Role of Anion and Cation in the 1-Methyl-3-butyl Imidazolium Ionic Liquids BMImX: The Knoevenagel Condensation

1-Methyl-3-butylimidazolium ionic liquids BMImX (X anions: Ac−, HCO3−, Cl−, BF4−, PF6−, I−, CF3CO2−, (CF3SO2)2N−, CF3SO3−) were used as catalysts in the Knoevenagel condensation reaction. The catalytic activity was compared with that of the inorganic salts NaAc, NaHCO3, NaCl. Whereas it is quite important to select suitable cation and anion depending on the purpose, the basicity of the anion X−and the ability of the counter-ion BMIm+to avoid the ion pairing with anion X−was investigated. 1-Methyl-3-butyl imidazolium acetate [BMImAc] and 1-methyl-3-butyl imidazolium hydrogen carbonate [BMImHCO3] show the most significant catalytic power and their catalytic effect was studied on a wide range of aromatic, heteroaromatic or aliphatic aldehydes or ketones with active methylene compounds. The corresponding substituted alkenes were obtained in excellent yields (up to 98%) in the absence of any solvent at room temperature within short times. The interesting feature of this study includes explanation on role of the cation BMIm+as proton donor (versus anions Ac−or HCO3−), in ion pair formation (with anion X−) and activator of the aldehyde structure

First direct evidence of N-heterocyclic carbene in BMIm acetate ionic liquid. An electrochemical and chemical study on the role of temperature

Cyclic voltammetry provides the first direct evidence of N-­heterocyclic carbene (NHC) presence in neat 1-‐butyl-­3-­methylimidazolium acetate ionic liquid (BMImAcO) at 120°C. The NHC existence, proved by its oxidation current in cyclic voltammetry, was confirmed by the formation of a PhCHO-­NHC adduct in pure ionic liquid. The role of the temperature was considered

Electrochemically modified Corey-Fuchs reaction for the synthesis of arylalkynes. the case of 2-(2,2-dibromovinyl)naphthalene

The electrochemical reduction of 2-(2,2-dibromovinyl)naphthalene in a DMF solution (Pt cathode) yields selectively 2-ethynylnaphthalene or 2-(bromoethynyl)naphthalene in high yields, depending on the electrolysis conditions. In particular, by simply changing the working potential and the supporting electrolyte, the reaction can be directed towards the synthesis of the terminal alkyne (Et4NBF4) or the bromoalkyne (NaClO4). This study allowed to establish that 2-(bromoethynyl)naphthalene can be converted into 2-ethynylnaphthalene by cathodic reduction

NHC in Imidazolium Acetate Ionic Liquids: Actual or Potential Presence?

Ionic liquids (ILs) are considered in the majority of cases green solvents, due to their virtually null vapor pressure and to the easiness in recycling them. In particular, imidazolium ILs are widely used in many fields of Chemistry, as solvents or precursors of N-heterocyclic carbenes (NHCs). The latter are easily obtained by deprotonation of the C2-H, usually using strong bases or cathodic reduction. Nevertheless, it is known that weaker bases (e.g., triethylamine) are able to promote C2-H/D exchange. From this perspective, the possibility of deprotonating C2-H group of an imidazolium cation by means of a basic counter-ion was seriously considered and led to the synthesis of imidazolium ILs spontaneously containing NHCs. The most famous of this class of ILs are N,N'-disubstituted imidazolium acetates. Due to the particular reactivity of this kind of ILs, they were appointed as "organocatalytic ionic liquids" or "proto-carbenes." Many papers report the use of these imidazolium acetates in organocatalytic reactions (i. e., catalyzed by NHC) or in stoichiometric NHC reactions (e.g., with elemental sulfur to yield the corresponding imidazole-2-thiones). Nevertheless, the actual presence of NHC in N,N'-disubstituted imidazolium acetate is still controversial. Moreover, theoretical studies seem to rule out the presence of NHC in such a polar environment as an IL. Aim of this Mini Review is to give the reader an up-to-date overview on the actual or potential presence of NHC in such an "organocatalytic ionic liquid," both from the experimental and theoretical point of view, without the intent to be exhaustive on N,N'-disubstituted imidazolium acetate applications

Electrogenerated N-Heterocyclic Carbene in Ionic Liquid: An Insight into the Mechanism of the Oxidative Esterification of Aromatic Aldehydes

An N-heterocyclic carbene (NHC), generated by cathodic reduction of BMImBF4, mediates the oxidative esterification of aromatic aldehydes with organic bromides in the corresponding ionic liquid as solvent. The product recovery by simple extractive work-up with diethyl ether allowed the ionic liquid to be recycled up to 9 times for subsequent electrolyses, with no significant loss in the product yield. The isolation of an intermediate, whose structure was confirmed by synthesis and transformation into the ester, provided the key for a mechanistic insight into the reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Effects of passive upper extremity joint mobilization on pain sensitivity and function in participants with secondary carpometacarpal osteoarthritis: A case series

