Search

Breast cancer is the leading cause of cancer death among women worldwide. For this reason, the development of new therapies is still essential. In this work we have analyzed the antitumor potential of levoglucosenone, a chiral building block derived from the pyrolysis of cellulose-containing materials such as soybean hulls, and three structurally related analogues. Employing human and murine mammary cancer models, we have evaluated the effect of our compounds on cell viability through MTS assay, apoptosis induction by acridine orange/ethidium bromide staining and/or flow cytometry and the loss of mitochondrial potential by tetramethylrhodamine methyl ester staining. Autophagy and senescence induction were also evaluated by Western blot and β-galactosidase activity respectively. Secreted metalloproteases activity was determined by quantitative zymography. Migratory capacity was assessed by wound healing assays while invasive potential was analyzed using Matrigel-coated transwell chambers. In vivo studies were also performed to evaluate subcutaneous tumor growth and experimental lung colonization. All compounds impaired in vitro proliferation with IC50 values in a range of low micromolar. Apoptosis was identified as the main mechanism responsible for the reduction of monolayer cell content induced by the compounds without detecting modulations of autophagy or senescence processes. Two of the four compounds (levoglucosenone and its brominated variant) were able to modulate in vitro events associated with tumor progression, such as migratory potential, invasiveness, and proteases secretion. Furthermore, tumor volume and metastatic spread were significantly reduced in vivo after the treatment these two compounds. Here, we could obtain from soybean hulls, a material with almost no commercial value, a variety of chemical compounds useful for breast cancer treatment.

Fe de erratas del artículo Antineoplastic activity of products derived from cellulose-containing materials: levoglucosenone and structurally-related derivatives as new alternatives for breast cancer treatment. Fil: Delbart, Damian Ignacio. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Giri, Germán Francisco. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Cammarata, Agostina. Comisión Nacional de Energía Atómica. Gerencia de Investigación y Aplicaciones; Argentina. Fil: Pan, Melisa Denise. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Unidad de Transferencia Genética; Argentina. Fil: Bareño, Lizeth Ariza. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Amigo, Natalia Loreley. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Bechis, Andrés. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Suarez, Alejandra Graciela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Spanevello, Rolando Ángel. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Spanevello, Rolando Ángel. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina. Fil: Villaverde, Marcela Solange. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Unidad de Transferencia Genética; Argentina. Fil:Villaverde, Marcela Solange. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina. Fil: Todaro, Laura Beatriz. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Todaro, Laura Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina. Fil: Urtreger, Alejandro Jorge. Universidad de Buenos Aires. Instituto de Oncología Ángel H. Roffo. Área Investigación; Argentina. Fil: Urtreger, Alejandro Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Scientific Research Career; Argentina.

Purpose: Breast cancer is the leading cause of cancer death among women worldwide. For this reason, the development of new therapies is still essential. In this work we have analyzed the antitumor potential of levoglucosenone, a chiral building block derived from glucose, and three structurally related analogues obtained from soybean hulls pyrolysis.Methods: Employing human and murine mammary cancer models, we have evaluated the effect of our compounds on cell viability through MTS assay, apoptosis induction by acridine orange / ethidium bromide staining and/or flow cytometry and the loss of mitochondrial potential by tetramethylrhodamine methyl ester staining. Autophagy and senescence induction were also evaluated by Western blot and β-galactosidase activity respectively. Secreted metalloproteases activity was determined by quantitative zymography. Migratory capacity was assessed by wound healing assays while invasive potential was analyzed using Matrigel-coated transwell chambers. In vivo studies were also performed to evaluate subcutaneous tumor growth and experimental lung colonization.Results: Apoptosis was identified as the main mechanism responsible for the reduction of monolayer cell content induced by the compounds without detecting modulations of autophagy or senescence processes. Two of the four compounds were able to modulate in vitro events associated with tumor progression, such as migratory potential, invasiveness, and proteases secretion. Furthermore, tumor volume and metastatic spread were significantly reduced in vivo after treatment with the compounds.Conclusion: We could obtain from soybean hulls, a material with almost no commercial value, a variety of chemical compounds useful for breast cancer treatment.

The Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) has provided advice in relation to the Chemical Weapons Convention on assistance and protection. We present the SAB's response to a request from the OPCW Director-General in 2014 for information on the best practices for preventing and treating the health effects from acute, prolonged, and repeated organophosphorus nerve agent (NA) exposure. The report summarises pre- and post-exposure treatments, and developments in decontaminants and adsorbing materials, that at the time of the advice, were available for NAs. The updated information provided could assist medics and emergency responders unfamiliar with treatment and decontamination options related to exposure to NAs. The SAB recommended that developments in research on medical countermeasures and decontaminants for NAs should be monitored by the OPCW, and used in assistance and protection training courses and workshops organised through its capacity building programmes. Fil: Timperley, Christopher M.. Defence Science and Technology Laboratory; Reino Unido Fil: Abdollahi, Mohammad. Tehran University of Medical Sciences; Irán Fil: Al-Amri, Abdullah Saeed. Saudi Basic Industries Corporation; Arabia Saudita Fil: Baulig, Augustin. Secrétariat Général de la Défense Et de la Sécurité Nationale; Francia Fil: Benachour, Djafer. Université Ferhat Abbas Sétif 1; Argelia Fil: Borrett, Veronica. Bai Scientific; Australia. University of Melbourne; Australia Fil: Cariño, Flerida A.. University Of The Philippines Diliman; Filipinas Fil: Geist, Michael. Basf Se; Alemania Fil: Gonzalez, David. Universidad de la República Facultad de Química; Uruguay Fil: Kane, William. Monsanto Company; Estados Unidos Fil: Kovarik, Zrinka. Institut Za Medicinska Istrazivanja I Medicinu Rada; Croacia Fil: Martínez Álvarez, Roberto. Universidad Complutense de Madrid; España Fil: Mourão, Nicia Maria Fusaro. ABIQUIM; Brasil Fil: Neffe, Slawomir. Military University of Technology; Polonia Fil: Raza, Syed K.. Institute of Pesticides Formulation Technology; India Fil: Rubaylo, Valentin. State Scientific Research Institute of Organic Chemistry and Technology; Rusia Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Takeuchi, Koji. National Institute of Advanced Industrial Science and Technology; Japón Fil: Tang, Cheng. National Defence University; China Fil: Trifirò, Ferruccio. Universidad de Bologna; Italia Fil: van Straten, Francois Mauritz. South African Nuclear Energy Corporation SOC Ltd.; Sudáfrica Fil: Vanninen, Paula S.. University of Helsinki; Finlandia Fil: Vucinic, Slavica. Vojnomedicinska Akademija; Serbia Fil: Zaitsev, Volodymyr. Pontifícia Universidade Católica do Rio de Janeiro; Brasil. Taras Shevchenko National University Of Kyiv; Ucrania Fil: Zafar Uz Zaman, Muhammad. National Engineering and Scientific Commission; Pakistán Fil: Zina, Mongia Saïd. Université de Tunis El Manar. Faculté Des Sciences de Tunis; Túnez Fil: Holen, Stian. Opcw Scientific Advisory Board Secretary; Países Bajos Fil: Forman, Jonathan E.. Opcw Scientific Advisory Board Secretary And Science Policy Adviser; Países Bajos. Organisation for The Prohibition of Chemical Weapons; Países Bajos Fil: Alwan, Wesam S.. Monash University Victorian College Of Pharmacy; Australia. OPCW Office of Strategy and Policy; Países Bajos Fil: Suri, Vivek. Opcw Office Of Strategy And Policy; Países Bajos

The discovery of efficient organocatalysts is generally carried out by thorough experimental screening of different candidates. We recently reported an efficient organocatalyst for iminium-ion-based asymmetric Diels-Alder reactions following a rational design approach. This result encouraged us to test this optimal catalyst in the mechanistically related Friedel-Crafts alkylation of indoles, but to our surprise, almost null enantioselectivity was observed. The results did not significantly improve with structurally related catalysts, and a totally unexpected facial selectivity inversion was also noticed. Using DFT calculations by modeling the competing transition structures with ONIOM, we could unravel the origins of those findings, further employed to predict the most efficient catalyst for this new transformation. The computational results were validated experimentally (up to 92:8 er), providing another successful example of a general strategy to accelerate catalyst development which still remains underexplored. Fil: Gerosa, Gabriela Guillermina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Marcarino, Maribel Oriana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Fil: Comba, Maria Betina. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Rosario. Instituto de Quimica Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquimicas y Farmaceuticas. Instituto de Quimica Rosario; Argentina

The need to find sustainable alternatives to reduce the dependence on fossil sources has led to significant research efforts on the conversion of biomass into platform chemicals. Modern organic chemistry requires easily obtainable chiral building blocks that show high chemical versatility for their application in the synthesis of enantiopure compounds. The selective pyrolytic conversion of cellulose or cellulose-containing materials produces levoglucosenone, a highly functionalized chiral structure. This compound has been innovatively used as a template for the synthesis of key intermediates of biologically active products and for the preparation of chiral auxiliaries, catalysts, and organocatalysts for their application in asymmetric synthesis.

