Synthesis,spectroscopic characterization (IR, 1H, 13C and 119Sn NMR,electrospray mass spectrometry) and toxicity of new organotin(IV) complexes with N,N′,O‐ and N,N′,S‐scorpionate ligands

New organotin(IV) derivatives containing the anionic ligands bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate [LCS₂]⁻ and bis(3,5‐dimethylpyrazol‐1‐yl)acetate [LCO₂]⁻ have been synthesized from reaction between (CH₃)₂SnCl₂ and lithium salts of the ligands. Mononuclear complexes of the type {[LCX₂](CH₃)₂SnCl} (X = S or O) have been obtained and fully characterized by elemental analyses and FT‐IR in the solid state and by NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy, conductivity measurements and electrospray ionization mass spectrometry in solution. The acute toxicity of new organotin(IV) derivatives on rat was studied, comparing their effect with those of dimethyltin chloride (CH₃)₂SnCl₂. The comparison of LD₅₀ of organotin(IV) complexes and (CH₃)₂SnCl₂ administered intraperitoneally, as a single dose, evaluated in vivo on rats, showed that toxicity decreases as follows: (CH₃)₂SnCl₂ > LCO₂ > LCS₂. The effect of these organotin(IV) complexes on DNA was evaluated in vitro and in vivo on rats treated with different doses of these compounds (1/20 LD₅₀ and 1/100 LD₅₀). The lymphocyte DNA status was assessed by the comet assay, a rapid and sensitive single‐cell electrophoresis technique, used to detect primary DNA damage in individual cells. After 36 h from the start of treatment the two new organotin(IV) derivatives induced a significant rise in comet assay parameters, indicating an increasing presence of damaged DNA. Copyright © 2005 John Wiley & Sons, Ltd.     

High quantum yield photoluminescence of new polyamides containing oligo‐PPV amino derivatives and related oligomers

The synthesis and the chemical physical characterization of new photoluminescent (PL) chromophores and polymers are reported. Chromophores (oligo‐PPV symmetric derivatives ending with amino groups) are strong blue emitters with a PL quantum yield of ～70% in dioxane solution. They have been used to prepare polyamides by reaction with aliphatic acyl dichlorides in which emitting and non emitting units are alternated. PL properties of the synthesized polyamides have been evaluated in solution and reveal a strong blue emission (PL quantum yield ～60%), To increase the solubility of these systems, oligomers have been purposely prepared and then characterized. They show a peculiar white emission when excited in DMF solution; to get insight into this interesting behavior, asymmetric monoacetylated chromophores have been prepared as model compounds for the chromophoric end groups of the polyamide chains. The emission spectra of these compounds reveal a broad excimeric yellow emission which is responsible, along with the blue emission of the inner chromophoric units, of the overall white emission of the oligomers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2677–2689, 2009     

Optically active synthons containing tetra- and dihydropyrimidine rings

Optically active condensed derivatives of hydroxytetrahydropyrimidines and dihydropyrimidines were prepared by condensation of (+)pulegone with amidines and guanidine. The structure, the possible mechanism of formation of these compounds, and the existence of amidinic tautomerism are discussed on the basis of the measured spectral data and x-ray diffraction analysis.     

Integrated analytical methodologies for the study of corrosion processes in archaeological bronzes

The investigations on structure and micro-chemical composition of archaeological metal alloys are needed in archaeometry. The aim of this study is devoted both to acquire information about their provenance and production technology, and to improve our understanding about the corrosion processes. In this paper we present the study of the corrosion phenomena of bronze samples, laboratory-made according to binary, ternary and quaternary alloys typical of Roman archaeometallurgical production through an integrated methodology based on the use of non or micro invasive physical techniques. Among the analysed samples, two were artificially aged through burial in the archaeological site of Tharros, along the west coast of Sardinia (Italy). The corrosion products, typical of the bronzes in archaeological sites near the sea, have been characterized by non invasive and micro-destructive measurements. In particular, the corrosion patinas were examined through optical microscopy, scanning electron microscopy and microanalysis, X-ray fluorescence and laser ablation spectroscopy. The use of integrated technologies allowed us to determine both the elemental composition and surface morphology of the patina, highlighting the correlation between patina nature and chemical composition of the burial context. Moreover, data obtained by the laser-induced breakdown spectroscopy along the depth profile on the samples, have yielded information about the stratigraphic layers of corrosion products and their growth. Finally, the depth profiles allowed us to verify both the chemical elements constituting the patina, the metal ions constituting the alloy and the occurrence of migration phenomena from bulk to the surface.     

