Fabienne Dumoulin

Acıbadem Mehmet Ali Aydınlar Üniversitesi · Biomedical Engineering

Two different amphiphilic copolymers, a random copolymer (RCP) and a block copolymer (BCP), have been used to encapsulate a far-red photosensitizing hydrophobic zinc phthalocyanine while forming self-assembled nanocarriers of different topology: self-folded single-chain nanoparticles (SCNPs) and star-like aggregates (SLAs), respectively. Different...

Two phthalocyanine derivatives tetra-peripherally substituted with tert-butylsulfonyl groups and coordinating either zinc(II) or platinum(II) ions have been synthesized and subsequently investigated in terms of their optical and photochemical properties, as well as biological activity in cellular, tissue-engineered, and animal models. Our research...

Dr Fabienne Dumoulin and Professor Shirley Nakagaki are delighted to introduce the RSC Advances Emerging Investigators series, which highlights some of the very best work of early career researchers.

This work introduces rationally designed, improved amphiphilic single‐chain polymer nanoparticles (SCNPs) for imaging and photodynamic therapy (PDT) in zebrafish embryo xenografts. SCNPs are ultrasmall polymeric nanoparticles with sizes similar to proteins, making them ideal for biomedical applications. Amphiphilic SCNPs result from the self‐assemb...

The European Network for diagnosis and treatment of antibiotic-resistant bacterial infections—EURESTOP COST Action CA21145 focuses on tackling the burden of antimicrobial resistance (AMR) and has gathered many members working on photodynamic approaches. This European consortium is presented here in the One Health context, to highlight the potential...

An octahydroxylated photosensitizing Zn phthalocyanine has been used as an initiator in ring-opening polymerization of [Formula: see text]-caprolactone. Three different phthalocyanine-core star polymers have been obtained, with each arm functionalized with either 20, 30, or 40 units. To benefit from the absorption of these polymers in the first nea...

Phthalocyanines are tetrapyrrolic artificial porphyrinoids that play major roles in advanced biological and technological applications. Research on this family of dyes is particularly active in Türkiye, with many derivatives being prepared from 4,5-dihexylthiophthalonitrile DiSHexPN, which is one of the most popular noncommercially available buildi...

A quantum-classical protocol that incorporates Jahn–Teller vibronic coupling effects and cluster analysis of molecular dynamics simulations is reported, providing a tool for simulations of absorption spectra and ultrafast nonadiabatic dynamics in large molecular photosystems undergoing aggregation in solution. Employing zinc phthalocyanine dyes as...

Phthalocyanines are ideal candidates as photosensitizers for photodynamic therapy (PDT) of cancer due to their favorable chemical and photophysical properties. However, their tendency to form aggregates in water reduces PDT efficacy and poses challenges in obtaining efficient forms of phthalocyanines for therapeutic applications. In the current wor...

Using a fast and simple one-step electrochemical method, we developed transparent and conductive ZnO nanoporous layers encapsulating molecular catalysts, showcasing dual functionality as a window layer for thin-film solar cells and a catalytic layer for solar-to-fuel conversion. As a proof of concept, tetraammonium-substituted Co phthalocyanine (Co...

Dr Fabienne Dumoulin and Professor Shirley Nakagaki are delighted to introduce the RSC Advances Emerging Investigators Series, which highlights some of the very best work of early career researchers.

[Formula: see text]-bridged diiron porphyrinoid complexes are powerful oxidation biomimetic catalysts. Their use as oxidation catalysts is quite recent, as it started approximately one decade ago. Many mechanistic works and elucidation of properties are conducted on simple derivatives which are not functionalized, preventing their covalent incorpor...

Investigation into the reactive oxygen species (ROS) generating abilities of photosensitizers outside of in-vitro/vivo conditions is a crucial element in the wider study of photodynamic therapy (PDT) in clinical settings. Zinc(II) phthalocyanine tetrasulfonic acid (ZnPcTS) is a water-soluble photosensitizer that can generate ROS as singlet oxygen (...

Zn phthalocyanines tetra- and octa- substituted in peripheral positions by mercaptophenol moieties were prepared. Photophysical, photochemical, physicochemical and biological properties relevant from a photodynamic therapy point of view have been determined, showing that the tetra-substituted derivatives have better potential, confirmed by in vitro...

We report the first example of direct far-red triplet sensitized molecular photoswitching in a condensed phase wherein a liquid azobenzene derivative (Azo1) co-assembled within a liquid surfactant-protein film undergoes triplet sensitized Z-to-E photoswitching upon far-red/red light excitation in air. The role of triplet sensitization in photoswitc...

