Nanostructured Cellulose-Based Sorbent Materials for Water Decontamination from Organic Dyes.

Nanostructured materials have been recently proposed in the field of environmental remediation. The use of nanomaterials as building blocks for the design of nano-porous micro-dimensional systems is particularly promising since it can overcome the (eco-)toxicological risks associated with the use of nano-sized technologies. Following this approach, we report here the application of a nanostructured cellulose-based material as sorbent for effective removal of organic dyes from water. It consists of a micro- and nano-porous sponge-like system derived by thermal cross-linking among (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidized cellulose nanofibers (TOCNF), branched polyethylenimine 25 kDa (bPEI), and citric acid (CA). The sorbent efficiency was tested for four different organic dyes commonly used for fabric printing (Naphthol Blue Black, Orange II Sodium Salt, Brilliant Blue R, Cibacron Brilliant Yellow), by conducting both thermodynamic and kinetic studies. The material performance was compared with that of an activated carbon, commonly used for this application, in order to highlight the potentialities and limits of this biomass-based new material. The possibility of regeneration and reuse of the sorbent was also investigated.

TEMPO-mediated oxidation of polysaccharides: An ongoing story.

The oxidation of natural polysaccharides by TEMPO has become by now an "old chemical reaction" which led to numerous studies mainly conducted on cellulose. This regioselective oxidation of primary alcohol groups of neutral polysaccharides has generated a new class of polyuronides not identified before in nature, even if the discovery of enzymes promoting an analogous oxidation has been more recently reported. Around the same time, the scientific community discovered the surprising biological and techno-functional properties of these anionic macromolecules with a high potential of application in numerous industrial fields. The objective of this review is to establish the state of the art of TEMPO chemistry applied to polysaccharide oxidation, its history, the resulting products, their applications and the associated modifying enzymes.

Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy.

Two different formulations of cyclodextrin nanosponges (CDNS), obtained by polycondensation of ß-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn), were treated with aqueous solutions of ibuprofen sodium salt (IbuNa) affording hydrogels that, after lyophilisation, gave two solid CDNS-drug formulations. 1H fast MAS NMR and 13C CP-MAS NMR spectra showed that IbuNa was converted in situ into its acidic and dimeric form (IbuH) after freeze-drying. 13C CP-MAS NMR spectra also indicated that the structure of the nanosponge did not undergo changes upon drug loading compared to the unloaded system. However, the 13C NMR spectra collected under variable contact time cross-polarization (VCT-CP) conditions showed that the polymeric scaffold CDNS changed significantly its dynamic regime on passing from the empty CDNS to the drug-loaded CDNS, thus showing that the drug encapsulation can be seen as the formation of a real supramolecular aggregate rather than a conglomerate of two solid components. Finally, the structural features obtained from the different solid-state NMR approaches reported matched the information from powder X-ray diffraction profiles.

Mechanical and Drug Release Properties of Sponges from Cross-linked Cellulose Nanofibers.

All-organic porous sponges were obtained throughout the direct and solvent-free (oven 105 °C, time>6 h) crosslinking of TEMPO-oxidized cellulose nanofibers (TOCNF) with 25 kDa branched polyethyleneimine (bPEI) in the presence of different amounts of citric acid (CA) as co-crosslinker. The chemical and mechanical stability of these materials was provided by the formation of amide bonds between the carboxylic moieties of TOCNF and CA with the primary amines of bPEI. The mechanical properties were investigated under static and dynamic loads with both dry and wet samples. The materials had the interesting capability to recover their shape with reduced losses in mechanical resistance, while their Young's modulus progressively increased with the content of CA. In work toward developing possible applications of bPEI-TOCNF sponges in drug delivery, amoxicillin (AM) and ibuprofen (IB) were considered as model drugs. All materials showed very good performance in adsorbing both AM and IB (ca. 200 mg g-1 ) from methanol solution. In particular, an increased adsorption of IB was observed in parallel to the increase of citrate moieties in the samples. Moreover, samples crosslinked in presence of CA showed slower kinetic release in aqueous environments than materials obtained without CA.

An aerogel obtained from chemo-enzymatically oxidized fenugreek galactomannans as a versatile delivery system.

