Is a Catalyst Always Needed? The Case of the Knoevenagel Reaction with Malononitrile

2022

The aim of this Perspective is to start a discussion about the real usefulness of more or less sophisticated catalytic systems for the Knoevenagel reaction with malononitrile, a reaction that can take place under mild conditions without the need of a catalyst. From a sustainable viewpoint the questions are: Is it useful to increase the rate of a reaction that already occurs under mild conditions? Is it useful to spend resources and time in designing, characterizing and realizing complex catalytic systems for such reaction? Does it make sense to carry out the reaction under conditions such as to have a slower reaction rate and therefore to find a catalyst that is able to increase it?

ChemInform Abstract: Hydrophobically Directed Aldol Reactions: Polystyrene-Supported L-Proline as a Recyclable Catalyst for Direct Asymmetric Aldol R…

2008

A simple synthetic methodology for the preparation of a polystyrene-supported L-proline material is reported, and this material has been used as catalyst in direct asymmetric aldol reactions between several ketones and arylaldehydes to furnish aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water or methanol, at lower levels of conversion in the latter case. This solvent effect, coupled with the observed high stereoselectivities, has been explained in terms of the formation of a hydrophobic core in the inner surface of the resin, whereas the hydrophilic proline moiety lies at the resin/water interfac…

L-prolinammide supportata su polistirene come organocatalizzatore altamente enantioselettivo nella reazione aldolica diretta

2007

SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor

2019

Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material w…

Sintesi e studio fotofisico di sistemi Eu@POSS: controllo dell’emissione attraverso isomeria cis-trans.

Light-induced trans-cis isomerization of terpyridine functionalized POSS nanostructures self-assembled in presence of Eu3+ ions

Concentration dependence of amplified spontaneous emission in PPV oligomers

2004

Low-loading asymmetric organocatalysis

2011

Asymmetric organocatalysis is now recognized as the third pillar of asymmetric synthesis. Recent years have witnessed increasing interest towards the use of highly active and stereoselective organocatalysts. This critical review documents the advances in the development of chiral organocatalysts which are systematically used in ≤3 mol% loading in all the sub-areas of the field, namely aminocatalysis, Brønsted acids and bases, Lewis acids and bases, hydrogen bond-mediated catalysis, phase transfer and N-heterocyclic carbene catalyses (194 references).

Novel Hydroxyproline-derivatives as powerful aldolase-I mimics

2008

Recyclable Organocatalysts in Asymmetric Reactions

2011

An E-Factor Minimized Protocol for a Sustainable and Efficient Heck Reaction in Flow

2014

A highly sustainable and waste-minimized protocol for Heck coupling has been defined. Optimal conditions have been defined by exploiting a heterogeneous catalyst based on supported ionic liquid-like phases featuring high Pd loading (10 wt %) and by optimizing its efficiency in a recoverable green reaction medium (acetonitrile/water azeotrope). Pure products 4a–l and 6a–h have been isolated chromatography-free in high yields (74–99%) and with extremely low environmental factor (E-factor) values (2.3–5.0). With the application of flow technology, the selected heterogeneous base and Pd catalyst have been fully recovered and reused, and minimum palladium leaching allowed for isolation of the fi…

Lipase-catalyzed resolution of anti-6-substituted 1,3-dioxepan-5-ols

2006

Abstract Several anti-6-substituted 1,3-dioxepan-5-ols were kinetically resolved using an immobilized lipase (Amano PS–C II) in toluene in the presence of vinyl acetate at 30 °C. This approach provided, in some cases, the alcohol and the acetate in high enantiomeric purity, depending on the nature of the substituent (R = N3, SePh, I, OBn) and the acetal group (unsubstituted or dimethyl). The role of the size of substituents is also discussed. Enantiopure anti-6-substituted 1,3-dioxepan-5-ols are useful building blocks.

New concepts and applications in macromolecular chemistry of fullerenes

2010

A new classification on the different types of fullerene-containing polymers is presented according to their different properties and applications they exhibit in a variety of fields. Because of their interest and novelty, water-soluble and biodegradable C(60)-polymers are discussed first, followed by polyfullerene-based membranes where unprecedented supramolecular structures are presented. Next are compounds that involve hybrid materials formed from fullerenes and other components such as silica, DNA, and carbon nanotubes (CNTs) where the most recent advances have been achieved. A most relevant topic is still that of C(60)-based donor-acceptor (D-A) polymers. Since their application in pho…

Materiali ibridi a base di POSS-Imidazolio per la conversione della CO2 in carbonati ciclici

2018

Lo sviluppo di catalizzatori per i processi di conversione della CO2 è una tematica che sta rivestendo un ruolo di rilevante importanza in ambito non soltanto accademico ma anche industriale grazie alla possibilità di trasformare un rifiuto, quale il diossido di carbonio, in una vasta gamma di prodotti. Nel presente lavoro, nuovi materiali ibridi costituiti da silsesquiossani poliedrici oligomerici (POSS) supportati su silice e funzionalizzati con sali di imidazolio sono stati progettati per la fissazione della CO2. 1 Tutti i solidi sono stati ampiamente caratterizzati e testati per la sintesi di carbonati ciclici tramite reazione tra CO2 ed epossidi in condizioni di reazione solvent-free (…

Bisoxazoline-Fullerene Hybrid Systems for Asymmetric Catalysis

Molecular wires – long-range electron tunneling and hopping in novel donor-acceptor ensambles

2004

Photophysics and Photovoltaic Devices of a pi-Extended Tetrathiafulvalene-Fullerene Dyad

2004

Organocatalisi: sviluppo di nuovi materiali supportati riciclabili ed ottimizzazione di reazioni in fase omogenea.

2011

ORGANOCATALISI: SVILUPPO DI NUOVI MATERIALI SUPPORTATI ED OTTIMIZZAZIONE DI REAZIONI IN FASE OMOGENEA

2011

Recyclable Chiral Imidazolidinone Catalyst for α-Alkylation of Aldehydes

2014

Design of POSS-Imidazolium Supported Hybrids for the Conversion of Carbon Dioxide into Cyclic Carbonates

2018

Nowadays, the design of heterogeneous catalysts for the conversion of CO2 into useful chemical products is attracting the attention of the scientific community. The catalytic processes involving carbon dioxide as C1 feedstock are of growing interest for the sustainable development.1 The synthesis of cyclic carbonates by coupling CO2 with epoxides is one of the most interesting pathways for the conversion of carbon dioxide in terms of both atom economy and final products applications. Moreover, ionic liquids emerged as one of the most active catalysts for the production of cyclic carbonates starting from CO2 and epoxides.2 Herein, a series of heterogeneous catalytic systems bearing imidazoli…

Fullerene polymers: synthesis and properties

2007

ChemInform Abstract: New Ionic Liquid-Modified Silica Gels as Recyclable Materials for L-Proline- or H-Pro-Pro-Asp-NH2-Catalyzed Aldol Reaction.

2008

L-proline and the tripeptide H–Pro–Pro–Asp–NH2 (1) have been supported, by adsorption, onto the surface of modified silica gels functionalized with a monolayer of covalently attached 1,2-dimethyl-imidazolium chloride, tetrafluoroborate or hexafluorophosphate ionic moieties, respectively. Three different linkers were used to attach the ionic liquid moiety to the surface of these supports. The resulting materials have been used as catalysts for the aldol reaction between acetone and several substituted benzaldehydes. Good yields and enantioselectivities, comparable to or better than those obtained under homogeneous conditions, were obtained. These materials are easily recovered by filtration,…

Thiazolium salts as catalysts for etherification reaction

2014

ChemInform Abstract: Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under …

2013

3-Mercaptopropyl-modified silica-supported bis-imidazolium Pd-catalysts are developed and successfully utilized for Suzuki reactions.

Modified Nanocarbons for Catalysis

2018

Nanocarbons represent useful scaffolds in the preparation of last generation nanostructured catalysts, and their chemical functionalization through covalent or non-covalent modification is becoming an important tool for introducing well-distributed anchoring points and, in the meantime, could be the first step toward the assembling of hybrid nanostructured materials with a hierarchical order. In this Review are reported synthesis and catalytic applications of chemically modified nanocarbons such as fullerene, carbon nanotubes, graphene, nanohorns and nanodiamonds in organocatalytic and metal-based (metal nanoparticles, organometallic complexes) reactions, covering major chemical reactions e…

Stereoselective aldol reaction catalyzed by a highly recyclable polystyrene supported substituted prolinamide catalyst

2008

Polystyrene supported substituted prolinamide was used as catalyst in the aldol reaction between cyclohexanone or acetone and several substituted benzaldehydes in chloroform/water. This catalyst afforded aldol products in high yields and stereoselectivities, especially in the case of reactions performed with acetone. The catalyst was easily recovered by filtration and reused, after regeneration with formic acid, up to 22 times.

Supported Poly(Ionic Liquid)-Heteropolyacid Based Materials for Heterogeneous Catalytic Fructose Dehydration in Aqueous Medium

2022

Two sets of four different supported catalyst materials were prepared. One set was obtained by polymerization of a bis-vinylimidazolium salt, which formed a poly(ionic liquid) coating on SiO2, TiO2, boron nitride BN, and carbon nitride C3N4. The other set was, instead, obtained by immobilizing Keggin heteropolyacid H3PW12O40 onto poly-imidazolium functionalized materials. All the catalysts, including the bare supports, were subjected to physical and chemical characterization by XRD, SEM, Specific Surface Area and pore size measurements, TGA, FTIR, and acidity-basicity measurements. The catalytic activity of the materials was tested versus the fructose dehydration in water solution at two di…

Prolinamide-Supported Polystyrene: a Novel Highly Recyclable Organocatalyst for the Asymmetric Aldol Reaction

2008

Multilayered supported ionic liquids as catalysts for chemical fixation of carbon dioxide

2011

Multilayered, covalently supported ionic liquid phase (mlc-SILP) materials were synthesized by using a new approach based on the grafting of bis-vinylimidazolium salts on different types of silica or polymeric supports. The obtained materials were characterized and tested as catalysts in the reaction of supercritical carbon dioxide with various epoxides to produce cyclic carbonates. The material prepared by supporting a bromide bis-imidazolium salt on the ordered mesoporous silica SBA-15 was identified as the most active catalyst for the synthesis of cyclic carbonates and displayed improved productivity compared with known supported ionic liquid catalysts. The catalyst retained its high act…

ChemInform Abstract: Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives

2012

L-prolina supportata su polistirene: un versatile organocatalizzatore eterogeneo

2007

Supported Organocatalysts: a Powerful Tool in Organic Synthesis

2012

Polymer solar cells with novel fullerene-based acceptor

2004

Abstract Alternative acceptor materials are possible candidates to improve the optical absorption and/or the open circuit voltage of polymer–fullerene solar cells. We studied a novel fullerene-type acceptor, DPM-12, for application in polymer–fullerene bulk heterojunction photovoltaic devices. Though DPM-12 has the identical redox potentials as methanofullerene PCBM, surprisingly high open circuit voltages in the range V OC =0.95 V were measured for OC 1 C 10 -PPV:DPM-12-based samples. The potential for photovoltaic application was studied by means of photovoltaic characterization of solar cells including current–voltage measurements and external quantum yield spectroscopy. Further studies …

