A Photoelectrochemical Sensor for the Detection of Hypochlorous Acid with a Phenothiazine-Based Photosensitizer.

This paper presents the development of a photoelectrochemical sensor for hypochlorous acid (HOCl) detection, employing a phenothiazine-based organic photosensitizer (Dye-PZ). The designed probe, Dye-PZ, follows a D-π-A structure with phenothiazine as the electron-donating group and a cyano-substituted pyridine unit as the electron-accepting group. A specific reaction of the phenothiazine sulfur atom with HOCl enables selective recognition. The covalent immobilization of Dye-PZ onto a titanium dioxide nanorod-coated fluorine-doped tin oxide electrode (FTO/TiO2) using bromo-silane coupling agent (BrPTMS) resulted in the fabrication of the photoanode FTO/TiO2/BrPTMS/Dye-PZ. The photoanode exhibited a significant photoresponse under visible-light irradiation, with a subsequent reduction in photocurrent upon reaction with HOCl. The oxidation of the phenothiazine sulfur atom to a sulfoxide diminished the internal charge transfer (ICT) effect. Leveraging this principle, the successful photoelectrochemical sensing of HOCl was achieved. The sensor showed high stability, excellent reproducibility, and selective sensitivity for HOCl detection. Our study provides a novel approach for the development of efficient photoelectrochemical sensors based on organic photosensitizers, with promising applications in water quality monitoring and biosensing.

Nickel/Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling of Racemic α-Chloro Esters with Aryl Iodides.

A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions.

Reactive oxygen species play key roles in the nitrite formation by the inorganic nitrate photolysis in the presence of urban water-soluble organic carbon.

Inorganic nitrates were considered to be a potential source of atmospheric NO2-/HONO during the daytime. To better evaluate the contribution of nitrate photochemistry on NO2-/HONO formation, the photolysis of nitrates in the real atmospheric environment needs to be further explored. Here, the NO2- generation by the photolysis of inorganic nitrates in the presence of total water-soluble organic carbon (WSOC) was quantified. The physicochemical properties of WSOC were measured to understand the underlying mechanism for the photolysis of inorganic nitrates with WSOC. WSOC enhanced or suppressed the photochemical conversion of nitrates to NO2-, with the quantum yield of NO2- (ΦNO2-) varying from (0.07 ± 0.02)% to (3.11 ± 0.04)% that depended on the light absorption properties of WSOC. Reactive oxygen species (ROS) generated from WSOC, including O2-/HO2 and OH, played a dual role in the NO2- formation. Light-absorbing substances in WSOC, such as N-containing and carbonyl aromatics, produced O2-/HO2 that enhanced the secondary conversion of NO2 to NO2-. On the other hand, OH deriving from the WSOC photochemistry inhibited the nitrate photodegradation and the NO2- formation. HONO source strength by the aqueous photolysis of nitrates with WSOC was estimated to be lower than 100 ppt h-1, which may partly contribute to the atmospheric HONO source in some cases.

Rational design and performance prediction of organic photosensitizer based on TATA+ dye for hydrogen production by photocatalytic decomposition of water.

In comparison to metal complexes, organic photosensitive dyes employed in photocatalytic hydrogen production exhibit promising developmental prospects. Utilizing the organic dye molecule TA+0 as the foundational structure, a series of innovative organic dyes, denoted as TA1-1 to TA2-6, were systematically designed. Employing first-principles calculations, we methodically explored the modifying effects of diverse electron-donating groups on the R1 and R2 positions to assess their application potential. Our findings reveal that, relative to the experimentally synthesized TATA+03, the TA2-6 molecule boasts a spatial structure conducive to intramolecular electron transfer, showcasing the most negative reduction potential (Ered = -2.11 eV) and the maximum reaction driving force (△G0 2 = -1.26 eV). This configuration enhances its compatibility with the reduction catalyst, thereby facilitating efficient hydrogen evolution. The TA2-6 dye demonstrates outstanding photophysical properties and a robust solar energy capture capacity. Its maximum molar extinction coefficient (ε) stands at 2.616 × 104 M-1·cm-1, representing a remarkable 292.8% improvement over TATA+03. In conclusion, this research underscores the promising potential of the TA2-6 dye as an innovative organic photosensitizer, positioning it as an efficacious component in homogeneous photocatalytic systems.

