A new pyridine-based 12-membered macrocycle functionalised with different fluorescent subunits; coordination chemistry towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II)

The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.     

Effect of temperature on the photophysics of rhodamine 101 in a polar solvent

The absorption and emission properties of rhodamine 101 in polar, aprotic propionitrile-butyronitrile (4:5 v/v) solvent have been investigated. The equilibrium between the neutral zwitterionic and lactonic (colourless) forms is strongly affected by the temperature in the range 293–144 K. In dilute solution (1.12×10⁻⁵M), at room temperature the lactonic form is 98%, while at 144 K the zwitterionic form predominates, being 79%. These findings are discussed in terms of differential stabilization of the lactonic and zwitterionic forms through non-specific solute-solvent interactions involving the COO⁻¹ group.     

Electrophilic catalysis in nucleophilic substitution reactions in ionic liquids

2-Chlorotropone was obtained from 2-tosyloxytropone in 88% yield in the recyclable ionic medium BMIMBF₄/LiCl. That Li⁺ acts as a Lewis acid was proven by the lack of reactivity of 2-tosyloxytropone, under the above conditions, on replacing LiCl with NaCl or BMIMCl, or using BMIMCl alone, or a BMIMBF₄/MeCN/KCl mixture. 2-Bromo- and 2-iodotropone were obtained along similar lines from LiBr or LiI, respectively, whereas LiF proved unreactive.     

A mechanistic study of the permeation kinetics through biomembrane models: gemcitabine-phospholipid bilayer interaction

The kinetics of the interaction between Gemcitabine (a new anticancer drug) and phospholipid membrane models was investigated. This kind of study is of particular importance both in hypothesizing the interaction of Gemcitabine with mammalian cell membranes and in evaluating the potentiality of liposomes as a Gemcitabine delivery system. Unilamellar (LUV) and multilamellar (MLV) membrane models were made up of dimyristoylphosphatidylcholine (DMPC), dimyristoylphosphatidic acid sodium salt (DMPA), or a DMPC-DMPA mixture (1:1 molar ratio). Gemcitabine-phospholipid vesicle interaction was studied by differential scanning calorimetry (DSC) measurements performed at different time intervals. The findings showed slower permeation kinetics of Gemcitabine through MLV than LUV which, at the same lipid/water ratio, are characterized by a larger lipid surface in contact with the drug aqueous solution. Another interesting difference between LUV and MLV is the onset of a transient two-peak structure during the DSC scans of MLVs. The effect is due to the unequal distribution of the drug between the outer and inner bilayers of the multilamellar vesicles during the permeation kinetics. At equilibrium the two-peak structure merges into a unique peak. This finding may provide useful information about the lipid bilayer permeability in model membranes.     

Rogiolenyne D,the likely immediate precursor of rogiolenyne A and B,branched C15 acetogenins isolated from the red seaweed Laurencia microcladia of II Rogiolo. Conformation and absolute configuration in the whole series

It is shown that in the red seaweed Jaurencia microcladia, collected in the Mediterranean off the torrent Il Rogiolo, the new branched C₁₅ acetogenin rogiolenyne D ( = (+)-(2S,3S,7R))-3-(bromomethyl)-7-[(Z)-1-chlorohexen-3-en-5-nyyl)]-2-ethyl-2,3,6,7-tetrahydrooxepin; (+)- ?3 co-occurs with the already reported rogiolenyne A ((?)- 1 ) and B ((?)- 2a , suggesting the lineage (+)- 3 →(?)- 1 (?)- 2a ,Which is realized here chemically. The relative configurations are established via NMR analysis and chemical transformations as regards the seven-membered ring, while recourse is made to conformational analysis for the side chain. The absolute configuration is established via the Mosher's NMR method applied to the MPTA esters of (?)- 2a .     

Electronic energy transfer and collection in luminescent molecular rods containing ruthenium(II) and osmium(II) 2,2':6',2"-terpyridine complexes linked by thiophene-2,5-diyl spacers

