Photoinduced Electron Transfer Research Articles

Ultrafast and nanomolar detection of Al3+: Furazan based fluorescent chemosensor and its practices in Smartphone, test kit, water samples and living–cell

A new fluorescent chemoprobe (SDAF) was successfully synthesized and utilized as a sensor for the recognition of Al3+ in EtOH:HEPES (3:2, v:v, pH: 7.0) media. The SDAF depicted a selective “turn–on” response at λem = 467 nm to Al3+ over competitive cations, and the SDAF–Al3+ complex had a reversible response with F−. The limit of detection (LOD) was found about at nano–molar level (28.0 nM), demonstrating the sensitivity of the chemoprobe toward Al3+. The binding stoichiometry of SDAF–Al3+ was investigated by TOF–MS, Job's plot, 1H NMR and 13C NMR methods and found as 1:1. The recognition mechanisms of SDAF for the detection of Al3+ were the –C = N isomerization and photoinduced electron transfer (PET) mechanisms, and they were confirmed by density functional theory (DFT) computation. Furthermore, the SDAF was successfully employed in living–cell bioimaging and cytotoxicity, it was also utilized in Smartphone, test–kit and natural spring water (recovery values; 89.01 %– 96.33 %)applications.

Simultaneous detection of Cu2+ and amoxicillin based on the copper and nitrogen-regulated fluorescent probe

A novel fluorescence-based probe represented as Cu, N-CDs, was developed for the dual sensingdetection of Cu2+ and amoxicillin (AMO), which had a high quantum yield up to 60.08 %, along with excellent photoluminescent properties and remarkable stability. When detecting Cu2+, the fluorescence signal from Cu, N-CDs probe experienced quenching due to photoinduced electron transfer (PET). Subsequently, the introduction of AMO led to the recovery of the probe's fluorescence. This recovery was likely attributed to the superior affinity between Cu2+ and AMO, resulting in the displacement of Cu2+ from the Cu, N-CDs and blocked the PET process. Notably, the detection limits of Cu2+ and AMO were determined 18 nM and 9 nM, respectively. We further demonstrated the practical utility of the Cu, N-CDs probe through its successful application in the analysis of Cu2+ and AMO in Chinese herbal medicine and milk samples. Overall, our findings highlighted the potency of Cu, N-CDs as versatile and effective tools for the detection of Cu2+ and AMO, paving the way for their broad applications in the safety analysis of food and pharmaceutical.

Optical recordings of organellar membrane potentials and the components of membrane conductance in lysosomes.

The eukaryotic cell is highly compartmentalized with organelles. Owing to their function in transporting metabolites, metabolic intermediates and byproducts of metabolic activity, organelles are important players in the orchestration of cellular function. Recent advances in optical methods for interrogating the different aspects of organellar activity promise to revolutionize our ability to dissect cellular processes with unprecedented detail. The transport activity of organelles is usually coupled to the transport of charged species; therefore, it is not only associated with the metabolic landscape but also entangled with membrane potentials. In this context, the targeted expression of fluorescent probes for interrogating organellar membrane potential (Ψorg) emerges as a powerful approach, offering less-invasive conditions and technical simplicity to interrogate cellular signalling and metabolism. Different research groups have made remarkable progress in adapting a variety of optical methods for measuring and monitoring Ψorg. These approaches include using potentiometric dyes, genetically encoded voltage indicators, hybrid fluorescence resonance energy transfer sensors and photoinduced electron transfer systems. These studies have provided consistent values for the resting potential of single-membrane organelles, such as lysosomes, the Golgi and the endoplasmic reticulum. We can foresee the use of dynamic measurements of Ψorg to study fundamental problems in organellar physiology that are linked to serious cellular disorders. Here, we present an overview of the available techniques, a survey of the resting membrane potential of internal membranes and, finally, an open-source mathematical model useful to interpret and interrogate membrane-bound structures of small volume by using the lysosome as an example.

Photoinduced One-Electron Chloride Oxidation in Water Using a Pentacationic Ir(III) Photosensitizer.

