New Phthalimide-based Sensors for Chiral and Achiral Anions and Peroxides

The first part of this work describes the synthesis of fluorescent and non-fluorescent phthalimide derivatives via straightforward synthetic routes, including multicomponent reactions (MCRs) and aromatic substitutions and reductions. In the second part the synthesis of new photocages based on aminophthalimide-serine was carried out and the fluorescence quenching behaviour of these photocages was investigated. In order to obtain new chiral sensors for achiral and chiral anion recognition fluorescent sensors were synthesized in the third part of this work. The syntheses are based on urea-activated phthalimides with stereogenic centers that were synthesized using an efficient procedure involving a Curtius rearrangement. A non-fluorescent sensor based on a thiourea-activated phthalimide with a stereogenic center was synthesized following a synthetic route involving five steps each of which could be performed with good yields. This work demonstrates the capability of a new series of fluorescent and non-fluorescent chiral sensors to recognize achiral and chiral anions and peroxides. Photophysical properties of the sensors such as absorption, excitation, emission, wavelengths, Stokes shifts, singlet energies, fluorescence lifetimes, quantum fluorescence yields and fluorescence rate constants were determined in several solvents in order to compare the solvent effects on the different photophysical properties of the sensor. The recognition of the achiral and chiral anions was performed through absorption, fluorescence and NMR experiments. To consolidate the experimental results, theoretical calculations based on DFT methods at B31YP/6-31G* level were carried out. Recognition of peroxides was conducted by fluorescence experiments before and after irradiation of the sensor−peroxide solutions at 350 nm. In the last part of this thesis the photophysical properties of luminol derivatives were compared with the parent luminol. Furthermore, comparative studies of the chemoluminescence efficiency of these luminol derivatives were carried out

Decarboxylative Photorelease coupled with Fluorescent Up/Down Reporter Function based on the Aminophthalimide-serine System

