Claudio Cassino

University of Piemonte Orientale Amedeo Avogadro | UNIPMN · Dipartimento di Scienze e Innovazione Tecnologica DISIT

Cardiovascular diseases represent a global challenge due to heart-limited regenerative capabilities. 3D-bioprinted cell-laden constructs are a promising approach as cardiac patches or in vitro models. However, developing bioinks with optimal mechanical, rheological, and biological properties remains challenging. Although alginate (Alg)-based bioink...

Background/Objectives: Chronic skin wounds (CSWs) are a worldwide healthcare problem with relevant impacts on both patients and healthcare systems. In this context, innovative treatments are needed to improve tissue repair and patient recovery and quality of life. Cord blood platelet lysate (CB-PL) holds great promise in CSW treatment thanks to its...

In situ-forming hydrogels based on the Schiff-base chemistry are promising for drug delivery applications, thanks to their stability under physiological conditions, injectability, self-healing properties, and pH-responsiveness. In this work, two water-soluble poly(ethylene glycol)-based poly(ether urethane)s (PEUs) were engineered. A high-molecular...

Bi-functional catalysts possess various catalytic sites and can catalyze different types of reactions in a single-pot cascade manner. Herein, we report the synthesis and characterization of mono- and bifunctional silica-based mesoporous hybrid catalysts involving acid and base active sites. The ability for cooperative catalysis has been investigate...

Cardiovascular diseases represent a worldwide social and economic challenge, due to heart tissue limited regenerative capabilities. 3D bioprinted cell-laden constructs are a promising approach to develop patches for cardiac regeneration or in vitro models for new drug preclinical discovery and validation. However, the development of bioinks with op...

Physical and chemical hydrogels are promising platforms for tissue engineering/regenerative medicine (TERM). In particular, physical hydrogels are well-suitable to design drug delivery systems due to their reversibility and responsiveness to...

Per- and polyfluoroalkyl substances (PFASs), also called forever chemicals, are known for their high physicochemical stability. In the last decades, these chemicals have been widely employed for numerous industrial applications. However, their persistence in the environment has increasingly raised concern regarding their potential toxicity to livin...

Temperature and light responsiveness are widely exploited stimuli to tune the physico-chemical properties of double network hydrogels. In this work, new amphiphilic poly(ether urethane)s bearing photo-sensitive moieties (i.e., thiol, acrylate and norbornene functionalities) were engineered by exploiting the versatility of poly(urethane) chemistry a...

Bioartificial hydrogels are hydrophilic systems extensively studied for regenerative medicine due to the synergic combination of features of synthetic and natural polymers. Injectability is another crucial property for hydrogel mini-invasive administration. This work aimed at engineering injectable bioartificial in situ cross-linkable hydrogels by...

Two polymorphs of ye’elimite are known to exist in calcium sulfoaluminate cements, namely, orthorhombic (iron free), C4A3$ and cubic/pseudo-cubic (iron incorporated), C4A3-xFx$ forms. The very early hydration behaviour of cubic ye’elimite (nominal composition: Ca3.8Na0.2Al5.6Fe0.2Si0.2O12SO4) has been investigated using a time-resolved in situ mult...

Supporting Information

Supporting Information

Pharmaceutical active compounds, including hundreds of different substances, are counted among the emerging contaminants in waterbodies, whose presence raises a growing concern for the ecosystem. Drugs are metabolized and excreted mainly through urine as an unchanged active ingredient or in the form of metabolites. These emerging contaminants are n...

A strategy to enhance drug effectiveness while minimizing controversial effects consists in exploiting host-guest interactions. Moreover, these phenomena can induce the self-assembly of physical hydrogels as effective tools to treat various pathologies (e.g., chronic wounds or cancer). Here, two Poloxamers®/Pluronics® (P407/F127 and P188/F68) were...

The very early hydration behavior of a hydraulic binder phase, ye'elimite, Ca 4 Al 6 O 12 SO 4 , in the absence and in the presence of calcium sulfate, has been investigated. A time-resolved in situ multinuclear magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopic suite involving 1 H and 27 Al MAS as well as two-dimensional 27...

