Search

Cardanol (CA) is a natural and renewable organic raw material obtained as the major by-product from the distillation of cashew nut shell liquid (CNSL). Thanks to its amphiphilic properties under alkaline conditions, was developed an environmental-friendly technology to produce engineered “green nanocarriers”, without use of any organic solvents, in which CA acts as the solvent as well as being the main component of the nanodispersions.

Nanotechnology has been utilized recently in medicine for the development of Drug Delivery Systems able to alter the kinetic profile of drug release that is very important in the administration of therapies for long periods as chemotherapy treatments, preventing damages to the normal surrounding tissue. This work aims to test new types of engineered green nanocarriers produced by an environmentalfriendly procedure for epithelial tumors treatment. Epithelial cancer is the largest single cause of death in both men and women, claiming over 6 million lives each year worldwide. For this reason, recently nanotechnology is attracting great interest in the search for new cancer therapies.

A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities toward the degradation of 4-nitrophenol (4-NP) by heterogeneous photo Fenton-like processes.

Biomimetic catalysts such as metalloporphyrins have been used to perform oxidation reactions. The increasing demand for such catalysts gave input to various researches for new efficient systems able to mime natural enzymatic models such as cytochrome P-450 monoxygenase and other biomimetic processes based on metalloporphyrin catalysts. However, natural porphyrins, depending on their molecular structure and process parameters, are unstable under catalytic oxidation conditions due to their self-destruction. An alternative approach consists in the preparation of robust catalysts miming the catalytic center of natural enzymes which can be obtained by immobilization of conveniently functionalized metalloporphyrins onto appropriate supports. In the light of these considerations, new composite materials inspired to mime the functions of material systems in nature have been designed in order to perform photocatalytic processes for the degradation of organic pollutants. In the last years a new category of TiO2 based composites prepared by impregnation of bare polycrystalline TiO2 powders with different porphyrins and phthalocyanines (acting as sensitizers) permitted the improvement of the photocatalytic processes for degradation of pollutants both under UV or visible light irradiation. In this context will be reported the synthesis of different metal free porphyrins (H2Pps) and their corresponding metal complexes (MPps) as well as the preparation of MPps/TiO2-based composites used as efficient catalysts (compared with bare TiO2) for the photodegradation of pollutants in water as well as in vapor phase reactions.

The nitration reaction of 5,10,15,20-tetranaphthylporphyrin (TNP) was investigated in detail and the mono-, di-, and tri-nitro-TNPs were synthesized in high yield using 65% HNO(3). The (1)H-NMR study shows that the preferred site of nitration of the naphthyl substituted porphyrin is the carbon atom of the meso-substituents para to its bond to the porphyrin ring. The reaction leads to exquisite regioselectivity in favor of the mono, di, and tri-nitro-TNP. Quantum-chemical ab initio calculations at different levels of theory were performed in order to explain the experimentally observed reactivity.

The new millennium is marked by a growing search for renewable fuels and alternative raw materials from biomass in the petrochemicals industry. Thus, the preparation of fine chemicals and innovative materials from natural and renewable resources is an attractive topic for academic and industrial research especially when the purpose is to recycle huge amount of agro-industrial wastes. Cashew nut shell liquid (CNSL), well known by-product from the cashew industry rich in natural phenols, is widely produced in many countries (Africa, Brazil, India). Cardanol, obtained as the main product by vacuum distillation of the CNSL, has been used for the preparation of fine chemicals and hybrid materials [1, 2]. In the last years, different classes of compounds, such for example porphyrins, phthalocyanines, fullerenes cardanol based and others fine chemicals, have been synthesized from selected components of CNSL through environmentally sustainable strategies [1-5]. Moreover, innovative composites and hybrid cardanol based compounds have been used to design eco-friendly functional materials and processes [6-9]. References: 1) Mele G., Vasapollo G. (2008) Mini-Rev. Org. Chem. 5, 243. 2) Mazzetto S.E, Lomonaco, Mele G. (2009) Quim. Nova, 32, 732. 3) Attanasi O.A., Mele G., Filippone P., Mazzetto S.E., Vasapollo G. (2009) Arkivoc VIII, 69. 4) Mele G., Li J., Margapoti E., Martina F., Vasapollo G. (2009) Catalysis Today 140, 37. 5) Guo Y.C., Mele G., Martina F., Margapoti E., Vasapollo G., Xiao W.J. (2006) J. Organomet. Chem. 691, 5383-5390. 6) Calò E., Maffezzoli A., Mele G., Martina F., Mazzetto S.E., Tarzia A., Stifani C. (2007) Green Chemistry 9, 754. 7) D’Amico D., Martina F., Ingrosso G., Mele G., Maffezzoli A., Tarzia A., Stifani C. (2009) Int. J. Mat. Prod. Tech. 36, 155. 8) Mele G., Del Sole R., Vasapollo G., Garcìa-Lòpez E., Palmisano L., Mazzetto S.E., Attanasi O.A., Filippone P. (2004). Green Chemistry 6 (102) 604. 9) Lomonaco D., Pinheiro Santiago G. M., Silva Ferreira Y., Campos Arriaga A. M, Mazzetto S.E., Mele G., Vasapollo G. (2009) Green Chemistry 11, 31.

The luminescencequenchingofexcitedTris(2,2-bipyridine)ruthenium(II)ionsby trans-[RuCl2{P(OR)3}4] complexeswithdifferentalkylchainligands(R ¼ C2H5, C2H5Cl, nC4H9, iC3H7 o-tolyland tC4H9) was investigated.NoneoftheacceptorRu(II)phosphitecomplexeswereluminescent,andtherateconstants of thebimolecularsystemweredeterminedwithintherangeof1.15and0.28108M1 s1 for R ¼ C2H5 and tC4H9, respectively.Theresultsindicateadirecteffectofthealkylchainsintherateconstants, showing adecreaseof kq as afunctionofincreasedofthealkylchains(R)intheruthenium(II) tetraphosphitecomplexes.ThegreatertheRgroupcontentinthephosphiteligand,themoredifficult the electrontransfer is.

