287 research outputs found

    Ruptured Splenic Hemangioma Presenting As Small Bowel Obstruction: A Case Report

    Get PDF
    Introduction: Splenic hemangioma is a rare vascular tumor of the spleen. Typically asymptomatic, these lesions can present with rupture and hemoperitoneum. Clinical Findings: We report the case of a patient with no previous abdominal surgery that presented with symptoms and imaging consistent with small bowel obstruction (SBO), and an incidental finding of a splenic lesion. Main diagnoses, therapeutic interventions, and outcomes: At diagnostic laparoscopy, a ruptured splenic hemangioma was identified, with obstructive ileus due to hemoperitoneum. The patient subsequently underwent splenectomy to prevent recurrent bleeding. Conclusions: Splenic hemangiomas are rare vascular neoplasms of the spleen, which can be complicated by rupture. While obstructive ileus is a common post-operative phenomenon, it is rarely seen in association with vascular anomalies. This case represents a rare presentation of small bowel obstruction, highlighting the utility of diagnostic laparoscopy in patients with no previous abdominal surgery

    Reinventing the De Mayo reaction: synthesis of 1,5-diketones or 1,5-ketoesters via visible light [2+2] cycloaddition of beta-diketones or beta-ketoesters with styrenes

    Full text link
    [EN] A visible light mediated De Mayo reaction between 1,3-diketones and styrenes following a [2+2] cycloaddition pathway via a photosensitization mechanism gives access to 1,5-diketones. The reaction has been applied to substituted styrenes and aryl- and alkyl-substituted ketones. Moreover, the method converts -ketoesters, -amido esters, and -cyano ketones. Seven membered rings, a frequent structural motif of natural products, are also accessible using this methodology.This work was supported by the Deutsche Forschungsgemein-schaft DFG (GRK 1626, Chemical Photocatalysis). L. M. thanks the Alexander von Humboldt foundation for a postdoctoral fellowship. R. M.-H. thanks the DAAD for a short-term research grant. We thank Ms Regina Hoheisel (University of Regensburg) for her assistance in cyclic voltammetry measurements.Martínez-Haya, R.; Marzo, L.; König, B. (2018). Reinventing the De Mayo reaction: synthesis of 1,5-diketones or 1,5-ketoesters via visible light [2+2] cycloaddition of beta-diketones or beta-ketoesters with styrenes. Chemical Communications. 54(82):11602-11605. https://doi.org/10.1039/c8cc07044jS11602116055482Mayo, P. D., & Takeshita, H. (1963). PHOTOCHEMICAL SYNTHESES: 6. THE FORMATION OF HEPTANDIONES FROM ACETYLACETONE AND ALKENES. Canadian Journal of Chemistry, 41(2), 440-449. doi:10.1139/v63-061Begley, M. J., Mellor, M., & Pattenden, G. (1983). New synthetic approaches to fused-ring carbocycles based on intramolecular photocycloadditions of 1,3-dione enol esters. Journal of the Chemical Society, Perkin Transactions 1, 1905. doi:10.1039/p19830001905Oppolzer, W. (1982). The intramolecular [2 + 2] photoaddition/cyclobutane-fragmentation sequence in organic synthesis. Accounts of Chemical Research, 15(5), 135-141. doi:10.1021/ar00077a002Crimmins, M. T. (1988). Synthetic applications of intramolecular enone-olefin photocycloadditions. Chemical Reviews, 88(8), 1453-1473. doi:10.1021/cr00090a002Kärkäs, M. D., Porco, J. A., & Stephenson, C. R. J. (2016). Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis. Chemical Reviews, 116(17), 9683-9747. doi:10.1021/acs.chemrev.5b00760Winkler, J. D., Rouse, M. B., Greaney, M. F., Harrison, S. J., & Jeon, Y. T. (2002). The First Total Synthesis of (±)-Ingenol. Journal of the American Chemical Society, 124(33), 9726-9728. doi:10.1021/ja026600aWinkler, J. D., Muller, C. L., & Scott, R. D. (1988). A new method for the formation of nitrogen-containing ring systems via the intramolecular photocycloaddition of vinylogous amides. A synthesis of mesembrine. Journal of the American Chemical Society, 110(14), 4831-4832. doi:10.1021/ja00222a053Winkler, J. D., Scott, R. D., & Williard, P. G. (1990). Asymmetric induction in the vinylogous amide photocycloaddition reaction. A formal synthesis of vindorosine. Journal of the American Chemical Society, 112(24), 8971-8975. doi:10.1021/ja00180a049Winkler, J. D., Bowen, C. M., & Liotta, F. (1995). [2 + 2] Photocycloaddition/Fragmentation Strategies for the Synthesis of Natural and Unnatural Products. Chemical Reviews, 95(6), 2003-2020. doi:10.1021/cr00038a010Y.-J. Wu , in Name Reactions for Carbocyclic Ring Formations , ed. J. J. Li , John Wiley & Sons, Inc. , Hoboken, New Jersey , 2010 , ch. 5, pp. 451–488A. C. Weedon , in CRC Handbook of Organic Photochemistry and Photobiology , ed. W. M. Horspool and P.-S. Song , CRC Press , Boca Raton , 1995 , pp. 670–684Ravelli, D., Protti, S., & Fagnoni, M. (2016). Carbon–Carbon Bond Forming Reactions via Photogenerated Intermediates. Chemical Reviews, 116(17), 9850-9913. doi:10.1021/acs.chemrev.5b00662Skubi, K. L., Blum, T. R., & Yoon, T. P. (2016). Dual Catalysis Strategies in Photochemical Synthesis. Chemical Reviews, 116(17), 10035-10074. doi:10.1021/acs.chemrev.6b00018Goddard, J.-P., Ollivier, C., & Fensterbank, L. (2016). Photoredox Catalysis for the Generation of Carbon Centered Radicals. Accounts of Chemical Research, 49(9), 1924-1936. doi:10.1021/acs.accounts.6b00288Yoon, T. P. (2016). Photochemical Stereocontrol Using Tandem Photoredox–Chiral Lewis Acid Catalysis. Accounts of Chemical Research, 49(10), 2307-2315. doi:10.1021/acs.accounts.6b00280Margrey, K. A., & Nicewicz, D. A. (2016). A General Approach to Catalytic Alkene Anti-Markovnikov Hydrofunctionalization Reactions via Acridinium Photoredox Catalysis. Accounts of Chemical Research, 49(9), 1997-2006. doi:10.1021/acs.accounts.6b00304Staveness, D., Bosque, I., & Stephenson, C. R. J. (2016). Free Radical Chemistry Enabled by Visible Light-Induced Electron Transfer. Accounts of Chemical Research, 49(10), 2295-2306. doi:10.1021/acs.accounts.6b00270Ghosh, I., Marzo, L., Das, A., Shaikh, R., & König, B. (2016). Visible Light Mediated Photoredox Catalytic Arylation Reactions. Accounts of Chemical Research, 49(8), 1566-1577. doi:10.1021/acs.accounts.6b00229Meggers, E. (2015). Asymmetric catalysis activated by visible light. Chemical Communications, 51(16), 3290-3301. doi:10.1039/c4cc09268fGuo, L.-N., Wang, H., & Duan, X.-H. (2016). Recent advances in catalytic decarboxylative acylation reactions via a radical process. Organic & Biomolecular Chemistry, 14(31), 7380-7391. doi:10.1039/c6ob01113fMarzo, L., Pagire, S. K., Reiser, O., & König, B. (2018). Visible-Light Photocatalysis: Does It Make a Difference in Organic Synthesis? Angewandte Chemie International Edition, 57(32), 10034-10072. doi:10.1002/anie.201709766Lu, Z., & Yoon, T. P. (2012). Visible Light Photocatalysis of [2+2] Styrene Cycloadditions by Energy Transfer. Angewandte Chemie International Edition, 51(41), 10329-10332. doi:10.1002/anie.201204835Mojr, V., Svobodová, E., Straková, K., Neveselý, T., Chudoba, J., Dvořáková, H., & Cibulka, R. (2015). Tailoring