Bernardo Melai

Validation of the copper(i)-catalyzed azide-alkyne coupling in ionic liquids. Synthesis of a triazole-linked C-disaccharide as a case study.

The first study of a copper(I)-catalyzed azide-alkyne click reaction in ionic liquids (ILs) is reported. The cycloaddition of a sugar azide with a sugar acetylene (CuI, i-Pr2EtN, 80 degrees C) was carried out in 10 ILs as well as in standard molecular solvents (toluene and DMF) to give the 1,4-disubstituted triazole-linked C-disaccharide. The highest yields (84 and 95%) were registered in Ammoeng 110 and [C(8)dabco][N(CN)(2)]. The latter solvent was recycled in four subsequent reactions without loss of the reaction efficiency. Reactions carried out in the absence of the Hünigs base afforded mixtures of 1,4- and 1,5-disubstituted triazole regioisomers.

Water sorption by anhydrous ionic liquids

The kinetics of water vapour sorption by several anhydrous hydrophobic and hydrophilic ionic liquids (ILs) were gravimetrically determined at 25 °C and two levels of humidity, namely 43 and 81%. A simple equation was used to fit the data. The kinetic parameters obtained from the different ILs were compared and the differences were related to the IL structures. Results showed that even hydrophobic ILs absorb water at an unexpected speed.

Microwave-enhanced ionothermal CuAAC for the synthesis of glycoclusters on a calix[4]arene platform.

A tetra-azido calix[4]arene derivative was allowed to react with ethynyl tetra- O-benzyl- C-galactoside in the presence of CuI and i-Pr 2EtN in three different ionic liquids, that is, [C 8dabco][N(CN) 2], [C 8dabco][Br], and Ammoeng 110. Reactions were performed at 80 degrees C by thermal and MW dielectric heating. In all cases, multiple cycloadditions took place to give a triazole-linked tetra- C-galactosyl-calix[4]arene in up to 90% yield. The [C 8dabco][N(CN) 2] ionic liquid was also used to perform the multiclick reactions with propargyl O-lactoside and S-sialoside.

The Role of Diallyl Sulfides and Dipropyl Sulfides in the In Vitro Antimicrobial Activity of the Essential Oil of Garlic, Allium sativum L., and Leek, Allium porrum L.

The in vitro antibacterial activity of essential oils (EOs) obtained from fresh bulbs of garlic, Allium sativum L., and leek, Allium porrum L. ( Alliaceae), was studied. A. sativum (garlic) EO showed a good antimicrobial activity against Staphylococcus aureus (inhibition zone 14.8 mm), Pseudomonas aeruginosa (inhibition zone 21.1 mm), and Escherichia coli (inhibition zone 11.0 mm), whereas the EO of A. porrum (leek) had no antimicrobial activity. The main constituents of the garlic EO were diallyl monosulfide, diallyl disulfide (DADS), diallyl trisulfide, and diallyl tetrasulfide. The EO of A. porrum was characterized by the presence of dipropyl disulfide (DPDS), dipropyl trisulfide, and dipropyl tetrasulfide. The antimicrobial activities of the DADS and DPDS were also studied. The results obtained suggest that the presence of the allyl group is fundamental for the antimicrobial activity of these sulfide derivatives when they are present in Allium or in other species (DADS inhibition zone on S. aureus 15.9 mm, P. aeruginosa 21.9 mm, E. coli 11.4 mm). Copyright

An unusual common ion effect promotes dissolution of metal salts in room-temperature ionic liquids: a strategy to obtain ionic liquids having organic–inorganic mixed cations

A simple strategy has been reported to prepare new ionic liquids with binary systems of organic–inorganic cations exploiting the common ion effect, i.e. dissolving metal salts with organic or inorganic anions (bistriflylimide or nitrate) in ionic liquids bearing the same anions. The resulting concentrated solutions of metal cations in ionic environments, which may have great potential for electrochemical processes, have been characterized by X-Ray photoelectron spectroscopy (XPS) and electrospray ionization mass spectrometry (ESI-MS)

Synthesis and properties of glycerylimidazolium based ionic liquids: a promising class of task-specific ionic liquids

A series of task-specific ionic liquids (TSILs) based on glycerylimidazolium cations have been prepared by reaction of 1-chloropropanediol, a compound obtainable from glycerol (a widely available and in-expensive waste product), with the appropriate base (1-H-imidazole, 1,2-dimethylimidazole and 1-methyl-1-H-imidazole). The reaction of 3-(1H-imidazol-1-yl)propane-1,2-diol with chloroalkanes, bromoalkanes and alkyl mesylates gave the corresponding salts which were characterized. The possibility to use these ILs in palladium catalyzed reactions was evaluated, evidencing good catalyst stability and a high recyclability.

