Shape Memory Polymers with Patternable Recovery Onset Regulated by Light.

Shape memory polymers (SMPs) show attractive prospects in emerging fields such as soft robots and biomedical devices. Although their typical trigger-responsive character offers the essential shape-changing controllability, having to access external stimulation is a major bottleneck toward many applications. Recently emerged autonomous SMPs exhibit unique stimuli-free shape-shifting behavior with its controllability achieved via a delayed and programmable recovery onset. Achieving multi-shape morphing in an arbitrary fashion, however, is infeasible. In this work, a molecular design that allows to spatio-temporally define the recovery onset of an autonomous shape memory hydrogel (SMH) is reported. By introducing nitrocinnamate groups onto an SMH, its crosslinking density can be adjusted by light. This affects greatly the phase separation kinetics, which is the basis for the autonomous shape memory behavior. Consequently, the recovery onset can be regulated between 0 to 85 min. With masked light, multiple recovery onsets in an arbitrarily defined pattern which correspondingly enable multi-shape morphing can be realized. This ability to achieve highly sophisticated morphing without relying on any external stimulation greatly extends the versatility of SMPs.

Photoswitchable dynamics and RNAi synergist with tailored interface and controlled release reprogramming tumor immunosuppressive niche.

Immunosuppressive tumor microenvironment (ITM) severely limited the efficacy of immunotherapy against triple-negative breast cancer (TNBC). Herein, Apt-LPR, a light-activatable photodynamic therapy (PDT)/RNAi immune synergy-enhancer was constructed by co-loading miR-34a and photosensitizers in cationic liposomes (in phase III clinical trial). Interestingly, the introduction of tumor-specific aptamers creates a special "Liposome-Aptamer-Target" interface, where the aptamers are initially in a "lying down" state but transform to "standing up" after target binding. The interfacing mechanism was elaborately revealed by computational and practical experiments. This unique interface endowed Apt-LPR with neutralized surface potential of cationic liposomes to reduce non-specific cytotoxicity, enhanced DNase resistance to protect aptamers, and preserved target-binding ability for selective drug delivery. Upon near-infrared irradiation, the generated reactive oxygen species would oxidize unsaturated phospholipids to destabilize both liposomes and lysosomes, realizing stepwise lysosomal escape of miR-34a for tumor cell apoptosis and downregulation of PD-L1 to suppress immune escape. Together, tumor-associated antigens released from PDT-damaged mitochondria and endoplasmic reticulum could activate the suppressive immune cells to establish an "immune hot" milieu. The collaborative immune-enhancing strategy effectively aroused systemic antitumor immunity and inhibited primary and distal tumor progression as well as lung metastasis in 4T1 xenografted mouse models. The photo-controlled drug release and specific tumor-targeting capabilities of Apt-LPR were also visualized in MDA-MB-231 xenografted zebrafish models. Therefore, this photoswitchable PDT/RNAi immune stimulator offered a powerful approach to reprogramming ITM and reinforcing cancer immunotherapy efficacy.

Mechanical strain effect on the optoelectronic properties and photocatalysis applications of layered AlN/GaN nanoheterostructure.

CONTEXT: The aim of this work is to use first principles calculations to examine the effects of different mechanical strains on the optoelectronic and photocatalytic capabilities of the 2D/2D nanoheterostructure of AlN/GaN. By utilizing the lmBJ (Meta-GGA) and PBEsol (GGA) functional, the bandgap of the nanoheterostructure is calculated and found to be 4.89 eV and 3.24 eV. Simulated 2D AlN/GaN nanoheterostructure exhibits exceptional optical and electronic characteristics under applied biaxial tensile and compressive strains. The band gap changes from 4.89 to 3.77 eV, while the energy gap nature transitions from direct to indirect during tensile strain fluctuations of 0% to 8%. Strain is also found to have a significant effect on the optical absorption peaks. And a 0-8% rise in tensile strain causes the initial absorption peak of the 2D AlN/GaN nanoheterostructure to shift from 4.88 to 4.20 eV, which results in a 14% red shift in photon energy for every 2% change in strain. Furthermore, the optimum bandgap and band edge positions of the 2D AlN/GaN nanoheterostructure enable the water redox process to produce hydrogen and oxygen for wide range of pH. Thus, modification via strain may be an effective method for altering the optical as well as electronic characteristics of a 2D AlN/GaN nanoheterostructure, and this study may pave the way for new applications of this material in optoelectronic devices in the future. METHODS: In the current work, density functional theory is used to explore every attribute of the 2D AlN/GaN nanoheterostructure. To characterize the electronic exchange-correlation, we used the PBEsol functional. In order to prevent any interlayer contact between periodicity of images, a vacuum is produced along the z-direction of approximately 10 Å. To increase the precision of bandgap prediction, the electronic and optical characteristics were computed using the meta-GGA lmBJ functional. To account for interlayer van der Waals interactions, nanoheterostructure computations were performed using the DFT-D3 functional.