A novel iridium(III) photosensitizer containing pyridinium-decorated terpyridines has been used for the photo-oxidation of chloride in water. Despite its abundance, the very positive one-electron reduction potential (E° Cl•/- = 2.1-2.4 V vs NHE) restricted its use in energy conversion schemes and artificial photosynthesis. The kinetics of the photoinduced electron transfer process were investigated through Stern-Volmer quenching experiments and nanosecond transient absorption spectroscopy, which provided unambiguous evidence that photoinduced chloride oxidation occurred with a quenching rate constant kq = 5.0 × 1010 M-1 s-1. Complementary spectroelectrochemistry and photolysis experiments confirmed the formation of the reduced photosensitizer and showcased the redox and photostability of the Ir(III) photosensitizer that holds great promise for the HX splitting approach.

Novel Covalent Bonds and Hydrogen Bonds Linked Porous Organic Frameworks as Chemosensor for Detecting 2,4,6-Trinitrophenol in Water and Soil Samples.

A novel and unconventional structural porous organic framework combined through the synergistic effect of covalent bonds and hydrogen bonds was prepared with the combination of 4,4',4″,4‴-(pyrene-1,3,6,8-tetrayl)tetraaniline (Py) and 5-hydroxyisophthalaldehyde (HP). It was the second example of CHOF until now and had been designated as Py-HP CHOF. The suspension of Py-HP CHOF in various solvents, such as ethanol, CH3CN, and methanol, exhibited a remarkably selective and sensitive "on-off" fluorescence response toward 2,4,6-trinitrophenol (TNP) compared with other explosives, with exceptionally low detection limits. The X-ray diffraction (XRD) spectra confirmed that the framework of Py-HP CHOF collapsed after interaction with TNP and acid, further indicating the existence of hydrogen bonds in the framework of Py-HP CHOF. The fluorescence quenching can be ascribed to the photoinduced electron transfer and the absorption competition quenching, as supported by XRD, X-ray photoelectron spectroscopy results, UV-vis absorption spectra, and density functional theory calculations. Fluorescence channels can be utilized by Py-HP CHOF to function as chemosensor, enabling the identification and detection of TNP in water and soil, and Py-HP CHOF is also the second CHOF example of sensing TNP reported to date. The application of this technique exhibits considerable potential in the analysis and detection of environmental pollutants, thereby presenting substantial practical implications.

Facile Layer Diffusion Technique for Synthesis of Terbium-Based Metal Organic Framework for Fluorometric Sensing of Hydroquinone.

A photoluminescent terbium (III)-based Metal Organic Framework (MOF) was synthesized at room temperature by layer diffusion method utilizing mixed carboxylate linkers (4,4'-oxybis(benzoic acid) and benzene-1,3,5 tricarboxylic acid). Synthesized MOF has crystalline nature and rod-shaped morphology and is thermally stable up to 455°C. The fluorescence emission spectra and theoretical results revealed that carboxylate linkers functioned as sensitizers for Tb(III) photoluminescence which resulted in four distinct emission peaks at 495, 547, 584, and 621nm corresponding to the transitions 5D4 → 7F6, 5D4 → 7F5, 5D4 → 7F4, and 5D4 → 7F3. Using synthesized MOF as fluorescent probe, hydroquinone was detected in aqueous medium with a detection limit of 0.048μM, remarkable recovery (95.6-101.1%), and relative standard deviation less than 2.25%. The quenching phenomenon may be ascribed to electron transfer from synthesized probe to oxidized hydroquinone via carboxylic groups on thesurface of MOF, which is further supported by photo-induced electron transfer mechanism. This study introduces a cheaper, faster, and more accurate method for hydroquinone detection.

Development of a fluorescent scaffold by utilizing quercetin template for selective detection of Hg2+: Experimental and theoretical studies along with live cell imaging

Quercetin is an important antioxidant with high bioactivity and it has been used as SARS-CoV-2 inhibitor significantly. Quercetin, one of the most abundant flavonoids in nature, has been in the spot of numerous experimental and theoretical studies in the past decade due to its great biological and medicinal importance. But there have been limited instances of employing quercetin and its derivatives as a fluorescent framework for specific detection of various cations and anions in the chemosensing field. Therefore, we have developed a novel chemosensor based on quercetin coupled benzyl ethers (QBE) for selective detection of Hg2+ with “naked-eye” colorimetric and “turn-on” fluorometric response. Initially QBE itself exhibited very weak fluorescence with low quantum yield (Φ = 0.009) due to operating photoinduced electron transfer (PET) and inhibition of excited state intramolecular proton transfer (ESIPT) as well as intramolecular charge transfer (ICT) within the molecule. But in presence of Hg2+, QBE showed a sharp increase in fluorescence intensity by 18-fold at wavelength 444 nm with high quantum yield (Φ = 0.159) for the chelation-enhanced fluorescence (CHEF) with coordination of Hg2+, which hampers PET within the molecule. The strong binding affinity of QBE towards Hg2+ has been proved by lower detection limit at 8.47 µM and high binding constant value as 2 × 104 M−1. The binding mechanism has been verified by DFT study, Cyclic voltammograms and Jobs plot analysis. For the practical application, the binding selectivity of QBE with Hg2+ has been capitalized in physiological medium to detect intracellular Hg2+ levels in living plant tissue by using green gram seeds. Thus, employing QBE as a fluorescent chemosensor for the specific identification of Hg2+ will pave the way for a novel approach to simplifying the creation of various chemosensors based on quercetin backbone for the precise detection of various biologically significant analytes.