[EN] Levoglucosenone, directly produced from cellulose-containing residual biomass via pyrolysis treatments, is believed to be a promising bio-renewable platform for both fine and commodity chemicals. In this work, the possibilities given by tuneable catalysts based on Pd and Pt supported on metallic oxides to produce the desired product in the one-pot hydrogenation of levoglucosenone are evaluated. Particularly, the excellent catalytic performance of Pd/ZrO2 and Pt/ZrO2 type materials for the synthesis of dihydrolevoglucosenone (or Cyrene) and levoglucosanol, respectively, during the mild hydrogenation of levoglucosenone is demonstrated. In the Cyrene synthesis, the Pd/t-ZrO2 material showed the best catalytic activity compared to other Pd-supported on metallic oxides. This catalyst achieved nearly 95% yields of Cyrene by working under mild reaction conditions, with very low catalyst loadings (¿3 wt%) and using water as the solvent. On the other hand, the one-pot hydrogenation of levoglucosenone to levoglucosanol is reported for the first time with a Pt-based heterogeneous catalyst (Pt/ZrO2-mix, yield ¿90%), by working at low temperatures and mild H2 pressures with water as the solvent. Comparison of the results attained with other Pt-supported metallic oxides let us to conclude that the metal crystal facets (specifically the 100 facet) play an important role in the hydrogenation process to give levoglucosanol selectively. In addition, the stability and re-usability of both catalysts under operational conditions are also evaluated. Finally, catalytic tests including the use of crude bio-liquids obtained from cellulose-rich biomass pyrolysis and containing ¿66 wt% of levoglucosenone are also assayed, thus demonstrating the possibility of scaling-up the process over these metals supported on zirconia catalysts., Financial support by the Spanish Government (CTQ-201567592, SEV-2016-0683 and PGC2018-097277-B-100) is gratefully acknowledged. R.S. thanks the CONICET financial support (CONICET-CSIC, PVCE Program, RD 4183/15). J.M. thanks MICINN (CTQ2015-67592) for the PhD fellowship. Authors also thank the Electron Microscopy Service of Universitat Politecnica de Valencia for their support.

Las preocupaciones internacionales respecto de la promoción de la vocación científica y el uso responsable del conocimiento científico nos involucra en la búsqueda de nuevas formas de enseñanza de la química que supere la enseñanza meramente propedéutica y se oriente a la formación para un ejercicio responsable de la ciudadanía en lo que respecta a ciencia y tecnología. En el presente trabajo se presentan los resultados de un estudio realizado sobre la percepción que estudiantes de Nivel Secundario tienen sobre la química, sus implicancias e importancia en la vida cotidiana. Para ello se diseñó un cuestionario estructurado en 4 secciones que fue respondido por 795 estudiantes. El análisis de los resultados muestra que los estudiantes asocian la química con expresiones y términos referidos a su dimensión estrictamente disciplinar, reconociendo su impacto en la sociedad como muy positivo. Asimismo, se observó una clara tendencia a vincular la química con algunos elementos del contexto inmediato de los estudiantes lo que posibilitaría la implementación de nuevas metodologías de enseñanza que recupera elementos del contexto para el desarrollo de saberes vinculados con la disciplina desde una perspectiva centrada en la responsabilidad y el desarrollo sostenible. International concerns regarding the promotion of scientific vocation and the responsible use of scientific knowledge involve us in the search for new ways of teaching chemistry that goes beyond the mere propaedeutic education and is oriented towards training for a responsible exercise of citizenship in respect of science and technology. In this research we present the results of a study carried out on the perception that students of Secondary School have about chemistry, its implications and importance in everyday life. For this reason, a structured questionnaire was designed in 4 sections, which was answered by 795 students. The analysis of the results shows that students associate chemistry with expressions and terms referring to its strictly disciplinary dimension, recognizing its impact on society as very positive. Likewise, there was a clear tendency to link chemistry with some elements of the students’ immediate context, which would allow the implementation of new teaching methodologies that retrieves elements of the context for the development of knowledge related to the discipline from a perspective centred on the responsibility and sustainable development. Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Calviño, Néstor Gabriel. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Drogo, Claudia. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Bottai, Hebe María. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Reinoso, Amelia Rosa. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina

The Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) has provided advice on assistance and protection in relation to the Chemical Weapons Convention. In this, the first of several papers describing the SAB's work on this topic, we describe advice given in response to questions from the OPCW Director-General in 2013 and 2014 on the status of available medical countermeasures and treatments to organophosphorus nerve agents. This paper provides the evidence base for this advice which recommended to the OPCW pretreatments, emergency care, and long-term treatments that were available at the time of the request for this class of chemical warfare agent (CWA). It includes a bibliography of over 140 scientific references, which can be used as a platform for watching future medical countermeasure developments. The information provided in this paper should serve as a valuable reference for medical professionals and emergency responders who may have no knowledge of the symptoms and treatment options of exposure to nerve agents. Fil: Timperley, Christopher M.. Defence Science and Technology Laboratory; Reino Unido Fil: Forman, Jonathan E.. OPCW Scientific Advisory Board Secretary and Science Policy Adviser; Países Bajos Fil: Abdollahi, Mohammad. Tehran University Of Medical Sciences; Irán Fil: Al-Amri, Abdullah Saeed. Saudi Basic Industries Corporation; Arabia Saudita Fil: Baulig, Augustin. Secrétariat Général de la Défense et de la Sécurité Nationale; Francia Fil: Benachour, Djafer. Ferhat Abbas University, Setif-1; Argelia Fil: Borrett, Veronica. Bai Scientific; Australia. University of Melbourne; Australia Fil: Cariño, Flerida A.. University of the Philippines; Filipinas Fil: Geist, Michael. Basf Se; Alemania Fil: Gonzalez, David. Universidad de la República Facultad de Química; Uruguay. Universidad de la República; Uruguay Fil: Kane, William. Monsanto Company; Estados Unidos Fil: Kovarik, Zrinka. Institute for Medical Research and Occupational Health; Croacia Fil: Martínez Álvarez, Roberto. Universidad Complutense de Madrid; España Fil: Mourão, Nicia Maria Fusaro. ABIQUIM; Brasil Fil: Neffe, Slawomir. Military University of Technology; Polonia Fil: Raza, Syed K.. Institute Of Pesticide Formulation Technology (ipft); India Fil: Rubaylo, Valentin. State Scientific Research Institute of Organic Chemistry and Technology; Rusia Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Takeuchi, Koji. National Institute of Advanced Industrial Science and Technology; Japón Fil: Tang, Cheng. National Defence University; China Fil: Trifirò, Ferruccio. Universidad de Bologna; Italia Fil: van Straten, Francois Mauritz. South African Nuclear Energy Corporation SOC Ltd; Sudáfrica Fil: Vanninen, Paula S.. Helsingin Yliopisto; Finlandia Fil: Vucinic, Slavica. Vojnomedicinska Akademija; Serbia Fil: Zaitsev, Volodymyr. Pontifícia Universidade Católica do Rio de Janeiro; Brasil. Taras Shevchenko National University of Kyiv, Kyiv; Ucrania Fil: Zafar Uz Zaman, Muhammad. National Engineering And Scientific Commission (nescom); Pakistán Fil: Zina, Mongia Saïd. Université de Tunis El Manar, Faculté Des Sciences de Tunis; Túnez Fil: Holen, Stian. Opcw Scientific Advisory Board Secretary; Países Bajos

Diels–Alder cycloaddition between an enantiomerically pure protected cis-cyclohexadiene diol metabolite and optically pure levoglucosenone derived from cellulose gave rise to complex pentacyclic natural product like structures in a chemically succinct process. The adducts were fully characterized and the observed results were in accord with theoretical calculations performed on the possible course of the reaction.

A series of levoglucosenone-derived 1,2,3-triazoles and isoxazoles featuring a flexible spacer between the heteroaromatic and anhydropyranose cores have been designed and synthesized following an hetero Michael // 1,3-dipolar cycloaddition path. The use of a design of experiments approach allowed the optimization of the oxa-Michael reaction with propargyl alcohol as nucleophile, a key step for the synthesis of the target compounds. All of the compounds were tested for their anticancer activity on MDA-MB-231 cells, featuring mutant p53. The results highlighted the importance of the introduction of the flexible spacer as well as the higher activity of oxa-Michael isoxazole-derivatives. The most prominent compounds also showed anti-proliferative activities against lung and colon cancer cell lines. The compounds showed enhanced cytotoxic effects in the presence of mutant p53, determined both by endogenous mutant p53 knock down (R280K) and by reintroducing p53 R280K in cells lacking p53 expression.

The design and synthesis of biomass-derived triazoles and the in vitro evaluation as potential anticancer agents are described. The discovery of base-catalyzed retro-aza-Michael//aza-Michael isomerizations allowed the exploration of the chemical space by affording novel types of triazoles, difficult to obtain otherwise. Following this strategy, 2,4-disubstituted 1,2,3-triazoles could be efficiently obtained from the corresponding 1,4-disubstituted analogues. Fil: Tsai, Yi Hsuan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Borini Etichetti, Carla Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Di Benedetto, Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Girardini Brovelli, Javier Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Martins, Felipe Terra. Universidade Federal de Goiás; Brasil Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