Hydrophobically directed aldol reactions: polystyrene-supported L-proline as a recyclable catalyst for direct asymmetric aldol reactions in the prese…

2007

A simple synthetic methodology for the preparation of a polystyrene- supported L-proline material is reported, and this material has been used as catalyst in direct asymmetric aldol reactions between several ketones and arylaldehydes to furnish aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water or methanol, at lower levels of conversion in the latter case. This solvent effect, coupled with the observed high stereoselectivities, has been ex- Introduction In the last decade organocatalysis has became a field of great interest.[1] Organocatalysts are metal-free small organic molecules that are able t…

Carbon Nanostructures: Covalent and Macromolecular Chemistry

2012

The aim of this introductory chapter is to bring to the attention of the readers the achievements made in the chemistry of carbon nanostructures and, mostly, in the chemistry of fullerenes, carbon nanotubes (CNTs), and the most recent graphenes. Since the discovery of fullerenes in 1985 and their further preparation in multigram amounts, the chemistry and reactivity of these molecular carbon allotropes have been well established. Actually, this chemical reactivity has been used as a benchmark for further studies carried out in the coming carbon nanotubes (single and multiple wall) and graphenes. Assuming that the fundamental chemistry of fullerenes is known and basically corresponds to that…

Cover Feature: Tuneable Emission of Polyhedral Oligomeric Silsesquioxane Based Nanostructures that Self‐Assemble in the Presence of Europium(III) Ion…

2020

A study on the stability of carbon nanoforms–polyimidazolium network hybrids in the conversion of co2 into cyclic carbonates

2021

Three different carbon nanoforms (CNFs), single-walled and multi-walled carbon nanotubes (SWCNTs, MWCNTs) and carbon nanohorns (CNHs), have been used as supports for the direct polymerization of variable amounts of a bis-vinylimidazolium salt. Transmission electron microscopy confirmed that all CNFs act as templates on the growth of the polymeric network, which perfectly covers the nanocarbons forming a cylindrical (SWCNTs, MWCNTs) or spherical (CNHs) coating. The stability of these hybrid materials was investigated in the conversion of CO2 into cyclic carbonate under high temperature and CO2 pressure. Compared with the homopolymerized monomer, nanotube-based materials display an improved c…

Asymmetric Aldol Reaction with Polystyrene-Supported Proline-Based Catalysts

2009

REVERSE ELECTRODIALYSIS HEAT ENGINE: Low-grade Waste Heat into Electricity

Our society is undergoing a progressive change about the life style and habits. The world population is continuously increasing with 7.6 billion of human beings in 2018, resulting in an increasingly demand of resources in terms of food, water and energy. The exploitation of the planet resources since the first Industrial Revolution, results today in an unsustainable condition, which requires fundamental changes. In particular, in the energy sector the adoption of fossil fuels as the main energy source for human beings’ activities resulted in a strong impact on our planet, leading to climate changes and environmental pollution. Nowadays these aspects have induced society to a substantial cha…

Nuovi ibridi [60]fullerene-liquido ionico

2014

Donor-Acceptor Polythiophene Copolymers with Tunable Acceptor content for Photoelectric Conversion Devices

2004

The synthesis and characterization of a new series of substituted polythiophenes containing an electron acceptor anthraquinone moiety in the side chain are reported. The acceptor molar content was varied by the co-polymerization of both alkylthiophene and thiophene bearing anthraquinone monomers in different ratios. NMR analysis shows a good correlation between the monomer feed composition at the beginning of the polymerization and the actual unit composition of the backbone. The conjugation length and the chemical composition of the copolymers as a function of the molecular weight have been studied by size exclusion chromatography. Small angle X-ray scattering and UV-Vis absorption spectra…

White light emitting silsesquioxane based materials: the importance of a ligand with rigid and directional arms

2022

The synthesis of a novel polyhedral oligomeric silsesquioxane functionalized with eight rigid and directional terpyridine-based arms (Ter-POSS) was successfully achieved via a Sonogashira reaction. The POSS based ligand was extensively characterized using different techniques including 1H, 13C and 29Si NMR as well as UV-Vis and fluorescence spectroscopies. The assembly of these nano-caged units in the presence of different transition metal ions (Fe2+, Zn2+ and Cu2+) as well as of a cation from the lanthanides (Eu3+) was investigated using absorption and emission spectroscopies. The final materials display an evident emission in different regions of the visible spectrum as a function of the …

Palladium Supported on Cross-Linked Imidazolium Network on Silica as Highly Sustainable Catalysts for the Suzuki Reaction under Flow Conditions

2013

Highly cross-linked imidazolium-based materials, obtained by radical oligomerization of bis-vinylimidazolium salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer-Emmett-Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy). The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds in high yields working with only 0.1 mol% of …

L-Prolina supportata su polistirene: un versatile catalizzatore eterogeneo

2007

Cross-Linked Polyamine from Imidazolium-Based Materials: A Simple Route to Useful Catalytic Materials

2018

Cross-linked polyamine-based materials were easily prepared by reduction of the corresponding cross-linked imidazolium-based materials with sodium borohydride in hot ethanol. Overall, the synthetic procedure is based on the polymerization of a suitable bis-vinylimidazolium salt with or without a suitable support, such as silica or silica-coated magnetic nanoparticles (γ-Fe2O3@SiO2), followed by reduction. This simple approach allows the synthesis of materials based on a network of secondary and tertiary amines. Materials were characterized by13C cross-polarization magic angle spinning NMR (13C CPMAS NMR), proton spin-lattice relaxation times in the rotating frame (T1ρH) and thermogravimet…

Heterogenizing palladium tetraiodide catalyst for carbonylation reactions

2022

We report the first example of successful heterogenization of the classical PdI42- carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI4@MWCNT-imi-X, X = Br, I) present the PdI42- anion supported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI4@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reaction, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50–84%, starting from various substrates). The heterogeneous catalyst could be easil…

Thiazolium-based catalysts for the etherification reaction of benzylic alcohols under solvent-free condition

2015

Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction me…

Correction: Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions

2017

Correction for ‘Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions’ by Francesco Giacalone et al., J. Mater. Chem. A, 2016, 4, 17193–17206.

Recyclable Heterogeneous and Low-Loading Homogeneous Chiral Imidazolidinone Catalysts for α-Alkylation of Aldehydes

2014

Two polystyrene-supported and six homogeneous MacMillan imidazolidinone catalysts were prepared and tested for the asymmetric α-alkylation of propanal with benzodithiolylium tetrafluoroborate. The chiral imidazolidinone was linked to polystyrene through the N-3 atom or through the phenyl ring and their catalytic activity was compared with that of their unsupported precursors. This comparison has allowed us to find an unsupported catalyst that displays high catalytic activity down to 5 or 2 mol % at room temperature with a high level of enantioselectivity also when used with hexanal and 3-phenylpropanal. In addition, one of the heterogeneous materials was revealed to be highly recyclable for…

New substituted imidazolidinone as low loading catalyst for α-alkylation of aldehydes

2013

Sistemi TEMPO-C60 come Catalizzatori Riciclabili Attivi nell’Ossidazione di Alcoli

2013

Modified nanocarbons as catalysts in organic processes

2019

The application of nanocarbons as useful scaffolds for the production of a wide range of catalytic systems is an ever-growing field as witnessed by the huge amount of research on this topic. Both covalent and non-covalent modifications of nanocarbons represent the main routes to gain access to hybrid nanostructured catalysts. In this chapter the attention will be focused on nanocarbons, namely, fullerene, nanotubes, and graphene, employed for catalytic purposes covering both organocatalytic and metal-based (metal nanoparticles, organometallic complexes) reactions, whereas simple physical mixtures of nanocarbons and metal nanoparticles as well as examples dealing with electrocatalysis or pho…

Salt extraction regeneration technologies

2022

Abstract A salinity gradient power heat engine is a novel sustainable technology for the conversion of low-grade waste heat (T  This chapter presents an overview of the main regeneration technologies based on the “salt extraction strategy” reported in the literature. A salt extraction regeneration unit takes advantage of the property of specific chemical compounds to shift from a soluble form to separable species in solution allowing the salt transfer between the exhausted solutions and aiding their regeneration. The regeneration processes reported here are classified into (i) switchable solubility salts and (ii) thermolytic salts. The first class includes compounds characterized by thermal…

Fullerene-Containing Polymers: An Overview

2009

Supported Imidazolium Functionalized POSS Hybrids as Palladium Platform for C-C Cross-Couplings

2018

Lo sviluppo di catalizzatori per i processi di conversione della CO2 è una tematica che sta rivestendo un ruolo di rilevante importanza in ambito non soltanto accademico ma anche industriale grazie alla possibilità di trasformare un rifiuto, quale il diossido di carbonio, in una vasta gamma di prodotti. Nel presente lavoro, nuovi materiali ibridi costituiti da silsesquiossani poliedrici oligomerici (POSS) supportati su silice e funzionalizzati con sali di imidazolio sono stati progettati per la fissazione della CO2. 1 Tutti i solidi sono stati ampiamente caratterizzati e testati per la sintesi di carbonati ciclici tramite reazione tra CO2 ed epossidi in condizioni di reazione solvent-free (…

ChemInform Abstract: Novel Prolinamide-Supported Polystyrene as Highly Stereoselective and Recyclable Organocatalyst for the Aldol Reaction.

2008

A new prolinamide derivative anchored to a polystyrene support has been straightforwardly prepared and employed as heterogeneous catalyst in the direct asymmetric aldol reaction with good results in terms of yield and stereoselectivity. The optimal reaction conditions were found when a 1:2 (v/v) water/chloroform mixture was used. This mixture was the best compromise between the good swelling properties of chloroform and the formation of a concentrated organic phase due to the presence of water. Noticeably, the enantioselectivities obtained employing acetone as ketone were, to the best of our knowledge, the highest achieved with a supported proline derivative. This catalyst can be easily rec…

Probing molecular wire: synthesis of donor-acceptor ensembles exhibiting long range electron transfer

2005

A series of donor–acceptor arrays (C60–oligo-PPV–exTTF; 16–20) incorporating p-conjugated oligo(phenylenevinylene) wires (oligo-PPV) of different length between p-extended tetrathiafulvalene (exTTF) as electron donor and C60 as electron acceptor has been prepared by multistep convergent synthetic approaches. The electronic interactions between the three electroactive species present in 16–20 were investigated by UV-visible spectroscopy and cyclic voltammetry (CV). Our studies clearly show that, although the C60 units are connected to the exTTF donors through a p-conjugated oligo- PPV framework, no significant electronic interactions are observed in the ground state. Interestingly, photoindu…

Cross-Linked Imidazolium Salts as Scavengers for Palladium.

