Photochemical Research Articles

The Impact of Extended H2O Cross Sections on Temperate Anoxic Planet Atmospheres: Implications for Spectral Characterization of Habitable Worlds

JWST has created a new era of terrestrial exoplanet atmospheric characterization, and with it, the possibility to detect potential biosignature gases like CH4. Our interpretation of exoplanet atmospheric spectra, and the veracity of these interpretations, will be limited by our understanding of atmospheric processes and the accuracy of input modeling data. Molecular cross sections are essential inputs to these models. The photochemistry of temperate planets depends on photolysis reactions whose rates are governed by the dissociation cross sections of key molecules. H2O is one such molecule; the photolysis of H2O produces OH, a highly reactive and efficient sink for atmospheric trace gases. We investigate the photochemical effects of improved H2O cross sections on anoxic terrestrial planets as a function of host star spectral type and CH4 surface flux. Our results show that updated H2O cross sections, extended to wavelengths >200 nm, substantially impact the predicted abundances of trace gases destroyed by OH. The differences for anoxic terrestrial planets orbiting Sun-like host stars are greatest, showing changes of up to 3 orders of magnitude in surface CO levels, and over an order of magnitude in surface CH4 levels. These differences lead to observable changes in simulated planetary spectra, especially important in the context of future direct-imaging missions. In contrast, the atmospheres of planets orbiting M-dwarf stars are substantially less affected. Our results demonstrate a pressing need for refined dissociation cross-section data for H2O, where uncertainties remain, and other key molecules, especially at mid-UV wavelengths >200 nm.

Photochemical wet etching of (0 0 1) plane ß-phase Ga2O3, and its anisotropic etching behavior

The photochemical (PC) wet etching behavior of (001) plane β-phase Ga2O3(β-Ga2O3)single crystal was investigated using potassium hydroxide etchant solution under ultraviolet illumination in the temperature range of 80–95 °C. The etch rate was 1.65 nm/min at 80 °C, and increased up to 4.88 nm/min at 95 °C. The etch rate of the (001) plane β-Ga2O3shows strong temperature dependence with the activation energy of 0.798 eV. The PC wet etching characteristics of the (001) plane β-Ga2O3was compared with those of (2¯01) and (010) plane β-Ga2O3. The etch rates increased in order of the (010), (2¯01), and (001) plane, which is accordance with the increasing surface energy trend. The oval line-shaped grooves aligned along [010] direction were observed on the etched (001) plane β-Ga2O3 crystal surface after 30 min. PC wet etching at 80 °C.

Does photobiomodulation alter mitochondrial dynamics?

Mitochondrial dysfunction is one of the leading causes of disease development. Dysfunctional mitochondria limit energy production, increase reactive oxygen species generation, and trigger apoptotic signals. Photobiomodulation is a noninvasive, nonthermal technique involving the application of monochromatic light with low energy density, inducing non-thermal photochemical effects at the cellular level, and it has been used due to its therapeutic potential. This review focuses on the mitochondrial dynamic's role in various diseases, evaluating the possible therapeutic role of low-power lasers (LPL) and light-emitting diodes (LED). Studies increasingly support that mitochondrial dysfunction is correlated with severe neurodegenerative diseases such as Parkinson's, Huntington's, Alzheimer's, and Charcot-Marie-Tooth diseases. Furthermore, a disturbance in mitofusin activity is also associated with metabolic disorders, including obesity and type 2 diabetes. The effects of PBM on mitochondrial dynamics have been observed in cells using a human fibroblast cell line and invivo models of brain injury, diabetes, spinal cord injury, Alzheimer's disease, and skin injury. Thus, new therapies aiming to improve mitochondrial dynamics are clinically relevant. Several studies have demonstrated that LPL and LED can be important therapies to improve health conditions when there is dysfunction in mitochondrial dynamics.

Carbene-Mediated Polymer Modification Using Diazo Compounds under Photo or Thermal Activation Conditions.

