Closeup view of an External Tank (ET) Attach Ring undergoing ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Close-up view of an External Tank (ET) Attach Ring undergoing preparations in the Processing Building of the Rotation Processing and Surge Facility at Kennedy Space Center. After preparations are complete the ET Attach Ring will be mated to the top of the Aft Motor Segment. The most prominent features in this view are the ET/Solid Rocket Booster Struts in the center and left in the view and the Aft Integrated Electronics Assembly located on the right side if the ring in this view. - Space Transportation System, Solid Rocket Boosters, Lyndon B. Johnson Space Center, 2101 NASA Parkway, Houston, Harris County, TX

Dual annular rotating [open quotes]windowed[close quotes] nuclear reflector reactor control system

DOEpatents

Jacox, M.G.; Drexler, R.L.; Hunt, R.N.M.; Lake, J.A.

1994-03-29

A nuclear reactor control system is provided in a nuclear reactor having a core operating in the fast neutron energy spectrum where criticality control is achieved by neutron leakage. The control system includes dual annular, rotatable reflector rings. There are two reflector rings: an inner reflector ring and an outer reflector ring. The reflectors are concentrically assembled, surround the reactor core, and each reflector ring includes a plurality of openings. The openings in each ring are capable of being aligned or non-aligned with each other. Independent driving means for each of the annular reflector rings is provided so that reactor criticality can be initiated and controlled by rotation of either reflector ring such that the extent of alignment of the openings in each ring controls the reflection of neutrons from the core. 4 figures.

Mechanisms and rates of proton transfer to coordinated carboxydithioates: studies on [Ni(S2CR){PhP(CH2CH2PPh2)2}](+) (R = Me, Et, Bu(n) or Ph).

PubMed

Alwaaly, Ahmed; Clegg, William; Henderson, Richard A; Probert, Michael R; Waddell, Paul G

2015-02-21

The complexes [Ni(S2CR)(triphos)]BPh4 (R = Me, Et, Bu(n) or Ph; triphos = PhP{CH2CH2PPh2}2) have been prepared and characterised. X-ray crystallography (for R = Et, Ph, C6H4Me-4, C6H4OMe-4 and C6H4Cl-4) shows that the geometry of the five-coordinate nickel in the cation is best described as distorted trigonal bipyramidal, containing a bidentate carboxydithioate ligand with the two sulfur atoms spanning axial and equatorial sites, the other axial site being occupied by the central phosphorus of triphos. The reactions of [Ni(S2CR)(triphos)](+) with mixtures of HCl and Cl(-) in MeCN to form equilibrium solutions containing [Ni(SH(S)CR)(triphos)](2+) have been studied using stopped-flow spectrophotometry. The kinetics show that proton transfer is slower than the diffusion-controlled limit and involves at least two coupled equilibria. The first step involves the rapid association between [Ni(S2CR)(triphos)](+) and HCl to form the hydrogen-bonded precursor, {[Ni(S2CR)(triphos)](+)HCl} (K) and this is followed by the intramolecular proton transfer (k) to produce [Ni(SH(S)CR)(triphos)](2+). In the reaction of [Ni(S2CMe)(triphos)](+) the rate law is consistent with the carboxydithioate ligand undergoing chelate ring-opening after protonation. It seems likely that chelate ring-opening occurs for all [Ni(S2CR)(triphos)](+), but only with [Ni(S2CMe)(triphos)](+) is the protonation step sufficiently fast that chelate ring-opening is rate-limiting. With all other systems, proton transfer is rate-limiting. DFT calculations indicate that protonation can occur at either sulfur atom, but only protonation at the equatorial sulfur results in chelate ring-opening. The ways in which protonation of either sulfur atom complicates the analyses and interpretation of the kinetics are discussed.

Acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with alcohols.

PubMed

Tait, Katrina; Horvath, Alysia; Blanchard, Nicolas; Tam, William

2017-01-01

The acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicylic alkene using alcohol nucleophiles were investigated. Although this acid-catalyzed ring-opening reaction did not cleave the cyclopropane unit as planned, this represent the first examples of ring-openings of cyclopropanated 3-aza-2-oxabicyclo[2.2.1]alkenes that lead to the cleavage of the C-O bond instead of the N-O bond. Different acid catalysts were tested and it was found that pyridinium toluenesulfonate in methanol gave the best yields in the ring-opening reactions. The scope of the reaction was successfully expanded to include primary, secondary, and tertiary alcohol nucleophiles. Through X-ray crystallography, the stereochemistry of the product was determined which confirmed an S N 2-like mechanism to form the ring-opened product.

Grignard reagent/CuI/LiCl-mediated stereoselective cascade addition/cyclization of diynes: a novel pathway for the construction of 1-methyleneindene derivatives.

PubMed

Li, De-Yao; Wei, Yin; Shi, Min

2013-11-11

Diynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through cyclopropyl ring opening. A plausible reaction mechanism has also been presented on the basis of deuterium labeling and control experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoswitchable Dihydroazulene Macrocycles for Solar Energy Storage: The Effects of Ring Strain.

PubMed

Vlasceanu, Alexandru; Frandsen, Benjamin N; Skov, Anders B; Hansen, Anne Schou; Rasmussen, Mads Georg; Kjaergaard, Henrik G; Mikkelsen, Kurt V; Nielsen, Mogens Brøndsted

2017-10-06

Efficient energy storage and release are two major challenges of solar energy harvesting technologies. The development of molecular solar thermal systems presents one approach to address these issues by tuning the isomerization reactions of photo/thermoswitches. Here we show that the incorporation of photoswitches into macrocyclic structures is a particularly attractive solution for increasing the storage time. We present the synthesis and properties of a series of macrocycles incorporating two dihydroazulene (DHA) photoswitching subunits, bridged by linkers of varying chain length. Independent of ring size, all macrocycles exhibit stepwise, light-induced, ring-opening reactions (DHA-DHA to DHA-VHF to VHF-VHF; VHF = vinylheptafulvene) with the first DHA undergoing isomerization with a similar efficiency as the uncyclized parent system while the second (DHA-VHF to VHF-VHF) is significantly slower. The energy-releasing, VHF-to-DHA, ring closures also occur in a stepwise manner and are systematically found to proceed slower in the more strained (smaller) cycles, but in all cases with a remarkably slow conversion of the second VHF to DHA. We managed to increase the half-life of the second VHF-to-DHA conversion from 65 to 202 h at room temperature by simply decreasing the ring size. A computational study reveals the smallest macrocycle to have the most energetic VHF-VHF state and hence highest energy density.

Mitigation of tip vortex cavitation by means of air injection on a Kaplan turbine scale model

NASA Astrophysics Data System (ADS)

Rivetti, A.; Angulo, M.; Lucino, C.; Liscia, S.

2014-03-01

Kaplan turbines operating at full-load conditions may undergo excessive vibration, noise and cavitation. In such cases, damage by erosion associated to tip vortex cavitation can be observed at the discharge ring. This phenomenon involves design features such as (1) overhang of guide vanes; (2) blade profile; (3) gap increasing size with blade opening; (4) suction head; (5) operation point; and (6) discharge ring stiffness, among others. Tip vortex cavitation may cause erosion at the discharge ring and draft tube inlet following a wavy pattern, in which the number of vanes can be clearly identified. Injection of pressurized air above the runner blade centerline was tested as a mean to mitigate discharge ring cavitation damage on a scale model. Air entrance was observed by means of a high-speed camera in order to track the air trajectory toward its mergence with the tip vortex cavitation core. Post-processing of acceleration signals shows that the level of vibration and the RSI frequency amplitude decrease proportionally with air flow rate injected. These findings reveal the potential mitigating effect of air injection in preventing cavitation damage and will be useful in further tests to be performed on prototype, aiming at determining the optimum air flow rate, size and distribution of the injectors.

Dual annular rotating "windowed" nuclear reflector reactor control system

DOEpatents

Jacox, Michael G.; Drexler, Robert L.; Hunt, Robert N. M.; Lake, James A.

1994-01-01

A nuclear reactor control system is provided in a nuclear reactor having a core operating in the fast neutron energy spectrum where criticality control is achieved by neutron leakage. The control system includes dual annular, rotatable reflector rings. There are two reflector rings: an inner reflector ring and an outer reflector ring. The reflectors are concentrically assembled, surround the reactor core, and each reflector ring includes a plurality of openings. The openings in each ring are capable of being aligned or non-aligned with each other. Independent driving means for each of the annular reflector rings is provided so that reactor criticality can be initiated and controlled by rotation of either reflector ring such that the extent of alignment of the openings in each ring controls the reflection of neutrons from the core.

Tube coupling device

NASA Technical Reports Server (NTRS)

Myers, William N. (Inventor); Hein, Leopold A. (Inventor)

1987-01-01

A first annular ring of a tube coupling device has a keyed opening sized to fit around the nut region of a male coupling, and a second annular ring has a keyed opening sized to fit around the nut of a female coupling. Each ring has mating ratchet teeth and these rings are biased together, thereby engaging these teeth and preventing rotation of these rings. This in turn prevents the rotation of the male nut region with respect to the female nut. For tube-to-bulkhead locking, one facet of one ring is notched, and a pin is pressed into an opening in the bulkhead. This pin is sized to fit within one of the notches in the ring, thereby preventing rotation of this ring with respect to the bulkhead.

Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory

NASA Astrophysics Data System (ADS)

Franke, J.-H.; Kosov, D. S.

2015-01-01

We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321)S. Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with a functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.

Aqueous phase hydrodeoxygenation of polyols over Pd/WO3-ZrO2: Role of Pd-WO3 interaction and hydrodeoxygenation pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Changjun; Sun, Junming; Brown, Heather M.

Aqueous-phase hydrodeoxygenation of sugar and sugar-derived molecules can be used to produce a range of alkanes and oxygenates. In this paper, we have identified the reaction intermediates and reaction chemistry for the aqueous-phase hydrodeoxygenation of sorbitol over a bifunctional catalyst (Pt/SiO2–Al2O3) that contains both metal (Pt) and acid (SiO2–Al2O3) sites. A wide variety of reactions occur in this process including Csingle bondC bond cleavage, Csingle bondO bond cleavage, and hydrogenation reactions. The key Csingle bondC bond cleavage reactions include: retro-aldol condensation and decarbonylation, which both occur on metal catalytic sites. Dehydration is the key Csingle bondO bond cleavage reaction andmore » occurs on acid catalytic sites. Sorbitol initially undergoes dehydration and ring closure to produce cyclic C6 molecules or retro-aldol condensation reactions to produce primarily C3 polyols. Isosorbide is the major final product from sorbitol dehydration. Isosorbide then undergoes ring opening hydrogenation reactions and a dehydration/hydrogenation step to form 1,2,6-hexanetriol. The hexanetriol is then converted into hexanol and hexane by dehydration/hydrogenation. Smaller oxygenates are produced by Csingle bondC bond cleavage. These smaller oxygenates undergo dehydration/hydrogenation reactions to produce alkanes from C1–C5. The results from this paper suggest that hydrodeoxygenation chemistry can be tuned to make a wide variety of products from biomass-derived oxygenates.« less

Ring opening of epoxides with C-nucleophiles.

PubMed

Faiz, Sadia; Zahoor, Ameer Fawad

2016-11-01

Ring opening of epoxides has been an area of interest for organic chemists, owing to their reactivity toward nucleophiles. Such reactions yield important products depending on the type of nucleophiles used. This review article covers the synthetic approaches (1991-2015) used for the ring opening of epoxides via carbon nucleophiles.

Nucleophilic ring opening reactions of aziridines.

PubMed

Akhtar, Rabia; Naqvi, Syed Ali Raza; Zahoor, Ameer Fawad; Saleem, Sameera

2018-05-04

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013-2017 for aziridine ring opening reactions as well as their synthetic applications is described.

Ring-through-ring molecular shuttling in a saturated [3]rotaxane

NASA Astrophysics Data System (ADS)

Zhu, Kelong; Baggi, Giorgio; Loeb, Stephen J.

2018-06-01

Mechanically interlocked molecules such as rotaxanes and catenanes comprise two or more components whose motion relative to each other can be controlled. A [2]rotaxane molecular shuttle, for example, consists of an axle bearing two recognition sites and a single macrocyclic wheel that can undergo a to-and-fro motion along the axle—shuttling between the recognition sites. The ability of mechanically interlocked molecules to undergo this type of large-amplitude change is the core mechanism behind almost every interlocked molecular switch or machine, including sophisticated mechanical systems such as a molecular elevator and a peptide synthesizer. Here, as a way to expand the scope of dynamics possible at the molecular level, we have developed a molecular shuttling mechanism involving the exchange of rings between two recognition sites in a saturated [3]rotaxane (one with no empty recognition sites). This was accomplished by passing a smaller ring through a larger one, thus achieving ring-through-ring molecular shuttling.

Single-ring ablation compared with standard circumferential pulmonary vein isolation using remote magnetic catheter navigation.

PubMed

Sohns, Christian; Bergau, Leonard; Seegers, Joachim; Lüthje, Lars; Vollmann, Dirk; Zabel, Markus

2014-10-01

In ablation of atrial fibrillation, the single-ring method aims for isolation of the posterior wall of the left atrium (LA) including the pulmonary veins (PVs) but avoiding posterior LA lesions. The aim of this randomized prospective study was to evaluate safety and efficacy of remote magnetic navigation (RMN)-guided single-ring ablation strategy as compared to standard RMN-guided circumferential PV ablation (PVA). Eighty consecutive patients undergoing PVA were enrolled prospectively and randomized equally into two study groups. RMN using the Stereotaxis system and open-irrigated 3.5-mm ablation catheters were used with a 3D mapping system in all procedures. Forty patients underwent RMN-guided single-ring ablation, and 40 patients received RMN-guided circumferential PVA. In the circumferential group, 3.3 ± 1.1 PVs were successfully isolated at the end of the procedure as compared to 3.1 ± 1.3 in the single-ring (box) group (p=0.38). All patients in the box group required additional posterior lesions in order to achieve electrical isolation of the PVs. Single-ring ablation was associated with longer procedure duration (p=0.01) and ablation time (p=0.001). After a single procedure, the proportion of patients free of any atrial tachycardia (AT)/atrial fibrillation (AF) episode at 12-month follow-up was 57 % in the box group and 58 % in the circ group. Using RMN, only minor complications have been observed. RMN-guided single-ring PVA provides comparable acute and long-term success rates as compared to RMN-guided circumferential PVA but requires additional posterior lesions to achieve PV isolation and increased procedure and ablation time. Procedural complication rates are low when using RMN.

Nitrenes, carbenes, diradicals, and ylides. Interconversions of reactive intermediates.

PubMed

Wentrup, Curt

2011-06-21

Rearrangements of aromatic and heteroaromatic nitrenes and carbenes can be initiated with either heat or light. The thermal reaction is typically induced by flash vacuum thermolysis, with isolation of the products at low temperatures. Photochemical experiments are conducted either under matrix isolation conditions or in solution at ambient temperature. These rearrangements are usually initiated by ring expansion of the nitrene or carbene to a seven-membered ring ketenimine, carbodiimide, or allene (that is, a cycloheptatetraene or an azacycloheptatetraene when a nitrogen is involved). Over the last few years, we have found that two types of ring opening take place as well. Type I is an ylidic ring opening that yields nitrile ylides or diazo compounds as transient intermediates. Type II ring opening produces either dienylnitrenes (for example, from 2-pyridylnitrenes) or 1,7-(1,5)-diradicals (such as those formed from 2-quinoxalinylnitrenes), depending on which of these species is better stabilized by resonance. In this Account, we describe our achievements in elucidating the nature of the ring-opened species and unraveling the connections between the various reactive intermediates. Both of these ring-opening reactions are found, at least in some cases, to dominate the subsequent chemistry. Examples include the formation of ring-opened ketenimines and carbodiimides, as well as the ring contraction reactions that form five-membered ring nitriles (such as 2- and 3-cyanopyrroles from pyridylnitrenes, N-cyanoimidazoles from 2-pyrazinyl and 4-pyrimidinylnitrenes, N-cyanopyrazoles from 2-pyrimidinylnitrenes and 3-pyridazinylnitrenes, and so forth). The mechanisms of formation of the open-chain and ring-contraction products were unknown at the onset of this study. In the course of our investigation, several reactions with three or more consecutive reactive intermediates have been unraveled, such as nitrene, seven-membered cyclic carbodiimide, and open-chain nitrile ylide. It has been possible in some cases to observe them all and determine their interrelationships by means of a combination of matrix-isolation spectroscopy, photochemistry, flash vacuum thermolysis, and computational chemistry. These studies have led to a deeper understanding of the nature of reactive intermediates and chemical reactivity. Moreover, the results indicate new directions for further exploration: ring-opening reactions of carbenes, nitrenes, and cyclic cumulenes can be expected in many other systems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franke, J.-H.; Kosov, D. S.

We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321){sup S}. Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with amore » functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.« less

Ab initio molecular orbital and density functional studies on the ring-opening reaction of oxetene.

PubMed

Jayaprakash, S; Jeevanandam, Jebakumar; Subramani, K

2014-11-01

Electrocyclic ring opening (ERO) reaction of 2H-Oxete (oxetene) has been carried out computationally in the gas phase and ring opening barrier has been computed. When comparing the ERO reaction of oxetene with the parent hydrocarbon (cyclobutene), the ring opening of cyclobutene is found to exhibit pericyclic behavior while oxetene shows mild pseudopericyclic nature. Computation of the nucleus-independent chemical shift (NICS) of oxetene adds evidence for pseudopericyclic behavior of oxetene. By locking of lone pair of electrons by hydrogen bonding, it is seen that the pseudopericyclic nature of the ring opening of oxetene is converted into a pericyclic one. CASSCF(5,6)/6-311+G** computation was carried out to understand the extent of involvement of lone pair of electrons during the course of the reaction. CR-CCSD(T)/6-311+G** computation was performed to assess the energies of the reactant, transition state and the product more accurately.

Study on ultrasonic assisted mechanism of ring opening polymerization of octamethylcyclotetrasiloxane (D4)

NASA Astrophysics Data System (ADS)

Ling, Huaxu; Yu, Xiaoxiang; Wang, Shifan; Wang, Xiaohui; Dong, Liming

2018-06-01

In this study, the linear high molecular weight polydimethylsiloxanes(PDMS) were synthesized by ultrasonic-assisted bulk ring-opening polymerization method, with D4 as the raw material, hexamethyldisilane(HMDS) as the capping agent and concentrated sulfuric acid as the catalyst. The mechanism of ring-opening polymerization assisted by ultrasound is discussed in detail, through the ultrasonic time, ultrasonic intensity and reaction temperature and other factors. The results showed that D4 ring-opening polymerization and PDMS depolymerization was a pair of reversible equilibrium reaction. Due to the influence of steric hindrance and viscosity, the ultrasonic action appears as the driving effect of D4 ring opening at the initial reaction, and the chain exchange or depolymerization of PDMS at the end of the reaction. Therefore, ultrasonic irradiation is believed to facilitate the rapid synthesis of high molecular weight PDMS at high monomer concentrations.

Photoisomerization among ring-open merocyanines. I. Reaction dynamics and wave-packet oscillations induced by tunable femtosecond pulses.

PubMed

Ruetzel, Stefan; Diekmann, Meike; Nuernberger, Patrick; Walter, Christof; Engels, Bernd; Brixner, Tobias

2014-06-14

Upon ultraviolet excitation, photochromic spiropyran compounds can be converted by a ring-opening reaction into merocyanine molecules, which in turn can form several isomers differing by cis and trans configurations in the methine bridge. Whereas the spiropyran-merocyanine conversion reaction of the nitro-substituted indolinobenzopyran 6-nitro-1',3',3'-trimethylspiro[2H-1-benzopyran-2,2'-indoline] (6-nitro BIPS) has been studied extensively in theory and experiments, little is known about photoisomerization among the merocyanine isomers. In this article, we employ femtosecond transient absorption spectroscopy with variable excitation wavelengths to investigate the excited-state dynamics of the merocyanine in acetonitrile at room temperature, where exclusively the trans-trans-cis (TTC) and trans-trans-trans (TTT) isomers contribute. No photochemical ring-closure pathways exist for the two isomers. Instead, we found that (18±4)% of excited TTC isomers undergo an ultrafast excited-state cis→trans photoisomerization to TTT within 200 fs, while the excited-state lifetime of TTC molecules that do not isomerize is 35 ps. No photoisomerization was detected for the TTT isomer, which relaxes to the ground state with a lifetime of roughly 160 ps. Moreover, signal oscillations at 170 cm(-1) and 360 cm(-1) were observed, which can be ascribed to excited-state wave-packet dynamics occurring in the course of the TTC→TTT isomerization. The results of high-level time-dependent density functional theory in conjunction with polarizable continuum models are presented in the subsequent article [C. Walter, S. Ruetzel, M. Diekmann, P. Nuernberger, T. Brixner, and B. Engels, J. Chem. Phys. 140, 224311 (2014)].

Helmet latching and attaching ring

NASA Technical Reports Server (NTRS)

Chase, E. W.; Viikinsalo, S. J. (Inventor)

1970-01-01

A neck ring releasably secured to a pressurized garment carries an open-ended ring normally in the engagement position fitted into an annular groove and adapted to fit into a complementary annular groove formed in a helmet. Camming means formed on the inner surface at the end of the helmet engages the open-ended ring to retract the same and allow for one motion donning even when the garment is pressurized. A projection on the end of the split ring is engageable to physically retract the split ring.

Effect of temperature and gap opening rate on the resiliency of candidate solid rocket booster O-ring materials

NASA Technical Reports Server (NTRS)

Lach, Cynthia L.

1992-01-01

In the redesign of the Space Shuttle solid rocket motor following the Challenger accident, the field and nozzle-to-case joints were designed to minimize gap opening caused by internal motor pressurization during ignition. The O-ring seals and glands for these joints were designed both to accommodate structural deflections and to promote pressure assisted sealing. The resiliency behavior of several candidate O-ring materials was evaluated for the effects of temperature and gap opening rates. The performance of three of the elastomeric materials was tested under the specific redesign gap opening requirement. Dynamic flexure conditions unique to launch produce low frequency vibrations in the gap opening. The effect of these vibrations on the ability of the O-ring to maintain contact with the sealing surface was addressed. The resiliency of the O-ring materials was found to be extremely sensitive to variations in temperature and gap opening rate. The top three elastomeric materials tracked the simulated solid rocket booster (SRB) field joint deflection at 75 and 120 F. The external tank/SRB attach strut load vibrations had a negligible effect on the ability of the O-ring to track the simulated SRB field joint deflection.

Synthetic space with arbitrary dimensions in a few rings undergoing dynamic modulation

NASA Astrophysics Data System (ADS)

Yuan, Luqi; Xiao, Meng; Lin, Qian; Fan, Shanhui

2018-03-01

We show that a single ring resonator undergoing dynamic modulation can be used to create a synthetic space with an arbitrary dimension. In such a system, the phases of the modulation can be used to create a photonic gauge potential in high dimensions. As an illustration of the implication of this concept, we show that the Haldane model, which exhibits nontrivial topology in two dimensions, can be implemented in the synthetic space using three rings. Our results point to a route toward exploring higher-dimensional topological physics in low-dimensional physical structures. The dynamics of photons in such synthetic spaces also provides a mechanism to control the spectrum of light.

O-Ring sealing arrangements for ultra-high vacuum systems

DOEpatents

Kim, Chang-Kyo; Flaherty, Robert

1981-01-01

An all metal reusable O-ring sealing arrangement for sealing two concentric tubes in an ultra-high vacuum system. An O-ring of a heat recoverable alloy such as Nitinol is concentrically positioned between protruding sealing rings of the concentric tubes. The O-ring is installed between the tubes while in a stressed martensitic state and is made to undergo a thermally induced transformation to an austenitic state. During the transformation the O-ring expands outwardly and contracts inwardly toward a previously sized austenitic configuration, thereby sealing against the protruding sealing rings of the concentric tubes.

Wavelength-tunable optical ring resonators

DOEpatents

Watts, Michael R [Albuquerque, NM; Trotter, Douglas C [Albuquerque, NM; Young, Ralph W [Albuquerque, NM; Nielson, Gregory N [Albuquerque, NM

2009-11-10

Optical ring resonator devices are disclosed that can be used for optical filtering, modulation or switching, or for use as photodetectors or sensors. These devices can be formed as microdisk ring resonators, or as open-ring resonators with an optical waveguide having a width that varies adiabatically. Electrical and mechanical connections to the open-ring resonators are made near a maximum width of the optical waveguide to minimize losses and thereby provide a high resonator Q. The ring resonators can be tuned using an integral electrical heater, or an integral semiconductor junction.

Wavelength-tunable optical ring resonators

DOEpatents

Watts, Michael R [Albuquerque, NM; Trotter, Douglas C [Albuquerque, NM; Young, Ralph W [Albuquerque, NM; Nielson, Gregory N [Albuquerque, NM

2011-07-19

Optical ring resonator devices are disclosed that can be used for optical filtering, modulation or switching, or for use as photodetectors or sensors. These devices can be formed as microdisk ring resonators, or as open-ring resonators with an optical waveguide having a width that varies adiabatically. Electrical and mechanical connections to the open-ring resonators are made near a maximum width of the optical waveguide to minimize losses and thereby provide a high resonator Q. The ring resonators can be tuned using an integral electrical heater, or an integral semiconductor junction.

Shape-Persistent, Thermoresponsive Polypeptide Brushes Prepared by Vapor Deposition Surface-Initiated Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides

DOE PAGES

Shen, Yong; Desseaux, Solenne; Aden, Bethany; ...

2015-04-20

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Device for controlling the pouring of molten materials

DOEpatents

Moore, A.F.; Duncan, A.L.

1994-02-15

A device is described for controlling the pouring of a molten material from a crucible or other container. The device includes an annular retainer ring for mounting in the drain opening in the bottom of a conventional crucible, the retainer ring defining a opening there through. The device also includes a plug member having an annular forward end portion for force-fit reception in the opening of the retainer ring to selectively seal the opening and for being selectively forced through the opening. The plug member has a rear end portion for being positioned within the crucible, the rear end portion including stop means for prohibiting the rear end portion from passing through the opening in the retainer ring when the forward end portion is selectively forced through the opening. The plug member defines at least one, and preferably a plurality of flutes, each extending from a point rearward the annular forward end portion of the plug member, and forward the stop means, to a point rearward of the stop means. The flutes permit fluid communication between the interior and exterior of the crucible when the forward end portion of the plug member is forced through the opening in the retaining ring such that the molten material is allowed to flow from the crucible. 5 figures.

Selective Ring Opening of 1-Methylnaphthalene Over NiW-Supported Catalyst Using Dealuminated Beta Zeolite.

PubMed

Kim, Eun-Sang; Lee, You-Jin; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-02-01

Nanoporous Beta zeolite was dealuminated by weak acid treatment for reducing the acidity. Bi-functional catalysts were prepared using commercial Beta zeolites and the dealuminated zeolites for acidic function, NiW for metallic function. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction has been investigated using the prepared bi-functional catalysts with different acidity in fixed bed reaction system. The dealuminated Beta zeolites, which crystal structure and nanoporosity were maintained, showed the higher SiO2/Al2O3 ratio and smaller acidity than their original zeolite. NiW-supported catalyst using the dealuminated Beta zeolite with SiO2/Al203 mole ratio of 55 showed the highest performance for the selective ring opening. The acidity of catalyst seemed to play an important role as active sites for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. The acidity of Beta zeolite could be controlled by the acid treatment and the catalyst with the optimum acidity for the selective ring opening could be prepared.

