Greta Bergamaschi

Recognition and sensing of nucleoside monophosphates by a dicopper(II) cryptate.

The dimetallic cryptate [Cu(2)(II)(1)](4+) selectively recognizes guanosine monophosphate with respect to other nucleoside monophosphates (NMPs) in a MeOH/water solution at pH 7. Recognition is efficiently signaled through the displacement of the indicator 6-carboxyfluorescein bound to the receptor, monitoring its yellow fluorescent emission. Titration experiments evidenced the occurrence of several simultaneous equilibria involving 1:1 and 2:1 receptor/NMP and receptor/indicator complexes. It was demonstrated that the added NMP displaces the indicator from the 2:1 receptor/indicator complex, forming the 1:1 receptor/analyte inclusion complex. Recognition selectivity is thus ascribed to the nature of nucleotide donor atoms involved in the coordination and their ability to encompass the Cu(II)-Cu(II) distance within the cryptate.

The Interaction of Fluoride with Fluorogenic Ureas: An ON1–OFF–ON2 Response

The anion binding tendencies of the two fluorogenic ureas L(1)H and L(2)H, containing the 2-anthracenyl and 1-pyrenyl moieties as signaling units, respectively, have been investigated in MeCN and DMSO by absorption, emission, and (1)H NMR spectroscopies. The formation of stable 1:1 receptor:anion H-bond complexes has been confirmed by structural studies on the crystalline [Bu4N][L(1)···Cl] and [Bu4N][L(2)H···CH3COO] salts. Complexation induces significant variations of the emission properties of L(1)H and L(2)H according to a multifaceted behavior, which depends upon the fluorogenic substituent, the solvent, and the basicity of the anion. Poorly basic anions (Cl(-), Br(-)) cause a red shift of the emission band(s). Carboxylates (CH3COO(-), C6H5COO(-)) induce fluorescence quenching due to the occurrence of an electron-transfer process taking place in the locally excited complex [*L-H···X](-). However, this excited complex may undergo an intracomplex proton transfer from one urea N-H fragment to the anion, to give the tautomeric excited complex [L···H-X](-)*, which emits at higher wavelength. F(-) displays a unique behavior: It forms with L(1)H a stable [L-H···F](-) complex which in the excited state undergoes intracomplex proton transfer, to give the poorly emissive excited tautomer [L···H-F](-)*. With L(2)H, on moderate addition of F(-), the 1:1 H-bond complex forms, and the blue fluorescence of pyrene is quenched. Large excess addition of F(-) promotes deprotonation of the ground-state complex, according to the equilibrium [L(2)H···F](-) + F(-) ⇆ [L(2)](-) + HF2(-). The deprotonated receptor [L(2)](-) is distinctly emissive (yellow fluorescence), which generates the fluorimetric response ON(1)-OFF-ON(2) of receptor L(2)H with respect to F(-).

99TcO4−: Selective Recognition and Trapping in Aqueous Solution

Too hot to handle: Unprecedented affinity and specificity for (99)TcO(4)(-) in aqueous solution was shown with the p-xylyl azacryptand in the hexaprotonated form. A crystal structure of the complex reveals how the anion fits within the cavity of the cage, and the formation of multiple H-bond interactions with protonated amino groups stabilize the adduct.

Pyridinium/urea-based anion receptor: methine formation in the presence of basic anions

The influence of the positively charged N-methylpyridinium substituent on the anion binding tendencies of urea-based receptors has been investigated by comparing molecules 1 and 2. These receptors have been studied in acetonitrile, by performing UV-vis. and (1)H NMR titrations with several anions. UV-vis. titrations have also been performed in DMSO, MeOH and CHCl(3)/CH(3)CN mixture (1/1, v/v). In the case of 1, the presence of both H-donor and H-acceptor groups (urea and pyridine, respectively) favours aggregation and the formation of dimers in the solid state. In solution, this tendency to aggregate reduces affinity for anions with respect to the similar urea-based receptor 3. The methylation of the pyridyl group of 1 leads to the pyridinium-containing receptor 2. The pyridinium positive charge enhances the acidity of urea and increases anion affinity, as evidenced by the comparison of the binding constants. Both receptors (1-2) form stable adducts with all investigated anions. However, in the case of 2, the formation of 1 : 1 adducts with basic anions, such as acetate and fluoride, is followed by a proton transfer process. Quite interestingly, deprotonation does not involve the urea group, thus preserving the 1 : 1 adduct, as demonstrated by the (1)H NMR measurements. In particular, the proton transfer process takes place at the methylene group linking the pyridinium fragment to the receptors skeleton. (1)H NMR studies indicate the formation of a stable neutral methine species, characterised by the loss of aromaticity by the pyridyl ring. These results open new perspectives in the field of anion recognition, as receptor 2 may by applied to the monitoring of both bound anion (through the urea unit) and excess anion in solution (through the development of the yellow methine species).