We describe a new aerogel obtained from laccase-oxidized galactomannans of the leguminous plant fenugreek (Trigonella foenum-graecum) and suggest its potential practical use. Laccase/TEMPO oxidation of fenugreek in aqueous solution caused a viscosity increase of over 15-fold. A structured, elastic, stable hydrogel was generated, due to formation of carbonyl groups from primary OH of galactose side units and subsequent establishment of hemiacetalic bonds with available free hydroxyl groups. Upon lyophilization of this hydrogel, a water-insoluble aerogel was obtained (EOLFG), capable of uptaking aqueous or organic solvents over 20 times its own weight. The material was characterized by scanning electron microscopy, FT-IR, elemental analysis and (13)C CP-MAS NMR spectroscopy and its mechanical properties were investigated. To test the EOLFG as a delivery system, the anti-microbial enzyme lysozyme was used as model active principle. Lysozyme was added before or after formation of the aerogel, entrapped or absorbed in the gel, retained and released in active form, as proven by its hydrolytic glycosidase activity on lyophilized Micrococcus lysodeikticus cells wall peptidoglycans. This new biomaterial, composed of a chemo-enzymatically modified plant polysaccharide, might represent a versatile, biocompatible "delivery system" of active principles in food and non-food products.

Surface-Functionalization of Nanostructured Cellulose Aerogels by Solid State Eumelanin Coating.

Bioinspired aerogel functionalization by surface modification and coating is in high demand for biomedical and technological applications. In this paper, we report an expedient three-step entry to all-natural surface-functionalized nanostructured aerogels based on (a) TEMPO/NaClO promoted synthesis of cellulose nanofibers (TOCNF); (b) freeze-drying for aerogel preparation; and (c) surface coating with a eumelanin thin film by ammonia-induced solid state polymerization (AISSP) of 5,6-dihydroxyindole (DHI) or 5,6-dihydroxyindole-2-carboxylic acid (DHICA) previously deposited from an organic solution. Scanning electron microscopy showed uniform deposition of the dark eumelanin coating on the template surface without affecting porosity, whereas solid state (13)C NMR and electron paramagnetic resonance (EPR) spectroscopy confirmed the eumelanin-type character of the coatings. DHI melanin coating was found to confer to TOCNF templates a potent antioxidant activity, as tested by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assays as well as strong dye adsorption capacity, as tested on methylene blue. The unprecedented combination of nanostructured cellulose and eumelanin thin films disclosed herein implements an original all-natural multifunctional aerogel biomaterial realized via an innovative coating methodology.

Functionalization of Cyclodextrins with N-Hydroxyphthalimide Moiety: A New Class of Supramolecular Pro-Oxidant Organocatalysts.

N-hydroxyphthalimide (NHPI) is an organocatalyst for free-radical processes able to promote the aerobic oxidation of a wide range of organic substrates. In particular, NHPI can catalyze the hydroperoxidation of polyunsaturated fatty acids (PUFA). This property could be of interest for biological applications. This work reports the synthesis of two ß-cyclodextrin derivatives (CD5 and CD6) having a different degree of methylation and bearing a NHPI moiety. These compounds, having different solubility in water, have been successfully tested for the hydroperoxidation of methyl linoleate, chosen as the PUFA model molecule.

Multicomponent versus domino reactions: One-pot free-radical synthesis of ß-amino-ethers and ß-amino-alcohols.

Following an optimized multicomponent procedure, an aryl amine, a ketone, and a cyclic ether or an alcohol molecule are assembled in a one-pot synthesis by nucleophilic radical addition of ketyl radicals to ketimines generated in situ. The reaction occurs under mild conditions by mediation of the TiCl4/Zn/t-BuOOH system, leading to the formation of quaternary ß-amino-ethers and -alcohols. The new reaction conditions guarantee good selectivity by preventing the formation of secondary products. The secondary products are possibly derived from a competitive domino reaction, which involves further oxidation of the ketyl radicals.

TEMPO-Oxidized Cellulose Cross-Linked with Branched Polyethyleneimine: Nanostructured Adsorbent Sponges for Water Remediation.

Adsorbent sponges for water remediation were prepared using TEMPO-oxidized cellulose nanofibers (TOCNFs) as three-dimensional scaffolds, and branched polyethyleneimine (bPEI, 25 KDa) as the cross-linking agent. TOCNFs were suspended in aqueous solution in the presence of variable amounts of bPEI. The mixtures were first freeze-dried and then thermally treated (from 60 to 102 °C over 10 h) promoting the formation of amide bonds between the carboxylic groups of TOCNF and the primary amines of bPEI. The resulting materials, which were characterized by FTIR and 13 C CP-MAS NMR spectroscopy, scanning electron microscopy, and elemental analysis, showed higher chemical and mechanical stability in water than non-reticulated cellulose composites. The high adsorption capability of the new sponges was verified for different organic pollutants (p-nitrophenol, 2,4,5-trichlorophenol, and amoxicillin), and heavy metal ion pollutants (Cu, Co, Ni, Cd), indicating their potential for water decontamination.

New advances in titanium-mediated free radical reactions.

