Shaping 1,2,4-Triazolium Fluorinated Ionic Liquid Crystals

The synthesis and thermotropic behaviour of some di-alkyloxy-phenyl-1,2,4-triazolium trifluoromethane-sulfonate salts bearing a seven-carbon atom perfluoroalkyl chain on the cation is herein described. The fluorinated salts presenting a 1,2,4-triazole as a core and differing in the length of two alkyloxy chains on the phenyl ring demonstrated a typical liquid crystalline behaviour. The mesomorphic properties of this set of salts were studied by differential scanning calorimetry and polarized optical microscopy. The thermotropic properties are discussed on the grounds of the tuneable structures of the salts. The results showed the existence of a monotropic, columnar, liquid crystalline phase…

Task Specific Dicationic Ionic Liquids: Recyclable Reaction Media for the Mononuclear Rearrangement of Heterocycles

Nine functionalized dicationic ionic liquids were used to study the base catalyzed mononuclear rearrangement of (Z)-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the corresponding triazole at 363 K. Ionic liquids were characterized by the presence of 1-(1-imidazolylmethyl)-3,5-di[1-(3'-octylimidazolylmethyl)]benzene cation, bearing on the structure a neutral imidazole unit as basic functionality. Besides anions generally used for monocationic ionic liquids, such as [Br(-)], [BF4(-)], and [NTf2(-)], also dianions having a rigid aromatic spacer such as 1,4-benzenedicarboxylate, 2,6-naphthalenedicarboxylate, and 1,5- and 2,6-naphthalenedisulfonate were taken into account. Further…

GEL POLIMERICI DA LIQUIDI IONICI: MATERIALI ECOSOSTENIBILI PER LA DESOLFORAZIONE DEI CARBURANTI

Ionic liquid gels and antioxidant carbon nanotubes: Hybrid soft materials with improved radical scavenging activity

Hypothesis: Performances of materials are frequently affected by the action of radicals that can induce their degradation. To overcome the above issue, natural antioxidants (AOs) can be added during manufacturing. Considering the high instability of AOs, they have been adsorbed on carbon nanomaterials surface. However, the inclusion of functionalized carbon nanomaterials into gel matrix could enhance the antioxidant efficiency and represent an easy way to disperse and handle the active species.Experiments: Carboxypropyl functionalized carbon nanotubes (f-CNT), pure or with physically adsorbed alpha-tocopherol (f-CNT-VE) and quercetin (f-CNT-Q), were incorporated in some ionic liquid gels (I…

Carbon-based ionic liquid gels: alternative adsorbents for pharmaceutically active compounds in wastewater

With the aim of obtaining adsorbent systems to be used for the removal of pharmaceutically active compounds (PhACs) from wastewater, some hybrid ionic liquid gels (HILGs) were obtained from the combination of ionic liquid-based supramolecular gels and carbon materials, like graphite, graphene and graphene oxide (graphene OX). The properties of HILGs were investigated by determining their gel–sol transition temperature and rheological features. They were tested for the removal of PhACs belonging to different pharmaceutical classes, like antibiotics, antidepressants, anti-inflammatory. In particular, the removal of carbamazepine (CBZ), diclofenac sodium salt (DCF), ciprofloxacin (CPX) and nal…

Fluorescent naphthalimide-imidazolium hydrogels for biomedical applications

Bioimaging and in vivo imaging are cornerstone technologies in support of biomedical diagnosis. However, in some cases imaging methods have increased cancer risks for patients. Moreover, the most widely used diagnostic medical imaging technique, X-ray imaging, is the largest man-made source of radiation exposure to the general population. Thus, the research of new efficient and less invasive materials for imaging is quite urgent. Supramolecular hydrogels have recently proved to be promising biological carriers to load versatile bioimaging agents for in vitro or in vivo bioimaging, thanks to the ability to undergo reversible swelling and gel–sol transition in response to various physiologica…

Amino acid-based cholinium ionic liquids as sustainable catalysts for pet depolymerization

Chemical recycling to monomers is one of the key strategies in tackling the issues deriving from persistent plastic pollution in the environment, and poly(ethylene terephthalate) (PET) is among the most used polymers in modern society. In this context, we herein describe the glycolysis of PET to bis-hydroxyethyl terephthalate (BHET), promoted by basic cholinium salts differing for the anions, also comprising amino acid anions. We investigated the optimal reaction conditions, finding that the best-performing catalyst is [Ch][Gly], in the presence of which a conversion of 85% and a yield of 51% are achieved at 150 °C after 6 h, from PET deriving from a clear water bottle. We used our protocol…