The purpose of this case series is to report on the effects of passive joint mobilization (PJM) of the shoulder, elbow, and wrist on pain intensity, pain sensitivity, and function in elderly participants with secondary carpometacarpal osteoarthritis (CMC OA). METHODS: Fifteen inpatients from the Department of Physical Therapy, Residenze Sanitarie Assistenziali, Collegno (Italy), with secondary CMC OA (70-90 years old) were included in this study. All patients received PJM of the dominant arm (shoulder, elbow, and wrist) for 4 sessions for 2 weeks. Pain severity was measured by visual analog scale, and pain sensitivity was measured with pressure pain threshold (PPT) at CMC joint, at the tubercle of the scaphoid bone, and at the unciform apophysis of the hamate bone. Tip and tripod pinch strength were measured by a pinch gauge. RESULTS: Passive joint mobilization reduced pain severity after the first follow-up by 30%, in addition to increased PPT by 13% in the hamate bone. Strength was enhanced after treatment. Tripod pinch increased by 18% in the dominant hand after treatment. CONCLUSIONS: This case series provides preliminary evidence that PJM of upper extremity joints diminished pain and may increase PPT tip and tripod pinch in some participants with secondary CMC OA.Fil: Villafañe, Jorge Hugo. Universidad Rey Juan Carlos; EspañaFil: Silva, Guillermo Benjamin. Universidad Católica de Córdoba. Facultad de Ciencias Químicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Chiarotto, Alessandro. Universidad Rey Juan Carlos; Españ

Social mindfulness: new systemic awareness for promoting group cohesion in organizations

openSocial Mindfulness significa ri-conoscere che siamo tutti parte di un unico sistema vivente interconnesso dove anche una piccola azione del singolo può avere un grande effetto a livello collettivo. Il senso di coesione e sicurezza che deriva dalla riscoperta dell’appartenenza ad un gruppo sociale, ci può dare la forza di affrontare i problemi complessi, le insicurezze e le sofferenze del mondo di oggi perché ci ricorda che non siamo soli. Riscoprendo la dimensione del Noi possiamo aspirare collettivamente a scopi più elevati per creare intenzionalmente futuri più sostenibili. Anche le organizzazioni hanno bisogno di investire nelle capacità relazionali dei propri membri per creare gruppi di lavoro identitari e coesi e mantenersi competitive. La consapevolezza sistemica e la sicurezza psicologica sono gli strumenti da cui partire. Solo così le organizzazioni potranno diventare luoghi di innovazione e di sviluppo creativo per l’organizzazione e per le persone che la compongono, in un processo ciclico generativo di reciproco benessere. Attraverso l’introduzione delle pratiche e dei programmi formativi di Social Mindfulness nelle aziende si può insegnare a sviluppare gentilezza, compassione, accettazione e nuove competenze relazionali per poter collaborare sfruttando il conflitto e la diversità.Social Mindfulness means re-awareness that we are all part of one interconnected living system where even a small action by an individual can have a big effect at a collective level. The sense of cohesion and security that comes from rediscovering belonging to a social group can give us the strength to face the complex problems, insecurities and suffering of today's world because it reminds us that we are not alone. By rediscovering the dimension of We, is possible aspire collectively to higher purposes to intentionally create more sustainable futures. Organisations also need to invest in the interpersonal skills of their members to create identity and cohesive teams and remain competitive. Systemic awareness and psychological safety are the tools to build on. Only in this way can organisations become places of innovation and creative development for the organisation itself and its member, in a cyclic generative process of mutual well-being. Through the introduction of Social Mindfulness practices and training programmes in companies, one can teach how to develop kindness, compassion, acceptance and new relational skills to be able to collaborate by exploiting conflict and diversity

Charge-tagged N-heterocyclic carbenes (NHCs): revealing the hidden side of NHC-catalysed reactions through electrospray ionization mass spectrometry

N‐heterocyclic carbenes (NHCs) are key intermediates in a variety of chemical reactions. Owing to their transient nature, the interception and characterization of these reactive species have always been challenging. Similarly, the study of reaction mechanisms in which carbenes act as catalysts is still an active research field. This Minireview describes the contribution of electrospray ionization mass spectrometry (ESI‐MS) to the detection of charge‐tagged NHCs resulting from the insertion of an ionic group into the molecular scaffold. The use of different mass spectrometric techniques, combined with the charge‐tagging strategy, allowed clarification of the involvement of NHCs in archetypal reactions and the study of their intrinsic chemistry