New Oxaliplatin-Pyrophosphato Analogs with Improved In Vitro Cytotoxicity

Two new Pt(II)-pyrophosphato complexes containing the carrier ligands cis-1,3-diaminocyclohexane (cis-1,3-DACH) and trans-1,2-diamine-4-cyclohexene (1,2-DACHEX), variants of the 1R,2R-diaminocyclohexane ligand present in the clinically used Pt-drug oxaliplatin, have been synthesized with the aim of developing new potential antitumor drugs with high bone tropism. The complexes are more stable at physiological pH than in acid conditions, with Na₂[Pt(pyrophosphato)(cis-1,3-DACH)] (1) slightly more stable than [Pt(dihydrogenpyrophosphato)(1,2-DACHEX)] (2). The greater reactivity at acidic pH ensures a greater efficacy at the tumor site. Preliminary NMR studies indicate that 1 and 2 react slowly with 5’-GMP (used as a model of nucleic acids), releasing the pyrophosphate ligand and affording the bis 5’-GMP adduct. In vitro cytotoxicity assays performed against a panel of four human cancer cell lines have shown that both compounds are more active than oxaliplatin. Flow cytometry studies on HCT116 cells showed that the pyrophosphato compounds with the non-classical 1,3- and 1,4-diaminocyclohexane ligands (1 and 4) are the most capable to induce cells’ death by apoptosis and necrosis.     

Diphenylalanine Motif Drives Self-Assembling in Hybrid PNA-Peptide Conjugates

Peptides and nucleic acids can self-assemble to give supramolecular structures that find application in different fields, ranging from the delivery of drugs to the obtainment of materials endowed with optical properties. Forces that stabilize the “suprastructures” typically are hydrogen bonds or aromatic interactions; in case of nucleic acids, Watson-Crick pairing drives self-assembly while, in case of peptides, backbone hydrogen bonds and interactions between aromatic side chains trigger the formation of structures, such as nanotubes or ribbons. Molecules containing both aromatic peptides and nucleic acids could in principle exploit different forces to self-assemble. In this work we meant to investigate the self-assembly of mixed systems, with the aim to understand which forces play a major role and determine formation/structure of aggregates. We therefore synthesized conjugates of the peptide FF to the peptide nucleic acid dimer “gc” and characterized their aggregates by different spectroscopic techniques, including NMR, CD and fluorescence.     

Retention of heavy metal ions on SBA-15 mesoporous silica functionalised with carboxylic groups

Three samples of SBA-15 functionalised with -(CH(2))(3)COOH groups have been prepared by co-condensation, starting from solutions of TEOS and 4-(triethoxysilyl)butyronitrile, acting as -(CH(2))(3)COOH precursor, of different molar compositions. Materials were characterised by X-ray diffraction, nitrogen adsorption, and FT-IR spectroscopy. The pK(a) and the acidic capacity were measured for all samples by potentiometric titration. The acidic capacity increases with increasing amount of -COOH precursor in the synthesis mixture only up to 10% molar of total alkoxysilane. The value for the pK(a)(4.75) is independent of the acidic capacity of the material. The sample prepared starting from an amount of -COOH precursor equal to 10% molar of total alkoxysilane was chosen to test selective interactions with heavy metals of environmental importance (Ag(+), Cd(2+), Fe(3+), Cu(2+), Zn(2+)) at different pH values and ionic strengths. The significant and selective adsorption exhibited by the material has been exploited in a preliminary cation-exchange chromatographic application showing the possibility of eluting the metal ions at different retention times.     

Thermodynamics of complex formation between hydroxypropyl-β-cyclodextrin and quercetin in water–ethanol solvents at T = 298.15 K

Journal of Thermal Analysis and Calorimetry - Quercetin (QCT) is a flavonoid possessing many activities, such as neuro-/cardioprotective, anti-inflammatory and anticancer, but its pharmacological...     