Based on the characteristics of commodity polymers in large quantities and low costs, modification of existing commodity polymers emerges as the most effective approach for exploring novel materials. Nevertheless, conventional modification methods typically involve high-energy processes (e.g., high temperature, high-energy radiation), which may lead to irreversible detrimental effects on the polymers, contradicting the desired performance enhancement through modification. In this work, we propose a carbene-mediated postpolymerization modification (PPM) strategy utilizing diazo compounds. Under photochemical or thermal activation conditions, insertion of the C-H bond can be achieved without compromising the performance of polymers. These diazo compounds can be easily synthesized in just two steps and applied to all C-H-containing polymers. This practical and effective modification strategy offers new opportunities and possibilities for enhancing the value and expanding the applications of polymers.

Anisotropic Plasmon Resonance Enables Spatially Controlled Photothermal and Photochemical Effects in Hot Carrier‐Driven Catalysis

Comprehensive SummaryLocalized surface plasmon resonance has been demonstrated to provide effective photophysical enhancement mechanisms in plasmonic photocatalysis. However, it remains highly challenging for distinct mechanisms to function in synergy for a collective gain in catalysis due to the lack of spatiotemporal control of their effect. Herein, the anisotropic plasmon resonance nature of Au nanorods was exploited to achieve distinct functionality towards synergistic photocatalysis. Photothermal and photochemical effects were enabled by the longitudinal and transverse plasmon resonance modes, respectively, and were enhanced by partial coating of silica nanoshells and epitaxial growth of a reactor component. Resonant excitation leads to a synergistic gain in photothermal‐mediated hot carrier‐driven hydrogen evolution catalysis. Our approach provides important design principles for plasmonic photocatalysts in achieving spatiotemporal modulation of distinct photophysical enhancement mechanisms. It also effectively broadens the sunlight response range and increases the efficacy of distinct plasmonic enhancement pathways towards solar energy harvesting and conversion.

Non-Photochemical Origin of Selectivity Difference between Light and Dark Catalytic Conditions.

The interest in introducing light into heterogeneous catalysis is driven not only by the urgent need of replacing fossil energy but also by the promise of controlling product selectivity by light. The product selectivity differences observed in recent studies between light and dark reactions are often attributed to photochemical effects. Here, we report the discovery of a non-photochemical origin of selectivity difference, at essentially the same CO2 conversion rate, between photothermal and thermal CO2 hydrogenation reactions over a Ru/TiO2-x catalyst. While the presence of the photochemical effect from ultraviolet light is confirmed, it merely enhances the catalytic activity. Systematic investigation reveals that the gradual formation of an adsorbate-mediated strong metal-support interaction under catalytic conditions is responsible for the variation in the catalytic selectivity. We demonstrate that differences in product selectivity under light/dark reactions do not necessarily originate from photochemical effects. Our study refines the basis for determining photochemical effects and highlights the importance of excluding non-photochemical effects in mechanistic studies of light-controlled product selectivity.

Novel D-π-A hemicyanine dye as photoinitiators for insitu hydrogel formation and DLP printing.

The field of biofabrication imposes stringent requirements on the polymerization activity and biosafety of photopolymeric hydrogel systems. In this investigation, we designed and synthesized four hemicyanine dyes with a D-π-A structure specifically tailored for biofabrication purposes. These novel dyes, incorporating carbazole (CZ), triphenylamine (TPA), anthracene (AN), and benzodithiophene (BDT) as electron donors, along with heterocyclic salt (IN) as electron acceptors, were prepared using a straightforward synthesis method. The absorption maxima of ANIN, CZIN, and TPAIN exceeded 500 nm, rendering them suitable co-initiators for the free radical photopolymerization of acrylates under green-red light exposure facilitated by light-emitting diodes (LEDs) and the co-initiator iodonium salt (ION). Notably, CZIN and TPAIN, due to their robust dye absorption and efficient electron transfer to ION, functioned as high-performance photosensitizers. Meanwhile, BDTIN, with its strong and broad absorption range (400-600 nm), enhanced the accuracy of visible light photopolymerization. These dyes exhibit characteristics such as facile synthesis, heightened photo stability, and non-toxicity and also demonstrate the ability to discern the alkalinity of a solution to some extent. Furthermore, we explored the application of these hemicyanine dyes in 3D printing, showing potential to enhance printing resolution in DLP 3D printing (digital light process 3D printing).