Unraveling an Ultrafast Electron Transport Mechanism in a Photocatalytic "Micromachine" for Their Potential Light Harvesting Applications.

Following the seminal discovery of Richard Feynman, several micromachines have been made that are capable of several applications, such as solar energy harvesting, remediation of environmental pollution, etc. Here we have synthesized a nanohybrid combining TiO2 nanoparticle and light harvesting robust organic molecule RK1 (2-cyano-3-(4-(7-(5-(4-(diphenylamino)phenyl)-4-octylthiophen-2-yl)benzo[c][1,2,5] thiadiazol-4-yl)phenyl) acrylic acid) as a model micromachine having solar light harvesting ability potential for application in photocatalysis, preparation of solar active devices, etc. Detailed structural characterization, including High Resolution Transmission Electronic Microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FTIR), has been performed on the nanohybrid. We have studied the excited-state ultrafast dynamics of the efficient push-pull dye RK1 in solution, on mesoporous semiconductor nanoparticles, and in insulator nanoparticles by streak camera (resolution of the order of 500 fs). The dynamics of such photosensitizers in polar solvents have been reported, and it has been observed that completely different dynamics occur when they are attached to the surface of the semiconductor/insulator nanosurface. A femtosecond-resolved fast electron transfer has been reported when photosensitizer RK1 has been attached to the surface of the semiconductor nanoparticle, which in turn plays a crucial role in the development of an efficient light harvesting material. The generation of reactive oxygen species as a result of femtosecond-resolved photoinduced electron injection in the aqueous medium is also investigated in order to explore the possibility of redox-active micromachines, which are found to be crucial for efficient and enhanced photocatalysis.

Synthesis, Characterization and Biodistribution of GdF3:Tb3+@RB Nanocomposites.

Herein we report the development of a nanocomposite for X-ray-induced photodynamic therapy (X-PDT) and computed tomography (CT) based on PEG-capped GdF3:Tb3+ scintillating nanoparticles conjugated with Rose Bengal photosensitizer via electrostatic interactions. Scintillating GdF3:Tb3+ nanoparticles were synthesized by a facile and cost-effective wet chemical precipitation method. All synthesized nanoparticles had an elongated "spindle-like" clustered morphology with an orthorhombic structure. The structure, particle size, and morphology were determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS) analysis. The presence of a polyethylene glycol (PEG) coating and Rose Bengal conjugates was proved by Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and ultraviolet-visible (UV-vis) analysis. Upon X-ray irradiation of the colloidal PEG-capped GdF3:Tb3+-Rose Bengal nanocomposite solution, an efficient fluorescent resonant energy transfer between scintillating nanoparticles and Rose Bengal was detected. The biodistribution of the synthesized nanoparticles in mice after intravenous administration was studied by in vivo CT imaging.

Turn-On Photocatalysis: Creating Lone-Pair Donor-Acceptor Bonds in Organic Photosensitizer to Enhance Intersystem Crossing.

There is growing interest in developing triplet photosensitizers in terms of implementing photochemical strategies in synthetic chemistry. However, synthesis of stable triplet organic photosensitizers is nontrivial and often requires the use of heavy atoms. Herein, an alternative strategy is demonstrated to enhance the triplet generation efficiency by implanting lone-pair donor-acceptor bonds in the conjugated covalent organic frameworks (COFs). This powerful method is validated using COFs that host triazine, a moiety that has been extensively investigated in photocatalysis. Spectroscopic analysis and theoretical calculations reveal substantial improvements in the photoabsorptivity and triple-state photogeneration efficiency, consistent with catalytic tests concerning industrially relevant sulfide oxidation. These systems represent a promising addition to the rapidly increasing arsenal of synthetic photocatalytic systems.