Lucia Tonucci | Università degli Studi "G. d'Annunzio" Chieti Pescara (original) (raw)

Papers by Lucia Tonucci

ACS Sustainable Chem. Eng., 2018

Hybrid nanoparticles with a large bridging organic group were prepared by mechanochemical-assiste... more Hybrid nanoparticles with a large bridging organic
group were prepared by mechanochemical-assisted sol−gel
reaction. Planetary ball mill (PBM) was used for the first time
to access the bis-silylated precursors, containing complex
functionalities (such as hydantoins or a symmetrical urea
obtained from α-amino esters). The process is based on a
sequential reaction pathway involving liquid-assisted grinding
(LAG) and 1,1′-carbonyldimidazole (CDI)-mediated one-pot/
two-step reactions. Then hydantoins and the symmetric urea
were used for the one-pot preparation of the corresponding bissilylated
compounds in a vibrational ball mill (VBM), followed by
the mechanochemical sol−gel preparation of biohybrid bridged
silsesquioxane nanospheres of uniform size.

Beilstein J. Org. Chem., 2017

The mechanochemical preparation of highly functionalized 3,5-disubstituted hydantoins was investi... more The mechanochemical preparation of highly functionalized 3,5-disubstituted hydantoins was investigated in the presence of various
poly(ethylene) glycols (PEGs), as safe grinding assisting agents (liquid-assisted grinding, LAG). A comparative study under drygrinding
conditions was also performed. The results showed that the cyclization reaction was influenced by the amount of the PEG
grinding agents. In general, cleaner reaction profiles were observed in the presence of PEGs, compared to dry-grinding procedures.

Tetrahedron, 2016

Few decades ago, the expertise gained from well-established extraction, processing and degradatio... more Few decades ago, the expertise gained from well-established extraction, processing and degradation techniques, paved the way for the use of ultrasounds as an alternative energy source in chemistry. Among other peculiar features, the locally extreme temperatures and pressures resulting from cavitation, proved to efficiently trigger reactions while maintaining mild average conditions, enhancing rates and yields and, hence, contributing to increase the popularity of sonochemistry up to the present level. The physical properties of the irradiated mixture are crucial for the effectiveness of cavitation, as well as for the proper transfer of acoustic energy to reactants. Therefore, the choice of a solvent that meets these requirements, while minimizing the environmental impact of the process is a fundamental one. Studies that combine sonochemistry with green, non-conventional solvents or with no solvents are surveyed in this review, evidencing how the most frequently investigated options are water phase, ionic liquids, followed by ethylene glycol and its oligomers, glycerol and few other biomass-based solvents. Numerous solvent-free, ultrasound-promoted procedures are also reported in the literature and are included in this contribution. The vast majority of the examples gathered here describe organic reactions, syntheses of nanosystems and polymerizations.

RSC Adv., 2015

A series of Pd and Pt nanoparticles (NPs) was prepared starting from the corresponding metal ions... more A series of Pd and Pt nanoparticles (NPs) was prepared starting from the corresponding metal ions and
lignosulphonates; NPs were tested as catalysts for allyl alcohols hydrogenation in water at room
temperature and pressure. All NPs were active with sharp differences in conversions and selectivities: Pt NPs
formed mainly saturated alcohols, whereas Pd NPS were more active, but less selective, forming, in addition
to saturated alcohols, also isomeric unsaturated alcohols and aldehydes, both saturated and unsaturated.

RSC Adv., 2015

Ultraviolet light can cause photodamage to the skin, such as sunburns and melanomas. TiO2 is intr... more Ultraviolet light can cause photodamage to the skin, such as sunburns and melanomas. TiO2 is introduced in
sunscreen formulations to reflect and scatter UV radiation. However, it can also photocatalyze the
production of reactive species like O2

c and OHc. Here, we aimed to remove the photocatalytic activity
of TiO2 (anatase and rutile), while preserving the UV filter property. Anatase and rutile were modified
through two preparative protocols. The first used HCl lignin precipitation of ethylene glycol lignin
solution in the presence of the cross-linker glutaraldehyde and anatase or rutile nanoparticles. The
second protocol used HNO3 lignin precipitation of lignin aqueous solution in the presence of anatase or
rutile nanoparticles. Both methodologies were performed at room temperature and ambient pressure in
green media, with vigorous mixing followed by 20 kHz sonication. The composite materials obtained
were fully characterized by SEM, XRD analysis and FT-IR spectroscopy, and their photostability, and
photo and shielding activities were evaluated through reference reactions: oxidation of 2-propanol, an
ene-reaction conducted on an a,b-unsaturated carboxylic derivative and photochemical transformation
of o-nitrobenzaldehyde to o-nitrosobenzoic acid. Therefore, in the near future, industrial use of these
new clusters can help to minimize TiO2 phototoxicity in sunscreen formulations, while preserving the
sunscreen photoprotection activity.