The wine industry routinely employs sulphur dioxide (SO2) as an additive for antiseptic, antioxidasic and antioxidant activities. Some of the most important wine metabolites such as acetaldehyde, diacetyl, pyruvic acid, α-ketoglutaric acid, hydroxymethylfurfural, furfural and acetoin are known to react with SO2 over time to form adducts. ¹H NMR spe...

Barbera d’Asti—including Barbera d’Asti superiore—and Nizza are two DOCG (Denominazione di Origine Controllata e Garantita) wines produced in Piemonte (Italy) from the Barbera grape variety. Differences among them arise in the production specifications in terms of purity, ageing, and zone of production, in particular with concern to Nizza, which fo...

The high drug loading capacity, cytocompatibility and easy functionalization of ordered mesoporous carbons (OMCs) make them attractive nanocarriers to treat several pathologies. OMCs’ efficiency could be further increased by embedding them into a hydrogel phase for an in loco prolonged drug release. In this work, OMCs were embedded into injectable...

The polyphenolic composition and antioxidant activity of grape seeds, as byproducts of red winemaking, depend on various factors, such as grape cultivar, vintage effect, grape maturity and winemaking methods. In the present work, the influence of the maceration length on the polyphenolic and antioxidant characteristics of the seeds of four Italian...

Barbera d'Asti - including Barbera d'Asti superiore - and Nizza are two DOCG (Denominazione di Origine Controllata e Garantita) wines produced in Piemonte (Italy) from Barbera grape variety. Differences among them arise in the production specifications in terms of purity, ageing and zone of production, in particular with concern to Nizza, which has...

The design of supramolecular hydrogels based on host-guest complexes represents an effective strategy to develop drug delivery systems. In this work, we designed SM hydrogels based on α-cyclodextrin and high-molar mass amphiphilic poly(ether urethane)s (PEUs, Mn 27 kDa) based on Poloxamer® 407 and differing in their chain extender. The successful f...

Relaxometric analyses and in particular the use of fast-field cycling techniques have become routine in the study of paramagnetic metal complexes. The field dependence of the solvent proton relaxation properties (nuclear magnetic relaxation dispersion, NMRD) can provide unparalleled insights into the chemistry of these complexes. However, analyzing...

Injectable therapeutic formulations locally releasing their cargo with tunable kinetics in response to external biochemical/physical cues are gaining interest in the scientific community, with the aim to overcome the cons of traditional administration routes. In this work, we proposed an alternative solution to this challenging goal by combining th...

Plasma treatment is a widely applied, easy, fast, and highly reproducible surface modification technique. In this work powder plasma treatment was exploited to expose carboxylic groups along the backbone of a water soluble polymer. Specifically, a custom-made amphiphilic poly(ether urethane) containing Poloxamer® 407 blocks (Mw = 54,000 Da) was fir...

The polyphenolic content and the antioxidant capacity of seven tannins with different botanical origin were measured with spectrophotometric methods (Folin-Ciocalteu, Total Polyphenols Index, DPPH, FRAP), HPLC (phloroglucinolysis), voltammetric analysis (Linear Sweep Voltammetry, LSV). The oxygen consumption rate (OCR) was measured in an oxygen sat...

During the past few decades, thiomers have attracted interest as responsive-polymers in the design of smart hydrogels, due to thiol reactivity to physical stimuli (i.e., pH, oxygen, UV/Vis irradiation). However, thiomer potentialities have been limited by their low thiolation degree and lack of multi-responsiveness to physical cues. In this work, a...

The use of selected starter cultures for grape must fermentation is nowadays practiced in most wine regions of the world, and as the range of available microorganisms increases this gives winemakers the possibility to increase biodiversity in guided fermentations. Nevertheless, little information is available regarding the oenological use of Saccha...

In the present work, a new combination of synthetic and natural biomaterials is proposed for bone tissue engineering (BTE) applications. In order to mimic the inorganic and organic phases of bone extracellular matrix (ECM), a bioactive glass-ceramic deriving from a SiO2–P2O5–CaO–MgO–Na2O–K2O parent glass, acting as a substrate in form of a slice, w...

The study of wine evolution during bottle aging is an important aspect of wine quality. Ten different red wines (Vitis vinifera) from Piedmont region were analysed 3 months after bottling and after a further 48 month conservation in a climate controlled wine cellar kept at a constant/controlled temperature of 12 °C. Two white wines (Vitis vinifera)...