Quantum chemical study of penicillin: Reactions after acylation

NASA Astrophysics Data System (ADS)

Li, Rui; Feng, Dacheng; Zhu, Feng

The density functional theory methods were used on the model molecules of penicillin to determine the possible reactions after their acylation on ?-lactamase, and the results were compared with sulbactam we have studied. The results show that, the acylated-enzyme tetrahedral intermediate can evolves with opening of ?-lactam ring as well as the thiazole ring; the thiazole ring-open products may be formed via ?-lactam ring-open product or from tetrahedral intermediate directly. Those products, in imine or enamine form, can tautomerize via hydrogen migration. In virtue of the water-assisted, their energy barriers are obviously reduced.

Rotor balance system

NASA Technical Reports Server (NTRS)

Novotny, Rudolph J. (Inventor)

1989-01-01

A balance ring (18) which is shrunk fit within each disk (12) of a rotor is selectively ground for detail balance. A plurality of openings (20) through the outer edge of the balance ring receive weights during the asssembly balance of the rotor. A snap ring (42) retains the weights within the openings.

Unbalanced-flow, fluid-mixing plug with metering capabilities

NASA Technical Reports Server (NTRS)

England, John Dwight (Inventor); Kelley, Anthony R. (Inventor); Van Buskirk, Paul D. (Inventor)

2009-01-01

A fluid mixer plug has holes formed therethrough such that a remaining portion is closed to fluid flow. The plug's inlet face defines a central circuit region and a ring-shaped region with the ring-shaped region including at least some of the plug's remaining portion so-closed to fluid flow. This remaining portion or closed region at each radius R of the ring shaped region satisfies a radius independent, flow-based relationship. Entry openings are defined in the plug's inlet face in correspondence with the holes. The entry openings define an open flow area at each radius of the ring-shaped region. The open flow area at each such radius satisfies the inverse of the flow-based relationship defining the closed regions of the plug.

Translational velocity oscillations of piston generated vortex rings

NASA Astrophysics Data System (ADS)

Kumar, Manoj; Arakeri, J. H.; Shankar, P. N.

1995-11-01

Experimental results are presented that show that the translational velocities of piston generated vortex rings often undergo oscillations, similar to those recently discovered for drop generated rings. An attempt has been made to minimize uncertainties by utilizing both dye and hydrogen bubbles for visualization and carefully repeating measurements on the same ring and on different realizations under the same nominal piston conditions. The results unambiguously show that under most conditions, both for laminar and turbulent rings and for rings generated from pipes and orifices, the oscillations are present. The present results, together with the earlier results on drop generated rings, give support to the view that translational velocity oscillations are probably an inherent feature of translating vortex ring fields.

Composite Materials with Improved Properties in Compression: Synthesis of 3-Methylene-1,1-Dichlorosilacyclobutane and 1,1-Dichlorosilacyclopent-3-ene

DTIC Science & Technology

1990-05-09

reagents may in fact be involved. Of synthetic interest, V undergoes intramolecular Grignard ring closure to yield III (10%). While the yield of III is low...VII) as the major product along with 1,4-bis(trichlorosilyl)- cis-2-butene (VIII). VII undergoes cyclization by an intramolec- ular Grignard ring...addition of methyl Grignard to III. The 1H 8 am NMR chemical shifts of I in diethyl ether are consistently about 0.4 ppm downfield from those previously

UV/vis and NIR light-responsive spiropyran self-assembled monolayers.

PubMed

Ivashenko, Oleksii; van Herpt, Jochem T; Feringa, Ben L; Rudolf, Petra; Browne, Wesley R

2013-04-02

Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SERS), and X-ray photoelectron spectroscopies (XPS). The SAMs obtained are composed of the ring-closed form (i.e., spiropyran) only. Irradiation with UV light results in conversion of the monolayer to the merocyanine form (MC), manifested in the appearance of an N(+) contribution in the N 1s region of the XPS spectrum of the SAMs, the characteristic absorption band of the MC form in the visible region at 555 nm, and the C-O stretching band in the SERS spectrum. Recovery of the initial state of the monolayer was observed both thermally and after irradiation with visible light. Several switching cycles were performed and monitored by SERS spectroscopy, demonstrating the stability of the SAMs during repeated switching between SP and MC states. A key finding in the present study is that ring-opening of the surface-immobilized spiropyrans can be induced by irradiation with continuous wave NIR (785 nm) light as well as by irradiation with UV light. We demonstrate that ring-opening by irradiation at 785 nm proceeds by a two-photon absorption pathway both in the SAMs and in the solid state. Hence, spiropyran SAMs on gold can undergo reversible photochemical switching from the SP to the MC form with both UV and NIR and the reverse reaction induced by irradiation with visible light or heating. Furthermore, the observation of NIR-induced switching with a continuous wave source holds important consequences in the study of photochromic switches on surfaces using SERS and emphasizes the importance of the use of multiple complementary techniques in characterizing photoresponsive SAMs.

Advances in Spiropyrans/Spirooxazines and Applications Based on Fluorescence Resonance Energy Transfer (FRET) with Fluorescent Materials.

PubMed

Xia, Hongyan; Xie, Kang; Zou, Gang

2017-12-18

Studies on the following were reviewed: (1) the structure of spiropyrans and spirooxazines (two kinds of spiro compounds) under external stimuli and (2) the construction and applications of composite systems based on fluorescence resonance energy transfer (FRET) with fluorescent materials. When treated with different stimuli (light, acids and bases, solvents, metal ions, temperature, redox potential, and so on), spiropyrans/spirooxazines undergo transformations between the ring-closed form (SP), the ring-opened merocyanine (MC) form, and the protonated ring-opened form (MCH). This is due to the breakage of the spiro C-O bond and the protonation of MC, along with a color change. Various novel, multifunctional materials based on photochromic spiropyrans and spirooxazines have been successfully developed because of the vastly differently physiochemical properties posssed by the SP, MC and MCH forms. Among the three different structural forms, the MC form has been studied most extensively. The MC form not only gives complexes with various inorganic particles, biological molecules, and organic chemicals but also acts as the energy acceptor (of energy from fluorescent molecules) during energy transfer processes that take place under proper conditions. Furthermore, spiropyran and spirooxazine compounds exhibit reversible physicochemical property changes under proper stimuli; this provides more advantages compared with other photochromic compounds. Additionally, the molecular structures of spiropyrans and spirooxazines can be easily modified and extended, so better compounds can be obtained to expand the scope of already known applications. Described in detail are: (1) the structural properties of spiropyrans and spirooxazines and related photochromic mechanisms; (2) composite systems based on spiropyrans and spirooxazines, and (3) fluorescent materials which have potential applications in sensing, probing, and a variety of optical elements.

Inflatable O-ring seal would ease closing of hatch cover plate

NASA Technical Reports Server (NTRS)

Neary, K. J.

1966-01-01

Inflatable O-ring seal provides positive sealing means that does not require the manual exertion of a large compressive force during opening or closing of a rotary-type hatch cover plate. The O-ring is deflated during opening and closing and inflated after closure by a gas pressure source.

Deactivation via ring opening: A quantum chemical study of the excited states of furan and comparison to thiophene

NASA Astrophysics Data System (ADS)

Gavrilov, Nemanja; Salzmann, Susanne; Marian, Christel M.

2008-06-01

Minimum nuclear arrangements of the ground and low-lying excited electronic states of furan were obtained by means of (time dependent) Kohn-Sham density functional theory. A combined density functional/multi-reference configuration interaction method (DFT/MRCI) was employed to compute the spectral properties at these points. Multiple minima were found on the first excited singlet (S 1) potential energy hypersurface with electronic structures S1, S2, S3 corresponding to the 1 1A 2 (π → 3s-Ryd), 1 1B 2 (π → π ∗), and 2 1A 1 (π → π ∗) states in the vertical absorption spectrum, respectively. In analogy to recently published studies in thiophene [S. Salzmann, M. Kleinschmidt, J. Tatchen, R. Weinkauf, C.M. Marian, Phys. Chem. Chem. Phys. 10 (2008) 380] a deactivation mechanism for electronically excited furan was detected that involves the opening of the pentacyclic ring. We found a nearly barrierless relaxation pathway from the Franck-Condon region along a C-O bond-breaking coordinate. Hereby the initially excited 1B 2 (π → π ∗) state undergoes a conical intersection with a 1B 1 (π → σ ∗) state. The system can return to the electronic ground state through a second conical intersection of the 1(π → σ ∗) state before the minimum of that B 1 state is reached.

Energy spectra of quantum rings.

PubMed

Fuhrer, A; Lüscher, S; Ihn, T; Heinzel, T; Ensslin, K; Wegscheider, W; Bichler, M

2001-10-25

Quantum mechanical experiments in ring geometries have long fascinated physicists. Open rings connected to leads, for example, allow the observation of the Aharonov-Bohm effect, one of the best examples of quantum mechanical phase coherence. The phase coherence of electrons travelling through a quantum dot embedded in one arm of an open ring has also been demonstrated. The energy spectra of closed rings have only recently been studied by optical spectroscopy. The prediction that they allow persistent current has been explored in various experiments. Here we report magnetotransport experiments on closed rings in the Coulomb blockade regime. Our experiments show that a microscopic understanding of energy levels, so far limited to few-electron quantum dots, can be extended to a many-electron system. A semiclassical interpretation of our results indicates that electron motion in the rings is governed by regular rather than chaotic motion, an unexplored regime in many-electron quantum dots. This opens a way to experiments where even more complex structures can be investigated at a quantum mechanical level.

Hydrolysis of Dihydrouridine and Related Compounds

NASA Technical Reports Server (NTRS)

House, Christopher H.; Miller, Stanley L.

1996-01-01

Dihydrouridine is absent from the tRNA of almost all hyperthermophiles and most Archaea but is ubiquitous in the tRNA of Eubacteria and Eukaryotes. In order to investigate whether this could be due to instability, the rate of ring opening of dihydrouridine was measured between 25 and 120 C. The dihydrouridine ring is stable at 25 C, but the half-life at 100 C and pH 7 is 9.1 h, which is comparable to the doubling time of hyperthermophiles. This suggests an explanation for the absence of dihydrouridine from the tRNA of hyperthermophiles. The rates of ring opening of dihydrouracil, dihydrothymine, and 1-N-methyldihydrouracil were measured at 100 C and pH 6-9, as were the equilibrium constants for ring closure of the ureido acids to the dihydrouracils. The pH rate profiles for ring opening and ring closing were calculated from the data. Possible roles for dihydrouracils in the pre-RNA world are discussed.

Catalytic asymmetric ring-opening of meso-aziridines with malonates under heterodinuclear rare earth metal Schiff base catalysis.

PubMed

Xu, Yingjie; Lin, Luqing; Kanai, Motomu; Matsunaga, Shigeki; Shibasaki, Masakatsu

2011-04-20

Catalytic asymmetric ring-opening of meso-aziridines with malonates is described. The combined use of two rare earth metal sources with different properties promoted the desired ring-opening reaction. A 1:1:1 mixture of a heterobimetallic La(O-iPr)(3)/Yb(OTf)(3)/Schiff base 1a (0.25-10 mol %) efficiently promoted the reaction of five-, six-, and seven-membered ring cyclic meso-aziridines as well as acyclic meso-aziridines with dimethyl, diethyl, and dibenzyl malonates, giving chiral cyclic and acyclic γ-amino esters in 99-63% yield and >99.5-97% ee.

Recent Advances in Ring-Opening Functionalization of Cycloalkanols by C-C σ-Bond Cleavage.

PubMed

Wu, Xinxin; Zhu, Chen

2018-06-01

Cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C-C bonds. Direct functionalization of cyclobutanols to build up other chemical bonds (e. g., C-F, C-Cl, C-Br, C-N, C-S, C-Se, C-C, etc.) has been achieved by using the ring-opening strategy. Mechanistically, the C-C cleavage of cyclobutanols can be involved in two pathways: (a) transition-metal catalyzed β-carbon elimination; (b) radical-mediated 'radical clock'-type ring opening. The recent advances of our group for the ring-opening functionalization of tertiary cycloalkanols are described in this account. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantioselective Ring Opening of Epoxides with 4-Methoxyphenol Catalyzed by Gallium Heterobimetallic Complexes: An Efficient Method for the Synthesis of Optically Active 1,2-Diol Monoethers.

PubMed

Iida, Takehiko; Yamamoto, Noriyoshi; Matsunaga, Shigeki; Woo, Hee-Gweon; Shibasaki, Masakatsu

1998-09-04

Useful chiral building blocks such as 1,2-diols can be obtained by the enantioselective ring opening of achiral epoxides with oxygen nucleophiles. The ring opening is carried out effectively (up to 94 % ee) with 4-methoxyphenol and catalytic amounts of gallium complexes. The novel complex GaSO 1 displays a particularly high catalytic activity. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Enumeration of Ring–Chain Tautomers Based on SMIRKS Rules

PubMed Central

2015-01-01

A compound exhibits (prototropic) tautomerism if it can be represented by two or more structures that are related by a formal intramolecular movement of a hydrogen atom from one heavy atom position to another. When the movement of the proton is accompanied by the opening or closing of a ring it is called ring–chain tautomerism. This type of tautomerism is well observed in carbohydrates, but it also occurs in other molecules such as warfarin. In this work, we present an approach that allows for the generation of all ring–chain tautomers of a given chemical structure. Based on Baldwin’s Rules estimating the likelihood of ring closure reactions to occur, we have defined a set of transform rules covering the majority of ring–chain tautomerism cases. The rules automatically detect substructures in a given compound that can undergo a ring–chain tautomeric transformation. Each transformation is encoded in SMIRKS line notation. All work was implemented in the chemoinformatics toolkit CACTVS. We report on the application of our ring–chain tautomerism rules to a large database of commercially available screening samples in order to identify ring–chain tautomers. PMID:25158156

Conductance of closed and open long Aharonov-Bohm-Kondo rings

NASA Astrophysics Data System (ADS)

Shi, Zheng; Komijani, Yashar

2017-02-01

We calculate the finite temperature linear dc conductance of a generic single-impurity Anderson model containing an arbitrary number of Fermi liquid leads, and apply the formalism to closed and open long Aharonov-Bohm-Kondo (ABK) rings. We show that, as with the short ABK ring, there is a contribution to the conductance from the connected four-point Green's function of the conduction electrons. At sufficiently low temperatures this contribution can be eliminated, and the conductance can be expressed as a linear function of the T matrix of the screening channel. For closed rings we show that at temperatures high compared to the Kondo temperature, the conductance behaves differently for temperatures above and below vF/L , where vF is the Fermi velocity and L is the circumference of the ring. For open rings, when the ring arms have both a small transmission and a small reflection, we show from the microscopic model that the ring behaves like a two-path interferometer, and that the Kondo temperature is unaffected by details of the ring. Our findings confirm that ABK rings are potentially useful in the detection of the size of the Kondo screening cloud, the π /2 scattering phase shift from the Kondo singlet, and the suppression of Aharonov-Bohm oscillations due to inelastic scattering.

Mitral valve stenosis caused by abnormal pannus extension over the prosthetic ring and leaflets after Duran ring mitral annuloplasty.

PubMed

Yunoki, Junji; Minato, Naoki; Katayama, Yuji; Sato, Hisashi

2009-01-01

We treated a 61-year-old woman with mitral stenosis caused by pannus formation after Duran ring annuloplasty. Pannus overgrowth on the ring with extension onto both leaflets narrowed the mitral orifice and severely restricted the mobility of the valve leaflets. Mitral valve replacement with a St. Jude Medical mechanical heart valve prosthesis was successfully performed, and the postoperative course was uneventful. Patients undergoing Duran ring annuloplasty should be followed up with the consideration of possible mitral stenosis caused by pannus extension, as the cause for pannus formation remains unclear.

Turbine nozzle positioning system

DOEpatents

Norton, Paul F.; Shaffer, James E.

1996-01-30

A nozzle guide vane assembly having a preestablished rate of thermal expansion is positioned in a gas turbine engine and being attached to conventional metallic components. The nozzle guide vane assembly includes an outer shroud having a mounting leg with an opening defined therein, a tip shoe ring having a mounting member with an opening defined therein, a nozzle support ring having a plurality of holes therein and a pin positioned in the corresponding opening in the outer shroud, opening in the tip shoe ring and the hole in the nozzle support ring. A rolling joint is provided between metallic components of the gas turbine engine and the nozzle guide vane assembly. The nozzle guide vane assembly is positioned radially about a central axis of the gas turbine engine and axially aligned with a combustor of the gas turbine engine.

Turbine nozzle positioning system

DOEpatents

Norton, P.F.; Shaffer, J.E.

1996-01-30

A nozzle guide vane assembly having a preestablished rate of thermal expansion is positioned in a gas turbine engine and being attached to conventional metallic components. The nozzle guide vane assembly includes an outer shroud having a mounting leg with an opening defined therein, a tip shoe ring having a mounting member with an opening defined therein, a nozzle support ring having a plurality of holes therein and a pin positioned in the corresponding opening in the outer shroud, opening in the tip shoe ring and the hole in the nozzle support ring. A rolling joint is provided between metallic components of the gas turbine engine and the nozzle guide vane assembly. The nozzle guide vane assembly is positioned radially about a central axis of the gas turbine engine and axially aligned with a combustor of the gas turbine engine. 9 figs.

Transient UV pump-IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone.

PubMed

Murdock, Daniel; Harris, Stephanie J; Luke, Joel; Grubb, Michael P; Orr-Ewing, Andrew J; Ashfold, Michael N R

2014-10-21

The heterocyclic ring-opening dynamics of thiophenone and furanone dissolved in CH3CN have been probed by ultrafast transient infrared spectroscopy. Following irradiation at 267 nm (thiophenone) or 225 nm (furanone), prompt (τ < 1 ps) ring-opening is confirmed by the appearance of a characteristic antisymmetric ketene stretching feature around 2150 cm(-1). The ring-opened product molecules are formed highly vibrationally excited, and cool subsequently on a ∼6.7 ps timescale. By monitoring the recovery of the parent (S0) bleach, it is found that ∼60% of the initially photoexcited thiophenone molecules reform the parent molecule, in stark contrast with the case in furanone where there is less than 10% parent bleach recovery. Complementary ab initio calculations of potential energy cuts along the S-C([double bond, length as m-dash]O) and O-C([double bond, length as m-dash]O) ring-opening coordinate reveals insights into the reaction mechanism, and the important role played by dissociative (n/π)σ* states in the UV-induced photochemistry of such heterocyclic systems.

Two-dimensional correlation and codistribution spectroscopy (2DCOS and 2DCDS) analyses of time-dependent ATR IR spectra of D-glucose anomers undergoing mutarotation process in water

NASA Astrophysics Data System (ADS)

Noda, Isao

2018-05-01

Two cyclic diastereoisomeric structures, known as α- and β-anomers of D-glucose with different configurations around C1 with OH groups in axial or equitroial positions, undergo the mutarotation conversion to each other in water. Two-dimensional correlation and codistribution spectroscopy (2DCOS and 2DCDS) analyses were applied to the time-dependent ATR IR spectra of aqueous solutions of α- and β-D-glucose undergoing such mutarotation conversion. 2DCOS analysis reveals that the increase and decrease in the IR intensities after the dissolution of α- or β-D-glucose are not fully synchronized, suggesting the mutarotation of D-glucose in water is not a simple binary conversion process but a multi-step reaction involving an intermediate species with a finite and observable concentration level and lifetime. 2DCDS analysis of the time-dependent ATR IR spectra clearly demonstrated the presence of intermediate species contributing to the band positions overlapped close to bands for α- and β-D-glucose. The fact that band positions identified for the intermediate species for α- to β-D-glucose conversion are the same for the reverse reaction suggests that they arise from the same species, most likely the open-ring structure produced by the hydrolysis.

Adolescent Experiences with the Vaginal Ring

PubMed Central

Epstein, Laura B.; Sokal-Gutierrez, Karen; Ivey, Susan L.; Raine, Tina; Auerswald, Colette

2011-01-01

Purpose To understand racial/ethnic minority adolescent females’ experiences with the vaginal ring. Methods We conducted in-depth interviews with a clinic-based sample of 32 young women aged 15–24 years who had used the vaginal ring. Results Qualitative analysis using grounded theory revealed that adolescents undergo a multi-stage process when trying the ring and adopting ring use. These stages include hearing about the ring, initial reactions, first experiences with insertion and removal, and first sexual experiences. Adolescents subsequently enter an assessment and adjustment stage in which they decide whether to adopt or discontinue ring use. Ultimately they share their experiences with friends. Conclusions The model developed provides a context within which providers may advise adolescents as they begin use of the ring. Some specific recommendations are offered. PMID:18565439

Initial Reactivity of Linkages and Monomer Rings in Lignin Pyrolysis Revealed by ReaxFF Molecular Dynamics.

PubMed

Zhang, Tingting; Li, Xiaoxia; Guo, Li

2017-10-24

The initial conversion pathways of linkages and their linked monomer units in lignin pyrolysis were investigated comprehensively by ReaxFF MD simulations facilitated by the unique VARxMD for reaction analysis. The simulated molecular model contains 15 920 atoms and was constructed on the basis of Adler's softwood lignin model. The simulations uncover the initial conversion ratio of various linkages and their linked aryl monomers. For linkages and their linked monomer aryl rings of α-O-4, β-O-4 and α-O-4 & β-5, the C α /C β ether bond cracking dominates the initial pathway accounting for at least up to 80% of their consumption. For the linkage of β-β & γ-O-α, both the C α -O ether bond cracking and its linked monomer aryl ring opening are equally important. Ring-opening reactions dominate the initial consumption of other 4-O-5, 5-5, β-1, β-2, and β-5 linkages and their linked monomers. The ether bond cracking of C α -O and C β -O occurs at low temperature, and the aryl ring-opening reactions take place at relatively high temperature. The important intermediates leading to the stable aryl ring opening are the phenoxy radicals, the bridged five-membered and three-membered rings and the bridged six-membered and three-membered rings. In addition, the reactivity of a linkage and its monomer aryl ring may be affected by other linkages. The ether bond cracking of α-O-4 and β-O-4 linkages can activate its neighboring linkage or monomer ring through the formed phenoxy radicals as intermediates. The important intermediates revealed in this article should be of help in deepening the understanding of the controlling mechanism for producing aromatic chemicals from lignin pyrolysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamamoto, Seiichi, E-mail: s-yama@met.nagoya-u.ac.jp; Okumura, Satoshi; Komori, Masataka

We developed a prototype positron emission tomography (PET) system based on a new concept called Open-close PET, which has two modes: open and close-modes. In the open-mode, the detector ring is separated into two halved rings and subject is imaged with the open space and projection image is formed. In the close-mode, the detector ring is closed to be a regular circular ring, and the subject can be imaged without an open space, and so reconstructed images can be made without artifacts. The block detector of the Open-close PET system consists of two scintillator blocks that use two types ofmore » gadolinium orthosilicate (GSO) scintillators with different decay times, angled optical fiber-based image guides, and a flat panel photomultiplier tube. The GSO pixel size was 1.6 × 2.4 × 7 mm and 8 mm for fast (35 ns) and slow (60 ns) GSOs, respectively. These GSOs were arranged into an 11 × 15 matrix and optically coupled in the depth direction to form a depth-of-interaction detector. The angled optical fiber-based image guides were used to arrange the two scintillator blocks at 22.5° so that they can be arranged in a hexadecagonal shape with eight block detectors to simplify the reconstruction algorithm. The detector ring was divided into two halves to realize the open-mode and set on a mechanical stand with which the distance between the two parts can be manually changed. The spatial resolution in the close-mode was 2.4-mm FWHM, and the sensitivity was 1.7% at the center of the field-of-view. In both the close- and open-modes, we made sagittal (y-z plane) projection images between the two halved detector rings. We obtained reconstructed and projection images of {sup 18}F-NaF rat studies and proton-irradiated phantom images. These results indicate that our developed Open-close PET is useful for some applications such as proton therapy as well as other applications such as molecular imaging.« less

Ring opening of azetidine cycle: First examples of 1-azetidinepropanamine molecules as a template in hybrid organic-inorganic compounds

NASA Astrophysics Data System (ADS)

Gurzhiy, Vladislav V.; Tyumentseva, Olga S.; Britvin, Sergey N.; Krivovichev, Sergey V.; Tananaev, Ivan G.

2018-01-01

Three novel uranyl selenate and sulfate oxysalts templated by protonated azetidine molecules, [AzH]+, and its ring-opened counterpart 1-azetidinepropanamine, [AzH(CH2)3NH3]2+, have been prepared and studied by X-ray structural analysis. Conformations of azetidinium cations were analysed by means of infrared vibrational assignments supported by the DFT calculations. Crystallization of [AzH]2 [(UO2)2(SeO4)3(H2O)] (I) from highly acidic solutions suggests that low pH does not necessarily result in the opening of azetidine ring. [AzH(CH2)3NH3][(UO2)2(SeO4)3(H2O)](H2O) (II) and [AzH(CH2)3NH3](H5O2)[(UO2)2(SO4)3(HSO4)] (III) are the first structurally characterized crystalline compounds bearing isolated ring-opened azetidine moiety.

In vitro contraction of cytokinetic ring depends on myosin II but not on actin dynamics.

PubMed

Mishra, Mithilesh; Kashiwazaki, Jun; Takagi, Tomoko; Srinivasan, Ramanujam; Huang, Yinyi; Balasubramanian, Mohan K; Mabuchi, Issei

2013-07-01

Cytokinesis in many eukaryotes involves the contraction of an actomyosin-based contractile ring. However, the detailed mechanism of contractile ring contraction is not fully understood. Here, we establish an experimental system to study contraction of the ring to completion in vitro. We show that the contractile ring of permeabilized fission yeast cells undergoes rapid contraction in an ATP- and myosin-II-dependent manner in the absence of other cytoplasmic constituents. Surprisingly, neither actin polymerization nor its disassembly is required for contraction of the contractile ring, although addition of exogenous actin-crosslinking proteins blocks ring contraction. Using contractile rings generated from fission yeast cytokinesis mutants, we show that not all proteins required for assembly of the ring are required for its contraction in vitro. Our work provides the beginnings of the definition of a minimal contraction-competent cytokinetic ring apparatus.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu

Unimolecular decomposition of nitrogen-rich energetic salt molecules bis(ammonium)5,5′-bistetrazolate (NH{sub 4}){sub 2}BT and bis(triaminoguanidinium) 5,5′-azotetrazolate TAGzT, has been explored via 283 nm laser excitation. The N{sub 2} molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product, subsequent to UV excitation. Initial decomposition mechanisms for the two electronically excited salt molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) ((NH{sub 4}){sub 2}BT) and ONIOM (CASSCF/6-31G(d):UFF) (TAGzT) levels illustrate that conical intersections play an essential role in the decomposition mechanism as they provide non-adiabatic, ultrafast radiationless internalmore » conversion between upper and lower electronic states. The tetrazole ring opens on the S{sub 1} excited state surface and, through conical intersections (S{sub 1}/S{sub 0}){sub CI}, N{sub 2} product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings open at the N2—N3 ring bond with the lowest energy barrier: the C—N ring bond opening has a higher energy barrier than that for any of the N—N ring bonds: this is consistent with findings for other nitrogen-rich neutral organic energetic materials. TAGzT can produce N{sub 2} either by the opening of tetrazole ring or from the N=N group linking its two tetrazole rings. Nonetheless, opening of a tetrazole ring has a much lower energy barrier. Vibrational temperatures of N{sub 2} products are hot based on theoretical predictions. Energy barriers for opening of the tetrazole ring for all the nitrogen-rich energetic materials studied thus far, including both neutral organic molecules and salts, are in the range from 0.31 to 2.71 eV. Energy of the final molecular structure of these systems with dissociated N{sub 2} product is in the range from −1.86 to 3.11 eV. The main difference between energetic salts and neutral nitrogen-rich energetic material is that energetic salts usually have lower excitation energy.« less

Fuel transfer tube quick opening hatch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meuschke, R. E.; Sherwood, D. G.; Silverblatt, B. L.