2014

Five imidazolium-based materials have been synthesised and used for the first time as palladium scavengers. Radical reactions of suitable bis-vinylimidazolium salts led to a series of insoluble materials through homo-polymerisation, immobilisation with a 3-mercaptopropyl-modified silica gel or co-polymerisation with ethylene glycol dimethylacrylate. These materials were screened as palladium scavengers with a set of palladium(0) and palladium(II) compounds in different solvents and at different starting amounts of palladium. In many cases, residual amounts of palladium were lower than 5 ppm, as requested for the manufacture of active pharmaceutical ingredients and fine chemicals. The applic…

An Atom-Economical Approach to Functionalized Single-Walled Carbon Nanotubes: Reaction with Disulfides

2013

Owing to their unique structure, thermal stability, and mechanical and electronic properties, single-walled carbon nanotubes (SWCNTs) have been a subject of continuous and intense interest. However, various applications in many fields, such as molecular electronics, solar cells, and nanomedicine, often require the development of reproducible protocols for the chemical modification of SWCNTs. In fact, one of the main drawbacks of the use of SWCNTs is their tendency to aggregate and intrinsic poor solubility, which prevent their manipulation and limit their potential. To date, several methods have been described for the chemical functionalization of SWCNTs; however, new versatile and reliable…

Long lived photoinduced charges in donor-acceptor anthraquinone substituted thiophene copolymers

2006

The photoinduced charge-transfer properties of a series of polyalkylthiophene copolymers, carrying anthraquinone substituents covalently linked to the conjugated backbone, have been studied in the solid state by photoinduced absorption (PA) and light-induced electron spin resonance (LESR) spectroscopy. The measurements indicate the formation of metastable charges arising from the photoinduced electron transfer from the polythiophene backbone to the anthraquinone moieties. At low temperatures (below 200 K), long-lived persistent charges are formed, exhibiting lifetimes that extend for several minutes; their recombination kinetics has been studied by following the formation and decay of the P…

Imidazolium-Functionalized Carbon Nanohorns for the Conversion of CO2 Unprecedented Increase of Catalytic Activity after Recycling

2017

Carbon nanohorns (CNHs) were selected as a novel catalytic platform for the design of imidazolium based hybrid materials able to promote the conversion of carbon dioxide into cyclic carbonates. Several heterogeneous catalysts were prepared using a one-step procedure based on the radical polymerization of various bis-vinylimidazolium salts in the presence of pristine CNHs. The as-synthesized materials were tested for the fixation of CO2 into epoxides. The excellent catalytic performances were evaluated in terms of turnover number and productivity. The versatility of the above hybrids was proved using several epoxides as substrate. Catalysts recyclability was successfully verified for several…

Testing molecular wires

2006

Materiali catalitici a base di nanoparticelle di palladio immobilizzate su nanoforme di carbonio

2019

Organocatalytic Alcohol Oxidation Catalyzed by Recyclable TEMPO-functionalized [60]fullerene

2014

New biocides based on imidazolinium-functionalised hybrid mesoporous silica nanoparticles

2022

Here, we report the development of a new biocide based on hybrid mesoporous silica nanoparticles (MSN). The MSN was synthesized by condensation method in emulsion followed by grafting with two different silylated ionic liquid moieties, namely butyl imidazolinium bromide and imidazolinium propansulfonate betaine. Features of nanoparticles were characterized by Thermogravimetry, Infrared and ss-NMR Spectroscopy, and Transmission Electron Microscopy. The antibacterial properties were tested against a Gram-positive bacterial strain previously isolated from artefacts of interest in the field of Cultural Heritage. Interestingly, the hybrid material presents an antibacterial activity higher than i…

Front Cover Picture: SBA‐15/POSS‐Imidazolium Hybrid as Catalytic Nanoreactor: the role of the Support in the Stabilization of Palladium Species for C…

2019

Proline- and prolinamide-supported polystyrene: powerful and highly recyclable organocatalysts for the asymmetric aldol reaction

2009

Encyclopedia of Polymer Science and Technology

2007

A general overview of the different types of C60-containing polymers according to their chemical structure and the consideration of their general synthetic routes as well as their plausible applications is given. The aim of this work is to establish a classification of the many fullerenecontaining polymers reported in the literature in order to clarify the field for all those chemists interested in the topic. Needless to say that not all the examples known are covered, but those more representative or appealing for the authors.

Hydrogen bonding donor–acceptor carbon nanostructures

2007

Supported proline and proline-derivatives as recyclable organocatalysts

2008

In the last eight years, L-proline and L-proline derivatives, such as substituted prolinamides or pyrrolidines, have been successfully used as organocatalysts in several reactions. In this critical review we summarize the immobilization procedures of such organocatalysts highlighting their application, recoverability and reusability (86 references).

Thiazolium-­‐based catalysts for the etherification of benzylic alcohols under solvent-­free conditions

2015

In this work, thiazolium and imidazolium hybrid materials (SBA-15-Thia and SBA-15-Imi) were prepared by grafting the bis-vinylthiazolium or imidazolium salts onto thiol functionalized SBA-15 mesostructured silica. The catalytic activity was tested for the etherification of 1-phenylethanol, in heterogeneous conditions. The reactions were performed under different gas phases and reaction times. The SBA-15-Thia displayed an excellent catalytic performance, also with others benzyl alcohols. This material was successfully used in seven consecutive runs. Further studies were carried out in homogenous conditions. The results obtained allow proving that oxygen play an active role in the reaction pr…

A Liquid-Liquid Biphasic Homogeneous Organocatalytic Aldol Protocol Based on the Use of a Silica Gel Bound Multilayered Ionic Liquid Phase

2012

An innovative two stage liquid–liquid biphasic homogeneous protocol for the asymmetric organocatalytic aldol reaction is proposed, based on the use of the cis-ion-tagged proline 8 dissolved in the liquid film of a multilayered ionic liquid covalently bonded to silica gel 4. The resulting catalytically active material 9 is first soaked with cyclohexanone in the presence of water, resulting in a semi-transparent gel, then the aldehyde is added and the mixture stirred at RT. In the first stage, 4 acts as a catalyst reservoir that delivers 8 to the cyclohexanone phase allowing the reaction to take place homogeneously. In the second stage, cyclohexanone is removed under vacuum and the resulting …

Hybrid catalysts for CO 2 conversion into cyclic carbonates

2019

The conversion of carbon dioxide into valuable chemicals such as cyclic carbonates is an appealing topic for the scientific community due to the possibility of valorizing waste into an inexpensive, available, nontoxic, and renewable carbon feedstock. In this regard, last-generation heterogeneous catalysts are of great interest owing to their high catalytic activity, robustness, and easy recovery and recycling. In the present review, recent advances on CO 2 cycloaddition to epoxide mediated by hybrid catalysts through organometallic or organo-catalytic species supported onto silica-, nanocarbon-, and metal-organic framework (MOF)-based heterogeneous materials, are highlighted and discussed.

Simple and low loading catalysts for asymmetric aldol reaction under aqueous condition

2009

ChemInform Abstract: Supported Proline and Proline-Derivatives as Recyclable Organocatalysts

2008

In the last eight years, L-proline and L-proline derivatives, such as substituted prolinamides or pyrrolidines, have been successfully used as organocatalysts in several reactions. In this critical review we summarize the immobilization procedures of such organocatalysts highlighting their application, recoverability and reusability (86 references).

ChemInform Abstract: Covalently Supported Ionic Liquid Phases: An Advanced Class of Recyclable Catalytic Systems

2016

In this review, the most recent advances in the synthesis and catalytic applications of covalently supported ionic liquid (IL) phases will be discussed. This class of recyclable catalytic materials is based on the covalent attachment of several types of ammonium salts, usually imidazolium, but also thiazolium, triazolium, and pyrrolidinium salts, on the surface of different supports, for example, silica, periodic mesoporous organosilica, polystyrene, magnetic-based materials, carbon nanotubes (NTs), halloysite NTs, polyhedral oligomeric silsesquioxane (POSS), and fullerenes. Moreover, poly(ionic liquid) materials, in which the IL-based structure also acts as a support, will be considered. T…

Imidazolium-Functionalized Carbon Nanohorns for the Conversion of Carbon Dioxide

2016

Six new hybrid materials composed of carbon nanohorns (CNHs) and highly cross-linked imidazolium salts were easily synthesized using a one-step procedure based on the radical oligomerization of bis-vinylimidazolium salts (bVImiX) in the presence of pristine CNHs. The hybrid materials were characterized and employed as the sole catalysts for the conversion of carbon dioxide into cyclic carbonate by reaction with epoxides. The solids displayed excellent turnover number and productivity. Moreover, four catalysts were investigated in recycling experiments. Two catalysts containing an octyl linker between the imidazolium units and a bromide or an iodide anion showed no loss in activity after thr…

Supported Organocatalysts as a Powerful Tool in Asymmetric Synthesis

2010

Advances in organic and organic-inorganic hybrid polymeric supports for catalytic applications

2016

In this review, the most recent advances (2014–2016) on the synthesis of new polymer-supported catalysts are reported, focusing the attention on the synthetic strategies developed for their preparation. The polymer-supported catalysts examined will be organic-based polymers and organic-inorganic hybrids and will include, among others, polystyrenes, poly-ionic liquids, chiral ionic polymers, dendrimers, carbon nanotubes, as well as silica and halloysite-based catalysts. Selected examples will show the synthesis and application in the field of organocatalysis and metal-based catalysis both for non-asymmetric and asymmetric transformations.

New recyclable catalysts for direct asymmetric aldol reaction. L-proline or H-Pro-Pro-Asp-NH2 immobilized on new ionic liquid modified silica gels

2008

Carbon Nanostructures: Covalent and Macromolecular Chemistry

2012

The aim of this introductory chapter is to bring to the attention of the readers the achievements made in the chemistry of carbon nanostructures and, mostly, in the chemistry of fullerenes, carbon nanotubes (CNTs), and the most recent graphenes. Since the discovery of fullerenes in 1985 and their further preparation in multigram amounts, the chemistry and reactivity of thesemolecular carbon allotropes have been well established. Actually, this chemical reactivity has been used as a benchmark for further studies carried out in the coming carbon nanotubes (single andmultiple wall) and graphenes. Assuming that the fundamental chemistry of fullerenes is known and basically corresponds to that o…

“Nonsolvent” Applications of Ionic Liquids in Organocatalysis

2012

This chapter is organized in three sections (see Figure 10.1 ): 2. Immobilization of ionic liquids and organocatalysts 2.1 Covalently attached “ ionic liquid ” moieties as supports 2.2 Covalently attached “ ionic liquid ” moieties as linkers 2.3 Covalently attached “ ionic liquid ” moieties as organocatalysts

Single-Walled Carbon Nanotube–Polyamidoamine Dendrimer Hybrids for Heterogeneous Catalysis

2016

We report the synthesis and catalytic properties of single-walled carbon nanotube-polyamidoamine dendrimers hybrids (SWCNT-PAMAM), prepared via a convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of [PdCl4](2-), led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (T…

Fullerene as a Platform for Recyclable TEMPO Organocatalysts for the Oxidation of Alcohols

2014

[60]Fullerene has been employed successfully as a molecular platform to anchor 12 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties. Such an octahedrally substituted C60-derivative has been employed as an organocatalyst for the oxidation of primary and secondary alcohols using the Anelli protocol. The reaction showed a general applicability to various alcohols, and the catalyst was recovered easily and could be recycled for at least seven cycles with no loss in catalytic activity. EPR spectroscopy studies revealed that the amount of radicals decreases during the catalytic cycles, even if the recovered material still displays unchanged catalytic activity. This new approach paves the way …

Water in stereoselective organocatalytic reactions

2009

In this review, recent advances in asymmetric organocatalytic reactions carried out with variable amounts of water, from substoichiometric to a large excess (reaction medium), are discussed. We also summarize several proposed mechanisms for the different possibilities of the action of water both in the increased activity of the catalyst and in the asymmetric induction. Finally, the application of this catalytic methodology to the enantioselective synthesis of valuable compounds through enamine or iminium catalysis is presented.