The fluorescence of caged phthalimide-serine couples 2 and 4 is up/down modulated by decarboxylative photorelease with fluorescence decrease (2) vs. moderate fluorescence increase (4) serving as reporter function.Soldevilla, A.; Pérez Ruiz, R.; Diaz Miara, Y.; Griesbeck, A. (2010). Decarboxylative Photorelease coupled with Fluorescent Up/Down Reporter Function based on the Aminophthalimide-serine System. Chemical Communications. 46(21):3747-3749. doi:10.1039/c001622e374737494621Pelliccioli, A. P., & Wirz, J. (2002). Photoremovable protecting groups: reaction mechanisms and applications. Photochemical & Photobiological Sciences, 1(7), 441-458. doi:10.1039/b200777kMcCray, J. A., & Trentham, D. R. (1989). Properties and Uses of Photoreactive Caged Compounds. Annual Review of Biophysics and Biophysical Chemistry, 18(1), 239-270. doi:10.1146/annurev.bb.18.060189.001323Majjigapu, J. R. R., Kurchan, A. N., Kottani, R., Gustafson, T. P., & Kutateladze, A. G. (2005). Release and Report:  A New Photolabile Caging System with a Two-Photon Fluorescence Reporting Function. Journal of the American Chemical Society, 127(36), 12458-12459. doi:10.1021/ja053654mPellois, J.-P., Hahn, M. E., & Muir, T. W. (2004). Simultaneous Triggering of Protein Activity and Fluorescence. Journal of the American Chemical Society, 126(23), 7170-7171. doi:10.1021/ja0499142Veldhuyzen, W. F., Nguyen, Q., McMaster, G., & Lawrence, D. S. (2003). A Light-Activated Probe of Intracellular Protein Kinase Activity. Journal of the American Chemical Society, 125(44), 13358-13359. doi:10.1021/ja037801xZhao, Y., Zheng, Q., Dakin, K., Xu, K., Martinez, M. L., & Li, W.-H. (2004). New Caged Coumarin Fluorophores with Extraordinary Uncaging Cross Sections Suitable for Biological Imaging Applications. Journal of the American Chemical Society, 126(14), 4653-4663. doi:10.1021/ja036958mCosa, G., Lukeman, M., & Scaiano, J. C. (2009). How Drug Photodegradation Studies Led to the Promise of New Therapies and Some Fundamental Carbanion Reaction Dynamics along the Way. Accounts of Chemical Research, 42(5), 599-607. doi:10.1021/ar8001969Lukeman, M., & Scaiano, J. C. (2005). Carbanion-Mediated Photocages:  Rapid and Efficient Photorelease with Aqueous Compatibility. Journal of the American Chemical Society, 127(21), 7698-7699. doi:10.1021/ja0517062Soldevilla, A., & Griesbeck, A. G. (2006). Chiral Photocages Based on Phthalimide Photochemistry. Journal of the American Chemical Society, 128(51), 16472-16473. doi:10.1021/ja066582nWarzecha, K.-D., Görner, H., & Griesbeck, A. G. (2006). Photoinduced Decarboxylative Benzylation of Phthalimide Triplets with Phenyl Acetates:  a Mechanistic Study. The Journal of Physical Chemistry A, 110(10), 3356-3363. doi:10.1021/jp055878xGriesbeck, A. G., & Schieffer, S. (2003). Intra- and intermolecular fluorescence quenching of N-activated 4,5-dimethoxyphthalimides by sulfides, amines, and alkyl carboxylates. Photochemical & Photobiological Sciences, 2(2), 113. doi:10.1039/b211008cKim, T. G., Wolford, M. F., & Topp, M. R. (2003). Ultrashort-lived excited states of aminophthalimides in fluid solutionDedicated to the memory of Nobel Laureate, Lord George Porter FRSC FRS OM. Photochemical & Photobiological Sciences, 2(5), 576. doi:10.1039/b300493gSaroja, G., Ramachandram, B., Saha, S., & Samanta, A. (1999). The Fluorescence Response of a Structurally Modified 4-Aminophthalimide Derivative Covalently Attached to a Fatty Acid in Homogeneous and Micellar Environments. The Journal of Physical Chemistry B, 103(15), 2906-2911. doi:10.1021/jp983676dGawroński, J., Gawrońska, K., & Brzostowska, M. (1999). 4,5-Dimethoxyphthalimide and 6,7-dimethoxy-2,3-naphthalimide — Two new chromophoric derivatives for the amino group. Tetrahedron Letters, 40(6), 1191-1194. doi:10.1016/s0040-4039(98)02562-3Ulrich, H., & Richter, R. (1973). 4-Isocyanatophthalic anhydride. Novel difunctional monomer. The Journal of Organic Chemistry, 38(14), 2557-2558. doi:10.1021/jo00954a034Casimir, J. R., Guichard, G., & Briand, J.-P. (2002). Methyl 2-((Succinimidooxy)carbonyl)benzoate (MSB):  A New, Efficient Reagent forN-Phthaloylation of Amino Acid and Peptide Derivatives†. The Journal of Organic Chemistry, 67(11), 3764-3768. doi:10.1021/jo016347hBlake, J. A., Gagnon, E., Lukeman, M., & Scaiano, J. C. (2006). Photodecarboxylation of Xanthone Acetic Acids:  C−C Bond Heterolysis from the Singlet Excited State. Organic Letters, 8(6), 1057-1060. doi:10.1021/ol052953dGörner, H., Griesbeck, A. G., Heinrich, T., Kramer, W., & Oelgemöller, M. (2001). Time-Resolved Spectroscopy of Sulfur- and Carboxy-SubstitutedN-Alkylphthalimides. Chemistry, 7(7), 1530-1538. doi:10.1002/1521-3765(20010401)7:73.0.co;2-lPérez-Ruiz, R., Díaz, Y., Goldfuss, B., Hertel, D., Meerholz, K., & Griesbeck, A. G. (2009). Fluoride recognition by a chiral urea receptor linked to a phthalimide chromophore. Organic & Biomolecular Chemistry, 7(17), 3499. doi:10.1039/b908433

