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  • Open access
  • 74 Reads
Effect of the Addition of [C3C1im][NTf2] in Pine Seed Germination and in Soil Microbial Activity
Despite the increasing number of papers about the study of the properties of the ionic liquids (ILs), the knowledge of their ecotoxicity and biodegradability are not still well established. In this work the effect of the addition of five different concentrations of aqueous solutions (10%, 1%, 0.1%, 0.01% and 0% (control) in weight) of the IL [C3C1im][NTf2] on the seed germination of six species of pine and on the microbial activity of a soil under P. radiata was determined. This IL was selected taking into account that his thermophysical properties make it a good candidate to being used as lubricant. Seed germination test of species of Eucalyptus globulus, Pinus halepensis, Pinus nigra, Pinus pinaster, Pinus sylvestris and Pinus radiata were carried out. The reason to select these species was their wide geographical distribution and their great economic, social and ecological interest. Five replies with 25 seeds per Petri dish were incubated for every species and treatments, in total 3750 seeds were incubated (6 species x 5 treatments x 5 replicates x .25 seeds) Germinated seeds were monitoring every Monday, Wednesday and Friday. Germination had been completed in all the species 45 days of incubation. On the other hand, calorimetric experiments were performed using a microcalorimeter 2277 Thermal Activity Monitor (TAM) Thermometric AB. Measurements were carried out in hermetically sealed 5 ml stainless steel ampoules. Soil samples of 1 g size at water-holding capacity were treated with 0.2 ml of aqueous glucose solution to activate the microbial metabolism.Additionally, a comparison between the effects of this IL in the seed germination and soil microbial activity and the corresponding to two well-known salts, sodium chloride and potassium nitrate, in the same conditions was stablished.Acknowledgements: This study was financed by the project EM2013/031 (Xunta de Galicia, Spain)
  • Open access
  • 67 Reads
Unexpected Transformatios of Aziridino-Heterocumulenes Built on Ortho-Benzene Scaffolds
Our research group has focused its investigations in the study of the reactivity of heteroculumenes. We have recently reported that N-aryl ketenimines and carbodiimides substituted at the ortho position by an azidomethyl function undergo, under mild thermal treatment, an intramolecular [3 + 2] cycloaddition reactions affording indolo[1,2-a]quinazolines and tetrazolo[5,1-b]quinazolines.   Within this frame we reasoned that an aziridine function could act as the three-atom component, by replacing the azido group, in analogous pericyclic reactions of related heterocumulenic compounds. With this aim, we designed N-aryl heterocumulenes bearing a 2-(ethoxycarbonyl)aziridine function at ortho position. These new ketenimines and carbodiimides should be easily accessible from phosphazene derivatives by aza-Wittig reaction with ketenes and isocyanates, respectively.   In this communication we disclose the synthetic route designed to obtain these heterocumulenes and the results of our attempts to thermally promote their intramolecular [3 + 2] cycloaddition reactions. Moreover, we also show the unexpected results reached when the phosphine used for preparing the phosphazene precursors of those azacumulenes is other than the usual triphenylphosphine.
  • Open access
  • 211 Reads
Photoelectrochemical Investigation of TiO2-Graphene Nanocomposites
Recently, renewable energy sources attract lots of attention. Graphene oxide nanostructures are currently under intensive research and development. Graphene consider for using as photovoltaic devises especially for solar cells because of its unique usages for electron transfer, harvesting light and convert it to photocurrent. The photosensitization of TiO2 with graphene is considered to be an effective approach to improving the visible spectral absorption and photo activity under visible light irradiation. Graphene oxide reduction was method of graphene synthesis.  TiO2 was added to different content of graphene oxide and with hydrothermal method 1, 3 and 5 percentage of graphene-TiO2 composite (TG) was synthesized the prepared samples were characterized by XRD, Raman, DRS, and SEM. A dispersed suspension of TiO2 and different percentages of TG were drop casted on FTO and dried in room temperature Photoelectrochemical experiments exhibited that the photocurrent response of three percentages of TG nanocomposite was higher than others.