Density functional theory guide for copolymerization mechanism between allyl radical with radicalophile: photo-driven radical mediated [3 + 2] cyclization.

CONTEXT: The challenge of activating inert allyl monomers for polymerization has persisted, prompting our proposal of the photo-driven radical mediated [3 + 2] cyclization reaction (PRMC). This innovative approach significantly expedites the homopolymerization of multi-allyl monomers, enabling the synthesis of embolic microspheres for hepatocellular carcinoma interventions. PRMC involves allyl monomers to form allylic radicals and then radicals participating in a cycloaddition reaction with unsaturated olefins as radicalophiles to form cyclopentane-based radical products. While extensively studied in the theoretical and experimental homopolymerization, PRMC's application in copolymerization remains unexplored. To address this knowledge gap, we explored the elementary reaction, selecting allyl methyl ether radicals (AMER) and α,ß-unsaturated ketones as radicalophiles for copolymerization investigations by density functional theory (DFT) analysis. We quantified energy differences between ground and excited states of reactants, elucidated frontier molecular orbitals, and assessed thermodynamic data for copolymerization feasibility. We also evaluated the electronic properties of reactants, predicting the reactivity of radicalophiles and the interactions of intermolecular reactions. Additionally, we applied transition state theory and interaction/deformation models and conducted a local orbital analysis to comprehensively study excess electron distribution and gyration radius of cyclic radical product. Our findings offer vital insights into PRMC's potential in copolymerization. This research provides a robust theoretical foundation for practical application, enhancing the polymerization field. METHODS: Based on density functional theory (DFT), the calculations were performed at the M06-2X/6-311 + + G(d,p) level in/by Gaussian 16 package. Subsequently, our analytical results apply time-dependent density-functional theory (TD-DFT) and solvent modeling (SMD). Single-point energy calculations determine the driving force behind the radicals' reaction with radicalophiles. Furthermore, we assessed the electrostatic potential (ESP) of the reactants. The results of the calculations were visualized by the Multiwfn 3.6 and VMD 1.9 programs.

An Efficient MnO2 Photocathode with an Excellent SnO2 Electron Transport Layer for Photo-Accelerated Zinc Ion Batteries.

Photo-accelerated rechargeable batteries play a crucial role in fully utilizing solar energy, but it is still a challenge to fabricate dual-functional photoelectrodes with simultaneous high solar energy harvesting and storage. This work reports an innovative photo-accelerated zinc-ion battery (PAZIB) featuring a photocathode with a SnO2@MnO2 heterojunction. The design ingeniously combines the excellent electronic conductivity of SnO2 with the high energy storage and light absorption capacities of MnO2. The capacity of the SnO2@MnO2-based PAZIB is ≈598 mAh g-1 with a high photo-conversion efficiency of 1.2% under illumination at 0.1 A g-1, which is superior to that of most reported MnO2-based ZIB. The boosting performance is attributed to the synergistic effect of enhanced photogenerated carrier separation efficiency, improved conductivity, and promoted charge transfer by the SnO2@MnO2 heterojunction, which is confirmed by systematic experiments and theoretical simulations. This work provides valuable insights into the development of dual-function photocathodes for effective solar energy utilization.

Dual, Photo-Responsive and Redox-Active Supramolecular Foldamers.

We report on dual, light-responsive and redox-active foldamers that demonstrate reversible and robust stimuli-induced behaviour. Herein, UV/Vis, 1H NMR and circular dichroism (CD) spectroscopy and cyclic voltammetry have been used to establish the reversibility and highly robust nature of the light- and redox-driven behaviour of these new foldamers with minimal levels of fatigue observed even upon multiple cyclic treatments with irradiative/non-irradiative and oxidative/reductive conditions. This proof-of-concept work paves the way towards the creation of novel stimuli-responsive foldamers of increasing sophistication capable of demonstrating reversible and robust responses to multiple distinct stimuli.

Novel use of deep neural networks on photographic identification of epaulette sharks (Hemiscyllium ocellatum) across life stages.