1985-05-28

A quick opening hatch for use on a transfer tube of a nuclear reactor plant that is adapted to replace the conventional hatch on the transfer tube. A locking ring is provided with a plurality of screw openings that is adapted for connection to the transfer tube, and a hatch cover fitably received within the locking ring for closing-off the transfer tube. To lock the cover to the ring, latches are movably connected with the cover for locking engagement with the locking ring, and a sprocket with a plurality of crank arms is movably connected with the cover and themore » latches for movement thereof into locking engagement with a latch housing on the locking ring for locking the cover to the ring and out of engagement with the latch housing for releasing the cover from the locking ring so as to permit removal of the hatch cover from the locking ring to provide access to the transfer tube. A davit assembly is provided which is connected with the transfer tube and the hatch cover to move the cover away and to provide guidance for closing-off the transfer tube. The locking ring and hatch cover also include cooperating keys and keyways for alignment when closing the transfer tube. The cover is provided with sealing rings and the latch housing and latches include cooperating cam surfaces to provide a tight locking engagement by compressing the sealing rings between the transfer tube and the hatch cover.« less

Turbine nozzle/nozzle support structure

DOEpatents

Boyd, Gary L.; Shaffer, James E.

1997-01-01

An axial flow turbine's nozzle/nozzle support structure having a cantilevered nozzle outer structure including an outer shroud and airfoil vanes extending radially inwardly therefrom, an inner shroud radially adjacent the inner end of the airfoil vanes and cooperatively disposed relative to the outer shroud to provide an annular fluid flow path, an inner and an outer support ring respectively arranged radially inside the inner shroud and axially adjacent a portion of the outer shroud, and pins extending through such portion and into the outer support ring. The inner support ring or inner shroud has a groove therein bounded by end walls for receiving and being axially abuttable with a locating projection from the adjacent airfoil vane, inner shroud, or inner support ring. The nozzle outer structure may comprise segments each of which has a single protrusion which is axially engageable with the outer support ring or, alternatively, a first and second protrusion which are arcuately and axially separated and which include axial openings therein whereby first and second protrusions on respective, arcuately adjacent nozzle segments have axial openings therein which are alignable with connector openings in the outer support ring and within each of such aligned openings a pin is receivable. The inner shroud may, likewise, comprise segments which, when assembled in operating configuration, have a 360 degree expanse.

Turbine nozzle/nozzle support structure

DOEpatents

Boyd, G.L.; Shaffer, J.E.

1997-01-07

An axial flow turbine`s nozzle/nozzle support structure is described having a cantilevered nozzle outer structure including an outer shroud and airfoil vanes extending radially inwardly therefrom, an inner shroud radially adjacent the inner end of the airfoil vanes and cooperatively disposed relative to the outer shroud to provide an annular fluid flow path, an inner and an outer support ring respectively arranged radially inside the inner shroud and axially adjacent a portion of the outer shroud, and pins extending through such portion and into the outer support ring. The inner support ring or inner shroud has a groove therein bounded by end walls for receiving and being axially abuttable with a locating projection from the adjacent airfoil vane, inner shroud, or inner support ring. The nozzle outer structure may comprise segments each of which has a single protrusion which is axially engageable with the outer support ring or, alternatively, a first and second protrusion which are arcuately and axially separated and which include axial openings therein whereby first and second protrusions on respective, arcuately adjacent nozzle segments have axial openings therein which are alignable with connector openings in the outer support ring and within each of such aligned openings a pin is receivable. The inner shroud may, likewise, comprise segments which, when assembled in operating configuration, have a 360 degree expanse. 6 figs.

Turbine nozzle/nozzle support structure

DOEpatents

Boyd, Gary L.; Shaffer, James E.

1996-01-01

An axial flow turbine's nozzle/nozzle support structure having a cantilevered nozzle outer structure including an outer shroud and airfoil vanes extending radially inwardly therefrom, an inner shroud radially adjacent the inner end of the airfoil vanes and cooperatively disposed relative to the outer shroud to provide an annular fluid flow path, an inner and an outer support ring respectively arranged radially inside the inner shroud and axially adjacent a portion of the outer shroud, and pins extending through such portion and into the outer support ring. The inner support ring or inner shroud has a groove therein bounded by end walls for receiving and being axially abuttable with a locating projection from the adjacent airfoil vane, inner shroud, or inner support ring. The nozzle outer structure may comprise segments each of which has a single protrusion which is axially engageable with the outer support ring or, alternatively, a first and second protrusion which are arcuately and axially separated and which include axial openings therein whereby first and second protrusions on respective, arcuately adjacent nozzle segments have axial openings therein which are alignable with connector openings in the outer support ring and within each of such aligned openings a pin is receivable. The inner shroud may, likewise, comprise segments which, when assembled in operating configuration, have a 360 degree expanse.

Turbine nozzle/nozzle support structure

DOEpatents

Boyd, G.L.; Shaffer, J.E.

1996-09-10

An axial flow turbine`s nozzle/nozzle support structure is described having a cantilevered nozzle outer structure including an outer shroud and airfoil vanes extending radially inwardly therefrom, an inner shroud radially adjacent the inner end of the airfoil vanes and cooperatively disposed relative to the outer shroud to provide an annular fluid flow path, an inner and an outer support ring respectively arranged radially inside the inner shroud and axially adjacent a portion of the outer shroud, and pins extending through such portion and into the outer support ring. The inner support ring or inner shroud has a groove therein bounded by end walls for receiving and being axially abuttable with a locating projection from the adjacent airfoil vane, inner shroud, or inner support ring. The nozzle outer structure may comprise segments each of which has a single protrusion which is axially engageable with the outer support ring or, alternatively, a first and second protrusion which are arcuately and axially separated and which include axial openings therein whereby first and second protrusions on respective, arcuately adjacent nozzle segments have axial openings therein which are alignable with connector openings in the outer support ring and within each of such aligned openings a pin is receivable. The inner shroud may, likewise, comprise segments which, when assembled in operating configuration, have a 360 degree expanse. 6 figs.

Turbine nozzle/nozzle support structure

DOEpatents

Boyd, Gary L.; Shaffer, James E.

1995-01-01

An axial flow turbine's nozzle/nozzle support structure having a cantilevered nozzle outer structure including an outer shroud and airfoil vanes extending radially inwardly therefrom, an inner shroud radially adjacent the inner end of the airfoil vanes and cooperatively disposed relative to the outer shroud to provide an annular fluid flow path, an inner and an outer support ring respectively arranged radially inside the inner shroud and axially adjacent a portion of the outer shroud, and pins extending through such portion and into the outer support ring. The inner support ring or inner shroud has a groove therein bounded by end walls for receiving and being axially abuttable with a locating projection from the adjacent airfoil vane, inner shroud, or inner support ring. The nozzle outer structure may comprise segments each of which has a single protrusion which is axially engageable with the outer support ring or, alternatively, a first and second protrusion which are arcuately and axially separated and which include axial openings therein whereby first and second protrusions on respective, arcuately adjacent nozzle segments have axial openings therein which are alignable with connector openings in the outer support ring and within each of such aligned openings a pin is receivable. The inner shroud may, likewise, comprise segments which, when assembled in operating configuration, have a 360 degree expanse.

Turbine nozzle/nozzle support structure

DOEpatents

Boyd, G.L.; Shaffer, J.E.

1995-08-15

An axial flow turbine`s nozzle/nozzle support structure is described having a cantilevered nozzle outer structure including an outer shroud and airfoil vanes extending radially inwardly therefrom, an inner shroud radially adjacent the inner end of the airfoil vanes and cooperatively disposed relative to the outer shroud to provide an annular fluid flow path, an inner and an outer support ring respectively arranged radially inside the inner shroud and axially adjacent a portion of the outer shroud, and pins extending through such portion and into the outer support ring. The inner support ring or inner shroud has a groove therein bounded by end walls for receiving and being axially abuttable with a locating projection from the adjacent airfoil vane, inner shroud, or inner support ring. The nozzle outer structure may comprise segments each of which has a single protrusion which is axially engageable with the outer support ring or, alternatively, a first and second protrusion which are arcuately and axially separated and which include axial openings therein whereby first and second protrusions on respective, arcuately adjacent nozzle segments have axial openings therein which are alignable with connector openings in the outer support ring and within each of such aligned openings a pin is receivable. The inner shroud may, likewise, comprise segments which, when assembled in operating configuration, have a 360 degree expanse. 6 figs.

Copper-Catalyzed Cyclopropanol Ring Opening Csp(3)-Csp(3) Cross-Couplings with (Fluoro)Alkyl Halides.

PubMed

Ye, Zhishi; Gettys, Kristen E; Shen, Xingyu; Dai, Mingji

2015-12-18

Novel and general copper-catalyzed cyclopropanol ring opening cross-coupling reactions with difluoroalkyl bromides, perfluoroalkyl iodides, monofluoroalkyl bromides, and 2-bromo-2-alkylesters to synthesize various β-(fluoro)alkylated ketones are reported. The reactions feature mild conditions and excellent functional group compatibility and can be scaled up to gram scale. Preliminary mechanistic studies suggest the involvement of radical intermediates. The difluoroalkyl-alkyl cross-coupling products can also be readily converted to more valuable and diverse gem-difluoro-containing compounds by taking advantage of the carbonyl group resulting from cyclopropanol ring opening.

Retention of Plasmodium falciparum ring-infected erythrocytes in the slow, open microcirculation of the human spleen.

PubMed

Safeukui, Innocent; Correas, Jean-Michel; Brousse, Valentine; Hirt, Déborah; Deplaine, Guillaume; Mulé, Sébastien; Lesurtel, Mickael; Goasguen, Nicolas; Sauvanet, Alain; Couvelard, Anne; Kerneis, Sophie; Khun, Huot; Vigan-Womas, Inès; Ottone, Catherine; Molina, Thierry Jo; Tréluyer, Jean-Marc; Mercereau-Puijalon, Odile; Milon, Geneviève; David, Peter H; Buffet, Pierre A

2008-09-15

The current paradigm in Plasmodium falciparum malaria pathogenesis states that young, ring-infected erythrocytes (rings) circulate in peripheral blood and that mature stages are sequestered in the vasculature, avoiding clearance by the spleen. Through ex vivo perfusion of human spleens, we examined the interaction of this unique blood-filtering organ with P falciparum-infected erythrocytes. As predicted, mature stages were retained. However, more than 50% of rings were also retained and accumulated upstream from endothelial sinus wall slits of the open, slow red pulp microcirculation. Ten percent of rings were retained at each spleen passage, a rate matching the proportion of blood flowing through the slow circulatory compartment established in parallel using spleen contrast-enhanced ultrasonography in healthy volunteers. Rings displayed a mildly but significantly reduced elongation index, consistent with a retention process, due to their altered mechanical properties. This raises the new paradigm of a heterogeneous ring population, the less deformable subset being retained in the spleen, thereby reducing the parasite biomass that will sequester in vital organs, influencing the risk of severe complications, such as cerebral malaria or severe anemia. Cryptic ring retention uncovers a new role for the spleen in the control of parasite density, opening novel intervention opportunities.

Robust gap repair in the contractile ring ensures timely completion of cytokinesis

PubMed Central

Maiato, Helder; Pinto, Inês Mendes; Rubinstein, Boris

2016-01-01

Cytokinesis in animal cells requires the constriction of an actomyosin contractile ring, whose architecture and mechanism remain poorly understood. We use laser microsurgery to explore the biophysical properties of constricting rings in Caenorhabditis elegans embryos. Laser cutting causes rings to snap open. However, instead of disintegrating, ring topology recovers and constriction proceeds. In response to severing, a finite gap forms and is repaired by recruitment of new material in an actin polymerization–dependent manner. An open ring is able to constrict, and rings repair from successive cuts. After gap repair, an increase in constriction velocity allows cytokinesis to complete at the same time as controls. Our analysis demonstrates that tension in the ring increases while net cortical tension at the site of ingression decreases throughout constriction and suggests that cytokinesis is accomplished by contractile modules that assemble and contract autonomously, enabling local repair of the actomyosin network. Consequently, cytokinesis is a highly robust process impervious to discontinuities in contractile ring structure. PMID:27974482

Development of a prototype Open-close positron emission tomography system

NASA Astrophysics Data System (ADS)

Yamamoto, Seiichi; Okumura, Satoshi; Watabe, Tadashi; Ikeda, Hayato; Kanai, Yasukazu; Toshito, Toshiyuki; Komori, Masataka; Ogata, Yoshimune; Kato, Katsuhiko; Hatazawa, Jun

2015-08-01

We developed a prototype positron emission tomography (PET) system based on a new concept called Open-close PET, which has two modes: open and close-modes. In the open-mode, the detector ring is separated into two halved rings and subject is imaged with the open space and projection image is formed. In the close-mode, the detector ring is closed to be a regular circular ring, and the subject can be imaged without an open space, and so reconstructed images can be made without artifacts. The block detector of the Open-close PET system consists of two scintillator blocks that use two types of gadolinium orthosilicate (GSO) scintillators with different decay times, angled optical fiber-based image guides, and a flat panel photomultiplier tube. The GSO pixel size was 1.6 × 2.4 × 7 mm and 8 mm for fast (35 ns) and slow (60 ns) GSOs, respectively. These GSOs were arranged into an 11 × 15 matrix and optically coupled in the depth direction to form a depth-of-interaction detector. The angled optical fiber-based image guides were used to arrange the two scintillator blocks at 22.5° so that they can be arranged in a hexadecagonal shape with eight block detectors to simplify the reconstruction algorithm. The detector ring was divided into two halves to realize the open-mode and set on a mechanical stand with which the distance between the two parts can be manually changed. The spatial resolution in the close-mode was 2.4-mm FWHM, and the sensitivity was 1.7% at the center of the field-of-view. In both the close- and open-modes, we made sagittal (y-z plane) projection images between the two halved detector rings. We obtained reconstructed and projection images of 18F-NaF rat studies and proton-irradiated phantom images. These results indicate that our developed Open-close PET is useful for some applications such as proton therapy as well as other applications such as molecular imaging.

Synframe: a preliminary report.

PubMed

Aebi, M; Steffen, T

2000-02-01

Both endoscopic lumbar spinal surgery and the non-standardized and unstable retractor systems for the lumbar spine presently on the market have disadvantages and limitations in relation to the minimally invasive surgical concept, which have been gradually recognized in the last few years. In an attempt to resolve some of these issues, we have developed a highly versatile retractor system, which allows access to and surgery at the lumbar, thoracic and even cervical spine. This retractor system - Synframe - is based on a ring concept allowing 360 degrees access to a surgical opening in anterior as well as posterior surgery. The ring is concentrically laid over the surgical opening for the approach and is used as a carrier for retractor arms, which are instrumented with either different sizes or types of blades and/or different sizes of Hohmann hooks. In posterior surgery, nerve root retractors can also be installed. This ring also functions as a carrier for fiberoptic illumination devices and different sizes of endoscopes, used to transmit the surgical procedure out of the depth of the surgical exposure for both teaching purposes and for the surgical team when it has no longer direct visual access to the procedure. The ring is stable, being fixed onto the operating table, allowing precise minimally open approaches and surgical procedures under direct vision with optimal illumination. This ring system also opens perspectives for an integrated minimally open surgical concept, where the ring may be used as a reference platform in computer-navigated surgery.

Synthesis and characterization of polymeric materials derived from 2,5-diketopiperazines and pyroglutamic acid

NASA Astrophysics Data System (ADS)

Parrish, Dennis Arch

The research presented in this dissertation describes the investigation of 2,5-diketopiperazines (DKPs) as property modifiers for addition polymers and the self association behavior of pyroglutamic acid derivatives. The first project involved the copolymerization of methyl methacrylate and styrene with DKP-based methacrylate monomers. Low incorporations of serine- and aspartame-based DKPs in the copolymer resulted in dramatic increases in the glass transition temperature (Ts). The research presented in Chapter II focuses on the ring-opening reactions of pyroglutamic diketopiperazine (pyDKP). The original intent was to synthesize polymers containing backbone DKPs through ring-opening polymerization of the five-membered rings. However, it was discovered that regioselective ring-opening occurs at the six-membered ring to give pyroglutamic acid derivatives. Since this reaction had not been reported previously, the focus of research was altered to investigate the scope and limitations of the new reaction. The ring-opening reactions of pyDKP with diamines to give bispyroglutamides is described in Chapter IV. While these materials are not polymeric, they display polymeric behavior. It was found that multi-functional pyroglutamides display Tgs during thermal analysis, exhibit high thermal stability, and form melt-drawn fibers. In contrast, the materials have low solution viscosities and are freely soluble in water, ethanol, and chloroform. This behavior is attributed to non-covalent supramolecular associations. The final part of this dissertation involved the investigation of thermoreversible organic solvent gelators. The ring-opening reaction of pyDKP with long alkyl amines unexpectedly gelled the reaction solvent. A series of analogous gelators were synthesized, and the minimum concentration required for gelation in various solvents was determined. It was found that the nature of the solvent, alkyl chain length, and optical activity of the gelator determined gelator efficiency and gel structure.

Kinetic or Dynamic Control on a Bifurcating Potential Energy Surface? An Experimental and DFT Study of Gold-Catalyzed Ring Expansion and Spirocyclization of 2-Propargyl-β-tetrahydrocarbolines.

PubMed

Zhang, Lei; Wang, Yi; Yao, Zhu-Jun; Wang, Shaozhong; Yu, Zhi-Xiang

2015-10-21

In classical transition state theory, a transition state is connected to its reactant(s) and product(s). Recently, chemists found that reaction pathways may bifurcate after a transition state, leading to two or more sets of products. The product distribution for such a reaction containing a bifurcating potential energy surface (bPES) is usually determined by the shape of the bPES and dynamic factors. However, if the bPES leads to two intermediates (other than two products), which then undergo further transformations to give different final products, what factors control the selectivity is still not fully examined. This missing link in transition state theory is founded in the present study. Aiming to develop new methods for the synthesis of azocinoindole derivatives, we found that 2-propargyl-β-tetrahydrocarbolines can undergo ring expansion and spirocyclization under gold catalysis. DFT study revealed that the reaction starts with the intramolecular cyclization of the gold-activated 2-propargyl-β-tetrahydrocarboline with a bPES. The cyclization intermediates can not only interconvert into each other via a [1,5]-alkenyl shift, but also undergo ring expansion (through fragmentation/protodeauration mechanism) or spirocyclization (through deprotonation/protodeauration mechanism). Detailed analysis of the complex PESs for substrates with different substituents indicated that the reaction selectivity is under dynamic control if the interconversion of the intermediates is slower than the ring expansion and spirocyclization processes. Otherwise, the chemical outcome is under typical kinetic control and determined by the relative preference of ring expansion versus spirocyclization pathways. The present study may enrich chemist's understanding of the determinants for selectivities on bPESs.

Preparation of Soypolymers by Ring-opening Polymerization of Epoxdized Soybean Oil

USDA-ARS?s Scientific Manuscript database

Ring opening polymerization of epoxidized soybean oil (ESO) initiated by boron trifluoride diethyl etherate in methylene chloride was conducted in an effort to develop useful biodegradable polymers. The resulting polymers (PESO) were characterized using Infrared (IR), differential scanning calorime...

Ring-opening Polymerization of Epoxidized Soybean Oil

USDA-ARS?s Scientific Manuscript database

Ring opening polymerization of epoxidized soybean oil (ESO) initiated by boron trifluoride diethyl etherate, (BF3•OEt2), in methylene chloride was conducted in an effort to develop useful biodegradable polymers. The resulting polymers (PESO) were characterized using Infrared (IR), differential scan...

Thermal decomposition of pyrazole to vinylcarbene + N 2: A first principles/RRKM study

NASA Astrophysics Data System (ADS)

da Silva, Gabriel

2009-05-01

Thermal decomposition of pyrazole, a five-membered nitrogen-containing heterocycle, has been studied using ab initio G3X theory and RRKM rate theory. The decomposition mechanism involves an intramolecular hydrogen shift to 3 H-pyrazole, followed by ring opening to 3-diazo-1-propene and dissociation to vinylcarbene (CH 2CHCH) + N 2. At 1 atm the calculated rate equation k [s -1] = 1.26 × 10 50T-10.699e -41200/T is obtained, which agrees with the results of flash vacuum pyrolysis experiments. The pyrazole decomposition product vinylcarbene is expected to rearrange to propyne, making pyrazole decomposition essentially thermoneutral. It is hypothesized that at high concentrations vinylcarbene could undergo a self-reaction to 1,3- and 1,4-cyclohexadiene.

Health Impact Assessment of a Predicted Air Quality Change by Moving Traffic from an Urban Ring Road into a Tunnel. The Case of Antwerp, Belgium.

PubMed

Van Brusselen, Daan; Arrazola de Oñate, Wouter; Maiheu, Bino; Vranckx, Stijn; Lefebvre, Wouter; Janssen, Stijn; Nawrot, Tim S; Nemery, Ben; Avonts, Dirk

2016-01-01

The Antwerp ring road has a traffic density of 300,000 vehicles per day and borders the city center. The 'Ringland project' aims to change the current 'open air ring road' into a 'filtered tunneled ring road', putting the entire urban ring road into a tunnel and thus filtering air pollution. We conducted a health impact assessment (HIA) to quantify the possible benefit of a 'filtered tunneled ring road', as compared to the 'open air ring road' scenario, on air quality and its long-term health effects. We modeled the change in annual ambient PM2.5 and NO2 concentrations by covering 15 kilometers of the Antwerp ring road in high resolution grids using the RIO-IFDM street canyon model. The exposure-response coefficients used were derived from a literature review: all-cause mortality, life expectancy, cardiopulmonary diseases and childhood Forced Vital Capacity development (FVC). Our model predicts changes between -1.5 and +2 μg/m³ in PM2.5 within a 1,500 meter radius around the ring road, for the 'filtered tunneled ring road' scenario as compared to an 'open air ring road'. These estimated annual changes were plotted against the population exposed to these differences. The calculated change of PM2.5 is associated with an expected annual decrease of 21 deaths (95% CI 7 to 41). This corresponds with 11.5 deaths avoided per 100,000 inhabitants (95% CI 3.9-23) in the first 500 meters around the ring road every year. Of 356 schools in a 1,500 meter perimeter around the ring road changes between -10 NO2 and + 0.17 μg/m³ were found, corresponding to FVC improvement of between 3 and 64ml among school-age children. The predicted decline in lung cancer mortality and incidence of acute myocardial infarction were both only 0.1 per 100,000 inhabitants or less. The expected change in PM2,5 and NO2 by covering the entire urban ring road in Antwerp is associated with considerable health gains for the approximate 352,000 inhabitants living in a 1,500 meter perimeter around the current open air ring road.

Health Impact Assessment of a Predicted Air Quality Change by Moving Traffic from an Urban Ring Road into a Tunnel. The Case of Antwerp, Belgium

PubMed Central

Van Brusselen, Daan; Arrazola de Oñate, Wouter; Maiheu, Bino; Vranckx, Stijn; Lefebvre, Wouter; Janssen, Stijn; Nawrot, Tim S; Nemery, Ben; Avonts, Dirk

2016-01-01

Background The Antwerp ring road has a traffic density of 300,000 vehicles per day and borders the city center. The ‘Ringland project’ aims to change the current ‘open air ring road’ into a ‘filtered tunneled ring road’, putting the entire urban ring road into a tunnel and thus filtering air pollution. We conducted a health impact assessment (HIA) to quantify the possible benefit of a ‘filtered tunneled ring road’, as compared to the ‘open air ring road’ scenario, on air quality and its long-term health effects. Materials and Methods We modeled the change in annual ambient PM2.5 and NO2 concentrations by covering 15 kilometers of the Antwerp ring road in high resolution grids using the RIO-IFDM street canyon model. The exposure-response coefficients used were derived from a literature review: all-cause mortality, life expectancy, cardiopulmonary diseases and childhood Forced Vital Capacity development (FVC). Results Our model predicts changes between -1.5 and +2 μg/m³ in PM2.5 within a 1,500 meter radius around the ring road, for the ‘filtered tunneled ring road’ scenario as compared to an ‘open air ring road’. These estimated annual changes were plotted against the population exposed to these differences. The calculated change of PM2.5 is associated with an expected annual decrease of 21 deaths (95% CI 7 to 41). This corresponds with 11.5 deaths avoided per 100,000 inhabitants (95% CI 3.9–23) in the first 500 meters around the ring road every year. Of 356 schools in a 1,500 meter perimeter around the ring road changes between -10 NO2 and + 0.17 μg/m³ were found, corresponding to FVC improvement of between 3 and 64ml among school-age children. The predicted decline in lung cancer mortality and incidence of acute myocardial infarction were both only 0.1 per 100,000 inhabitants or less. Conclusion The expected change in PM2,5 and NO2 by covering the entire urban ring road in Antwerp is associated with considerable health gains for the approximate 352,000 inhabitants living in a 1,500 meter perimeter around the current open air ring road. PMID:27167124

Antitumor effects of hydroxycamptothecin-loaded poly[ethylene glycol]-poly [gamma-benzyl-L-glutamate] micelles against oral squamous cell carcinoma.

PubMed

Ding, Xue-Qiang; Chen, Dan; Wang, An-Xun; Li, Su; Chen, Yu; Wang, Ji

2007-01-01

Therapeutic use of hydroxycamptothecin (HCPT), a promising antitumor agent, is limited by its poor solubility and rapid destruction. Amphiphilic block copolymer micelle carriers possess significant potential for improving drug solubility and stability. Poly[ethylene glycol]-poly[gamma-benzyl-L-glutamate] (PEG-PBLG) micelles were prepared and loaded with the active lactone form of HCPT using an uncomplicated dialysis method. HPLC and scanning electron microscopy studies revealed an encapsulation efficiency of 56.8% and a core-shell figure with a mean diameter of 200 nm. Encapsulated HCPT lactone was compared with the less active, open ring-carboxylated HCPT-Na+ soluble form generated in vivo from the free active lactone for activity against oral squamous cell carcinoma. Cytotoxicity in vitro was measured in cultured Tca8113 cells by the MTT assay and microscopy techniques. The golden hamster cheek pouch squamous cell carcinoma model was employed for in vivo studies; encapsulated lactone and open ring-carboxylated forms of HCPT were administered intraperitoneally, followed by determinations of tumor growth rate and inhibition ratio. PEG-PBLG micelles were not cytotoxic in vitro. At 48 h of treatment, open ring-carboxylated HCPT proved significantly more cytotoxic in vitro than encapsulated HCPT lactone. At 96 h, however, the open ring-carboxylated and encapsulated drugs displayed comparable in vitro cytotoxicities. In the in vivo squamous cell carcinoma model, encapsulated HCPT lactone produced greater and more prolonged tumor suppression compared to the open ring-carboxylated form. The antitumor effects of HCPT/PEG-PBLG micelles against oral squamous cell carcinoma in vivo are concluded to be superior to those exerted by open ring-carboxylated HCPT.