We have developed a simple procedure for the preparation of chiral 1,3-aminoalcohols using the biomass derivative levoglucosenone, as the chiral starting material. 1,3-aminoalcohols, bearing primary and tertiary amino groups, were tested as chiral catalysts in the asymmetric addition of diethyl zinc to benzaldehyde. Fil: Zanardi, Maria Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Compounds that cause powerful sensory irritation to humans were reviewed by the Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) in response to requests in 2014 and 2017 by the OPCW Director-General to advise which riot control agents (RCAs) might be subject to declaration under the Chemical Weapons Convention (the "Convention"). The chemical and toxicological properties of 60 chemicals identified from a survey by the OPCW of RCAs that had been researched or were available for purchase, and additional chemicals recognised by the SAB as having potential RCA applications, were considered. Only 17 of the 60 chemicals met the definition of a RCA under the Convention. These findings were provided to the States Parties of the Convention to inform the implementation of obligations pertaining to RCAs under this international chemical disarmament and non-proliferation treaty. Fil: Timperley, Christopher M.. Defence Science And Technology Laboratory; Reino Unido. Organisation for the Prohibition of Chemical Weapons; Países Bajos Fil: Forman, Jonathan E.. Organisation for the Prohibition of Chemical Weapons; Países Bajos Fil: Åas, Pal. Norwegian Defence Research Establishment; Noruega Fil: Abdollahi, Mohammad. Tehran University of Medical Sciences; Irán Fil: Benachour, Djafer. Université Ferhat Abbas; Argelia Fil: Al Amri, Abdullah Saeed. Saudi Basic Industries Corporation; Arabia Saudita Fil: Baulig, Augustin. Secrétariat Général de la Défense Et de la Sécurité Nationale; Francia Fil: Becker Arnold, Renate. Basf; Alemania Fil: Borrett, Veronica. University of Melbourne; Australia Fil: Cariño, Flerida A.. University of the Philippines; Filipinas Fil: Curty, Christophe. Spiez Laboratory; Suiza Fil: Gonzalez, David. Universidad de la República; Uruguay Fil: Geist, Michael. Basf; Alemania Fil: Kane, William. Monsanto; Estados Unidos Fil: Kovarik, Zrinka. Institute for Medical Research and Occupational Health; Croacia Fil: Martínez Álvarez, Roberto. Universidad Complutense de Madrid; España Fil: Mikulak, Robert. Fil: Fusaro Mourão, Nicia Maria. Fil: Neffe, Slawomir. Fil: De Souza Nogueira, Evandro. Fil: Ramasami, Ponnadurai. Fil: Raza, Syed K.. Fil: Rubaylo, Valentin. Fil: Saeed, Ahmed E. M.. Fil: Takeuchi, Koji. Fil: Tang, Cheng. Fil: Trifirò, Ferruccio. Universidad de Bologna; Italia Fil: Mauritz Van Straten, Francois. Fil: Suarez, Alejandra Graciela. Fil: Waqar, Farhat. Fil: Vanninen, Paula S.. Fil: Zafar Uz Zaman, Mohammad. Fil: Vucinic, Slavica. Fil: Zaitsev, Volodymyr. Pontifícia Universidade Católica do Rio de Janeiro; Brasil. Taras Shevchenko National University Of Kyiv; Fil: Zina, Mongia Saïd. Fil: Holen, Stian. Fil: Izzati, Fauzia Nurul.

The trend for material and energy recovery from residues along with the need to reduce greenhouse gases has led to an increased interest in the thermal exploitation of biomass and/or their wastes. Due to the enormous quantity generated every year, agro-industrial byproducts have an attractive potential to be recycled. One way to do this is by means of pyrolysis, a thermal decomposition of high molecular weight polymers into simpler compounds. In this study, we applied an autographic assay to analyze the biological effect of bio-oils produced by pyrolysis of soybean hulls. The discovery of a compound with antimicrobial activity validated this novel approach as a tool for the generation of bioactive compounds. Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Viarengo, Gastón. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Furlan, Ricardo Luis Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Investigaciones para el Descubrimiento de Fármacos de Rosario. Universidad Nacional de Rosario. Instituto de Investigaciones para el Descubrimiento de Fármacos de Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Garcia Vescovi, Eleonora. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

The assignment of the relative configuration of spiroepoxides or related quaternary carbon-containing oxiranes can be troublesome and difficult to achieve. The use of GIAO NMR shift calculations can provide helpful assistance in challenging cases of structural elucidation. In this regard, the DP4 probability is one of the most popular methods to be employed when only one set of experimental data is available, though modest results were obtained when dealing with spiroepoxides. Recently, we introduced an improved probability (DP4+) that includes the use of both scaled and unscaled NMR data computed at higher levels of theory. Here, we report a comprehensive study to explore the scope and limitations of the DP4+ methodology in the stereoassignment of terminal or spiroepoxides bearing a wide variety of molecular complexity and conformational freedom. The excellent levels of correct classification achieved were interpreted on the basis of a constructive compensation of errors upon using both scaled and unscaled proton and carbon data. The advantages of the DP4+ methodology in solving two case studies that could not be unequivocally assigned by NOE experiments are also provided. Fil: Zanardi, Maria Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina. Pontificia Universidad Católica Argentina ; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A convenient procedure for the preparation of chiral 1,2-aminoalcohols starting from levoglucosenone, a biomass derivative, is described. The 1,2-aminoalcohols, bearing primary, secondary, and tertiary amino groups, were tested as chiral catalysts in the asymmetric addition of diethyl zinc to benzaldehyde. Fil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Botta, María Celeste. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina. Fil: Suarez, Alejandra Graciela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario (IQUIR-CONICET); Argentina.

