Leveraging the Photofunctions of Transition Metal Complexes for the Design of Innovative Phototherapeutics.

Despite the advent of various medical interventions for cancer treatment, the disease continues to pose a formidable global health challenge, necessitating the development of new therapeutic approaches for more effective treatment outcomes. Photodynamic therapy (PDT), which utilizes light to activate a photosensitizer to produce cytotoxic reactive oxygen species (ROS) for eradicating cancer cells, has emerged as a promising approach for cancer treatment due to its high spatiotemporal precision and minimal invasiveness. However, the widespread clinical use of PDT faces several challenges, including the inefficient production of ROS in the hypoxic tumor microenvironment, the limited penetration depth of light in biological tissues, and the inadequate accumulation of photosensitizers at the tumor site.

Potent BODIPY-based photosensitisers for selective mitochondrial dysfunction and effective photodynamic therapy.

The development of new and improved mitochondria-targeting photosensitisers (PSs) for photodynamic therapy (PDT) remains highly desirable, due to the critical role the mitochondria play in maintaining healthy cellular function. Here, we report the design, synthesis, photophysical properties and biological characterisation of a series of di-iodinated BODIPY-based PSs, BODIPY-Mito-I-n, for mitochondria-targeted PDT applications. Six BODIPY-Mito-I-n analogues were synthesised in good yields, with fast reaction times of between 30 and 60 min under mild conditions.

Exploiting the Potential of Iridium(III) -Nitrone Complexes as Phosphorogenic Bifunctional Reagents for Phototheranostics.

Cross-linking strategies have found wide applications in chemical biology, enabling the labeling of biomolecules and monitoring of protein-protein interactions. Nitrone exhibits remarkable versatility and applicability in bioorthogonal labeling due to its high reactivity with strained alkynes via the strain-promoted alkyne-nitrone cycloaddition (SPANC) reaction. In this work, four cyclometalated iridium(III) polypyridine complexes functionalized with two nitrone units were designed as novel phosphorogenic bioorthogonal reagents for bioimaging and phototherapeutics.

Shining New Light on Biological Systems: Luminescent Transition Metal Complexes for Bioimaging and Biosensing Applications.

Luminescence imaging is a powerful and versatile technique for investigating cell physiology and pathology in living systems, making significant contributions to life science research and clinical diagnosis. In recent years, luminescent transition metal complexes have gained significant attention for diagnostic and therapeutic applications due to their unique photophysical and photochemical properties. In this Review, we provide a comprehensive overview of the recent development of luminescent transition metal complexes for bioimaging and biosensing applications, with a focus on transition metal centers with a d, d, and d electronic configuration.

Construction of photofunctional peptide conjugates through selective modification of N-terminal cysteine with cyclometallated iridium(III) 2-formylphenylboronic acid complexes for organelle-specific imaging, enzyme activity sensing and photodynamic therapy.

Luminescent cyclometallated iridium(III) complexes bearing a 2-formylphenylboronic acid moiety were designed; one of the complexes was utilised to modify peptides containing an N-terminal cysteine to afford luminescent conjugates with selective organelle-targeting or furin-responsive properties.

Reproducibility and Relative Validity of a Short Food Frequency Questionnaire for Chinese Older Adults in Hong Kong.

Changes in an individual's digestive system, hormones, senses of smell and taste, and energy requirement accompanying aging could lead to impaired appetite, but older adults may not notice their risk of nutrient deficiency. When assessing the dietary intake of older adults, it was found that they had more difficulties with short-term recall and open-ended recall and would experience greater fatigue and frustration when compared to younger individuals when completing a lengthy questionnaire. There is a need to develop a brief dietary assessment tool to examine the nutritional needs of older adults.

Mitochondria-targeting biocompatible fluorescent BODIPY probes.

An increase in the mitochondrial membrane potential (MMP) is a characteristic feature of cancer and cardiovascular disease. Therefore, it remains of crucial importance to develop new and improved fluorescent probes that are sensitive to the MMP, to report on mitochondrial health and function. Reported here are the design, synthesis, photophysical properties and biological characterisation of a series of BODIPY dyes, BODIPY-Mito-, for mitochondria-targeted fluorescence imaging applications.

Bioorthogonal dissociative rhenium(i) photosensitisers for controlled immunogenic cell death induction.

Photosensitisers for photoimmunotherapy with high spatiotemporal controllability are rare. In this work, we designed rhenium(i) polypyridine complexes modified with a tetrazine unit a bioorthogonally activatable carbamate linker as bioorthogonally dissociative photosensitisers for the controlled induction of immunogenic cell death (ICD). The complexes displayed increased emission intensities and singlet oxygen (O) generation efficiencies upon reaction with -cyclooct-4-enol (TCO-OH) due to the separation of the quenching tetrazine unit from the rhenium(i) polypyridine core.