Hatch assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, J.R.; Hardin, R.T. Jr.

1987-07-07

This patent describes a nuclear reactor installation including means defining a fuel handling area and means defining a containment area separated from the fuel handling area and including a refuelling cavity; the improvement comprising: (a) a fuel transfer tube connecting the refuelling cavity with the fuel handling area; the fuel transfer tube having a first end in the fuel handling area and a second end in the refueling cavity; (b) valve means for opening and closing the first end; and (c) a hatch assembly mounted on the second end; the hatch assembly including (1) a hatch ring affixed to themore » fuel transfer tube at the second end the hatch ring has an integral annular seat surrounded by the hatch ring and defines a hatch opening in the second end of the fuel transfer tube; (2) a hatch cover adapts to be positioned on the annular seat for covering the hatch opening; (3) latching units are supported on the hatch ring about the hatch opening, each latching unit.« less

β-Lactam Ring Opening: A Useful Entry to Amino Acids and Relevant Nitrogen-Containing Compounds

NASA Astrophysics Data System (ADS)

Palomo, C.; Oiarbide, M.

The main strategies for the ring opening of β-lactams by chemical means are described. The discovery of each approach is put into context, sometimes in connection to processes occurring in biological systems, and the synthetic opportunities each approach offers are shown. Thus, this β-lactam route affords a number of synthetically relevant building-blocks, including α-amino acids, β-amino acids, their derived peptides, and other nitrogen containing heterocycles and open chain molecules. The content, which encompases references to initial work, further major development, and the most relevant recent literature contributions, is categorized according to the ring bond cleavaged (N 1-C 2, C 2-C 3, C 3 -C 4 , N 1-C 4), to finish with ring opening strategies leading to large heterocyclic compounds. Within each category, distinction has been made according to the type of nucleophilic agent employed, principally O-, N-, and C-nucleophiles. Also, a variety of applications of the strategy to the synthesis of interesting target compounds are shown.

Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

PubMed

Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

2016-04-01

Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1)H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Near-infrared continuous-wave light driving a two-photon photochromic reaction with the assistance of localized surface plasmon.

PubMed

Tsuboi, Yasuyuki; Shimizu, Ryosuke; Shoji, Tatsuya; Kitamura, Noboru

2009-09-09

We demonstrate that a photochromic reaction can be driven by irradiation from a weak, near-infrared continuous-wave (NIR-CW) laser light. A two-photon ring-opening photochromic reaction of a diarylethene (DE) derivative can be induced by irradiation with a NIR-CW laser light (lambda = 808 nm). An ultrathin polymer film doped with DE in its closed form was coated onto a gold-nanoparticle-integrated glass substrate. Upon irradiation of the sample with a CW laser at low fluence (0.1-4.0 W/cm(2)), we could clearly observe bleaching of the DE (ring-opening reaction). Following the IR irradiation, the bleached absorption could be reversibly recovered by applying UV irradiation (ring-closing reaction). We verified that the yield of the photochromic ring-opening reaction of the DE was proportional to the square of the irradiation fluence. The origin of this NIR-CW-induced two-photon photochromic reaction is an "enhancing effect" that acts on the electromagnetic field (localized surface plasmon) of the gold nanoparticles. The DE interacts with the surface plasmon and receives energy from two photons, which excites it to a state from which the ring-opening reaction can be initiated.

Manganese oxide helices, rings, strands, and films, and methods for their preparation

DOEpatents

Suib, Steven L.; Giraldo, Oscar; Marquez, Manuel; Brock, Stephanie

2003-01-07

Methods for the preparation of mixed-valence manganese oxide compositions with quaternary ammonium ions are described. The compositions self-assemble into helices, rings, and strands without any imposed concentration gradient. These helices, rings, and strands, as well as films having the same composition, undergo rapid ion exchange to replace the quaternary ammonium ions with various metal ions. And the metal-ion-containing manganese oxide compositions so formed can be heat treated to form semi-conducting materials with high surface areas.

Concise copper-catalyzed synthesis of tricyclic biaryl ether-linked aza-heterocyclic ring systems.

PubMed

Mestichelli, Paola; Scott, Matthew J; Galloway, Warren R J D; Selwyn, Jamie; Parker, Jeremy S; Spring, David R

2013-11-01

A new method for the synthesis of tricyclic biaryl ether-linked ring systems incorporating seven-, eight-, and nine-membered ring amines is presented. In the presence of catalytic quantities of copper(I), readily accessible acyclic precursors undergo an intramolecular carbon-oxygen bond-forming reaction facilitated by a "templating" chelating nitrogen atom. The methodology displays a broad substrate scope, is practical, and generates rare and biologically interesting tricyclic heteroaromatic products that are difficult to access by other means.

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

PubMed Central

Binyamin, Iris; Meidan-Shani, Shoval

2015-01-01

Summary The synthesis of P-chirogenic (±)-phosphine oxides and phosphinates via selective nucleophilic ring opening of the corresponding oxaphospholanes is described. Two representative substrates: the phosphonate 2-ethoxy-1,2-oxaphospholane 2-oxide and the phosphinate 2-phenyl-1,2-oxaphospholane 2-oxide were reacted with various Grignard reagents to produce a single alkyl/aryl product. These products may possess further functionalities in addition to the phosphorus center such as the γ-hydroxypropyl group which results from the ring opening and π-donor moieties such as aryl, allyl, propargyl and allene which originates from the Grignard reagent. PMID:26425187

Investigation of sliding DNA clamp dynamics by single-molecule fluorescence, mass spectrometry and structure-based modeling

PubMed Central

Gadkari, Varun V; Harvey, Sophie R; Raper, Austin T; Chu, Wen-Ting; Wang, Jin; Wysocki, Vicki H; Suo, Zucai

2018-01-01

Abstract Proliferating cell nuclear antigen (PCNA) is a trimeric ring-shaped clamp protein that encircles DNA and interacts with many proteins involved in DNA replication and repair. Despite extensive structural work to characterize the monomeric, dimeric, and trimeric forms of PCNA alone and in complex with interacting proteins, no structure of PCNA in a ring-open conformation has been published. Here, we use a multidisciplinary approach, including single-molecule Förster resonance energy transfer (smFRET), native ion mobility-mass spectrometry (IM-MS), and structure-based computational modeling, to explore the conformational dynamics of a model PCNA from Sulfolobus solfataricus (Sso), an archaeon. We found that Sso PCNA samples ring-open and ring-closed conformations even in the absence of its clamp loader complex, replication factor C, and transition to the ring-open conformation is modulated by the ionic strength of the solution. The IM-MS results corroborate the smFRET findings suggesting that PCNA dynamics are maintained in the gas phase and further establishing IM-MS as a reliable strategy to investigate macromolecular motions. Our molecular dynamic simulations agree with the experimental data and reveal that ring-open PCNA often adopts an out-of-plane left-hand geometry. Collectively, these results implore future studies to define the roles of PCNA dynamics in DNA loading and other PCNA-mediated interactions. PMID:29529283

The Effect of K and Acidity of NiW-Loaded HY Zeolite Catalyst for Selective Ring Opening of 1-Methylnaphthalene.

PubMed

Lee, You-Jin; Kim, Eun-Sang; Kim, Jeong-Rang; Kim, Joo-Wan; Kim, Tae-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Lee, Chang-Ha; Jeong, Soon-Yong

2016-05-01

Bi-functional catalysts were prepared using HY zeolites with various SiO2/Al2O3 ratios for acidic function, NiW for metallic function, and K for acidity control. 1-Methylnaphthalene was selected as a model compound for multi-ring aromatics in heavy oil, and its selective ring opening reaction was investigated using the prepared bi-functional catalysts with different levels of acidity in a fixed bed reactor system. In NiW/HY catalysts without K addition, the acidity decreased with the SiO2/Al2O3 mole ratio of the HY zeolite. Ni1.1W1.1/HY(12) catalyst showed the highest acidity but slightly lower yields for the selective ring opening than Ni1.1W1.1/HY(30) catalyst. The acidity of the catalyst seemed to play an important role as the active site for the selective ring opening of 1-methylnaphthalene but there should be some optimum catalyst acidity for the reaction. Catalyst acidity could be controlled between Ni1.1W1.1/HY(12) and Ni1.1W1.1/HY(30) by adding a moderate amount of K to Ni1.1W1.1/HY(12) catalyst. K0.3Ni1.1W1.1/HY(12) catalyst should have the optimum acidity for the selective ring opening. The addition of a moderate amount of K to the NiW/HY catalyst must improve the catalytic performance due to the optimization of catalyst acidity.

Cyclopropyl conjugation and ketyl anions: when do things begin to fall apart?

PubMed

Tanko, J M; Li, Xiangzhong; Chahma, M'hamed; Jackson, Woodward F; Spencer, Jared N

2007-04-11

Results pertaining to the electrochemical reduction of 1,2-diacetylcyclopropane (5), 1-acetyl-2-phenylcyclopropane (6), 1-acetyl-2-benzoylcyclopropane (7), and 1,2-dibenzoylcyclopropane (8) are reported. While 6*- exists as a discrete species, the barrier to ring opening is very small (<1 kcal/mol) and the rate constant for ring opening is >10(7) s(-1). For 7 and 8, the additional resonance stabilization afforded by the benzoyl moieties results in significantly lower rate constants for ring opening, on the order of 10(5)-10(6) s(-1). Electron transfer to 8 serves to initiate an unexpected vinylcyclopropane --> cyclopentene type rearrangement, which occurs via a radical ion chain mechanism. The results for reduction of 5 are less clear-cut: The experimental results suggest that the reduction is unexceptional, with a symmetry coefficient alpha

Formation of muconaldehyde, an open-ring metabolite of benzene, in mouse liver microsomes: an additional pathway for toxic metabolites.

PubMed Central

Latriano, L; Goldstein, B D; Witz, G

1986-01-01

It has been proposed that a ring-opened form may be responsible for the toxicity of benzene. The present studies demonstrate that incubation of [14C]benzene with liver microsomes (obtained from male CD-1 mice treated with benzene) in the presence of NADPH results in the formation of a ring-opened product. Evidence for the identity of this product was obtained by derivatizing with 2-thiobarbituric acid (TBA), which resulted in the formation of an adduct with a 490-nm absorbance maximum. This maximum is identical to that observed after authentic trans,trans-muconaldehyde has reacted with TBA. Separation of muconaldehyde, both with and without trapping with TBA, from other benzene metabolites in the incubation mixture was accomplished by HPLC. The radioactivity profile of fractions collected during HPLC analysis contained peaks that eluted with muconaldehyde and the muconaldehyde-TBA adduct. The structure of the ring-opened product was confirmed by mass spectrometry, studies in which the HPLC peak from the microsomal incubation mixture that eluted at the retention time of authentic muconaldehyde was collected and derivatized with 2,4-dinitrophenylhydrazine. The high-resolution mass spectrum of this sample contained an ion with an m/z of 291.0729, corresponding to muconaldehyde mono-dinitrophenylhydrazone. These results indicate that benzene is metabolized in vitro to a ring-opened product identified as muconaldehyde. PMID:3464956

The chemistry of (ring)Ru sup 2+ (ring = tetramethylthiophene, p-cymene)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganja, E.A.; Rauchfuss, T.B.; Stern, C.L.

1991-01-01

Described are the compounds ((ring)Ru(OTf){sub 2}){sub x}, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to ((ring)RuL{sub 3}){sup 2+}, where L{sub 3} = (H{sub 2}O){sub 3}, (NH{sub 3}){sub 3}, and (PH{sub 3}){sub 3}. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf){sub 2}. The addition of thiophenes to CH{sub 2}Cl{sub 2} solutions of 1 or 2 leads to the precipitation of the sandwich compounds ((ring)(SC{sub 4}R{sub 4})Ru)(OTf){sub 2}, where SC{sub 4}R{sub 4} = thiophene, 2,5-dimethylthiophene, and TMT. ((TMT)Ru(H{sub 2}O){sub 3})(OTf){sub 2} was characterized by single-crystal X-ray crystallography, which established amore » piano-stool geometry with a planar TMT ligand. ((TMT)Ru(D{sub 2}O){sub 3})(OTf){sub 2} decomposes in D{sub 2}O solution at 150C to give ((TMT){sub 2}Ru){sup 2+}, which undergoes selective deuteration at the 2,5-methyl groups. D{sub 2}O solutions of ((TMT){sub 2}Ru){sup 2+} undergo photochemical loss of one TMT ligand in water to give ((TMT)Ru(H{sub 2}O){sub 3}){sup 2+}. A procedure is described for the reversible loading of 1 onto {gamma}-alumina, which in turn was characterized by {sup 13}C CP-MAS NMR spectroscopy.« less

Vortex ring formation at the open end of a shock tube: A particle image velocimetry study

NASA Astrophysics Data System (ADS)

Arakeri, J. H.; Das, D.; Krothapalli, A.; Lourenco, L.

2004-04-01

The vortex ring generated subsequent to the diffraction of a shock wave from the open end of a shock tube is studied using particle image velocimetry. We examine the early evolution of the compressible vortex ring for three-exit shock Mach numbers, 1.1, 1.2, and 1.3. For the three cases studied, the ring formation is complete at about tUb/D=2, where t is time, Ub is fluid velocity behind shock as it exits the tube and D is tube diameter. Unlike in the case of piston generated incompressible vortex rings where the piston velocity variation with time is usually trapezoidal, in the shock-generated vortex ring case the exit fluid velocity doubles from its initial value Ub before it slowly decays to zero. At the end of the ring formation, its translation speed is observed to be about 0.7 Ub. During initial formation and propagation, a jet-like flow exists behind the vortex ring. The vortex ring detachment from the tailing jet, commonly referred to as pinch-off, is briefly discussed.

Pressure Seal For Frequently Opened Hatch

NASA Technical Reports Server (NTRS)

Kennedy, Steven E.; Kramer, Joel M.

1994-01-01

Pressure-assisted seal for frequently opened hatch includes two sealing rings retained positively so not pulled out during opening. Seal makes contact with hatch well before hatch starts to squeeze rings extending distance over which seal becomes engaged. Improvements include more-secure mounting, redundancy, and better initial sealing action. Also minimizes loss of gas during closure by deflecting inward and closing gap. This action helps differential pressure to force hatch closed.

Sulfuric acid as a catalyst for ring-opening of biobased bis-epoxides

USDA-ARS?s Scientific Manuscript database

Vegetable oils can be relatively and easily transformed into bio-based epoxides. Because of this, the acid-catalyzed epoxide ring-opening has been explored for the preparation of bio-based lubricants and polymers. Detailed model studies are carried out only with mono-epoxide made from methyl oleate,...

Two-dimensional correlation and codistribution spectroscopy (2DCOS and 2DCDS) analyses of time-dependent ATR IR spectra of d-glucose anomers undergoing mutarotation process in water.

PubMed

Noda, Isao

2018-05-15

Two cyclic diastereoisomeric structures, known as α- and β-anomers of d-glucose with different configurations around C1 with OH groups in axial or equitroial positions, undergo the mutarotation conversion to each other in water. Two-dimensional correlation and codistribution spectroscopy (2DCOS and 2DCDS) analyses were applied to the time-dependent ATR IR spectra of aqueous solutions of α- and β-d-glucose undergoing such mutarotation conversion. 2DCOS analysis reveals that the increase and decrease in the IR intensities after the dissolution of α- or β-d-glucose are not fully synchronized, suggesting the mutarotation of d-glucose in water is not a simple binary conversion process but a multi-step reaction involving an intermediate species with a finite and observable concentration level and lifetime. 2DCDS analysis of the time-dependent ATR IR spectra clearly demonstrated the presence of intermediate species contributing to the band positions overlapped close to bands for α- and β-d-glucose. The fact that band positions identified for the intermediate species for α- to β-d-glucose conversion are the same for the reverse reaction suggests that they arise from the same species, most likely the open-ring structure produced by the hydrolysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Mitral Valve Stenosis after Open Repair Surgery for Non-rheumatic Mitral Valve Regurgitation: A Review.

PubMed

Shabsigh, Muhammad; Lawrence, Cassidy; Rosero-Britton, Byron R; Kumar, Nicolas; Kimura, Satoshi; Durda, Michael Andrew; Essandoh, Michael

2016-01-01

Mitral stenosis (MS) after mitral valve (MV) repair is a slowly progressive condition, usually detected many years after the index MV surgery. It is defined as a mean transmitral pressure gradient (TMPG) >5 mmHg or a mitral valve area (MVA) <1.5 cm(2). Pannus formation around the mitral annulus or extending to the mitral leaflets is suggested as the main mechanism for developing delayed MS after MV repair. On the other hand, early stenosis is thought to be a direct result of an undersized annuloplasty ring. Furthermore, in MS following ischemic mitral regurgitation (MR) repair, subvalvular tethering is the hypothesized pathophysiology. MS after MV repair has an incidence of 9-54%. Several factors have been associated with a higher risk for developing MS after MV repair, including the use of flexible Duran annuloplasty rings versus rigid Carpentier-Edwards rings, complete annuloplasty rings versus partial bands, small versus large anterior leaflet opening angle, and anterior leaflet tip opening length. Intraoperative echocardiography can measure the anterior leaflet opening angle, the anterior leaflet tip opening dimension, the MVA and the mean TMPG, and may help identify patients at risk for developing MS after MV repair.

Mitral Valve Stenosis after Open Repair Surgery for Non-rheumatic Mitral Valve Regurgitation: A Review

PubMed Central

Shabsigh, Muhammad; Lawrence, Cassidy; Rosero-Britton, Byron R.; Kumar, Nicolas; Kimura, Satoshi; Durda, Michael Andrew; Essandoh, Michael

2016-01-01

Mitral stenosis (MS) after mitral valve (MV) repair is a slowly progressive condition, usually detected many years after the index MV surgery. It is defined as a mean transmitral pressure gradient (TMPG) >5 mmHg or a mitral valve area (MVA) <1.5 cm2. Pannus formation around the mitral annulus or extending to the mitral leaflets is suggested as the main mechanism for developing delayed MS after MV repair. On the other hand, early stenosis is thought to be a direct result of an undersized annuloplasty ring. Furthermore, in MS following ischemic mitral regurgitation (MR) repair, subvalvular tethering is the hypothesized pathophysiology. MS after MV repair has an incidence of 9–54%. Several factors have been associated with a higher risk for developing MS after MV repair, including the use of flexible Duran annuloplasty rings versus rigid Carpentier–Edwards rings, complete annuloplasty rings versus partial bands, small versus large anterior leaflet opening angle, and anterior leaflet tip opening length. Intraoperative echocardiography can measure the anterior leaflet opening angle, the anterior leaflet tip opening dimension, the MVA and the mean TMPG, and may help identify patients at risk for developing MS after MV repair. PMID:27148540

Packer arrangements for oil wells and the like

DOEpatents

Harvey, Andrew C.; McFadden, David H.

1981-11-24

The packer includes an elongated tubular casing, and a metal ring is disposed in its entirety within an annular recess in the casing. The recess has a circumferential opening extending entirely around the peripheral outer surface of the casing. Hydraulic fluid is flowed into the recess to apply pressure to the inner peripheral surface of the metal ring to expand the ring radially outwardly and force its outer peripheral surface through the circumferential opening and into annular sealing engagement with the opposed surface of the well casing.

Five- and six-membered ring opening of pyroglutamic diketopiperazine.

PubMed

Parrish, Dennis A; Mathias, Lon J

2002-03-22

A variety of ring-opening reactions of pyroglutamic diketopiperazine at both the five-membered and six-membered rings is described. Mild, basic conditions facilitate nucleophilic attack by amines at the diketopiperazine carbonyls giving pyroglutamides in excellent yield. Reaction with nucleophiles under acidic conditions give bis-glutamate derivatives of 2,5-diketopiperazine (DKP). These reactions provide simple, two-step sequences to pyroglutamides and symmetrical diketopiperazines from commercial pyroglutamic acid with control of product dictated by reaction conditions, catalyst, and nucleophile.

Telomere Length in Predicting Toxicity in Older Patients With Stage III-IV Colorectal Cancer Undergoing Chemotherapy

ClinicalTrials.gov

2018-02-06

Mucinous Adenocarcinoma of the Colon; Mucinous Adenocarcinoma of the Rectum; Signet Ring Adenocarcinoma of the Colon; Signet Ring Adenocarcinoma of the Rectum; Stage IIIA Colon Cancer; Stage IIIA Rectal Cancer; Stage IIIB Colon Cancer; Stage IIIB Rectal Cancer; Stage IIIC Colon Cancer; Stage IIIC Rectal Cancer; Stage IV Colon Cancer; Stage IV Rectal Cancer

Formal radical cyclization onto benzene rings: a general method and its use in the synthesis of ent-nocardione A.

PubMed

Clive, Derrick L J; Fletcher, Stephen P; Liu, Dazhan

2004-05-14

An indirect method is described for effecting radical cyclization onto a benzene ring. Cross-conjugated dienones 6, which are readily prepared from phenols, undergo radical cyclization (6 --> 7 --> 8), and the products (8) are easily aromatized. The method has been applied to the synthesis of ent-nocardione A (21).

A clinical study of the LiVac laparoscopic liver retractor system.

PubMed

Gan, Philip; Bingham, Judy

2016-02-01

All retractors for laparoscopic operations on the gallbladder or stomach apply an upward force to the under-surface of the liver or gallbladder, most requiring an additional skin incision. The LiVac laparoscopic liver retractor system (LiVac retractor) comprises a soft silicone ring attached to suction tubing and connected to a regulated source of suction. The suction tubing extends alongside existing ports. When placed between the liver and diaphragm, and suction applied, a vacuum is created within the ring, keeping these in apposition. Following successful proof-of-concept animal testing, a clinical study was conducted to evaluate the performance and safety of the retractor in patients. The study was a dual-centre, single-surgeon, open-label study and recruited ten patients scheduled to undergo routine upper abdominal laparoscopic surgery including cholecystectomy, primary gastric banding surgery or fundoplication. The study was conducted at two sites and was approved by the institutions' ethics committees. The primary objective of the study was to evaluate the performance of the LiVac retractor in patients undergoing upper abdominal single- or multi-port laparoscopic surgery. Performance was measured by the attainment of milestones for the retractor and accessory bevel, where used, and safety outcomes through the recording of adverse events, physical parameters, pain scales, blood tests and a post-operative liver ultrasound. The LiVac retractor achieved both primary and secondary performance and safety objectives in all patients. No serious adverse events and no device-related adverse events or device deficiencies were reported. The LiVac retractor achieved effective liver retraction without clinically significant trauma and has potential application in multi- or single-port laparoscopic upper abdominal surgery. As a separate incision is not required, the use of the LiVac retractor in multi-port surgery therefore reduces the number of incisions.

New Pioglitazone Metabolites and Absence of Opened-Ring Metabolites in New N-Substituted Thiazolidinedione.

PubMed

Campos, Michel Leandro; Cerqueira, Letícia Bonancio; Silva, Bruna Cristina Ulian; Franchin, Taísa Busaranho; Galdino-Pitta, Marina Rocha; Pitta, Ivan Rocha; Peccinini, Rosângela Gonçalves; Pontarolo, Roberto

2018-06-01

Thiazolidinediones (TZDs) are drugs used to treat type 2 diabetes mellitus; however, several safety concerns remain regarding the available drugs in this class. Therefore, the search for new TZD candidates is ongoing; metabolism studies play a crucial step in the development of new candidates. Pioglitazone, one of the most commonly used TZDs, and GQ-11, a new N -substituted TZD, were investigated in terms of their metabolic activity in rat and human liver microsomes to assess their metabolic stability and investigate their metabolites. Methods for preparation of samples were based on liquid-liquid extraction and protein precipitation. Quantitation was performed using liquid chromatography (LC)-tandem mass spectrometry, and the metabolite investigation was performed using ultraperformance LC coupled to a hybrid quadrupole-time of flight mass spectrometer. The predicted intrinsic clearance of GQ-11 was 70.3 and 46.1 ml/kg per minute for rats and humans, respectively. The predicted intrinsic clearance of pioglitazone was 24.1 and 15.9 ml/kg per minute for rats and humans, respectively. The pioglitazone metabolite investigation revealed two unpublished metabolites (M-D and M-A). M-A is a hydration product and may be related to the mechanism of ring opening and the toxicity of pioglitazone. The metabolites of GQ-11 are products of oxidation; no ring-opening metabolite was observed for GQ-11. In conclusion, under the same experimental conditions, a ring-opening metabolite was observed only for pioglitazone. The resistance of GQ-11 to the ring opening is probably related to N -substitution in the TZD ring. Copyright © 2018 by The American Society for Pharmacology and Experimental Therapeutics.

Ring-Opening Polymerization of Lactide to Form a Biodegradable Polymer

ERIC Educational Resources Information Center

Robert, Jennifer L.; Aubrecht, Katherine B.

2008-01-01

In this laboratory activity for introductory organic chemistry, students carry out the tin(II) bis(2-ethylhexanoate)/benzyl alcohol mediated ring-opening polymerization of lactide to form the biodegradable polymer polylactide (PLA). As the mechanism of the polymerization is analogous to that of a transesterification reaction, the experiment can be…

Bismuth(III) trifluoromethanesulfonate catalyzed ring opening reaction of mono epoxy oleochemicals to form keto and diketo derivatives

USDA-ARS?s Scientific Manuscript database

Using a catalytic system, methyl oleate is transformed into long chain keto and diketo derivatives via an epoxide route. Methyl 9(10)-oxooctadecanoate and methyl 9,10-dioxooctadecanoate were made by a ring opening reaction of epoxidized methyl oleate using bismuth triflate catalyst. Lower reaction t...