Fluorescent interaction Eu-IL: when the anion plays a role

Multifunctional Carrier Based on Halloysite/Laponite Hybrid Hydrogel for Kartogenin Delivery

[Image: see text] A novel carrier system based on halloysite nanotubes (HNT), for the potential intraarticular delivery of kartogenin (KGN) by means laponite (Lap) hydrogel (HNT/KGN/Lap), is developed. The drug was first loaded into HNT, and the hybrid composite obtained was used as filler for laponite hydrogel. Both the filler and the hydrogel were thoroughly investigated by several techniques and the hydrogel morphology was imaged by transmission electron microscopy. Furthermore, the gelating ability of laponite in the presence of the filler and the rheological properties of the hybrid hydrogel were also investigated. The kinetic release of kartogenin from HNT and HNT/Lap hybrid hydrogel …

Functionalised Imidazolium Dicationic Ionic Liquids used as reaction media for base catalyzed organic reactions

Insights into the effect of the spacer on the properties of imidazolium based AIE luminogens

Abstract With the aim to obtain organic salts with potential applications in high performance molecular electronics, we combined properties of π-conjugated spacers, like 1,4-diethynylbenzene and 1,6-diethynylpyrene, with the ones of both imidazole and imidazolium units. Physico-chemical properties of obtained fluorescent organic salts were investigated performing thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC) and cyclic voltammetry measurements (CV). Photophysical behavior of the salts was analyzed in conventional solvents and ionic liquids, by UV–vis and fluorescence investigation. Solution phase aggregation study revealed that these salts self-assemble in conve…

Host-guest interactions between DMpillar[5]arene and fluorescent imidazolium salts

Two-Component Hydrogels Formed by Cyclodextrins and Dicationic Imidazolium Salts

In the framework of our recent interest in studying the gelling behaviour of imidazolium salts, we took into account the possibility of obtaining two-component hydrogels by combining cyclodextrins and dicationic imidazolium salts. In particular, we used diimidazolium salts differing in the alkyl chain length and in the size, shape, and coordination ability of the anion, namely the 3,3′-di-n-decyl- and 3,3′-di-n-dodecyl-1,1′-(1,4-phenylenedimethylene)diimidazolium dibromide, and 3,3′-di-n-dodecyl-1,1′-(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate and dihexafluorophosphate. As far as cyclodextrins are concerned, to gain information on the effects of different sized cyclic oligos…

Insights into the Formation and Structures of Molecular Gels by Diimidazolium Salt Gelators in Ionic Liquids or “Normal” Solvents

Insights are provided into the properties of molecular gels formed by diimidazolium salts both in “normal” solvents and ionic liquids. These materials can be interesting for applications in green and sustainable chemistry in which ionic liquids play a significant role, like catalysis and energy. In particular, two positional isomers of a diimidazolium cation have been examined with a wide range of anions for their ability to form gel phases. In particular, di-, tri-, and tetravalent anions bearing aliphatic or aromatic spacers were paired with the divalent cations. The properties of the organo- and ionogels formed have been analyzed by means of several different techniques, including calori…

Ionic Liquids Binary Mixtures: Promising Reaction Media for Carbohydrates Conversion in 5-HMF

Anion and ionic liquid effects on ionogel phases formation

Geminal organic salts have been recently introduced as the third generation of ionic liquids.1 Like their monocationic precursors they generally show high thermal stability and low corrosiveness, as well as high polarity and structural order degree.2 All these features make them good candidates to be used in the formation of conductive gel phases, that afterwards may find application as organized reaction media or in the preparation of dye sensitized solar cells.3 In this context, we have recently synthesized some task specific geminal organic salts and investigated their behaviour as gelators. The obtained salts were able to gel ionic liquid solutions. In order to have information about th…

Two component chiral gels: a study of properties and behavior as recognition systems

Growth of Differential Identities

In this paper we study the growth of the differential identities of some algebras with derivations, i.e., associative algebras where a Lie algebra L (and its universal enveloping algebra U(L)) acts on them by derivations. In particular, we study in detail the differential identities and the cocharacter sequences of some algebras whose sequence of differential codimensions has polynomial growth. Moreover, we shall give a complete description of the differential identities of the algebra UT2 of 2 × 2 upper triangular matrices endowed with all possible action of a Lie algebra by derivations. Finally, we present the structure of the differential identities of the infinite dimensional Grassmann …

Supramolecular Hydro- and Ionogels: A Study of Their Properties and Antibacterial Activity.