The bidentate benzimidazolic hpbm (1), [2-(2-hydroxyphenyl)-1H-benzimidazole], was obtained under mild conditions, and its corresponding metal complexes, di-m-oxo dimanganese(IV,IV) [Mn2O2(hpbm)4 2Py 5H2O] (2), and mononuclear complex [Co(hpbm)2] (3), were prepared and characterized. The crystal structures of 2 and 3 have been established by X-ray diffraction. Complex 2 consists of two six-coordinate manganese(IV) coordinated to two hpbm ligands and bridged by two O2 with a Mn–Mn distance of 2.777A ˚ . For 3, a Co(II) is coordinated to two deprotonated hpbm in a nearly tetrahedral environment. Hydrogen bonds play pivotal roles in constructing the dimensional structures of both the compounds.

The new millennium is marked by a growing search for renewable fuels and alternative raw materials from biomass in the petrochemicals industry. However, there are many challenges to overcome regarding technological and human resources aspects. In this scenario, cashew nut oil, which is rich in natural phenols, is considered to be very promising for the development of synthetic and functional products and as a feedstock for production of fine chemicals and a wide variety of new materials.

In the last years a new category of TiO2 based composites prepared by impregnation of bare polycrystalline TiO2 powders with different sensitizers (i.e. phthalocyanines, porphyrins) permitted the improvement of the photocatalytic degradation of 4-nitrophenol (4-NP) under UV1-3 as well as under visible light irradiation.4 On the other hand growing interest devoted to the photodegradation of organic pollutants in water solutions by means of economically advantageous and environmental friendly processes are regarding this topic. Continuing our research in this area, we report here our recent results concerning: i) the preparation of new TiO2 and TiO2 based photocatalysts containing Fe and Cu species; ii) improvement of the photodegradation processes and conditions. 1. Mele, G.; Del Sole, R.; Vasapollo, G.; García-López, E.; Palmisano, L.; Schiavello, M. J. Catal. 2003, 217, 334. 2. Mele, G. ; Del Sole, R.; Vasapollo, G.; Marcì, G.; Garcìa-Lòpez, E.; Palmisano, L.; Coronado, J. M.; Hernández-Alonso, M. D.; Malitesta, C.; Guascito, R. J. Phys Chem. B 2005, 109, 12347. 3. Mele, G.; García-López, E.; Palmisano, L.; Dyrda, G.; Słota, R. J. Phys. Chem. C, 2007, 111, 6581. 4. Wang, C.; Li, J.; Mele, G.; Yang, G. M.; Zhang, F. X.; Palmisano, L.; Vasapollo, G. Appl. Catal. B: Environ. 2007, 76, 218.

Cardanol, a low-cost largely available renewable material obtained from distillation of CNSL (Cashew Nut Shell Liquid), has been used for the preparation of fine chemicals and hybrid materials. The long chain attached to the meta position of the phenolic ring of cardanol makes this compound a unique natural source because it confers to all derivatives, particular properties (good solubility, good processability, interesting physical properties and so on). New fine chemicals as well as new cardanol hybrid materials combined with porphyrins, phthalocyanines and fullerenes have been synthesized recently, developing at the same time new synthetic strategies for the preparation of new eco-friendly fine chemicals, composites and functional organic materials. The aim of this review is also to show that the chemistry of cardanol is becoming a stimulating area in academic and industrial research.

The novel porphyrins 5,10,15,20-tetra-[4-(3-phenoxy)-propoxy]phenyl porphyrin, H2Pp(a) and 5,10,15,20-tetra-[2-(3-phenoxy)-propoxy]- phenyl porphyrin, H2Pp(b) and their corresponding copper(II) complexes CuPp(a), CuPp(b) were synthesized and characterized by using various spectroscopic techniques. The photocatalytic activity of polycrystalline TiO2 samples impregnated with H2Pp(a), H2Pp(b), CuPp(a) and CuPp(b) as sensitizers have been investigated by carrying out the photo-degradation of 4-nitrophenol (4-NP) as a probe reaction in aqueous suspension and under visible light. The maximum photocatalytic activity was obtained using TiO2 loaded with a monolayer of the copper porphyrin CuPp(b) in the amount of 18 mmol per gram of TiO2. The photocatalytic efficiency decreased in the following order: TiO2-CuPp(b), TiO2-CuPp(a), TiO2-H2Pp(b), TiO2-H2Pp(a). A possible mechanism of the photocatalytic degradation is also proposed.

The aim of this work is to obtain a chemically cross-linked hydrogel from hyaluronic acid and cellulose derivatives that exhibits sensitivity to variation of the composition of the external absorbing medium and an equilibrium sorption capacity higher than a common hyaluronic acid-based hydrogel, in view of its potential use in prevention of postsurgical soft tissue adhesion. This has been achieved by chemical stabilization of hyaluronic acid (HA) and cellulose derivatives, hydroxyethylcellulose (HEC) and carboxymethylcellulose (CMCNa) through the difunctional cross-linker divinyl sulfone. Significant increase in sorption capacity, both in water and in water solutions at different ionic strength, has been observed for these samples in comparison with hydrogels obtained through chemical stabilization of hyaluronic acid. Moreover, different dehydration procedures adopted for the xerogel synthesis have been used, which resulted in a modulation of the equilibrium sorption capacity. Hyaluronic acid stability has been confirmed by means of NMR analysis.

Lerici (La Spezia)