A new use for an old molecule: N-phenyl-2-(2-hydroxynaphthalen-1-ylmethylene)hydrazinecarbothioamide as a ratiometric ‘Off–On’ fluorescent probe for iron

N-Phenyl-2-(2-hydroxynaphthalen-1-ylmethylene)hydrazinecarbothioamide has been investigated as a fluorescent sensor for the determination of Fe(III) in aqueous solutions. The probe was prepared by the facile Schiff base condensation of 2-hydroxy-1-napthaldehyde with N-phenylhydrazinecarbothioamide. The sensor displayed good selectivity for Fe(III) when tested against a range of biologically and environmentally important cations. A concentration dependent increase in the emission of two fluorescent bands at 425 and 495 nm was observed upon increasing Fe(III) addition resulting in a linear ratiometric response in the 17–37 lM range. The binding stoichiometry was confirmed as 1:1 (host/guest) with the binding constant (logb) calculated as 4.56

A New Fluorescent Sensor for the Determination of Iron(III) in Semi-Aqueous Solution

A simple fluorescent sensor 1 has been developed for the recognition of Fe(III) in semi-aqueous solution at pH 7.0. The sensor, containing two Schiff base type receptors directly connected to naphthalene fluorophores, shows a concentration dependent decrease in emission intensity upon Fe(III) addition. The sensor was selective for Fe(III) over other metal ions and can measure Fe(III) ion concentration between 0.05 and 0.12 mM. The binding stoichiometry was established as 1:1 (host: guest) with a binding constant (Logβ) of 4.01. Furthermore, the addition of Fe(III) to a solution of 1 caused a colour change from light yellow to colourless meaning 1 is also capable of detecting Fe(III) by the naked eye

Iodinated Cyanine Dyes: A New Class of Sensitisers for use in NIR Activated Photodynamic Therapy (PDT)

Iodinated cyanine dye 6a has been developed for use as a NIR excited photosensitiser in photodynamic therapy.</p

Intracellular guest exchange between dynamic supramolecular hosts

Decyl and oligo(ethylene glycol) chains were appended to the same poly(methacrylate) backbone to generate an amphiphilic polymer with a ratio between hydrophobic and hydrophilic segments of 2.5. At concentrations greater than 10 μg mL(-1) in neutral buffer, multiple copies of this particular macromolecule assemble into nanoparticles with a hydrodynamic diameter of 15 nm. In the process of assembling, these nanoparticles can capture anthracene donors and borondipyrromethene acceptors within their hydrophobic interior and permit the transfer of excitation energy with an efficiency of 95%. Energy transfer is observed also if nanocarriers containing exclusively the donors are mixed with nanoparticles preloaded separately with the acceptors in aqueous media. The two sets of supramolecular assemblies exchange their guests with fast kinetics upon mixing to co-localize complementary chromophores within the same nanostructured container and enable energy transfer. After guest exchange, the nanoparticles can cross the membrane of cervical cancer cells and bring the co-entrapped donors and acceptors within the intracellular environment. Alternatively, intracellular energy transfer is also established after sequential cell incubation with nanoparticles containing the donors first and then with nanocarriers preloaded with the acceptors or vice versa. Under these conditions, the nanoparticles exchange their cargo only after internalization and allow energy transfer exclusively within the cell interior. Thus, the dynamic character of such supramolecular containers offers the opportunity to transport independently complementary species inside cells and permit their interaction only within the intracellular space

Highly luminescent biocompatible Carbon Quantum Dots by encapsulation with an amphiphilic polymer

Highly luminescent, water-soluble and biocompatible Carbon Quantum Dots (aqCQDs) were prepared by encapsulating the parent hydrophobic CQDs in an amphiphilic polymer. The resulting aqCQDs were non-toxic to living cells, and were found to cross the cell membrane and localise primarily in the cytosol

Water soluble quantum dots as hydrophilic carriers and two-photon excited energy donors in photodynamic therapy †