flavins for visible light photocatalysis: organocatalytic [2+2] cycloadditions mediated by a flavin derivative and visible light. Chemical Communications, 51(60), 12036-12039. doi:10.1039/c5cc01344ePagire, S. K., Hossain, A., Traub, L., Kerres, S., & Reiser, O. (2017). Photosensitised regioselective [2+2]-cycloaddition of cinnamates and related alkenes. Chemical Communications, 53(89), 12072-12075. doi:10.1039/c7cc06710kZhao, J., Brosmer, J. L., Tang, Q., Yang, Z., Houk, K. N., Diaconescu, P. L., & Kwon, O. (2017). Intramolecular Crossed [2+2] Photocycloaddition through Visible Light-Induced Energy Transfer. Journal of the American Chemical Society, 139(29), 9807-9810. doi:10.1021/jacs.7b05277Hörmann, F. M., Chung, T. S., Rodriguez, E., Jakob, M., & Bach, T. (2018). Evidence for Triplet Sensitization in the Visible‐Light‐Induced [2+2] Photocycloaddition of Eniminium Ions. Angewandte Chemie International Edition, 57(3), 827-831. doi:10.1002/anie.201710441Alonso, R., & Bach, T. (2014). A Chiral Thioxanthone as an Organocatalyst for Enantioselective [2+2] Photocycloaddition Reactions Induced by Visible Light. Angewandte Chemie International Edition, 53(17), 4368-4371. doi:10.1002/anie.201310997Blum, T. R., Miller, Z. D., Bates, D. M., Guzei, I. A., & Yoon, T. P. (2016). Enantioselective photochemistry through Lewis acid–catalyzed triplet energy transfer. Science, 354(6318), 1391-1395. doi:10.1126/science.aai8228Miller, Z. D., Lee, B. J., & Yoon, T. P. (2017). Enantioselective Crossed Photocycloadditions of Styrenic Olefins by Lewis Acid Catalyzed Triplet Sensitization. Angewandte Chemie International Edition, 56(39), 11891-11895. doi:10.1002/anie.201706975Hanss, D., Freys, J. C., Bernardinelli, G., & Wenger, O. S. (2009). Cyclometalated Iridium(III) Complexes as Photosensitizers for Long-Range Electron Transfer: Occurrence of a Coulomb Barrier. European Journal of Inorganic Chemistry, 2009(32), 4850-4859. doi:10.1002/ejic.200900673Prier, C. K., Rankic, D. A., & MacMillan, D. W. C. (2013). Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis. Chemical Reviews, 113(7), 5322-5363. doi:10.1021/cr300503rTeegardin, K., Day, J. I., Chan, J., & Weaver, J. (2016). Advances in Photocatalysis: A Microreview of Visible Light Mediated Ruthenium and Iridium Catalyzed Organic Transformations. Organic Process Research & Development, 20(7), 1156-1163. doi:10.1021/acs.oprd.6b00101Flamigni, L., Barbieri, A., Sabatini, C., Ventura, B., & Barigelletti, F. (s. f.). Photochemistry and Photophysics of Coordination Compounds: Iridium. Topics in Current Chemistry, 143-203. doi:10.1007/128_2007_131Luo, J., & Zhang, J. (2016). Donor–Acceptor Fluorophores for Visible-Light-Promoted Organic Synthesis: Photoredox/Ni Dual Catalytic C(sp3)–C(sp2) Cross-Coupling. ACS Catalysis, 6(2), 873-877. doi:10.1021/acscatal.5b02204Fukuzumi, S., & Ohkubo, K. (2014). Organic synthetic transformations using organic dyes as photoredox catalysts. Org. Biomol. Chem., 12(32), 6059-6071. doi:10.1039/c4ob00843jRomero, N. A., & Nicewicz, D. A. (2016). Organic Photoredox Catalysis. Chemical Reviews, 116(17), 10075-10166. doi:10.1021/acs.chemrev.6b00057Ni, T., Caldwell, R. A., & Melton, L. A. (1989). The relaxed and spectroscopic energies of olefin triplets. Journal of the American Chemical Society, 111(2), 457-464. doi:10.1021/ja00184a008Xie, Z.-F., Suemune, H., & Sakai, K. (1989). A Facile Ring Enlargement. Synthetic Communications, 19(5-6), 987-992. doi:10.1080/00397918908051019Li, C.