Photophysical and biological investigation of novel luminescent Ru(II)-polypyridyl-1,8-naphthalimide Tröger's bases as cellular imaging agents

The synthesis and photophysical properties of 1 and 2, two Ru(II)-polypyridyl based-1,8-naphthalimide Tr?ger's bases, are described; these were found to stabilize double stranded DNA, undergo rapid cellular uptake, displaying good luminescence without affecting cell viability even after 24 hours of incubation.     

Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors

This review article focuses primarily on the work carried in our laboratories over the last few years using luminescent and colorimetric sensors, where the anion recognition occurs through hydrogen bonding in organic or aqueous solvents. This review begins with the story of the discovery of fluorescent photoinduced electron transfer (PET) sensors for anions using charged neutral urea or thiourea receptors where both fluorescent and NMR spectroscopic methods monitored anion recognition. This work led to the development of dual luminescent and colorimetric anion sensors based on the use of the ICT based naphthalimide chromophore, where ions such as fluoride gave rise to changes in both the fluorescence and the absorption spectra of the sensors, but at different concentrations. Here, the former changes were due to hydrogen bonding interactions, whereas the latter was due to the deprotonation of acidic protons, giving rise to the formation of the bifluoride anion (HF₂⁻). Modification of the 4-amino-l,8-naphthalimide moiety has facilitated the formation of colorimetric anion sensors that work both in organic or aqueous solutions. Such charge neutral receptor motifs have also been incorporated into organic scaffolds with norbomyl and calixarene backbones, which have enabled us to produce anion directed self-assembled structures.     

Maghemite in basalt studied by Mössbauer spectroscopy in external magnetic field

In the present study, we investigate the feasibility of detecting and determining the presence of maghemite in rock samples, by obtaining Mössbauer spectra in an external magnetic field of 1.6 T at room temperature. The interaction of the external magnetic field and the magnetic moments of the sublattices will induce differential shifts in the peak positions. By this method, we can assign some lower limit of the amount of maghemite in the sample. The results are compared with a model for a mixture of maghemite and stoichiometric magnetite.     

Highly selective fluorescent chemosensors for cadmium in water

The design, synthesis and photophysical evaluation of two new chemosensors 1 and 2 is described for the selective detection of Cd(II) in water at pH 7.4. Both are based on the use of aromatic iminodiacetate receptors that connected to an anthracene fluorophore by covalent methyl spacers. These are highly water-soluble sensors where the fluorescence is ‘switched off’ between pH 3-11, due to photoinduced electron transfer (PET) quenching of the anthracene excited state by the receptor. Upon protonation of the receptor, the emission was however, ‘switched on’. From these changes pK_as of 1.8 and 2.5 were determined for 1 and 2 respectively. Both showed good selectivity for Cd(II) over competitive ions such as group II and Zn(II), Cu(II), Co(II). For 1, having a single receptor, only a weak monomer anthracene emission was observed for the free sensor at pH 7.4 (HEPES buffer, 135 mM NaCl). Upon Zn(II) titration, a broad red shifted emission occurred, centred at 468 nm. In the presence of Cd(II), a similar red shifted emission was also observed, however, this time centred at 506 nm. In contrast to these results, the fluorescence of 2 in the presence of Zn(II) gave rise to typical monomeric anthracene emission, due to suppression of PET, that is, the anthracene emission was ‘switched on’. Nevertheless, in the presence of Cd(II) a broad emission centred at 500 nm was observed, similar to that seen for 1. These ion induced long wavelength emission bands were assigned to the formation of charge-transfer complexes (exciplexes) between the anthracene moieties and the ion-receptor complexes. Importantly, for both 1 and 2, a selective detection of Cd(II) was possible, even in the presence of Zn(II).     

Effect on pKa of metal-bound water molecules in lanthanide ion-induced cyclen "cavities"

[reaction: see text] The macrocyclic cyclen conjugates 1-4 were synthesized with the aim of forming lanthanide ion-based macrocyclic conjugates possessing deep cavities, formed upon complexation to various lanthanide ions. These complexes all possess metal-bound water molecules, where the pKa of the water molecules depends on the nature of the cavity.     

Anion sensing using colorimetric amidourea based receptors incorporated into a 1,3-disubstituted calix[4]arene

The synthesis of amidourea-based colorimetric anion sensors 1 and 2 and the evaluation of these sensors using anions such as acetate , fluoride (F⁻), hydrogen phosphate and hydrogenpyrophosphate (pyr) in DMSO is described. While 1 has a single amidourea moiety, 2 has two such receptors incorporated into a lower-rim 1,3-disubstituted calix[4]arene scaffold. Whilst both sensors gave rise to red shifts in their absorption spectra upon anion recognition, the sensing of F⁻ and pyr gave rise to large changes with concomitant colour changes from yellow to purple, which were visible to the naked eye.     

Synthesis and characterisation of bis-cyclen based dinuclear lanthanide complexes

The design and synthesis of several bis-macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) ligands and their corresponding lanthanum or europium complexes is described; these dinuclear lanthanide systems were made by connecting two macrocyclic cyclen moieties through a rigid, covalent, p-xylylenediamide bridge or a flexible aliphatic hexane bridge. These ligands were subsequently functionalised with six acetamide pendant arms (CONR1R2: R1 = R2 = H or CH3, or R1 = H, R2 = CH3). The corresponding lanthanide bis-complexes were then formed by reaction with La(III) and Eu(III) triflates, yielding overall cationic (+VI charged) complexes.     

Fe mineralogy of rocks from the Vredefort impact structure investigated with Mössbauer spectroscopy

The Vredefort impact structure in South Africa is the largest and oldest remnant impact structure on Earth. Observations from above the crater reveal lower than average magnetic field intensities, but the rocks in the crater have been shown to possess much higher magnetic intensities than the regional average that varies on a centimeter scale. Various mechanisms, including the presence of single domain magnetite structures, have been proposed for this anomaly. Mössbauer spectroscopy has been applied to study the Fe-mineralogy of samples from near the centre of the Vredefort crater. Transmission Mössbauer measurements on bulk and microtomics sections of samples showed that the magnetic minerals were magnetite and hematite, and we suggest that oxidation of olivine during the impact is responsible for the magnetic properties of the rocks.     

Fluorescent sensing of pyrophosphate and bis-carboxylates with charge neutral PET chemosensors

[reaction: see text] The fluorescent photoinduced electron transfer (PET) chemosensors 2 and 3 were designed for the recognition of anions possessing two binding sides such as dicarboxylates and pyrophosphate; the anion recognition in DMSO takes place through the two charge neutral thiourea receptor sites with concomitant PET quenching of the anthracene moiety. The anion binding of acetate, phosphate, and pyrophosphate to 2 and 3 was also evaluated by using 1H NMR in DMSO-d6.     

Cyclen based lanthanide ion ribonuclease mimics: the effect of pyridine cofactors upon phosphodiester HPNP hydrolysis

The cyclen based pyridine complexes 1Ln-3Ln (Ln = La(III) and Eu(III)) were synthesised as metallo-ribonuclease mimics and their ability to hydrolytically cleave the phosphodiester of HPNP at 37 °C was investigated using UV-vis spectroscopy, whereas the binding of the substrate was evaluated using ³¹P NMR and Eu(III)-luminescent measurements. In contrast 2La gave rise to fast pH dependent hydrolysis of HPNP, with maximum efficiency at ca. pH 8.2, and with a half-lifetime of ∼1 h, the 1Ln and 3Ln complexes were found to be inactive, emphasizing the importance of the nature of the pyridine isomer as a cofactor in the hydrolytic process.