Fundamentos de la Nutrición - NU138 - 202101

El curso de Fundamentos de la Nutrición contempla el estudio de los aspectos básicos de la alimentación y nutrición. Busca que el estudiante identifique los conceptos básicos de alimentación y nutrición así como los diversos componentes de los alimentos para beneficio de las personas. De igual forma, busca que el estudiante conozca los principales campos de acción del nutricionista y el marco legal que regula su quehacer profesional. Está dirigido a los estudiantes de primer ciclo de la Carrera de Nutrición y Dietética. Desarrolla el primer nivel de la Competencia general de Ciudadanía y el primer nivel de las Competencias específicas de Nutrición básica y Profesionalismo

Steric Enhancement of the Chemiluminescence of Luminols

A surprising 20-fold increase in chemiluminescence efficiency was observed for dialkyl luminol derivatives in comparison with the parent compound. This effect could be a direct consequence of steric gearing which facilitates the transition from the intermediate endoperoxide to the electronically excited phthalate. Mechanistic aspects of this process have been supported by computational calculations (CASPT2//CASSCF)

Time-Series of Phytoplankton Taxonomy and Density collected by the CARIACO Ocean Time-Series Project from November 1995 to January 2017

Dataset: phytoplankton taxonomyThe CARIACO Ocean Time-Series Program (formerly known as CArbon Retention In A Colored Ocean) started on November 1995 (CAR-001) and ended on January 2017 (CAR-232). Monthly cruises were conducted to the CARIACO station (10.50° N, 64.67° W) onboard the R/V Hermano Ginés of the Fundación La Salle de Ciencias Naturales de Venezuela. The program studied the relationship between surface primary production, physical forcing variables like the wind, and the settling flux of particulate carbon in the Cariaco Basin. This depression, located on the continental shelf of Venezuela, shows marked seasonal and interannual variation in hydrographic properties and primary production (carbon fixation rates by photosynthesis of planktonic algae). One of the monthly measurements taken by the program was water sampling at different depths for phytoplankton taxonomy (occurrence and density). Those water samples were collected with Niskin bottles during the first CTD Cast of the morning at 1, 7, 25, 35, 75, and 100 m depth. Phytoplankton taxonomy and density was determined at each depth at the level of species or genera. Values of zero are real and denote that a specific species was not found at that cruise/depth. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/3095NSF Division of Ocean Sciences (NSF OCE) OCE-9401537, NSF Division of Ocean Sciences (NSF OCE) OCE-9729697, NSF Division of Ocean Sciences (NSF OCE) OCE-0326268, NSF Division of Ocean Sciences (NSF OCE) OCE-9216626, NSF Division of Ocean Sciences (NSF OCE) OCE-9711318, National Aeronautics & Space Administration (NASA) NAS5-97128, NSF Division of Ocean Sciences (NSF OCE) OCE-9415790, NSF Division of Ocean Sciences (NSF OCE) OCE-9729284, National Aeronautics & Space Administration (NASA) NAG5-6448, NSF Division of Ocean Sciences (NSF OCE) OCE-0963028, NSF Division of Ocean Sciences (NSF OCE) OCE-0752139, Fondo Nacional de Ciencia, Tecnología e Innovación of Venezuela (FONACIT) 96280221, NSF Division of Ocean Sciences (NSF OCE) OCE-0326313, National Aeronautics & Space Administration (NASA) NNX14AP62A, Fondo Nacional de Ciencia, Tecnología e Innovación of Venezuela (FONACIT) 2000001702, Fondo Nacional de Ciencia, Tecnología e Innovación of Venezuela (FONACIT) 201100035