Diimidazolium-based organic salts, bearing peptides or amino acids as anions have been synthesised and tested for their gelling ability in biocompatible solvents. These low molecular weight salts were successfully used as gelators in phosphate buffered saline (PBS) solution and ionic liquids. Then, the properties of the obtained soft materials were analysed in terms of melting temperature and gel strength as accounted for by rheological investigations. The gel-phase formation was studied by using UV/Vis and resonance light scattering measurements, whereas the morphology of the soft materials was analysed by using polarised optical microscopy and scanning electron microscopy. To get informat…

Chemo-enzymatic Conversion of Glucose in 5-Hydroxymethylfurfural: The Joint Effect of Ionic Liquids and Ultrasound

For the valorization of lignocellulosic biomass, a key step is unlocking the conversion of glucose to suitable chemical platforms. To this aim, we herein describe the sequential chemo-enzymatic conversion of glucose into 5-hydroxymethylfurfural (5-HMF), in two steps: glucose isomerization to fructose, catalyzed by glucose isomerase (GI) and fructose dehydration to 5-HMF promoted by Amberlyst 15. The novelty of our approach lies in the use of crude cell extracts of Streptomyces coelicolor showing GI activity, as isomerization catalysts, along with a commercial immobilized GI. Under optimized reaction conditions, we obtained a conversion to 5-HMF (C5‑HMF) from glucose of 50% in the H2O/[bmim]…

Two components organogels as molecular recognition systems: properties, behavior and future applications

Functionalised diimidazolium salts: the anion effect on the catalytic ability

The catalytic ability of some functionalised diimidazolium ionic liquids was tested using the Michael addition of malononitrile to t-chalcone as probe reaction. Diimidazolium salts characterized by the presence of 1-(1-imidazolylmethyl)-3,5-di-[1-(3-octylimidazolylmethyl)]benzene cation and differing in the anion structure were used. Both mono- and dianions were employed and among these some chiral anions generally used as organocatalysts were taken into account. Data collected were analysed both as function of ionic liquids structure and basicity, evaluated using the Hammett basicity function. Although the use of chiral anions did not allow performing a stereochemical control of the reacti…

Naphthalimide imidazolium-based supramolecular hydrogels as bioimaging and theranostic soft materials

1,8-Naphthalimide-based imidazolium salts differing for the alkyl chain length and the nature of the anion were synthesized and characterized to obtain fluorescent probes for bioimaging applications. First, their self-assembly behavior and gelling ability were investigated in water and water/dimethyl sulfoxide binary mixtures. Only salts having longer alkyl chains were able to give supramolecular hydrogels, whose properties were investigated by using a combined approach of fluorescence, resonance light scattering, and rheology measurements. Morphological information was obtained by scanning electron microscopy. In addition, conductive properties of organic salts in solution and gel state we…

Liquidi ionici biocompatibili come leganti per sistemi termocromici

SALI ORGANICI: “TECTONI” PER LO STUDIO DI PROCESSI DI SELF-ASSEMBLY IN SOLVENTI ORGANICI

Studio dell’interazione Im-Eu-X: nuovi leganti ecocompatibili per l’Europio

LIQUIDI IONICI E CARBON DOTS UNITI NEI GEL IBRIDI!

La ricerca di materiali sempre più efficienti abbraccia svariati campi della società attuale e l’unione di due componenti con peculiarità complementari può generare materiali altamente innovativi. I gel formati da carbon nanodots e liquidi ionici non soltanto preservano le caratteristiche dei singoli componenti, ma ne migliorano le prestazioni, generando così un materiale ibrido performante e facilmente modulabile in base alle applicazioni richieste.

Diimidazolium organic salts and supramolecular gels exerting antimicrobial activity

The importance of supramolecular reaction media in catalysis

New “AIE” Luminogens based on π-conjugated imidazolium salts

Diimidazolium-based organic salts as low molecular weight hydro- and organogelator

Task-specific dicationic ionic liquids used as reaction media for Michael addition

π-Conjugated diimidazolium salts: rigid structure to obtain organized materials.