The electronic absorption spectra, luminescence spectra and lifetimes (in MeCN at room temperature and in frozen n-C3H7CN at 77 K), and electrochemical potentials (in MeCN) of the novel dinuclear [(tpy)Ru(3)Os(tpy)]4+ and trinuclear [(tpy)Ru(3)Os(3)Ru(tpy)]6- complexes (3 = 2,5-bis(2,2':6',2'-terpyridin-4-yl)thiophene) have been obtained and are compared with those of model mononuclear complexes and homometallic [(tpy)Ru(3)Ru(tpy)]4+, [(tpy)Os(3)Os(tpy)]4+ and [(tpy)Ru(3)Ru(3)Ru(tpy)]6+ Complexes. The bridging ligand 3 is nearly planar in the complexes, as seen from a preliminary X-ray determination of [(tpy)Ru(3)Ru(tpy)][PF6]4, and confers a high degree of rigidity upon the polynuclear species. The trinuclear species are rod-shaped with a distance of about 3 nm between the terminal metal centres. For the polynuclear complexes, the spectroscopic and electrochemical data are in accord with a significant intermetal interaction. All of the complexes are luminescent (phi in the range 10(-4)-10(-2) and tau in the range 6-340 ns, at room temperature), and ruthenium- or osmium-based luminescence properties can be identified. Due to the excited state properties of the various components and to the geometric and electronic properties of the bridge, Ru --> Os directional transfer of excitation energy takes place in the complexes [(tpy)Ru(3)Os(tpy)]4+ (end-to-end) and [(tpy)Ru(3)Os(3)Ru(tpy)]6+ (periphery-to-centre). With respect to the homometallic case, for [(tpy)Ru(3)Os(3)Ru(tpy)]6+ excitation trapping at the central position is accompanied by a fivefold enhancement of luminescence intensity.     

Synthesis and x-ray characterization of the [Ir6(CO)15COEt]-Anionic Cluster

The reaction of Ir₆(CO)₁₆ with a mixture of CO, H₂, and ethylene yields the [Ir₆(CO)₁₅COEt]^- anion, which has been shown by X-ray diffraction to contain an octahedral iridium cluster bearing a —bonded acyl group; the arrangement of the 11 terminal and 4 edge-bridging carbonyl groups is different from that found in both the analogous rhodium complex and the parent Ir₆(CO)₁₆ carbonyl.     

Eilatin complexes of ruthenium and osmium. synthesis, electrochemical behavior, and near-IR luminescence

The synthesis and characterization of new Ru(II) and Os(II) complexes of the ligand eilatin (1) are described. The new complexes [Ru(bpy)(eil)(2)](2+) (2), [Ru(eil)(3)](2+) (3), and [Os(eil)(3)](2+) (4) (bpy = 2,2'-bipyridine; eil = eilatin) were synthesized and characterized by NMR, fast atom bombardment mass spectrometry, and elemental analysis. In the series of complexes [Ru(bpy)(x)(eil)(y)()](2+) (x + y = 3), the effect of sequential substitution of eil for bpy on the electrochemical and photophysical properties was examined. The absorption spectra of the complexes exhibit several bpy- and eil-associated pi-pi and metal-to-ligand charge-transfer (MLCT) transitions in the visible region (400-600 nm), whose energy and relative intensity depend on the number of ligands bound to the metal center (x and y). On going from [Ru(bpy)(2)(eil)](2+) (5) to 2 to 3, the d(pi)(Ru) --> pi(eil) MLCT transition undergoes a red shift from 583 to 591 to 599 nm, respectively. Electrochemical measurements performed in dimethyl sulfoxide reveal several ligand-based reduction processes, where each eil ligand can accept up to two electrons at potentials that are significantly anodically shifted (by ca. 1 V) with respect to the bpy ligands. The complexes exhibit near-IR emission (900-1100 nm) of typical (3)MLCT character, both at room temperature and at 77 K. Along the series 5, 2, and 3, upon substitution of eil for bpy, the emission maxima undergo a blue shift and the quantum yields and lifetimes increase. The radiative and nonradiative processes that contribute to deactivation of the excited level are discussed in detail.     

Evaluation of behaviour of linear monoamines CH3-(CH2)n−1-NH2 (n=1-6) in ion chromatography

This paper reports the results on a study of ion chromatography (IC) behaviour on strong cationic exchange column of CH₃-(CH₂)_n−1-NH₂ (n=1-6) type linear monoamines. The eluents were mixtures of HCl-NaCl, HNO₃-NaNO₃, HClO₄-NaClO₄, H₂SO₄-Na₂SO₄, HClO₄-NaClO₄-CH₃CN. Amines were revealed with an amperometric detector. The influence of different counter-ions on retention factors, k′, is discussed. Relationships between k′ and pE (E=sum of Na⁺ and H⁺ concentrations), and length of alkylic chain, and sensitivity coefficient S, are reported and discussed. The addition of acetonitrile (ACN) in the eluent was also taken into account. Suitable considerations are derived from these data. An example of monoamines separation is given.     

Zinc(II), cadmium(II) and mercury(II) halide pyrrolidine-2-thione complexes

Summary White crystalline complexes of general formula ML₂X₂, where M = Zn, Cd, Hg; X = Cl, 13r, I and L = pyrrolidine-2-thione, were prepared and studied by i.r. spectroscopy in the 4000-200 cm^–1 range. Evidence for coordination of the ligand to the metal through sulphur was found in each case. The previous assignment of the band present in the ligand at 1110 cm^–1 to the(CS) fundamental is discussed.This work was supported by the National Research Council (C.N.R.) of Italy.