Journal of Molecular Catalysis a Chemical, 2001

A catalytic system consisting of iron- or ruthenium-sulfophthalocyanine and hydrogen peroxide or ... more A catalytic system consisting of iron- or ruthenium-sulfophthalocyanine and hydrogen peroxide or mono-persulfate was effective in the oxidation of simple primary and secondary alcohols as well as of simple ketones. The oxidation reactions were conducted in aqueous media with turnover rates, defined as moles of product per mole of catalyst per minute, up to 5. Primary alcohols, including methanol, were

Catal. Sci. Technol., 2014

The deoxydehydration (DODH) of glycerol is effectively catalyzed by rhenium derivatives, either i... more The deoxydehydration (DODH) of glycerol is effectively catalyzed by rhenium derivatives, either in neat glycerol or in the presence of solvents (in particular alcohols), in air or under hydrogen bubbling. Methyltrioxorhenium (MTO) and ReO3 were the only rhenium catalysts tested that can selectively catalyze the DODH reaction at very low temperatures (140 °C). The presence of oxygen is not necessary, although under nitrogen the reaction requires higher temperatures to occur. On the other hand, the presence of hydrogen often noticeably increased the selectivity versus allyl alcohol formation, reaching the considerable value of 90% in the case of reaction conducted in 2,4-dimethyl-3-pentanol with ReO3. The DODH reaction always exhibits a definite induction time that, in the case of MTO, corresponds more or less to the time required for its demethylation. Metal catalysts in both high – likely rhenium(VI) – and low oxidation states are involved. Re-addition of fresh glycerol at the end of the reaction indicates the feasibility of the reuse of the catalysts.

Rivista Italiana Delle Sostanze Grasse

Chlorophyll photosensitized oxidation of virgin olive oil: a comparison between selected unsatura... more Chlorophyll photosensitized oxidation of virgin olive oil: a comparison between selected unsaturated model esters and real oil samples The effects of chlorophyll on photooxidation of virgin olive oil was evaluated. A purified chlorophyll fraction from spinach leaves was used as a photosensitiser to oxidise tiglic acid, as a model unsaturated compound that is useful to tune reaction conditions. Oleic and linoleic acid methyl esters were used to test photosensitised oxygenation. Virgin olive oil samples with the added spinach chlorophyll were photooxidised and the formation of hydroperoxides was monitored by 13 C NMR. The virgin olive oil showed a behaviour similar to oleic acid methyl esters, as the olive oil contains more than 75% oleic acid. Headspace gas chromatography-mass spectrometry analysis of the irradiated reaction mixtures showed several short-chain products for the linoleic acid methyl esters, while for the oleic acid methyl esters, octane was the only product that was de...

Inorganica Chimica Acta, 2013

Palladium nanoparticles of a definite shape (spherical) and dimension (8–14 and 16–20 nm) were pr... more Palladium nanoparticles of a definite shape (spherical) and dimension (8–14 and 16–20 nm) were prepared employing two water soluble lignin samples as both reducing and stabilizing agent in definitely green experimental conditions, namely aqueous solution, aerobic conditions, moderate temperature, short times. The above nanoparticles were employed as catalyst for a series of carbon–carbon coupling reactions carried out in water at mild conditions. Heck and Suzuki reactions were performed for several substrates, by changing the nature of halogen, the substituents at the aromatic ring, the bases employed and the temperature. Product yields were satisfactory and selectivities very good. Other two cross-coupling reactions, namely Sonogashira and Stille, were also tested: iodine derivatives showed always the best reactivity, while chlorine derivatives did not react.

Apatites are a group of phosphate minerals, which are widely distributed in many geological envir... more Apatites are a group of phosphate minerals, which are widely distributed in many geological environments and in the bone tissues of vertebrates. In the apatite's structural channel, F ions are on the mirror plane, while OH ions are about 0.03nm above or below the plane (Hughes et.al. 1989). Because of apatite's importance in medical, geological, and material sciences, there are several publications involving the substitution and interaction between the channel ions F and OH. As a few of them are about the NMR behavior of these ions, the aim of current study is to investigate the dependence of 1 H NMR spectral behavior of OH-on F-ions in the channel.

ChemInform, 2015

Six different platinum nanoparticles and six different palladium nanoparticles are prepared and ... more Six different platinum nanoparticles and six different palladium
nanoparticles are prepared and screened as catalysts for the hydrogenation of allylic
alcohols. It is found that the allylic alcohols are hydrogenated with sharp differences in
conversions and selectivities. Platinum nanoparticles mainly lead to saturated alcohols,
whereas palladium nanoparticles were more active, but less selective, forming in addition
to saturated alcohols also isomeric unsaturated alcohols and aldehydes, both saturated
and unsaturated.