-J., Chen, D.-L., Lu, Y.-Q., Haberman, J. X., & Mague, J. T. (1998). Metal-mediated two-atom carbocycle enlargement in aqueous medium. Tetrahedron, 54(11), 2347-2364. doi:10.1016/s0040-4020(98)00004-0Hong, B.-C., Chen, S.-H., Kumar, E. S., Lee, G.-H., & Lin, K.-J. (2003). Intramolecular [2+2] Photocycloaddition-Fragmentation: Facile Entry to a Novel Tricyclic 5-6-7 Ring System. Journal of the Chinese Chemical Society, 50(4), 917-926. doi:10.1002/jccs.200300129Roscini, C., Davies, D. M. E., Berry, M., Orr-Ewing, A. J., & Booker-Milburn, K. I. (2008). Product Selection through Photon Flux: Laser-Specific Lactone Synthesis. Angewandte Chemie International Edition, 47(12), 2283-2286. doi:10.1002/anie.200704816Tobita, S., Ohba, J., Nakagawa, K., & Shizuka, H. (1995). Recovery mechanism of the reaction intermediate produced by photoinduced cleavage of the intramolecular hydrogen bond of dibenzoylmethane. Journal of Photochemistry and Photobiology A: Chemistry, 92(1-2), 61-67. doi:10.1016/1010-6030(95)04158-xMoriyasu, M., Kato, A., & Hashimoto, Y. (1986). Kinetic studies of fast equilibrium by means of high-performance liquid chromatography. Part 11. Keto–enol tautomerism of some β-dicarbonyl compounds. J. Chem. Soc., Perkin Trans. 2, (4), 515-520. doi:10.1039/p29860000515Casey, B. M., Eakin, C. A., Jiao, J., Sadasivam, D. V., & Flowers, R. A. (2009). Solvent-dependent oxidative coupling of 1-aryl-1,3-dicarbonyls and styrene. Tetrahedron, 65(52), 10762-10768. doi:10.1016/j.tet.2009.06.118Ko, T. Y., & Youn, S. W. (2016). Cooperative Indium(III)/Silver(I) System for Oxidative Coupling/Annulation of 1,3-Dicarbonyls and Styrenes: Construction of Five-Membered Heterocycles. Advanced Synthesis & Catalysis, 358(12), 1934-1941. doi:10.1002/adsc.201600280Casals, P.-F., Ferard, J., & Ropert, R. (1976). Photoaddition de dicetones-1,3 aromatiques sur divers carbures styreniques : orientation et stereospecificite de l’addition. Tetrahedron Letters, 17(35), 3077-3080. doi:10.1016/0040-4039(76)80074-3Kikuchi, A., Oguchi, N., & Yagi, M. (2009). Optical and Electron Paramagnetic Resonance Studies of the Excited States of 4-tert-Butyl-4′-Methoxydibenzoylmethane and 4-tert-Butyl-4′-Methoxydibenzoylpropane. The Journal of Physical Chemistry A, 113(48), 13492-13497. doi:10.1021/jp905236mTurro, N. J. (1966). Triplet-triplet excitation transfer in fluid solution: Applications to organic photochemistry. Journal of Chemical Education, 43(1), 13. doi:10.1021/ed043p13Dilling, W. L. (1969). Photochemical cycloaddition reactions of nonaromatic conjugated hydrocarbon dienes and polyenes. Chemical Reviews, 69(6), 845-877. doi:10.1021/cr60262a005N. J. Turro , in Modern Molecular Photochemistry , Benjamin/Cummings , California , 1978 , ch. 9, pp. 296–359Albini, A. (1981). Photosensitization in Organic Synthesis. Synthesis, 1981(04), 249-264. doi:10.1055/s-1981-29405Kalyanasundaram, K. (1982). Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues. Coordination Chemistry Reviews, 46, 159-244. doi:10.1016/0010-8545(82)85003-0Juris, A., Balzani, V., Barigelletti, F., Campagna, S., Belser, P., & von Zelewsky, A. (1988). Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence. Coordination Chemistry Reviews, 84, 85-277. doi:10.1016/0010-8545(88)80032-8Cismesia, M. A., & Yoon, T. P. (2015). Characterizing chain processes in visible light photoredox catalysis. Chemical Science, 6(10), 5426-5434. doi:10.1039/c5sc02185

