A comprehensive strategy is required to mitigate risks to astronauts' health, well-being, and performance. This strategy includes developing countermeasures to prevent or reduce adverse responses to the stressors astronauts encounter during spaceflight, such as weightlessness. Because artificial gravity (AG) by centrifugation simultaneously affects all physiological systems, AG could mitigate the effects of weightlessness in multiple systems.
View Article and Find Full Text PDFThis Nano Focus article reviews recent developments in surface-enhanced Raman spectroscopy (SERS) and its application to homeland security. It is based on invited talks given at the "Nanorods and Microparticles for Homeland Security" symposium, which was organized by one of the authors and presented at the 238th ACS National Meeting and Exhibition in Washington, DC. The three-day symposium included approximately 25 experts from academia, industry, and national laboratories and included both SERS and non-SERS approaches to detection of chemical and biological substances relevant to homeland security, as well as fundamental advances.
View Article and Find Full Text PDFRaman spectroscopy is a newly developed, noninvasive preclinical imaging technique that offers picomolar sensitivity and multiplexing capabilities to the field of molecular imaging. In this study, we demonstrate the ability of Raman spectroscopy to separate the spectral fingerprints of up to 10 different types of surface enhanced Raman scattering (SERS) nanoparticles in a living mouse after s.c.
View Article and Find Full Text PDFIntroduction into the long-known bicyclo[3.1.0]hex-2-ene system of a large substituent in an electronically inactive, interconnected pair of positions brings to light the importance of sterics as a major factor in the determination of products.
View Article and Find Full Text PDFThe effect of a large increase in mass and extension of substituents on the thermal rearrangement of a 1,2-divinylcyclobutane system has been investigated by the introduction of two 3-cholest-4-ene units. The ratio of two types of exit channel, fragmentation and stereomutation (Fr/St), from a widely accepted diradical intermediary (caldera) has increased significantly relative to the ratio in a simpler system. We believe this to be the first example of the influence of a ponderal effect on the ratio of two competing processes in a thermal rearrangement.
View Article and Find Full Text PDFTo obtain a more reliable temperature dependence of the kinetic deuterium isotope effect in a 1,5-hydrogen shift, the title compound has been designed to repress compromising side reactions, arguably arising from second-order ene-ene unions. The values of kH/kD, 4.58-5.
View Article and Find Full Text PDFA dual-mode molecular beacon on a multiplexed substrate has been developed and applied to the measurement of unlabeled human viral RNA. The detection system is based on a combined surface-enhanced Raman scattering (SERS) and fluorescent molecular beacon assay that is assembled on Nanobarcodes™ particles. In this assay, a molecular beacon probe terminated with a fluorescent Raman label dye is conjugated to the metallic Nanobarcodes™ particles.
View Article and Find Full Text PDFFurther insight into the behavior of suppositional diradicals in a caldera is sought in the thermal rearrangements among the four "Delta2-thujenes", two 1-isopropyl-4-methylbicyclo[3.1.0]hex-2-enes [(-)-cis-1 and (+)-trans-2] and two isomers, exo- and endo-3-isopropyl-6-methylbicyclo[3.
View Article and Find Full Text PDFPrompted by extensive theoretical interest in the role of tunneling in the intramolecular 1,5-hydrogen shift in 1,3(Z)-pentadienes and the large uncertainty in the published values of the theoretically relevant kinetic deuterium-isotope effect and its dependence on temperature, we have examined a degenerate bicyclic version, 2-methyl-10-methylenebicyclo[4.4.0]dec-1-ene, which is locked into the rearrangement-competent cisoid conformation, in the hope of obtaining more precise and accurate values.
View Article and Find Full Text PDFPressure dependent rate constants and volumes of activation for stereomutational interconversions of the cyclobutanes, anti- and syn-2,9-dicyanodispiro[5.0.5.
View Article and Find Full Text PDFObjective: To evaluate the benefits of bilateral electrical stimulation for hearing-impaired adult subjects using the Nucleus 24 cochlear implant in a multicenter study, and to compare and quantify performance on speech perception measures in quiet and in noise and localization ability for unilateral and bilateral cochlear implant use.
Design: : Repeated single subject measures were carried out for each subject, with each subject serving as their own control. Assessment of unilateral and bilateral listening conditions for performance on tests of speech comprehension and sound localization were performed.
The acyclic 1,5-dienyl hydrogen shift is accelerated by radical-stabilizing phenyl substituents without regard to the type of position occupied in the 1,3(Z)-pentadiene system. 1-Phenyl-5-p-tolyl-1,3(Z)-pentadiene has a corrected energy of activation 5.8 kcal mol(-)(1) lower than that of the parent, while the 2- and 3-phenyl analogues, examined in cyclic systems specifically designed to obviate the otherwise general need for a thermochemical correction to the immediately precursory s-cis conformation, reveal stabilizing effects of 3.