Luminescent iridium(III) porphyrin complexes as near-infrared-emissive biological probes.

We report herein the design, synthesis and characterisation of a series of luminescent iridium(III) porphyrin complexes [Ir(ttp)(CHCHOH)] (Http = 5,10,15,20-tetra-4-tolylporphyrin) (1), [Ir(tpp-Ph-NO)(CO)Cl] (Htpp-Ph-NO = 5-(4-((4-nitrophenoxy)carbonyloxymethyl)phenyl)-10,15,20-triphenylporphyrin) (2), [Ir(tpp-COOMe)(Py)](Cl) (Htpp-COOMe = 5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrin; Py = pyridine) (3) and [Ir(tpp-COOH)(Py)](Cl) (Htpp-COOH = 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrin) (4). All the complexes displayed long-lived near-infrared (NIR) emission attributed to an excited state of mixed triplet intraligand (IL) (π → π*) (porphyrin) and triplet metal-to-ligand charge transfer (MLCT) (dπ(Ir) → π*(porphyrin)) character. The cytotoxicity of the complexes toward HeLa cells was examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay.

Dual-emissive Iridium(III) Complexes as Phosphorescent Probes with Orthogonal Responses to Analyte Binding and Oxygen Quenching.

Phosphorescent probes often show sensitive response toward analytes at a specific wavelength. However, oxygen quenching usually occurs at the same wavelength and thus hinders the accurate detection of analytes. In this study, we have developed dual-emissive iridium(III) complexes that exhibit phosphorescence responses to copper(II) ions at a wavelength distinct from that where oxygen quenching occurs.

Relative Validity of a Short Food Frequency Questionnaire for Disadvantaged Families in Hong Kong.

Individuals with lower socioeconomic status are more vulnerable in securing good nutritional quality. It was also found that people who had received a lower education level had greater difficulty in completing the conventional dietary assessment such as a food frequency questionnaire (FFQ). Previous studies have demonstrated the validity of a short FFQ in Hong Kong's pregnant women, but its validity among a wider community was still unknown.

A Concerted Enzymatic and Bioorthogonal Approach for Extra- and Intracellular Activation of Environment-Sensitive Ruthenium(II)-Based Imaging Probes and Photosensitizers.

In this article, we report a novel targeting strategy involving the combination of an enzyme-instructed self-assembly (EISA) moiety and a strained cycloalkyne to generate large accumulation of bioorthogonal sites in cancer cells. These bioorthogonal sites can serve as activation triggers in different regions for transition metal-based probes, which are new ruthenium(II) complexes carrying a tetrazine unit for controllable phosphorescence and singlet oxygen generation. Importantly, the environment-sensitive emission of the complexes can be further enhanced in the hydrophobic regions offered by the large supramolecular assemblies, which is highly advantageous to biological imaging.

Strategic Design of Luminescent Rhenium(I), Ruthenium(II), and Iridium(III) Complexes as Activity-Based Probes for Bioimaging and Biosensing.

The rapid development of responsive fluorescent probes has advanced optical imaging for biological research and biomedical applications. Among different sensing strategies, activity-based sensing, which exploits the unique reactivity of the target chemical species to achieve high chemoselectivity, has emerged as a promising paradigm for the development of responsive probes for selective molecular imaging. Luminescent transition metal complexes have received considerable attention for bioimaging and biosensing applications over the last decade due to their remarkable photophysical behavior including intense emission with large Stokes' shifts, long emission lifetimes, strong two-photon absorption, and high photostability.

Photofunctional cyclometallated iridium(III) polypyridine methylsulfone complexes as sulfhydryl-specific reagents for bioconjugation, bioimaging and photocytotoxic applications.

We report herein near-infrared (NIR)-emitting cyclometallated iridium(III) complexes bearing a heteroaromatic methylsulfone moiety as sulfhydryl-specific reagents; one of the complexes was conjugated to cysteine and cysteine-containing peptides and proteins for bioimaging and photocytotoxic applications.

Luminescent and Photofunctional Transition Metal Complexes: From Molecular Design to Diagnostic and Therapeutic Applications.

There has been emerging interest in the exploitation of the photophysical and photochemical properties of transition metal complexes for diagnostic and therapeutic applications. In this Perspective, we highlight the major recent advances in the development of luminescent and photofunctional transition metal complexes, in particular, those of rhenium(I), ruthenium(II), osmium(II), iridium(III), and platinum(II), as bioimaging reagents and phototherapeutic agents, with a focus on the molecular design strategies that harness and modulate the interesting photophysical and photochemical behavior of the complexes. We also discuss the current challenges and future outlook of transition metal complexes for both fundamental research and clinical applications.

Carotenoids and Vitamin A in Breastmilk of Hong Kong Lactating Mothers and Their Relationships with Maternal Diet.