In search of strategies to develop deeply penetrating agents for use in Photodynamic Therapy (PDT), we have devised a Quantum Dot-Rose Bengal conjugate that is effective at producing singlet oxygen upon two-photon irradiation. The CdSe/ZnS Quantum Dot, with its high two photon absorption cross section, serves as a two-photon absorbing antenna and transfers its excited state energy to the attached photosensitiser which engages with molecular oxygen to produce cytotoxic singlet oxygen. Thus, we were able to excite the photosensitiser indirectly, which has an absorption maximum of 565 nm, with two-photon irradiation at 800 nm. Given the tissue penetration depth of 800 nm light is at least four times greater than 565 nm light, this offers the opportunity to access much deeper-seated tumours than is currently possible with pharmaceutically approved photosensitisers. Furthermore, the attachment of the photosensitiser to the hydrophilic quantum dot improved the aqueous solubility of the photosensitiser by 48 fold, thus overcoming another limitation of currently used photosensitisers, that of poor aqueous solubility

Probing the intracellular fate of supramolecular nanocarriers and their cargo with FRET schemes

We designed a strategy to monitor self-assembling supramolecular nanocarriers and their cargo simultaneously in the intracellular space with fluorescence measurements. It is based on Fӧrster resonance energy transfer (FRET) between complementary chromophores covalently integrated in the macromolecular backbone of amphiphilic polymers and/or noncovalently encapsulated in supramolecular assemblies of the amphiphilic components. Indeed, these polymers assemble into a micelles in aqueous phase to bring energy donors and acceptors in close proximity and allow energy transfer. The resulting supramolecular assemblies maintain their integrity after travelling into the intracellular space and do not lose their molecular guests in the process. Furthermore, this mechanism can also be exploited to probe the fate of complementary nanoparticles introduced within cells in consecutive incubation steps. Efficient energy transfer occurs in the intracellular space after the sequential incubation of nanocarriers incorporating donors first and then nanoparticles containing acceptors or vice versa. The two sets of nanostructured assemblies ultimately co-localize in the cell interior to bring donors and acceptors together and enable energy transfer. Thus, this protocol is particularly valuable to monitor the transport properties of supramolecular nanocarriers inside living cells and can eventually contribute to the fundamental understating of the ability of these promising vehicles to deliver contrast agents and/or drugs intracellularly in view of possible diagnostics and/or therapeutic applications

Supramolecular nanoreactors for intracellular singlet-oxygen sensitization

An amphiphilic polymer with multiple decyl and oligo(ethylene glycol) chains attached to a common poly(methacrylate) backbone assembles into nanoscaled particles in aqueous environments. Hydrophobic anthracene and borondipyrromethene (BODIPY) chromophores can be co-encapsulated within the self-assembling nanoparticles and transported across hydrophilic media. The reversible character of the noncovalent bonds, holding the supramolecular containers together, permits the exchange of their components with fast kinetics in aqueous solution. Incubation of cervical cancer (HeLA) cells with a mixture of two sets of nanoparticles, pre-loaded independently with anthracene or BODIPY chromophores, results in guest scrambling first and then transport of co-entrapped species to the intracellular space. Alternatively, incubation of cells with the two sets of nanocarriers in consecutive steps permits the sequential transport of the anthracene and BODIPY chromophores across the plasma membrane and only then allows their co-encapsulation within the same supramolecular containers. Both mechanisms position the two sets of chromophores with complementary spectral overlap in close proximity to enable the efficient transfer of energy intracellularly from the anthracene donors to the BODIPY acceptors. In the presence of iodine substituents on the BODIPY platform, intersystem crossing follows energy transfer. The resulting triplet state can transfer energy further to molecular oxygen with the concomitant production of singlet oxygen to induce cell mortality. Furthermore, the donor can be excited with two near-infrared photons simultaneously to permit the photoinduced generation of singlet oxygen intracellularly under illumination conditions compatible with applications in vivo. Thus, these supramolecular strategies to control the excitation dynamics of multichromophoric assemblies in the intracellular environment can evolve into valuable protocols for photodynamic therapy