Titanium complexes have been widely used as catalysts for C­C bond-forming processes via free-radical routes. Herein we provide an overview of some of the most significant contributions in the field, that covers the last decade, emphasizing the key role played by titanium salts in the promotion of selective reactions aimed at the synthesis of multifunctional organic compounds, including nucleophilic radical additions to imines, pinacol and coupling reactions, ring opening of epoxides and living polymerization.

New domino radical synthesis of aminoalcohols promoted by TiCl4-Zn/t-BuOOH system: selective hydroxyalkylation of amines in alcohol or in cyclic ether cosolvents.

We report a new and fast domino synthesis of aminoalcohols under mild conditions. The free-radical reaction of aliphatic and aromatic amines with alcohol cosolvents is promoted by means of the TiCl(4)-Zn/t-BuOOH system. According to the proposed mechanism, the amine reacts with two molecules of alcohol in an electrophilic-nucleophilic cascade process. This procedure, if compared with the TiCl(3)/t-BuOOH-mediated protocol previously reported, appears to be more selective, of more general applicability and affords the desired products in higher yields. Besides, with the same catalytic system it was possible to promote the reaction of primary arylamines with two molecules of cyclic ether, leading to the formation of a wider range of functionalized aminoalcohols.

Free-radical addition to ketimines generated in situ. New one-pot synthesis of quaternary alpha-aminoamides promoted by a H2O2/TiCl4-Zn/HCONH2 system.

A free radical multicomponent reaction mediated by an acidic TiCl(4)-Zn/H(2)O(2) system allows the assembly of an amine, a ketone, and formamide in one pot, affording instant access to quaternary alpha-amino acid derivatives.

Key role of Ti(IV) in the selective radical-radical cross-coupling mediated by the Ingold-Fischer effect.

We report an innovative approach for the selective synthesis of polyfunctional derivatives by cross-combination of different radicals generated under mild conditions. The coordinating effect of Ti(IV) plays a key role in the reaction mechanism: due to its chelating action on the hydroxyl groups, it promotes the homolytic C-C bond cleavage of alpha,beta-dihydroxy ketones by enhancing the captodative effect and the consequent stabilization of the corresponding alpha-hydroxy-alpha-carbonyl radicals. When these radicals are generated in the presence of stoichiometric amounts of TiCl(4) and 2,2'-azo-bis-isobutyronitrile (AIBN) is employed as a source of alpha-cyanoisopropyl radicals, the selective radical-radical cross-coupling is observed, affording the corresponding beta-hydroxynitriles in high yields. This innovative methodology allows application of the well-known Ingold-Fischer effect to a wider range of stabilized carbon-centered radicals, whose formation derives from the chelating action of Ti(IV).

A new one-pot, four-component synthesis of 1,2-amino alcohols: TiCl3/t-BuOOH-mediated radical hydroxymethylation of imines.

An amine, an aldehyde, and methanol can be readily assembled in one pot under very mild conditions through a free-radical multicomponent reaction by using an aqueous acidic TiCl3/t-BuOOH system to afford 1,2-amino alcohols in fair to excellent yields.

Free-radical version of the strecker synthesis of alpha-aminoamides promoted by aqueous H2O2/TiCl3/HCONH2 system.

A new reaction of general synthetic interest representing the free-radical version of the Strecker synthesis to alpha-aminoamides is reported. A hydroxy radical, generated by Ti(III) one-electron reduction of H2O2, abstracts a H atom from the C-H bond of formamide, and the resulting carbamoyl radical adds to the C atom of aldimines formed in situ, leading to a one-pot synthesis of alpha-aminoamides. Several types of aldehydes can participate in this process.

Reactivity of methyl mandelate-Ti(IV)-enediolate: oxidative homocoupling versus aldol and direct Mannich-type syn-diastereoselective condensation.

[reaction: see text] Methyl mandelate undergoes quantitative oxidative homocoupling on treatment with TiCl4/amine at room temperature. In the presence of ArCHO, quantitative syn-diastereoselective aldol condensation takes over the dimerization, whereas exclusive Mannich-type syn-diastereoselective reaction is observed in the presence of both ArCHO and PhNH2. The subsequent reactions of the title intermediate do not depend on how it is generated.

One-pot four-component reaction: aqueous TiCl3/PhN2+-mediated alkyl radical addition to imines generated in situ.

Ti(III)-induced free-radical decomposition of a phenyldiazonium salt, followed by phenyl radical iodine-atom abstraction from alkyl iodides, leads to a one-pot selective alkyl radical addition to the C-atom of imines generated in situ under aqueous acidic conditions. [reaction: see text]