A fully calibrated and validated TGA-GC–MS is proposed for the quantitative analysis of diethylphosphate- end capped polymers. It allows the determination of the amount of phosphorous in polymeric samples and also thedetermination of the number of repeating units per chain end. Since no sample pretreatments are required polymeric films supported on...

The traceability of foodstuffs is now a relevant aspect of the food market. Scientific research has been devoted to addressing this issue by developing analytical protocols in order to find the link between soil and food items. In this view, chemical parameters that can act as soil markers are being sought. In this work, the role of rare earth elem...

Multimeric systems assembled by linking Gd(III) complexes to a central scaffold can be Magnetic Resonance Imaging (MRI) contrast agents of improved efficiency at high magnetic fields. Two novel mononuclear GdDO3A-derivatives (DO3A = 1,4,7,10-tetraazacyclododecane-N,N’,N”-triacetic acid) featuring a flexible (hexanoic acid, GdL1) or rigid (methyl be...

Barbera is one of the most common red grape in Italy, found in almost every region of the country. The widespread market of the corresponding wine deserves studies on its traceability and authenticity. To this end, the ¹H-NMR database of several wine metabolites was built using spectra recorded in a wine-like matrix containing ethanol and tartaric...

An hyphenated method based on thermal gravimetric, gas chromatographic and mass spectrometric analyses (TGA-GC-MS) is proposed for the quantitative analysis of diethylphosphate-end capped polymers with varying chain length, in bulk and as ultra thin film. The method fully calibrated and validated, revealed a powerful and affordable tool in the dete...

Polymer nanoparticles (nps) have gained growing interest as carriers for anticancer drugs as they can target tumor tissues by both, passive and active pathways. While the passive targeting mechanisms mainly relies on the small size of the carriers, active targeting requires surface modifications of the polymer core in order to introduce specific fu...

Numerous studies on molluscs have been carried out to clarify the physiological roles of haemolymph serum proteins and haemocytes. However, little is known about the presence and functional role of the serum metabolites. In this study, Nuclear Magnetic Resonance (NMR) was used to assess whether changes of the metabolic profile of Mytilus galloprovi...

This study correlates the antioxidant composition profiles and the overall antioxidant capacities of 36 Italian red wine samples. The samples were fully characterized by chromatographic and spectrophotometric techniques. The overall antioxidant capacity was determined by titrating a solution of the semistable free radical DPPH (1,1-diphenyl-2-picry...

The design of biomimetic scaffolds that reproduce the biochemical, mechanical and structural functions of the ECM is a fundamental requirement to develop functional substrate for tissue engineering. To this aim, materials which combine the easy processability and mechanical properties of synthetic polymers with the biochemical cues provided by natu...

Two small series of Pt(IV) complexes of the general formula cis,cis,trans-[PtA2Cl2L2] (A = 2 × NH3, series 1, or cyclohexane-1R,2R-diamine, dach, series 2, L = aromatic carboxylate of different chain length, i.e. –OCO(CH2)nC6H5, n = 0 (a), 1 (b), and 2 (c)) were synthesized and fully characterized, including X-ray structure analysis of one of them....

A series composed of a tetra-, a tris- and a bisphosphonated ligand based on a pyridine scaffold (L(4) , L(3) and L(2) , respectively) was studied within the frame of lanthanide (Ln) coordination. The stability constants of the complexes formed with lanthanide cations (Ln=La, Nd, Eu, Gd, Tb, Er and Lu) were determined by potentiometry in aqueous so...

Three new seco-cucurbitane triterpenes, viz. roseic acid (1) and roseolactones A (2) and B (3), all bearing a furan moiety condensed to the B-ring, were isolated from Russula aurora and R. minutula. Their structures were elucidated using 1D and 2D NMR spectroscopy, and ESI HRMS. Compounds 2 and 3 were found to be epimers at C-23. A detailed ab init...

Gd3+ chelates of macrocyclic bifunctional chelators (BFCs) can differentiate into two regioisomers: corner and side. These isomers afford different orientations of chelate relative to conjugate. These differences alter the self-assembly, tumbling, and effectiveness as magnetic resonance imaging contrast agents of the two biphenyl conjugate isomers.