View Article and Find Full Text PDFAims: To assess hospital mortality and morbidity in diabetic and non-diabetic patients with acute myocardial infarction and to compare the results between the two groups.
Methods: All patients admitted in 1999 to the intensive care unit of the Schwabing City Hospital with diagnosis of acute myocardial infarction were assessed for hospital mortality and co-morbidity.
Results: Three hundred and thirty patients with acute myocardial infarction were admitted.
Objective: The myocardial infarction (MI) registry of the Academic Schwabing Hospital, Munich, investigates the hospital course of diabetic and nondiabetic patients with acute MI. The aim of this study was to improve quality care management and to compare hospital mortality and therapeutic approaches (i.e.
View Article and Find Full Text PDFSurface-enhanced Raman scattering is capable of providing rich vibrational information at the level of single molecules and single nanoparticles, but the practical applications of this enormous enhancement effect are still a challenge. Here we report a new class of dye-embedded core-shell nanoparticles that are highly efficient for surface Raman enhancement and could be used as spectroscopic tags for multiplexed detection and spectroscopy. The core-shell particles contain a metallic core for optical enhancement, a reporter molecule for spectroscopic signature, and an encapsulating silica shell for protection and conjugation.
View Article and Find Full Text PDFThere being no study of a cyclobutane so fused to another cyclic system that an antiperiplanar conformation of the related diradical be precluded, the system in the title has been synthesized and studied for its thermal behavior. In comparison to the thermal behavior of unconstrained 1,2-dicyanocyclobutane in stereomutation and fragmentation to acrylonitrile, the constrained system shows a approximately 10-fold higher ratio of stereomutation to fragmentation to the three cis-1,4-bis-beta-cyanovinylcyclohexanes. In these diolefins, a stereochemical correlation between the two olefinic fragmentation products is preserved.
View Article and Find Full Text PDFThis paper addresses the decades-old problem of gaining a measure of intellectual control over the fate of the diradical intermediate in not-obviously-concerted thermal rearrangements. It focuses mainly on the stereochemistry of the thermal rearrangement of cis- and trans-1-cyano-2-trans-propenylcyclobutane to the related ring-enlarged products, 4-cyano-3-methylcyclohexenes. The complete stereochemical profile is revealed by the incorporation of a pair of cis deuterons to serve as a stereochemical lighthouse.
View Article and Find Full Text PDFEnthalpies of stabilization of polyenyl radicals of increasing order previously obtained by thermal geometrical isomerization are applied to the ethylene-cyclobutane paradigm. Progressively lower enthalpies of activation for thermal cyclodimerization and its reverse, cycloreversion, are predicted and realized. Photochemical dimerization at -75 degrees C of the optically pure tetraene of the title (1) at the semicyclic double bond produces in the main only one (4-axx) of the three allowed cyclobutanes (4), to which the tentative configuration anti-exo,exo is assigned.
View Article and Find Full Text PDFFresenius J Anal Chem
November 2000
A sequential injection (SI) method for the determination of mercury via cold vapor atomic absorption spectrophotometry is presented. The method differs from flow injection (FI) cold vapor methods for the determination of mercury because of the simplicity of the system required for the method: one pump, one valve, a gas-liquid separator, and an atomic absorption spectrophotometer equipped with a quartz cell. Under optimal conditions, the method has the following figures of merit: a linear calibration range of 1.
View Article and Find Full Text PDFEvaluation of two different noise reduction algorithms for speech intelligibility enhancement in cochlear implant (CI) users is described in this report. The algorithms accomplish sophisticated interchannel processing of the noisy speech signals, picked up with two microphones, to form an improved monaural output signal, which is directly fed into the auxiliary input of the CI speech processor. Speech intelligibility tests were carried out in different realistic everyday life listening conditions to provide general and expressive performance assessment.
View Article and Find Full Text PDFEarly action of angiotensin-converting enzyme (ACE) inhibitors after myocardial infarction (MI) has been shown in large scale clinical trials to reduce mortality over the first weeks. However, the mechanisms involved are yet unclear and several trials showed a tendency toward a small, albeit unexpected, rise in cardiogenic shock or mortality. Since cardiopulmonary exercise testing (CPX) has become a "gold standard" in assessing the severity of heart failure, we studied--after finishing a pilot trial--the effect of captopril versus placebo in 208 patients who were individually titrated (titrated dose, mean 46/69 mg/day after 7 days/4 weeks, respectively) in order to preserve their blood pressure in the acute phase of myocardial infarction; we followed the development of congestive heart failure (CHF) over 4 weeks by measuring oxygen consumption.
View Article and Find Full Text PDFThe aim of this study was to investigate the effect of battery capacity, internal current drain, and stimulation energy on pulse generators longevity, and if battery impedance measurements can reliably predict pulse generators end-of-life. For this purpose, the records of 577 patients with a mean age of 65 +/- 14 years who had undergone implantation of two different dual chamber pulse generators (PG1: 409; PG2: 168) were retrospectively reviewed. Battery capacity were 2.
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