J. Chin. Ceram. Soc., 2002

The effect of 1H NMR spettroscopic characteristics of OH- on F- ions in the apatite structure was... more The effect of 1H NMR spettroscopic characteristics of OH- on F- ions in the apatite structure was investigated. The samples include hydrothermal synthesized hydroxyapatite (HAP, sample code F0) and fluoridated hydroxyapatite (F-HAP) with F/F+OH mole ratio from 5% to 95%. The following figures are found: (1) There is difference in the 1H NMR chemical shift for hydroixyl in apatite structure (δ = - 0.04 x 10-6 – 1.61x10-6). (2) the chemical shift of 1H due to H-O bond (δA) shifts to lower region as f content increase in apatite. (3) As F enters the structure, a new NMR resonance occurs near 0.90x10-6 – 1.61x10-6, whose intensity increase with F. This phenomena indicates that a F-H bond is formed in apatite structural channel. As the position and intensity peaks correlated positively with the F content, it is possible to use the chemical shift of 1H and the relative intensity of the spectral peaks to distinguish the crystalline HAP and non-crystalline phosphates, and estimate the F and...

Waste and Biomass Valorization, 2012

Two commercial Ca2? and NH4 ? lignin derivatives were catalytically oxidised and photooxidised ... more Two commercial Ca2? and NH4
? lignin derivatives
were catalytically oxidised and photooxidised both
aerobically and in presence of H2O2 (Fenton system), under
green conditions (water solution, 20C, 1 atm), to obtain
fractions with reduced degrees of polymerisation. Analyses
of the oxidised solutions were carried out using NMR, MS
and UV spectrometry. The catalytic and photocatalytic systems
used showed satisfactory conservation of the organic
material, except for the Fenton system. Lignins showed
some mineralisation when irradiated in the presence of
H5[PMo10V2O40] 9 H2O (POM-1), K5[Ru(H2O)PW11O39]
(POM-2), K4[SiW12O40]8H2O (POM-3) and TiO2. When
thePOMs were used as thermal catalysts, POM-3 was almost
inactive, while the reactivities of POM-1 and POM-2 under
both thermal and photochemical conditions were comparable,
revealing little effect of irradiation on the reaction
mechanism. The best compromise appears to be the TiO2
photosystem, which shows low carbon consumption, good
preservation of aromatic rings, and greatly reduced mineralisation.
Alternatively,POM-1 can be used, and particularly
under thermal conditions.

Green Chemistry, 2009

A new catalytic aerobic oxidation of alcohols to aldehydes under green conditions was developed ... more A new catalytic aerobic oxidation of alcohols to aldehydes under green conditions was developed
(room temperature and pressure, water solution, open vials). The water-soluble platinum(II)
tetrasulfophthalocyanine (PtPcS) catalyst showed the best selectivity for carbonyl derivatives, and
in particular for a,b-unsaturated alcohols; the reactions are slow.

New Journal of Chemistry, 2003

... Dibenzothiophene (DBT) and its alkylated analogues are among the most abundant polycyclic aro... more ... Dibenzothiophene (DBT) and its alkylated analogues are among the most abundant polycyclic aromatic sulfur hydrocarbons (PASH) in crude oils and are usually selected for model studies of desulfurization, both reductive and oxidative.1 In December 2000, the US EPA issued ...

New Journal of Chemistry, 2001

A catalytic system consisting of water-soluble metal sulfophthalocyanines (MPcS) or various ruthe... more A catalytic system consisting of water-soluble metal sulfophthalocyanines (MPcS) or various ruthenium complexes and mono-persulfate as the oxidant was effective in the oxidation of cyclohexanone, cyclohexanol and cyclohexane to adipic acid with different yields and selectivity. Oxidations were conducted at room temperature and under atmospheric pressure in aqueous media (or, in the case of cyclohexane, in a water-neat substrate double phase). The oxidation of cyclohexanol involved step-by-step formation of cyclohexanone, epsilon -caprolactone and 6-hydroxyhexanoic acid, all of which have been identified in the reaction mixtures; in selected cases moderate over-oxidation of adipic acid to glutaric and succinic acid was also observed. Various MPcS catalysts were examined (M = Fe, Co, Ni, Cu and Ru), and the ruthenium derivative exhibited the best performances in terms of rate and selectivity. Mono-persulfate was found to be a more convenient oxidizing reagent than hydrogen peroxide; related patterns were observed when H2O2 was used, however extended dismutation of the oxidant limited the overall yields. Cyclohexane underwent slow oxidation when reacted with persulfate (water-substrate double phase) in the presence of the water-soluble metal catalysts; adipic acid was selectively produced (95%) in the presence of RuPcS catalyst with yields as high as 21% (48 h). The catalytic performance of simpler ruthenium derivatives, such as [RuCl2(DMSO)(4)] (RuDMS) and K-5[Ru(H2O)P11O39] (RuPW), was also examined for comparison purposes. A kinetic scheme for cyclohexane oxidation is proposed.