Diagnosing ozone–NOx–VOC–aerosol sensitivity and uncovering causes of urban–nonurban discrepancies in Shandong, China, using transformer-based estimations

Abstract. Narrowing surface ozone disparities between urban and nonurban areas escalate health risks in densely populated urban zones. A comprehensive understanding of the impact of ozone photochemistry on this transition remains constrained by current knowledge of aerosol effects and the availability of surface monitoring. Here we reconstructed spatiotemporal gapless air quality concentrations using a novel transformer deep learning (DL) framework capable of perceiving spatiotemporal dynamics to analyze ozone urban–nonurban differences. Subsequently, the photochemical effect on these discrepancies was analyzed by elucidating shifts in ozone regimes inferred from an interpretable machine learning method. The evaluations of the model exhibited an average out-of-sample cross-validation coefficient of determination of 0.96, 0.92, and 0.95 for ozone, nitrogen dioxide, and fine particulate matter (PM2.5), respectively. The ozone sensitivity in nonurban areas, dominated by a nitrogen-oxide-limited (NOx-limited) regime, was observed to shift towards increased sensitivity to volatile organic compounds (VOCs) when extended to urban areas. A third “aerosol-inhibited” regime was identified in the Jiaodong Peninsula, where the uptake of hydroperoxyl radicals onto aerosols suppressed ozone production under low NOx levels during summertime. The reduction of PM2.5 could increase the sensitivity of ozone to VOCs, necessitating more stringent VOC emission abatement for urban ozone mitigation. In 2020, urban ozone levels in Shandong surpassed those in nonurban areas, primarily due to a more pronounced decrease in the latter resulting from stronger aerosol suppression effects and less reduction in PM2.5. This case study demonstrates the critical need for advanced spatially resolved models and interpretable analysis in tackling ozone pollution challenges.

Photocatalytic Activity and Antibacterial Properties of ZnO/CNTs Composites

Photocatalytic technology is one of the promising technologies for wastewater treatment. Herein, zinc oxide/multi-walled carbon nanotubes (ZnO/CNTs) photocatalyst was successfully prepared by hydrothermal method with combining in-situ synthesis technology. The micro-morphology, crystalline structure, surface chemical elements, and optical properties were characterized by SEM, TEM, XRD, FTIR, UV-Vis, and DRS technologies. The ZnO/CNTs photo-catalyst exhibited enhancement photo activity for degradation of organic pollutants under simulated light irradiation. Specifically, the photo-catalytic activity of the ZnO/CNTs catalysts improved with the rise of CNTs content in the composites. Investigation on the photo-degradation mechanism verified that the presence of CNTs in the catalyst not only optimized the band structure of ZnO semiconductor but also contributed to the transfer of photo-generated electrons and reducing the recombination of electron-hole pairs due to its excellent conductivity. Moreover, the active radical groups such as superoxide radical (O-2), hole (h+), and hydroxyl radical (·OH) played the dominated role for the pollutants degradation under the simulated sunlight irradiation. In addition, ZCT20 catalysts and light irradiation had synergistic effects on antibacterial activity, whose antibacterial rates against E. coli and S. aureus were up to 99.96% and 99.94%, respectively. Investigation on antibacterial mechanisms revealed that the existence of ROS and the continuous release of Zn2+ played an important role for improving the antibacterial activity of the ZCT20 catalyst under the simulated sunlight irradiation.