Phenylene ethynylene based diimidazolium salts differing in the alkyl chain length borne on the imidazolium ion and anion nature were synthesized. Their properties were studied both in solution and in the solid state. Salts obtained were able to aggregate in organic solvent solution. Aggregate formation was studied by performing concentration dependent measurements using UV-vis, fluorescence and Resonance Light Scattering. Furthermore, features of the aggregates were also investigated in the solid state by means of fluorescence and Scanning Electron Microscopy measurements. Finally, Density Functional Theory calculations were performed to obtain insights into the interaction geometry in the…

Organic Salts as Tectons for Self-assembly Processes in Solution

The literature, covering the last decade, about the self-assembly processes of organic salts in conventional solvents was analyzed. In particular, data reported about imidazolium and ammonium salts have been considered. The analysis shows that these processes are highly determined by structural features of the salts. Indeed, besides the nature of the cationic head, features of the alkyl chain borne on the cation structure and its possible functionalization, as well as the nature of the anion play a pivotal role. These factors determine not only the nature of the solvent in which the process occurs but also the nature of the self-assembly mechanism. Consequently, the structure tunability of …

IONOGEL IBRIDI: SISTEMI ADSORBENTI PER LA RIMOZIONE DI COMPOSTI FARMACEUTICI DALLE ACQUE INQUINATE

FDA-Approved Fluorinated Heterocyclic Drugs from 2016 to 2022

The inclusion of fluorine atoms or heterocyclic moiety into drug structures represents a recurrent motif in medicinal chemistry. The combination of these two features is constantly appearing in new molecular entities with various biological activities. This is demonstrated by the increasing number of newly synthesized fluorinated heterocyclic compounds among the Food and Drug Administration FDA-approved drugs. In this review, the biological activity, as well as the synthetic aspects, of 33 recently FDA-approved fluorinated heterocyclic drugs from 2016 to 2022 are highlighted.

Growth of central polynomials of algebras with involution

Let A be an associative algebra with involution ∗ over a field of characteristic zero. A central ∗-polynomial of A is a polynomial in non- commutative variables that takes central values in A. Here we prove the existence of two limits called the central ∗-exponent and the proper central ∗-exponent that give a measure of the growth of the central ∗-polynomials and proper central ∗-polynomials, respectively. Moreover, we compare them with the PI-∗-exponent of the algebra.

Ionogels formed by geminal imidazolium salts: a preliminary investigation

Nitrogen-Doped Carbon Nanodots-Ionogels: Preparation, Characterization, and Radical Scavenging Activity

Hybrid diimidazolium-based ionogels were obtained by dispersing nitrogen-doped carbon nanodots (NCNDs) in ionic liquid (IL) solutions and by using dicationic organic salts as gelators. The properties of the NCND-ionogels were studied in terms of thermal stability, mechanical strength, morphology, rheological, and microscopic analyses. Insights into the formation of the hybrid soft material were attained from kinetics of sol-gel phase transition and from estimating the size of the aggregates, obtained from opacity and resonance light-scattering measurements. We demonstrate that, on one hand, NCNDs were able to favor the gel formation both in the presence of gelating and nongelating ILs. On t…

Activity of a Heterogeneous Catalyst in Deep Eutectic Solvents: The Case of Carbohydrate Conversion into 5-Hydroxymethylfurfural

Obtaining industrially relevant products from renewable resources and developing processes under the light of sustainable chemistry is a prominent endeavor of present-day chemical research. In this context, herein we investigated the dehydration of fructose and sucrose in deep eutectic solvents promoted by the ion-exchange resin Amberlyst 15 as heterogeneous catalyst. We optimized the reaction conditions in terms of temperature, catalyst loading, and initial amount of substrate. Then, we looked at the effect of structural variations in the solvent components on the reaction outcome. Under the best experimental conditions, we obtained very good yields of 78% at 60 °C and 69% at 80 °C for fru…

Carbohydrate-supramolecular gels : adsorbents for chromium(VI) removal from wastewater.

Abstract Hypothesis To overcome the contamination of water by heavy metals the adsorption of the pollutant on gel phases is an attractive solution since gels are inexpensive, potentially highly efficient and form a distinct phase while allowing diffusion of the contaminated water throughout the material. This work tests the chromium(VI) adsorbent capacity of new supramolecular gels for Chromium(VI) removal from wastewater. Experiments First hydrophobic imidazolium salts of carbohydrate anions were synthesised as new gelators. Subsequently, they were dissolved in a solvent by heating and, after cooling overnight, to give the formation of supramolecular gels. The properties of the resulting g…

Non-stoichiometric dicationic organic salts form supramolecular gels

Studio delle proprietà di ionogel formati da sali organici dicationici

Differential Identities and Varieties of Almost Polynomial Growth

Let V be an L-variety of associative L-algebras, i.e., algebras where a Lie algebra L acts on them by derivations, and let c(n)(L) (V), n >= 1, be its Lcodimension sequence. If V is generated by a finite-dimensional L-algebra, then such a sequence is polynomially bounded only if V does not contain UT2, the 2 x 2 upper triangular matrix algebra with trivial L-action, and UT2 epsilon where L acts on UT2 as the 1-dimensional Lie algebra spanned by the inner derivation epsilon induced by e11. In this paper we completely classify all the L-subvarieties of var(L)(UT2) and var(L)(UT2 epsilon) by giving a complete list of finite-dimensional L-algebras generating them.