Series of Viologen-Based Metal-Organic Polyhedra with Photo/Electrochromic Behavior for Inkless Printing and UV Detection.

The fabrication of molecular crystalline materials with fast, multistimuli-responsive behavior and the construction of the corresponding structure-activity relationship are of extraordinary significance for the development of smart materials. In this context, three multistimuli-responsive functional metal-organic polyhedra (MOP), {[Dy2(bcbp)3(NO3)1.5(H2O)7]·Cl4.2·(NO3)0.3·H2O}n (1), {[Dy2(bcbp)4(H2O)8]Cl6}n (2), and {[Eu2(bcbp)4(H2O)10]Cl6·H2O}n (3; bcbp = 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium), were successfully prepared and characterized. All of the compounds exhibit rapid and reversible photochromic and electrochromic dual-responsive behaviors. Furthermore, benefiting from the well-defined crystal structure and different responsive behaviors, the photoinduced electron transfer (PIET) process and structure-activity relationship were explored. In addition, considering the excellent photochromic performance, function filter paper and smart organic glass were successfully prepared and used for ink-free printing and UV light detection.

Confinement of Sustainable Carbon Dots Results in Long Afterglow Emitters and Photocatalyst for Radical Photopolymerization.

Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature-dependent emission spectra gave information on temperature-assisted delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo-ATRP initiator, ethyl(bromo)phenyl acetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and living radical polymerization based on photo-ATRP protocol worked successfully. Metal-free photo-ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.

Confinement of Sustainable Carbon Dots Results in Long Afterglow Emitters and Photocatalyst for Radical Photopolymerization

Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature‐dependent emission spectra gave information on temperature‐assisted delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo‐ATRP initiator, ethyl(bromo)phenyl acetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and living radical polymerization based on photo‐ATRP protocol worked successfully. Metal‐free photo‐ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.

Determination of genotoxic impurities of aromatic aldehydes in pharmaceutical preparations by high performance liquid chromatography after derivatization with N-Cyclohexyl-4-hydrazino-1,8-naphthalenediimide

The detection of aromatic aldehydes, considered potential genotoxic impurities, holds significant importance during drug development and production. Current analytical methods necessitate complex pre-treatment processes and exhibit insufficient specificity and sensitivity. This study presents the utilization of naphthalenediimide as a pre-column derivatisation reagent to detect aromatic aldehyde impurities in pharmaceuticals via high-performance liquid chromatography (HPLC). We screened a series of derivatisation reagents through density functional theory (DFT) and investigated the phenomenon of photoinduced electron transfer (PET) for both the derivatisation reagents and the resulting products. Optimal experimental conditions for derivatisation were achieved at 40 °C for 60 min. This approach has been successfully applied to detect residual aromatic aldehyde genotoxic impurities in various pharmaceutical preparations, including 4-Nitrobenzaldehyde, 2-Nitrobenzaldehyde, 1,4-Benzodioxane-6-aldehyde, and 5-Hydroxymethylfurfural. The pre-column derivatisation method significantly enhanced detection sensitivity and reduced the limit of detection (LOD), which ranged from 0.002 to 0.008 μg/ml for the analytes, with relative standard deviations < 3 %. The correlation coefficient (R2) >0.998 demonstrated high quality. In chloramphenicol eye drops, the concentration of 4-Nitrobenzaldehyde was measured to be 8.6 µg/mL below the specified concentration, with recoveries ranging from 90.0 % to 119.2 %. In comparison to existing methods, our work simplifies the pretreatment process, enhances the sensitivity and specificity of the analysis, and offers comprehensive insights into impurity detection in pharmaceutical preparations.