Improved performance in flexible organic solar cells by using copolymeric phase-separation modulators

2018

One of the main problems related to the low performance of the organic solar cells (OSCs), concerns the low mobility of the materials constituting the heterojunction. Indeed, the poor charge transport in the active layer is the principal cause of a competition between separation and recombination of the photogenerated carriers. In this regard, a major obstacle to enhance OSCs efficiency is developing strategies to optimize the exciton dissociation and, consequently, the charge collection at the electrodes. Donor and acceptor systems must be well mixed on the length scale of 5 – 20 nm (exciton diffusion length) to meet the criteria for efficient exciton dissociation. In addition, the network…

Cyclodextrin-[60]fullerene conjugates: synthesis, characterization, and electrochemical behavior

2006

Three different functionalized β-cyclodextrins (β-CDs) bearing the C60 moiety linked covalently have been prepared in good yields by reaction between the parent β-CD and [60]fullerene via 1,3-dipolar cycloaddition. These compounds have been fully spectroscopically characterized and their electrochemical behavior has been investigated. Surprisingly, the electrochemical properties of the C60 cage remain unaltered even after chemical functionalization, making these systems very appealing as supramolecular hosts for electron-transfer processes.

Catechol-Functionalized Carbon Nanotubes as Support for Pd Nanoparticles

2022

Carbon nanotubes have been covalently functionalized with catechol moieties through the formation of the corresponding aryl radicals obtained by reacting 4-aminocatechol with isoamyl nitrite. The functionalized multiwalled carbon nanotubes have been in turn used to immobilize Pd(II) ions on its surface forming catechol-Pd complexes, which were reduced to Pd nanoparticles (NPs). The so-obtained hybrid material has been characterized by means of thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). This latter technique allowed to estimate the nanoparticle size (5.7 +/- 2.8 nm) wh…

Mimicking Photosynthesis: Covalent And Supramolecular [60]Fullerene Based Donor-Acceptor Ensembles

2004

Buckyballs

2013

Buckyballs represent a new and fascinating molecular allotropic form of carbon that has received a lot of attention by the chemical community during the last two decades. The unabating interest on this singular family of highly strained carbon spheres has allowed the establishing of the fundamental chemical reactivity of these carbon cages and, therefore, a huge variety of fullerene derivatives involving [60] and [70]fullerenes, higher fullerenes, and endohedral fullerenes have been prepared. Much less is known, however, of the chemistry of the uncommon non-IPR fullerenes which currently represent a scientific curiosity and which could pave the way to a range of new fullerenes. In this revi…

Main-Chain and Side-Chain C60-Polymers

2009

Polystyrene-supported organocatalysts for alfa-selenenylation and Michael reactions. A common post-modification approach for catalytic differentiation

2011

Three different resin-supported catalysts have been prepared by using the well established post-modification approach by means of thiol-ene coupling reaction. Two catalysts were tested for the first time in the asymmetric α-selenenylation of propanal, while the third catalyst was used in the Michael addition reaction. While the preliminary results are not encouraging in the case of supported Jørgensen’ catalyst, interesting data have been collected with both for the supported MacMillan and prolyl-prolinol catalysts. In fact, these catalysts displayed good activity and selectivity. A reversed enantioselectivity in the α-selenenylation was observed by changing the polarity of the solvent. Fin…

Highly selective detection of Epinephrine at oxidized Single-Wall Carbon Nanohorns modified Screen Printed Electrodes (SPEs)

2014

Oxidized Single-Wall Carbon Nanohorns (o-SWCNHs) were used, for the first time, to assemble chemically modified Screen Printed Electrodes (SPEs) selective towards the electrochemical detection of Epinephrine (Ep), in the presence of Serotonine-5-HT (S-5HT), Dopamine (DA), Nor-Epineprhine (Nor-Ep), Ascorbic Acid (AA), Acetaminophen (Ac) and Uric Acid (UA). The Ep neurotransmitter was detected by using Differential Pulse Voltammetry (DPV), in a wide linear range of concentration (2-2500 μM) with high sensitivity (55.77 A M(-1) cm(-2)), very good reproducibility (RSD% ranging from 2 to 10 for different SPEs), short response time for each measurement (only 2s) and low detection of limit (LOD=0.…

Supported Organocatalysts as a Powerful Tool in Organic Synthesis

2010

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Tetrathiafulvalene-based molecular nanowires.

2008

A new molecular wire suitably functionalized with sulfur atoms at terminal positions and endowed with a central redox active TTF unit has been synthesized and inserted within two atomic-sized Au electrodes; electrical transport measurements have been performed in STM and MCBJ set-ups in a liquid environment and reveal conductance values around 10(-2) G0 for a single molecule.

Immobilizzazione di dipeptidi su resina polistirenica ed impiego in sintesi stereoselettive: risultati preliminari

2008

Tuning of the photoinduced charge transfer process in donor-acceptor "double cable" copolymers

2003

The covalent linking of acceptor molecules to electron donating conjugated polymer is an approach for the development of new photoactive materials for the fabrication of organic photoelectric conversion devices. With this strategy we have designed a polyalkylthiophene copolymer series containing in the side chain anthraquinone molecules as electron acceptor. The peculiar features of the copolymers are the good processability and the ease in tailoring the content of acceptor moieties. Their potential use as photoactive materials is investigated in terms of the photoinduced charge transfer properties, studied by FTIR photoinduced absorption and Light Induced Electron Spin Resonance spectrosco…

Non-conventional methods and media for the activation and manipulation of carbon nanoforms

2013

Very often, chemical transformations require tedious and long procedures, which, sometimes, can be avoided using alternative methods and media. New protocols, enabling us to save time and solvents, allow us also to explore new reaction profiles. This Tutorial Review focuses on the physical and chemical behavior of carbon nanoforms, CNFs (fullerenes, nanotubes, nanohorns, graphene, etc.) when non-conventional methods and techniques, such as microwave irradiation, mechano-chemistry or highly ionizing radiations are employed. In addition, the reactivity of CNFs in non-conventional media such as water, fluorinated solvents, supercritical fluids, or ionic liquids is also discussed.

Mimicking photosynthesis: covalent [60]fullerene-based donor–acceptor ensembles

2004

Abstract Within the context of exploring photophysical properties of [60]fullerene-based donor–acceptor ensembles, we highlight in this contribution an approach towards the synthesis of a novel series of donor-bridge-acceptor, C 60 –wire– ex TTF , ensembles that incorporate p -phenylenevinylene oligomers, in which the conjugation length has been systematically increased, as bridges that connect π-extended tetrathiafulvalenes (exTTF) (electron donor) with [60]fullerene (electron acceptor). This molecular design allows probing the effects of distance and rate, at which electron transfer processes occur, as well as the molecular-wire behavior of the oligo-PPV fragments.

Catalytic Synergism in a C60IL10TEMPO2 Hybrid in the Efficient Oxidation of Alcohols

2014

A novel fullerene (5:1)hexakisadduct bearing two 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals and ten 1-propyl-3-methylimida- zolium bromide moieties has been synthesized and characterized. Such an C60IL10TEMPO2 hybrid has been successfully employed as a catalyst in the se- lective oxidation of a wide series of alcohols and is highly active at just 0.1 mol% loading. Moreover, it can be easily recovered by adsorption onto a multi- layered covalently-linked SILP phase (mlc-SILP) through a "release and catch" approach and reused for up to 12 cycles without loss in efficiency. Inter- estingly, a catalytic synergistic effect of TEMPO and imidazolium bromide moieties combined in the same…

Multi-layered, covalently supported ionic liquid phase (mlc-SILP) as highly cross-linked support for recyclable palladium catalysts for the suzuki re…

2011

The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, sma…

DNA-Binding and Anticancer Activity of Pyrene-Imidazolium Derivatives

2016

DNA-binding investigations showed that two different derivatives endowed with pyrene and imidazolium moieties, 1 and 2, strongly bind both double-stranded DNA and telomeric sequences in G-quadruplex (G4) conformation. The values of the DNA-binding constants indicate that 1 and 2 show preferential affinity for G4-DNA, of about one and two orders of magnitude, respectively. Moreover, 1 and 2 inhibit short and long-term proliferation of breast cancer cell lines in a time- and dose-dependent fashion. Remarkably, senescence assays indicate that telomeric G4-DNA is a possible biotarget for the cytotoxic activity of 2. Molecular dynamics simulations suggest that the stronger binding of 2 with G4-D…

A Straightforward Electroactive π-Extended Tetrathiafulvalene (exTTF) Building Block

2012

The synthesis and X-ray structure of a new and readily available exTTF derivative (6) bearing a methyltriphenylphosphonium bromide moiety as a new building block for the construction of electroactive molecules is reported. The phosphonium salt 6, which was prepared in one step from 2-hydroxymethyl-exTTF as a stable yellow solid in 84 % yield, efficiently undergoes Wittig olefination reactions with a variety of aldehydes to predominantly form the E isomer. Electronic spectra and cyclic voltammetry of the novel compounds reveal the electronic communication between the electroactive units.

