Colorimetric and fluorometric detection of copper ion (Cu2+) has attracted much attention due to the biological, environmental and medical significance of the Cu2+ ion. Colorimetric and fluorescent detection of metal ions have proven to be powerful methods due to their simplicity, cost effectiveness, high detection limit and applicability to bioimaging. This review will consolidate selective and sensitive Cu2+ ion detection achieved by various receptor types in the years between 2013 to 2015.

Colorimetric and fluorescent chemosensors for Cu2+. A comprehensive review from the years 2013–15

This review describes the recent advances in the development of imaging agents based on silica nanoparticles. Different techniques (magnetic resonance imaging, optical imaging, positron emission tomography, X-ray computed tomography, and ultrasound imaging) are described as well as the possibility of combining together different imaging techniques in the same nanoplatform and simultaneously performing imaging and therapy.

Silica-based nanoparticles: a versatile tool for the development of efficient imaging agents

A new fluorescent sensor, M201-DPA, based on [5]helicene derivative was utilized as dual-analyte sensor for determination of Cu2+ or Zn2+ in different media and different emission wavelengths. The sensor could provide selective and bifunctional determination of Cu2+ in HEPES buffer containing Triton-X100 and Zn2+ in Tris buffer/methanol without interference from each other and other ions. In HEPES buffer, M201-DPA demonstrated the selective ON–OFF fluorescence quenching at 524 nm toward Cu2+. On the other hand, in Tris buffer/methanol, M201-DPA showed the selective OFF–ON fluorescence enhancement upon the addition of Zn2+, which was specified by the hypsochromic shift at 448 nm. Additionally, M201-DPA showed extremely large Stokes shifts up to ∼150 nm. By controlling the concentration of Zn2+ and Cu2+ in a living cell, the imaging of a HepG2 cellular system was performed, in which the fluorescence of M201-DPA in the blue channel was decreased upon addition of Cu2+ and was enhanced in UV channel upon addit...

Dual-Analyte Fluorescent Sensor Based on [5]Helicene Derivative with Super Large Stokes Shift for the Selective Determinations of Cu2+ or Zn2+ in Buffer Solutions and Its Application in a Living Cell.

In order to study the spin-orbit charge transfer induced intersystem crossing (SOCT-ISC), Bodipy (BDP)-carbazole (Cz) compact electron donor/acceptor dyads were prepared. Charge transfer (CT) emission bands were observed for dyads showing strong electronic coupling between the donor and the acceptor (coupling matrix elements VDA, 0.06 eV-0.18 eV). Depending on the coupling magnitude, the CT state of the dyads can be either dark or emissive. Equilibrium between the 1LE (locally excited) state and the 1CT state was confirmed by temperature-dependent fluorescence studies. Efficient ISC was observed for the dyads with Cz connected at the meso-position of the BDP. Interestingly, the dyad with non-orthogonal geometry shows the highest ISC efficiency (ΦΔ = 58%), which is different from the previous conclusion. The photo-induced charge separation (CS, time constant: 0.7 ps) and charge recombination (CR, ∼3.9 ns) were studied by femtosecond transient absorption spectroscopy. Nanosecond transient absorption spectroscopy indicated that the BDP-localized triplet state was exceptionally long-lived (602 µs). Using pulsed laser excited time-resolved electron paramagnetic resonance spectroscopy, the SOCT-ISC mechanism was confirmed, and we show that the electron spin polarization of the triplet state is highly dependent on the mutual orientation of the donor and acceptor. The dyads were used as triplet photosensitizers for triplet-triplet-annihilation (TTA) upconversion, and the quantum yield is up to 6.7%. TTA-based delayed fluorescence was observed for the dyads (τDF = 41.5 µs). The dyads were also used as potent photodynamic therapy reagents (light toxicity of IC50 = 0.1 µM and dark toxicity of IC50 = 70.8 µM).