The chemistry of phthalocyanines and porphyrazines is reviewed after a presentation of the different derivatives and an introduction to all structural variability aspects. The key points of the synthetic methods and strategies are presented. Synthetic access to the different precursors is detailed, after which their conversion into the expected sym...

A critical factor in developing an efficient photosensitizer‐gold nanoparticle (PS‐AuNP) hybrid system with improved plasmonic photosensitization is to allocate a suitable space between AuNPs and PS. Poly(amidoamine) (PAMAM) dendrimer is selected as a spacer between the PS and confeito‐like gold nanoparticles (confeito‐AuNPs), providing the require...

ABSTRACT Methicillin resistant Staphylococcus aureus infections are increasing, especially in intensive care units. A new method for photodynamic inactivation (PDI) generates reactive oxygen species by photosensitization to kill bacteria. We investigated the PDI effect of tetraethylene glycolsubstituted Zn(II) phthalocyanine (TEG-P) on S. aureus st...

Exploiting organic heterojunction effects in electrical devices are an important strategy to improve the electrical conductivity, which can be utilized into improving the conductometric gas sensors performances. In this endeavor, the present article reports fabrication of organic heterostructures in a bilayer device configuration incorporating octa...

A monoazido Zn phthalocyanine has been grafted onto three different alkynyl-functionalized peptoid helices using copper-catalyzed azide–alkyne cycloaddition, demonstrating the feasibility of such conjugates. Their photoproperties have been examined relatively to the spatial geometry induced by the peptoid helix.

TEG-Pc, a Zn(II) phthalocyanine tetra substituted in non-peripheral position by tetraethylene glycol chains, proved to have good efficiency during in vitro photodynamic experiments. Its in vivo phototoxic effects have been investigated in tumor-bearing Wistar albino rats at an enzymatic level. The evolution of different oxidative markers are review...

Phthalocyanines exhibit superior photoproperties that make them a surely attractive class of photosensitisers for photodynamic therapy of cancer. Several derivatives are at various phases of clinical trials, and efforts have been put continuously to improve their photodynamic efficacy. To this end, various strategies have been applied to develop ad...

Alkylthio-tetrasubstituted μ-nitrido diiron phthalocyanine complexes are synthesized with n-butyl, iso-butyl, tert-butyl, and n-hexadecyl alkyl moieties. For the first time, a spectroelectrochemical investigation of μ-nitrido diiron phthalocyanines is achieved at all the redox steps. The complexes are stable in all their redox states, unlike their...

The administration of photosensitizers and their biocompatibility is crucial to the success of photodynamic therapy treatment. Amongst the various strategies developed to administer photosensitizers of low water-solubility, the use of polyvinylpyrrolidone (PVP), an FDA-approved food additive, is emerging as extremely promising. Its effect on photod...

Mono or diamino phthalocyanines with A3B or crosswise ABAB substitution patterns have been synthesized and used as building blocks for the preparation of dimeric and polymeric phthalocyanines. For this, 4,5-di(dodecylsulfanyl) phthalonitrile was converted into 1,3-diimino-6,7-di-([Formula: see text]-dodecylsulfanyl)-isoiminoindoline and then reacte...

Mesoporous Organosilica Nanoparticles (PHT-PMO) have been prepared from an octa-triethoxysilylated Zn phthalocyanine precursor. These PHT-PMO nanoparticles had no dark toxicity but high phototoxicity when irradiated at 650 nm, and remarkable near-infrared phototoxicity when excited at 760 and 810 nm. PHT-PMO were then aminated to promote electrosta...

Molecular catalysts that combine high product selectivity and high current density for CO2 electrochemical reduction to CO or other chemical feedstocks are urgently needed. While earth-abundant metal-based molecular electrocatalysts with high selectivity for CO2 to CO conversion are known, they are characterized by current densities that are signif...

In an attempt to investigate its potential as a PDT 19F MRI molecular theranostic, a Zn phthalocyanine with 24 pseudo-equivalent fluorine atoms was designed and prepared. Compared to its H analogues, the fluorinated derivative has a much higher generation of singlet oxygen. 19F NMR signals in CDCl 3 showed that all the fluorine atoms are magnetical...

Photosensitizing nanogels were obtained through a surfactant free single step protocol by using a porphyrin based crosslinker for stabilizing self-assembled nanosized aggregates of thermoresponsive copolymers. Nanogels with varying amounts of porphyrin retained the singlet oxygen generation ability of the porphyrin core and were also capable of ind...

Welcome to this Photochemical & Photobiological Sciences themed issue entitled: ‘Nano- and Molecular Engineering of Photosensitisers’.