Porphyrin-BODIPY Dyad: Enhancing Photodynamic Inactivation via Antenna Effect.

A porphyrin-BODIPY dyad (P-BDP) was obtained through covalent bonding, featuring a two-segment design comprising a light-harvesting antenna system connected to an energy acceptor unit. The absorption spectrum of P-BDP resulted from an overlap of the individual spectra of its constituent parts, with the fluorescence emission of the BODIPY unit experiencing significant quenching (96 %) due to the presence of the porphyrin unit. Spectroscopic, computational, and redox investigations revealed a competition between photoinduced energy and electron transfer processes. The dyad demonstrated the capability to sensitize both singlet molecular oxygen and superoxide radical anions. Additionally, P-BDP effectively induced the photooxidation of L-tryptophan. In suspensions of Staphylococcus aureus cells, the dyad led to a reduction of over 3.5 log (99.99 %) in cell survival following 30 min of irradiation with green light. Photodynamic inactivation caused by P-BDP was also extended to the individual bacterium level, focusing on bacterial cells adhered to a surface. This dyad successfully achieved the total elimination of the bacteria upon 20 min of irradiation. Therefore, P-BDP presents an interesting photosensitizing structure that takes advantage of the light-harvesting antenna properties of the BODIPY unit combined with porphyrin, offering potential to enhance photoinactivation of bacteria.

Photoinduced electron transfer in Eu2+ and Sm3+ co-doped CaF2 nanocrystals prepared by co-precipitation

We report on the photoinduced electron transfer in Eu2+ and Sm3+ co-doped CaF2 nanocrystals prepared by a facile co-precipitation method using CaCl2, EuCl2, SmCl3 and NH4F. The doping of divalent Eu2+ was realized by employing granular zinc in the CaCl2/EuCl2 solution under nitrogen to reduce Eu3+→ Eu2+. The CaF2:xEu,0.2%Sm nanocrystals were prepared with different Eu concentrations of x = 0, 0.2, 0.5, 1.5, and 2.5%, resulting in an average crystallite size between 54 and 36 ± 1 nm. The maximum luminescence intensities of Eu2+ and Sm2+ were obtained for the x = 0.5% sample. Photoinduced electron transfer and back transfer in the CaF2:0.5%Eu,0.2%Sm nanocrystals were measured by detecting the Eu2+ and Sm2+ luminescence, upon exposure to 340 and 310 nm UV LED light. Interestingly, the photoionization of Eu2+ occurred 6 times faster for the sample co-doped with 0.2% Sm. Upon exposure to 340 nm light, a reduction and increase of the Eu2+ and the Sm2+ luminescence were observed, respectively. Subsequent exposure to 310 nm light decreased the Sm2+ luminescence, but the luminescence of Eu2+ kept on being bleached, albeit at a lower rate. Whilst the Sm valence state could be reversibly changed between the trivalent and divalent state by 340 and 310 nm light, the observation that the Eu2+ luminescence did not recover may indicate that a third centre is involved in the photoinduced electron transfer mechanisms.

Construction of a novel Eu-MOF material based on different detection mechanisms and its application in sensing pollutants aniline, F- and Hg2+

Aniline is an organic pollutant with carcinogenicity and teratogenicity, while F- and Hg2+ are toxic ions that are easily soluble in water. When they are released to the environment, they will pose a threat to human health. Designing a material that can simultaneously detect three types of pollutants is of great significance. In this paper, a novel rare earth metal organic framework material (Eu-MOF) with three-dimensional structure based on 1-methylimidazole-4,5-dicarboxylic acid was synthesized for the first time through solvent thermal method. It has excellent luminescent performance and can be used as a multifunctional fluorescent probe to detect aniline, F-, and Hg2+ based on photoinduced electron transfer, energy competitive absorption, and ion exchange mechanisms, with detection limits of 1.79 × 10-8, 8.13 × 10-8, and 8.83 × 10-7 M, respectively. It is worth noting that Eu-MOF can detect F- and Hg2+ in real water samples, such as lake water and green tea water, with favorable recovery rates.