Photographic identification (photo ID) is an established method that is used to count animals and track individuals' movements. This method performs well with some species of elasmobranchs (i.e., sharks, skates, and rays) where individuals have distinctive skin patterns. However, the unique skin patterns used for ID must be stable through time to allow re-identification of individuals in future sampling events. More recently, artificial intelligence (AI) models have substantially decreased the labor-intensive process of matching photos in extensive photo ID libraries and increased the reliability of photo ID. Here, photo ID and AI are used for the first time to identify epaulette sharks (Hemiscyllium ocellatum) at different life stages for approximately 2 years. An AI model was developed to assess and compare the reliability of human-classified ID patterns in juvenile and neonate sharks. The model also tested the persistence of unique patterns in adult sharks. Results indicate that immature life stages are unreliable for pattern identification, using both human and AI approaches, due to the plasticity of these subadult growth forms. Mature sharks maintain their patterns through time and can be identified by AI models with approximately 86% accuracy. The approach outlined in this study has the potential of validating the stability of ID patterns through time; however, testing on wild populations and long-term datasets is needed. This study's novel deep neural network development strategy offers a streamlined and accessible framework for generating a reliable model from a small data set, without requiring high-performance computing. Since many photo ID studies commence with limited datasets and resources, this AI model presents practical solutions to such constraints. Overall, this approach has the potential to address challenges associated with long-term photo ID data sets and the application of AI for shark identification.

In situ DRIFTs-based comprehensive reaction mechanism of photo-thermal synergetic catalysis for dry reforming of methane over Ru-CeO2 catalyst.

Solar-driven photo-thermal dry reforming of methane (DRM) is an environmentally friendly production route for high-value-added chemicals. However, the lack of thorough understanding of the mechanism for photo-thermal reaction has limited its further development. Here, we systematically investigated the mechanism of photo-thermal DRM reaction with the representative of Ru/CeO2 catalyst. Through in situ DRIFTs and transient experiments, comprehensive investigation into the reaction steps and their reactive sites in the process of DRM reaction were conducted. Besides, the excitation and migration direction of photo-electron was determined by ISI-XPS experiments, and the change of surface defect structure induced by light was characterized by ISI-EPR experiments. Based on the above results, the photo-enhancement effect on each micro-reaction step was determined. This study provides a theoretical basis for the industrialization of photo-thermal DRM reaction and its development of catalysts.

Type II photoinitiators with collagen-based cyanine for cell encapsulation under green-red LED.

3D bioprinting with cell-laden materials is an emerging technique for fabricating functional tissue constructs. However, current cell-laden bioinks often lack sufficient cytocompatibility with commonly used UV-light sources. In this study, green to red photoinduced hydrogel crosslinking was obtained by introducing synthesized biosafety photoinitiators and used in light-based direct ink writing (DIW) 3D printing for enabling cell encapsulation successfully. The novel type II photointiators contain iodonium (ONI) and synthesized cyanine dyes CZBIN, TDPABIN, Col-SH-CZ, and Col-SH-TD with strong absorption in the range of 400-600 nm. Collagen-based macromolecule dyes Col-SH-CZ and Col-SH-TD showed excellent cytocompatibility. The photochemistry of these photoinitiators revealed an efficient photoinduced electron transfer (PET) process from the singlet excited states of the dyes to iodonium (ONI), facilitating the crosslinking of the biogels. L929 cells were encapsulated in Gel-MA hydrogels containing various photoinitiating systems and exposed to near-ultraviolet, green, or red LED irradiation. DIW-type 3D printing of Gel-MA bioink with L929 cells was also evaluated. The cell viability achieved with green light encapsulation reached 90 %. This novel approach offers promising prospects for bioprinting functional tissues with enhanced cytocompatibility under visible light conditions.

Study on Thermophysical Properties and Phase Change Regulation Mechanism of Optically-Controlled Phase Change Materials: Synthesis, Crystal Structure and Molecular Dynamics.