A photoelectrochemical biosensor based on self-calibration platform of carbon-rich plasmonic probe with near-infrared driving signal amplification

Exploring the photochemical (PEC) method induced by low-energy light source makes great significance to achieve high stability and accurate analysis. A sensing platform driven by near-infrared (NIR) light was designed by making the biochemically encoded carbon rich plasmonic hybrid (CPH) probe, the peptide@C–Mo2C. The inherent plasmonic effect of C–Mo2C CPH can directly absorb NIR light, thus starting effective electronic-hole pairs separation. Moreover, the photothermal effect of C–Mo2C CPH also promoted the reaction yield of photothermal catalyst reaction on sensing interface to assist the PEC signal amplification. In the presence of target trypsin, it cleaves the peptides, resulting in the release of peptide@C–Mo2C probe from interface, which leads to a relative decrease in PEC signal. More importantly, a self-calibration system consisting of two independent PEC test channels attempted to eliminate the influence of background signal and baseline drift. The test channel was used to specify the recognition target, while the blank channel was used as a reference. Therefore, the signal difference between two channels was recorded, so as to obtain results with less error and higher stability. In this NIR driven PEC sensor, the carbon rich probe with direct and efficient NIR light conversion promoted the sensitivity and a self-calibration system guaranteed the stability which provided innovative thoughts for developing ingenious PEC sensor.

Hydrogen‐Bonding Interactions Between Terpolymers Enable Excellent Device Efficiency and Operational Stability of Non‐Halogenated Solvent‐Processed Polymer Solar Cells

AbstractAlthough polymer solar cells (PSCs) have shown considerable power conversion efficiency (PCE) potential, their poor operational stability is a major obstacle for their future commercialization. In this study, the ternary‐blend strategy based on D1–A–D1–D2‐type conjugated random terpolymers containing hydrogen–bonding sites is employed to simultaneously improve device efficiency and long‐term stability. Notably, the PM6‐ThEG:PM6‐ThOH:Y6‐BO ternary‐blend system exhibits a remarkable PCE of 17.2% with superior photo, thermal, and mechanical stability, outperforming those of binary devices based on PM6, PM6‐ThEG, and PM6‐ThOH polymer donors. These outstanding results are likely attributed to the robust molecular lock via hydrogen bonds between PM6‐ThEG and PM6‐ThOH terpolymers, which can induce strong intermolecular packing, a dense 3D terpolymer network, and optimized morphology. These results also correlate well with the computational study. A comprehensive analysis of optoelectronic and morphological properties as well as the exploration of underlying physical mechanisms collectively verifies the effectiveness of this approach based on mixed random terpolymers with hydrogen‐bonding moiety to achieve the non‐halogenated solvent‐processed PSCs with exceptional efficiency and operational stability.

A large role of missing volatile organic compound reactivity from anthropogenic emissions in ozone pollution regulation

Abstract. There are thousands of volatile organic compound (VOC) species in ambient air, while existing techniques can only detect a small part of them (approximately several hundred). The large number of unmeasured VOCs prevents us from understanding the photochemistry of ozone and aerosols in the atmosphere. The major sources and photochemical effects of these unmeasured VOCs in urban areas remain unclear. The missing VOC reactivity, which is defined as the total OH reactivity of the unmeasured VOCs, is a good indicator for constraining the photochemical effect of unmeasured VOCs. Here, we identified the dominant role of anthropogenic emission sources in the missing VOC reactivity (accounting for up to 70 %) by measuring missing VOC reactivity and tracer-based source analysis in a typical megacity in China. Omitting the missing VOC reactivity from anthropogenic emissions in model simulations will remarkably affect the diagnosis of sensitivity regimes for ozone formation, overestimating the degree of VOC-limited regimes by up to 46 %. Therefore, a thorough quantification of missing VOC reactivity from various anthropogenic emission sources is urgently needed for constraints of air quality models and the development of effective ozone control strategies.