The first application of chiral auxiliaries synthesized from levoglucosenone (a biomass-derived anhydrosugar) in asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides is herein reported. The corresponding pyrrolidinic cores were obtained in excellent levels of regio and stereocontrol, good to excellent π-facial selectivities, and could be isolated enantiomerically pure by column chromatography. Unexpected NMR observations coupled with DFT calculations allowed the stereochemical assignment of the synthesized adducts. The stereochemical assignment performed in silico was further unambiguously validated by structural X-ray diffraction analysis. Fil: Llompart, David Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Corne, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Castellano, Eduardo E.. Universidade de Sao Paulo; Brasil. Instituto de Física de São Carlos; Brasil

Fil: Testero, Sebastian Andres. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Rosario. Instituto de Quimica Rosario; Argentina

Alternative sources of starting materials Biomass is the source of renewable carbon that will allow to achieve the future development of our society. With the prospect of the fossil resources depletion, it is necessary to find new alternative sources of energy and raw materials. Chemistry will play a key role to design new materials from biomass which will reshape our way of living and consumption.

The 1,3-dipolar cycloaddition reactions of azomethine ylides is one of the preferred methods for the synthesis of polysubstituted pyrrolidines. The use of chiral dipolarophiles derived from carbohydrates yields enantiomerically pure pyrrolidines, usually in good to excellent endo selectivities, along with other minor stereoisomers. Recently, we found an unusual isomerization event that allowed the isolation of useful pyrrolidines with relative stereochemistries difficult to obtain otherwise. Although a simple and efficient protocol to promote these transformations was developed, the mechanism was not fully unravelled. Herein, after a combination of experimental, spectroscopic and computational studies (using DFT methods) we propose that this isomerization event takes place through a retro-Mannich//Mannich cascade, via the formation of an iminium ion with E geometry. Fil: Gerosa, Gabriela Guillermina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Grimblat, Nicolas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Education and outreach are long term strategic tools for the implementation of the Chemical Weapons Convention (CWC) that actively promote the peaceful use of chemistry. Thousands of new chemicals are reported every day; which can render enormous benefits for the common good. However, as with any science, there is always the possibility that chemistry may be misused as it has been done in the past. This work will refer to preliminary initiatives undertaken to address awareness-raising about the multiple uses of chemical substances and the potential dual -use of scientific knowledge which are being implemented in different levels of chemistry education and public outreach programs. The OPCW has placed a priority on education and engagement with the development of tools and materials relevant to the Convention; we will describe these tools and the regional and national meetings that were organized to highlight the incorporation of the CWC's issues into the chemical curricula in South America. The paper will give special consideration to The Hague Ethical Guidelines, another initiative to support a culture of responsibility in the chemical sciences and to guard against the misuse of chemistry. These guidelines were recently formulated by an international group of chemistry practitioners and serve as a set of elements to engage scientists in the ethical dimensions of their work. Education and outreach to future generations to promote the peaceful uses of chemistry is an essential part of achieving the goal of a world free of chemical weapons. Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Chemicals have essential roles in the advancement of human well-being and for a thriving global economy but at the same time many can be used as weapons or for making them. As the events in Syria over the past few years have shown, in spite of the progress toward complete destruction of the world's declared stocks of chemical weapons, they remain a threat to global peace and security. The global chemistry community can play an important role in helping to prevent their re-emergence. In March and September 2015, the Organisation for the Prohibition of Chemical Weapons hosted two workshops with representatives from academia, industry, and chemical societies to explore the development of ethical guidelines for chemistry professionals. As a result, in October 2015 The Hague Ethical Guidelines were published to provide a framework for promoting the debate on the vital dimension of ethics in relation to chemical disarmament and non-proliferation on all levels of education, research, and practice of the chemical sciences and industries. Fil: Jo Husbands. National Academies of Sciences; Estados Unidos Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A synthetic strategy has been developed for the preparation of immobilized 1,2-aminoalcohols starting from easily available and renewable chiral building blocks. They were tested as chiral ligands for the asymmetric diethylzinc addition to carbonyl compounds. Enantioselectivities were comparable to those observed for non-immobilized analogs. These results provide strong evidence for the flexibility of our approach to generate highly valuable supported chiral ligands derived from cellulose-rich materials.