Depolymerization dynamics of individual filaments of bacterial cytoskeletal protein FtsZ

PubMed Central

Mateos-Gil, Pablo; Paez, Alfonso; Hörger, Ines; Rivas, Germán; Vicente, Miguel; Tarazona, Pedro; Vélez, Marisela

2012-01-01

We report observation and analysis of the depolymerization filaments of the bacterial cytoskeletal protein FtsZ (filament temperature-sensitive Z) formed on a mica surface. At low concentration, proteins adsorbed on the surface polymerize forming curved filaments that close into rings that remain stable for some time before opening irreversibly and fully depolymerizing. The distribution of ring lifetimes (T) as a function of length (N), shows that the rate of ring aperture correlates with filament length. If this ring lifetime is expressed as a bond survival time, (Tb ≡ NT), this correlation is abolished, indicating that these rupture events occur randomly and independently at each monomer interface. After rings open irreversibly, depolymerization of the remaining filaments is fast, but can be slowed down and followed using a nonhydrolyzing GTP analogue. The histogram of depolymerization velocities of individual filaments has an asymmetric distribution that can be fit with a computer model that assumes two rupture rates, a slow one similar to the one observed for ring aperture, affecting monomers in the central part of the filaments, and a faster one affecting monomers closer to the open ends. From the quantitative analysis, we conclude that the depolymerization rate is affected both by nucleotide hydrolysis rate and by its exchange along the filament, that all monomer interfaces are equally competent for hydrolysis, although depolymerization is faster at the open ends than in central filament regions, and that all monomer–monomer interactions, regardless of the nucleotide present, can adopt a curved configuration. PMID:22566654

The Jumping Ring Experiment

ERIC Educational Resources Information Center

Baylie, M.; Ford, P. J.; Mathlin, G. P.; Palmer, C.

2009-01-01

The jumping ring experiment has become central to liquid nitrogen shows given as part of the outreach and open day activities carried out within the University of Bath. The basic principles of the experiment are described as well as the effect of changing the geometry of the rings and their metallurgical state. In general, aluminium rings are…

46 CFR 160.002-3 - Materials.

Code of Federal Regulations, 2012 CFR

2012-10-01

... warp and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant... of the type specified in paragraph (j) of this section. (g) Dee rings and snap hook. The dee rings...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

46 CFR 160.005-3 - Materials.

Code of Federal Regulations, 2014 CFR

2014-10-01

... and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant substance... of the type specified in paragraph (j) of this section. (g) Dee rings and snap hook. The dee rings...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

46 CFR 160.002-3 - Materials.

Code of Federal Regulations, 2013 CFR

2013-10-01

... warp and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant... of the type specified in paragraph (j) of this section. (g) Dee rings and snap hook. The dee rings...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

46 CFR 160.002-3 - Materials.

Code of Federal Regulations, 2014 CFR

2014-10-01

... warp and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant... of the type specified in paragraph (j) of this section. (g) Dee rings and snap hook. The dee rings...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

46 CFR 160.005-3 - Materials.

Code of Federal Regulations, 2012 CFR

2012-10-01

... and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant substance... of the type specified in paragraph (j) of this section. (g) Dee rings and snap hook. The dee rings...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

46 CFR 160.005-3 - Materials.

Code of Federal Regulations, 2013 CFR

2013-10-01

... and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant substance... of the type specified in paragraph (j) of this section. (g) Dee rings and snap hook. The dee rings...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

Dynamics starting at a conical intersection: Application to the photochemistry of pyrrole

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sellner, Bernhard; Barbatti, Mario; Lischka, Hans

The photochemical ring opening process in pyrrole has been investigated by performing classical on-the-fly dynamics using the multiconfiguration self-consistent field method for the computation of energies and energy gradients. As starting point for the dynamics the conical intersection corresponding to the ring-puckered ring-opened structure, determined previously [Barbatti et al., J. Chem. Phys. 125, 164323 (2006)], has been chosen. Two sets of initial conditions for the nuclear velocities were constructed: (i) nuclear velocities in the branching (g,h) plane of the conical intersection and (ii) statistical distribution for all atoms. Both sets of initial conditions show very similar results. Reactive trajectories aremore » only found in a very limited sector in the (g,h) plane and reaction products are very similar. Within the simulation time of 1 ps, ring opening of pyrrole to the biradical NH=CH-CH-CH=CH chain followed by ring closure to a substituted cyclopropene structure (NH=CH-C{sub 3}H{sub 3}) is observed. The computed structural data correlate well with the experimentally observed dissociation products.« less

Application of combinatorial biocatalysis for a unique ring expansion of dihydroxymethylzearalenone

USDA-ARS?s Scientific Manuscript database

Combinatorial biocatalysis was applied to generate a diverse set of dihydroxymethylzearalenone derivatives with modified ring structure. In one chemoenzymatic reaction sequence, dihydroxymethylzearalenone was first subjected to a unique enzyme-catalyzed oxidative ring opening reaction that creates ...

Distinguishing and quantifying the torquoselectivity in competitive ring-opening reactions using the stress tensor and QTAIM.

PubMed

Guo, Huan; Morales-Bayuelo, Alejandro; Xu, Tianlv; Momen, Roya; Wang, Lingling; Yang, Ping; Kirk, Steven R; Jenkins, Samantha

2016-12-05

Currently the theories to explain and predict the classification of the electronic reorganization due to the torquoselectivity of a ring-opening reaction cannot accommodate the directional character of the reaction pathway; the torquoselectivity is a type of stereoselectivity and therefore is dependent on the pathway. Therefore, in this investigation we introduced new measures from quantum theory of atoms in molecules and the stress tensor to clearly distinguish and quantify the transition states of the inward (TSIC) and outward (TSOC) conrotations of competitive ring-opening reactions of 3-(trifluoromethyl)cyclobut-1-ene and 1-cyano-1-methylcyclobutene. We find the metallicity ξ(r b ) of the ring-opening bond does not occur exactly at the transition state in agreement with transition state theory. The vector-based stress tensor response β σ was used to distinguish the effect of the CN, CH 3 , and CF 3 groups on the TSIC and TSOC paths that was consistent with the ellipticity ε, the total local energy density H(r b ) and the stress tensor stiffness S σ . We determine the directional properties of the TSIC and TSOC ring-opening reactions by constructing a stress tensor UσTS space with trajectories TσTS (s) with length l in real space, longer l correlated with the lowest density functional theory-evaluated total energy barrier and hence will be more thermodynamically favored. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Actin turnover maintains actin filament homeostasis during cytokinetic ring contraction

PubMed Central

Palani, Saravanan; Sommese, Ruth; Kamnev, Anton; Hatano, Tomoyuki; Sivaramakrishnan, Sivaraj

2017-01-01

Cytokinesis in many eukaryotes involves a tension-generating actomyosin-based contractile ring. Many components of actomyosin rings turn over during contraction, although the significance of this turnover has remained enigmatic. Here, using Schizosaccharomyces japonicus, we investigate the role of turnover of actin and myosin II in its contraction. Actomyosin ring components self-organize into ∼1-µm-spaced clusters instead of undergoing full-ring contraction in the absence of continuous actin polymerization. This effect is reversed when actin filaments are stabilized. We tested the idea that the function of turnover is to ensure actin filament homeostasis in a synthetic system, in which we abolished turnover by fixing rings in cell ghosts with formaldehyde. We found that these rings contracted fully upon exogenous addition of a vertebrate myosin. We conclude that actin turnover is required to maintain actin filament homeostasis during ring contraction and that the requirement for turnover can be bypassed if homeostasis is achieved artificially. PMID:28655757

Methods/Labor Standards Application Program - Phase IV

DTIC Science & Technology

1985-01-01

Engine Platform a. Pressure switch b. Compressor motor c. Voltage regulator d. Open and clean generator exciter and main windings S3 . Main Collector...clean motors b. Slip rings Gantry #3 Annual: S2. Engine Platform a. Pressure switch b. Compressor motor Voltage regulator d. Open and clean generator...Travel Motors Open and clean motorsa. b. Slip rings Gantry #4 S2 . S3. S4 . S5 . Engine Platform a. Pressure switch b. Compressor motor Voltage regulator

Insertion of benzene rings into the amide bond: one-step synthesis of acridines and acridones from aryl amides.

PubMed

Pintori, Didier G; Greaney, Michael F

2010-01-01

Insertion of benzene rings into the amide bond using the reactive intermediate benzyne is described. Aromatic amides undergo smooth insertion when treated with O-triflatophenyl silane benzyne precursors, producing versatile aminobenzophenone products in good to excellent yield. The process is entirely metal-free and has been exemplified on the synthesis of biologically active acridones and acridines.

Organocatalytic Ring-Opening Polymerization of Trimethylene Carbonate to Yield a Biodegradable Polycarbonate

ERIC Educational Resources Information Center

Chan, Julian M. W.; Zhang, Xiangyi; Brennan, Megan K.; Sardon, Haritz; Engler, Amanda C.; Fox, Courtney H.; Frank, Curtis W.; Waymouth, Robert M.; Hedrick, James L.

2015-01-01

In this laboratory experiment, students work in pairs to synthesize a simple aliphatic polycarbonate via ring-opening polymerization of trimethylene carbonate using 1,8-diazabicyclo[5.4.0]undec-7-ene and thiourea as organocatalysts. Following polymer isolation, students cool the material in a dry ice/acetone bath to observe its glass-transition…

Gasket and snap ring installation tool

DOEpatents

Southerland, Jr., James M.; Barringer, Jr., Curtis N.

1994-01-01

A tool for installing a gasket and a snap ring including a shaft, a first plate attached to the forward end of the shaft, a second plate slidably carried by the shaft, a spring disposed about the shaft between the first and second plates, and a sleeve that is free to slide over the shaft and engage the second plate. The first plate has a loading surface with a loading groove for receiving a snap ring and a shoulder for holding a gasket. A plurality of openings are formed through the first plate, communicating with the loading groove and approximately equally spaced about the groove. A plurality of rods are attached to the second plate, each rod slidable in one of the openings. In use, the loaded tool is inserted into a hollow pipe or pipe fitting having an internal flange and an internal seating groove, such that the gasket is positioned against the flange and the ring is in the approximate plane of the seating groove. The sleeve is pushed against the second plate, sliding the second plate towards the first plate, compressing the spring and sliding the rods forwards in the openings. The rods engage the snap ring and urge the ring from the loading groove into the seating groove.

Where the Small Moon Rules

NASA Image and Video Library

2016-09-19

Pan may be small as satellites go, but like many of Saturn's ring moons, it has a has a very visible effect on the rings. Pan (17 miles or 28 kilometers across, left of center) holds open the Encke gap and shapes the ever-changing ringlets within the gap (some of which can be seen here). In addition to raising waves in the A and B rings, other moons help shape the F ring, the outer edge of the A ring and open the Keeler gap. This view looks toward the sunlit side of the rings from about 8 degrees above the ring plane. The image was taken in visible light with the Cassini spacecraft narrow-angle camera on July 2, 2016. The view was acquired at a distance of approximately 840,000 miles (1.4 million kilometers) from Saturn and at a sun-Saturn-spacecraft, or phase, angle of 128 degrees. Image scale is 5 miles (8 kilometers) per pixel. Pan has been brightened by a factor of two to enhance its visibility. http://photojournal.jpl.nasa.gov/catalog/PIA20499

PMIX_Ring patch for SLURM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moody, A. T.

2014-04-20

This code adds an implementation of PMIX_Ring to the existing PM12 Library in the SLURM open source software package (Simple Linux Utility for Resource Management). PMIX_Ring executes a particular communication pattern that is used to bootstrap connections between MPI processes in a parallel job.

A Prospective Randomized Trial to Assess Fixation Strategies for Severe Open Tibia Fractures: Modern Ring External Fixators Versus Internal Fixation (FIXIT Study).

PubMed

OʼToole, Robert V; Gary, Joshua L; Reider, Lisa; Bosse, Michael J; Gordon, Wade T; Hutson, James; Quinnan, Stephen M; Castillo, Renan C; Scharfstein, Daniel O; MacKenzie, Ellen J

2017-04-01

The treatment of high-energy open tibia fractures is challenging in both the military and civilian environments. Treatment with modern ring external fixation may reduce complications common in these patients. However, no study has rigorously compared outcomes of modern ring external fixation with commonly used internal fixation approaches. The FIXIT study is a prospective, multicenter randomized trial comparing 1-year outcomes after treatment of severe open tibial shaft fractures with modern external ring fixation versus internal fixation among men and women of ages 18-64. The primary outcome is rehospitalization for major limb complications. Secondary outcomes include infection, fracture healing, limb function, and patient-reported outcomes including physical function and pain. One-year treatment costs and patient satisfaction will be compared between the 2 groups, and the percentage of Gustilo IIIB fractures that can be salvaged without soft tissue flap among patients receiving external fixation will be estimated.

An Introductory Organic Chemistry Review Homework Exercise: Deriving Potential Mechanisms for Glucose Ring Opening in Mutarotation

ERIC Educational Resources Information Center

Murdock, Margaret; Holman, R. W.; Slade, Tyler; Clark, Shelley L. D.; Rodnick, Kenneth J.

2014-01-01

A unique homework assignment has been designed as a review exercise to be implemented near the end of the one-year undergraduate organic chemistry sequence. Within the framework of the exercise, students derive potential mechanisms for glucose ring opening in the aqueous mutarotation process. In this endeavor, 21 general review principles are…

Bifunctional Asymmetric Catalysis with Hydrogen Chloride: Enantioselective Ring-Opening of Aziridines Catalyzed by a Phosphinothiourea

PubMed Central

Mita, Tsuyoshi; Jacobsen, Eric N.

2009-01-01

Ring-opening of aziridines with hydrogen chloride to form β-chloroamine derivatives is catalyzed by a chiral phosphinothiourea derivative in high yields and with high enantioselectivities. On the basis of 31P NMR studies, activation of HCl appears to proceed via quantitative protonation of the catalyst to afford a phosphonium chloride complex. PMID:20161432

Torso sizing ring construction for hard space suit

NASA Technical Reports Server (NTRS)

Vykukal, H. C.

1986-01-01

A hard suit for use in space or diving applications having an adjustable length torso covering that will fit a large variety of wearers is described. The torso covering comprises an upper section and a lower section which interconnect so that the covering will fit wearers with short torsos. One or more sizing rings may be inserted between the upper and lower sections to accommodate larger torso sizes as required. Since access of the astronaut to the torso covering is preferably through an opening in the back of the upper section (which is closed off by the backpack), the rings slant upward-forward from the lower edge of the opening. The lower edge of the upper covering section has a coupler which slants upward-forward from the lower edge of the back opening. The lower torso section has a similarly slanted coupler which may interfit with the upper section coupler to accommodate the smallest torso size. One or more sizing rings may be inserted between the coupler sections of the upper and lower torso sections to accommodate larger torsos. Each ring has an upper coupler which may interfit with the upper section coupler and a lower coupler which may interfit with the lower section coupler.

HST Multicolor (255-1042 nm) Photometry of Saturn's Main Rings. 1; Radial Profiles, Phase and Opening Angle Variations, and Regional Spectra

NASA Technical Reports Server (NTRS)

Cuzzi, Jeffrey N.; French, Richard G.; Dones, Luke; DeVincenzi, Donald (Technical Monitor)

2001-01-01

The main rings of Saturn were observed with the Planetary Camera of the WFPC2 instrument on the Hubble Space Telescope (HST) from September 1996 to August 2000 as the'ring opening angle to Earth and Sun increased from 4 deg to 24 deg, with a spread of phase angles between 0.3 deg and 6 deg at each opening angle. The rings were routinely observed in the five HST wideband UBVRI filters (F336W, F439W, F555W, F675W, and F814W) and occasionally in the F255W, F785LP, and F1042M filters. The emphasis in this series of papers will be on radial color (implying compositional) variations. In this first paper we describe the analysis technique and calibration procedure, note revisions in a previously published Voyager ring color data analysis, and present new results based on over 100 HST images. In the 300-600 nm spectral range where the rings are red, the 555nm/336nm ratio increases by about 14% as the phase angle increases from 0.3 deg to 6 deg. This effect, never reported previously for the rings, is significantly larger than the phase reddening which characterizes other icy objects, primarily because of the redness of the rings. However, there is no discernible tendency for color to vary with ring opening angle at a given phase angle, and there is no phase variation of color where the spectrum is flat. We infer from this combination of facts that multiple intraparticle scattering, either in a regolith or between facets of an unusually rough surface, is important in these geometries, but that multiple interparticle scattering in a vertically extended layer is not. Voyager color ratios at a phase angle of 14 deg are compatible with this trend, but calibration uncertainties prevent their use in quantitative modeling. Overall ring-average spectra are compatible with those of earlier work within calibration uncertainties, but ring spectra vary noticeably with region. We refine and subdivide the regions previously defined by others. The variation seen between radial profiles of ratios between different wavelength suggests the presence of multiple compositional components with different radial distributions. We present new radial profiles of far UV color ratio (F336W/F255W) showing, substantial global variations having a different radial structure than seen between 555 and 336nm. We also find evidence for absorption in the 850nm spectral range (a feature previously only weakly indicated in ring-averaged spectra) primarily through its radial variation; it is located primarily in the C ring, where the particles are known to have lower albedo, and is consistent with "interplanetary pollution" of the rings.

Is Conventional Open Repair for Abdominal Aortic Aneurysm Feasible in Nonagenarians?

PubMed

Uehara, Kyokun; Matsuda, Hitoshi; Inoue, Yosuke; Omura, Atsushi; Seike, Yoshimasa; Sasaki, Hiroaki; Kobayashi, Junjiro

2017-09-25

Background : Although endovascular repair for abdominal aortic aneurysm has been found to be beneficial in very elderly patients, some patients have contraindications to this procedure. For nonagenarians, the results of open repair remain unclear. The purpose of this study was to compare the outcomes of open vs. endovascular repair for abdominal aortic aneurysm in nonagenarian patients. Methods and Results : Fourteen patients undergoing open surgical repair and 24 undergoing endovascular repair for abdominal aortic aneurysm were evaluated. There was no significant difference in early mortality between the open and endovascular groups (0% vs. 4.1%, p=0.16). The open repair group required much longer hospital stays (26.4 vs. 10.6 days, respectively, p=0.003). Finally, 12 patients (86%) undergoing open repair vs. 21 (88%) undergoing endovascular repair returned home (p=0.49). During a mean follow-up period of 23.4±23.5 months, cumulative estimated 1- and 3-year survival rates were 90.0% and 48.0%, respectively in the open repair group and 90.6% and 54.9%, respectively in the endovascular repair group (p=0.51). Conclusion : Although endovascular repair for abdominal aortic aneurysm was superior in terms of recovery, the results of conventional open repair were acceptable even in nonagenarian patients. Open repair remains an alternative for patients with contraindications to endovascular repair.

High-power microwave-induced TM{sub 01} plasma ring

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schamiloglu, E.; Jordan, R.; Moreland, L.D.

1996-02-01

Open-shutter photography was used to capture the air breakdown pattern induced by a TM{sub 01} mode radiated by a high-power backward wave oscillator. The resultant plasma ring was formed in air adjacent to a conical horn antenna fitted with a membrane to keep the experiment under vacuum. This image was digitized and further processed using Khoros 2.0 software to obtain the dimensions of the plasma ring. This information was used in an air breakdown analysis to estimate the radiated power, and agrees within 10% with the power measured using field mapping with an open-ended WR-90 waveguide.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mcwilliams, A. J.; Daugherty, W. L.; Skidmore, T. E.

The 9975 Type B shipping package is used within the DOE complex for shipping special nuclear materials. This package is re-certified annually in accordance with Safety Analysis Report for Packaging (SARP) requirements. The package is also used at the Savannah River Site as part of the long-term storage configuration of special nuclear materials. As such, the packages do not undergo annual recertification during storage, with uncertainty as to how long some of the package components will meet their functional requirements in the storage environment. The packages are currently approved for up to 15 years storage, and work continues to providemore » a technical basis to extend that period. This report describes efforts by the Savannah River National Laboratory (SRNL) to extend the service life estimate of Viton® GLT and GLT-S fluoroelastomer O-rings used in the 9975 shipping package. O-rings of both GLT and GLT-S compositions are undergoing accelerated aging at elevated temperature, and are periodically tested for compression stress relaxation (CSR) behavior. The CSR behavior of O-rings was evaluated at temperatures from 175 to 400 °F. These collective data were used to develop predictive models for extrapolation of CSR behavior to relevant service temperatures (< 156 °F). The predictive model developed from the CSR data conservatively indicates a service life of approximately 37 years for Viton GLT O-rings at the maximum effective service temperature of 156 °F. The estimated service life for Viton GLT-S O-rings is significantly longer.« less

Static analysis of C-shape SMA middle ear prosthesis

NASA Astrophysics Data System (ADS)

Latalski, Jarosław; Rusinek, Rafał

2017-08-01

Shape memory alloys are a family of metals with the ability to change specimen shape depending on their temperature. This unique property is useful in many areas of mechanical and biomechanical engineering. A new half-ring middle ear prosthesis design made of a shape memory alloy, that is undergoing initial clinical tests, is investigated in this research paper. The analytical model of the studied structure made of nonlinear constitutive material is solved to identify the temperature-dependent stiffness characteristics of the proposed design on the basis of the Crotti-Engesser theorem. The final integral expression for the element deflection is highly complex, thus the solution has to be computed numerically. The final results show the proposed shape memory C-shape element to behave linearly in the analysed range of loadings and temperatures. This is an important observation that significantly simplifies the analysis of the prototype structure and opens wide perspectives for further possible applications of shape memory alloys.

Prototyping of an Open-Architecture CMG System

DTIC Science & Technology

2012-12-01

Digital Absolute Optical Encoder .....................................................63  5.  Slip Ring ...After [71]) ................64  Figure 43.  Dynapar absolute encoder (replacement for the original encoder) ..................65  Figure 44.  Slip ring ...location on gimbal assembly .............................................................65  Figure 45.  MOOG SRA-73683–18 slip ring (From [74

Multistep Dst development and ring current composition changes during the 4-6 June 1991 magnetic storm

NASA Astrophysics Data System (ADS)

Kozyra, J. U.; Liemohn, M. W.; Clauer, C. R.; Ridley, A. J.; Thomsen, M. F.; Borovsky, J. E.; Roeder, J. L.; Jordanova, V. K.; Gonzalez, W. D.

2002-08-01

The 4-6 June 1991 magnetic storm, which occurred during solar maximum conditions, is analyzed to investigate two observed features of magnetic storms that are not completely understood: (1) the mass-dependent decay of the ring current during the early recovery phase and (2) the role of preconditioning in multistep ring current development. A kinetic ring current drift-loss model, driven by dynamic fluxes at the nightside outer boundary, was used to simulate this storm interval. A strong partial ring current developed and persisted throughout the main and early recovery phases. The majority of ions in the partial ring current make one pass through the inner magnetosphere on open drift paths before encountering the dayside magnetopause. The ring current exhibited a three-phase decay in this storm. A short interval of charge-exchange loss constituted the first phase of the decay followed by a classical two-phase decay characterized by an abrupt transition between two very different decay timescales. The short interval dominated by charge-exchange loss occurred because an abrupt northward turning of the interplanetary magnetic field (IMF) trapped ring current ions on closed trajectories, and turned-off sources and ``flow-out'' losses. If this had been the end of the solar wind disturbance, decay timescales would have gradually lengthened as charge exchange preferentially removed the short-lived species; a distinctive two-phase decay would not have resulted. However, the IMF turned weakly southward, drift paths became open, and a standard two-phase decay ensued as the IMF rotated slowly northward again. As has been shown before, a two-phase decay is produced as open drift paths are converted to closed in a weakening convection electric field, driving a transition from the fast flow-out losses associated with the partial ring current to the slower charge-exchange losses associated with the trapped ring current. The open drift path geometry during the main phase and during phase 1 of the two-phase decay has important consequences for the evolution of ring current composition and for preconditioning issues. In this particular storm, ring current composition changes measured by the Combined Release and Radiation Effects Satellite (CRRES) during the main and recovery phase of the storm resulted largely from composition changes in the plasma sheet transmitted into the inner magnetosphere along open drift paths as the magnetic activity declined. Possible preconditioning elements were investigated during the multistep development of this storm, which was driven by the sequential arrival of three southward IMF Bz intervals of increasing peak strength. In each case, previous intensifications (preexisting ring currents) were swept out of the magnetosphere by the enhanced convection associated with the latest intensification and did not act as a significant preconditioning element. However, plasma sheet characteristics varied significantly between subsequent intensifications, altering the response of the magnetosphere to the sequential solar wind drivers. A denser plasma sheet (ring current source population) appeared during the second intensification, compensating for the weaker IMF Bz at this time and producing a minimum pressure-corrected Dst* value comparable to the third intensification (driven by stronger IMF Bz but a lower density plasma sheet source). The controlling influence of the plasma sheet dynamics on the ring current dynamics and its role in altering the inner magnetospheric response to solar wind drivers during magnetic storms adds a sense of urgency to understanding what processes produce time-dependent responses in the plasma sheet density, composition, and temperature.

Influence of chain topology on polymer crystallization: poly(ethylene oxide) (PEO) rings vs. linear chains.

PubMed

Zardalidis, George; Mars, Julian; Allgaier, Jürgen; Mezger, Markus; Richter, Dieter; Floudas, George

2016-10-04

The absence of entanglements, the more compact structure and the faster diffusion in melts of cyclic poly(ethylene oxide) (PEO) chains have consequences on their crystallization behavior at the lamellar and spherulitic length scales. Rings with molecular weight below the entanglement molecular weight (M < M e ), attain the equilibrium configuration composed from twice-folded chains with a lamellar periodicity that is half of the corresponding linear chains. Rings with M > M e undergo distinct step-like conformational changes to a crystalline lamellar with the equilibrium configuration. Rings melt from this configuration in the absence of crystal thickening in sharp contrast to linear chains. In general, rings more easily attain their extended equilibrium configuration due to strained segments and the absence of entanglements. In addition, rings have a higher equilibrium melting temperature. At the level of the spherulitic superstructure, growth rates are much faster for rings reflecting the faster diffusion and more compact structure. With respect to the segmental dynamics in their semi-crystalline state, ring PEOs with a steepness index of ∼34 form some of the "strongest" glasses.

A Photo-Favorskii Ring Contraction Reaction: The Effect of Ring Size

PubMed Central

Kammath, Viju Balachandran; Šolomek, Tomáš; Ngoy, Bokolombe Pitchou; Heger, Dominik; Klán, Petr; Rubina, Marina; Givens, Richard S.

2012-01-01

The effect of ring size on the photo-Favorskii induced ring-contraction reaction of the hydroxybenzocycloalkanonyl acetate and mesylate esters (7a–d, 8a–c) has provided new insight into the mechanism of the rearrangement. By monotonically decreasing the ring size in these cyclic derivatives, the increasing ring strain imposed on the formation of the elusive bicyclic spirocyclopropanone 20 results in a divergence away from rearrangement and toward solvolysis. Cycloalkanones of seven or eight carbons undergo a highly efficient photo-Favorskii rearrangement with ring contraction paralleling the photochemistry of p-hydroxyphenacyl esters. In contrast, the five-carbon ring does not rearrange but is diverted to the photosolvolysis channel avoiding the increased strain energy that would accompany the formation of the spirobicyclic ketone, the “Favorskii intermediate 20”. The six-carbon analogue demonstrates the bifurcation in reaction channels, yielding a solvent-sensitive mixture of both. Employing a combination of time-resolved absorption measurements, quantum yield determinations, isotopic labeling, and solvent variation studies coupled with theoretical treatment, a more comprehensive mechanistic description of the rearrangement has emerged. PMID:22686289

Controlled Ring-Opening Metathesis Polymerization by Molybdenum and Tungsten Alkylidene Complexes

DTIC Science & Technology

1988-07-29

weights and low polydispersities (as low as 1.03) consistent with a living catalyst system employing 50, 100, 200, and 400 eq of monomer. The reactions are...secondary metathesis of polymer chains Bulky alkoxide ligands Wittig-like reaction Ring-opening metathesis polymerization (ROMP) Feast monomer Cyclic...olefins Retro Diels-Alder reaction Norbornene (NBE) Low temperature column chromatography Endo-,endo-5,6-dicarbomethoxynorbornene Discrete, soluble

Efficacy of a dual-ring wound protector for prevention of incisional surgical site infection after Whipple's procedure (pancreaticoduodenectomy) with preoperatively-placed intrabiliary stents: protocol for a randomised controlled trial.

