of time-domain vibrational signals with high sensitivity. As a proof-of-principle experiment, we performed 2D-ISRS of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) in solution. Through 2D Fourier transformation of the high-quality time-time oscillatory signal, we obtained a 2D frequency-frequency correlation map of excited-state TIPS-pentacene in the broad frequency window of 0-2000 cm-1. The data clearly resolve a number of cross peaks that signify the correlations among excited-state vibrational manifolds. The high capability of the rapid-scan-based 2D-ISRS spectrometer presented in this study enables the systematic investigation of various photochemical reaction systems, thereby further promoting the understanding and applications of this new multidimensional spectroscopy.

Quantum-Coherence-Enhanced Hot-Electron Injection under Modal Strong Coupling.

Modal strong coupling between localized surface plasmon resonance and a Fabry-Pérot nanocavity has been studied to improve the quantum efficiency of artificial photosynthesis. In this research, we employed Au nanodisk/titanium dioxide/Au film modal strong coupling structures to investigate the mechanism of quantum efficiency enhancement. We found that the quantum coherence within the structures enhances the apparent quantum efficiency of the hot-electron injection from the Au nanodisks to the titanium dioxide layer. Under near-field mapping using photoemission electron microscopy, the existence of quantum coherence was directly observed. Furthermore, the coherence area was quantitatively evaluated by analyzing the relationship between the splitting energy and the particle number density of the Au nanodisks. This quantum-coherence-enhanced hot-electron injection is supported by our theoretical model. Based on these results, applying quantum coherence to photochemical reaction systems is expected to effectively enhance reaction efficiencies.

Synergistic, Orthogonal, and Antagonistic Photochemistry for Light‐Induced 3D Printing

Abstract3D printing techniques are often based on light‐induced chemical reactions, driven by the fascinating and powerful possibilities to control light in space and time. To date, these approaches are usually restricted to a single color of light, which does not do justice to light as an entire spectrum of distinct wavelengths. It is possible to further tap into the vast potential of light‐induced 3D printing by introducing a second color of light. While the complexity of photochemical interactions in two‐color systems is greatly increased, it concomitantly allows for enhanced control over manufacturing speed and resolution. In general, three types of two‐color interactions can be distinguished, i.e., synergistic, orthogonal, and antagonistic. In recent years, intriguing printing techniques with superior potential for the fabrication of 3D structures are emerging that require two colors of light. Their future development potential is vast yet needs to be critically underpinned by an advance in complex tunable photochemical reaction systems. The current perspective will thus explore the potential for using synergistic, orthogonal, and antagonistic photochemistries in 3D printing.

Light- and mechanic field controlled dynamic soft matter materials

A photochemical reaction system that fuses photo- and mechanochemistry into one macromolecular design for light- and mechano-reversible modification of polymer endgroups is introduced.

Photosensitized Dimerization of Tyrosine: The Oxygen Paradox.

In electron-transfer initiated photosensitization processes, molecular oxygen (O2 ) is not involved in the first bimolecular event, but almost always participates in subsequent steps giving rise to oxygenated products. An exception to this general behavior is the photosensitized dimerization of tyrosine (Tyr), where O2 does not participate as a reactant in any step of the pathway yielding Tyr dimers (Tyr2 ). In the pterin (Ptr) photosensitized oxidation of Tyr, O2 does not directly participate in the formation of Tyr2 and quenches the triplet excited state of Ptr, the reactive species that initiates the process. However, O2 is necessary for the dimerization, phenomenon that we have named as the oxygen paradox. Here, we review the literature on the photosensitized formation of Tyr2 and present results of steady-state and time resolved experiments, in search of a mechanistic model to explain the contradictory role of O2 in this photochemical reaction system.

Photochemical Disulfide-Ene Modification Enhances Protein Sequencing and Disulfide Mapping by Mass Spectrometry.

A new photochemical disulfide-ene reaction system capable of alkylating protein disulfide bonds in seconds has been established. The system is simple, containing acetone and isopropanol for disulfide reduction under 254 nm UV irradiation and norbornene as a highly efficient alkylation reagent. Enhanced characterization of disulfide-rich proteins with significantly shortened analysis time is demonstrated by coupling the reaction online with mass spectrometry.

Direct Excitation of Triplet State of Molecule by Enhanced Magnetic Field of Dielectric Metasurfaces.