Chiral acrylic esters derived from biomass were developed as models to have a better insight in the aryl-vinyl π-stacking interactions. Quantum chemical calculations, NMR studies and experimental evidences demonstrated the presence of equilibriums of at least four different conformations: π-stacked and face-to-edge, each of them in an s-cis/s-trans conformation. The results show that the stabilization produced by the π-π interaction makes the π-stacked conformation predominant in solution and this stabilization is slightly affected by the electron density of the aromatic counterpart. Fil: Corne, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: De Arellano, Carmen Ramirez. Universidad de Valencia; España Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

An efficient and straightforward synthesis of a novel 3-thiomannoside derivative (1,2,4,6-tetra-O-acetyl-3-S-acetyl-3-thio-β-d-mannopyranoside) was developed starting from levoglucosenone. A xanthate-thiocarbonate exchange under acidic conditions was the key step for the new C-S bond. The product was obtained enantiospecifically in very good overall yield. Fil: Comba, María Betina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Giordano, Enrique David Victor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

A synthetic strategy has been developed for the preparation of immobilized 1,2-aminoalcohols starting from easily available and renewable chiral building blocks. They were tested as chiral ligands for the asymmetric diethylzinc addition to carbonyl compounds. Enantioselectivities were comparable to those observed for non-immobilized analogs. These results provide strong evidence for the flexibility of our approach to generate highly valuable supported chiral ligands derived from cellulose-rich materials. Fil: Botta, María Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Biava, Hernan Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Mata, Ernesto Gabino. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

An experimental and computational study was conducted to assess the effect of chlorine and bromine substitution in Diels–Alder reactions involving chiral α-halo enones as dienophiles. An important rate enhancement was observed in the case of acyclic dienes, while the use of cyclic dienes resulted in prolonged reaction times and lower yields. DFT calculations suggest that these reactions are governed by finely balanced geometric and electronic features at the TSs.

An appealing inversion in the regiochemical outcome of Diels–Alder reactions between levoglucosenone ( 1 ) and its α-bromo derivative ( 5 ) with isoprene ( 2 ) was studied computationally. Based on different DFT calculations we concluded that both reactions should display the same regioselectivity. This result was further validated experimentally.

The Diels-Alder reaction of a pyranose-derived nitroalkene 1 with cyclopentadiene is described, and the unexpected facial selectivity of the cycloaddition is analyzed by a computational study.

Chiral alcohols were designed and easily prepared from levoglucosenone, a biomass-derived valuable synthon. These alcohols were tested as chiral auxiliaries in asymmetric Diels–Alder reactions between the corresponding acrylates with acyclic and cyclic dienes. The regio, stereo, and facial selectivity varied from very good to excellent, depending upon the benzylic substitution of the auxiliary and the diene employed. As a consequence, after removal of the auxiliary, the resulting carboxylic acid derivatives were obtained in 72–99% ee.

The synthesis of a chiral alcohol derived from levoglucosenone has been studied. The alcohol was employed as chiral template in an asymmetric Diels–Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene, and was shown to be an efficient asymmetric inductor. The oxidation reaction detected during the hydrogenation of a secondary allylic alcohol intermediate with Pd/C was also investigated.

New chiral auxiliaries derived from levoglucosenone were developed in a simple and efficient way and evaluated as chiral inductors in asymmetric Diels–Alder reactions between the corresponding acrylate derivatives and cyclopentadiene. The results showed an important influence of the absolute configuration of the C(2) center of the auxiliary on the level of stereoinduction obtained.

An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity. Fil: Gerosa, Gabriela Guillermina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

Ozonolysis of a carbohydrate derived norbornene system afforded a stable intramolecular cross-ozonide through a stereocontrolled pathway involving a regioselective fragmentation of the primary ozonide.

The Diels–Alder reaction of the acrylate derived from levoglucosenone with cyclopentadiene was studied under several conditions, in the presence and absence of a Lewis acid. The results showed satisfactory diastereomeric excess and the ratio of cycloadducts was found to depend on the reaction conditions. A reversal in stereoselectivity was observed when EtAlCl 2 or Et 2 AlCl were employed as Lewis acids.

A two-step general approach to a new chiral auxiliary starting from levoglucosenone is reported. The compound is obtained by a [4+2] cycloaddition reaction with anthracene followed by a diastereoselective reduction of the C-2 keto function in high overall yield. The auxiliary has been used as chiral template in an asymmetric Diels–Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene and shown to be efficient for asymmetric induction.

The oxirane ring-opening of an anhydro sugar with diethylaluminum cyanide (Et2AlCN) is a direct approach for obtaining a cyano derivative. Methyl 2,3-anhydro-4,6-O-benzylidene-α- d -allopyranoside showed anomalous chemical behavior when treated with Et2AlCN. The reaction afforded the corresponding β-cyanohydrin as the minor component from a mixture of compounds resulting from the benzylidene acetal ring-opening caused by the attack of ethyl or cyano groups.