Fluorinated, arylsulfone-based inhibitors of Matrix Metalloproteinases (MMP) have been used, in the [(18)F]-radiolabelled version, as radiotracers targeted to MMP-2/9 for Positron Emission Tomography (PET). Although they showed acceptable tumour uptake, specificity was rather low. To get further insights into the reason of low specificity, the bind...

Nuclear Magnetic Relaxation Dispersion (NMRD) profiles and 17O NMR chemical shifts and transverse relaxation rates of aqueous solutions of [Mn(H2O)6]2+ were recorded to determine the parameters governing the relaxivity in this complex and the 17O and 1H hyperfine coupling constants (HFCCs). The analysis of the NMRD and 17O NMR data provided a water...

A dimeric GdAAZTA-like complex (AAZTA is 6-amino-6-methylperhydro-1,4-diazepinetetraacetic acid) bearing an adamantyl group (Gd2L1) able to form strong supramolecular adducts with specific hosts such as β-cyclodextrin (β-CD), poly-β-CD, and human serum albumin (HSA) is reported. The relaxometric properties of Gd2L1 were investigated in aqueous solu...

A novel octadentate ligand derived from the core structure of EGTA (ethyleneglycol-bis(2-aminoethylether)-N,N,N',N'-tetraacetic acid) with two piperidine-cis-dicarboxylic acid moieties spaced by a triethylenedioxy chain (L1) has been synthesised with the aim to assess the effect of the structural rigidity on the thermodynamic and kinetic stabilitie...

Four aristolane sesquiterpenes were isolated from the fruiting bodies of Russula lepida and R. amarissima, namely (1R,2S)-1,2-dihydroxyaristolone (6), (2S,11S)-2,12-dihydroxy-aristolone (7), (1R,2S,11S)-1,2,12-trihydroxyaristolone (8), (1S,2S,11S)-1,2,12-trihydroxy-aristolone (9). In addition, a seco-cucurbitane triterpene, i.e. 3,4-secocucurbita-4...

The lanthanide(III) complexes of five EGTA [ethyleneglycol-bis(2-aminoethyl) ether-N,N,N′,N′-tetraacetic acid] derivatives fused with aromatic (benzene: L1; naphthalene: L2) and functionalized aromatic (L3–L5) moieties on the oxyethylene bridge were investigated in aqueous solution. 1H and 13C NMR spectra of the LaIII and LuIII complexes of L1 and...

Sulfonated aromatic pollutants such as 1,5-naphthalenedisulfonic acid (NDS or Armstrong's acid) are persistent compounds and thus resist environmental breakdown and microbial treatment. This study investigated the photo-oxidative degradation of such a persistent polar pollutant in the absence and presence of H2O2. The degradation of aqueous NDS sol...

Two novel octadentate ligands have been synthesized by attaching two terminal iminodiacetic groups to either 1,4-diazepane (BCAED) or piperazine (BCAEP) as central scaffold. The introduction of the seven- or six-membered ring into the ligand backbone is expected to modify their overall flexibility and then to affect the stability of the correspondi...

Nuclear medicine imaging of cell proliferation has gained broad interest in clinical oncology. A good tracer to image cell proliferation, possibly associated to tumour progression, should rapidly and specifically be incorporated into growing DNA. Following this idea, we have singled out thymidine as a potential biological carrier for delivery of th...

While several tools are already available for the separate measurement of the oxidant and antioxidant pools, a single, quick and easy method for determining total oxidative stress would be advantageous. In the present study, we compare the plasma of untreated patients with leukemia/solid gynecological tumors (n = 50) and current regular smokers (n...

Sulfonated aromatic pollutants such as Armstrong's acid, or 1,5-naphthalenedisulfonic acid (NDS), are recalcitrant to environmental breakdown and microbial treatment. This study investigated the effects of H(2)O(2) concentration, pH, microwave (MW) power and irradiation time on the oxidative degradation of NDS in aqueous solutions. The formation of...

Metallothioneins (MTs) are cysteine-rich proteins involved in homeostasis of essential metals, detoxification of toxic metals and scavenging of free radicals. Scavenging of the stable 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical was measured by means of ESR spectroscopy for two recombinant MTs from aquatic species: MT-10 from the sea mussel Mytilus...