In order to investigate the substitution position effect on the spectroscopic, electrochemical, and magnetic properties of copper phthalocyanines, a detailed structure-property analysis has been performed by examining two copper phthalocyanines that are octasubstituted by hexylsulfanyl chains respectively in the peripheral (Cu-P) and non-peripheral...

We previously developed a new zinc (II) phthalocyanine (ZnPc) derivative (Pc 1) conjugated to poly-L-glutamic acid (PGA) (1-PG) to address the limitations of ZnPc as part of an antitumor photodynamic therapy approach, which include hydrophobicity, phototoxicity and non-selectivity in biodistribution and tumor targeting. During this study, we discov...

In line with current efforts to direct PDT photosensitizers to specific organelles such as mitochondria, a triphenylphosphonium-tetrasubstituted Zn phthalocyanine was designed, taking into account synthetic constraints. Triphenylphosphonium moieties were successfully introduced on alkyl bromide substituents on a pre-formed phthalocyanine. Photophys...

Triplet photosensitizers showing strong absorption in red/deep red spectra region, high intersystem crossing, long-lived triplet state and high triplet state energy level are crucial for triplet-triplet annihilation upconversion. Herein we selected two tetra sulfonyl-substituted phthalocyanine Pt(II) and Pd(II) complexes (Pd-Pc and Pt-Pc) likely to...

A meso-tetra-6b,10b-dihydrobenzo[j]cyclobut[a]acenaphthylene free-base porphyrin was synthesised and its photophysical, photochemical and electrochemical properties were compared with those of free-base meso-tetraphenylporphyrin. The frontier orbitals and the HOMO–LUMO energy gaps of both compounds were also determined. It was demonstrated that the...

The tumor micro-environment is rich in glutathione. To exploit this feature for tumor-Activatable porphyrin-based photosensitizers, a dimeric disulfide-bridged porphyrin has been designed and prepared, together with two reference derivatives, a non-cleavable dimer and a monomer. The three compounds have been investigated from a photochemical and ph...

Tetrasulfonated Zn phthalocyanine was conjugated to a ssDNA aptamer moiety to produce a HER2 targeted photosensitizer. The tetraconjugate obtained was subjected to purification and the monoconjugate was successfully isolated, purified and characterized. This monoconjugate retained the ability to bind to HER2 as well as the potency to generate singl...

A cyclotriphosphazene substituted with six 3,5-bis(trifluoromethyl) benzyloxy units was designed as a novel ¹⁹F MRI contrast agent. The resulting molecule has 36 magnetically equivalent fluorine atoms and exhibited suitable MRI properties with high imaging sensitivity, confirming the proof-of-concept as a convenient scaffold for the production of n...

Porphyrin- or phthalocyanine-bridged silsesquioxane nanoparticles (BSPOR and BSPHT) were prepared. Their endocytosis in MCF-7 cancer cells was shown with two-photon excited fluorescence imaging (TPEF) imaging. With two-photon excited photodynamic therapy...

Two structural factors (sulfonyl vs sulfanyl, 4,5- vs 3,6- position) of phthalonitriles - which are used in several material-related applications - have been comparatively investigated in terms of crystallographic properties and Hirshfeld surface analyses. The unexpected FT-IR spectra of the sulfonyl-substituted derivatives have been supported by D...

A systematic structure-photoproperties relationship study of the interactions of porphyrin-fullerene dyads with molecular oxygen was conducted on a set of three porphyrin-fullerene dyads, as this approach of related applications - oxygen sensitivity and photo-induced singlet oxygen generation - of such dyads remained to be endeavoured. To promote e...

A new efficient synthetic route was used to obtain symmetrically and asymmetrically substituted gallium (III) phthalocyanines (5-GaCl and 6-GaCl) containing azido groups with chlorine atoms at axial positions, using corresponding ZnPc derivatives (5-Zn and 6-Zn) as precursors. The photophysical and photochemical properties - fluorescence, singlet o...

Nitric oxide (NO) is a reactive gas well-known as an air pollutant causing severe environmental problems. NO is also an important signaling molecule having a strong affinity towards heme proteins in the body. Taking this specialty as a model, a biomimetic membrane was developed by modification of the membrane surface with iron-porphyrin which depic...

In photodynamic therapy (PDT), the low absorptivity of photosensitizers in an aqueous environment reduces singlet oxygen generation efficiency and thereby decreases photosensitizing efficacy in biological conditions. To circumvent this problem, we designed a phthalocyanine-poly-L-glutamic acid conjugate (1-PG) made from a new phthalocyanine (Pc 1)...

The photophysical properties of a newly synthesized unsymmetrically substituted zinc phthalocyanine derivative (1) bearing in its peripheral positions six n-hexylsulfanyl substituents and one amino-terminated n-hexylsulfanyl substituent were investigated. This mono-amino phthalocyanine exhibited a high tendency to form H-type aggregates in all of t...