A short and efficient methodology for the synthesis of chiral dioxa-caged Compounds from levoglucose-none, a biomass-derived enone, is herein Presented. The key transformation, that involves a cascade 3-step cationic cyclization, was efficiently carried out in high yields and selectivities by Montmorillonite K-10 catalysis. The usefulness of K-10 in related semi-pinacol rearrangements to obtain pyran-3-ones is also shown. Interesting differences in the reactivity pattern was found for epimeric alcohols, and the origins of these findings were determined by DFT calculations. Fil: Zurita, Mariano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Avila, Aylén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

Zingerone (1) and both chiral forms of zingerol (2) were obtained from dehydrozingerone (3) by biotransformation with filamentous fungi. The bioconversion of 3 with A. fumigatus, G. candidum or R. oryzae allowed the production of 1 as the sole product at 8 h and in 81%–90% at 72 h. In turn, A. flavus, A. niger, C. echinulata, M. circinelloides and P. citrinum produced 1 at 8 h, but at 72 h alcohol 2 was obtained as the major product (74%–99%). Among them, A. niger and M. circinelloides led to the anti-Prelog zingerol (R)-2 in only one step with high conversion rates and ee. Instead, C. echinulata and P. citrinum allowed to obtain (S)-2 in only one step, with high conversion rates and ee. Both chiral forms of 2 were tested for antifungal properties against a panel of clinically important fungi, showing that (R)-, but not (S)-2 possessed antifungal activity Fil: Svetaz, Laura Andrea. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Di Liberto, Melina Gabriela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Zanardi, Maria Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Zacchino, Susana Alicia Stella. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

The first application of levoglucosenone-derived chiral auxiliaries in asymmetric 1,3-dipolar cycloaddition reactions of azomethine ylides is given.

A general method for the regioselective solvent free Friedel-Crafts acylation of 2-substituted-1,4-benzodioxin derivatives in excellent yields employing the AlCl3DMA reagent with acyl halides or anhydrides as acylating agents is described. The acylation of 2-substituted-1,4-benzodioxin derivatives provides the 6-acyl compound as the major product. However, the saturated analogs affords the 7-acyl regioisomer as the main compound.

Fil: Testero, Sebastian Andres. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Rosario. Instituto de Quimica Rosario; Argentina

Modern organic chemistry requires easily obtainable chiral building blocks that show high chemical versatility for their application in the synthesis of enantiopure compounds. Biomass has been demonstrated to be a widely available raw material that represents the only abundant source of renewable organic carbon. Through the pyrolitic conversion of cellulose or cellulose-containing materials it is possible to produce levoglucosenone, a highly functionalized chiral structure. This compound has been innovatively used as a template for the synthesis of key intermediates of biologically active products and for the preparation of chiral auxiliaries, catalysts, and organocatalysts for their application in asymmetric synthesis. Fil: Biava, Hernan Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Mata, Ernesto Gabino. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Mangione, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Corne, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Botta, María Celeste. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Giordano, Enrique David Victor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Giri, German Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina Fil: Llompart, David Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Rosario. Instituto de Química Rosario; Argentina

For the DA reactions between nitropyrrole derivatives and isoprene, the combination of microwave irradiation and protic ionic liquid, has a notable synergistic effect. DFT calculations suggest that a supplementary energy ranking in the IR region of 1700-1400 cm-1 can favour the structural changes in the reactants to reach the TS. Fil: Mancini, Pedro Maximo Emilio. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina Fil: Ormachea, Carla. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina Fil: Della Rosa, Claudia Daniela. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina Fil: Kneeteman, Maria Nelida. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Domingo, Luis R.. Universidad de Valencia; España

Using either luminescence intensity or lifetime measurements, we have studied the binding interactions of View the MathML source (NN = α-diimine ligands) with non-ionic solutions of surfactant p -(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycol), Triton X-100 (TX-100). The titration curves consisted of two curved regions with different slopes. This biphasic behavior of lifetime-TX-100 concentration data revealed the presence of premicellar aggregates at low TX-100 concentration and the formation of normal micelles at high surfactant concentration. The results were analyzed with a model that includes binding of View the MathML source (probe) to small premicellar aggregates and to micelles. There is a good correlation between the hydrophobicity of the ligands of Cr(III) complex and the strength of the binding of the complexes to the micelles. A comparison with the binding of View the MathML source to sodium dodecylsulfate (SDS) is discussed. Fil: Bazán, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Investigaciones en Físicoquímica de Córdoba; Argentina Fil: Pagliero, Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Investigaciones en Físicoquímica de Córdoba; Argentina Fil: Suarez, Alejandra Graciela. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Arguello, Gerardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Instituto de Investigaciones en Físicoquímica de Córdoba; Argentina

Cellulose-derived chiral pyrrolidines were synthesized in excellent yields, regioselectivities, and stereoselectivities via a 1,3-dipolar cycloaddition reaction between levoglucosenone and azomethine ylides. An unprecedented isomerization event led to a new family of pyrrolidines with an unusual relative stereochemistry. Preliminary results showed that these compounds are promising organocatalysts for iminium ion-based asymmetric Diels-Alder reactions. © 2012 American Chemical Society. Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Spanevello, Rolando Angel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Suarez, Alejandra Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina Fil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina