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

Synthesis and characterization of new D-π-A and A-π-D-π-A type oligothiophene derivatives

In this work we present a series of newly synthesized conjugated oligothiophene derivatives, with different numbers of central thiophene units, and different donor/acceptor architectures. Electrochemical and spectroscopic data have also been reported. We used thiophene or bithiophene as central Donor core units, 3-octylthiophenes as π-bridge and solubilizing sub-units, and ethyl cyanoacetate or rhodanine moieties as Acceptor end groups, in order to get D-π-A and A-π-D-π-A molecular architectures. The length of synthesized oligothiophenes ranges from three to eight thiophene units, a variety that is sufficient to put in evidence different optical and electrochemical as well as semiconducting characteristics. Oligothiophene compounds can be regarded not only as models for the study of structure-property relationships relatives to polythiophenes, but also they present a large number of applications in the field of Organic Electronics (i.e.: as donors in bulk-heterojunction solar cells as well as hole-transporting layer materials in perovskite solar cells, among others)

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

A case of intersex occurrence in Steindachneridion parahybae (Steindachner, 1877) (Siluriformes: Pimelodidae) under captivity condition: A cytogenetic and morphological study

Poco se sabe sobre la biología reproductiva de Steindachneridion parahybae , una especie de teleósteo gonocorístico en peligro de extinción que habita la cuenca del río Paraíba do Sul y en éste trabajo se describe por primera vez la aparición de individuo intersexo en juvenil de S. parahybae . También se describió el aspecto normal de los ovarios y de los testículos de individuos juveniles procedentes del mismo lote de cría para su comparación; se realizó además el análisis citogenético. Un espécimen fue clasificado a priori como hembra debido a las características macroscópicas de los ovarios, con pequeños oocitos amarillos, sin flecos (característica principal de los bagres macho) y más grande que los testículos; sin embargo el análisis microscópico reveló la presencia de un ovotestis, incluyendo una espermatogénesis completa. S. parahybae presentó un número diploide, 2n = 56 cromosomas, sin evidencia de cromosomas sexuales diferenciados o supernumerarios entre ellos. Estos hallazgos pueden deberse al resultado de la exposición de los individuos a desorganizadores endocrinos o estar influenciados por las condiciones ambientales. Sin embargo no se puede descartar la posibilidad de la presencia de intersexos de forma espontánea. Por lo tanto, la importancia funcional y las consecuencias reproductivas de estas anomalías permanecen aún sin ser determinadas, sugiriendo que esta especie puede ser susceptible a los disruptores endocrinos. Estos resultados contribuyen a ampliar el conocimiento de la biología reproductiva de esta especie en peligro de extinción en condiciones de cautiverio.Little is known about reproductive biology of endangered Steindachneridion parahybae , a gonochoristic teleost species inhabiting the Paraíba do Sul River Basin, and herein is the first description of intersex in S. parahybae juvenile. The normal appearance of ovaries and testes in juvenile from the same lot of breeding were also described for comparison, even as cytogenetic analysis was performed in these juveniles. One specimen was a priori classified as female due to the macroscopic characteristic of ovaries, with small yellow oocytes, without fringes (a main characteristic of catfish male), and larger than testes; however the microscopic analysis revealed the presence of ovotestes, including the complete spermatogenesis. S. parahybae had diploid number, 2n = 56 chromosomes with no evidence of differentiated sex chromosomes or supernumerary chromosomes among them. These findings may be due to the result of exposure to endocrine disrupting compounds or may also be influenced by environmental conditions. The possibility of intersexes might also happen spontaneously and it cannot be ruled out. Therefore, the functional significance and reproductive consequences of this anomaly remain to be determined, suggesting that this species may be susceptible to endocrine disruption. These results contribute to gain expertise about reproductive biology of an endangered species in captivity.Fil: Honji, Renato Massaaki. Universidade de Sao Paulo; Brasil. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Caneppele, Danilo. Companhia Energética de São Paulo. Unidade de Hidrobiologia e Aquicultura; BrasilFil: Pandolfi, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Biodiversidad y Biología Experimental y Aplicada. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Biodiversidad y Biología Experimental y Aplicada; ArgentinaFil: Lo Nostro, Fabiana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Biodiversidad y Biología Experimental y Aplicada. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Biodiversidad y Biología Experimental y Aplicada; ArgentinaFil: Moreira, Renata G.. Universidade de Sao Paulo; Brasi

Exploring the anti-biofilm activity of cinnamic acid derivatives in Candida albicans

Some compounds, characterized by phenylethenyl moiety, such as methyl cinnamate and caffeic acid phenethyl ester, are able to inhibit C. albicans biofilm formation. On these bases, and as a consequence of our previous work, we synthesized a series of cinnamoyl ester and amide derivatives in order to evaluate them for the activity against C. albicans biofilm and planktonically grown cells. The most active compounds 7 and 8 showed ⩾50% biofilm inhibition concentrations (BMIC50) of 2 μg/mL and 4 μg/mL respectively, against C. albicans biofilm formation; otherwise, 7 showed an interesting activity also against mature biofilm, with BMIC50 of 8 μg/m

New N,N-dimethylcarbamate inhibitors of acetylcholinesterase: design synthesis and biological evaluation

A series of N,N-dimethylcarbamates containing a N,N-dibenzylamino moiety was synthesized and tested to evaluate their ability to inhibit Acetylcholinesterase (AChE). The most active compounds 4 and 8, showed 85 and 69% of inhibition at 50 mM, respectively. Furthermore, some basic SAR rules were outlined: an alkyl linker of six methylene units is the best spacer between the carbamoyl and dibenzylamino moieties; electron-withdrawal substituents on aromatics rings of the dibenzylamino group reduce the inhibitory power. Compound 4 produces a slow onset inhibition of AChE and this is not due to the carbamoylation of the enzyme, as demonstrated by the time-dependent inhibition assay of AChE with compound 4 and by MALDI-TOF MS analysis of trypsinized AChE inhibited by compound 4. Instead, compound 4 could act as a slow-binding inhibitor of AChE, probably because of its high conformational freedom due to the linear alkyl chain

Reaction of Electrogenerated Cyanomethyl Anion with Cyclohexylisocyanate: Synthesis of N-(cyclohexylcarbamoyl) acetamide. An Unexpected Product

The contamination with water of the cathodic ACN-Et4NBF4 solution gave us the opportunity to investigate alkyl isocyanate reactivity toward electrogenerated anions. The cathodic reduction of a ACN-Et4NBF4 solution led to the formation of both hydroxide and cyanomethyl anions. The reaction of the catholyte with cyclohexylisocyanate led to the exclusive formation of acetamidated product, with no traces of cyanomethylated one. On the contrary, when reacting with benzaldehyde only the cyanomethylated was isolated. Considering that the acetamidated product of benzaldehyde is reported to be unstable (thus its formation cannot be excluded), various experiments were carried out in order to understand the anomalous reactivity of cyclohexylisocyanate. Moreover, computational analysis allowed to state the higher stability of acetamidated product with respect to the cyanomethylated one. The possibility of a concerted reaction, instead of acetamide anion formation prior to the reaction, is still an open question

An insight into the reactivity of the electrogenerated radical cation of caffeine

Controlled potential electrolyses of caffeine (CAF) were carried out at a Pt electrode in undried acetonitrile (ACN) and ACN-H2O and the products of the anodic oxidation were analyzed by HPLC-PDA-ESI-MS/MS. A higher current efficiency occurred in ACN-H2O, but an analogous chromatographic outline was found in both media, evidencing a reactive pathway of the electrogenerated radical cation CAF•+ with water, added or in trace, as nucleophile. No dimeric forms were evidenced, excluding any coupling reactions. Neither was 1,3,7-trimethyluric acid found, reported in the literature as the main oxidative route for CAF in water. Four main chromatographic peaks were evidenced, assigned to four proposed structures on the base of chromatographic and spectral data: a 4,5-diol derivative and an oxazolidin-2-one derivative were assigned as principal oxidation products, supporting a mechanism proposed in a previous work for the primary anodic oxidation of the methylxanthines olefinic C4 = C 5 bond. Two highly polar degradation products were also tentatively assigned, that seemed generating along two different pathways, one opening the imidazolic moiety and another one opening the purinic one

Frameworks de metaheurísticas para problemas de optimización complejos

Las Metaheurísticas son técnicas estocásticas que permiten resolver problemas de optimización continuos y discretos en general. Cuando se aborda un problema muy complejo con muchas variantes, las técnicas matemáticas no alcanzan para obtener soluciones fiables ya que el tiempo computacional aumenta de manera exponencial con el tamaño del problema (Problemas NP). Las Metaheurísticas actúan a favor de este problema ya que explora mejor el espacio de búsqueda eligiendo lugares prometedores y descartando el espacio donde las soluciones no aportan al resultado final. Debido a que existen muchas técnicas Metaheurísticas y cada una puede ser mejor adaptada en problemas específicos debido a la representación de soluciones, se plantea el diseño y construcción de un framework de Metaheurísticas genérico para trabajar con problemas de optimización continua y discreta. Dicho framework contará con las técnicas Metaheurísticas más utilizadas en la literatura e incorporará benchmarks de pruebas con problemas estándares de resolución NP. Dichos problemas serán obtenidos de las variantes CEC 2005 y CEC 2009 donde plantean diferentes formulas matemáticas de optimización de varias variables para poder ejecutar y probar los algoritmos diseñados de manera eficaz.Eje: Agentes y Sistemas InteligentesRed de Universidades con Carreras en Informática (RedUNCI