    Investigating Determinants of Project Portfolio Management Adoption

    Get PDF
    Recently, there has been an emphasis on managing projects strategically within the organization using project portfolio management (PPM). However, the extent of adoption of this innovation and the enabling factors are not well understood in academics and practice. This research-inprogress investigates a model of PPM adoption using data being collected from project managers. The model identifies a total of nine variables capturing various environmental, PPM, and organizational factors that could potentially impact the adoption decision of PPM. The survey is hosted on the Project Management Institute’s (PMI) website in order to collect data from PMI members worldwide. The data will be analyzed using logistic regression to identify the factors that have a significant impact on PPM adoption. This research is part of a larger multi-method research of PPM adoption and infusion and the results of this research will help practitioners and researchers better understand factors that impact PPM adoption decisions

    Empowering Women Entrepreneurs in Emerging Economies: a Conceptual Model

    Get PDF
    Cyberfeminism is a woman-centered perspective that advocates women’s use of new information and communications technologies for empowerment. This paper explores the role of information technologies, in particular the role of social media, in empowering women entrepreneurship in emerging economies via increased social capital and improved self-efficacy. A conceptual model is offered and propositions are explicated

    The dynamics of the hydrogen exchange reaction at 2.20 eV collision energy: Comparison of experimental and theoretical differential cross sections

    Get PDF
    The H+D2(v = 0, j = 0)→HD(v′, j′)+D isotopic variant of the hydrogen atom exchange reaction has been studied in a crossed molecular beam experiment at a collision energy of 2.20 eV. Kinetic energy spectra of the nascent D atoms were obtained by using the Rydberg atom time-of-flight technique. The extensive set of spectra collected has permitted the derivation of rovibrationally state-resolved differential cross sections in the center-of-mass frame for most of the internal states of the HD product molecules, allowing a direct comparison with theoretical predictions. Accurate 3D quantum mechanical calculations have been carried out on the refined version of the latest Boothroyd-Keogh-Martin-Peterson potential energy surface, yielding an excellent agreement with the experimentally determined differential cross sections. The comparison of the results from quasi-classical trajectory calculations on the same potential surface reveals some discrepancies with the measured data, but shows a good global accordance. The theoretical calculations demonstrate that, at this energy, reactive encounters are predominantly noncollinear and that collinear collisions lead mostly to nonreactive recrossing. The experimental results are satisfactorily accounted for by theoretical calculations without consideration of Geometric Phase effects. © 1999 American Institute of Physics.Financial support through the program ‘‘Acciones para la Incorporación de Doctores y Tecnólogos’’ of the Ministry of Education and Culture of Spain. We also gratefully acknowledge the computer resources ~Cray T-90! provided by the Leibniz Rechenzentrum in Munich ~Germany. Funded by the German Science Foundation ~Grant No. SCH 435/3! and the Deutscher Akademischer Austauchdienst‘‘Acciones Integradas’’. The Spanish part was financed by the DGICYT ~PB95-0918-C03! and by the ‘‘Acciones Integradas’’ Program of the Ministry of Educationand Culture.Peer Reviewe