Organocatalizzatori e liquidi ionici supportati: nuovi materiali in sintesi organica

2011

Nell’ultimo decennio l’organocatalisi e i liquidi ionici hanno rappresentato due campi di grande interesse scientifico. Gli organocatalizzatori hanno trovato particolare impiego in sintesi enantioselettive conducendo a prodotti finali con alte rese e selettività. I liquidi ionici sono stati estensivamente utilizzati come solventi alternativi e, opportunamente modificati, come catalizzatori o loro supporti. Uno sviluppo attuale che accomuna questi due campi di ricerca consiste nella possibilità di immobilizzazione di organocatalizzatori e liquidi ionici per trasformarli in materiali riciclabili con ampie capacità di utilizzo in chimica organica. Negli ultimi anni, il nostro gruppo di ricerca…

Templating effect of carbon nanoforms on highly cross-linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles

2019

Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and re…

Asymmetric aldol reaction in water catalyzed by polystyrene-supported proline

2007

Covalently Supported Ionic Liquid Phases: An Advanced Class of Recyclable Catalytic Systems

2016

In this review, the most recent advances in the synthesis and catalytic applications of covalently supported ionic liquid (IL) phases will be discussed. This class of recyclable catalytic materials is based on the covalent attachment of several types of ammonium salts, usually imidazolium, but also thiazolium, triazolium, and pyrrolidinium salts, on the surface of different supports, for example, silica, periodic mesoporous organosilica, polystyrene, magnetic-based materials, carbon nanotubes (NTs), halloysite NTs, polyhedral oligomeric silsesquioxane (POSS), and fullerenes. Moreover, poly(ionic liquid) materials, in which the IL-based structure also acts as a support, will be considered. T…

ChemInform Abstract: Non-Conventional Methods and Media for the Activation and Manipulation of Carbon Nanoforms

2014

Very often, chemical transformations require tedious and long procedures, which, sometimes, can be avoided using alternative methods and media. New protocols, enabling us to save time and solvents, allow us also to explore new reaction profiles. This Tutorial Review focuses on the physical and chemical behavior of carbon nanoforms, CNFs (fullerenes, nanotubes, nanohorns, graphene, etc.) when non-conventional methods and techniques, such as microwave irradiation, mechano-chemistry or highly ionizing radiations are employed. In addition, the reactivity of CNFs in non-conventional media such as water, fluorinated solvents, supercritical fluids, or ionic liquids is also discussed.

ChemInform Abstract: First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis-Hillman Reaction Between Alkyl Vinyl Ketones and Aryl …

2008

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …

Molecular Wires: Long-Range Electron Tunneling and Hopping in Novel Donor-Acceptor Ensembles

2004

Piezoresistive semi-transparent flexible sensors by bithiophene fulleropyrrolidine thin films

Piezoresistive sensors are considered among the fundamental components of the future wearable electronic devices, given their potential applications in artificial skin, motion capture and personalized medicine.[1-5] Here, we present a cost-effective, viable fabrication approach to realize piezoresistive sensors using a novel polymeric biotiophene fulleropyrrolidine system (bis-C60Bi) synthesized on flexible ITO/PET supports by electrochemical chronoamperometry. By applying an anodic potential (1.5 V) to a solution containing the monomer, it is possible to obtain a homogeneous semi-transparent thin film on the ITO/PET surface (see Figure). AFM, XPS, UV-vis have been employed to characterize …

ChemInform Abstract: Water in Stereoselective Organocatalytic Reactions

2009

In this review, recent advances in asymmetric organocatalytic reactions carried out with variable amounts of water, from substoichiometric to a large excess (reaction medium), are discussed. We also summarize several proposed mechanisms for the different possibilities of the action of water both in the increased activity of the catalyst and in the asymmetric induction. Finally, the application of this catalytic methodology to the enantioselective synthesis of valuable compounds through enamine or iminium catalysis is presented.

Cross-Linked Thiazolidine Network as Support for Palladium: A New Catalyst for Suzuki and Heck Reactions

2015

A thiazolidine-based material was used for the first time as support for palladium. The support was prepared by starting from a highly cross-linked thiazolium-based material, obtained by radical oligomerization of a bisvinylthiazolium dibromide salt in the presence of 3-mercaptopropyl-modified silica SBA-15. Palladium was immobilized by treatment with tetrachloropalladate salt. Reduction with sodium borohydride afforded a thiazolidine-based material that acted as ligands for the Pd species. The thiazolidine-based palladium catalyst was fully characterized and, working in only 0.1 mol% amount, displayed good activity in the Suzuki-Miyaura and in the Heck reactions. Several biphenyl and alken…

Supported C60-IL-PdNPs as extremely active nanocatalysts for C-C cross-coupling reactions

2016

A C60-ionic liquid hybrid has been covalently linked to three different solid supports, namely amorphous silica, SBA-15 and Fe2O3@SiO2, and the resulting materials have been employed as covalently supported ionic liquid phases (cSILP) in order to immobilize and stabilize palladium nanoparticles (PdNPs). These novel hybrid materials are based on a sort of "matryoshka" system (PdNPs@imidazolium-salt@C60@support) in which the imidazolium-based moieties have not been directly linked to the surface of the support, but they are present in an octopus-like spatial arrangement on the uniformly surface-distributed fullerenes. These materials have been fully characterized and successfully employed as …

Water in Organocatalytic Reactions

2013

Water is a green solvent: it is cheap, safe and environmentally friendly compared with organic solvents. Pfizer Corp. has defined a solvent guide that encourages the use of preferred solvents, for example, water or ethyl acetate, over usable solvents, for example, dimethyl sulfoxide (DMSO), and undesirable solvents, for example, dimethylformamide (DMF) [1]. However, chemical reactions carried out in or on water are not necessarily green reactions. Indeed, if we consider a reaction involving two species (A and B) and a product (C), the requirement for an ideal situation is when the product C has zero solubility and is quantitatively recovered by filtration, leaving no starting compounds A an…

Piezoresistive Sensors from Bithiophene-fulleropyrrolidine Bisadducts Thin-Films

The phenomenon of piezoresistivity in materials is based on the separation of conductive domains triggered by mechanical strains, resulting in a variation of the electrical resistance.1 This property is at the core of sensors for wearable electronics, e-skins, human motion detectors and machine learning devices.2 Fundamental requirements include lightness, good transparency, high flexibility and sensitivity to tiny deformations. However, the fabrication of a system integrating all these features is challenging. Herein, we show a semitransparent piezoresistive sensor realized by an electropolymerized bithiophene‐fulleropyrrolidine bisadduct onto ITO/PET3 (see Figure 1a). The good outcome of …

Sali di imidazolio multistrato supportati covalentemente: attività catalitica per la produzione di carbonati ciclici in scCO2 e nuovi supporti per ca…

2011

I liquidi ionici supportati (SILP) hanno trovato interessanti applicazioni sia nel campo delle reazioni catalizzate da metalli che in organocatalisi [1]. Inoltre, i SILP sono stati efficacemente impiegati in reazioni di apertura di epossidi in CO2 supercritica per fornire carbonati ciclici [2]. I liquidi ionici vengono generalmente supportati covalentemente attraverso la modificazione dei gruppi funzionali presenti sulla superficie del supporto, conducendo in tal modo alla formazione di un monostrato di liquido ionico supportato. Gli esempi di SILP legati covalentemente, in maniera tale da ottenere dei multistrato, sono rari. In questa comunicazione viene riportato un metodo per preparare d…

Chemical Fixation of Carbon Dioxide Catalysed by Multilayered Supported Ionic Liquids

2011

Chemical modification of carbon nanomaterials (SWCNTs, DWCNTs, MWCNTs and SWCNHs) with diphenyl dichalcogenides

2015

Control over chemical functionalization is a crucial point in the field of nanotechnology. Herein, we present the covalent functionalization of several carbon nanoforms (single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanohorns) by means of diphenyl dichalcogenides. These ones show different reactivity to the nanomaterials and are able to modify their electronic properties depending on the electronegativity of the functionalizing heteroatom. Theoretical calculations were also performed to support the experimental results. All the modified structured nanocarbons were thoroughly characterized by TGA Raman, XPS, UV/Vis/nIR, IR and TEM te…

Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Buildi…

2019

Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values,…

POSS nanostructures in catalysis

2020

Polyhedral oligomeric silsesquioxanes (POSS) are organic-inorganic hybrid molecules piquing the interest of researchers thanks to their synergistic features. The great versatility of POSS nanostructures arises from the easy tunability of peripheral organic moieties combined with the high thermal and chemical stability of the inner inorganic core. In this review, we highlight the use of POSS nanostructures as molecular precursors for the synthesis of homogeneous and heterogeneous catalysts able to promote many processes including alkene epoxidation, C-C bond formation, CO2 conversion, "click reactions", hydrogenation, and ethylene polymerisation, among others. In this scenario, POSS units fo…

Donor-acceptor “double-cable” polythiophene with tunable acceptor content

2004

Sintesi efficiente mediata da microonde di derivati di fullerene per dispositivi fotovoltaici organici

2014

Catalizzatori a base di nanocorni di carbonio-liquidi ionici per la conversione della CO2

2017

Nel presente lavoro sono stati impiegati nanocorni di carbonio (CNHs) come piattaforma catalitica per il design di nuovi materiali ibridi a base di sali di imidazolio per la conversione della CO2 in carbonati ciclici. A tale scopo sono stati preparati una serie di catalizzatori eterogenei mediante una procedura sintetica one-pot basata sulla polimerizzazione radicalica di vari sali di bis vinilimidazolio in presenza di nanocorni di carbonio. I suddetti materiali sono stati caratterizzati e testati con successo per la reazione di fissazione della CO2 in epossidi (Figura 1). Figura 1 Conversione della CO2 catalizzata da liquidi ionici supportati su CNHs Le performances catalitiche, valutate i…

Hydrogen Bonding Donor–Acceptor Carbon Nanostructure

2012

The natural process of photosynthesis is paradigmatic in converting sunlight into energy. This complicated process requires a cascade of energy- and electron-transfer events in a highly organised matrix of electron–donor, electron–acceptor and antennae units and has prompted researchers to emulate it. In fact, energy- and electron-transfer processes play a pivotal role in molecular-scale optoelectronics. In this chapter we compile a number of remarkable examples of noncovalent aggregates formed by the combination of carbon-based electroactive species (fullerenes and carbon nanotubes) hydrogen bonded with a variety of moieties. We will show that: (a) the connection of complementary electroac…

Carbon nanotube supported aluminum porphyrin-imidazolium bromide crosslinked copolymer

2022

The increased awareness of the catastrophic consequences caused by the accumulation of greenhouse gases into the atmosphere has generated a large mobilization aimed at CO2 mitigation. Herein, in the spirit of the transformation of a waste as CO2 into value added products, we propose an efficient preparation of two different hybrid systems based on aluminum chloride tetrastyrylporphyrin (TSP-Al-Cl) and 1,4-butanediyl-3,3′-bis-1-vinylimidazolium dibromide copolymerized in the presence (MWCNT-TSP-AlCl-imi) and in absence (TSP-AlCl-imi) of multi-walled carbon nanotubes (MWCNTs) for the CO2 utilization in the synthesis of cyclic carbonates. The so-prepared materials have been thoroughly characte…

Recyclable organocatalysts

2010

Molecular engineering of donor-acceptor ensembles: modulating the competition between photoinduced energy and electron transfer processes

2004

Molecular wires - long range electron tunneling and hopping in novel donor-acceptor ensembles

2004

As the change in ternary agent structure influence the chiral recognition ability of pyrene/heptakis-(6-amino)-(6-deoxy)-b-cyclodextrin

Advances towards highly active and stereoselective simple and cheap proline-based organocatalysts

2010

Ten 4-acyloxy-L-prolines were screened as catalysts at loadings of 2–0.1 mol-% for the direct asymmetric aldol reaction in water by using variable amounts of water. Among them, a new catalyst, the L-proline carrying a trans-4-(2,2-diphenylacetoxy) group, and a catalyst previously synthesized by us, the L-proline carrying a trans-4-(4-phenylbutanoyloxy) group, were found to be excellent catalysts for the aldol reaction between cyclohexanone or cyclopentanone and substituted benzaldehydes when employed in only 1 and 0.5 mol-%,respectively, at room temperature without additives. For such catalysts, high turnover numbers were obtained, which are among the highest values obtained for enamine org…

Polystyrene-supported proline and prolinamide. Versatile heterogeneous organocatalysts both for asymmetric aldol reaction in water and α-selenenylati…

2007

A simple and efficient synthesis of polystyrene-supported proline and prolinamide has been carried out. Polystyrene-supported proline has been used as organocatalyst in the asymmetric aldol reaction between cyclohexanone and substituted benzaldehydes in water without any additive. High yields, diastereoselectivities and ee values have been observed. The versatility of this resin was demonstrated in the α-selenenylation of aldehydes. Both proline and prolinamide resins gave high yields. Recycling studies showed that the proline resin gave better results than prolinamide resin.