PubMed

Bressan, Alexsander K; Roberts, Derek J; Edwards, Janet P; Bhatti, Sana U; Dixon, Elijah; Sutherland, Francis R; Bathe, Oliver; Ball, Chad G

2014-08-21

Among surgical oncology patients, incisional surgical site infection is associated with substantially increased morbidity, mortality and healthcare costs. Moreover, while adults undergoing pancreaticoduodenectomy with preoperative placement of an intrabiliary stent have a high risk of this type of infection, and wound protectors may significantly reduce its risk, no relevant studies of wound protectors yet exist involving this patient population. This study will evaluate the efficacy of a dual-ring wound protector for prevention of incisional surgical site infection among adults undergoing pancreaticoduodenectomy with preoperatively-placed intrabiliary stents. This study will be a parallel, dual-arm, randomised controlled trial that will utilise a more explanatory than pragmatic attitude. All adults (≥18 years) undergoing a pancreaticoduodenectomy at the Foothills Medical Centre in Calgary, Alberta, Canada with preoperative placement of an intrabiliary stent will be considered eligible. Exclusion criteria will include patient age <18 years and those receiving long-term glucocorticoids. The trial will employ block randomisation to allocate patients to a commercial dual-ring wound protector (the Alexis Wound Protector) or no wound protector and the current standard of care. The main outcome measure will be the rate of surgical site infection as defined by the Centers for Disease Control and Prevention criteria within 30 days of the index operation date as determined by a research assistant blinded to treatment allocation. Outcomes will be analysed by a statistician blinded to allocation status by calculating risk ratios and 95% CIs and compared using Fisher's exact test. This will be the first randomised trial to evaluate the efficacy of a dual-ring wound protector for prevention of incisional surgical site infection among patients undergoing pancreaticoduodenectomy. Results of this study are expected to be available in 2016/2017 and will be disseminated using an integrated and end-of-grant knowledge translation strategy. ClinicalTrials.gov identifier NCT01836237. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Quantum Mechanics/Molecular Mechanics Simulations Identify the Ring-Opening Mechanism of Creatininase.

PubMed

Jitonnom, Jitrayut; Mujika, Jon I; van der Kamp, Marc W; Mulholland, Adrian J

2017-12-05

Creatininase catalyzes the conversion of creatinine (a biosensor for kidney function) to creatine via a two-step mechanism: water addition followed by ring opening. Water addition is common to other known cyclic amidohydrolases, but the precise mechanism for ring opening is still under debate. The proton donor in this step is either His178 or a water molecule bound to one of the metal ions, and the roles of His178 and Glu122 are unclear. Here, the two possible reaction pathways have been fully examined by means of combined quantum mechanics/molecular mechanics simulations at the SCC-DFTB/CHARMM22 level of theory. The results indicate that His178 is the main catalytic residue for the whole reaction and explain its role as proton shuttle during the ring-opening step. In the first step, His178 provides electrostatic stabilization to the gem-diolate tetrahedral intermediate. In the second step, His178 abstracts the hydroxyl proton of the intermediate and delivers it to the cyclic amide nitrogen, leading to ring opening. The latter is the rate-limiting step with a free energy barrier of 18.5 kcal/mol, in agreement with the experiment. We find that Glu122 must be protonated during the enzyme reaction, so that it can form a stable hydrogen bond with its neighboring water molecule. Simulations of the E122Q mutant showed that this replacement disrupts the H-bond network formed by three conserved residues (Glu34, Ser78, and Glu122) and water, increasing the energy barrier. Our computational studies provide a comprehensive explanation for previous structural and kinetic observations, including why the H178A mutation causes a complete loss of activity but the E122Q mutation does not.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yong; Desseaux, Solenne; Aden, Bethany

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Newly Developed Techniques on Polycondensation, Ring-Opening Polymerization and Polymer Modification: Focus on Poly(Lactic Acid)

PubMed Central

Hu, Yunzi; Daoud, Walid A.; Cheuk, Kevin Ka Leung; Lin, Carol Sze Ki

2016-01-01

Polycondensation and ring-opening polymerization are two important polymer synthesis methods. Poly(lactic acid), the most typical biodegradable polymer, has been researched extensively from 1900s. It is of significant importance to have an up-to-date review on the recent improvement in techniques for biodegradable polymers. This review takes poly(lactic acid) as the example to present newly developed polymer synthesis techniques on polycondensation and ring-opening polymerization reported in the recent decade (2005–2015) on the basis of industrial technique modifications and advanced laboratory research. Different polymerization methods, including various solvents, heating programs, reaction apparatus and catalyst systems, are summarized and compared with the current industrial production situation. Newly developed modification techniques for polymer properties improvement are also discussed based on the case of poly(lactic acid). PMID:28773260

Effect of temperature and O-ring gland finish on sealing ability of Viton V747-75

NASA Technical Reports Server (NTRS)

Lach, Cynthia L.

1993-01-01

As a part of the redesign project of the Space Shuttle solid rocket motor (SRM) following the Challenger accident, the field joint was redesigned to minimize the relative joint motion caused by internal motor pressurization during ignition. The O-ring seals and glands for the field joint were designed both to accommodate structural deflections and to promote pressure-assisted sealing. Tests were conducted in various face seal fixtures to evaluate the ability of Viton V747-75 O-rings to seal for a range of temperatures and surface finishes of the redesigned O-ring gland. The effect of surface finish on the sealing performance and wear characteristics of the O-rings was evaluated during simulated launch conditions that included low-frequency vibrations, gap openings, and rapid pressurizations. The effect of contamination on the sealing performance was also investigated. The O-rings sealed throughout the 75 deg F leak check test and for the seal tests from 50 deg F to 120 deg F for the range of surface finishes investigated. Although abrasions were found in the O-rings from pressurization against the rougher finishes, these abrasions were not detrimental to sealing. Below 50 deg F, Viton V747-75 O-rings were insufficiently resilient to track the test gap opening.

Decreased morbidity following long saphenous vein harvesting using a minimally invasive technique: a randomised controlled trial comparing two techniques for long saphenous vein harvest

PubMed Central

Mahmood, Zahid; Al Benna, Sammy; Nkere, Udim; Murday, Andrew

2006-01-01

Objectives The objective of this study was to compare the morbidity associated with long saphenous vein harvesting using the traditional open technique (A) against a minimally invasive technique using the Mayo vein stripper (B) that involves multiple short incisions. Design We conducted a prospective randomized controlled study in 80 patients undergoing first time coronary artery bypass grafting. Pain and healing was assessed on each postoperative day. Rings of long saphenous vein were subjected to organ-bath evaluation of endothelium-dependent and endothelium-independent relaxation. Results Three patients were excluded from the study, leaving 38 patients in Group A and 39 in Group B. With respect to operative procedure, Group A had a greater length of vein harvested than Group B. There was no statistical difference in pain scores and endothelium-dependent or endothelium-independent relaxation between the two groups. However there were significantly more infections in Group A compared with Group B. Conclusion Harvesting vein through multiple incisions using the Mayo vein stripper is quicker, results in fewer infections and has no deleterious effect on endothelial function compared to open technique. PMID:16759395

Selective polymerization catalysis: controlling the metal chain end group to prepare block copolyesters.

PubMed

Zhu, Yunqing; Romain, Charles; Williams, Charlotte K

2015-09-30

Selective catalysis is used to prepare block copolyesters by combining ring-opening polymerization of lactones and ring-opening copolymerization of epoxides/anhydrides. By using a dizinc complex with mixtures of up to three different monomers and controlling the chemistry of the Zn-O(polymer chain) it is possible to select for a particular polymerization route and thereby control the composition of block copolyesters.

Efficient synthesis of isochromanones and isoquinolines via Yb(OTf)3-catalyzed tandem oxirane/aziridine ring opening/Friedel-Crafts cyclization.

PubMed

Wei, Lai; Zhang, Junliang

2012-03-07

The first example of Yb(OTf)(3)-catalyzed tandem ring opening/Friedel-Crafts cyclization of oxiranyl and aziridinyl ketones via selective C-C bond cleavage under mild conditions was developed. Isochromanones and isoquinolines are formed in reasonable yields, which often serve as building blocks for complex chemical synthesis. This journal is © The Royal Society of Chemistry 2012

New insights into the by-product fatigue mechanism of the photo-induced ring-opening in diarylethenes.

PubMed

Mendive-Tapia, David; Perrier, Aurélie; Bearpark, Michael J; Robb, Michael A; Lasorne, Benjamin; Jacquemin, Denis

2014-09-14

The photochromic properties of diarylethenes, some of the most studied class of molecular switches, are known to be controlled by non-adiabatic decay at a conical intersection seam. Nevertheless, as their fatigue-reaction mechanism - leading to non-photochromic products - is yet to be understood, we investigate the photo-chemical formation of the so-called by-product isomer using three complementary computational methods (MMVB, CASSCF and CASPT2) on three model systems of increasing complexity. We show that for the ring-opening reaction a transition state on S1(2A) involving bond breaking of the penta-ring leads to a low energy S1(2A)/S0(1A) conical intersection seam, which lies above one of the transition states leading to the by-product isomer on the ground state. Therefore, radiationless decay and subsequent side-product formation can take place explaining the photo-degradation responsible for the by-product generation in diarylethene-type molecules. The effect of dynamic electron correlation and the possible role of inter-system crossing along the penta-ring opening coordinate are discussed as well.

Ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts.

PubMed

Vincent, Guillaume; Kouklovsky, Cyrille

2011-03-01

Strained nitroso Diels-Alder bicyclo[2.2.1] or [2.2.2] adducts functionalized with alkene side chains of diverse length undergo a ring-rearrangement metathesis process with external alkenes and Grubbs II or Hoveyda-Grubbs II ruthenium catalysts, under microwave irradiation or classical heating, to deliver cis-fused bicycles of various ring sizes, which contain a N-O bond. These scaffolds are of synthetic relevance for the generation of molecular diversity and to the total synthesis of alkaloids. The observation of unexpected reactions, such as epimerization or one-carbon homologation of the alkene side chain, is also reported. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Changes in the distance between carina and orotracheal tube during open or videolaparoscopic bariatric surgery].

PubMed

de Figueiredo Locks, Giovani; Simões de Almeida, Maria Cristina; Sperotto Ceccon, Maurício; Campos Pastório, Karen Adriana

2015-01-01

To examine whether there are changes in the distance between the orotracheal tubeand carina induced by orthostatic retractor placement or by pneumoperitoneum insufflation in obese patients undergoing gastroplasty. 60 patients undergoing bariatric surgery by two techniques: open (G1) or videola-paroscopic (G2) gastroplasty were studied. After tracheal intubation, adequate ventilation of both hemitoraxes was confirmed by lung auscultation. The distance orotracheal tube-carina was estimated with the use of a fiber bronchoscope before and after installation of orthostatic retractors in G1 or before and after insufflation of pneumoperitoneum in patients in G2. G1 was composed of 22 and G2 of 38 patients. No cases of endobronchial intubationwere detected in either group. The mean orotracheal tube-carina distance variation was estimated in -0.03 cm (95% CI 0.06 to -0.13) in the group of patients undergoing open gastroplastyand in -0.42 cm (95% CI -0.56 to -1.4) in the group of patients undergoing videolaparoscopic gastroplasty. The extremes of variation in each group were: 0.5 cm to -1.6 cm in patients under-going open surgery and 0.1 cm to -2.2 cm in patients undergoing videolaparoscopic surgery. There was no significant change in orotracheal tube-CA distance after placementof orthostatic retractors in patients undergoing open gastroplasty. There was a reduction inorotracheal tube-CA distance after insufflation of pneumoperitoneum in patients undergoing videolaparoscopic gastroplasty. We recommend attention to lung auscultation and to signals of ventilation monitoring and reevaluation of orotracheal tube placement after peritoneal insufflation. Copyright © 2014 Sociedade Brasileira de Anestesiologia. Publicado por Elsevier Editora Ltda. All rights reserved.

Changes in the distance between carina and orotracheal tube during open or videolaparoscopic bariatric surgery.

PubMed

de Figueiredo Locks, Giovani; Simões de Almeida, Maria Cristina; Sperotto Ceccon, Maurício; Campos Pastório, Karen Adriana

2015-01-01

To examine whether there are changes in the distance between the orotracheal tube and carina induced by orthostatic retractor placement or by pneumoperitoneum insufflation in obese patients undergoing gastroplasty. 60 patients undergoing bariatric surgery by two techniques: open (G1) or videolaparoscopic (G2) gastroplasty were studied. After tracheal intubation, adequate ventilation of both hemitoraxes was confirmed by lung auscultation. The distance orotracheal tube-carina was estimated with the use of a fiber bronchoscope before and after installation of orthostatic retractors in G1 or before and after insufflation of pneumoperitoneum in patients in G2. G1 was composed of 22 and G2 of 38 patients. No cases of endobronchial intubation were detected in either group. The mean orotracheal tube-carina distance variation was estimated in -0.03cm (95% CI 0.06 to -0.13) in the group of patients undergoing open gastroplasty and in -0.42cm (95% CI -0.56 to -1.4) in the group of patients undergoing videolaparoscopic gastroplasty. The extremes of variation in each group were: 0.5cm to -1.6cm in patients undergoing open surgery and 0.1cm to -2.2cm in patients undergoing videolaparoscopic surgery. There was no significant change in orotracheal tube-CA distance after placement of orthostatic retractors in patients undergoing open gastroplasty. There was a reduction in orotracheal tube-CA distance after insufflation of pneumoperitoneum in patients undergoing videolaparoscopic gastroplasty. We recommend attention to lung auscultation and to signals of ventilation monitoring and reevaluation of orotracheal tube placement after peritoneal insufflation. Copyright © 2014 Sociedade Brasileira de Anestesiologia. Published by Elsevier Editora Ltda. All rights reserved.

Quick actuating closure

NASA Technical Reports Server (NTRS)

White, III, Dorsey E. (Inventor); Updike, deceased, Benjamin T. (Inventor); Allred, Johnny W. (Inventor)

1989-01-01

A quick actuating closure for a pressure vessel 80 in which a wedge ring 30 with a conical outer surface 31 is moved forward to force shear blocks 40, with conical inner surfaces 41, radially outward to lock an end closure plug 70 within an opening 81 in the pressure vessel 80. A seal ring 60 and a preload ramp 50 sit between the shear blocks 40 and the end closure plug 70 to provide a backup sealing capability. Conical surfaces 44 and 55 of the preload ramp 50 and the shear blocks 40 interact to force the seal ring 60 into shoulders 73 and 85 in the end closure plug 70 and opening 81 to form a tight seal. The end closure plug 70 is unlocked by moving the wedge ring 30 rearward, which causes T-bars 32 of the wedge ring 30 riding within T -slots 42 of the shear blocks 40 to force them radially inward. The end closure plug 70 is then removed, allowing access to the interior of the pressure vessel 80.

Basic study of entire whole-body PET scanners based on the OpenPET geometry

NASA Astrophysics Data System (ADS)

Yoshida, Eiji; Yamaya, Taiga; Nishikido, Fumihiko; Inadama, Naoko; Murayama, Hideo

2010-09-01

A conventional PET scanner has a 15-25 cm axial field-of-view (FOV) and images a whole body using about six bed positions. An OpenPET geometry can extend the axial FOV with a limited number of detectors. The entire whole-body PET scanner must be able to process a large amount of data effectively. In this work, we study feasibility of the fully 3D entire whole-body PET scanner using the GATE simulation. The OpenPET has 12 block detector rings with the ring diameter of 840 mm and each block detector ring consists of 48 depth-of-interaction (DOI) detectors. The OpenPET has the axial length of 895.95 mm with five parts of 58.95 mm open gaps. The OpenPET has higher single data loss than a conventional PET scanner at grouping circuits. NECR of the OpenPET decreases by single data loss. But single data loss is mitigated by separating the axially arranged detector into two parts. Also, multiple coincidences are found to be important for the entire whole-body PET scanner. The entire whole-body PET scanner with the OpenPET geometry promises to provide a large axial FOV with the open space and to have sufficient performance values. But single data loss at the grouping circuits and multiple coincidences are limited to the peak noise equivalent count rate (NECR) for the entire whole-body PET scanner.

Aim44p regulates phosphorylation of Hof1p to promote contractile ring closure during cytokinesis in budding yeast

PubMed Central

Wolken, Dana M. Alessi; McInnes, Joseph; Pon, Liza A.

2014-01-01

Whereas actomyosin and septin ring organization and function in cytokinesis are thoroughly described, little is known regarding the mechanisms by which the actomyosin ring interacts with septins and associated proteins to coordinate cell division. Here we show that the protein product of YPL158C, Aim44p, undergoes septin-dependent recruitment to the site of cell division. Aim44p colocalizes with Myo1p, the type II myosin of the contractile ring, throughout most of the cell cycle. The Aim44p ring does not contract when the actomyosin ring closes. Instead, it forms a double ring that associates with septin rings on mother and daughter cells after cell separation. Deletion of AIM44 results in defects in contractile ring closure. Aim44p coimmunoprecipitates with Hof1p, a conserved F-BAR protein that binds both septins and type II myosins and promotes contractile ring closure. Deletion of AIM44 results in a delay in Hof1p phosphorylation and altered Hof1p localization. Finally, overexpression of Dbf2p, a kinase that phosphorylates Hof1p and is required for relocalization of Hof1p from septin rings to the contractile ring and for Hof1p-triggered contractile ring closure, rescues the cytokinesis defect observed in aim44∆ cells. Our studies reveal a novel role for Aim44p in regulating contractile ring closure through effects on Hof1p. PMID:24451263

Dynamic apical surface rings in superficial layer cells of koi Cyprinus carpio scale epidermis.

PubMed

DePasquale, J A

2016-09-01

This study examined the novel ring-shaped structures found in the apical surface of individual cells of the scale epidermis of koi Cyprinus carpio. These apical rings are highly dynamic structures with lifetimes ranging from a few to several minutes. While several ring forms were observed, the predominant ring morphology is circular or oval. Two distinct ring forms were identified and designated type I and type II. Type I rings have a well-defined outer border that encircles the surface microridges. Type II rings are smooth-surfaced, dinner-plate-like structures with membranous folds or compressed microridges in the centre. Type II rings appear less frequently than type I rings. Type I rings form spontaneously, arising from swollen or physically interrupted microridges but without initially perturbing the encircled microridges. After persisting for up to several minutes the ring closes in a centripetal movement to form a circular or irregular-shaped structure, the terminal disc. The terminal disc eventually disappears, leaving behind a submembranous vesicle-like structure, the terminal body. Type I rings can undergo multiple cycles of formation and closing. Recycling epidermal apical rings form through centrifugal expansion from the terminal disc followed by apparent contraction back to the disc structure, whereupon the cycle may repeat or cease. The findings demonstrate a novel skin surface structure in fishes and are discussed with respect to communication with the external aqueous environment. © 2016 The Fisheries Society of the British Isles.

Copper(I)-Catalyzed Chemoselective Coupling of Cyclopropanols with Diazoesters: Ring-Opening C-C Bond Formations.

PubMed

Zhang, Hang; Wu, Guojiao; Yi, Heng; Sun, Tong; Wang, Bo; Zhang, Yan; Dong, Guangbin; Wang, Jianbo

2017-03-27

Reported herein is an exceptional chemoselective ring-opening/C(sp 3 )-C(sp 3 ) bond formation in the copper(I)-catalyzed reaction of cyclopropanols with diazo esters. The conventional O-H insertion product is essentially suppressed by judicious choice of reaction conditions. DFT calculations provide insights into the reaction mechanism and the rationale for this unusual chemoselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural.

PubMed

Brentzel, Zachary J; Barnett, Kevin J; Huang, Kefeng; Maravelias, Christos T; Dumesic, James A; Huber, George W

2017-04-10

A process for the synthesis of 1,5-pentanediol (1,5-PD) with 84 % yield from furfural is developed, utilizing dehydration/hydration, ring-opening tautomerization, and hydrogenation reactions. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD. 2-Hydroxytetrahydropyran (2-HY-THP) is the key reaction pathway intermediate that allows for a decrease in the minimum selling price of 1,5-PD. The reactivity of 2-HY-THP is 80 times greater than that of THFA over a bimetallic hydrogenolysis catalyst. This enhanced reactivity is a result of the ring-opening tautomerization to 5-hydoxyvaleraldehyde and subsequent hydrogenation to 1,5-PD. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substituent effects on rates and torquoselectivities of electrocyclic ring-openings of N-substituted 2-azetines.

PubMed

Lopez, Steven A; Houk, K N

2014-07-03

Transition structures for the conrotatory electrocyclic ring-opening reactions of N-substituted 2-azetines were computed with the density functional M06-2X/6-31+G(d,p). A wide range of substituents from π acceptors (e.g., CHO, CN) to π donors (NMe2, OMe) was explored. Acceptor substituents delocalize the nitrogen lone pair and stabilize the reactant state of 2-azetines, while donors destabilize the 2-azetine reactant state. The conrotatory ring-opening is torquoselective, and the transition state for the outward rotation of the N-substituent and inward rotation of the nitrogen lone pair is preferred. This transition structure is stabilized by an interaction between the nitrogen lone pair and the vacant π* orbital. The activation free energies are linearly related to the reaction free energies and the Taft σR(0) parameter.

Different mechanisms at different temperatures for the ring-opening polymerization of lactide catalyzed by binuclear magnesium and zinc alkoxides.

PubMed

Sun, Yangyang; Cui, Yaqin; Xiong, Jiao; Dai, Zhongran; Tang, Ning; Wu, Jincai

2015-10-07

Two binuclear magnesium and zinc alkoxides supported by a bis-salalen type dinucleating heptadentate Schiff base ligand were synthesized and fully characterized. The two complexes are efficient initiators for the ring-opening polymerization (ROP) of L-lactide, affording polymers with narrow polydispersities and desirable molecular weights. Interestingly, the mechanisms for the ROP of lactide are different at different temperatures. At a high temperature of 130 °C, a coordination-insertion mechanism is reasonable for the bulk melt polymerization of lactide. At a low temperature, the alkoxide cannot initiate the ROP reaction; however, upon the addition of external benzyl alcohol into the system, the ROP of lactide can smoothly proceed via an "activated monomer" mechanism. In addition, these complexes display slight stereo-selectivity for the ring-opening polymerization of rac-lactide, affording partially isotactic polylactide in toluene with a Pm value of 0.59.

Biotransformation of two β-secretase inhibitors including ring opening and contraction of a pyrimidine ring.

PubMed

Lindgren, Anders; Eklund, Göran; Turek, Dominika; Malmquist, Jonas; Swahn, Britt-Marie; Holenz, Jörg; von Berg, Stefan; Karlström, Sofia; Bueters, Tjerk

2013-05-01

Recently, the discovery of the aminoisoindoles as potent and selective inhibitors of β-secretase was reported, including the close structural analogs compound (S)-1-pyridin-4-yl-4-fluoro-1-(3-(pyrimidin-5-yl)phenyl)-1H-isoindol-3-amine [(S)-25] and (S)-1-(2-(difluoromethyl)pyridin-4-yl)-4-fluoro-1-(3-(pyrimidin-5-yl)phenyl)-1H-isoindol-3-amine hemifumarate (AZD3839), the latter being recently progressed to the clinic. The biotransformation of (S)-25 was investigated in vitro and in vivo in rat, rabbit, and human and compared with AZD3839 to further understand the metabolic fate of these compounds. In vitro, CYP3A4 was the major responsible enzyme and metabolized both compounds to a large extent in the commonly shared pyridine and pyrimidine rings. The main proposed metabolic pathways in various in vitro systems were N-oxidation of the pyridine and/or pyrimidine ring and conversion to 4-pyrimidone and pyrimidine-2,4-dione. Both compounds were extensively metabolized, and more than 90% was excreted in feces after intravenous administration of radiolabeled compound to the rat. Here, the main pathways were N-oxidation of the pyridine and/or pyrimidine ring and a ring contraction of the pyrimidine ring into an imidazole ring. Ring-contracted metabolites accounted for 25% of the total metabolism in the rat for (S)-25, whereas the contribution was much smaller for AZD3839. This metabolic pathway was not foreseen on the basis of the obtained in vitro data. In conclusion, we discovered an unusual metabolic pathway of aryl-pyrimidine-containing compounds by a ring-opening reaction followed by elimination of a carbon atom and a ring closure to form an imidazole ring.

Report of the eRHIC Ring-Ring Working Group

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aschenauer, E. C.; Berg, S.; Blaskiewicz, M.

2015-10-13

This report evaluates the ring-ring option for eRHIC as a lower risk alternative to the linac-ring option. The reduced risk goes along with a reduced initial luminosity performance. However, a luminosity upgrade path is kept open. This upgrade path consists of two branches, with the ultimate upgrade being either a ring-ring or a linac-ring scheme. The linac-ring upgrade could be almost identical to the proposed linac-ring scheme, which is based on an ERL in the RHIC tunnel. This linac-ring version has been studied in great detail over the past ten years, and its significant risks are known. On the othermore » hand, no detailed work on an ultimate performance ring-ring scenario has been performed yet, other than the development of a consistent parameter set. Pursuing the ring-ring upgrade path introduces high risks and requires significant design work that is beyond the scope of this report.« less

INSIDE-OUT PLANET FORMATION. III. PLANET–DISK INTERACTION AT THE DEAD ZONE INNER BOUNDARY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Xiao; Tan, Jonathan C.; Chatterjee, Sourav

The Kepler mission has discovered more than 4000 exoplanet candidates. Many of them are in systems with tightly packed inner planets. Inside-out planet formation (IOPF) has been proposed as a scenario to explain these systems. It involves sequential in situ planet formation at the local pressure maximum of a retreating dead zone inner boundary (DZIB). Pebbles accumulate at this pressure trap, which builds up a pebble ring and then a planet. The planet is expected to grow in mass until it opens a gap, which helps to both truncate pebble accretion and also induce DZIB retreat that sets the location ofmore » formation of the next planet. This simple scenario may be modified if the planet undergoes significant migration from its formation location. Thus, planet–disk interactions play a crucial role in the IOPF scenario. Here we present numerical simulations that first assess the degree of migration for planets of various masses that are forming at the DZIB of an active accretion disk, where the effective viscosity is undergoing a rapid increase in the radially inward direction. We find that torques exerted on the planet by the disk tend to trap the planet at a location very close to the initial pressure maximum where it formed. We then study gap opening by these planets to assess at what mass a significant gap is created. Finally, we present a simple model for DZIB retreat due to penetration of X-rays from the star to the disk midplane. Overall, these simulations help to quantify both the mass scale of first (“Vulcan”) planet formation and the orbital separation to the location of second planet formation.« less

Inside-out Planet Formation. III. Planet-Disk Interaction at the Dead Zone Inner Boundary

NASA Astrophysics Data System (ADS)

Hu, Xiao; Zhu, Zhaohuan; Tan, Jonathan C.; Chatterjee, Sourav

2016-01-01

The Kepler mission has discovered more than 4000 exoplanet candidates. Many of them are in systems with tightly packed inner planets. Inside-out planet formation (IOPF) has been proposed as a scenario to explain these systems. It involves sequential in situ planet formation at the local pressure maximum of a retreating dead zone inner boundary (DZIB). Pebbles accumulate at this pressure trap, which builds up a pebble ring and then a planet. The planet is expected to grow in mass until it opens a gap, which helps to both truncate pebble accretion and also induce DZIB retreat that sets the location of formation of the next planet. This simple scenario may be modified if the planet undergoes significant migration from its formation location. Thus, planet-disk interactions play a crucial role in the IOPF scenario. Here we present numerical simulations that first assess the degree of migration for planets of various masses that are forming at the DZIB of an active accretion disk, where the effective viscosity is undergoing a rapid increase in the radially inward direction. We find that torques exerted on the planet by the disk tend to trap the planet at a location very close to the initial pressure maximum where it formed. We then study gap opening by these planets to assess at what mass a significant gap is created. Finally, we present a simple model for DZIB retreat due to penetration of X-rays from the star to the disk midplane. Overall, these simulations help to quantify both the mass scale of first (“Vulcan”) planet formation and the orbital separation to the location of second planet formation.