Optically-controlled phase change materials, which are prepared by introducing molecular photoswitches into traditional phase change materials (PCMs), can convert and store solar energy into photochemical enthalpy and phase change enthalpy. However, the thermophysical properties of optically controlled PCMs, which are crucial in the practical, are rarely paid attention to. 4-(phenyldiazenyl)phenyl decanoate (Azo-A-10) is experimentally prepared as an optically-controlled PCMs, whose energy storage density is 210.0 kJ·kg-1, and the trans single crystal structure is obtained. The density, phase transition temperature, thermal conductivity, and other parameters in trans state are measured experimentally. Furthermore, a microscopic model of Azo-A-10 is established, and the thermophysical properties are analyzed based on molecular dynamics. The results show that the microstructure parameter (order parameters) and thermophysical properties (density, radial distribution function, self-diffusion coefficient, phase change temperature, and thermal conductivity) of partially or completely isomerized Azo-A-10, which are challenging to observe in experiments, can be predicted by molecular dynamics simulation. The optically-controlled phase change mechanism can be clarified according to the differences in microstructure. The optically-controlled switchability of thermophysical properties of an optically-controlled PCM is analyzed. This study provides ideas for the improvement, development, and application of optically-controlled PCMs in the future.

Site-specific photo-crosslinking of Hsc70 with the KFERQ pentapeptide motif in a chaperone-mediated autophagy and microautophagy substrate in mammalian cells.

Heat shock cognate protein 70 (Hsc70/HSPA8) belongs to the Hsp70 family of molecular chaperones. The fundamental functions of Hsp70 family molecular chaperones depend on ATP-dependent allosteric regulation of binding and release of hydrophobic polypeptide substrates. Hsc70 is also involved in various other cellular functions including selective pathways of protein degradation: chaperone-mediated autophagy (CMA) and endosomal microautophagy (eMI), in which Hsc70 recruits substrate proteins containing a KFERQ-like pentapeptide motif from the cytosol to lysosomes and late endosomes, respectively. However, whether the interaction between Hsc70 and the pentapeptide motif is direct or mediated by other molecules has remained unknown. In the present study, we introduced a photo-crosslinker near the KFERQ motif in a CMA/eMI model substrate and successfully detected its crosslinking with Hsc70, revealing the direct interaction between Hsc70 and the KFERQ motif for the first time. In addition, we demonstrated that the loss of the Hsc70 ATPase activity by the D10 N mutation appreciably reduced the crosslinking efficiency. Our present results suggested that the ATP allostery of Hsc70 is involved in the direct interaction of Hsc70 with the KFERQ-like pentapeptide.

Assessing the impact of simulated ocean acidification on the photodegradation of selected microplastics.

This study investigated the impact of ocean acidification on the photodegradation of three microplastics (MPs): polypropylene (PP), expanded polystyrene (EPS), and ethylene-vinyl acetate (EVA), under accelerated UV radiation at three pH levels (i.e., 8.1, 7.8, and 7.5), simulating marine conditions. The acidification system simulated current and projected future environmental conditions. As expected, an increase in partial pressure of CO2, total inorganic carbon, bicarbonate ion, and CO2 resulted in more acidic pH levels, with the reverse being true for the carbonate ion. Structural changes of MPs were evaluated, revealing that all weathered samples underwent higher degradation rate compared to the virgin samples. The oxidation state and crystallinity of PP and EVA MPs were higher in samples exposed to the lowest pH, whereas no significant increase in the degradation rate of EPS samples was observed. Saltwater acidification in this study contributed to enhance the photo-oxidation of MPs depending on their polymeric composition.

Antibacterial properties of photo-crosslinked chitosan/methacrylated hyaluronic acid nanoparticles loaded with bacitracin.

The current treatments for wounds often fail to induce adequate healing, leaving wounds vulnerable to persistent infections and development of drug-resistant microbial biofilms. New natural-derived nanoparticles were studied to impair bacteria colonization and hinder the formation of biofilms in wounds. The nanoparticles were fabricated through polyelectrolyte complexation of chitosan (CS, polycation) and hyaluronic acid (HA, polyanion). UV-induced photo-crosslinking was used to enhance the stability of the nanoparticles. To achieve this, HA was methacrylated (HAMA, degree of modification of 20 %). Photo-crosslinked nanoparticles obtained from HAMA and CS had a diameter of 478 nm and a more homogeneous size distribution than nanoparticles assembled solely through complexation (742 nm). The nanoparticles were loaded with the antimicrobial agent bacitracin (BC), resulting in nanoparticles with a diameter of 332 nm. The encapsulation of BC was highly efficient (97 %). The BC-loaded nanoparticles showed significant antibacterial activity against gram-positive bacteria Staphylococcus aureus, Methicillin-resistant S. aureus and S. epidermidis. Photo-crosslinked HAMA/CS nanoparticles loaded with BC demonstrated inhibition of biofilm formation and a positive effect on the proliferation of mammalian cells (L929). These crosslinked nanoparticles have potential for the long-term treatment of wounds and controlled antibiotic delivery at the location of a lesion.