Study on bladder cancer related to toxic habits in Cuba

Aretrospective descriptive crosssectionalobservational study wasconducted at the Urology Service ofthe Celestino Hernández Hospital, in the Municipality ofSanta Clara, Villa Clara Province, in the period from 2014-2019 with the aim of characterizing epidemiological, clinical,diagnostic and therapeutic patients with bladdertumors who have been active smokers for most of their lives.The population was conformed by 147 patients withTransitional Papillary Bladder Carcinoma. Among the mostfrequent variables was found the toxic habits of these patientsthrough the means used to diagnose the disease.In the applied surgical treatment, postoperative tumor recurrence,postoperative complications and localization ofmetastases at the time of diagnosis made the continuityof tobacco consumption impossible. Smoking was moreprevalent in 83%. Pulmonary metastases were the mostfrequent with 9.52% of the population

Study on bladder cancer related to toxic habits in Cuba

Aretrospective descriptive crosssectionalobservational study wasconducted at the Urology Service ofthe Celestino Hernández Hospital, in the Municipality ofSanta Clara, Villa Clara Province, in the period from 2014-2019 with the aim of characterizing epidemiological, clinical,diagnostic and therapeutic patients with bladdertumors who have been active smokers for most of their lives.The population was conformed by 147 patients withTransitional Papillary Bladder Carcinoma. Among the mostfrequent variables was found the toxic habits of these patientsthrough the means used to diagnose the disease.In the applied surgical treatment, postoperative tumor recurrence,postoperative complications and localization ofmetastases at the time of diagnosis made the continuityof tobacco consumption impossible. Smoking was moreprevalent in 83%. Pulmonary metastases were the mostfrequent with 9.52% of the population

L'impact de la gestion des processus sur les agences gouvernementales

The challenge of all organization is to achieve the operations of the item that they develop efficiently. At present, the integration of the markets and the competition specialized of the private sector, they have influence like pillars in order that the users of the public utility catch up with products and services of quality. In front of the present-day circumstances, the public administration tends to modernize its processes and to measure up to the circumstances of competitiveness; The implementation of the step for processes, you come getting successes in many from the organisms, identifying the proposal of value to the customer, where his processes work of efficacious form, surpassing the dissatisfaction in relation to the items that you offer the public administration. In that connection, this implementation with an orientation of quality and continuous improvement implies for organizations continuously to improve his efficiency and efficacy where the interrelation of his processes keys, obtain results that have influence upon the end customerEl reto de toda organización es cumplir eficientemente las operaciones del rubro que desarrollan. Actualmente, la integración de los mercados y la competencia especializada del sector privado, influyen como pilares para que los usuarios del servicio público alcancen productos y servicios de calidad. Ante las circunstancias actuales, la administración pública tiende a modernizar sus procesos y estar a la altura de las circunstancias de la competitividad; la implementación de la gestión por procesos, viene obteniendo éxitos en muchos de los organismos, identificando la propuesta de valor al cliente, donde sus procesos funcionen de forma eficaz, superando la insatisfacción en relación con los rubros que brinda la administración pública. En ese sentido, esta implementación, con una orientación de calidad y mejora continua, implica que las organizaciones continuamente mejoren su eficiencia y eficacia, donde la interrelación de sus procesos claves obtenga resultados que repercutan en el cliente finalLe défi de toute organisation est de mener efficacement les opérations de la zone qu'elle développe. Actuellement, l'intégration des marchés et la compétence spécialisée du secteur privé, influencent en tant que piliers pour les utilisateurs du service public pour atteindre des produits et des services de qualité. Dans les circonstances actuelles, l'administration publique tend à moderniser ses processus et à être à la hauteur des circonstances de compétitivité; la mise en œuvre de la gestion par processus, vient obtenir des succès dans beaucoup d'organismes, en identifiant la proposition de valeur pour le client, où leurs processus fonctionnent de manière efficace, dépassant l'insatisfaction par rapport aux rubriques que l'administration publique offre. En ce sens, cette mise en œuvre avec une orientation vers la qualité et l'amélioration continue implique que les organisations améliorent continuellement leur efficacité et leur efficience lorsque l'interrelation de leurs processus clés permet d'obtenir des résultats qui ont un impact sur le client fina