Ionic liquids binary mixtures and zeolites: a combination to promote carbohydrates conversion into 5-hydroxymethylfurfural

Catalysis in Supramolecular Systems: the Case of Gel Phases

Supramolecular gels are a fascinating class of materials, originated by the self-assembly of low molecular weight molecules. Underpinned by non-covalent interactions, they find application in a diverse range of fields. Among these, supramolecular gels can be considered as organized, non-conventional reaction media, able to influence reactivity in a radically different way, compared with what happens in solution. This short review will focus on this aspect, covering literature from 2010 onwards, addressing the application of supramolecular gels as reaction media. In particular, in the first section we explore organocatalytic reactions in gel phase, with wide synthetic relevance, such as aldo…

Solution and thermal behaviour of novel dicationic imidazolium ionic liquids

A new class of functionalised dicationic ionic liquids, containing a central cationic unit capped by a basic functionality (imidazole), has been synthesised. These salts have been characterised in isotropic solution using proton and 2D-NMR spectroscopy, and their thermal stability has been studied by DSC and TGA. All these novel salts contain the 1-(1-imidazolylmethyl)-3,5-di{1-(3'-octylimidazolylmethyl)}-benzene cation as a defining structural motif. Salts of both singly and doubly charged anions were prepared and, in particular, the selected monoanions (Br(-), [BF4](-), or [NTf2](-)) differ in size, shape and hydrogen-bonding ability, whereas the dianions differ in the nature of the space…

Self-Sustaining Supramolecular Ionic Liquid Gels for Dye Adsorption

Water contamination is one of the main problems of modern society, and scientific research is continuously involved in identifying solutions able to preserve this valuable source. In this context, we characterized novel ionogels formed by organic salts with different anions. In particular, they show self-strengthening behavior, a quite unusual property for supramolecular gels, and they also exhibit a good load-bearing capacity. These ionogels are able to remove cationic dyes from wastewater. Thanks to their properties, they can be used in different apparatuses like dialysis membranes and as loading in adsorption columns. In the latter case over 95% removal is achieved in less than 10 min. I…

Ionic liquids: “normal” solvents or nanostructured fluids?

Ionic liquids (ILs) are a class of non-conventional solvents, which, for almost two decades, have continued to generate burgeoning interest in different fields of present-day chemical research with few similar precedents. Among the various aspects related to ILs, a topic worthy of in-depth analysis is their influence on organic reactivity and reaction rates. In light of this, the present short review aims to provide an overview of the literature from 2010 to the present day that addresses this issue. In particular, we herein present two main different viewpoints by which the solvent effect of ILs is explained: the first is mainly based on considering the bulk polarity of ILs and linear solv…

Acidic imidazolium salts: catalysts for biomass transformation

Ionic liquid binary mixtures: Promising reaction media for carbohydrate conversion into 5-hydroxymethylfurfural

Abstract The conversion of carbohydrates into 5-hydroxymethylfurfural (5-HMF) has been studied in binary mixtures of ionic liquids (ILs), using strongly acidic resin Amberlyst 15 as the catalyst. In particular, both mono- and disaccharides, such as fructose, glucose and sucrose have been investigated. Considering the favorable effect exerted by chloride-based ionic liquids in the dissolution of carbohydrates, we used binary mixtures of 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) with [bmim + ] based ionic liquids differing in size, shape and coordination ability of the anion ([bmim][BF 4 ], [bmim][N(CF 3 SO 2 ) 2 ], [bmim][N(CN) 2 ], [bmim][SbF 6 ] and [bmim][CF 3 SO 3 ]). Carbohydrat…

Self-assembly process of diimidazolium salts: the effect of the alkyl chain length and isomeric substitution

Environmentally Friendly Eutectogels Comprising l-amino Acids and Deep Eutectic Solvents: Efficient Materials for Wastewater Treatment.