Novel prolinamide-supported polystyrene as highly stereoselective and recyclable organocatalyst for the aldol reaction

2008

A new prolinamide derivative anchored to a polystyrene support has been straightforwardly prepared and employed as heterogeneous catalyst in the direct asymmetric aldol reaction with good results in terms of yield and stereoselectivity. The optimal reaction conditions were found when a 1:2 (v/v) water/chloroform mixture was used. This mixture was the best compromise between the good swelling properties of chloroform and the formation of a concentrated organic phase due to the presence of water. Noticeably, the enantioselectivities obtained employing acetone as ketone were, to the best of our knowledge, the highest achieved with a supported proline derivative. This catalyst can be easily rec…

Solid film versus solution-phase charge-recombination dynamics of exTTF-bridge-C60 dyads.

2005

The charge-recombination dynamics of two exTTF-C 6 0 dyads (exTTF=9,10-bis(l,3-dithiol-2-ylidene)-9,10-dihydroanthracene), observed after photoinduced charge separation, are compared in solution and in the solid state. The dyads differ only in the degree of conjugation of the bridge between the donor (exTTF) and the acceptor (C 6 0 ) moieties. In solution, photoexcitation of the nonconjugated dyad C 6 0 -BN-exTTF (1) (BN=1,1'-binaphthyl) shows slower charge-recombination dynamics compared with the conjugated dyad C 6 0 -TVB-exTTF (2) (TVB = bisthienylvinylenebenzene) (lifetimes of 24 and 0.6 μs, respectively), consistent with the expected stronger electronic coupling in the conjugated dyad.…

Cyclodextrin-[60]fullerene conjugates: Synthesis, characterization and electrochemical behavior

Supported Fullerene C60-Ionic Liquid Hybryds as New Catalytic Materials

2015

Imidazolium Based Cross-Linked Nanostructures from POSS molecular bricks for the Efficient Conversion of Carbon Dioxide

2019

Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular bricks for the synthesis of imidazolium cross-linked networks as heterogeneous catalyst for the conversion of carbon dioxide into cyclic carbonates via reaction with epoxides. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid state NMR, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates and outstanding productivity values. Several epoxides were r…

Polystyrene-supported organocatalysts for α-selenenylation and Michael reactions

2011

Abstract Three different resin-supported catalysts have been prepared by using the well established post-modification approach by means of thiol-ene coupling reaction. Two catalysts were tested for the first time in the asymmetric α-selenenylation of propanal, while the third catalyst was used in the Michael addition reaction. While the preliminary results are not encouraging in the case of supported Jorgensen’ catalyst, interesting data have been collected with both for the supported MacMillan and prolyl-prolinol catalysts. In fact, these catalysts displayed good activity and selectivity. A reversed enantioselectivity in the α-selenenylation was observed by changing the polarity of the sol…

A Simple Procedure for Oxidation of Alcohols using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl Acetate

2015

Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.

Concentration dependence of amplified spontaneous emission in two oligo-(p-phenylenevinylene) derivatives

2005

Amplified spontaneous emission sASEd in optically pumped polystyrene sPSd films doped with two different oligo-sp-phenylenevinylened derivatives sOPVsd, with three s3-OPVd and five s5-OPVd monomer units is reported. It is observed that there is a maximum content of oligomer s25 wt. % for 3-OPV and 20 wt. % for 5-OPVd that can be introduced in the films, due to degradation sin 3-OPVd and ASE quenching sin 5-OPVd. Optimal concentrations swith minimum pump-intensity thresholds for the observation of ASEd of 15 wt. % and 9 wt. % are measured for the trimer and the pentamer, respectively. The concentration dependence of the ASE threshold is discussed in terms of the optical absorption spectra. G…

Cross-Linked Polyamine from Imidazolium-Based Materials: A Simple Route to Useful Catalytic Materials

2018

Fullerene-containing Polymers

2012

In the present chapter, the different C60-based polymers have been classified according to structural parameters and the different synthetic strategies to prepare them have been highlighted. Two new families have been added, namely fullerene–nanotubes hybrid and DNA–fullerene hybrid, due to the nondiscrete nature of the corresponding members. Finally, fullerene-containing polymers’ most promising applications have been discussed, mainly focusing on nonlinear optics, DNA-cleaving and photovoltaic properties.

Novel Imidazolium Based Catalyst for the Chemical Fixation of Carbon Dioxide

2015

Bending Sensors Based on Thin Films of Semitransparent Bithiophene-Fulleropyrrolidine Bisadducts

2020

In this study, a novel bithiophene‐fulleropyrrolidine bisadducts system (bis‐Th2PC 60 ) was synthesized and electropolymerized by chronoamperometry onto flexible ITO/PET substrates. The resulting semitransparent thin film was characterized by XPS, FT‐IR, cyclic voltammetry and optical techniques, confirming the good outcome of the electropolymerization process. AFM investigations permitted to highlight an inherent disordered granular morphology, in which the grain‐to‐grain separation depends upon the application of bending. The electrical resistance of the thin film was characterized as function of bending (in the range 0°‐90°), showing promising responsivity to low bending angles (10°‐30°)…

POSS-Al-porphyrin-imidazolium cross-linked network as catalytic bifunctional platform for the conversion of CO2 with epoxides

2023

Two heterogeneous catalysts were prepared with the aim of following the promising path of CO2 fixation into epoxides. The synthetic procedure involves a radical copolymerization of an octavinylsilsesquioxane as inorganic core building block and tetrastyrylporphyrin aluminum chloride monomer (TSP-AlCl) in presence (POSS-TSP-AlCl-imiBr) or in absence (POSS-TSP-AlCl) of a bis-vinylimidazolium bromide salt (bis-imiBr), in order to investigate if the bifunctional heterogeneous material can display better catalytic performance than the separate species. All the solids were fully characterized and tested in the synthesis of cyclic carbonates starting from CO2 and several epoxides. The synergic coo…

Design, Synthesis And Photovoltaic Properties Of [60]Fullerene Based Molecular Materials

2004

Supported Ionic Liquids: A Versatile and Useful Class of Materials.

2017

Supported ionic liquids (SILs) represent a class of materials with peculiar properties and a huge potential regarding their possible applications in different fields of chemistry. Herein, we report our ongoing research about the use of SILs as support for organocatalysts, their role as catalysts themselves, and their application as support and stabilizers of palladium nanoparticles (PdNPs). The use of SILs based materials allowed achieving good results. Moreover, in some cases, after the functionalization of the catalytic species with an ion-tag moiety, a release and catch approach was employed in order to improve the catalytic activity and to facilitate the recovery of the hybrid system fo…

Fullerene-ionic-liquid conjugates: a new class of hybrid materials with unprecedented properties.

2015

A modular approach has been followed for the synthesis of a series of fullerene-ionic-liquid (IL) hybrids in which the number of IL moieties (two or twelve), anion, and cation have been varied. The combination of C60 and IL give rise to new unique properties in the conjugates such as solubility in water, which was higher than 800 mg mL(-1) in several cases. In addition, one of the C60 -IL hybrids has been employed for the immobilization of palladium nanoparticles through ion exchange followed by reduction with sodium borohydride. Surprisingly, during the reduction several carbon nanostructures were formed that comprised nano-onions and nanocages with few-layer graphene sidewalls, which have…

Synthesis of New Materials

2013

Recyclable Catalyst Reservoir: Oxidation of Alcohols Mediated by Noncovalently Supported Bis(imidazolium)-Tagged 2,2,6,6-Tetramethylpiperidine 1-Oxyl

2013

Bis(imidazolium)-tagged 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) catalysts were adsorbed on different supports such as silica gel, silica gel modified with highly cross-linked polymeric imidazolium networks, and highly cross-linked polymeric imidazolium networks entrapping magnetic particles. These systems provided a convenient tool for the oxidation of both primary and secondary alcohols working as recyclable reservoirs for the bis(imidazolium)-tagged TEMPO catalysts. By using EPR spectroscopy it was demonstrated that the catalyst was released as the corresponding oxoammonium salt in the solution during the recycling step, thus promoting the oxidative process in a homogeneous fashion. …

Polystyrene-supported proline as recyclable catalyst in the Baylis–Hillman reaction of arylaldehydes and methyl or ethyl vinyl ketone

2008

Abstract Polystyrene-supported proline has been used as co-organocatalyst (10 mol%) with imidazole (10 mol%) in the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and arylaldehydes. Recycling studies showed that the proline resin can be used up to five cycles with high isolated yields. This study represents the first example of supported proline as heterogeneous catalyst in the above reaction and broaden the scope of this catalytic material.

Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2

2018

Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic spec…

A polyhedral oligomeric silsesquioxane-based catalyst for the efficient synthesis of cyclic carbonates

2015

Polyhedral oligomeric silsesquioxane functionalized with imidazolium chloride peripheries (POSS-Imi) was successfully synthesized through a novel synthesis protocol. The solid was extensively characterized via1H NMR, 13C NMR and IR spectroscopy as well as combustion chemical analysis, mass spectrometry and transmission electron microscopy. Moreover, an in-depth investigation through 29Si NMR was performed. POSS-Imi was used for the first time as a catalyst for the conversion of CO2 and epoxides into cyclic carbonates with excellent results in terms of both yield and selectivity. The catalyst displayed improved catalytic performance with respect to unsupported 1-butyl-3-methylimidazolium chl…

Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Reaction in Water

2009

Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …

Tuneable Emission of Polyhedral Oligomeric Silsesquioxane Based Nanostructures that Self-Assemble in the Presence of Europium(III) Ions: Reversible t…

2020

[EN] Hybrid nanostructures with switchable and reversible "blue-red-green" emission were efficiently synthesized. These nanostructures comprise polyhedral oligomeric silsesquioxanes (POSS) that behave as a nanocage that can be functionalized with terpyridine-based organic ligands, which can be easily complexed with europium (III) ions. The complexes were characterized by UV-Vis and fluorescence spectroscopy and their stoichiometry was also confirmed by H-1 NMR spectroscopy. In the presence of the Eu(III) ions, the octafunctionalized nanocages self-assemble to form 3D architectures that display an intense red-emission, especially in the solid state. The presence of an alkenyl group bridging …

Electronic communication through pi-conjugated wires in covalently linked porphyrin/C60 ensembles

2005

Novel photo- and electroactive triads, in which pi-conjugated p-phenylenevinylene oligomers (oPPVs) of different length are connected to a photoexcited-state electron donor (i.e., zinc tetraphenylporphyrin) and an electron acceptor (i.e., C(60)), were designed, synthesized, and tested as electron-transfer model systems. A detailed physicochemical investigation, concentrating mainly on long-range charge separation and charge recombination and kinetics, revealed small attenuation factors beta of 0.03+/-0.005 A(-1). Energy matching between the HOMO levels of C(60) and oPPVs emerged as a key parameter for supporting molecular-wire-like behavior: It favors rapid and efficient electron or hole in…

Chemical Modification of Carbon Nanotubes with Sulfonylamides

First Evidence of Tris(catecholato)silicate Formation from Hydrolysis of an Alkyl Bis(catecholato)silicate

2022

The hydrolysis of 3-ammoniumpropylbis(catecholato)silicate 1, giving two different silica-based materials containing different amounts of tris(catecholato)silicate, is reported. The latter species can be formed through an attack of catechol to the silicon atom in the pentacoordinate complex, in which the silicon-carbon bond is further activated toward electrophilic proton cleavage. The Knoevenagel reaction was used as a probe in order to test the availability of functional groups on the surface of such materials.

New Hybrid Organic-inorganic Multifunctional Materials Based on Polydopamine-like Chemistry

2021

Taking inspiration from the chemistry of dopamine, a simple and economic synthetic approach toward the synthesis of a series of silica-based polydopamine-like materials has been developed. Mild conditions and easy manipulation are the strongest aspects of this methodology. Such hybrid materials were successfully used as recyclable catalysts for Knoevenagel reactions.

Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane-Imidazolium Tetrachloro- palladate Salt as a Precatalyst for the Su…

2016

A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of …

Polyhedral Oligomeric Silsesquioxane Based Catalyst for the Efficient Synthesis of Cyclic Carbonates

2015

In this work, the synthesis of a novel imidazolium-based polyhedral oligomeric silsesquioxane (POSS-mim-Cl) material is presented. The new nanometer-size organosilica based compound was employed for chemical fixation of CO2 into epoxide under homogeneous conditions. The target reaction was represented by the obtention of cyclic carbonates starting from epoxides and CO2. Particularly, styrene oxide was chosen as reference substrate. In addition, different parameters (solvent, temperature, pressure of CO2, and mass of the catalyst) were modified to find the best condition for CO2 conversion. The catalyst POSS-mim-Cl displayed good catalytic performances, the best results being obtained at 40 …

ChemInform Abstract: New Simple Hydrophobic Proline Derivatives as Highly Active and Stereoselective Catalysts for the Direct Asymmetric Aldol Reacti…

2009

New 4-substituted acyloxyproline derivatives with different hydrophobic properties of the acyl group were easily synthesized and used as catalysts in the direct asymmetric aldol reaction between cyclic ketones (cyclohexanone and cyclopentanone) and several substituted benzaldehydes. Reactions were carried out using water, this being the best reaction medium examined. Screening of these catalysts showed that compounds bearing the most hydrophobic acyl chains [4-phenylbutanoate and 4-(pyren-1-yl)butanoate] provided better results. The latter catalysts were successfully used in only 2 mol% at room temperature without additives to give aldol products in excellent stereoselectivities. These resu…

Straightforward preparation of highly loaded MWCNT-polyamine hybrids and their application in catalysis

2020

Multiwalled carbon nanotubes (MWCNTs) were easily and efficiently functionalised with highly cross-linked polyamines. The radical polymerisation of two bis-vinylimidazolium salts in the presence of pristine MWCNTs and azobisisobutyronitrile (AIBN) as a radical initiator led to the formation of materials with a high functionalisation degree. The subsequent treatment with sodium borohydride gave rise to the reduction of imidazolium moieties with the concomitant formation of secondary and tertiary amino groups. The obtained materials were characterised by thermogravimetric analysis (TGA), elemental analysis, solid state 13C-NMR, Fourier-transform infrared spectroscopy (FT-IR), transmission ele…

ChemInform Abstract: A Liquid-Liquid Biphasic Homogeneous Organocatalytic Aldol Protocol Based on the Use of a Silica Gel Bound Multilayered Ionic Li…

2012

Key feature of the title protocol is the use of a cis-ion-tagged proline dissolved in a liquid film on a multilayered ionic liquid covalently bound to silica. The resulting catalytically active material is soaked in cyclohexanone and water to form a semi-transparent gel which then reacts with the aldehyde.

Simple and Cheap Highly Active Proline-Based Organocatalysts

2011

Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives

2011

ChemInform Abstract: A Simple Procedure for the Oxidation of Alcohols Using [Bis(acetoxy)iodo]benzene and a Catalytic Amount of Bromide Ions in Ethyl…

2015

Primary and secondary benzylic alcohols and secondary aliphatic alcohols were oxidized to the corresponding aldehydes and ketones by using [bis(acetoxy)iodo]benzene (BAIB) and a catalytic amount of bromide ions, from tetrabutylammonium bromide or KBr, in ethyl acetate. The catalytic role of the bromide ions was also highlighted in the oxidation of primary aliphatic alcohols and secondary allylic alcohols carried out in the presence of 1 mol% TEMPO.

Topological effects of a rigid chiral spacer on the electronic interactions in donor-acceptor ensembles

2005

Two triads (donor-spacer-acceptor), etTTF-BN-C 6 0 (6) and ZnP-BN-C 6 0 (7), in which electron donors (i.e., exTTF or ZnP) are covalently linked to C 6 0 through a chiral binaphthyl bridge (BN), have been prepared in a multistep synthetic procedure starting from a highly soluble enantiomerically pure binaphthyl building block (1). Unlike other oligomeric bridges, with hinaphthyl bridges, the conjugation between the donor and the acceptor units is broken and geometric conformational changes are facilitated. Consequently, distances and electronic interactions between the donor and C 6 0 are drastically changed. Both donor-spacer-acceptor (D-s-A) systems (i.e., 6 and 7) exhibit redox processes…

Evidences of release and catch mechanism in the Heck reaction catalyzed by palladium immobilized on highly cross-linked-supported imidazolium salts

2014

Abstract Palladium (10 wt%) on a highly cross-linked imidazolium-based material was used as catalyst in 0.1 mol% in the Heck reaction between several alkenes and aryl iodides. Products were obtained from good to high yields. Deeper investigations showed a release of Pd species in solution and their capture by the imidazolium-based support. When a sixfold amount of support was employed the re-captured Pd species (0.5–0.6 wt%) were not anymore catalytically active. This result represents a new interesting aspect of this work since the highly cross-linked imidazolium-based material can act also as Pd scavenger avoiding the release of the metal in solution. Important differences between Heck an…

Diphenylmethanofullerene (DPM): a new and efficient acceptor in bulk heterojunction solar cells

2005

Novel supported dipeptides as recyclable catalysts for asymmetric aldol reaction

2009

Highly Loaded Multi-Walled Carbon Nanotubes Non-Covalently Modified with a Bis-Imidazolium Salt and their Use as Catalyst Supports

2016

The surfaces of multi-walled carbon nanotubes (MWCNTs) were non-covalently modified using two bis-imidazolium dibromide derivatives having phenyl or pyrene groups. Due to the presence of the two pyrene groups the bis(pyren-1-ylmethylimidazolium) dibromide derivative was immobilised at a loading of about 15-16 wt %, whereas only <3 wt % of the phenyl derivative was immobilised. The presence of the two imidazolium cations helped the immobilisation of tetrachloropalladate ions after exchange with bromide ions. Tetrachloropalladate was used as pre-catalyst in several Suzuki-Miyaura carbon-carbon cross-coupling reactions in water or water/ethanol at 50 °C in only 0.1 mol % and compared with the …

Design, synthesis and photovoltaic properties of [60]fullerene based molecular materials

2005

Abstract The possibility to use new organic semiconductor materials, in place of silicon wafers, in the fabrication of photovoltaic devices on substrates offer the prospect of lower manufacturing costs, particularly for large area applications. Thus, one of the most promising areas in fullerene research involves its potential application, mixed with conjugated polymers, in mimicking photosynthesis and in the related solar energy conversion. The tendency to phase segregation in blends of C60 derivatives and conjugated polymers has to be optimized to improve both charge photogeneration and transport in photovoltaic devices. In order to optimize device performances, a great deal of work has be…

Pressure Retarded Osmosis: a Membrane Process for Environmental Sustainability

2016

Salinity Gradient Power (SGP) based on the controlled mixing between two solutions at different salinities is a viable alternative to produce power from renewable sources. Pressure Retarded Osmosis (PRO) is one of the most promising technologies proposed so far for the exploitation of such energy source. Apart from the typical source of salinity gradients, namely river water and seawater, more and more interest has been raised recently towards the use of non-conventional saline solutions. In this work, water originating from a sewage treatment plant is used as the dilute solution (feed solution), while brine exiting from a desalination plant is used as the concentrate (draw solution), thus …

Desalination of oilfield produced waters via reverse electrodialysis: A techno-economical assessment

2023

Produced waters (PWs) are oilfield waste streams rich in minerals and hydrocarbons whose production rate is largely increased in last decades following the corresponding increase of energy demand. The high salinity level of PWs inhibits the adoption of cheap biological treatments. Also, desalination techniques based on osmotic membranes would require severe pre-treatments. As an alternative, Reverse ElectroDialysis (RED) and Assisted Reverse ElectroDialysis (ARED) are here proposed for the first time to reduce the salinity level of PWs. RED may also guarantee an operation cost reduction thanks to its energy generation. An ad-hoc model for RED and ARED is here developed in order to deal suit…

Enhanced power-conversion efficiency in organic solar cells incorporating copolymeric phase-separation modulators

2018

A new class of copolymers containing oligothiophene moieties with different lengths and fullerene units have been designed and prepared by an easy and inexpensive one-step synthetic approach. The incorporation of small quantities of these copolymers into bulk heterojunction (BHJ) solar cells with donor regioregular polythiophene (P3HT) and an acceptor fullerene derivate (PCBM) results in good control of the phase separation process without further affecting the BHJ optoelectronic properties. Indeed, under thermal annealing these copolymers allow the modulation of the growth of domains whose size depends on the length of the copolymer repetitive units. Domain size on the same length scale as…