Efficient excitation of a triplet (T1 ) state of a molecule has far-reaching effects on photochemical reaction and energy conversion systems. Because the optical transition from a ground singlet (S0 ) to a T1 state is spin-forbidden, a T1 state is generated via intersystem crossing (ISC) from an excited singlet (S1 ) state. Although the excitation efficiency of a T1 state can be increased by enhancing ISC utilizing a heavy atom effect, energy loss during S1 →T1 relaxation is inevitable. Here, a general approach to directly excite a T1 state from a ground S0 state via magnetic dipole transition, which is boosted by enhanced magnetic field induced by a dielectric metasurface, is proposed. As a dielectric metasurface, a hexagonal array of silicon (Si) nanodisks is employed; the nanodisk array induces a strongly enhanced magnetic field on the surface due to the toroidal dipole (TD) resonance. A proof-of-concept experiment is performed using ruthenium (Ru) complexes placed on a metasurface and demonstrates that the phosphorescence is 35-fold enhanced on a metasurface when the TD resonance is tuned to the wavelength of the direct S0 →T1 transition. These results indicate that photon energy necessary to excite the T1 state can be reduced by more than 400 meV compared to the process involving the ISC. By combining optical measurements with numerical simulations, the mechanism of the phosphorescence enhancement is quantitatively discussed.

Dual-Wavelength Gated oxo-Diels-Alder Photoligation.

The control of chemical functionalization with orthogonal light stimuli paves the way toward manipulating materials with unprecedented spatiotemporal resolution. To reach this goal, we herein introduce a photochemical reaction system that enables two-color control of covalent ligation via an oxo-Diels–Alder cycloaddition between two separate light-responsive molecular entities: a UV-activated photocaged diene based on ortho-quinodimethanes and a carbonyl dienophile appended to a diarylethene photoswitch, whose reactivity can be modulated upon illumination with UV and visible light.

Improving removal rate and efficiency of As(V) by sulfide from strongly acidic wastewater in a modified photochemical reactor

ABSTRACT Employing ultraviolet light to enhance the removal of As(V) by sulfide (S(-II)) from strongly acidic wastewater is a potential method. However, we found the arsenic trisulfide (As2S3) and elemental sulfur (S8) particles formed in this method not only vastly hinder light transmission in the wastewater but also undergo light-induced redissolution, leading to a decrease in removal rate and efficiency of As(V). Herein, As(V) removal by sulfide from strongly acidic wastewater was performed in a modified photochemical reactor to weaken the effect of the formed particles on As(V) removal. It was found that in this study, the formed particles could be efficiently removed from the photoreactor by three operations, i.e. circulation-filtration, septum setting, and lamp sleeve cleaning. The removal of As(V) was approximately 11-fold faster than that without three operations, saving 90.9% of the reaction time and 89.4% of energy consumption. The removal efficiency of As(V) also increased through weakening the light-induced redissolution of the formed particles. This study facilitates the practical application of the UV light promoted As(V) removal technology and also provides a new method to lessen the light-blocking effect in the particle-forming photochemical reaction systems.

Combining Photodeprotection and Ligation into a Dual-Color Gated Reaction System.

We report a photochemical reaction system which requires activation by two colors of light. Specifically, a dual wavelength gated system is established by fusing the visible light mediated deprotection of a dithioacetal with the UV light activated Diels–Alder reaction of an o‐methylbenzaldehyde with n‐ethylmaleimide. Critically, both light sources are required to achieve the Diels–Alder adduct, irradiation with visible or UV light alone does not lead to the target product. The introduced dual gated photochemical system is particularly interesting for application in light driven 3D printing, where two color wavelength activated photoresists may become reality.

Recent Progress in Photon Upconverting Gels.

Recent progress in the development of gels showing triplet-triplet annihilation based photon upconversion (TTA-UC) is reviewed. Among the two families of upconverting gels reported, those display TTA-UC based on molecular diffusion show performances comparable to those in solutions, and the TTA-UC therein are affected by dissolved molecular oxygen. Meanwhile, air-stable TTA-UC is achieved in organogels and hydrogels by suitably accumulating TTA-UC chromophores which are stabilized by hydrogen bonding networks of the gelators. The unique feature of the air-stable upconverting gels is that the self-assembled nanostructures are protected from molecular oxygen dissolved in the microscopically interconnected solution phase. The presence of the bicontinuous structures formed by the upconverting fibrous nanoassemblies and the solution phase is utilized to design photochemical reaction systems induced by TTA-UC. Future challenges include in vivo applications of hydrogels showing near infrared-to-visible TTA-UC.

