Partial salvage of avulsed tissue after dog bite.

Injuries to the nose can be severe from both a functional and cosmetic perspective. After suffering a dog bite to the central part of the face, an 18-year old woman underwent replantation of the avulsed tissue with the help of microsurgical arterial anastomosis. A venous anastomosis was impossible and venous congestion was treated with leech therapy. Subsequent skin necrosis occurred after a few days and the replantation was revised, revealing healthy tissue immediately below. The defect was covered with a full-thickness skin graft. At follow-up review eight months later, the functional and cosmetic result was satisfactory. To our knowledge, this is one of few cases where an injury of this severity healed with a cosmetically acceptable result.

An old workhorse for new applications: Fe(dpm)3 as a precursor for low-temperature PECVD of iron(III) oxide.

An iron(III) ß-diketonate complex, Fe(dpm)3 (Hdpm = 2,2,6,6-tetramethyl-3,5-heptanedione), has been investigated as a potential precursor for plasma enhanced chemical vapor deposition (PECVD) of iron(III) oxide nanomaterials. Thanks to the combined experimental-theoretical approach, spectroscopic properties, spin state, thermal behavior and fragmentation pathways of Fe(dpm)3 have been carefully analysed, obtaining an excellent agreement between simulation and experiment. Preliminary PECVD tests evidenced the possibility of obtaining pure and homogeneous Fe2O3 deposits with controlled nano-organization at temperatures as low as 100 °C, even on flexible plastic substrates. The present results open up intriguing perspectives for the exploitation of Fe(dpm)3 as an efficient molecular source for the preparation of nanostructured iron(III) oxides to be used in energetics and gas sensing applications.

Synthesis and characterization of [M(III)(PS)2(L)] mixed-ligand compounds (M = Re, 99Tc; PS = phosphinothiolate; L = dithiocarbamate) as potential models for the development of new agents for SPECT imaging and radiotherapy.

The synthesis and characterization of a new series of neutral, six-coordinated mixed-ligand compounds [M(III)(PS)2(L)] (M = Re; (99)Tc), where PS is bis(arylalkyl)- or trialkylphosphinothiolate and L is dithiocarbamate, are reported. Stable [M(III)(PS)2(L)] complexes were easily synthesized, in good yield, starting from precursors where the metal was in different oxidation states (III, V, and VII), involving ligand-exchange and/or redox-substitution reactions. The compounds were characterized by elemental analysis, positive-ion electrospray ionization mass spectrometry, multinuclear NMR spectroscopy, cyclic voltammetry, and X-ray diffraction analysis. All complexes are constituted by the presence of the [M(III)(PS)2](+) moiety, where two phosphinothiolate ligands are tightly bound to the metal and the remaining two positions are saturated by a dithiocarbamate chelate, also carrying bulky bioactive molecules [e.g., (2-methoxyphenyl)piperazine]. X-ray analyses were performed on crystalline specimens of four different Re/(99)Tc compounds sharing a distorted trigonal-prismatic geometry, with a P2S4 coordination donor set. The possibility of easily preparing these [M(III)(PS)2(L)] complexes, starting from the corresponding permetalate anions, in mild reaction conditions and in high yield, lays the first stone to the preparation of a new series of M(III)-based (M = (99m)Tc/(188)Re) compounds potentially useful in theragnostic applications.

Synthesis, characterization, crystal structure and preliminary reactivity behaviour of new heteropolytopic ligands based on the 1,3,5-triazine spacer and pyrazolyl, tris-pyrazolylmethyl and tris-pyrazolylethoxy bonding fragments.

Four new potentially polytopic nitrogen donor ligands based on the 1,3,5-triazine fragment, L(1)-L(4) (L(1) = 2-chloro-4,6-di(1H-pyrazol-1-yl)-1,3,5-triazine, L(2) = N,N'-bis(4,6-di(1H-pyrazol-1-yl)-1,3,5-triazin-2-yl)ethane-1,2-diamine, L(3) = 2,4,6-tris(tri(1H-pyrazol-1-yl)methyl)-1,3,5-triazine, and L(4) = 2,4,6-tris(2,2,2-tri(1H-pyrazol-1-yl)ethoxy)-1,3,5-triazine) have been synthesized and characterized. The X-ray crystal structure of L(3) confirms that its molecular nature consists of a 1,3,5-triazine ring bearing three tripodal tris(pyrazolyl) arms. L(1), L(2), and L(4) react with Cu(I), Cu(II), Pd(II) and Ag(I) salts yielding mono-, di-, and oligonuclear derivatives: [Cu(L(1))(Cy(3)P)]ClO(4), [{Ag(2)(L(2))}(CF(3)SO(3))(2)]·H(2)O, [Cu(2)(L(2))(NO(3))(2)](NO(3))(2)·H(2)O, [Cu(2)(L(2))(CH(3)COO)(2)](CH(3)COO)(2)·3H(2)O, [Pd(2)(L(2))(Cl)(4)]·2H(2)O, [Ru(L(2))(Cl)(OH)]·CH(3)OH, [Ag(3)(L(4))(2)](CF(3)SO(3))(3) and [Ag(3)(L(4))(2)](BF(4))(3). The interaction of L(3) with Ag(I), Cu(II), Zn(II) and Ru(II) complexes unexpectedly produced the hydrolysis of the ligand with formation, in all cases, of tris(pyrazolyl)methane (TPM) derivatives. In detail, the already known [Ag(TPM)(2)](CF(3)SO(3)) and [Cu(TPM)(2)](NO(3))(2), as well as the new [Zn(TPM)(2)](CF(3)SO(3))(2) and [Ru(TMP)(p-cymene)]Cl(OH)·2H(2)O complexes have been isolated. Single-crystal XRD determinations on the latter derivatives confirm their formulation, evidencing, for the Ru(II) complex, an interesting supramolecular arrangement of the anions and crystallization water molecules.

Solution behaviour and biological activity of bisamidine complexes of platinum(II).

A series of platinum(II) amidine complexes were previously prepared with the aim of obtaining a new class of platinum-based antitumour drugs. This series includes compounds of the type cis--[PtCl2{Z-HN=C(NHMe)Me}2] and trans-[PtCl2{Z-HN=C(NHMe)Me}2] (1, 2), cis-[PtCl2{E-HN=C(NMe2)Me}2] and trans-[PtCl2{E-HN=C(NMe2)Me}2] (3, 4), cis-[PtCl2{Z-HN=C(NHMe)Ph}2] and trans-[PtCl2{Z-HN=C(NHMe)Ph}2] (5, 6), and cis-[PtCl2{HN=C(NMe2)Ph}2] and trans-[PtCl2{HN=C(NMe2)Ph}2] (7, 8). The reactions with dimethyl sulfoxide were studied for complexes 5-8; the formation of cationic species containing coordinated dimethyl sulfoxide was demonstrated by NMR experiments and electrospray ionization mass spectrometry. In this work, the amidine platinum(II) complexes were tested for their in vitro cytotoxicity on a panel of various human cancer cell lines. The results indicate that the benzamidine complex 8 was the most effective derivative also circumventing acquired cisplatin resistance as demonstrated by chemosensitivity tests performed on cisplatin-sensitive and cisplatin-resistant cell lines. The studies concerning the cellular DNA damage on both parental chemosensitive and resistant sublines suggest for the new trans-amidine complex a different mechanism of action compared with that exhibited by cisplatin.