Carotenoids and vitamin A are nutrients crucial to infants’ development. To date, there is limited data on their availability in breastmilk and the associated dietary factors, especially in Hong Kong, where people follow a westernized Chinese diet. This study determined the selected breastmilk’s carotenoid and vitamin A (retinol) contents by ultraperformance liquid chromatography with photodiode detection (UPLC-PDA) and the dietary intakes by three-day food records in 87 Hong Kong lactating mothers, who were grouped into tertiles based on their daily carotenoid intake.

Phosphorogenic Iridium(III) bis-Tetrazine Complexes for Bioorthogonal Peptide Stapling, Bioimaging, Photocytotoxic Applications, and the Construction of Nanosized Hydrogels.

The dual functionality of 1,2,4,5-tetrazine as a bioorthogonal reactive unit and a luminescence quencher has shaped tetrazine-based probes as attractive candidates for luminogenic labeling of biomolecules in living systems. In this work, three cyclometalated iridium(III) complexes featuring two tetrazine units were synthesized and characterized. Upon photoexcitation, the complexes were non-emissive but displayed up to 3900-fold emission enhancement upon the inverse electron-demand Diels-Alder (IEDDA) [4+2] cycloaddition with (1R,8S,9s)-bicyclo[6.

Levels of polyphenols and phenolic metabolites in breast milk and their association with plant-based food intake in Hong Kong lactating women.

Dietary polyphenols are phytonutrients exhibiting multiple health benefits in humans including those in infants. However, data on breast milk (poly)phenolic composition are limited, especially among Asian populations. This study aimed to assess the levels of dietary polyphenols and their microbial-derived metabolites in the breast milk of Hong Kong lactating women, and how maternal diet correlated with the phenolic composition in breast milk.

Tuning the organelle specificity and cytotoxicity of iridium(III) photosensitisers for enhanced phototheranostic applications.

Luminescent cyclometallated iridium(III) complexes with a polyhedral oligomeric silsesquioxane (POSS) unit were designed as efficient theranostic agents that displayed tuneable organelle-targeting properties, minimal dark cytotoxicity and substantial photocytotoxicity even under hypoxic conditions.

Luminescent rhenium(I) perfluorobiphenyl complexes as site-specific labels for peptides to afford photofunctional bioconjugates.

We report herein new luminescent rhenium(I) perfluorobiphenyl complexes that reacted specifically with the cysteine residue of the π-clamp sequence (FCPF) to afford novel peptide-based imaging reagents, photosensitisers for singlet oxygen and enzyme sensors.

Luminescent Neutral Cyclometalated Iridium(III) Complexes Featuring a Cubic Polyhedral Oligomeric Silsesquioxane for Lipid Droplet Imaging and Photocytotoxic Applications.

New neutral iridium(III) complexes featuring a cubic polyhedral oligomeric silsesquioxane (POSS) unit, [Ir(NC)(L1-POSS)] [HNC = 2-phenylpyridine (Hppy; ), 2-phenylbenzothioazole (Hbt; ), and 2-(1-naphthyl)benzothiazole (Hbsn; ); L1-POSS = ()-4-[(2-hydroxybenzylidene)amino]benzyl 3-heptakis(isobutyl)POSS-propyl carbamate], were designed and synthesized. Their POSS-free counterparts, [Ir(NC)(L1)] [L1 = ()--(4-hydroxymethylphenyl)-1-(2-hydroxyphenyl)methanimine; HNC = Hppy (), Hbt (), and Hbsn ()], and the poly(ethylene glycol) (PEG) derivatives [Ir(NC)(L1-PEG)] [L1-PEG = ()-4-[(2-hydroxybenzylidene)amino]benzyl 3-[2-[ω-methoxypoly(1-oxapropyl)]ethyl]carbamate; HNC = Hppy (), Hbt (), and Hbsn ()] were also prepared. The photophysical, photochemical, and biological properties of the POSS complexes were compared with those of their POSS-free and PEG-modified counterparts.

Design of Dielectric Resonator Antenna Using Dielectric Paste.

In this publication, the use of a dielectric paste for dielectric resonator antenna (DRA) design is investigated. The dielectric paste can serve as an alternative approach of manufacturing a dielectric resonator antenna by subsequently filling a mold with the dielectric paste. The dielectric paste is obtained by mixing nanoparticle sized barium strontium titanate (BST) powder with a silicone rubber.

Bioorthogonal control of the phosphorescence and singlet oxygen photosensitisation properties of iridium(III) tetrazine complexes.

In this work, we demonstrate bioorthogonal control of the phosphorescence and singlet oxygen photosensitisation properties of new iridium(iii) tetrazine complexes by different reaction partners; the system was exploited for organelle-specific staining and modulated photocytotoxic activity applications.