3,934 research outputs found

    The political and legal aspects of space applications

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    The political and legal repercussions of space programs both domestic and foreign are explored. Emphasis are placed on earth resources exploration (exploration based on information rights), jurisdictional problems, problems of sharing space benefits with other countries, criminal launch and use of satellites, intrusion into territorial sovereignty, and problems of establishing data ownership

    Reactivity of (1-methoxycarbonylpentadienyl)iron(1+) cations with hydride, methyl, and nitrogen nucleophiles

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    The reaction of tricarbonyl and (dicarbonyl)triphenylphosphine (1-methoxycarbonyl-pentadientyl)iron(1+) cations 7 and 8 with methyl lithium, NaBH3CN, or potassium phthalimide affords (pentenediyl)iron complexes 9a-c and 11a-b, while reaction with dimethylcuprate, gave (E,Z-diene)iron complexes 10 and 12. Oxidatively induced-reductive elimination of 9a-c gave vinylcyclopropanecarboxylates 17a-c. The optically active vinylcyclopropane (+)-17a, prepared from (1S)-7, undergoes olefin cross-metathesis with excess (+)-18 to yield (+)-19, a C9C16 synthon for the antifungal agent ambruticin. Alternatively reaction of 7 with methanesulfonamide or trimethylsilylazide gave (E,E-diene)iron complexes 14d and e. Huisgen [3 + 2] cyclization of the (azidodienyl)iron complex 14e with alkynes afforded triazoles 25a-e

    Senior Recital: Alexandria Hanessian, clarinet

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    Short Enantioselective Total Synthesis of Tatanan A and 3-epi-Tatanan A Using Assembly-Line Synthesis

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    Short and highly stereoselective total syntheses of the sesquilignan natural product tatanan A and its C3 epimer are described. An assembly-line synthesis approach, using iterative lithiation–borylation reactions, was applied to install the three contiguous stereocenters with high enantio- and diastereoselectivity. One of the stereocenters was installed using a configurationally labile lithiated primary benzyl benzoate, resulting in high levels of substrate-controlled (undesired) diastereoselectivity. However, reversal of selectivity was achieved by using a novel diastereoselective Matteson homologation. Stereospecific alkynylation of a hindered secondary benzylic boronic ester enabled completion of the synthesis in a total of eight steps

    Intermolecular-medium and intramolecular-weak hydrogen bonding chains in the crystals of chiral trifluoromethylated amino alcohols

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    A structural feature of hydrogen bonding chains found in the crystals of trifluoromethylated amino alcohols is reported. Hydrogen bondings of 3-(N,N-dialkylamino)-1,1,1-trifluoro-2-propanols construct chiral spiral hydrogen bonding chains. Lone pairs on the nitrogen atoms of the amino alcohols participate in two hydrogen bondings. Detailed structural analysis of the hydrogen bonds of the 3-(N,N-dimethylamino)-1,1,1-trifluoro-2-propanol suggested that the chain built up with alternating intermolecular medium and intramolecular weak hydrogen bonds. The medium intermolecular hydrogen bond, which transfers a proton from the hydroxy group to the amino nitrogen, would make a tentative zwitterionic form of the molecule. Then, electrostatic attraction between the charges in the zwitterion centers induced a weak intramolecular hydrogen bond.</p

    Efficient Syntheses of Diverse, Medicinally Relevant Targets Planned by Computer and Executed in the Laboratory

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    The Chematica program was used to autonomously design synthetic pathways to eight structurally diverse targets, including seven commercially valuable bioactive substances and one natural product. All of these computer-planned routes were successfully executed in the laboratory and offer significant yield improvements and cost savings over previous approaches, provide alternatives to patented routes, or produce targets that were not synthesized previously. Although computers have demonstrated the ability to challenge humans in various games of strategy, their use in the automated planning of organic syntheses remains unprecedented. As a result of the impact that such a tool could have on the synthetic community, the past half century has seen numerous attempts to create in silico chemical intelligence. However, there has not been a successful demonstration of a synthetic route designed by machine and then executed in the laboratory. Here, we describe an experiment where the software program Chematica designed syntheses leading to eight commercially valuable and/or medicinally relevant targets; in each case tested, Chematica significantly improved on previous approaches or identified efficient routes to targets for which previous synthetic attempts had failed. These results indicate that now and in the future, chemists can finally benefit from having an ???in silico colleague??? that constantly learns, never forgets, and will never retire. Multistep synthetic routes to eight structurally diverse and medicinally relevant targets were planned autonomously by the Chematica computer program, which combines expert chemical knowledge with network-search and artificial-intelligence algorithms. All of the proposed syntheses were successfully executed in the laboratory and offer substantial yield improvements and cost savings over previous approaches or provide the first documented route to a given target. These results provide the long-awaited validation of a computer program in practically relevant synthetic design