Current concerns for sustainability and the environment make low-impact materials desirable for environmental remediation and, in particular wastewater treatment. We obtained supramolecular gels of l-amino acids in the deep eutectic solvent formed by choline chloride and phenylacetic acid. After gel characterization, and investigating gel-sol transition temperatures, gelation kinetics, rheological properties, and morphology, the gels were applied as sorbents to remove cationic dyes from aqueous solutions. The effects of the pH, dye nature, volume, and concentration of wastewater were analyzed, and the best result was obtained with a l-phenylalanine-based eutectogel. It can be reused for at …

Two components hydrogels formed by host-guest interactions

Diimidazolium-based supramolecular ionogels for dye removal from wastewaters

Supramolecular complexes formed by dimethoxypillar[5]arenes and imidazolium salts: A joint experimental and computational investigation

To gain more insights into the factors acting on the stability of complexes formed by pillar[5]arenes, we investigated the interaction of dimethoxypillar[5]arene with some 1-(n-alkyl)-3-(9-anthracenylmethyl)-imidazolium based organic salts. In particular, we used salts differing in not only the anion nature ([Cl−], [BF4−], [NTf2−] and [SbF6−]) and alkyl chain length (butyl, octyl and dodecylimidazolium derivatives), but also the presence of a hydrogenated or fluorinated tail (octyl and perfluorooctylimidazolium derivatives). Host–guest systems were analysed in solution, solid state and gas phase, using a combined approach of different techniques like fluorescence, 1H NMR, ESI-MS, DSC and DF…

The ultrasounds-ionic liquids synergy on the copper catalyzed azide-alkyne cycloaddition between phenyl acetylene and 4-azidoquinoline

Abstract The effect of ultrasound irradiation on the copper catalyzed azide–alkyne cycloaddition between phenylacetylene and 4-azidoquinoline has been studied in solution of different ionic liquids. In particular, we used ionic liquids featuring both aliphatic and aromatic mono- and dications, as well as anions differing in size, symmetry and coordination ability. We also examined the influence of the ionic liquids structural features on the reaction outcomes, finding that under magnetic stirring reactivity is favorably affected by the solvent structural organization, while under sonochemical conditions an opposite trend was observed. In all cases examined, sonochemical activation leads to …

Bio-based chitosan and cellulose ionic liquid gels: polymeric soft materials for the desulfurization of fuel

Desulfurization of fuel that avoids the introduction in the atmosphere of toxic sulfur volatile compounds, usually formed during combustion, is a viable strategy to reduce pollution. To find new efficient and eco-sustainable adsorbent materials, bio-based polymers such as chitosan (CS), cellulose (CE) and cellulose acetate (CEOAc) were dissolved in ionic liquids (ILs) to form ionic liquid gels (ILGs). Gelling and swelling ability, porosity, morphology, rheology and mechanical response were studied as a function of the polymer and ionic liquid (IL) used. The best performing gels were tested for fuel desulfurization using a fuel mimicking solution of thiophene (T), benzothiophene (BT) and dib…

Ionic Liquid Binary Mixtures, Zeolites, and Ultrasound Irradiation: A Combination to Promote Carbohydrate Conversion into 5-Hydroxymethylfurfural

The efficient conversion of biomass into value-added compounds under mild and safer conditions is a cornerstone of present research efforts to meet the needs of the chemical industry with sustainable development. In this work, we studied the dehydration of fructose, glucose, and sucrose into 5-hydroxymethylfurfural (5-HMF), catalyzed by HY zeolite, in three ionic liquid mixtures differing for the cation, aromatic, or aliphatic. We investigated the effect of several operational parameters such as temperature, catalyst loading, zeolite counterion, solvent mixture, and added chloride. In the optimal experimental conditions, we obtained good conversions to 5-HMF especially for fructose and sucr…

Fully ionic metallogels from dicationic diimidazolium salts

Hybrid supramolecular gels of Fmoc-F/halloysite nanotubes: Systems for sustained release of camptothecin

Supramolecular gel hybrids obtained by self-assembly of Fmoc-L-phenylalanine (Fmoc-F) in the presence of functionalized halloysite nanotubes (f-HNT) were obtained in biocompatible solvents and employed as carriers for the delivery of camptothecin (CPT) molecules. The synthesis of the new f-HNT material as well as its characterization are described. The properties of the hybrid hydrogels and organogels were analyzed by several techniques. The presence of small amounts of f-HNT allows good dispersion of the tubes and the subsequent formation of homogeneous gels. The experimental results show that f-HNT functions only as an additive in the hybrid gels and does not demonstrate gelator behavior.…

Dicationic organic salts: gelators for ionic liquids

Diimidazolium and dipyrrolidinium organic salts were tested for their ability to gel both organic solvents and ionic liquids. Organic salts containing 1-(1-imidazolylmethyl)-3,5-di-(3'-octylimidazolylmethyl)-benzene and 1-(N-pyrrolidylmethyl)-3,5-di-(N,N-octylpyrrolidylmethyl)-benzene cations were used. In addition to the simple bromide anion, also dianions having a naphthalene core such as 1,5- and 2,6-naphthalenedisulfonate and 2,6-naphthalenedicarboxylate were taken into account. Gelation tests demonstrated that organic salts used were able to harden ionic liquids. The materials obtained were investigated for their thermal stability and also for electric conductivity properties using mic…

Ionic Liquid Gels: Supramolecular Reaction Media for the Alcoholysis of Anhydrides.

