Umile Gianfranco Spizzirri

Covalent Insertion of Antioxidant Molecules on Chitosan by a Free Radical Grafting Procedure

In this work, the synthesis of gallic acid-chitosan and catechin-chitosan conjugates was carried out by adopting a free radical-induced grafting procedure. For this purpose, an ascorbic acid/hydrogen peroxide redox pair was employed as radical initiator. The formation of covalent bonds between antioxidant and biopolymer was verified by performing UV, FT-IR, and DSC analyses, whereas the antioxidant properties of chitosan conjugates were compared with that of a blank chitosan, treated in the same conditions but in the absence of antioxidant molecules. The good antioxidant activity shown by functionalized materials proved the efficiency of the reaction method.

Molecularly imprinted polymers for the selective extraction of glycyrrhizic acid from liquorice roots

Abstract A new Molecularly Imprinted Solid Phase Extraction (MISPE) protocol was developed for the selective extraction and purification of glycyrrhizic acid (GL) from liquorice roots. Non-covalent MIP were synthesized using methacrylic acid (MAA), 2-(dimethylamino)ethyl methacrilate (DMAEM) or 2-hydroxyethylmetacrylate (HEMA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent. After the evaluation of the selectivity of the GL imprinted polymers, the performance of these materials as Solid Phase Extraction (SPE) sorbents was investigated. MIP having HEMA as functional monomer were found to be able to selectively extract almost 80% of GL content in liquorice roots. The proposed MISPE-HPLC procedure has good precision, thus it can be successfully used for the purification of GL from natural sources.

Imprinted hydrophilic nanospheres as drug delivery systems for 5-fluorouracil sustained release

Molecularly imprinted hydrogel nanospheres as devices for the controlled/sustained release of 5-fluororacil in biological fluids were synthesized employing one-pot precipitation technique as the polymerization method. Methacrylic acid as a functional monomer and ethylene glycole dimethacrylate as a cross-linker were used in polymeric feed. Morphological and hydrophilic properties were determined by scanning electron microscopy and water content measurement, and recognition and selectivity properties of spherical molecularly imprinted polymers were compared with the spherical non-imprinted polymers, both in organic (acetonitrile) and water media. Finally, in vitro release studies were performed in plasma simulating fluids.

Biological Activity of a Gallic Acid−Gelatin Conjugate

Goal of the present study was the characterization of the biological properties of a gelatin-gallic acid conjugate (Gel-GA) to evaluate its applicability in biomedicine and pharmacy. The macromolecular conjugate was synthesized by free radical grafting reaction between gelatin and gallic acid (GA) to form a covalent conjugate that was found to retain the antioxidant and enzymatic activities of free GA. In particular, the peroxynitrite scavenging power was found to be consistent with a IC(50) value of 2.17 ± 0.4 mg mL(-1). The enzymatic capacities of GA, which are regarded beneficial for cell functions, are partly retained in the Gel-GA conjugate. In particular, acetylcholinesterase inhibition (IC(50) of 7.1 ± 1.3 mg mL(-1)) implies the conjugates usefulness in the chemoprevention of Alzheimers disease, while the inhibition of α-amylase (IC(50) of 9.8 ± 1.1 mg mL(-1)) suggests that the conjugate can be a preferred alternative for inhibition of carbohydrate breakdown and control of glycemic index of food products. Finally, the anticancer activity of Gel-GA was proven in prostate carcinoma and renal cell carcinoma cell lines, confirming the potential of the proposed protein-polyphenol conjugate in medicine.

Selective Determination of Melamine in Aqueous Medium by Molecularly Imprinted Solid Phase Extraction

A molecularly imprinted polymer able to recognize melamine in partially aqueous medium was synthesized using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linking agent. The bound specificity and selectivity of the obtained material were verified by performing binding experiments with melamine and its structural analogue, 2,4,6-trimethoxy-1,3,5-triazine, respectively, using different aqueous binding media. Finally, the ability of MIP to selectively extract melamine from two real samples, a food supplement and a freeze-dried meat sample, was demonstrated.

Synthesis of Methacrylic−Ferulic Acid Copolymer with Antioxidant Properties by Single-Step Free Radical Polymerization

A novel, simple, and cheap method to synthesize antioxidant methacrylic-ferulic acid copolymer (PMAA-FA) by free radical polymerization was developed by employing a hydrogen peroxide-ascorbic acid pair to produce hydroxyl radicals acting as radical initiators. FT-IR spectra were performed to verify the insertion of ferulic acid into the polymeric chain, and the antioxidant activity of PMAA-FA was compared to that of a control polymer synthesized in the absence of antioxidant molecule. Good antioxidant activity was demonstrated by obtained materials, showing the efficiency of the polymerization method. This material could be useful in the pharmaceutical field and in the food industry (food packaging).

Antioxidant multi-walled carbon nanotubes by free radical grafting of gallic acid: new materials for biomedical applications

Objectives  To prove the possibility of covalently functionalizing multi‐walled carbon nanotubes (CNTs) by free radical grafting of gallic acid on their surface with the subsequent synthesis of materials with improved biological properties evaluated by specific in‐vitro assays.

Molecularly imprinted polymers as drug delivery systems for the sustained release of glycyrrhizic acid

Objectives The aim was to synthesize molecularly imprinted polymers (MIPs) with high recognition properties towards glycyrrhizic acid and to evaluate the performance of these materials to act as base excipients in glycyrrhizic acid sustained release in gastrointestinal simulating fluids.

Incorporation of carbon nanotubes into a gelatin–catechin conjugate: Innovative approach for the preparation of anticancer materials

A new hybrid material made of gelatin, catechin and carbon nanotubes was prepared by the non-covalent incorporation of carbon nanotubes (CNTs) into a gelatin-catechin covalent conjugate. The composite materials was tested by means of determination of the dispersion stability in water and the functionalization degree was assessed by the Folin-Ciocalteu method, finding a 0.9 mg of CT/g of protein conjugate. Subsequently, the complete retention of the antioxidant properties of the flavonoid after incorporation into the composite was proved by DPPH and ABTS assays and IC50 values of 5.74 mg mL(-1) and 0.39 mg mL(-1) were recorded. The presence of CNT into the materials did not interfere with the scavenging activities of the catechin. Finally, the anticancer activity on HeLa cancer cells was evaluated and a considerable increase in the therapeutic activity of the flavonoid was recorded moving from the free to the conjugated form in the presence of CNT, while in absence of CNT a reduction of the efficiency was observed.

Polyphenol Conjugates and Human Health: A Perspective Review

In recent years, antioxidants have gained great importance because of their potential use in food, pharmaceutical, and cosmetic industries. This interest is rooted in the cumulative evidence connecting active oxygen and free radicals with numerous human degenerative disorders, such as cardiovascular diseases, cancer, aging, and atherosclerosis. Polyphenols are the major class of antioxidant able to reduce the oxidative damages of lipids, proteins, enzymes, carbohydrates, and DNA in living cells and tissues. Among the realm of polyphenol compounds, polyphenol conjugates have been proposed as innovative materials which, by combining the advantageous properties of both the components, can increase the efficiency of antioxidants and their range of application in nutritional and biomedical fields. This work is an overview of the different class of polyphenol conjugates, which will be analyzed in terms of nutritional and biological properties, showing how these bio-conjugates will positively affect the human health.