Fluorescent sensing of 99Tc pertechnetate in water

The selective binding of 99Tc pertechnetate (99TcO4−) in water is a big challenge. Recently, our group reported on the p-xylyl aza-cryptand, as the first molecular receptor for 99TcO4− in aqueous solution. Here, we show that the introduction of a fluorescent unit in the azacryptands framework leads to a new molecular system, able to selectively recognize and sense the pertechnetate anion at μM concentration. In water at pH 2, where the cage is in the hexaprotonated form, pertechnetate recognition is signalled by the quenching of the receptors emission. Noticeably, environmentally ubiquitous anions, such as chloride, nitrate and sulfate do not interfere in the sensing, as they have no effect on our chemo-sensors fluorescence. These unprecedented results are promising for the development of simple and smart devices for the recovery of 99TcO4− from contaminated aqueous solutions.

Supramolecular receptors in solid phase: developing sensors for anionic radionuclides

New solid-phases for the binding, separation and extraction of perrhenate and pertechnetate (ReO(4)(-) and TcO(4)(-)) from water solutions have been developed from a selective molecular receptor. Host compounds being capable of encapsulating these oxoanions are of great interest. The azacryptand, containing two tripodal tetra-amine subunits covalently linked by p-xylyl spacers, is known to display high affinity for ReO(4)(-) and TcO(4)(-) in water. The syntheses of new solid phases, obtained by fixing the receptor on mesoporous silica MCM-41 and Amberlite CG50 supports, are here described. FT-IR, micro-Raman, elemental analysis (CHN), sorption isotherms, (29)Si MAS NMR, and SEM/EDS were employed for solids characterisation. Promising performances were found for silica derivatives, for which the amount of the receptor fixed on silica ranged from 0.2 to 0.3 mmol g(-1). The perrhenate sorption mechanism was investigated with the aim to select the conditions for application in batch and fixed bed column systems.

An Automatic Molecular Dispenser of Chloride

The combined activity of the 1.1.1-cryptand and of a dicopper(II) bistren cryptate complex including chloride makes the Cl(-) ion be continuously and slowly delivered to the solution, without any external intervention. The 1.1.1-cryptand slowly releases OH(-) ions, according to a defined kinetics, and each OH(-) ion displaces a Cl(-) ion from the cryptate. Chloride displacement induces a sharp colour change from bright yellow to aquamarine and can be conveniently monitored spectrophotometrically, even in diluted solutions. The 1.1.1-cryptand is the motor of a molecular dispenser (the dicopper(II) cryptate) delivering chloride ion automatically, from the inside of the solution.

A bistren cryptand with a remote thioether function: Cu( ii ) complexation in solution and on the surface of gold nanostars

A new macrobicyclic ligand capable of binding two Cu2+ cations has been synthesized and its protonation and coordinative properties fully determined in aqueous solution. A thioether moiety was appended on the ligand backbone. This does not influence the ligand coordination ability but allows us to graft its bis-copper complex on the surface of a self-assembled monolayer of gold nanostars (GNS), in turn grafted on glass slides pre-functionalized with a layer of a silane-bearing polyethyleneimine polymer. The release of copper ions from the GNS monolayers was also investigated, finding a general agreement with the coordination properties of the complex in solution, although the bis-copper complex displays an increased kinetic inertness when grafted on the glass slides. The photothermal properties of the GNS monolayer were studied with and without the overlayer of the Cu2+ complex, finding no influence of the latter but disclosing that the bis-copper complex detachment is promoted by local T increase due to laser irradiation.

Synthesis and Study in Solution of a New Dansyl-Modified Azacryptand

We report the synthesis of a new asymmetric azacryptand (L1), characterized by three p-xylyl spacers, one of which carries a dansyl side arm. The fluorescent sensor has been studied by potentiometric, UV-Vis, and emission studies in MeOH : water 3 : 2 mixture (0.07 M NaNO3), determining, in particular, the protonation constants of the free ligand and metal ion complexation equilibria. Interestingly, the obtained results revealed that the new receptor is fluorescent at neutral pH with a typical emission band of the dansyl group. Metal addition induced a partial quenching of the dansyl emission band; this behavior is more pronounced with Cu(II) that reduces the receptor’s emission by 60%. With all the studied cations, quenching follows the formation of a dimetallic complex. Similar studies on the model compound L2 confirmed that fluorescence quenching is mainly driven by a static mechanism, attributable to the formation of the inclusion dicopper complex [L1Cu2]4

Photochemical and photocatalytic properties of transition metal compounds

This chapter reviews the major advances in the field of photochemistry and photocatalysis by transition metal compounds published in 2013–2014. Particular attention has been given to (i) photocatalysis in synthesis, and in the conversion of sunlight energy into chemical energy; (ii) photoreactivity; (iii) biomedical applications of photoactive transition metal complexes, e.g. as photo-CORMs and PDT agents.