The search of new enantioselective catalysts, able to promote synthetically useful organic reactions with high levels of asymmetric induction, should be associated with the attention to the suitable reaction medium able to achieve the best efficiency in chemical processes. We have investigated the enantioselective desymmetrization of cyclic meso-anhydrides in nonconventional reaction media such as ionic liquids and supramolecular gels. With this aim, we examined several variables in the reacting system: the nature of ionic liquid used as the reaction medium, the gelation solvent, the structure of the anhydrides, the structure of alcohols, the chiral catalysts, and the reaction conditions, i…

How mixing ionic liquids affects a Diels-Alder reaction

Task-Specific Organic Salts and Ionic Liquids Binary Mixtures: A Combination to Obtain 5-Hydroxymethylfurfural From Carbohydrates

The increase in energy demand and depletion of fossil fuels are among major issues of modern society. Valorization and transformation of raw materials in products of industrial value represents a challenge. This justifies the growing interest of scientific research towards the identification of suitable media and methodologies able to pursue above goals, paying attention to matter of sustainability. On this subject, we studied sulfonic-acid functionalized diimidazolium salts as catalysts for the conversion of fructose and sucrose to 5-hydroxymethylfurfural (5-HMF) in an ionic liquid mixture. In general, using these salts allowed us to obtain 5-HMF in good yields from both substrates in mild…

Azolium and acetate ions in DMF: Formation of free N-heterocyclic carbene. A voltammetric analysis

In order to reveal the possible formation of free N-heterocyclic carbene (NHC) in DMF-azolium and acetate solutions, the proton exchange equilibrium between azolium cations and CH3COO− was investigated (by cyclic voltammetry) by adding CH3COOH or tetrabutylammonium acetate to DMF solutions of imidazolium or thiazolium salts of different acidity.The voltammetric analysis confirms that the deprotonation of the azolium cation by CH3COO− (with the formation of free NHC) is significant in the case of the more acidic thiazolium cations, while it is not effective with the less acidic imidazolium ones.Accordingly, the NHC-catalyzed benzoin condensation was carried out in DMF solutions of azolium sa…

Cathodic behaviour of dicationic imidazolium bromides: the role of the spacer

The cathodic reduction of dicationic imidazolium bromides, whose spacer is either an aliphatic chain or a xylyl group, leads to the formation of the corresponding N-heterocyclic carbenes (NHCs), which were isolated as the corresponding thiones, after reaction with elemental sulfur. The behaviour of the dications was compared with the corresponding monocations. The behaviour of dicarbenes depends on the nature of the spacer. This study evidenced that dicarbenes deriving from xylyl dications are less stable than the corresponding aliphatic ones (giving lower yields in thiones), due to a debenzylation reaction. On the other hand, the yields in thiones starting from aliphatic dications are high…

Differential identities, 2 × 2 upper triangular matrices and varieties of almost polynomial growth

Abstract We study the differential identities of the algebra U T 2 of 2 × 2 upper triangular matrices over a field of characteristic zero. We let the Lie algebra L = Der ( U T 2 ) of derivations of U T 2 (and its universal enveloping algebra) act on it. We study the space of multilinear differential identities in n variables as a module for the symmetric group S n and we determine the decomposition of the corresponding character into irreducibles. If V is the variety of differential algebras generated by U T 2 , we prove that unlike the other cases (ordinary identities, group graded identities) V does not have almost polynomial growth. Nevertheless we exhibit a subvariety U of V having almo…

NMR Spectroscopic characterization and thermal behaviour of a new class of dicationic imidazolium ionic liquids