Basic ionic liquids based on monoquaternized 1,4-diazobicyclo[2.2.2]octane (dabco) and dicyanamide anion: Physicochemical and solvent properties

In this paper, we report on the synthesis and application of monosubstituted diazabicyclo[2.2.2]octane (dabco) cations associated with a basic anion, dicyanamide. Key properties of these salts—phase transitions, density, and conductivity—were measured and compared to those of other common ionic liquids (ILs). Moreover, solvatochromic dyes were used to assess their solvation properties. The Heck cross-coupling reaction was evaluated in dabco-based ILs and compared with the behavior in common unfunctionalized ILs, evidencing good catalyst stability and a high recyclability in these basic ILs.

Essential oil composition of Helichrysum italicum (Roth) G. Don ssp. italicum from Elba Island (Tuscany, Italy).

The composition of 21 essential‐oil samples isolated from Helichrysum italicum collected in seven locations of Elba Island (Tuscany, Italy), characterized by different soil types, during three different periods (January, May, and October 2010) was determined by GC‐FID and GC/EI‐MS analyses. In total, 115 components were identified, representing 96.8–99.8% of the oil composition. The oils were characterized by a high content of oxygenated monoterpenes (38.6–62.7%), while monoterpene and sesquiterpene hydrocarbons accounted for 2.3–41.9 and 5.1–20.1% of the identified constituents, respectively. The main oxygenated derivatives were nerol (2.8–12.8%) and its ester derivative neryl acetate (5.6–45.9%). To compare the chemical variability of the species within Elba Island and between the island and other localities within the Mediterranean area, studied previously, multivariate statistical analysis was performed. The results obtained showed a difference in the composition of the essential oils of H. italicum from Elba Island, mainly due to the environment where the plant grows, and, in particular, to the soil type. These hypotheses were further confirmed by the comparison of these oils with essential oils obtained from H. italicum collected on other islands of the Tuscan archipelago.

Determination of total and unbound warfarin and warfarin alcohols in human plasma by high performance liquid chromatography with fluorescence detection

Two analytical procedures are presented for the determination of the total content and unbound fraction of both warfarin and warfarin alcohols in human plasma. Chromatographic separation was carried out in isocratic conditions at 25°C on a C-18 reversed-phase column with a mobile phase consisting of a 70% buffer phosphate 25mM at pH=7, 25% methanol and 5% acetonitrile at a flow rate of 1.2mL/min. Fluorescence detection was performed at 390nm (excitation wavelength 310nm). Neither method showed any detectable interference or matrix effect. Inter-day recovery of the total warfarin and warfarin alcohols at a concentration level of 1000ng/mL was 89±3% and 73±3%, respectively, whereas for their unbound fraction (at a concentration level of 10ng/mL) was 66±8% and 90±7%, respectively. The intra- and inter-day precision (assessed as relative standard deviation) was <10% for both methods. The limits of detection were 0.4 and 0.2ng/mL for warfarin and warfarin alcohols, respectively. The methods were successfully applied to a pooled plasma sample obtained from 69 patients undergoing warfarin therapy.

Photochirogenesis in chiral ionic liquid: enantiodifferentiating [4+4] photocyclodimerization of 2-anthracenecarboxylic acid in (R)-1-methyl-3-(2,3-dihydroxypropyl)imidazolium bistriflimide

Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid and its alkali metal salts performed in a chiral ionic liquid gave chiral cyclodimers in good enantiomeric excesses of up to 41%, which is the highest ever reported for a photochirogenic reaction in chiral media.