European Journal of Inorganic Chemistry, 2004

Ruthenium catalysts — water-soluble ruthenium sulfophthalocyanine and heterogeneous ruthenium hy... more Ruthenium catalysts — water-soluble ruthenium sulfophthalocyanine and heterogeneous ruthenium hydroxyapatite complexes — proved to be effective for the hydration of propargylic alcohols in entirely aqueous media. 1-Phenyl-2-propyn-1-ol underwent an unprecedented catalytic hydration-decarbonylation-dehydration reaction, giving rise to styrene and carbon monoxide; 2-propyn-1-ol and 3-butyn-2-ol gave predominantly the products of anti-Markovnikov addition, together with products of hydration-dehydration (α,β-rearrangement) and, to a minor extent, the decarbonylation products, ethene or propene, respectively. Hydrations were also conducted in D2O, giving indications of the mechanism of the reactions and apparently ruling out the allenylidene route for the α,β-rearrangement. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Journal of Porphyrins and Phthalocyanines, 2003

Two water-soluble metal sulfophthalocyanines, namely Ni(II)PcS and Co(II)PcS, were structurally ... more Two water-soluble metal sulfophthalocyanines, namely Ni(II)PcS and Co(II)PcS,
were structurally characterized by electrospray ionization mass spectrometry (ESI-MS) and UV-vis
and NMR spectroscopy. The dominant ion in ESI-MS was a penta-protonated monomeric Ni(II)
complex and a tetra-protonated form with the Co(II) ion being oxidized to Co(III), confirming the
facile oxidation of the central cobalt atom of the phthalocyanine ring by a soft ionization method as
ESI. Experiments at various ESI voltages were also performed to ascertain the target of the oxidation,
whether it was the metal or the phthalocyanine unsaturated system. Addition of small amounts of
oxidizing agents, like potassium persulfate, resulted in a definite attenuation of the Q band in the
UV-vis spectra, while ESI-MS detected a variety of complexes, containing at least one oxygen
atom, which rapidly replaced the initial complexes. Copyright © 2003 Society of Porphyrins &
Phthalocyanines.

Journal of Porphyrins and Phthalocyanines, 2010

Water-soluble, metal-tetrasubstituted phthalocyanines (-SO3H, MPcS and -COOH, MPcC) of platinum a... more Water-soluble, metal-tetrasubstituted phthalocyanines (-SO3H, MPcS and -COOH, MPcC) of platinum and ruthenium were synthesized and their photostability to visible light irradiation was determined. For the ruthenium phthalocyanines, the characteristic visible Q band of the phthalocyanines was almost totally suppressed after five days of irradiation. The platinum derivatives were instead more resistant to photodegradation, and the Q band did not decrease by more than 25%. The addition of carbonyl compounds to the phthalocyanine solution in water (at concentrations at least 1400-fold those of the phthalocyanines) dramatically accelerated the photobleaching of these phthalocyanine complexes. PtPcS turned from blue to green and to colorless with one day of visible-light irradiation in the presence of acetone. This effect decreased with the increase in molecular weight of the ketones (from acetone to 2-pentanone). The addition of alcohols (i.e. 1-butanol) or other organics (i.e. phenylacetic acid) did not affect the photostability of these metal-tetrasubstituted phthalocyanines. Dioxygen also had an important role, as when the solutions of phthalocyanines were carefully deaerated before irradiation, the visible spectra were preserved. The platinum phthalocyanines, as with the palladium analogs, sensitize the photoproduction of 1O2, as shown by the formation of endoperoxide and its rearranged products in the presence of furfuryl alcohol (a singlet oxygen trapping agent).

Journal of Photochemistry and Photobiology A: Chemistry, 2006

The degradation of cyclohexanol that can be photoinduced by Fe(III) derivatives (e.g. nitrate, py... more The degradation of cyclohexanol that can be photoinduced by Fe(III) derivatives (e.g. nitrate, pyrophosphate and sulfate) has been investigated in aqueous media at room temperature and under neutral to alkaline conditions with continuous irradiation at 254, 366 and around 500nm for 24h. The conditions chosen are those putative to the Martian soil, and the experiments were relevant in view of

ACS Sustainable Chem. Eng., 2018

Hybrid nanoparticles with a large bridging organic group were prepared by mechanochemical-assiste... more Hybrid nanoparticles with a large bridging organic
group were prepared by mechanochemical-assisted sol−gel
reaction. Planetary ball mill (PBM) was used for the first time
to access the bis-silylated precursors, containing complex
functionalities (such as hydantoins or a symmetrical urea
obtained from α-amino esters). The process is based on a
sequential reaction pathway involving liquid-assisted grinding
(LAG) and 1,1′-carbonyldimidazole (CDI)-mediated one-pot/
two-step reactions. Then hydantoins and the symmetric urea
were used for the one-pot preparation of the corresponding bissilylated
compounds in a vibrational ball mill (VBM), followed by
the mechanochemical sol−gel preparation of biohybrid bridged
silsesquioxane nanospheres of uniform size.

Beilstein J. Org. Chem., 2017

The mechanochemical preparation of highly functionalized 3,5-disubstituted hydantoins was investi... more The mechanochemical preparation of highly functionalized 3,5-disubstituted hydantoins was investigated in the presence of various
poly(ethylene) glycols (PEGs), as safe grinding assisting agents (liquid-assisted grinding, LAG). A comparative study under drygrinding
conditions was also performed. The results showed that the cyclization reaction was influenced by the amount of the PEG
grinding agents. In general, cleaner reaction profiles were observed in the presence of PEGs, compared to dry-grinding procedures.

Tetrahedron, 2016

Few decades ago, the expertise gained from well-established extraction, processing and degradatio... more Few decades ago, the expertise gained from well-established extraction, processing and degradation techniques, paved the way for the use of ultrasounds as an alternative energy source in chemistry. Among other peculiar features, the locally extreme temperatures and pressures resulting from cavitation, proved to efficiently trigger reactions while maintaining mild average conditions, enhancing rates and yields and, hence, contributing to increase the popularity of sonochemistry up to the present level. The physical properties of the irradiated mixture are crucial for the effectiveness of cavitation, as well as for the proper transfer of acoustic energy to reactants. Therefore, the choice of a solvent that meets these requirements, while minimizing the environmental impact of the process is a fundamental one. Studies that combine sonochemistry with green, non-conventional solvents or with no solvents are surveyed in this review, evidencing how the most frequently investigated options are water phase, ionic liquids, followed by ethylene glycol and its oligomers, glycerol and few other biomass-based solvents. Numerous solvent-free, ultrasound-promoted procedures are also reported in the literature and are included in this contribution. The vast majority of the examples gathered here describe organic reactions, syntheses of nanosystems and polymerizations.

RSC Adv., 2015

A series of Pd and Pt nanoparticles (NPs) was prepared starting from the corresponding metal ions... more A series of Pd and Pt nanoparticles (NPs) was prepared starting from the corresponding metal ions and
lignosulphonates; NPs were tested as catalysts for allyl alcohols hydrogenation in water at room
temperature and pressure. All NPs were active with sharp differences in conversions and selectivities: Pt NPs
formed mainly saturated alcohols, whereas Pd NPS were more active, but less selective, forming, in addition
to saturated alcohols, also isomeric unsaturated alcohols and aldehydes, both saturated and unsaturated.

RSC Adv., 2015

Ultraviolet light can cause photodamage to the skin, such as sunburns and melanomas. TiO2 is intr... more Ultraviolet light can cause photodamage to the skin, such as sunburns and melanomas. TiO2 is introduced in
sunscreen formulations to reflect and scatter UV radiation. However, it can also photocatalyze the
production of reactive species like O2

c and OHc. Here, we aimed to remove the photocatalytic activity
of TiO2 (anatase and rutile), while preserving the UV filter property. Anatase and rutile were modified
through two preparative protocols. The first used HCl lignin precipitation of ethylene glycol lignin
solution in the presence of the cross-linker glutaraldehyde and anatase or rutile nanoparticles. The
second protocol used HNO3 lignin precipitation of lignin aqueous solution in the presence of anatase or
rutile nanoparticles. Both methodologies were performed at room temperature and ambient pressure in
green media, with vigorous mixing followed by 20 kHz sonication. The composite materials obtained
were fully characterized by SEM, XRD analysis and FT-IR spectroscopy, and their photostability, and
photo and shielding activities were evaluated through reference reactions: oxidation of 2-propanol, an
ene-reaction conducted on an a,b-unsaturated carboxylic derivative and photochemical transformation
of o-nitrobenzaldehyde to o-nitrosobenzoic acid. Therefore, in the near future, industrial use of these
new clusters can help to minimize TiO2 phototoxicity in sunscreen formulations, while preserving the
sunscreen photoprotection activity.

Journal of Molecular Catalysis a Chemical, 2001

A catalytic system consisting of iron- or ruthenium-sulfophthalocyanine and hydrogen peroxide or ... more A catalytic system consisting of iron- or ruthenium-sulfophthalocyanine and hydrogen peroxide or mono-persulfate was effective in the oxidation of simple primary and secondary alcohols as well as of simple ketones. The oxidation reactions were conducted in aqueous media with turnover rates, defined as moles of product per mole of catalyst per minute, up to 5. Primary alcohols, including methanol, were

Catal. Sci. Technol., 2014

The deoxydehydration (DODH) of glycerol is effectively catalyzed by rhenium derivatives, either i... more The deoxydehydration (DODH) of glycerol is effectively catalyzed by rhenium derivatives, either in neat glycerol or in the presence of solvents (in particular alcohols), in air or under hydrogen bubbling. Methyltrioxorhenium (MTO) and ReO3 were the only rhenium catalysts tested that can selectively catalyze the DODH reaction at very low temperatures (140 °C). The presence of oxygen is not necessary, although under nitrogen the reaction requires higher temperatures to occur. On the other hand, the presence of hydrogen often noticeably increased the selectivity versus allyl alcohol formation, reaching the considerable value of 90% in the case of reaction conducted in 2,4-dimethyl-3-pentanol with ReO3. The DODH reaction always exhibits a definite induction time that, in the case of MTO, corresponds more or less to the time required for its demethylation. Metal catalysts in both high – likely rhenium(VI) – and low oxidation states are involved. Re-addition of fresh glycerol at the end of the reaction indicates the feasibility of the reuse of the catalysts.

Rivista Italiana Delle Sostanze Grasse

Chlorophyll photosensitized oxidation of virgin olive oil: a comparison between selected unsatura... more Chlorophyll photosensitized oxidation of virgin olive oil: a comparison between selected unsaturated model esters and real oil samples The effects of chlorophyll on photooxidation of virgin olive oil was evaluated. A purified chlorophyll fraction from spinach leaves was used as a photosensitiser to oxidise tiglic acid, as a model unsaturated compound that is useful to tune reaction conditions. Oleic and linoleic acid methyl esters were used to test photosensitised oxygenation. Virgin olive oil samples with the added spinach chlorophyll were photooxidised and the formation of hydroperoxides was monitored by 13 C NMR. The virgin olive oil showed a behaviour similar to oleic acid methyl esters, as the olive oil contains more than 75% oleic acid. Headspace gas chromatography-mass spectrometry analysis of the irradiated reaction mixtures showed several short-chain products for the linoleic acid methyl esters, while for the oleic acid methyl esters, octane was the only product that was de...

Inorganica Chimica Acta, 2013

Palladium nanoparticles of a definite shape (spherical) and dimension (8–14 and 16–20 nm) were pr... more Palladium nanoparticles of a definite shape (spherical) and dimension (8–14 and 16–20 nm) were prepared employing two water soluble lignin samples as both reducing and stabilizing agent in definitely green experimental conditions, namely aqueous solution, aerobic conditions, moderate temperature, short times. The above nanoparticles were employed as catalyst for a series of carbon–carbon coupling reactions carried out in water at mild conditions. Heck and Suzuki reactions were performed for several substrates, by changing the nature of halogen, the substituents at the aromatic ring, the bases employed and the temperature. Product yields were satisfactory and selectivities very good. Other two cross-coupling reactions, namely Sonogashira and Stille, were also tested: iodine derivatives showed always the best reactivity, while chlorine derivatives did not react.

Apatites are a group of phosphate minerals, which are widely distributed in many geological envir... more Apatites are a group of phosphate minerals, which are widely distributed in many geological environments and in the bone tissues of vertebrates. In the apatite's structural channel, F ions are on the mirror plane, while OH ions are about 0.03nm above or below the plane (Hughes et.al. 1989). Because of apatite's importance in medical, geological, and material sciences, there are several publications involving the substitution and interaction between the channel ions F and OH. As a few of them are about the NMR behavior of these ions, the aim of current study is to investigate the dependence of 1 H NMR spectral behavior of OH-on F-ions in the channel.

ChemInform, 2015

Six different platinum nanoparticles and six different palladium nanoparticles are prepared and ... more Six different platinum nanoparticles and six different palladium
nanoparticles are prepared and screened as catalysts for the hydrogenation of allylic
alcohols. It is found that the allylic alcohols are hydrogenated with sharp differences in
conversions and selectivities. Platinum nanoparticles mainly lead to saturated alcohols,
whereas palladium nanoparticles were more active, but less selective, forming in addition
to saturated alcohols also isomeric unsaturated alcohols and aldehydes, both saturated
and unsaturated.

J. Chin. Ceram. Soc., 2002

The effect of 1H NMR spettroscopic characteristics of OH- on F- ions in the apatite structure was... more The effect of 1H NMR spettroscopic characteristics of OH- on F- ions in the apatite structure was investigated. The samples include hydrothermal synthesized hydroxyapatite (HAP, sample code F0) and fluoridated hydroxyapatite (F-HAP) with F/F+OH mole ratio from 5% to 95%. The following figures are found: (1) There is difference in the 1H NMR chemical shift for hydroixyl in apatite structure (δ = - 0.04 x 10-6 – 1.61x10-6). (2) the chemical shift of 1H due to H-O bond (δA) shifts to lower region as f content increase in apatite. (3) As F enters the structure, a new NMR resonance occurs near 0.90x10-6 – 1.61x10-6, whose intensity increase with F. This phenomena indicates that a F-H bond is formed in apatite structural channel. As the position and intensity peaks correlated positively with the F content, it is possible to use the chemical shift of 1H and the relative intensity of the spectral peaks to distinguish the crystalline HAP and non-crystalline phosphates, and estimate the F and...

Waste and Biomass Valorization, 2012

Two commercial Ca2? and NH4 ? lignin derivatives were catalytically oxidised and photooxidised ... more Two commercial Ca2? and NH4
? lignin derivatives
were catalytically oxidised and photooxidised both
aerobically and in presence of H2O2 (Fenton system), under
green conditions (water solution, 20C, 1 atm), to obtain
fractions with reduced degrees of polymerisation. Analyses
of the oxidised solutions were carried out using NMR, MS
and UV spectrometry. The catalytic and photocatalytic systems
used showed satisfactory conservation of the organic
material, except for the Fenton system. Lignins showed
some mineralisation when irradiated in the presence of
H5[PMo10V2O40] 9 H2O (POM-1), K5[Ru(H2O)PW11O39]
(POM-2), K4[SiW12O40]8H2O (POM-3) and TiO2. When
thePOMs were used as thermal catalysts, POM-3 was almost
inactive, while the reactivities of POM-1 and POM-2 under
both thermal and photochemical conditions were comparable,
revealing little effect of irradiation on the reaction
mechanism. The best compromise appears to be the TiO2
photosystem, which shows low carbon consumption, good
preservation of aromatic rings, and greatly reduced mineralisation.
Alternatively,POM-1 can be used, and particularly
under thermal conditions.

Green Chemistry, 2009

A new catalytic aerobic oxidation of alcohols to aldehydes under green conditions was developed ... more A new catalytic aerobic oxidation of alcohols to aldehydes under green conditions was developed
(room temperature and pressure, water solution, open vials). The water-soluble platinum(II)
tetrasulfophthalocyanine (PtPcS) catalyst showed the best selectivity for carbonyl derivatives, and
in particular for a,b-unsaturated alcohols; the reactions are slow.

New Journal of Chemistry, 2003

... Dibenzothiophene (DBT) and its alkylated analogues are among the most abundant polycyclic aro... more ... Dibenzothiophene (DBT) and its alkylated analogues are among the most abundant polycyclic aromatic sulfur hydrocarbons (PASH) in crude oils and are usually selected for model studies of desulfurization, both reductive and oxidative.1 In December 2000, the US EPA issued ...

New Journal of Chemistry, 2001

A catalytic system consisting of water-soluble metal sulfophthalocyanines (MPcS) or various ruthe... more A catalytic system consisting of water-soluble metal sulfophthalocyanines (MPcS) or various ruthenium complexes and mono-persulfate as the oxidant was effective in the oxidation of cyclohexanone, cyclohexanol and cyclohexane to adipic acid with different yields and selectivity. Oxidations were conducted at room temperature and under atmospheric pressure in aqueous media (or, in the case of cyclohexane, in a water-neat substrate double phase). The oxidation of cyclohexanol involved step-by-step formation of cyclohexanone, epsilon -caprolactone and 6-hydroxyhexanoic acid, all of which have been identified in the reaction mixtures; in selected cases moderate over-oxidation of adipic acid to glutaric and succinic acid was also observed. Various MPcS catalysts were examined (M = Fe, Co, Ni, Cu and Ru), and the ruthenium derivative exhibited the best performances in terms of rate and selectivity. Mono-persulfate was found to be a more convenient oxidizing reagent than hydrogen peroxide; related patterns were observed when H2O2 was used, however extended dismutation of the oxidant limited the overall yields. Cyclohexane underwent slow oxidation when reacted with persulfate (water-substrate double phase) in the presence of the water-soluble metal catalysts; adipic acid was selectively produced (95%) in the presence of RuPcS catalyst with yields as high as 21% (48 h). The catalytic performance of simpler ruthenium derivatives, such as [RuCl2(DMSO)(4)] (RuDMS) and K-5[Ru(H2O)P11O39] (RuPW), was also examined for comparison purposes. A kinetic scheme for cyclohexane oxidation is proposed.

European Journal of Inorganic Chemistry, 2004

Ruthenium catalysts — water-soluble ruthenium sulfophthalocyanine and heterogeneous ruthenium hy... more Ruthenium catalysts — water-soluble ruthenium sulfophthalocyanine and heterogeneous ruthenium hydroxyapatite complexes — proved to be effective for the hydration of propargylic alcohols in entirely aqueous media. 1-Phenyl-2-propyn-1-ol underwent an unprecedented catalytic hydration-decarbonylation-dehydration reaction, giving rise to styrene and carbon monoxide; 2-propyn-1-ol and 3-butyn-2-ol gave predominantly the products of anti-Markovnikov addition, together with products of hydration-dehydration (α,β-rearrangement) and, to a minor extent, the decarbonylation products, ethene or propene, respectively. Hydrations were also conducted in D2O, giving indications of the mechanism of the reactions and apparently ruling out the allenylidene route for the α,β-rearrangement. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Journal of Porphyrins and Phthalocyanines, 2003

Two water-soluble metal sulfophthalocyanines, namely Ni(II)PcS and Co(II)PcS, were structurally ... more Two water-soluble metal sulfophthalocyanines, namely Ni(II)PcS and Co(II)PcS,
were structurally characterized by electrospray ionization mass spectrometry (ESI-MS) and UV-vis
and NMR spectroscopy. The dominant ion in ESI-MS was a penta-protonated monomeric Ni(II)
complex and a tetra-protonated form with the Co(II) ion being oxidized to Co(III), confirming the
facile oxidation of the central cobalt atom of the phthalocyanine ring by a soft ionization method as
ESI. Experiments at various ESI voltages were also performed to ascertain the target of the oxidation,
whether it was the metal or the phthalocyanine unsaturated system. Addition of small amounts of
oxidizing agents, like potassium persulfate, resulted in a definite attenuation of the Q band in the
UV-vis spectra, while ESI-MS detected a variety of complexes, containing at least one oxygen
atom, which rapidly replaced the initial complexes. Copyright © 2003 Society of Porphyrins &
Phthalocyanines.

Journal of Porphyrins and Phthalocyanines, 2010

Water-soluble, metal-tetrasubstituted phthalocyanines (-SO3H, MPcS and -COOH, MPcC) of platinum a... more Water-soluble, metal-tetrasubstituted phthalocyanines (-SO3H, MPcS and -COOH, MPcC) of platinum and ruthenium were synthesized and their photostability to visible light irradiation was determined. For the ruthenium phthalocyanines, the characteristic visible Q band of the phthalocyanines was almost totally suppressed after five days of irradiation. The platinum derivatives were instead more resistant to photodegradation, and the Q band did not decrease by more than 25%. The addition of carbonyl compounds to the phthalocyanine solution in water (at concentrations at least 1400-fold those of the phthalocyanines) dramatically accelerated the photobleaching of these phthalocyanine complexes. PtPcS turned from blue to green and to colorless with one day of visible-light irradiation in the presence of acetone. This effect decreased with the increase in molecular weight of the ketones (from acetone to 2-pentanone). The addition of alcohols (i.e. 1-butanol) or other organics (i.e. phenylacetic acid) did not affect the photostability of these metal-tetrasubstituted phthalocyanines. Dioxygen also had an important role, as when the solutions of phthalocyanines were carefully deaerated before irradiation, the visible spectra were preserved. The platinum phthalocyanines, as with the palladium analogs, sensitize the photoproduction of 1O2, as shown by the formation of endoperoxide and its rearranged products in the presence of furfuryl alcohol (a singlet oxygen trapping agent).

Journal of Photochemistry and Photobiology A: Chemistry, 2006

The degradation of cyclohexanol that can be photoinduced by Fe(III) derivatives (e.g. nitrate, py... more The degradation of cyclohexanol that can be photoinduced by Fe(III) derivatives (e.g. nitrate, pyrophosphate and sulfate) has been investigated in aqueous media at room temperature and under neutral to alkaline conditions with continuous irradiation at 254, 366 and around 500nm for 24h. The conditions chosen are those putative to the Martian soil, and the experiments were relevant in view of

I residui della lavorazione agroindustriale sono una preziosa opportunità di reddito grazie alla ... more I residui della lavorazione agroindustriale sono una preziosa opportunità di reddito grazie alla possibilità di trasformarli in biomassa e materia prima per altre produzioni industriali. Anche in Abruzzo, vengono prodotte tonnellate di rifiuti agroindustriali: un settore di grande potenzialità che necessita però di informazione completa e competente. Minimizzando la descrizione dell’impiego di tali sottoprodotti come fonte energetica, nel presente libro vengono descritte le principali possibilità di valorizzarli chimicamente per arrivare a molteplici obiettivi: la riduzione della quantità di scarti da smaltire, l’incremento del valore economico aggiunto che si può ottenere da essi e la possibilità di avere materie prime rinnovabili per importanti produzioni industriali.

Photosensitizers in Medicine, Environment, and Security, 2011

This chapter resumes the general strategies and the last progresses in the design of photosensit... more This chapter resumes the general strategies and the last progresses in the
design of photosensitisers, with chosen examples, many of them being extracted for
the last 5 years literature.