Two-Component Hydrogels Formed by Cyclodextrins and Dicationic Imidazolium Salts

In the framework of our recent interest in studying the gelling behaviour of imidazolium salts, we took into account the possibility of obtaining two-component hydrogels by combining cyclodextrins and dicationic imidazolium salts. In particular, we used diimidazolium salts differing in the alkyl chain length and in the size, shape, and coordination ability of the anion, namely the 3,3′-di-n-decyl- and 3,3′-di-n-dodecyl-1,1′-(1,4- phenylenedimethylene)diimidazolium dibromide, and 3,3′-di-n-dodecyl-1, 1′-(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate and dihexafluorophosphate. As far as cyclodextrins are concerned, to gain information on the effects of different sized cyclic olig…

MODIFICAZIONI COVALENTI DI NANOTUBI DI ALLOSITE PER APPLICAZIONE NEL DRUG DELIVERY

Nell'ampio scenario dei nanomateriali, i sistemi nanotubolari godono di un consolidato e crescente interesse sia nell'ambito scientifico che industriale. Fra la miriade di sistemi tubolari, recentemente i nanotubi allosite (HNT) hanno attirato l’attenzione della comunità scientifica.1 Grazie alla presenza di una cavità vuota, gli HNT trovano, principalmente, applicazione come nanocontainer per il rilascio controllato di composti chimici, in particolare, farmaci. L’introduzione di modificazioni covalenti su entrambe le superfici permette di modulare le proprietà dell’allosite, aumentando così i suoi campi di applicazione. In questa comunicazione verranno presentati recenti risultati ottenuti…

Ionic liquids gels: Soft materials for environmental remediation

Abstract Hypothesis Nanostructured sorbents and, in particular, supramolecular gels are emerging as efficient materials for the removal of toxic contaminants from water, like industrial dyes. It is also known that ionic liquids can dissolve significant amounts of dyes. Consequently, supramolecular ionic liquids gels could be highly efficient sorbents for dyes removal. This would also contribute to overcome the drawbacks associated with dye removal by liquid–liquid extraction with neat ionic liquids which would require large volumes of extractant and a more difficult separation of the phases. Experiments Herein we employed novel supramolecular ionic liquid gels based on diimidazolium salts b…

Central polynomials of graded algebras: Capturing their exponential growth

Let G be a finite abelian group and let A be an associative G-graded algebra over a field of characteristic zero. A central G-polynomial is a polynomial of the free associative G-graded algebra that takes central values for all graded substitutions of homogeneous elements of A. We prove the existence and the integrability of two limits called the central G-exponent and the proper central G-exponent that give a quantitative measure of the growth of the central G-polynomials and the proper central G-polynomials, respectively. Moreover, we compare them with the G-exponent of the algebra.

Supramolecular aggregation of bis-imidazolium functionalised perylene bisimides

Natural eutectogels: sustainable catalytic systems for C–C bond formation reactions

Natural eutecto gels were prepared combining properties of amino acids with the ones of deep eutectic solvents. Soft materials obtained were fully characterised determining the gel-sol transition temperatures and analysing mechanical and morphological features through rheological measurements and polarised optical microscopy. All eutecto gels were tested as catalytic reaction media for the enantioselective aldol reaction and, the best performing one was also used to carry out the Michael addition. In both cases, eutecto gels proved to have a great potential as sustainable reaction media, allowing to perform processes under mild conditions, obtaining excellent yields and, in some cases, also…

SINTESI E PROPRIETÁ DI SALI ORGANICI POLICATIONICI UTILIZZATI COME MEZZI DI REAZIONE

Carbon Nanomaterial Doped Ionic Liquid Gels for the Removal of Pharmaceutically Active Compounds from Water.

Due to large drug consumption, pharmaceutically active compounds (PhACs) can be found as water contaminants. The removal of PhACs is a significant issue, as they can easily overtake traditional purification methods. Because of their surface properties, carbon nanomaterials are among the most efficient materials able to adsorb PhACs. However, their limitation is their recovery after use and their possible leakage into the aquatic system. Consequently, new hybrid supramolecular ionic liquid gels (HILGs) have been designed for the adsorption of some antibiotic drugs (ciprofloxacin and nalidixic acid) from water. The chemical&ndash

Functionalized Diatonic Ionic Liquids Applied to the Study of Michael Addition

CONVERSIONE CHEMO-ENZIMATICA DI GLUCOSIO IN 5-HMF IN MISCELE IL/H2O, PROMOSSA DA ESTRATTO CELLULARE BATTERICO E ULTRASUONI

Algebras with involution and multiplicities bounded by a constant

Abstract Let A be an algebra with involution ⁎ over a field of characteristic zero. In this paper we characterize in two different ways when the multiplicities of the ⁎-cocharacter of A are bounded by a constant. As a consequence, we characterize the algebras with involution of bounded colength.