Folates and folate-like molecules represent a class of vectors for drug targeting and delivery. The folate receptor (FR) is overexpressed in many human cancers, therefore folate-cytotoxic drug conjugates can deliver therapeutic agents specifically to FR positive tumours. We have linked, directly through one of the carboxylate functionalities of the...

The growing number of studies on platinum(II) complexes is stimulated by their importance as antitumour chemotherapeutics. 195Pt NMR spectroscopy is a very useful tool for characterizing and investigating these complexes. An accurate estimation of NMR chemical shifts plays an important role in the evaluation of molecular structure. Moreover, the pr...

Here we report the findings from a study on the electrochemical behaviour of two RuIII complexes [LH][trans-RuIIICl4L2] (L = imidazole, ICR, or indazole, IndCR) in aqueous solution at different pH values. An electrochemically reversible and chemically quasi-reversible one-electron reduction is observed for both compounds. Despite the similarity of...

Titanocene dichloride exhibits anti-proliferative activity in a wide spectrum of murine and human tumors. Although it is still unclear as to which species are active in biological media, they all readily deliver Ti(IV) to transferrin, the protein that transports iron in the blood. In this article, we report that aging of the complex in alcohols (na...

This paper describes the synthesis and the spectroscopic characterisation of cis-dichloro[N-(4-(17alpha-ethynylestradiolyl)-benzyl)-ethylenediamine]platinum(II) and cis-diamino[2-(4-(17alpha-ethynylestradiolyl)-benzoylamino)-malonato]platinum(II). These complexes were synthesised in good yield according to multi-step procedures based on the classic...

Thirteen newly synthesized or resynthesized diamine-platinum(II) complexes were characterized, and their cytotoxic activities (IC50) were tested on parental and resistant ovarian cancer cell lines. They represent models of conjugates between biologically active vectors and cytotoxic Pt(II) moieties within the "drug targeting and delivery strategy"....

The imidazolium trans-tetrachloro(dimethylsulfoxide)imidazoleruthenate(III) complex [ImH][Ru(III)Cl(4)(DMSO)(Im)], NAMI-A, has shown an interesting antimetastatic activity. Since Ru(III) complexes are coordinatively more inert than the corresponding Ru(II) derivatives, an "activation by reduction" mechanism has been proposed to explain the biologic...

An electrochemical and biological study of interaction between the prototypical antimetastatic drug imidazolium trans-tetrachlorodimethylsulfoxideimidazoleruthenate (III) complex, [ImH][RuCl(4)(DMSO)(Im)] (DMSO = dimethylsulfoxide, Im = imidazole), nicknamed NAMI-A, and several biomolecules, namely DNA, bovine (BSA) and human (HSA) serum albumin, i...

Starting from ethynylestradiol (1), or, more precisely, from its 3,17β-bis-(triethylsilyloxy) derivative 2, two new ligands containing the ethylenediamino motif were synthesised by a Mannich aminomethylation, namely N-methyl-N-(prop-2-ynyl-3-(17α-estradiolyl))-N′,N′-dimethylethylenediamine (3) and N-(prop-2-ynyl-3-(17α-estradiolyl))-N′-methylpipera...

A systematic study on intracellular Pt uptake and Pt accumulation ratio in breast cancer MCF-7 cell line has been performed on a number of Pt(II)-complexes, namely cisplatin, carboplatin and oxaliplatin, clinically employed as antitumor drugs, trans- and cis-[Pt(Cl)2(pyridine)2] and cis-[Pt(Cl)2(pyridine)(5-SO3H-isoquinoline)] complexes, previously...

Telomerase is a ribonucleoprotein polymerase that synthesizes telomeric DNA (TTAGGG) repeats. Previously, we have studied the effect on telomerase enzyme of several cis-platinum(II) complexes bearing aromatic amines as bulky carrier groups. All these complexes possess cis-geometry, according to the Cleare and Hoschele's rule. Since recent reports h...

The cytotoxicity of some ferrocenium salts and the lack of activity of the corresponding ferrocenes has been already demonstrated. The cytotoxic activity in different conditions of decamethylferrocenium tetrafluoroborate (DEMFc(+)) in comparison with four other ferrocenium derivatives on MCF-7 cell line is reported. The relative stability in aqueou...