Effect of organotin compounds on trout AMP‐deaminases

The comparative toxicity of the organotin compounds tributyltin chloride (TBTC), dibutylin dichloride (DBTC) and monobutyltin trichloride (MBTC) was investigated on 5′ adenylic acid deaminase (AMP‐deaminase) purified from trout skeletal muscle and heart. Treatment with TBTC of both enzymatic forms of AMP‐deaminase rapidly decreases the enzyme activity, and the organotin derivatives DBTC and MBTC have a significant minor inhibitory effect. Differences were observed in TBTC inhibition rate between trout muscle and heart purified enzymes that could be related to the different cellular localization of the two AMP‐deaminases. Copyright © 2001 John Wiley & Sons, Ltd.     

Zinc (II) and AIEgens: The “Clip Approach” for a Novel Fluorophore Family. A Review

Aggregation-induced emission (AIE) compounds display a photophysical phenomenon in which the aggregate state exhibits stronger emission than the isolated units. The common term of “AIEgens” was coined to describe compounds undergoing the AIE effect. Due to the recent interest in AIEgens, the search for novel hybrid organic–inorganic compounds with unique luminescence properties in the aggregate phase is a relevant goal. In this perspective, the abundant, inexpensive, and nontoxic d¹⁰ zinc cation offers unique opportunities for building AIE active fluorophores, sensing probes, and bioimaging tools. Considering the novelty of the topic, relevant examples collected in the last 5 years (2016–2021) through scientific production can be considered fully representative of the state-of-the-art. Starting from the simple phenomenological approach and considering different typological and chemical units and structures, we focused on zinc-based AIEgens offering synthetic novelty, research completeness, and relevant applications. A special section was devoted to Zn(II)-based AIEgens for living cell imaging as the novel technological frontier in biology and medicine.     

Virus-ligand interactions: identification and characterization of ligand binding by NMR spectroscopy

We demonstrate the detection and characterization of ligand binding to viruses via NMR. To illustrate the methodology, the interaction of an antiviral compound with human rhinovirus serotype 2 (HRV2) was investigated. Specific interaction of a capsid-binding inhibitor and native HRV2 was monitored utilizing saturation transfer difference (STD) NMR. STD NMR experiments at atomic resolution allowed those regions of the ligand that are involved in the interaction with the virus to be determined. The approach allows for (i) the fast and robust assessment of binding, (ii) the determination of the ligand binding epitope at atomic resolution without the necessity to crystallize virus-ligand complexes, and (iii) the reuse of the virus in subsequent assays. This methodology enables one to easily identify binding of drugs, peptides, and receptor or antibody fragments to the viral capsid.     

A Friendly Complexing Agent for Spectrophotometric Determination of Total Iron

Iron, one of the most common metals in the environment, plays a fundamental role in many biological as well as biogeochemical processes, which determine its availability in different oxidation states. Its relevance in environmental and industrial chemistry, human physiology, and many other fields has made it necessary to develop and optimize analysis techniques for accurate determination. Spectrophotometric methods are the most frequently applied in the analytical determination of iron in real samples. Taking advantage of the fact that desferrioxamine B, a trihydroxamic acid used since the 1970s in chelation therapy for iron overload treatment, forms a single stable 1:1 complex with iron in whichever oxidation state it can be found, a smart spectrophotometric method for the analytical determination of iron concentration was developed. In particular, the full compliance with the Lambert-Beer law, the range of iron concentration, the influence of pH, and the interference of other metal ions have been taken into account. The proposed method was validated in terms of LoD, LoQ, linearity, precision, and trueness, and has been applied for total iron determination in natural water certified material and in biological reference materials such as control human urine and control serum.