Abstract 5816: An effective delivery platform for nucleic acid therapeutics: Enhanced cancer cell internalization and endosomal escape

Abstract Nucleic acid therapeutics (NATs), such as siRNA and mRNA, show great potential as cancer medicines. However, translation of these compounds has been held back by their limited bioavailability in target tissues. The aim of this study was to test the use of a novel cell-penetrating peptide (CPP)-based delivery platform to enhance uptake of NAT into cancer cells. This platform consists of a highly efficient CPP that combines the advantages of multimerization and cyclization of the archetypal CPP, TAT peptide1, plus a photochemical (PC) strategy to promote endosomal release of NAT into the cytoplasm2. Negatively charged NATs form complexes with cationic CPPs through charge:charge interaction. NATs (siRNA or mRNA) were incubated with CPP at different molar ratios and assessed in gel retardation assays. Efficiency of internalization of Cy3-NAT:CPP complexes was evaluated using live cell confocal imaging with quantification of intracellular fluorescence. The mechanism of cellular uptake of NAT:CPP was investigated using inhibitors of endocytosis (chlorpromazine, NaN3, amiloride and methyl-β-cyclodextrin). To trigger NAT release from intracellular vesicles, 420 nm/50 mA LED light irradiation was applied following pre-treatment of cells with a photosensitizer, fimaprofin. CPP-PC mediated internalization and endosomal release was used for delivery of glyceraldehyde 3-phosphate dehydrogenase (GAPDH) siRNA. GAPDH enzymatic activity assays (Sigma, USA) were conducted to confirm inhibition of GAPDH in HeLa, HEK293T and MDA-MB-231 cells. Transfection efficiency of mRNA encoding enhanced green fluorescence protein (eGFP) was evaluated by flow cytometry in HeLa cells. NAT:CPP complexes were found to be maximally efficient at a 10:1 molar ratio. Analysis of live cell confocal images indicated that GAPDH Cy3-siRNA:CPP complexes were more efficiently internalized compared to Cy3-siRNA + monomeric TAT or Cy3-siRNA + lipofectamine (****p<0.0001, one-way ANOVA). The combined CPP-PC platform delivers NAT via a clathrin-mediated endocytosis pathway. CPP-PC delivery of GAPDH siRNA caused marked GAPDH enzyme activity downregulation in HeLa (91%), MDA-MB-231 (51%) and HEK293T (44%) cells. These results were similar to the level of downregulation achieved with lipofectamine + GAPDH siRNA. Flow cytometric analysis revealed that 52.4% of HeLa cells expressed eGFP at 1 h following delivery of mRNA-eGFP by CPP-PC. Functional siRNA and mRNA were efficiently delivered into the cytoplasm of cancer cells through combined use of a multimeric/cyclized CPP plus photochemical-mediated endosomal release. This approach holds promise for clinical application, particularly in the treatment of intraluminal tumors. 1. Tietz, O. et al. Nat Chem. 14: 284-93, 2022. 2. Selbo, P. K. et al. J Control Release. 148, 2-12, 2010. Citation Format: Siqi Li, Ole Tietz, Afaf H. El-Sagheer, Tom Brown, Katherine A. Vallis. An effective delivery platform for nucleic acid therapeutics: Enhanced cancer cell internalization and endosomal escape [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 5816.

Synergistic RB5 dye degradation and oxygen evolution reaction (OER) catalysis by WO3 nano-pellets: mechanistic insights and water remediation applications

Transition metal oxides (TMO), a non-noble element based oxides, establish remarkable potential in the realm of textile wastewater remediation and water splitting due to their sustainable catalytic performance. Highly functional TMO materials, in form of nanostrcutures, are of great interest owing to their robust photo and electro-catalytic activities for instituting sustainable development for the water and energy resource management framework. In the present article, we have reported catalytically active WO3 nano-pellets (NP) synthesized using microwave-assisted for photocatalytic wastewater remediation and electrocatalytic oxygen evolution reaction (OER). Promisingly, WO3 NP abetted degradation of the reactive black 5 (RB5) dye by almost 95 % in short time interval of 60 min in exposer of sun light. Present work includes the strategies to remove and observe the progression of reaction kinetics of dye degradation in neutral and alkaline media. By varying concentration of the catalyst (ranging from 250 mg/L to 1000 mg/L, in the step of 250 mg/L), we have prolifically verified that 750 mg/L turn out optimal dosage for 100% degradation in time interval of 120 min. Besides, WO3 NP has shown highest photocatalytic behaviour at 9 pH. The WO3 NP shows the electrocatalytic OER performance in an alkaline condition (1M KOH) with an overpotential of 418 mV to generate the geometric current density of 10 mA/cm² and Tafel slope of 178 mV dec⁻¹. Owing to robust nature, WO3 NP shows the almost similar photocatalytic response for ten cycles dye degradation and demonstrates the stable electrochemical charge transport for OER at 10 mA/cm2 for 50 hours.