Constructing cuprous oxide-modified zinc tetraphenylporphyrin ultrathin nanosheets heterojunction for enhanced photocatalytic carbon dioxide reduction to methane

The application of supermolecular naonostructures in the photocatalytic carbon dioxide reduction reaction (CO2RR) has attracted increasing attentions. However, it still faces significant challenges, such as low selectivity for multi-electron products and poor stability. Here, the cuprous oxide (Cu2O)-modified zinc tetraphenylporphyrin ultrathin nanosheets (ZnTPP NSs) are successfully constructed through the aqueous chemical reaction. Comprehensive characterizations confirm the formation of type-II heterojunction between Cu2O and ZnTPP in Cu2O@ZnTPP, and the electron transfer from Cu2O to ZnTPP through the Zn-O-Cu bond under the static contact. Under the visible-light irradiation (λ > 420 nm), the optimized Cu2O@ZnTPP sample as catalyst for photocatalytic CO2RR exhibits the methane (CH4) evolution rate of 120.9 μmol/g/h, which is ∼ 4 and ∼ 10 times those of individual ZnTPP NSs (28.0 μmol/g/h) and Cu2O (12.8 μmol/g/h), respectively. Meanwhile, the CH4 selectivity of ∼ 98.7 % and excellent stability can be achieved. Further experiments reveal that Cu2O@ZnTPP has higher photocatalytic conversion efficiency than Cu2O and ZnTPP NSs, and the photoinduced electron transfer from ZnTPP to Cu2O can be identified via the path of ZnTPP→ (ZnTPP•ZnTPP)*→ ZnTPP-→ Zn-O-Cu → Cu2O. Consequently, Cu2O@ZnTPP exhibits a shorter electron-hole separation lifetime (3.3 vs. 9.3 ps) and a longer recombination lifetime (23.1 vs. 13.4 ps) than individual ZnTPP NSs. This work provides a strategy to construct the organic nanostructures for photocatalytic CO2RR to multi-electron products.

Highly effective recognition of Fe3+ and lysine based on hydrosoluble N-doped carbon dots

In this study, dual-color nitrogen-doped carbon dots (NCDs) were synthesized using a simple solvothermal method. These fluorescent NCDs displayed excitation-independent emission in red (598 nm in ethanol) and orange (553 nm in water) due to their effect of two different solvents. Both types of NCDs exhibited high stability under UV irradiation for 80 min. The water-soluble NCDs showed excellent sensitivity to Fe3+ ions by the quenching of their photoluminescent (PL) intensity. Quantitative analysis revealed a gradual decline in PL intensity, with a low detection limit of approximately 0.97 µM. Interestingly, the quenched fluorescence of NCDs caused by Fe3+ could be restored by the addition of lysine to the (NCDs + Fe3+) solution, with an estimated detection limit of about 0.37 µM. This phenomenon could be explained in the terms of non-radiative electron/hole recombination, leading to aggregation through efficient photo-induced electron transfer (PET). Utilizing their high selectivity and sensitivity, these NCDs served as “On-Off-On” switches and were successfully employed for the detection of Fe3+ in real water samples, contributing to environmental safety and control efforts.

Detection mechanism of glutathione by off–on fluorescent probe based on excited state intramolecular proton transfer

The mechanism of Glutathione detection probes 2-(benzo[d]thiazol-2-yl)-6-formyl-4-methylphenyl 2,4-dinitrobenzenesulfonate (BTFMD) and BTFM-OH have been investigated. The analysis of structural parameters, interaction region indicator (IRI) value and infrared vibration spectra show the hydrogen bond is strengthened in the S1 state, which is beneficial to excited state intramolecular proton transfer (ESIPT). Combined with hole electron analysis and frontier molecular orbitals (FMOs), the electron density of BTFMD is transferred from benzothiazole and 5-methylsalicylaldehyde to 2,4-dinitrobenzenesulfonyl and the fluorescence properties changed due to photoinduced electron transfer (PET). The potential energy curve explains the single fluorescence emission and the ESIPT process in the S1 state.

