Trialkoxysilane Grafting in Alcohols: A Simple Approach towards Modified Silica-Based Materials.

The grafting of trialkoxysilanes is the most common method for the surface functionalization of silica gel, and it is usually carried out in the presence of toluene or other solvents such as acetonitrile or acetone. Here, we replaced these solvents with alcohols to afford silica materials containing alkoxy groups linked to the silicon atom. The grafting of -dimethyl-3-amino- or 3-amino-propyltrimethoxysilane was carried out in the presence of several alcohols containing an unsubstituted alkyl chain (C7 and C14), a PEG functionalized chain, or an amino-substituted chain (-dimethylamino, pyridyl).

Quaternary Ammonium Salts-Based Materials: A Review on Environmental Toxicity, Anti-Fouling Mechanisms and Applications in Marine and Water Treatment Industries.

The adherence of pathogenic microorganisms to surfaces and their association to form antibiotic-resistant biofilms threatens public health and affects several industrial sectors with significant economic losses. For this reason, the medical, pharmaceutical and materials science communities are exploring more effective anti-fouling approaches. This review focuses on the anti-fouling properties, structure-activity relationships and environmental toxicity of quaternary ammonium salts (QAS) and, as a subclass, ionic liquid compounds.

Highly Functionalized SWCNTs with a Dopamine Derivative as a Support for Pd Nanoparticles: A Recyclable Catalyst for the Reduction of Nitro Compounds and the Heck Reaction.

Single-walled carbon nanotubes (SWCNTs) were functionalized with a dopamine derivative in which the amine group was converted to azide (dopamine azide). The direct reaction of SWCNTs and dopamine azide in o-dichlorobenzene at high temperature (160 °C) led to very highly functionalized CNTs (≈60 wt.%).

Antifouling Systems Based on a Polyhedral Oligomeric Silsesquioxane-Based Hexyl Imidazolium Salt Adsorbed on Copper Nanoparticles Supported on Titania.

The reaction of octakis(3-chloropropyl)octasilsesquioxane with four equivalents of 1-hexylimidazole or 1-decylimidazole gave two products labelled as HQ-POSS (hexyl-imidazolium quaternized POSS) and DQ-POSS (decyl-imidazolium quaternized POSS) as regioisomer mixtures. An investigation of the biological activity of these two compounds revealed the higher antimicrobial performances of HQ-POSS against Gram-positive and Gram-negative microorganisms, proving its broad-spectrum activity. Due to its very viscous nature, HQ-POSS was adsorbed in variable amounts on the surface of biologically active oxides to gain advantages regarding the expendability of such formulations from an applicative perspective.

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

The hydrolysis of 3-ammoniumpropylbis(catecholato)silicate 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.

A Study on the Stability of Carbon Nanoforms-Polyimidazolium Network Hybrids in the Conversion of CO into Cyclic Carbonates: Increase in Catalytic Activity after Reuse.

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 CO into cyclic carbonate under high temperature and CO pressure.

Site-specific halloysite functionalization by polydopamine: A new synthetic route for potential near infrared-activated delivery system.

Halloysite nanotubes (HNTs) represent a versatile core structure for the design of functional nanosystems of biomedical interest. However, the development of selective methodologies for the site-controlled functionalization of the nanotubes at specific sites is not an easy task. This study aims to accomplish a procedure for the site-selective/specific, "pin-point", functionalization of HNTs with polydopamine (HNTs@PDA).

TiO/AgO immobilized on cellulose paper: A new floating system for enhanced photocatalytic and antibacterial activities.

Paper-TiO-AgO floating photocatalysts were produced under mild condition and their photocatalytic activity for the degradation of aromatic amine under sunlight stimulant was investigated. Characterizations by Raman, XRD, XPS, DRS and PL confirmed the presence of TiO and AgO, and the morphology of the appended TiO/AgO layer was probed by FE-SEM. The photocatalytic activity of the prepared samples was investigated by the degradation of aniline (AN) in water under simulated sun-light illumination and constrained conditions, i.

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

A novel bithiophene-fulleropyrrolidine bisadducts system (bis-Th2PC ) 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.

New Mussel Inspired Polydopamine-Like Silica-Based Material for Dye Adsorption.

A straightforward and economic procedure has been developed for the synthesis of a new polydopamine-like silica-based material that has been obtained by oxidation of catechol with KIO followed by reaction with 3-aminopropyltrimethoxysilane. All techniques adopted for characterization showed that the obtained material is rich in different functional groups and the morphological analyses revealed dimensions in the nanometric range. The hybrid material has been characterized by several techniques showing its polydopamine-like nature, and preliminary observations for dye adsorption have been reported.

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

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.

Paper Functionalized with Nanostructured TiO/AgBr: Photocatalytic Degradation of 2-Propanol under Solar Light Irradiation and Antibacterial Activity.

A facile method to produce paper-TiO decorated with AgBr nanoparticles by a mild hydrothermal process at 140 °C was reported. The synthesis method was based on the immersion of the paper in a ready-made suspension of TiO/AgBr, comprising TiO sol solution prepared in acidic conditions and AgBr solution (10 M). A paper-TiO sample was prepared and used as reference.

Tuneable Emission of Polyhedral Oligomeric Silsesquioxane Based Nanostructures that Self-Assemble in the Presence of Europium(III) Ions: Reversible trans-to-cis Isomerization.

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 NMR spectroscopy.

Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks.

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, C and Si 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.

Effect of halloysite nanotubes filler on polydopamine properties.

Hypothesis: Polydopamine (PDA) is widely used as hydrophilic coating for several applications. However, most of the methods studied to improve or manipulate PDA properties are multistep and time-consuming, and there is a need for versatile strategies aimed at controlling and modifying the properties of PDA.

Experiments: PDA-halloysite nanocomposites were produced under different oxidation conditions in alkaline and acidic media and were characterized by UV-visible and attenuated total refraction- Fourier Transform Infrared spectroscopies, thermogravimetric analysis, porosimetry, scanning electron microscopy, X-ray diffraction and contact angle measurements against the reference PDA polymer.

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

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.

Imidazolium-Functionalized Carbon Nanohorns for the Conversion of Carbon Dioxide: Unprecedented Increase of Catalytic Activity after Recycling.

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.

Advances in Organic and Organic-Inorganic Hybrid Polymeric Supports for Catalytic Applications.

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.

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

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.

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

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.

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

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.

Cross-Linked Imidazolium Salts as Scavengers for Palladium.

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.

Low-loading asymmetric organocatalysis.

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).

Multilayered supported ionic liquids as catalysts for chemical fixation of carbon dioxide: a high-throughput study in supercritical conditions.

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.

Synthesis and characterization of new polyamino-cyclodextrin materials.

With the aim of the synthesis of chemically modified cyclodextrins bearing polyamine pendant groups, potentially useful as capping agents for the preparation of nanosized metal systems or as auxiliaries for gene transfection, the reaction between the heptakis-(6-iodo)-(6-deoxy)-β-cyclodextrin and various polyamines has been explored. This synthetic approach allows obtaining materials constituted by mixtures of cyclodextrins, having different degrees of substitution, which were satisfactorily characterized by means of various complementary techniques (ESI-MS, NMR, potentiometric titration). The products obtained were successfully subjected to preliminary tests for their binding abilities towards suitable organic guests and as capping agents for the preparation of stable silver nanoparticles.