Exploring Tunable Properties, Solvent-Modulated Dynamics, and Novel C(sp3)-H Activation Mechanisms in Electron Donor-Acceptor Complexes.

Electron donor-acceptor (EDA) complex photochemistry has emerged as a vibrant area in visible-light-mediated synthetic radical chemistry. However, theoretical insights into the reaction mechanisms remain limited. Our study investigates the influence of solvent polarity and halogen atom types on radical reaction pathways in EDA complexes. We demonstrate that solvent polarity modulates the charge transfer and spatial arrangement within EDA complexes, thereby influencing their stability and reaction kinetics. Iodide ions play a crucial role in facilitating free radical generation and stabilizing reaction intermediates. Different halogen atom types exhibit distinct effects on radical reactions. Variations in radical concentration and solvent environment further affect the pathway selectivity. Additionally, light conditions influence the free radical generation and pathway selectivity. Our findings enhance the understanding of EDA complex photochemistry and radical reactions, offering insights for organic synthesis and photochemistry applications.

Enhancing Photo and Electrocatalytic Activity of Graphene Quantum Dots/Manganese Oxide Nanostructures for Visible Light Photocatalytic and Hydrogen Peroxide Sensing Applications

AbstractDesigning and developing high‐efficiency multifunctional catalysts materials is a significant challenge. In this view, we synthesized Graphene Quantum Dots (gQDs)/Gadolinium Manganese Oxide (GMO) nanostructures for photocatalytic dye degradation and hydrogen peroxide sensing. The structural, optical, composition, and morphology properties of the gQDs/GMO nanostructures were analyzed by using various analytical tools. The gQDs/GMO catalyst shows higher degradation efficiency compared to pure catalysts under visible light irradiation which is due to the large surface area, lower band gap, small amount of hydrogen peroxide (H2O2), and synergetic effect of gQDs/GMO. Furthermore, we extensively investigate the nonenzymatic H2O2 sensing and the gQDs/GMO catalytic materials show higher sensing behavior. From our results, the gQDs embedded in gadolinium‐modified manganese oxide (gQDs/GMO) serve as an efficient photocatalyst material for environmental pollutant degradation under visible light irradiation with and the sensitive electrocatalyst for nonenzymatic H2O2 sensing applications.

Photoresponsive Covalent Organic Frameworks: Visible‐Light Controlled Conversion of Porous Structures and Its Impacts

AbstractCovalent organic frameworks are a novel class of crystalline porous polymers that enable molecular design of extended polygonal skeletons to attain well‐defined porous structures. However, construction of a framework that allows remote control of pores remains a challenge. Here we report a strategy that merges covalent, noncovalent, and photo chemistries to design photoresponsive frameworks with reversibly and remotely controllable pores. We developed a topology‐guided multicomponent polycondensation system that integrates protruded tetrafluoroazobenzene units as photoresponsive sites on pore walls at predesigned densities, so that a series of crystalline porous frameworks with the same backbone can be constructed to develop a broad spectrum of pores ranging from mesopores to micropores. Distinct from conventional azobenzene‐based systems, the tetrafluoroazobenzene frameworks are highly sensitive to visible lights to undergo high‐rate isomerization. The photoisomerization exerts profound effects on pore size, shape, number, and environment, as well as molecular uptake and release, rendering the system able to convert and switch pores reversibly and remotely with visible lights. Our results open a way to a novel class of smart porous materials with pore structures and functions that are convertible and manageable with visible lights.