Phthalonitriles are key precursors of phthalocyanines. Self-quenching dimeric phthalocyanines likely to be cleaved into monomeric species are of potential interest for tumour-site activated photosensitisers. Disulfide linkers can be specifically cleaved in tumoral tissue do to their reductive nature. Hence, a disulfide-linked phthalonitrile was des...

An organosoluble phthalocyanine substituted by four silylated tetraethyleneglycol chains was designed. This phthalocyanine become water-soluble after acid-promoted removal of the TBDMS moieties (which does not occur in acetonitrile), and is therefore a naked-eye observation system of acid aqueous media. Fluoride anion sensitivity based on the same...

Cavitands and porphyrinoids are two major groups of molecules. If cyclodextrins are maybe the most famous type of cavitands, the properties of resorcinarenes are now well known and rise rapidly increasing attention. This mini-review aims at detailing all the combinations of resorcinarenes with porphyrinoids reported so far, evidencing the bright fu...

A phthalocyanine-chalcone conjugate was previously reported to retain the full photodynamic activity of the phthalocyanine and a slightly lowered antivascular effect of the chalcone. Assuming that it was due to an insufficient release of the chalcone, we described here several grafting modes applied to the preparation of phthalocyanine-chalcone con...

A novel Bodipy derivative was designed for bimedical applications. Its mono-quaternized structure ensured of its water-solubility and suitable amphiphilicity. Showing no singlet oxygen generation to avoid damage to healthy cells, this new derivative proved to be an extremely promising antimicrobial agent, with activity equal or superior to ampicill...

A library of five phthalonitriles, dimeric or trimeric all connected by an aromatic spacer (catechol, resorcinol, hydroquinone, phloroglucinol and catechol with two tert-butyl moieties) was selected to be comparatively studied from a structural point of view. Hirshfeld Surface analysis and DFT calculations were performed as well.

Two of the properties important for photodynamic therapy applications are systematically investigated on a trihydroxylated monohalogenated porphyrin core. Singlet oxygen generation can be increased thanks to the heavy atom effect, frequently provided by the introduction of halogen atoms on the photosensitizer. We compare the effect of the presence...

Background: The biomedical photodynamic principle is based on the light-induced and photosensitiser-mediated killing of unwanted or harmful cells by overproduction of reactive oxygen species. Motivated by the success of photodynamic therapy (PDT) against several types of tumours, further applications of this approach are constantly identified whic...

Two mono-benzimidazolium salts of resorcinarene have been prepared and used as ligands in Suzuki-Miyaura cross-coupling reactions. They have been fully characterized by 1H and 13C NMR, MALDI, and FT-IR spectroscopic methods, and their structures were confirmed by X-ray diffraction analysis. These two new resorcinarene-based mono-benzimidazolium sal...

Iron(IV)-oxo species have been identified as the active intermediates in key enzymatic processes, and their catalytic properties are strongly affected by the equatorial and axial ligands bound to the metal, but details of these effects are still unresolved. In our aim to create better and more efficient oxidants of H-atom abstraction reactions, we...

A monohydroxylated octasubstituted phthalocyanine, aimed at being used as a synthon for further conjugation, has been designed to offer rigorous comparison conditions to study the effect of the presence of an active moiety, compared to its non-functionalized symmetric analogs. After the validation of the concept using computational methods, the des...

Photodynamic therapy (PDT) and vascular-disrupting agents (VDA) each have their advantages in the treatment of solid tumors, but also present drawbacks. In PDT, hypoxia at the center of the tumor limits conversion of molecular oxygen into singlet oxygen, while VDAs are deficient at affecting the rim of the tumor. A phthalocyanine–chalcone conjugate...

This review summarizes synthetic strategies for the preparation of asymmetric phthalocyanines and their analogues. Cross-condensation between two phthalonitrile components, cross-condensation between one phthalonitrile and one non-nitrile component, targeted synthesis of AABB-type compounds, the subphthalocyanine ring-expansion method, as well as p...

A porphyrin monosubstituted by three triethyleneglycol chains grafted on a pentaerythritol skeleton was designed to display an optimized amphiphilicity for an enhanced cellular uptake and thus to exert enhanced photocytotoxicity. This porphyrin proved to be an excellent photosensitiser with submicromolar IC50.

4-tert-Butylbenzenesulfonamide was used as a substituent of tetra peripherally substituted Fe(II) phthalocyanine, taking into account several parameters crucial for the design of potential oxidation catalysts such as solubility and stability. The resulting phthalocyanine exhibits a remarkable stability under oxidative conditions. The main product o...