    Characteristics of patients misdiagnosed with Alzheimer’s disease and their medication use: an analysis of the NACC-UDS database

    Get PDF
    BACKGROUND: This study compared individuals whose clinical diagnosis of Alzheimer’s disease (AD) matched or did not match neuropathologic results at autopsy on clinical and functional outcomes (cognitive impairment, functional status and neuropsychiatric symptoms). The study also assessed the extent of potentially inappropriate medication use (using potentially unnecessary medications or potentially inappropriate prescribing) among misdiagnosed patients. METHODS: Longitudinal data from the National Alzheimer’s Coordinating Center Uniform Data Set (NACC-UDS, 2005–2010) and corresponding NACC neuropathological data were utilized to compare 88 misdiagnosed and 438 accurately diagnosed patients. RESULTS: Following adjustment of sociodemographic characteristics, the misdiagnosed were found to have less severe cognitive and functional impairment. However, after statistical adjustment for sociodemographics, dementia severity level, time since onset of cognitive decline and probable AD diagnosis at baseline, the groups significantly differed on only one outcome: the misdiagnosed were less likely to be depressed/dysphoric. Among the misdiagnosed, 18.18% were treated with potentially inappropriate medication. An additional analysis noted this rate could be as high as 67.10%. CONCLUSIONS: Findings highlight the importance of making an accurate AD diagnosis to help reduce unnecessary treatment and increase appropriate therapy. Additional research is needed to demonstrate the link between potentially inappropriate treatment and adverse health outcomes in misdiagnosed AD patients

    Effect of Student Involvement on Patient Perceptions of Ambulatory Care Visits

    Get PDF
    OBJECTIVE: To determine if patient satisfaction with ambulatory care visits differs when medical students participate in the visit. DESIGN: Randomized controlled trial. SETTING: Academic general internal medicine practice. PARTICIPANTS: Outpatients randomly assigned to see an attending physician only (N = 66) or an attending physician plus medical student (N = 68). MEASUREMENTS AND MAIN RESULTS: Patient perceptions of the office visit were determined by telephone survey. Overall office visit satisfaction was higher for the “attending physician only” group (61% vs 48% excellent), although this was not statistically significant (P = .16). There was no difference between the study groups for patient ratings of their physician overall (80% vs 85% excellent; P = .44). In subsidiary analyses, patients who rated their attending physician as “excellent” rated the overall office visit significantly higher in the “attending physician only” group (74% vs 55%; P = .04). Among patients in the “attending physician plus medical student” group, 40% indicated that medical student involvement “probably” or “definitely” did not improve their care, and 30% responded that they “probably” or “definitely” did not want to see a student at subsequent office visits. CONCLUSIONS: Although our sample size was small, we found no significant decrement in patient ratings of office visit satisfaction from medical student involvement in a global satisfaction survey. However, a significant number of patients expressed discontent with student involvement in the visit when asked directly. Global assessment of patient satisfaction may lack sensitivity for detection of dissatisfaction. Future research in this area should employ more sensitive measures of patient satisfaction

    The H+D2 reaction in the vicinity of the conical intersection

    Get PDF
    Scattering measurements performed at an energy slightly higher than that of the lowest crossing between the ground and the first electronically excited state of the H3 system are reported. The essentials of the reactive dynamics are describable in terms of a classical motion of the nuclei on the lowest adiabatic electronic potential. © 1997 American Institute of Physics.The German part of this work was supported by the German Science Foundation. The Spanish part was funded by the DGICYT of Spain under Grant PB95-0918-C02. Both parts are grateful to the German–Spanish scientific exchange program ‘‘Acciones Integradas.’’ Partial funding by the Alexander von Humboldt StiftungPeer Reviewe
    corecore