Photoresponsive Covalent Organic Frameworks: Visible-Light Controlled Conversion of Porous Structures and Its Impacts.

Covalent organic frameworks are a novel class of crystalline porous polymers that enable molecular design of extended polygonal skeletons to attain well-defined porous structures. However, construction of a framework that allows remote control of pores remains a challenge. Here we report a strategy that merges covalent, noncovalent, and photo chemistries to design photoresponsive frameworks with reversibly and remotely controllable pores. We developed a topology-guided multicomponent polycondensation system that integrates protruded tetrafluoroazobenzene units as photoresponsive sites on pore walls at predesigned densities, so that a series of crystalline porous frameworks with the same backbone can be constructed to develop a broad spectrum of pores ranging from mesopores to micropores. Distinct from conventional azobenzene-based systems, the tetrafluoroazobenzene frameworks are highly sensitive to visible lights to undergo high-rate isomerization. The photoisomerization exerts profound effects on pore size, shape, number, and environment, as well as molecular uptake and release, rendering the system able to convert and switch pores reversibly and remotely with visible lights. Our results open a way to a novel class of smart porous materials with pore structures and functions that are convertible and manageable with visible lights.

Polyrotaxanated covalent organic frameworks based on β-cyclodextrin towards high-efficiency synergistic inactivation of bacterial pathogens

As an emerging artificial porous material, covalent organic frameworks (COFs) with customizable structure and function, have always been the focus of polymer science. Controllable fabrication of COFs with brand-new structure is the top priority for its development. Here, the ‘supramolecular binding’ strategy is developed as a simple but efficient method to prepare COFs with novel structures and functions. By this means, polymeric rotaxanes threaded COFs, denoted as Por-CD-COF, was facilely prepared via the combination of dynamic covalent imine-bond formation with supramolecular self-assembly, in which the polyrotaxane formed via inclusion of aromatic linker with bactericidal active β-cyclodextrin macrocycle (CD) was condensed with the photosensitive porphyrin via the combination of mechanical grinding and solvothermal synthesis. The formation of polyrotaxane could change the distance between layers, avoiding the quench of photoactivity caused by the severe aggregation of layered structure. Under the same molar amount of reaction monomers, the weight of the Por-CD-COF is approaching five times of the CD-free COF, which could greatly reduce the use of photoactive ingredients. Further experiments demonstrated the introduction of CDs could also significantly improve the biocompatibility. Impressively, this special porphyrin-involved CD-COF, displays excellent photo activity, which could act as an efficient broad spectrum antibacterial agents realizing the combinational action of cyclodextrin enhanced photothermal and photodynamic antimicrobial at an extremely low quality of the effective photosensitizer (Porphyrin). Meanwhile, even at the same dose of fungicide, the bactericidal effect of Por-CD-COF is far exceeding the CD-free therapeutic agent. This novel synthetic strategy allows the incorporation of mechanically interlocked CDs (MIMs) into the porous polymeric materials, providing an easy access to low-cost preparation of COFs for the specific applications.

Laser Technology for Perovskite: Fabrication and Applications

AbstractPerovskite has attracted considerable attention in the electronic and optical fields in recent years, fulfilling the requirements of the ever‐growing demand in energy, environment, security, and big data storage. Laser direct writing technology is a flexible and mask‐free approach for fabricating, structuring, modifying, and patterning perovskites. Laser irradiation can directly induce perovskites from precursors due to the photothermal and photochemical effects of laser. Therefore, various laser‐induced perovskites, such as perovskite quantum dots, nanowires, nanocrystals, and films, are summarized. In particular, the laser‐induced perovskites in glass are intensively investigated for their high stability and flexibility in 3D printing. The second part of this review examines various applications of perovskites based on laser technology, such as solar cells, flat lenses, microlasers, photoluminescence, lithography, sensors, optical encryption, and data storage. Diverse laser treatments employed for modulating and patterning perovskite devices, such as laser annealing, laser ablation, and laser‐induced defects, are discussed. Prospective challenges and future trends in this research field are also concluded.