Photo-Thermal Dry Reforming of Methane with PGM-Free and PGM-Based Catalysts: A Review.

Dry reforming of methane (DRM) is considered one of the most promising technologies for efficient greenhouse gas management thanks to the fact that through this reaction, it is possible to reduce CO2 and CH4 to obtain syngas, a mixture of H2 and CO, with a suitable ratio for the Fischer-Tropsch production of long-chain hydrocarbons. Two other main processes can yield H2 from CH4, i.e., Steam Reforming of Methane (SRM) and Partial Oxidation of Methane (POM), even though, not having CO2 as a reagent, they are considered less green. Recently, scientists' challenge is to overcome the many drawbacks of DRM reactions, i.e., the use of precious metal-based catalysts, the high temperatures of the process, metal particle sintering and carbon deposition on the catalysts' surfaces. To overcome these issues, one proposed solution is to implement photo-thermal dry reforming of methane in which irradiation with light is used in combination with heating to improve the efficiency of the process. In this paper, we review the work of several groups aiming to investigate the pivotal promoting role of light radiation in DRM. Focus is also placed on the catalysts' design and the progress needed for bringing DRM to an industrial scale.

Mechanism exploration of synergistic photo-immunotherapy strategy based on a novel exosome-like nanosystem for remodeling the immune microenvironment of HCC.

The immunosuppressive tumor microenvironment (TME) has become a major challenge in cancer immunotherapy, with abundant tumor-associated macrophages (TAMs) playing a key role in promoting tumor immune escape by displaying an immunosuppressive (M2) phenotype. Recently, it was reported that M1 macrophage-derived nanovesicles (M1NVs) can reprogram TAMs to an anti-tumor M1 phenotype, thereby significantly alleviating the immunosuppressive TME and enhancing the anti-tumor efficacy of immunotherapy. Herein, we developed M1NVs loaded with mesoporous dopamine (MPDA) and indocyanine green (ICG), which facilitated the recruitment of M2 TAMs through synergistic photothermal and photodynamic therapy. Thereafter, M1NVs can induce M1 repolarization of TAMs, resulting in increased infiltration of cytotoxic T lymphocytes within the tumor to promote tumor regression. This study investigated the effect of phototherapy on the immune environment of liver cancer using single-cell RNA sequencing (scRNA-seq) by comparing HCC tissues before and after MPDA/ICG@M1NVs + NIR treatment. The results showed significant shifts in cell composition and gene expression, with decreases in epithelial cells, B cells, and macrophages and increases in neutrophils and myeloid cells. Additionally, gene analysis indicated a reduction in pro-inflammatory signals and immunosuppressive functions, along with enhanced B-cell function and anti-tumor immunity, downregulation of the Gtsf1 gene in the epithelial cells of the MPDA/ICG @M1NVs + NIR group, and decreased expression of the lars2 gene in immune subpopulations. Eno3 expression is reduced in M1 macrophages, whereas Clec4a3 expression is downregulated in M2 macrophages. Notably, the B cell population decreased, whereas Pou2f2 expression increased. These genes regulate cell growth, death, metabolism, and tumor environment, indicating their key role in HCC progression. This study highlights the potential for understanding cellular and molecular dynamics to improve immunotherapy.

Copper single-atom catalysts for broad-spectrum antibiotic-resistant bacteria (ARBs) antimicrobial: Activation of peroxides and mechanism of ARBs inactivation.

Antibiotic-resistant bacteria (ARBs) have been widely detected in wastewater and become a potential threat to human health. This work found that low-load single-atom copper (0.1 wt%) anchored on g-C3N4 (SA-Cu/g-C3N4) exhibited excellent ability to activate H2O2 and inactivate ARBs during the photo-Fenton process. The presence of SA-Cu/g-C3N4 (0.4 mg/mL) and H2O2 (0.1 mM) effectively inactivated ARBs. More than 99.9999 % (6-log) of methicillin-resistant Staphylococcus aureus (MRSA), and carbapenem-resistant Acinetobacter baumannii (CRAB) could be inactivated within 5 min. Extended-spectrum ß-lactamase-producing pathogenic Escherichia coli (ESBL-E) and vancomycin-resistant Enterococcus faecium (VRE) were killed within 10 and 30 min, respectively. In addition, more than 5-log of these ARBs were killed within 60 min in real wastewater. Furthermore, D2O-labeling with Raman spectroscopy revealed that SA-Cu/g-C3N4 completely suppressed the viable but nonculturable (VBNC) state and reactivation of bacteria. Electron paramagnetic resonance spectroscopy results demonstrated that g-C3N4 mainly produced 1O2, while SA-Cu/g-C3N4 simultaneously produced both 1O2 and •OH. The •OH and 1O2 cause lipid peroxidation damage to the cell membrane, resulting in the death of the bacteria. These findings highlight that the SA-Cu/g-C3N4 catalyst is a promising photo-Fenton catalyst for the inactivation of ARBs in wastewater.