Characterization Techniques as Supporting Tools for the Interpretation of Biochar Adsorption Efficiency in Water Treatment: A Critical Review

Over the past decade, biochar (BC) has received significant attention in many environmental applications, including water purification, since it is available as a low-cost by-product of the energetic valorisation of biomass. Biochar has many intrinsic characteristics, including its porous structure, which is similar to that of activated carbon (AC), which is the most widely used sorbent in water treatment. The physicochemical and performance characteristics of BCs are usually non-homogenously investigated, with several studies only evaluating limited parameters, depending on the individual perspective of the author. Within this review, we have taken an innovative approach to critically survey the methodologies that are generally used to characterize BCs and ACs to propose a comprehensive and ready-to-use database of protocols. Discussion about the parameters of chars that are usually correlated with adsorption performance in water purification is proposed, and we will also consider the physicochemical properties of pollutants (i.e., K_ow). Uniquely, an adsorption efficiency index BC/AC is presented and discussed, which is accompanied by an economic perspective. According to our survey, non-homogeneous characterization approaches limit the understanding of the correlations between the pollutants to be removed and the physicochemical features of BCs. Moreover, the investigations of BC as an adsorption medium necessitate dedicated parallel studies to compare BC characteristics and performances with those of ACs.     

Studies in organic mass spectrometry. Part 9—mass spectra of 9,10-disubstituted 2,3,6,7-tetraalkoxy-9,10-dihydroanthracenes: A remarkable loss of radicals from even-electron ions

The electron impact-induced fragmentations of 23 9,10-disubstituted 2,3,6,7-tetraalkoxy-9,10-dihydroanthracenes, including six stereoisomeric pairs, were studied. The loss of the 9-(or 10-)substituent constitutes the main fragmentation route. The resulting ions give rise to a remarkable violation of the so-called ‘even-electron rule’ as they eject the second substituent at the 10-(or 9-)position as a radical. The latter aspect was particularly investigated with the aid of low-energy (nominal value 15 eV) and mass-analysed ion kinetic energy spectra.     

Phenolic and Volatile Composition and Antioxidant Properties of the Leaf Extract of Brassica fruticulosa subsp. fruticulosa (Brassicaceae) Growing Wild in Sicily (Italy)

In continuation of research conducted on species of the spontaneous flora of Sicily (Italy) belonging to the Brassicaceae family, Brassica fruticulosa subsp. fruticulosa was selected. It is an edible species utilized in Sicilian traditional medicine. In this study, for the first time, the phenolic and the volatile compounds and the antioxidant properties of the hydroalcoholic extract obtained from the leaves of B. fruticulosa subsp. fruticulosa were characterized. Through HPLC-PDA/ESI-MS analysis, a total of 22 polyphenolic compounds (20 flavonoids and 2 phenolic acids) were identified, with 3-hydroxiferuloylsophoroside-7-O-glucoside (1.30 mg/g ± 0.01) and kaempferol-3-O-feruloylsophoroside-7-O-glucoside (1.28 mg/g ± 0.01) as the most abundant compounds. Through SPME-GC/MS several volatiles belonging to different chemical classes were characterized, with nitriles and aldehydes accounting for more than 54% of the whole volatile fraction. The extract of B. fruticulosa subsp. fruticulosa showed moderate activity in the DPPH assay (IC₅₀ = 1.65 ± 0.08 mg/mL), weak reducing power (17.47 ± 0.65 ASE/mL), and good chelating properties (IC₅₀ = 0.38 ± 0.02 mg/mL), reaching approximately 90% activity at the highest tested concentration. Lastly, the extract was non-toxic against Artemia salina, indicating its potential safety. According to the findings, it can be stated that B. fruticulosa subsp. fruticulosa represents a new valuable source of bioactive compounds.     

Divalent pairing ion for ion-interaction chromatography of sulphonates and car☐ylates

An ion-interaction method for the simultaneous separation and UV detection of compounds with weak or strong ionic groups, using a divalent cationic ion pair reagent, namely hexamethonium bromide, has been studied and developed. The analytes considered were tartaric, fumaric, pyruvic, maleic, phthalic, benzoic, sorbic, 4-hydroxybenzoic, benzene and toluene-4-sulphonic acids, and they were chosen for their practical importance. The chromatographic optimization for their separation has been achieved by varying eluent composition (methanol, NaCl and hexamethonium concentrations) and studying the performance of different stationary phases (octyl- and octadecyl-silica based columns). The method developed has been successfully applied to benzoate and sorbate determination in orange juices.