  • Open access
  • 66 Reads
Extended Anthracenes and Their Use as Dienes in Diels-Alder Reactions
9-Anthranylcarbaldehydes were converted to alkyl 9-anthranylacrylates and 9-phenacylethenylanthracenes. Alkyl 9-anthranylacrylates are brominated to alkyl 9-bromoanthran-10-ylacrylate. Suzuki-reactions with arylboronic lead to alkyl 9,10-arylanthranylacrylates. The alkyl 9-anthranylacrylates and 9-phenacylethenylanthracenes were subjected to cycloaddition reactions to give the respective cycloadducts.
  • Open access
  • 50 Reads
Ring Rearrangements and Reactivity of 3-((4-oxo-4H-chromen-3-yl)methylene)-4-phenyl-1H-[1,5]benzodiazepin-2(3H)-one Towards Some Nucleophiles
Condensation of 4-phenyl-1H-[1,5]benzodiazepin-2(3H)-one (1) with 3-formylchromone (2) afforded a mixture of 3-(chromenylmethylene)-[1,5]benzodiazepinone 3 and 14-chromenylbenzodiazepino[2,3:6,5]pyrano[2,3-b]benzodiazepine 4. Ring rearrangements of compound 3 with different nucleophilic reagents, such as; potassium hydroxide and/or ammonium acetate led to rearrangement into pyranobenzodiazepine 5 and pyridobenzodiazepine 6, respectively. Treatment of compound 3 with hydrazine hydrate, hydroxylamine hydrochloride, malononitrile, cyanothioacetamide, 2-cyano-3,3-disufanylacrylonitrile, and/or 2-cyano-3-phenylamino-3-sufanylacrylonitrile, have been carried out at different conditions, leading to versatile heterocyclic substituted benzodiazepines at position 3, viz; pyrazole 8, isoxazole 9, pyridines 10 and 11, 1,3-dithiine 12, and 1,3-thiazine 13 derivatives.
  • Open access
  • 146 Reads
Synthesis of L-Carnosine and its Applications in Biomedical Field
Chelation therapy is the administration of chelating agents to remove heavy metals from the body. Chelation therapy has a long history of use in clinical toxicology. For the most common forms of heavy metal intoxication – lead, arsenic, or mercury. a number of chelating agents are available are Ethylenediaminetetraacetate (EDTA), Dimercaptosuccinic acid (DMSA), 2,3-dimercapto-1-propanesulfonic acid (DMPS), alpha lipoic acid (ALA) and Carnosine. their used in conventional and alternative medicine. In this work synthesise of Carnosine has been studied. Carnosine (beta-alanyl-L-histidine) is a dipeptide of the amino acids beta-alanine and histidine. Carnosine is found naturally in healthy muscles, heart, brain, liver, kidneys and other tissues. N-Protected amino acids are important intermediates in organic synthesis. The use of N-phthalylamino acids as coupling agents in the synthesis of peptides has been studied by several groups of investigators. hydrolysis of the phthalyl group with hydrazine at room temperature affords a direct synthesis of L-Carnosine. The molecular structures of the compounds were definite by using UV-Vis, FT-IR, and 1H NMR spectroscopy.
  • Open access
  • 89 Reads
Microwave Assisted Synthesis of Tripodal Tris(1H-1,2,3-triazol-4-yl) Cyanurates and Melamines
2,4,6-tris(prop-2-yn-1-yloxy)-1,3,5-triazine and N2,N4,N6-tri(prop-2-yn-1-yl)-1,3,5-triazine-2,4,6-triamine are used in click reactions to prepare tripodal compounds and dendrimer cores. So, 1,3-cycloaddition with benzyl azide under microwave irradiation afforded 2,4,6-tris((1-benzyl-1H-1,2,3-triazol-4-yl)methoxy)-1,3,5-triazine and N2,N4,N6-tris((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1,3,5-triazine-2,4,6-triamine, in a 1 minute reaction with good yields.