    Re-Homing Exotic Species--A Pilot Program to Prevent Release of Exotic Aquatic Pet Species

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    An educational poster program designed to inform pet owners of the dangers of releasing exotic species and provide a re-homing mechanism was evaluated as a means to reduce unwanted environmental releases. The poster provided a URL to the program partners\u27 Web site, which listed participating re-homing pet shops in Maryland. Survey results revealed that 201 aquatic animals were re-homed.1 Survey respondents rated the poster at 94% and 92% percent for educating consumers of the potential of re-homing and benefits to the pet industry, respectively. The program provides a proactive opportunity and alternative to environmental release of exotic species

    Designing the prototype of acousto-optic processor for astrophysical applications

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    The development of a new instrument is presented in this thesis. It will serve as a perspective prototype able to estimate the performance of their applications for practical measurements in astronomical spectroscopy covering from visible to near infrared range. A very obvious advantage of this arrangement is the relative schematic simplicity due to the absence of any large aperture components. Another important advantage, is the possibility of change the spectral range and the resolution using only one dispersing element, that will increase the efficiency of the observing time. The system is a prototype of the triple product processor and it produce the folded spectrum, accumulating advantages of both space and time integrating. Separately, the space integrating gives a wide frequency bandwidth together with relatively low frequency resolution, while the time integration provides a high resolution for spectrum components accompanied by comparably narrow frequency bandwidth. The processor is able to provide really high frequency resolution, with a wide frequency bandwidth. The main attention is paid to the time-bandwidth product, because just this parameter can be taken as the most general one for the characterization of performance data inherent in each individual cell. Both the theoretical estimations and the experimental data obtained for a large-aperture acousto-optical cell based on a tellurium dioxide crystal, exploiting the anomalous light scattering, gives the time-bandwidth product equal to about 4000. The problem of optimizing the profile for the incident light beam has been studied. The need light-beam apodization, suppressing side lobes within registration of each individual resolvable spot and increasing the dynamic range, can be realized using a multi-prism beam expander. It has been shown that the dynamic range of about 40 dB in an optical system can be achieved.En esta tesis se presenta el prototipo de un nuevo instrumento. Este nos dar una perspectiva para estimar el rendimiento en aplicaciones para espectroscopia astronómica cubriendo un rango desde el visible hasta el cercano infrarrojo. Las ventajas de este arreglo esquemático son la relativa simplicidad debido a la ausencia de componentes de mucha apertura y la posibilidad de cambiar el rango espectral y la resolución usando solo un elemento dispersivo que incrementaría la eficiencia en el tiempo de observación. El sistema es un prototipo del procesador de triple producto que acumula las ventajas de la integración tiempo y espacio. Por separado, la integración en el espacio provee de un amplio ancho de banda en la frecuencia, pero relativamente baja resolución. Mientras que la integración en el tiempo provee una alta resolución para componentes del espectro acompañado con un estrecho ancho de banda. Este procesador es capaz de proveer una alta resolución con un amplio ancho de banda. Se presta mayor atención al producto tiempo-ancho de banda, puesto que este parámetro puede nos habla del rendimiento inherente de cada celda. Se estudian los regímenes de dispersión de la luz normal o anómala. Tanto las estimaciones teóricas como experimentales muestran que los datos obtenidos para una celda acusto-optica de dióxido de telurio de gran apertura en el régimen de dispersión de la luz anómala dan un producto tiempo-ancho de banda igual a 4000. Se estudia el problema de optimización del perfil del haz de luz incidente. La necesidad de apodizar el haz incidente de luz, suprimiendo los lóbulos secundarios sin registrar cada punto que se puede resolver y además incrementar el rango dinámico, se puede obtener utilizando un expansor de múltiples prismas. Se muestra que se puede alcanzar un rango dinámico de alrededor de 40 dB en un sistema óptico

    The emerging role of FTY720 (Fingolimod) in cancer treatment

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    FTY720 (Fingolimod) is a clinically approved immunomodulating therapy for multiple sclerosis that sequesters T-cells to lymph nodes through functional antagonism of sphingosine-1-phosphate 1 receptor. FTY720 also demonstrates a proven efficacy in multiple in vitro and in vivo cancer models, suggesting a potential therapeutic role in cancer patients. A potential anticancer mechanism of FTY720 is through the inhibition of sphingosine kinase 1, a proto-oncogene with in vitro and clinical cancer association. In addition, FTY720's anticancer properties may be attributable to actions on several other molecular targets. This study focuses on reviewing the emerging evidence regarding the anticancer properties and molecular targets of FTY720. While the clinical transition of FTY720 is currently limited by its immune suppression effects, studies aiming at FTY720 delivery and release together with identifying its key synergetic combinations and relevant patient subsets may lead to its rapid introduction into the clinic
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