Electronic coupling and spin-orbit charge transfer intersystem crossing (SOCT-ISC) in compact BDP-carbazole dyads with different mutual orientations of the electron donor and acceptor

Photodynamic therapy (PDT) is emerging as a significant complementary or alternative approach for cancer treatment. PDT drugs act as photosensitisers, which upon using appropriate wavelength light and in the presence of molecular oxygen, can lead to cell death. Herein, we reviewed the general characteristics of the different generation of photosensitisers. We also outlined the emergence of rhenium (Re) and more specifically, Re(I) tricarbonyl complexes as a new generation of metal-based photosensitisers for photodynamic therapy that are of great interest in multidisciplinary research. The photophysical properties and structures of Re(I) complexes discussed in this review are summarised to determine basic features and similarities among the structures that are important for their phototoxic activity and future investigations. We further examined the in vitro and in vivo efficacies of the Re(I) complexes that have been synthesised for anticancer purposes. We also discussed Re(I) complexes in conjunction with the advancement of two-photon PDT, drug combination study, nanomedicine, and photothermal therapy to overcome the limitation of such complexes, which generally absorb short wavelengths.

https://www.mdpi.com/1420-3049/25/18/4176/pdf

Recent Emergence of Rhenium(I) Tricarbonyl Complexes as Photosensitisers for Cancer Therapy

A highly selective copper fluorescent indicator based on aminoquinoline substituted BODIPY

A new fluorescent chemosensor 1, which based on hydroxyapatite (HA) nanoparticles covalently functionalized with a difluoroboron dipyrromethene, has been prepared by nucleophilic substitution of the fluorescent dye 3-chloro-4,4-difluoro-8-(4-tolyl)-5-[bis(pyridine2-ylmethyl)amino]-4-bora-3a,4a-diaza-s-indacene (2) with surface-modified HA nanoparticles. The HA particles were prepared by using SiO2 as templates (THA) with 3-(aminopropyl)triethoxysilane (THA-APTES). Substitution of the electron-withdrawing chlorine in 2 by an electron-donating amino group of HA changes the properties of the nanoparticles 1 and the corresponding fluorescent dye 2. Absorption and emission maxima of 1 in ethanol are red-shifted by 75 and 30 nm, respectively, in comparison with those of 2. In contrast to no selectivity of dye 2 for Cd2+ or Zn2+ in EtOH/H2O (95/5 V/V) solutions, the nanofluorescent probe 1 forms 1 : 1 complexes with Cd2+ or Zn2+, producing an instant color change along with large hypsochromic shifts in the absor...

Preparation of a fluorescent sensor based on BODIPY-functionalized hydroxyapatite nanoparticles and spectroscopic study of the Cd2+ and Zn2+ complex formation

A highly selective copper(II) sensor based on BODIPY-functionalized silica nanoparticles, BODIPY–DPA@SN, is designed and synthesized. Its absorption and fluorescence maxima in dry organic solvents are red-shifted by ∼75 and ∼50 nm compared with those of the BODIPY fluorophore and are blue-shifted by ∼55 and ∼15 nm, respectively, in aqueous–organic (1:1, v/v) media with fluorescence enhancement. The fluorescence intensity almost increases linearly as a function of water concentration (below 5%, v/v). BODIPY–DPA@SN exhibits high specificity for Cu2+ over other transition metal ions in aqueous–organic media, resulting in notable fluorescence quenching and a visible pink-to-yellow color change. Confocal microscopy experiments successfully proved that BODIPY–DPA@SN can be a biosensor for copper in living cells.

Synthesis and photochemical properties of BODIPY-functionalized silica nanoparticles for imaging Cu2+ in living cells

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A highly selective copper fluorescent indicator based on aminoquinoline substituted BODIPY

Preparation of a fluorescent sensor based on BODIPY-functionalized hydroxyapatite nanoparticles and spectroscopic study of the Cd2+ and Zn2+ complex formation

Synthesis and photochemical properties of BODIPY-functionalized silica nanoparticles for imaging Cu2+ in living cells