Anthrapyrazolone functionalized Oligo(ethylene glycol)methyl ether methacrylates based fluorescent polymeric hydrogel for selective detection of Tetracycline drug

Tetracycline (TC) antibiotics are essential for treating bacterial infections; however, overuse and improper disposal place the environment in danger and promote the growth of drug-resistant microorganisms. Monitoring their impact on living organisms is vital. Polymeric-based hydrogels offer promise in antibiotic detection due to their versatility and biocompatibility, despite their uncommon use for this purpose. In this study, we have synthesized a fluorescent polymeric hydrogel, P(OEGMA-co-DIMA) utilizing oligo(ethylene glycol)methyl ether methacrylates (OEGMA) and laboratory-synthesized fluorescent anthrapyrazolone containing monomer, 2-(benzo[1,2,3-cd:4,5,6-c’d]bis(indazole)-2(7H)-yl)ethyl methacrylate (DIMA) for the fluorometric detection of TC in the aqueous medium. The P(OEGMA-co-DIMA) hydrogel exhibited exceptional affinity towards TC while exhibiting high selectivity. The chemosensing behavior of the hydrogel was also compared with the DIMA monomer. Upon adding TC, emission analysis revealed a notable quenching in the emission intensity of the P(OEGMA-co-DIMA) hydrogel as well as the DIMA monomer. The Stern Volmer rate constants (Ksv) of the hydrogel (Ksv = 9.99 x 103 M−1) in water and DIMA (Ksv = 25.63 x 103 M−1) in acetonitrile showed a higher quenching rate constant with a limit of detections (LODs) of 1.3 nM and 0.11 nM. Turn-off fluorescence behavior occurs via a static quenching mechanism through a photoinduced electron transfer process and intermolecular hydrogen bonding. To validate the selectivity, the interference analyses in an aqueous medium with different antibiotics are provided. To rationalize the real-time applicability of the hydrogel, studies were extended to water samples obtained from deionized water, tap water, lake water, and also in milk samples. The recovery rate and LOD for real samples ranged from 83.8 % to 111 % and 0.83 to 3.6 nM, respectively.

Radiotherapy activates picolinium prodrugs in tumours.

Radiotherapy-induced prodrug activation provides an ideal solution to reduce the systemic toxicity of chemotherapy in cancer therapy, but the scope of the radiation-activated protecting groups is limited. Here we present that the well-established photoinduced electron transfer chemistry may pave the way for developing versatile radiation-removable protecting groups. Using a functional reporter assay, N-alkyl-4-picolinium (NAP) was identified as a caging group that efficiently responds to radiation by releasing a client molecule. When evaluated in a competition experiment, the NAP moiety is more efficient than other radiation-removable protecting groups discovered so far. Leveraging this property, we developed a NAP-derived carbamate linker that releases fluorophores and toxins on radiation, which we incorporated into antibody-drug conjugates (ADCs). These designed ADCs were active in living cells and tumour-bearing mice, highlighting the potential to use such a radiation-removable protecting group for the development of next-generation ADCs with improved stability and therapeutic effects.

A novel annulated dinuclear dizinc phthalocyanine cross-linked h-BN polyamides for efficient photocatalytic levofloxacin removal from real pharmaceutical wastewater

The alignment of the strong visible-light harvesting phthalocyanine and its metal derivatives onto wide-gap semiconductors has been recognized as a bright approach to fabricate highly effective photocatalysts for energy conversation and environmental restoration. However, the practical application of phthalocyanine-sensitized photocatalysts depends on their incorporation mode between phthalocyanine and basic materials. In this work, a novel high-effective dinuclear zinc (II) phthalocyanine-sensitized photocatalyst is fabricated via covalent immobilization of (Bis(82,112,152-tri-(6-oxyl-2-carboxyl)-naphthaoxytribenzo)[g,l,q]-5,10,15,20-tetraazaporphrinno[b,e]benzene) dizinc (II), (ZnTcPc)2 onto the amino functionalized hexagonal boron nitride (–NH2-h-BN) nanosheets for the first time by a facile condensation strategy. The optimized 9%(ZnTcPc)2/h-BN polymer displays remarkably improved photocatalytic activity in levofloxacin degradation from different aqueous solutions with long-term stability under visible-light illumination. Its decomposition rates reach 81.4%, 71.7% and 90.8% in deionized water, tap water and real pharmaceutical wastewater, respectively. It is approximately 7 times than that of bare h-BN nanosheets in deionized water. The detailed experimental data indicate that the critical role of for improving visible-light harvesting and photoinduced electron transfer capability of h-BN acted by the strongly chemical bond constructed between (ZnTcPc)2 and –NH2-h-BN. The improved photocatalytic mechanism for levofloxacin removal over 9%(ZnTcPc)2/h-BN polymer is proposed according to the results of ESR, UV–vis and fluorescence measurements. Therefore, this unique combination approach affords a carefully designed molecular photocatalyst with great potential application in environmental remediation.