S-scheme 3D/3D Bi/BiOBr/P Doped g-C3N4 with Oxygen Vacancies (Ov) for Photodegradation of Pharmaceuticals: In-situ H2O2 Production and Plasmon Induced Stability.

Highlights   S-scheme heterojunction was fabricated through in-situ solvothermal method 3D worm-like BOR and 3D rocky stone CNPO composite exhibited high photoactivity through •O2- 3D/3D junction occurred through bridging bond for efficient charge separation Waste H2O2 was turned into wealth •OH for mineralization of OTC and LVX Bi0 plasmon assisted stability and H2O2 decomposition and Ov influenced its production.

Forecasting Photo-Dissolution for Future Oil Spills at Sea: Effects of Oil Properties and Composition.

Photo-dissolution, the photochemical production of water-soluble species from oil, can transfer oil-derived dissolved organic carbon (DOC) from floating surface slicks to the underlying seawater. Photo-dissolution was likely a quantitatively relevant fate process for the Macondo crude oil spilled during the 2010 Deepwater Horizon spill, but the importance of photo-dissolution for other oils is poorly constrained. This study evaluated the photo-dissolution reactivities (apparent quantum yields) and modeled rates for oils with diverse physical properties and chemical compositions, including an ultra low sulfur fuel oil (ULSFO). Photo-dissolution from UV (310 nm) light was strongly positively correlated with the fraction of small, gas-oil range compounds (

Photo-annealable agarose microgels for jammed microgel printing: Transforming thermogelling hydrogel to a functional bioink.

Three-dimensional (3D) printing of hydrogel structures using jammed microgel inks offer distinct advantages of improved printing functionalities, as these inks are strain-yielding and self-recovering types. However, interparticle binding in granular hydrogel inks is a challenge to overcome the limited integrity and reduced macroscale modulus prevalent in the 3D printed microgel scaffolds. In this study, we prepared chemically annealable agarose microgels through a process of xerogel rehydration, applying a low-cost and high throughput method of spray drying. The crosslinked jammed microgel matrix is found to have superior mechanical properties with a Young's modulus of 2.23 MPa and extensibility up to 7.2%, surpassing those of traditional biopolymer-based and microgel-based inks. Furthermore, this study addresses the complexities encountered in the existing system of printing thermoresponsive agarose bioink using this jammed microgel printing approach. The jammed agarose microgel ink exhibited to be self-recovering, yield stress fluid and validated the temperature-independent printing. Furthermore, the 3D printed jammed microgel scaffold demonstrated good cell responsiveness as evaluated through the viability and morphological study in-vitro with mesenchymal stem cells cultured in it. This unique fabrication approach offers exciting possibilities to expand on microgel printing for varied requirements in tissue engineering.

Metal-free functionalized carbon nitride as a photocatalyst driven by sunlight for acetal synthesis and selective regeneration of NAD(P)H cofactor.

Nicotinamide Adenine Dinucleotide Phosphate (NAD(P)H) plays an important role in numerous biologically significant redox reactions. The photochemical restoration of its oxidized form (NAD(P)+) under physiological conditions is intriguing in the context of integrated photo and catalysis. Herein, we report the functionalized graphitic carbon-based solar light active photocatalyst by doping boron and fluorine in the native graphitic carbon nitride (GCN) (nonfunctionalized) for the regeneration of enzymatically visible light active coenzyme and in photo-acetalization reactions. The metal-free functionalized photocatalyst systems such as BFGCN-x leads to higher yield NADH and NADPH regeneration. They are also capable of catalyzing acetal reactions in the absence of any Lewis and Bronsted acids. The current research endeavor provides the advancement and the application of functionalized GCN-based photocatalysts for NADH (61.89%), NADPH (59.84%) regeneration, and photo-acetalization reactions.