Artificial Photosynthesis Model: Photochemical Reaction System with Efficient Light-Harvesting Function on Inorganic Nanosheets

In natural photosynthesis system, its complicated photofunctions are achieved with high efficiency through precise arrangements of dye molecules in proteins. However, it is difficult to imitate suc...

Reversible Photolysis of Nitrosobenzene cis-Dimer Monitored In Situ by Single Crystal Photocrystallography

A single crystal of the cis-dimer of nitrosobenzene was directly observed by photocrystallography to transition to a pair of monomers and reversibly redimerize. The remarkable displacement of the nitrogen atoms within the crystal—moving a total distance of 2.97(5) A for the two atoms—suggests that the breadth of solid-state photochemical reaction systems susceptible to X-ray diffraction studies need not be limited to those with very small atomic displacements.

Ultra-sensitive HPLC-photochemical reaction-luminol chemiluminescence method for the measurement of secondary amines after nitrosation

A novel method for the determination of secondary amines at the nanomolar level was developed. The method is based on the nitrosation reaction of secondary amines, with the generated N-nitrosamines being measured using an HPLC separation, photochemical reaction, and chemiluminescence detection system. The efficient nitrosation of secondary amines was performed using sodium nitrite (200 mM) and acetic acid (0.8 M) at 80 °C over 60 min. Although compounds bearing OH and SH functional groups also underwent the nitrosation reaction, the sensitivity of these compounds was 1000 times lower than that of the secondary amines. Our method was applied to the determination of low molecular weight secondary amines, including dimethylamine, morpholine, pyrrolidine, diethylamine, and piperidine, giving method detection limits of 0.7 nM, 0.2 nM, 0.4 nM, 0.7 nM, and 1.5 nM, respectively. The calibration curves were linear in the range of 5–100 nM. We then applied this method for the detection and quantification of these secondary amines in samples of tap water, river water, treated wastewater, and sea water. Dimethylamine was detected at concentrations up to 15.4 nM, <0.7 nM, and 48.5 nM in tap water, river water, and treated wastewater samples, respectively, with recoveries ranging from 94 to 103%. Other amines were also detected at nanomolar levels. These results indicate that our proposed method can be applied to the analysis of secondary amines in various environmental water samples. To the best of our knowledge, the proposed method is one of the most sensitive and selective methods for the determination of secondary amines without pre-concentration steps.

Confined Singlet Oxygen in Mesoporous Silica Nanoparticles: Selective Photochemical Oxidation of Small Molecules in Living Cells.

Chemical conversion of specific bioactive molecules by external stimuli in living cells is a powerful noninvasive tool for clarification of biomolecular interactions and to control cellular functions. However, in chaotic biological environments, it has been difficult to induce arbitrary photochemical reactions on specific molecules because of their poor molecular selectivity. Here we report a selective and nontoxic photochemical reaction system utilizing photoactivated mesoporous silica nanoparticles to control biological functions. Methylene blue modification within nanoparticle pores for photosensitization produced singlet oxygen confined to the pore that could mediate selective oxidation of small molecules without any damage to living cells. This intracellular photochemical system produced bioactive molecules in situ and remotely controlled the cell cycle phase. We also confirmed that this photoreaction could be applied to control cell cycle phase in tumor tissue transplanted in mice. The cell cycle phase in the cells in mice, to which our system was administered, was arrested at the G2/M phase upon photoirradiation. We demonstrate a simple and promising method for the exogenous conversion of an intracellular biomolecule to another functional compound.

(Invited) In-Situ Raman Observation of Reaction Intermediates at Plasmon-Induced Water Oxidation Processes

Efficient multi-electron transfer reaction is important target for the developments on various energy technologies in future. Plasmon-induced photochemical reaction system should be one of the choices. Although it has been demonstrated that the excitation of localized surface plasmon resonance (LSPR) at Au metal nanoparticle on metal oxide semiconductors enable efficient water oxidation even under near-infrared light illumination, mechanis. In this work, we observed plasmon-induced water oxidation process using in-situ surface enhanced Raman scattering (SERS) measurement. Size-controlled metal nanodimer arrays was fabricated on titanium dioxide single crystalline by angle-resolved nanosphere lithography. The phonon vibrations of metal oxides were observed as the intermediate of water oxidation. The formation of the intermediate at relatively negative potential is attributed to the water oxidation process via holes generated by LSPR. We concluded that novel mechanisms exist for water oxidation on plasmonic electrode, compared with that at bulk Au electrode.