  • Open access
  • 72 Reads
Synthesis and Characterization of the Photophysical Properties of Novel Heterocyclic Imines
Imine derivatives are an important class of compounds due their biological and optical properties making them suitable for several applications as chemosensor, photochromic, two-photon absorption (TPA) and nonlinear optical (NLO) materials. Additionally, Schiff bases can be used as ligands, able to complex with different metals in various oxidation states, showing great catalytic activity. Imines having intramolecular hydrogen-bonding are a versatile class of compounds for the design of optical materials since proton transfer in these systems origin the change of their optical properties.As part of an on-going research to develop efficient heterocyclic systems for optical applications (NLO, photochromic, chemosensor, etc) we report in this communication the synthesis and the photophysical characterization of heterocyclic imines 1 and 2 functionalized with thiadiazole or benzothiazole as acceptor groups linked to an aryl ring.AcknowledgementsThanks are due to Fundação para a Ciência e Tecnologia (FCT-Portugal) and FEDER-COMPETE for financial support through Centro de Química [PEst-C/QUI/UI0686/2011 (F-COMP-01-0124-FEDER-022716)] and a PhD grant to M.C.R. Castro (SFRH/BD/78037/2011). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased with funds from FCT and FEDER. We are also grateful to the Instituto da Educação of Universidade do Minho for providing the laboratory infrastructure necessary for the development of this work.
  • Open access
  • 218 Reads
Tributylstannyl Azide as Efficient Reagent in the Synthesis of Aryl Azides from Aryl Amines
The use of aryl azides as synthetic intermediates has attracted much attention due to their potential applications in organic and bioorganic chemistry. Because of their relatively high stability, these compounds have found biological and industrial use as photoaffinity labeling reagents for biomolecules, as cross-linkers in photoresistors, for conducting polymers, and for light-induced activation of polymer surfaces. In recent years, aryl azides have been popularized in the field of "click chemistry" due to their participation in Cu-(I)-catalyzed cycloaddition to alkynes (CuAAC). One of the most straightforward routes for the preparation of aryl azides involves diazotization of aryl amines with tert-butyl nitrite (t-BuONO), followed by addition of trimethylsilyl azide (TMSN3) under mild conditions. Although this procedure is highly efficient with excellent yields, the use of TMSN3 has some downsides; this compound is volatile and hydrolytically unstable resulting in the release of toxic and explosive hydrazoic acid. Furthermore, it has a high cost and a tedious synthetic method. On the other hand, trialkylstannyl azides, which can also act as transfer agent of N3 group, are more stable, more resistant to hydrolysis and are easily obtained by the reaction of the corresponding trialkyltin chloride with sodium azide. These properties, together with the importance of aryl azides, encouraged us to initiate a study on the reaction of aryl amines with tributylstannyl azide, using t-BuONO and p-toluenesulfonic acid for the diazotization process. We found that, under previously optimized reaction conditions, a variety of substituted aryl amines, with both electron-withdrawing and electron-donating groups were transformed into aryl azides in good to excellent yields. An important advantage of this method is that, despite their high toxicity, tin byproducts can be reconverted into the starting tributylstannyl azide by treatment with sodium azide and reused after chromatographic separation of the aryl azide.
  • Open access
  • 84 Reads
Natural Coumarins: QSTR Approaches Regarding Their Genotoxicity
Coumarins are a group of phytochemicals with multiple applications in different fields, such as food and medicine. Many of their benefits are based on the different activities that they display, within which stand antioxidant properties. However, some conflicting evidences suggest the need to clarify or estimate the safety aspects (genotoxicity) of this group of compounds. In this sense it has been shown in previous studies that some of them have presented pro-oxidant activity in vitro and clastogenic activity in silico. Therefore, in this paper chemical structures of natural coumarins that come from various natural sources were studied. This database became topological-structural information, using molecular descriptors from the TOPSMODE approach. A virtual screening was also held that used a model of structure-clastogenic activity relationship, and linear discriminant analysis (LDA) technique. The main results were interpreted in terms of safety.
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