Reverse electrodialysis heat engine (REDHE)

2022

Abstract Reverse electrodialysis (RED) is a membrane technology for the production of electricity via the “controlled mixing” of solutions at different salt concentrations, i.e., a diluted solution and a concentrated solution. The presence of ion-exchange membranes (IEMs) allows the production of renewable energy by converting the salinity gradient, which would be dissipated during a spontaneous (i.e., uncontrolled) mixing process, into an ionic current and, in a second step, into electricity at the electrodes. RED is the inverse process of the well-known electrodialysis process for salty water desalination, in which an electric field is applied at the electrodes and ionic currents are gene…

C60-TEMPO-IL hybrid: “release and catch” organocatalyst for the oxidation of alcohols

2014

Synthesis and Photoluminescent Properties of 1,1‘-Binaphthyl-Based Chiral Phenylenevinylene Dendrimers

2003

New chiral, soluble binaphthyl derivatives that incorporate stilbenoid dendrons at the 6,6′-positions have been prepared. The synthesis of the new enantiopure dendrimers was performed in a convergent manner by Horner-Wadsworth-Emmons (HWE) reaction of the appropriately functionalized 1,1′-binaphthyl derivative (R)-1 and the appropriate dendrons (R)2nGn-CHO. Different electroactive units were incorporated in the peripheral positions of the dendrons in order to tune both the optical and electrochemical behavior of these systems. Fluorescence measurements on the chiral dendrimers reveal a strong emission with maxima between 409 and 508 nm depending upon the substitution pattern. Finally, t…

Sensor Properties of Pristine and Functionalized Carbon Nanohorns

2016

Nanodispersions of pristine single-wall carbon nanohorns (i.e., p-SWCNHs) and oxidized-SWCNHs (i.e.; o-SWCNHs) were used to modify screen printed electrode (SPE). p-SWCNHs and o-SWCNHs were fully characterized by using several analytical techniques, as: HR-TEM (High Resolution-Transmission Electron Microscopy), FE-SEM/EDX (Field Emission-Scanning Electron Microscopy/Energy Dispersive X-ray Analysis), Raman spectroscopy, thermogravimetric analysis, differential thermal analysis (DTA), and the Brunauer-Emmett-Teller (BET) method. The chemically modified SPEs were also characterized with Cyclic Voltammetry (CV), using several different electro-active targets. In all cases, p-SWCNHs showed bett…

Direct asymmetric aldol reaction using polystyrene-supported proline amide

2008

Power Production from Produced Waters via Reverse Electrodialysis: A Preliminary Assessment

2022

Wastewaters generated by crude oil extraction processes, called &ldquo;produced waters&rdquo; (PWs), are complex solutions that contain organic compounds, mainly hydrocarbons, and often exhibit high salinity. The large amounts of PWs represent a global issue because of their environmental impact. An approach widely used in the oil industry is the reinjection of this wastewater into the extraction wells after a suitable treatment. The high salt concentration of such solutions may be used in salinity gradient technologies to produce green electricity. Among these technologies, reverse electrodialysis (RED) is one of the most promising. In this work, the application of RED for energy generatio…

Efficient microwave-mediated synthesis of fullerene acceptors for organic photovoltaics

2014

Two different processes, namely the Bamford–Stevens and [4 + 2] Diels Alder reactions, have been optimized under microwave irradiation for the functionalization of fullerenes. In this manner, all the main C60- and C70-based acceptor derivatives for organic solar cells such as PCBM, DPM, BHN and ICBA, have been prepared in higher yields and shorter reaction times with respect to the reported data. These findings represent a step forward toward the wide production of cheaper organic solar cells as a consequence of the cost abatement of the acceptors given by higher yields, lower waste production, and reduced reaction time which means a strong energy saving.

New proline derivatives as recyclable catalysts for aldol reaction

2009

ChemInform Abstract: Low-Loading Asymmetric Organocatalysis

2012

Asymmetric organocatalysis is now recognized as the third pillar of asymmetric synthesis. Recent years have witnessed increasing interest towards the use of highly active and stereoselective organocatalysts. This critical review documents the advances in the development of chiral organocatalysts which are systematically used in ≤3 mol% loading in all the sub-areas of the field, namely aminocatalysis, Bronsted acids and bases, Lewis acids and bases, hydrogen bond-mediated catalysis, phase transfer and N-heterocyclic carbene catalyses (194 references).

ChemInform Abstract: Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Rea…

2010

Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …

ChemInform Abstract: Recyclable Catalyst Reservoir: Oxidation of Alcohols Mediated by Noncovalently Supported Bis(imidazolium)-Tagged 2,2,6,6-Tetrame…

2014

First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis–Hillman Reaction Between Alkyl Vinyl Ketones and Aryl Aldehydes

2008

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …

New simple hydrophobic proline derivatives as highly active and stereoselective catalysts for the direct asymmetric aldol reaction in aqueous medium

2008

New 4-substituted acyloxyproline derivatives with different hydrophobic properties of the acyl group were easily synthesized and used as catalysts in the direct asymmetric aldol reaction between cyclic ketones (cyclohexanone and cyclopentanone) and several substituted benzaldehydes. Reactions were carried out using water, this being the best reaction medium examined. Screening of these catalysts showed that compounds bearing the most hydrophobic acyl chains [4-phenylbutanoate and 4-(pyren-1-yl)butanoate] provided better results. The latter catalysts were successfully used in only 2 mol% at room temperature without additives to give aldol products in excellent stereoselectivities. These resu…

Toward More Efficient Organocatalysts

2011

Modified Carbon Nanoforms Systems for Asymmetric Catalysis

Reconsidering TOF calculation in the transformation of epoxides and CO2 into cyclic carbonates

2020

Abstract The combination of Lewis acids and Lewis bases, currently defined as catalysts and co-catalysts (or promoter) respectively, in the reaction between epoxides and CO2 to give cyclic carbonates, is discussed, starting from examples in which the Lewis base was used in larger amount with respect to the Lewis acid. In these cases, turnover frequency (TOF) values have been usually calculated taking into account solely the amount of the Lewis acid employed. The occurrence of two distinct reaction pathways, one catalysed by the sole Lewis base and the other one catalysed by the Lewis acid/Lewis base couple, in which the Lewis acid alone does not play a catalytic role, should bring researche…

Palladium supported on cross-linked imidazolium network on silica as highly sustainable catalysts for the Suzuki reaction

2013

Polystyrene supported L-proline: a recyclable organocatalyst for the asymmetric aldol reaction in the presence of water

2007

Novel supported substituted prolinamide as recyclable catalyst for asymmetric aldol reaction

2010

New ionic liquid-modified silica gels as recyclable materials for L-proline- or H-Pro-Pro-Asp-NH2-catalyzed aldol reaction

2007

l-proline and the tripeptide H-Pro-Pro-Asp-NH2 (1) have been supported, by adsorption, onto the surface of modified silica gels functionalized with a monolayer of covalently attached 1,2-dimethyl-imidazolium chloride, tetrafluoroborate or hexafluorophosphate ionic moieties, respectively. Three different linkers were used to attach the ionic liquid moiety to the surface of these supports. The resulting materials have been used as catalysts for the aldol reaction between acetone and several substituted benzaldehydes. Good yields and enantioselectivities, comparable to or better than those obtained under homogeneous conditions, were obtained. These materials are easily recovered by filtration,…

Fullerene Polymers: Synthetic Strategies, Properties and Applications

2007

A general overview of the different C60-containing polymers according to their chemical structure and the general synthetic routes followed for their preparation as well as their potential applications is presented. The many fullerene-containing polymers reported in the recent literature have been classified depending upon the position of the fullerenes within the polymer chain and considering the type of chemical connectivity between them. The combination of fullerenes and polymer chemistry is a new interdisciplinary field in which all the knowledge on the synthesis and study of natural, as well as artificial macromolecules, can be applied to fullerenes to achieve novel fullerene-based arc…

From covalently linked catalysts to "release and catch" catalytic systems

2014

Low angle bending detection semi-transparent piezoresistive sensor

2022

We designed, fabricated, and validated a piezoresistive bending sensor, a fundamental component of wearable electronic devices for monitoring human motion. The most diffused opaque carbon-based resistance flex sensors suffer from low detection for small bending angles. The sensor we here present is based on a semi-transparent active material (fulleropyrrolidine bisadducts polymer) and has the remarkable advantage of good electrical properties for low bending angles. The fabrication steps are effective since a pre-patterned ITO/PET surface is functionalized by chronoamperometric deposition, and the silver electrical contacts are inkjet printed. We propose a fitting function of the measured t…

Advantages in supporting chiral organocatalysts

2010

An overview on the advances in supporting organocatalysts for their use and recycle in the asymmetric synthesis is presented, focusing on the main approaches for the immobilization and highlighting those examples in which supported and unsupported version of the catalyst behave similarly and high level of recyclability have been obtained.

Hydrophobically Directed Aldol Reactions: Polystyrene-SupportedL-Proline as a Recyclable Catalyst for Direct Asymmetric Aldol Reactions in the Presen…

2007

The cover picture shows the aldol reaction between ketones and arylaldehydes carried out by using a polystyrene-supported L-proline catalyst. This material furnishes aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water. This solvent effect, coupled with the high stereoselectivities observed, has been explained by the formation of a hydrophobic core in the inner surface of the resin with the hydrophilic proline moiety in the resin/water interface. Such a microenvironment promotes the aldol reaction and increases the stereoselectivity. Recycling investigations have shown that this material can be reus…

“Release and catch” catalytic systems

2013

In this perspective article the “release and catch” catalytic system concept is discussed. A “release and catch” catalytic system is prepared by non-covalent immobilization of the catalytic moiety on a suitable support, but differently from the usual non-covalently supported catalyst, the catalytic moiety is released in solution over the course of the reaction and it is recaptured at the end of the reaction. Such a “catalyst- sponge like” or “boomerang” system allows one to combine the benefits of homogeneous and heterogeneous catalysis and can be applied to organometallic-based catalysts, organocatalysts and metal-based catalysts.

Synthesis of Soluble Donor-Acceptor Double-Cable polymers based on polythiophene and tetracyanoanthraquinodimethane (TCAQ).

2003

[structure: see text] Novel suitably functionalized tetracyanoanthraquinodimethane (TCAQ) derivatives covalently linked to thiophene moieties have been synthesized. The thiophene-based monomers have been chemically polymerized and copolymerized to yield new and soluble donor-acceptor double-cable polymers. The absorption and emission data reveal that the optical properties can be finely tuned by modifying the ratio of monomers in the copolymerization process.

L-Prolina supportata su polistirene come catalizzatore eterogeneo nella reazione di condensazione aldolica “in the presence of water”

2006