Ligament-induced sacral fractures of the pelvis are possible.

PubMed

Steinke, Hanno; Hammer, Niels; Lingslebe, Uwe; Höch, Andreas; Klink, Thomas; Böhme, Jörg

2014-07-01

Pelvic ring stability is maintained passively by both the osseous and the ligamentous apparatus. Therapeutic approaches focus mainly on fracture patterns, so ligaments are often neglected. When they rupture along with the bone after pelvic ring fractures, disrupting stability, ligaments need to be considered during reconstruction and rehabilitation. Our aim was to determine the influence of ligaments on open-book injury using two experimental models with body donors. Mechanisms of bone avulsion related to open-book injury were investigated. Open-book injuries were induced in human pelves and subsequently investigated by anatomical dissection and endoscopy. The findings were compared to CT and MRI scans of open-book injuries. Relevant structures were further analyzed using plastinated cross-sections of the posterior pelvic ring. A fragment of the distal sacrum was observed, related to open-book injury. Two ligaments were found to be responsible for this avulsion phenomenon: the caudal portion of the anterior sacroiliac ligament and another ligament running along the ventral surface of the third sacral vertebra. The sacral fragment remained attached to the coxal bone by this second ligament after open-book injury. These results were validated using plastination and the structures were identified. Pelvic ligaments are probably involved in sacral avulsion caused by lateral traction. Therefore, ligaments should to be taken into account in diagnosis of open-book injury and subsequent therapy. Copyright © 2014 Wiley Periodicals, Inc.

Lipase-catalyzed ring-opening polymerization of lactones to polyesters and its mechanistic aspects.

PubMed

Namekawa, S; Suda, S; Uyama, H; Kobayashi, S

1999-01-01

Lipase catalysis induced a ring-opening polymerization of lactones with different ring-sizes. Small-size (four-membered) and medium-size lactones (six- and seven-membered) as well as macrolides (12-, 13-, 16-, and 17-membered) were subjected to lipase-catalyzed polymerization. The polymerization behaviors depended primarily on the lipase origin and the monomer structure. The macrolides showing much lower anionic polymerizability were enzymatically polymerized faster than epsilon-caprolactone. The granular immobilized lipase derived from Candida antartica showed extremely efficient catalysis in the polymerization of epsilon-caprolactone. Single-step terminal functionalization of the polyester was achieved by initiator and terminator methods. The enzymatic polymerizability of lactones was quantitatively evaluated by Michaelis-Menten kinetics.

Remarkable Regioselective Position-10 Bromination of Bacteriopyropheophorbide-a and Ring-B Reduced Pyropheophorbide-a

PubMed Central

Ethirajan, Manivannan; Joshi, Penny; William, White H.; Ohkubo, Kei; Fukuzumi, Shunichi; Pandey, Ravindra K.

2011-01-01

Both bacteriopyropheophorbide-a and ring-B reduced pyropheophorbide-a on reacting with NBS (N-bromosuccinamide) undergo electrophilic bromination to provide 10-bromo analogs. The electronic nature of the substituents present at position-3 did not make any difference in regioselective outcome of the brominated products. These relatively stable brominated chlorins and bacteriochlorins provide an easy way of introducing a wide variety of functionalities, which could be extremely useful in developing improved agents for biomedical applications and supramolecular chemistry. PMID:21417431

46 CFR 160.002-3 - Materials.

Code of Federal Regulations, 2010 CFR

2010-10-01

... warp and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

46 CFR 160.005-3 - Materials.

Code of Federal Regulations, 2010 CFR

2010-10-01

... and 70 pounds in the filling. If it is proposed to treat the fabric with a fire-retardant substance...-resistant material. Dee ring ends shall be welded to form a continuous ring. The webbing opening of the snap...

Zero-stress states of human pulmonary arteries and veins.

PubMed

Huang, W; Yen, R T

1998-09-01

The zero-stress states of the pulmonary arteries and veins from order 3 to order 9 were determined in six normal human lungs within 15 h postmortem. The zero-stress state of each vessel was obtained by cutting the vessel transversely into a series of short rings, then cutting each ring radially, which caused the ring to spring open into a sector. Each sector was characterized by its opening angle. The mean opening angle varied between 92 and 163 degrees in the arterial tree and between 89 and 128 degrees in the venous tree. There was a tendency for opening angles to increase as the sizes of the arteries and veins increased. We computed the residual strains based on the experimental measurements and estimated the residual stresses according to Hooke's law. We found that the inner wall of a vessel at the state in which the internal pressure, external pressure, and longitudinal stress are all zero was under compression and the outer wall was in tension, and that the magnitude of compressive stress was greater than the magnitude of tensile stress.

ISOPOOH interacting with plant surfaces - a new source of MVK?

NASA Astrophysics Data System (ADS)

Canaval, Eva; Partoll, Eva Maria; Mentler, Bernhard; Keutsch, Frank; Schnitzler, Jörg-Peter; Hansel, Armin

2017-04-01

Isoprene is the most dominant BVOC emitted into the atmosphere. In rural areas with low concentrations of NOx Isoprene can rapidly react with hydroxyl radicals forming several isoprene hydroxy hydroperoxide (ISOPOOH) isomeres. It is known that ISOPOOH undergoes catalytical conversion on metal surfaces forming MVK and MACR and other oxygenated species. Thus, standard PTR-MS instruments containing metal drift rings convert ISOPOOH to MVK and MACR and cannot measure ISOPOOH artifact free. In our studies we were interested in the surfaces catalyzed reactions of ISOPOOH on plant surfaces. For this aim we used poplar plants, which represent a major biomass producing species. For the experiments the poplars were placed in an enclosure setup with only PTFE, PFA and PEEK as ISOPOOH showed negligible decomposition on those materials. ISOPOOH was mixed quantitatively to the air stream with a Liquid Calibration Unit resulting in volume mixing ratios of 8-50 ppbv. A novel Switchable-Reagent-Ion-Time-of-Flight-MS (SRI-ToF-MS) instrument containing conductive peek drift rings was used to analyze the VOC composition switching between enclosure inlet and outlet in real-time. The use of H_3O+ and NH_4+ as reagent ions allows the fragmention free measurement of isoprene peroxides and C_5-diols. We investigated day/night (stomatal open-closed) changes and found under daytime conditions a strong uptake of ISOPOOH and a clear emission of MVK for low and high concentrations of ISOPOOH. Fumigation with 8-10 ppbv ISOPOOH under night conditions the poplar showed only a small uptake of ISOPOOH accompanied by no visible MVK emissions. But fumigation of poplar with 50 ppbv showed a clear uptake during night time conditions. This indicates that the plant surfaces also play an important role in producing MVK while undergoing surface assisted reactions with ISOPOOH. Moreover during long fumigation (6-8 h) with ISOPOOH the majority of investigated poplars showed increasing levels of stress indicating compounds like methyl salicylate.

Opening Furan for Tailoring Properties of Bio-based Poly(Furfuryl Alcohol) Thermoset.

PubMed

Falco, Guillaume; Guigo, Nathanael; Vincent, Luc; Sbirrazzuoli, Nicolas

2018-06-11

This work shows how furan ring-opening reactions were controlled by polymerization conditions to tune the cross-link density in bio-based poly(furfuryl alcohol) (PFA). The influence of water and isopropyl alcohol (IPA) on the polymerization of furfuryl alcohol, and particularly on furan ring-opening, was investigated by means of 13 C NMR and FT-IR spectroscopy. Results indicated that formation of open structures were favored in the presence of solvents, thus leading to modification of the thermo-mechanical properties compared to PFA cross-linked without solvent. Dynamic mechanical analyses showed that when slightly more open structures were present in PFA it resulted in an important decrease of the cross-link density. Despite lower glass-transition temperature and lower elastic modulus for PFA polymerized with solvent, the thermal stability remains very high (>350 °C) even with more open structures in PFA. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A perspective on reagent diversity and non-covalent binding of reactive carbonyl species (RCS) and effector reagents in nonenzymatic glycation (NEG): Mechanistic considerations and implications for future research

NASA Astrophysics Data System (ADS)

Rodnick, Kenneth J.; Holman, R. W.; Ropski, Pamela S.; Huang, Mingdong; Swislocki, Arthur L. M.

2017-06-01

This perspective focuses on illustrating the underappreciated connections between reactive carbonyl species (RCS), initial binding in the nonenzymatic glycation (NEG) process, and nonenzymatic covalent protein modification (here termed NECPM). While glucose is the central species involved in NEG, recent studies indicate that the initially-bound glucose species in the NEG of human hemoglobin (HbA) and human serum albumin (HSA) are non-RCS ring-closed isomers. The ring-opened glucose, an RCS structure that reacts in the NEG process, is most likely generated from previously-bound ring-closed isomers undergoing concerted acid/base reactions while bound to protein. The generation of the glucose RCS can involve concomitantly-bound physiological species (e.g., inorganic phosphate, water, etc.); here termed effector reagents. Extant NEG schemes do not account for these recent findings. In addition, effector reagent reactions with glucose in the serum and erythrocyte cytosol can generate RCS (e.g., glyoxal, glyceraldehyde, etc.). Recent research has shown that these RCS covalently modify proteins in vivo via NECPM mechanisms. A general scheme that reflects both the reagent and mechanistic diversity that can lead to NEG and NECPM is presented here. A perspective that accounts for the relationships between RCS, NEG, and NECPM can facilitate the understanding of site selectivity, may help explain overall glycation rates, and may have implications for the clinical assessment/control of diabetes mellitus. In view of this perspective, concentrations of ribose, fructose, Pi, bicarbonate, counter ions, and the resulting RCS generated within intracellular and extracellular compartments may be of importance and of clinical relevance. Future research is also proposed.

Minimally Invasive Surgical Staging for Ovarian Carcinoma: A Propensity-Matched Comparison With Traditional Open Surgery.

PubMed

Ditto, Antonino; Bogani, Giorgio; Martinelli, Fabio; Signorelli, Mauro; Chiappa, Valentina; Scaffa, Cono; Indini, Alice; Leone Roberti Maggiore, Umberto; Lorusso, Domenica; Raspagliesi, Francesco

2017-01-01

Growing evidence supports the safety of a laparoscopic approach for patients affected by apparent early-stage ovarian cancer. However, no well-designed studies comparing laparoscopic and open surgical staging are available. In the present investigation we aimed to provide a balanced long-term comparison between these 2 approaches. Retrospective study (Canadian Task Force classification II-2). Tertiary center. Data of consecutive patients affected by early-stage ovarian cancer who had laparoscopic staging were matched 1:1 with a cohort of patients undergoing open surgical staging. The matching was conducted by a propensity-score comparison. Laparoscopic and open surgical staging. Fifty patient pairs (100 patients: 50 undergoing laparoscopic staging vs 50 undergoing open surgical staging) were included. Demographic and baseline oncologic characteristics were balanced between groups (p > .2). We observed that patients undergoing laparoscopic staging experienced longer operative time (207.2 [71.6] minutes vs 180.7 [47.0] minutes; p = .04), lower blood loss (150 [52.7] mL vs 339.8 [225.9] mL; p < .001), and shorter length of hospital stay (4.0 [2.6] days vs 6.1 [1.6] days; p < .001) compared with patients undergoing open surgical staging. No conversion to open surgery occurred. Complication rate was similar between groups. No difference in survival outcomes were observed, after a mean (SD) follow-up of 49.5 (64) and 52.6 (31.7) months after laparoscopic and open surgical staging, respectively. Our findings suggest that the implementation of minimally invasive staging does not influence survival outcomes of patients affected by early-stage ovarian cancer. Laparoscopic staging improved patient outcomes, reducing length of hospital stay. Further large prospective studies are warranted. Copyright © 2016 AAGL. Published by Elsevier Inc. All rights reserved.

Regioselective copper-catalyzed alkylation of [2.2.2]-acylnitroso cycloadducts: remarkable effect of the halide of Grignard reagents.

PubMed

Crotti, Stefano; Bertolini, Ferruccio; di Bussolo, Valeria; Pineschi, Mauro

2010-04-16

Ring opening with organometallic reagents of [2.2.2]-acylnitroso cycloadducts, including an enantioselective kinetic resolution of these compounds, has been accomplished for the first time. By the careful choice of reaction conditions, it was possible to obtain new cyclohexenyl hydroxamic acids with complete anti-stereoselectivity and a nice regioalternating control. A remarkable effect of the halogen of the Grignard reagent was observed during ring opening.

Versatile organoaluminium catalysts based on heteroscorpionate ligands for the preparation of polyesters.

PubMed

Martínez, J; Martínez de Sarasa Buchaca, M; de la Cruz-Martínez, F; Alonso-Moreno, C; Sánchez-Barba, L F; Fernandez-Baeza, J; Rodríguez, A M; Rodríguez-Diéguez, A; Castro-Osma, J A; Otero, A; Lara-Sánchez, A

2018-05-22

A series of alkyl aluminium complexes based on heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters and ring-opening copolymerisation of epoxides and anhydrides. Treatment of AlX3 (X = Me, Et) with ligands bpzbeH [bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide], bpzteH [bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethoxide], and (R,R)-bpzmmH [(R,R)-bpzmm = (1R)-1-{(1R)-6,6-dimethyl-bicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide] for 2 hours at 0 °C afforded the mononuclear dialkyl aluminium complexes [AlMe2{κ2-bpzbe}] (1), [AlEt2{κ2-bpzbe}] (2), [AlMe2{κ2-(R,R)-bpzmm}] (3) and [AlEt2{κ2-(R,R)-bpzmm}] (4), and the dinuclear dialkyl complexes [AlMe2{κ2-bpzte}]2 (5) and [AlEt2{κ2-bpzte}]2 (6). The molecular structures of the new complexes were determined by spectroscopic methods and confirmed by X-ray crystallography. The alkyl-containing aluminium complexes can act as highly efficient single-component initiators for the ring-opening polymerisation of ε-caprolactone and l-lactide and for the ring-opening copolymerisation of cyclohexene oxide and phthalic anhydride to give a range of biodegradable polyesters.

The plasmasheet H+ and O+ contribution on the storm time ring current

NASA Astrophysics Data System (ADS)

Mouikis, C.; Bingham, S.; Kistler, L. M.; Spence, H. E.; Gkioulidou, M.; Claudepierre, S. G.; Farrugia, C. J.

2015-12-01

The source population of the storm time ring current is the night side plasma sheet. We use Van Allen Probes and Cluster observations to determine the contribution of the convecting plasma sheet H+ and O+ particles in the storm time development of the ring current. Using the Volland-Stern model with a dipole magnetic field together with the identification of the observed energy cutoffs in the particle spectra, we specify the pressure contributed by H+ and O+ populations that are on open drift paths vs. the pressure contributed by the trapped populations, for different local times. We find that during the storm main phase most of the ring current pressure in the pre-midnight inner magnetosphere is contributed by particles on open drift paths that cause the development of a strong partial ring current that causes most of the main phase Dst drop. These particles can reach as deep as L~2 and their pressure compares to the local magnetic field pressure as deep as L~3. During the recovery phase, if these particles are not lost at the magnetopause, will become trapped and will contribute to the symmetric ring current.

Theoretical study of the electronic and optical properties of photochromic dithienylethene derivatives connected to small gold clusters.

PubMed

Perrier, Aurélie; Maurel, François; Aubard, Jean

2007-10-04

In the course of developing electronic devices on a molecular scale, dithienylethenes photochromic molecules constitute promising candidates for optoelectronic applications such as memories and switches. There is thus a great interest to understand and control the switching behavior of photochromic compounds deposited on metallic surfaces or nanoparticles. Within the framework of the density functional theory, we studied the effect of small gold clusters (Au3 and Au9) on the electronic structure and absorption spectrum of a model dithienylethene molecule. The molecular orbital interactions between the photochromic molecule and the gold cluster made it possible to rationalize some experimental findings (Dulic, D.; van der Molen, S. J.; Kudernac, T.; Jonkman, H. T.; de Jong, J. J. D.; Bowden, T. N.; van Esch, J.; Feringa, B. L.; van Wees, B. J. Phys. Rev. Lett. 2003, 91, 207402). For the closed-ring isomer, grafting a photochromic molecule on a small gold cluster does not change the characteristics of the electronic transition involved in the ring-opening reaction. On the opposite, the absorption spectrum of the photochromic open-ring isomer is strongly modified by the inclusion of the metallic cluster. In agreement with experimental results, our study thus showed that the cycloreversion reaction which involves the closed-ring isomer should be still possible, whereas the ring-closure reaction which involves the open-ring isomer should be inhibited. Connecting a dithienylethene molecule to a small gold cluster hence provides a qualitative comprehension of the photochromic activities of dithienylethenes connected to a gold surface.

Metabolism of MRX-I, a novel antibacterial oxazolidinone, in humans: the oxidative ring opening of 2,3-Dihydropyridin-4-one catalyzed by non-P450 enzymes.

PubMed

Meng, Jian; Zhong, Dafang; Li, Liang; Yuan, Zhengyu; Yuan, Hong; Xie, Cen; Zhou, Jialan; Li, Chen; Gordeev, Mikhail Fedorovich; Liu, Jinqian; Chen, Xiaoyan

2015-05-01

MRX-I is an analog of linezolid containing a 2,3-dihydropyridin-4-one (DHPO) ring rather than a morpholine ring. Our objectives were to characterize the major metabolic pathways of MRX-I in humans and clarify the mechanism underlying the oxidative ring opening of DHPO. After an oral dose of MRX-I (600 mg), nine metabolites were identified in humans. The principal metabolic pathway proposed involved the DHPO ring opening, generating the main metabolites in the plasma and urine: the hydroxyethyl amino propionic acid metabolite MRX445-1 and the carboxymethyl amino propionic acid metabolite MRX459. An in vitro phenotyping study demonstrated that multiple non-cytochrome P450 enzymes are involved in the formation of MRX445-1 and MRX459, including flavin-containing monooxygenase 5, short-chain dehydrogenase/reductase, aldehyde ketone reductase, and aldehyde dehydrogenase (ALDH). H2 (18)O experiments revealed that two (18)O atoms are incorporated into MRX445-1, one in the carboxyethyl group and the other in the hydroxyl group, and three (18)O atoms are incorporated into MRX459, two in the carboxymethyl group and one in the hydroxyl group. Based on these results, the mechanism proposed for the DHPO ring opening involves the metabolism of MRX-I via FMO5-mediated Baeyer-Villiger oxidation to an enol lactone, hydrolysis to an enol, and enol-aldehyde tautomerism to an aldehyde. The aldehyde is reduced by short-chain dehydrogenase/reductase, aldehyde ketone reductase, ALDH to MRX445-1, or oxidized by ALDH to MRX459. Our study suggests that few clinical adverse drug-drug interactions should be anticipated between MRX-I and cytochrome P450 inhibitors or inducers. Copyright © 2015 by The American Society for Pharmacology and Experimental Therapeutics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@lamar.colostate.edu

Unimolecular decomposition of nitrogen-rich energetic molecules 1,2-bis(1H-tetrazol-1-yl)ethane (1-DTE), 1,2-bis(1H-tetrazol-5-yl)ethane (5-DET), N,N-bis(1H-tetrazol-5-yl)amine (BTA), and 5,5’-bis(tetrazolyl)hydrazine (BTH) has been explored via 283 nm two photon laser excitation. The maximum absorption wavelength in the UV-vis spectra of all four materials is around 186–222 nm. The N{sub 2} molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product from the four molecules, subsequent to UV excitation. Initial decomposition mechanisms for these four electronically excited isolated molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersectionsmore » play an essential role in the decomposition mechanism. The tetrazole ring opens on the S{sub 1} excited state and through conical intersections (S{sub 1}/S{sub 0}){sub CI}, N{sub 2} product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings of all four energetic molecules open at the N1—N2 ring bond with the lowest energy barrier: the C—N bond opening has higher energy barrier than that for any of the N—N ring bonds. Therefore, the tetrazole rings open at their N—N bonds to release N{sub 2}. The vibrational temperatures of N{sub 2} product from all four energetic materials are hot based on theoretical calculations. The different groups (CH{sub 2}—CH{sub 2}, NH—NH, and NH) joining the tetrazole rings can cause apparent differences in explosive behavior of 1-DTE, 5-DTE, BTA, and BTH. Conical intersections, non-Born-Oppenheimer interactions, and dynamics are the key features for excited electronic state chemistry of organic molecules, in general, and energetic molecules, in particular.« less

Development of a small single-ring OpenPET prototype with a novel transformable architecture.

PubMed

Tashima, Hideaki; Yoshida, Eiji; Inadama, Naoko; Nishikido, Fumihiko; Nakajima, Yasunori; Wakizaka, Hidekatsu; Shinaji, Tetsuya; Nitta, Munetaka; Kinouchi, Shoko; Suga, Mikio; Haneishi, Hideaki; Inaniwa, Taku; Yamaya, Taiga

2016-02-21

The single-ring OpenPET (SROP), for which the detector arrangement has a cylinder shape cut by two parallel planes at a slant angle to form an open space, is our original proposal for in-beam PET. In this study, we developed a small prototype of an axial-shift type SROP (AS-SROP) with a novel transformable architecture for a proof-of-concept. In the AS-SROP, detectors originally forming a cylindrical PET are axially shifted little by little. We designed the small AS-SROP prototype for 4-layer depth-of-interaction detectors arranged in a ring diameter of 250 mm. The prototype had two modes: open and closed. The open mode formed the SROP with the open space of 139 mm and the closed mode formed a conventional cylindrical PET. The detectors were simultaneously moved by a rotation handle allowing them to be transformed between the two modes. We evaluated the basic performance of the developed prototype and carried out in-beam imaging tests in the HIMAC using (11)C radioactive beam irradiation. As a result, we found the open mode enabled in-beam PET imaging at a slight cost of imaging performance; the spatial resolution and sensitivity were 2.6 mm and 5.1% for the open mode and 2.1 mm and 7.3% for the closed mode. We concluded that the AS-SROP can minimize the decrease of resolution and sensitivity, for example, by transforming into the closed mode immediately after the irradiation while maintaining the open space only for the in-beam PET measurement.

Heterogeneous kinetic modeling of the catalytic conversion of cycloparaffins

NASA Astrophysics Data System (ADS)

Al-Sabawi, Mustafa N.

The limited availability of high value light hydrocarbon feedstocks along with the rise in crude prices has resulted in the international recognition of the vast potential of Canada's oil sands. With the recent expansion of Canadian bitumen production come, however, many technical challenges, one of which is the significant presence of aromatics and cycloparaffins in bitumen-derived feedstocks. In addition to their negative environmental impact, aromatics limit fluid catalytic cracking (FCC) feedstock conversion, decrease the yield and quality of valuable products such as gasoline and middle distillates, increase levels of polyaromatic hydrocarbons prone to form coke on the catalyst, and ultimately compromise the FCC unit performance. Although cycloparaffins do not have such negative impacts, they are precursors of aromatics as they frequently undergo hydrogen transfer reactions. However, cycloparaffin cracking chemistry involves other competing reactions that are complex and need much investigation. This dissertation provides insights and understanding of the fundamentals of the catalytic cracking of cycloparaffins using carefully selected model compounds such as methylcyclohexane (MCH) and decalin. Thermal and catalytic cracking of these cycloparaffins on FCC-type catalysts are carried out using the CREC Riser Simulator under operating conditions similar to those of the industrial FCC units in terms of temperature, reaction time, reactant partial pressure and catalyst-to-hydrocarbon ratio. The crystallite size of the supported zeolites is varied between 0.4 and 0.9 microns, with both activity and selectivity being monitored. Catalytic conversions ranged between 4 to 16 wt% for MCH and between 8 to 27 wt% for decalin. Reaction pathways of cycloparaffins are determined, and these include ring-opening, protolytic cracking, isomerization, hydrogen transfer and transalkylation. The yields and selectivities of over 60 and 140 products, formed during MCH and decalin catalytic conversions respectively, are reported. Using these data, heterogeneous kinetic models accounting for intracrystallite molecular transport, adsorption and thermal and catalytic cracking of both cycloparaffin reactants are established. Results show that undesirable hydrogen transfer reactions are more pronounced and selectively favoured against other reactions at lower reaction temperatures, while the desirable ring-opening and cracking reactions predominate at the higher reaction temperatures. Moreover, results of the present work show that while crystallite size may have an effect on the overall conversion in some situations, there is a definite effect on the selectivity of products obtained during the cracking of MCH and decalin and the cracking of MCH in a mixture with co-reactants such as 1,3,5-triisopropylbenzene. Keywords. cycloparaffins, naphthenes, fluid catalytic cracking, kinetic modeling, Y-zeolites, diffusion, adsorption, ring-opening, hydrogen transfer, catalyst selectivity.

Conformation and Dynamics of Human Urotensin II and Urotensin Related Peptide in Aqueous Solution.

PubMed

Haensele, Elke; Mele, Nawel; Miljak, Marija; Read, Christopher M; Whitley, David C; Banting, Lee; Delépée, Carla; Sopkova-de Oliveira Santos, Jana; Lepailleur, Alban; Bureau, Ronan; Essex, Jonathan W; Clark, Timothy

2017-02-27

Conformation and dynamics of the vasoconstrictive peptides human urotensin II (UII) and urotensin related peptide (URP) have been investigated by both unrestrained and enhanced-sampling molecular-dynamics (MD) simulations and NMR spectroscopy. These peptides are natural ligands of the G-protein coupled urotensin II receptor (UTR) and have been linked to mammalian pathophysiology. UII and URP cannot be characterized by a single structure but exist as an equilibrium of two main classes of ring conformations, open and folded, with rapidly interchanging subtypes. The open states are characterized by turns of various types centered at K 8 Y 9 or F 6 W 7 predominantly with no or only sparsely populated transannular hydrogen bonds. The folded conformations show multiple turns stabilized by highly populated transannular hydrogen bonds comprising centers F 6 W 7 K 8 or W 7 K 8 Y 9 . Some of these conformations have not been characterized previously. The equilibrium populations that are experimentally difficult to access were estimated by replica-exchange MD simulations and validated by comparison of experimental NMR data with chemical shifts calculated with density-functional theory. UII exhibits approximately 72% open:28% folded conformations in aqueous solution. URP shows very similar ring conformations as UII but differs in an open:folded equilibrium shifted further toward open conformations (86:14) possibly arising from the absence of folded N-terminal tail-ring interaction. The results suggest that the different biological effects of UII and URP are not caused by differences in ring conformations but rather by different interactions with UTR.

Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy

DOE PAGES

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.; ...

2016-12-21

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Application of combinatorial biocatalysis for a unique ring expansion of dihydroxymethylzearalenone.

PubMed

Rich, Joseph O; Budde, Cheryl L; McConeghey, Luke D; Cotterill, Ian C; Mozhaev, Vadim V; Singh, Sheo B; Goetz, Michael A; Zhao, Annie; Michels, Peter C; Khmelnitsky, Yuri L

2009-06-01

Combinatorial biocatalysis was applied to generate a diverse set of dihydroxymethylzearalenone analogs with modified ring structure. In one representative chemoenzymatic reaction sequence, dihydroxymethylzearalenone was first subjected to a unique enzyme-catalyzed oxidative ring opening reaction that creates two new carboxylic groups on the molecule. These groups served as reaction sites for further derivatization involving biocatalytic ring closure reactions with structurally diverse bifunctional reagents, including different diols and diamines. As a result, a library of cyclic bislactones and bislactams was created, with modified ring structures covering chemical space and structure activity relationships unattainable by conventional synthetic means.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, M.S.; Saunders, R.

1997-02-18

Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands

PubMed Central

Pribisko, Melanie A.; Ahmed, Tonia S.; Grubbs, Robert H.

2014-01-01

Two new Ru-based metathesis catalysts, 3 and 4, have been synthesized for the purpose of comparing their catalytic properties to those of their cis-selective nitrate analogues, 1 and 2. Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2, they maintained high cis-selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis-selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer. PMID:25484484

Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands.

PubMed

Pribisko, Melanie A; Ahmed, Tonia S; Grubbs, Robert H

2014-12-14

Two new Ru-based metathesis catalysts, 3 and 4 , have been synthesized for the purpose of comparing their catalytic properties to those of their cis -selective nitrate analogues, 1 and 2 . Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2 , they maintained high cis -selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis -selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer.

Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources.

PubMed

Lalevée, Jacques; Mokbel, Haifaa; Fouassier, Jean-Pierre

2015-04-20

Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

Solventless sol-gel chemistry through ring-opening polymerization of bridged disilaoxacyclopentanes

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.

2000-05-01

Ring-opening polymerization (ROP) of disilaoxacyclopentanes has proven to be an excellent approach to sol-gel type hybrid organic-inorganic materials. These materials have shown promise as precursors for encapsulation and microelectronics applications. The polymers are highly crosslinked and are structurally similar to traditional sol-gels, but unlike typical sol-gels they are prepared by an organic base or Bronsted acid (formic or triflic acid), without the use of solvents and water, they have low VOC's and show little shrinkage during processing.

Nickel-catalyzed regio- and enantioselective aminolysis of 3,4-epoxy alcohols.

PubMed

Wang, Chuan; Yamamoto, Hisashi

2015-04-08

The first catalytic regio- and enantioselective aminolysis of 3,4-epoxy alcohols has been accomplished. Under the catalysis of Ni(ClO4)2·6H2O, the C4 selective ring opening of various 3,4-epoxy alcohols proceeded in a stereospecific manner with high regioselectivities. Furthermore, with the Ni-BINAM catalytic system the enantioselective ring opening of 3,4-epoxy alcohols furnished various γ-hydroxy-δ-amino alcohols as products with complete regiocontrol and high enantioselectivities (up to 94% ee).

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, Michael S.; Saunders, Randall

1997-01-01

Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

Chemistry and Biology of DNA Containing 1,N2-Deoxyguanosine Adducts of the α,β-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and 4-Hydroxynonenal

PubMed Central

2009-01-01

The α,β-unsaturated aldehydes (enals) acrolein, crotonaldehyde, and trans-4-hydroxynonenal (4-HNE) are products of endogenous lipid peroxidation, arising as a consequence of oxidative stress. The addition of enals to dG involves Michael addition of the N2-amine to give N2-(3-oxopropyl)-dG adducts, followed by reversible cyclization of N1 with the aldehyde, yielding 1,N2-dG exocyclic products. The 1,N2-dG exocyclic adducts from acrolein, crotonaldehyde, and 4-HNE exist in human and rodent DNA. The enal-induced 1,N2-dG lesions are repaired by the nucleotide excision repair pathway in both Escherichia coli and mammalian cells. Oligodeoxynucleotides containing structurally defined 1,N2-dG adducts of acrolein, crotonaldehyde, and 4-HNE were synthesized via a postsynthetic modification strategy. Site-specific mutagenesis of enal adducts has been carried out in E. coli and various mammalian cells. In all cases, the predominant mutations observed are G→T transversions, but these adducts are not strongly miscoding. When placed into duplex DNA opposite dC, the 1,N2-dG exocyclic lesions undergo ring opening to the corresponding N2-(3-oxopropyl)-dG derivatives. Significantly, this places a reactive aldehyde in the minor groove of DNA, and the adducted base possesses a modestly perturbed Watson−Crick face. Replication bypass studies in vitro indicate that DNA synthesis past the ring-opened lesions can be catalyzed by pol η, pol ι, and pol κ. It also can be accomplished by a combination of Rev1 and pol ζ acting sequentially. However, efficient nucleotide insertion opposite the 1,N2-dG ring-closed adducts can be carried out only by pol ι and Rev1, two DNA polymerases that do not rely on the Watson−Crick pairing to recognize the template base. The N2-(3-oxopropyl)-dG adducts can undergo further chemistry, forming interstrand DNA cross-links in the 5′-CpG-3′ sequence, intrastrand DNA cross-links, or DNA−protein conjugates. NMR and mass spectrometric analyses indicate that the DNA interstand cross-links contain a mixture of carbinolamine and Schiff base, with the carbinolamine forms of the linkages predominating in duplex DNA. The reduced derivatives of the enal-mediated N2-dG:N2-dG interstrand cross-links can be processed in mammalian cells by a mechanism not requiring homologous recombination. Mutations are rarely generated during processing of these cross-links. In contrast, the reduced acrolein-mediated N2-dG peptide conjugates can be more mutagenic than the corresponding monoadduct. DNA polymerases of the DinB family, pol IV in E. coli and pol κ in human, are implicated in error-free bypass of model acrolein-mediated N2-dG secondary adducts, the interstrand cross-links, and the peptide conjugates. PMID:19397281

Global Magnetospheric Evolution Effected by Sudden Ring Current Injection

NASA Astrophysics Data System (ADS)

Park, Geunseok; No, Jincheol; Kim, Kap-Sung; Choe, Gwangson; Lee, Junggi

2016-04-01

The dynamical evolution of the Earth's magnetosphere loaded with a transiently enhanced ring current is investigated by global magnetohydrodynamic simulations. Two cases with different values of the primitive ring current are considered. In one case, the initial ring current is strong enough to create a magnetic island in the magnetosphere. The magnetic island readily reconnects with the earth-connected ambient field and is destroyed as the system approaches a steady equilibrium. In the other case, the initial ring current is not so strong, and the initial magnetic field configuration bears no magnetic island, but features a wake of bent field lines, which is smoothed out through the relaxing evolution of the magnetosphere. The relaxation time of the magnetosphere is found to be about five to six minutes, over which the ring current is reduced to about a quarter of its initial value. Before reaching a quasi-steady state, the magnetosphere is found to undergo an overshooting expansion and a subsequent contraction. Fast and slow magnetosonic waves are identified to play an important role in the relaxation toward equilibrium. Our study suggests that a sudden injection of the ring current can generate an appreciable global pulsation of the magnetosphere.

Global Evolution of the Earth's Magnetosphere in Response to a Sudden Ring Current Injection

NASA Astrophysics Data System (ADS)

No, Jincheol; Choe, Gwangson; Park, Geunseok

2014-05-01

The dynamical evolution of the Earth's magnetosphere loaded with a transiently enhanced ring current is investigated by global magnetohydrodynamic simulations. Two cases with different values of the primitive ring current are considered. In one case, the initial ring current is strong enough to create a magnetic island in the magnetosphere. The magnetic island readily reconnects with the earth-connected ambient field and is destroyed as the system approaches a steady equilibrium. In the other case, the initial ring current is not so strong, and the initial magnetic field configuration bears no magnetic island, but features a wake of bent field lines, which is smoothed out through the relaxing evolution of the magnetosphere. The relaxation time of the magnetosphere is found to be about five to six minutes, over which the ring current is reduced to about a quarter of its initial value. Before reaching a steady state, the magnetosphere is found to undergo an overshooting expansion and a subsequent contraction. Fast and slow magnetosonic waves are identified to play an important role in the relaxation toward equilibrium. Our study suggests that a sudden injection of the ring current can generate an appreciable global pulsation of the magnetosphere.

Highly Sensitive and Selective Colorimetric and Off-On Fluorescent Reversible Chemosensors for Al3+ Based on the Rhodamine Fluorophore

PubMed Central

Mergu, Naveen; Singh, Ashok Kumar; Gupta, Vinod Kumar

2015-01-01

A series of rhodamine derivatives L1–L3 have been prepared and characterized by IR, 1H-NMR, 13C-NMR and ESI-MS. These compounds exhibited selective and sensitive “turn-on” fluorescent and colorimetric responses to Al3+ in methanol. Upon the addition of Al(III), the spiro ring was opened and a metal-probe complex was formed in a 1:1 stoichiometry, as was further confirmed by ESI-MS spectroscopy. The chemo-dosimeters L1–L3 exhibited good binding constants and low detection limits towards Al(III). We also successfully demonstrate the reversibility of the metal to ligand complexation (opened ring to spirolactam ring). PMID:25897498

A novel protocol for antibiotic prophylaxis based on preoperative kidney function in patients undergoing open heart surgery under cardiopulmonary bypass.

PubMed

Odaka, Mizuho; Minakata, Kenji; Toyokuni, Hideaki; Yamazaki, Kazuhiro; Yonezawa, Atsushi; Sakata, Ryuzo; Matsubara, Kazuo

2015-08-01

This study aimed to develop and assess the effectiveness of a protocol for antibiotic prophylaxis based on preoperative kidney function in patients undergoing open heart surgery. We established a protocol for antibiotic prophylaxis based on preoperative kidney function in patients undergoing open heart surgery. This novel protocol was assessed by comparing patients undergoing open heart surgery before (control group; n = 30) and after its implementation (protocol group; n = 31) at Kyoto University Hospital between July 2012 and January 2013. Surgical site infections (SSIs) were observed in 4 control group patients (13.3 %), whereas no SSIs were observed in the protocol group patients (P < 0.05). The total duration of antibiotic use decreased significantly from 80.7 ± 17.6 h (mean ± SD) in the control group to 55.5 ± 14.9 h in the protocol group (P < 0.05). Similarly, introduction of the protocol significantly decreased the total antibiotic dose used in the perioperative period (P < 0.05). Furthermore, antibiotic regimens were changed under suspicion of infection in 5 of 30 control group patients, whereas none of the protocol group patients required this additional change in the antibiotic regimen (P < 0.05). Our novel antibiotic prophylaxis protocol based on preoperative kidney function effectively prevents SSIs in patients undergoing open heart surgery.

Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: how does vinylene carbonate play its role as an electrolyte additive?

PubMed

Wang, Yixuan; Nakamura, Shinichiro; Tasaki, Ken; Balbuena, Perla B

2002-04-24

To elucidate the role of vinylene carbonate (VC) as a solvent additive in organic polar solutions for lithium-ion batteries, reductive decompositions for vinylene carbonate (VC) and ethylene carbonate (EC) molecules have been comprehensively investigated both in the gas phase and in solution by means of density functional theory calculations. The salt and solvent effects are incorporated with the clusters (EC)nLi+(VC) (n = 0-3), and further corrections that account for bulk solvent effects are added using the polarized continuum model (PCM). The electron affinities of (EC)nLi+(VC) (n = 0-3) monotonically decrease when the number of EC molecules increases; a sharp decrease of about 20.0 kcal/mol is found from n = 0 to 1 and a more gentle variation for n > 1. For (EC)nLi+(VC) (n = 1-3), the reduction of VC brings about more stable ion-pair intermediates than those due to reduction of the EC molecule by 3.1, 6.1, and 5.3 kcal/mol, respectively. This finding qualitatively agrees with the experimental fact that the reduction potential of VC in the presence of Li salt is more negative than that of EC. The calculated reduction potentials corresponding to radical anion formation are close to the experimental potentials determined with cyclic voltammetry on a gold electrode surface (-2.67, -3.19 eV on the physical scale for VC and EC respectively vs experimental values -2.96 and -2.94 eV). Regarding the decomposition mechanisms, the VC and EC moieties undergo homolytic ring opening from their respective reduction intermediates, and the energy barrier of VC is about one time higher than that of EC (e.g., 20.1 vs 8.8 kcal/mol for (EC)2Li+(VC)); both are weakly affected by the explicit solvent molecules and by a bulk solvent represented by a continuum model. Alternatively, starting from the VC-reduction intermediate, the ring opening of the EC moiety via an intramolecular electron-transfer transition state has also been located; its barrier lies between those of EC and VC (e.g., 17.2 kcal/mol for (EC)2Li+(VC)). On the basis of these results, we suggest the following explanation about the role that VC may play as additive in EC-based lithium-ion battery electrolytes; VC is initially reduced to a more stable intermediate than that from EC reduction. One possibility then is that the reduced VC decomposes to form a radical anion via a barrier of about 20 kcal/mol, which undergoes a series of reactions to give rise to more active film-forming products than those resulting from EC reduction, such as lithium divinylene dicarbonate, Li-C carbides, lithium vinylene dicarbonate, R-O-Li compound, and even oligomers with repeated vinylene and carbonate-vinylene units. Another possibility starting from the VC-reduction intermediate is that the ring opening occurs on the unreduced EC moiety instead of being on the reduced VC, via an intramolecular electron transfer transition state, the energy barrier of which is lower than that of the former, in which VC just helps the intermediate formation and is not consumed. The factors that determine the additive functioning mechanism are briefly discussed, and consequently a general rule for the selection of electrolyte additive is proposed.

Type II GaSb quantum ring solar cells under concentrated sunlight.

PubMed

Tsai, Che-Pin; Hsu, Shun-Chieh; Lin, Shih-Yen; Chang, Ching-Wen; Tu, Li-Wei; Chen, Kun-Cheng; Lay, Tsong-Sheng; Lin, Chien-chung

2014-03-10

A type II GaSb quantum ring solar cell is fabricated and measured under the concentrated sunlight. The external quantum efficiency confirms the extended absorption from the quantum rings at long wavelength coinciding with the photoluminescence results. The short-circuit current of the quantum ring devices is 5.1% to 9.9% more than the GaAs reference's under various concentrations. While the quantum ring solar cell does not exceed its GaAs counterpart in efficiency under one-sun, the recovery of the open-circuit voltages at higher concentration helps to reverse the situation. A slightly higher efficiency (10.31% vs. 10.29%) is reported for the quantum ring device against the GaAs one.

Kinetics and inhibition of cyclomaltodextrinase from alkalophilic Bacillus sp. I-5.

PubMed

Kim, M J; Park, W S; Lee, H S; Kim, T J; Shin, J H; Yoo, S H; Cheong, T K; Ryu, S; Kim, J C; Kim, J W; Moon, T W; Robyt, J F; Park, K H

2000-01-01

The cyclomaltodextrinase from alkalophilic Bacillus sp. I-5 (CDase I-5) was expressed in Escherichia coli and the purified enzyme was used for characterization of the enzyme action. The hydrolysis products were monitored by both HPLC and high-performance ion chromatography analysis that enable the kinetic analysis of the cyclomaltodextrin (CD)-degrading reaction. Analysis of the kinetics of cyclomaltodextrin hydrolysis by CDase I-5 indicated that ring-opening of the cyclomaltodextrin was the major limiting step and that CDase I-5 preferentially degraded the linear maltodextrin chain by removing the maltose unit. The substrate binding affinity of the enzyme was almost same for those of cyclomaltodextrins while the rate of ring-opening was the fastest for cyclomaltoheptaose. Acarbose and methyl 6-amino-6-deoxy-alpha-d-glucopyranoside were relatively strong competitive inhibitors with K(i) values of 1.24 x 10(-3) and 8.44 x 10(-1) mM, respectively. Both inhibitors are likely to inhibit the ring-opening step of the CD degradation reaction. Copyright 2000 Academic Press.

Effect of initiators on synthesis of poly(L-lactide) by ring opening polymerization

NASA Astrophysics Data System (ADS)

Pholharn, D.; Srithep, Y.; Morris, J.

2017-06-01

We studied the effect of several aliphatic alcohols, including1-dodecanol, 1-octanol and methanol, as initiators on synthesis of poly(L-lactide) (PLLA) by ring opening polymerization. The reaction starts with L-lactide monomer and uses stannous octoate as catalyst. Fourier transform infrared spectroscopy and X-ray diffraction analysis verified that PLLAs were produced successfully. Weight, number average molecular weight and polydispersity index of PLLAs were measured by gel permeation chromatography. The PLLA initiated by methanol (PLLA-Meth) presented the highest molecular weight and yield percent. From differential scanning calorimetry, PLLA-Meth showed the highest melting temperature at ∼167°C, crystallization temperature at 110°C and degree of crystallinity 80%. The thermal stability was assessed by thermogravimetric analysis: this confirmed that PLLA-Meth was superior with the highest degradation temperature compared to PLLA initiated by other initiators. We concluded that methanol was the most appropriate initiator for PLLA synthesis by ring opening polymerization.

The role of annular dimension and annuloplasty in tricuspid aortic valve repair.

PubMed

de Kerchove, Laurent; Mastrobuoni, Stefano; Boodhwani, Munir; Astarci, Parla; Rubay, Jean; Poncelet, Alain; Vanoverschelde, Jean-Louis; Noirhomme, Philippe; El Khoury, Gebrine

2016-02-01

Valve sparing reimplantation can improve the durability of bicuspid aortic valve repair compared with subcommissural annuloplasty, especially in patients with a large basal ring. This study analyses the effect of basal ring size and annuloplasty on valve repair in the setting of a tricuspid aortic valve. From 1995 to 2013, 382 patients underwent elective tricuspid aortic valve repair. We included only those undergoing subcommissural annuloplasty, valve sparing reimplantation or no annuloplasty and in whom intraoperative transoesophageal echocardiography images were available for retrospective pre- and post-repair basal ring measurements (n = 323, subcommissural annuloplasty: 146, valve sparing reimplantation: 154, no annuloplasty: 23). In a subgroup of patients with available echocardiographic images, basal ring was retrospectively measured at the latest follow-up or prior to reoperation. subcommissural annuloplasty and valve sparing reimplantation were compared after matching for degree of aortic regurgitation and root size. All three groups differed significantly for most of preoperative characteristics. Hospital mortality was 0.9%. The median follow-up was 4.7 years. At 8 years, overall survival was 80 ± 5%. Freedom from reoperation and freedom from aortic regurgitation >1+ were 92 ± 5% and 71 ± 8%, respectively. In multivariate analysis, predictors of aortic regurgitation >1+ were left ventricular end-diastolic diameter (P = 0.003), cusp repair (P = 0.006), body surface area (P = 0.01) and subcommissural annuloplasty (P = 0.05). In subcommissural annuloplasty, freedom from aortic regurgitation >1+ was lower for patients with basal ring ≥28 mm compared with patients with basal ring <28 mm (P = 0.0001). In valve sparing reimplantation, freedom from aortic regurgitation >1+ was independent of basal ring size (P = 0.38). In matched comparison between subcommissural annuloplasty and valve sparing reimplantation, freedom from aortic regurgitation >1+ was not significantly different (P = 0.06), but in patients with basal ring ≥28 mm, valve sparing reimplantation was superior to subcommissural annuloplasty (P = 0.04). Despite similar intraoperative reduction in basal ring size in subcommissural annuloplasty and valve sparing reimplantation, patients with subcommissural annuloplasty exhibited greater increase in basal ring size during the follow-up compared with the valve sparing reimplantation group (P < 0.001). As with a bicuspid aortic valve, a large basal ring predicts recurrence of aortic regurgitation in patients with tricuspid aortic valve undergoing repair with the subcommissural annuloplasty technique. This recurrence is caused by basal ring dilatation over time after subcommissural annuloplasty. With the valve sparing reimplantation technique, large basal ring did not predict aortic regurgitation recurrence, as prosthetic-based circumferential annuloplasty displayed better stability over time. Stable circumferential annuloplasty is recommended in tricuspid aortic valve repair whenever the basal ring size is ≥28 mm. © The Author 2015. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.

Mass Spectra of Some Perfluoroalkyl and Perfluoroalkylether Substituted 1,2,4-Oxadiazoles

NASA Technical Reports Server (NTRS)

Paciorek, Kazimiera J. L.; Nakahara, James H.; Kratzer, Reinhold H.; Rosser, Robert W.

1977-01-01

Electron impact fragmentation patterns were obtained for 1,4-bis[(5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl- benzene, its perfluoroalkylether substituted analogue, 3,5-bis(perfluoroalkyl)-, 3,5-bis(perfluoroalkylether)- and 3-perfluoroalkylether-5-perfluoroalkyl-1,2,4-oxadiazoles. In the compounds containing the phenylene group the molecular ion constituted the base peak; the main process was the breakdown of the oxadiazole ring with concurrent liberation of the perfluoroalkyl or perfluoroalkylether nitrile molecule; cleavage of the fluorinated chain ot to the oxadiazole ring was found to take place to a considerable degree. In the perfluorinated 1,2,4-oxadiazoles cleavage beta to the oxadiazole ring occurred preferentially; fragmentation of the ring itself took place to a limited degree only. The 3-perfluoroalkylether-5-perfluoroalkyl-1,2,4-oxadiazole appeared to undergo the primary beta-cleavage exclusively at the perfluoroalkylether sidechain.

Kinetics and thermochemistry of 2,5-dimethyltetrahydrofuran and related oxolanes: next next-generation biofuels.

PubMed

Simmie, John M

2012-05-10

The enthalpies of formation, entropies, specific heats at constant pressure, enthalpy functions, and all carbon-hydrogen and carbon-methyl bond dissociation energies have been computed using high-level methods for the cyclic ethers (oxolanes) tetrahydrofuran, 2-methyltetrahydrofuran, and 2,5-dimethyltetrahydrofuran. Barrier heights for hydrogen-abstraction reactions by hydrogen atoms and the methyl radical are also computed and shown to correlate with reaction energy change. The results show a pleasing consistency and considerably expands the available data for these important compounds. Abstraction by ȮH is accompanied by formation of both pre- and postreaction weakly bound complexes. The resulting radicals formed after abstraction undergo ring-opening reactions leading to readily recognizable intermediates, while competitive H-elimination reactions result in formation of dihydrofurans. Formation enthalpies of all 2,3- and 2,5-dihydrofurans and associated radicals are also reported. It is probable that the compounds at the center of this study will be relatively clean-burning biofuels, although formation of intermediate aldehydes might be problematic.

Interaction of vortex rings with multiple permeable screens

NASA Astrophysics Data System (ADS)

Musta, Mustafa N.; Krueger, Paul S.

2014-11-01

Interaction of a vortex ring impinging on multiple permeable screens orthogonal to the ring axis was studied to experimentally investigate the persistence and decay of vortical structures inside the screen array using digital particle image velocimetry in a refractive index matched environment. The permeable screens had porosities (open area ratios) of 83.8%, 69.0%, and 55.7% and were held by a transparent frame that allowed the screen spacing to be changed. Vortex rings were generated using a piston-cylinder mechanism at nominal jet Reynolds numbers of 1000, 2000, and 3000 with piston stroke length-to-diameter ratios of 2 and 3. The interaction of vortex rings with the porous medium showed a strong dependence of the overall flow evolution on the screen porosity, with a central flow being preserved and vortex ring-like structures (with smaller diameter than the primary vortex ring) being generated near the centerline. Due to the large rod size used in the screens, immediate reformation of the transmitted vortex ring with size comparable to the primary ring (as has been observed with thin screens) was not observed in most cases. Since the screens have lower complexity and high open area ratios, centerline vortex ring-like flow structures formed with comparable size to the screen pore size and penetrated through the screens. In the case of low porosity screens (55.7%) with large screen spacing, re-emergence of large scale (large separation), weak vortical structures/pairs (analogous to a transmitted vortex ring) was observed downstream of the first screen. Additional smaller scale vortical structures were generated by the interaction of the vortex ring with subsequent screens. The size distribution of the generated vortical structures were shown to be strongly affected by porosity, with smaller vortical structures playing a stronger role as porosity decreased. Finally, porosity significantly affected the decay of total energy, but the effect of screen spacing decreased as porosity decreased.

Progesterone bioavailability with a progesterone-releasing silicone vaginal ring in IVF candidates.

PubMed

Dragonas, C; Maltaris, T; Binder, H; Kat, M; Mueller, A; Cupisti, S; Hoffmann, I; Beckmann, M W; Dittrich, Ralf

2007-06-27

A vaginal ring made of silicone polymers and barium sulfate, and containing 1 g of pure micronized progesterone, was developed for luteal supplementation in women undergoing cycles of in vitro fertilization (IVF). The ring, modeled on the Estring, was designed as a means of providing continuous intravaginal delivery of progesterone. Bioavailability of progesterone in the blood was demonstrated for 24 hours in IVF candidates who had an endogenous progesterone deficiency after treatment with gonadotropin-releasing hormone (GnRH) analogues. After the first 4 h of increasing release of progesterone from the ring (with mean serum levels of 1.39 +/- 0.8 ng/ml after 4 h), only a slight increase in serum progesterone levels (with a mean peak of 1.5 +/- 0.45 ng/ml after 24 h) was observed during the rest of the test period. Gonadotropin levels were not affected after insertion of the ring. The ring was well tolerated by the patients. The maximum serum progesterone level was lower in comparison with other forms of progesterone application, but it should be sufficiently high, due to the uterine first-pass effect. This study demonstrated that progesterone administration through a silicone ring for luteal support is feasible in IVF treatment. As the vaginal ring is very well tolerated by the patients, these findings may encourage the pharmaceutical industry to design an appropriate progesterone ring for luteal support.

Effects of repeated gas sterilization on closure rates of ameroid ring constrictors in vitro.

PubMed

Kimberlin, William W; Wardlaw, Jennifer L; Madsen, Richard W

2016-01-01

To determine the effect of repeated gas sterilization on rate of closure of ameroid ring constrictors in vitro. Twenty-four 3.5-mm ameroid ring constrictors. Ameroid ring constrictors were allocated to 1 of 4 treatment groups (6/group) to undergo gas sterilization 0, 1, 5, or 10 times. After sterilization, constrictors were incubated in canine plasma at a protein concentration of 3 g/dL for 27 days. A digital camera was used to obtain images of the constrictors prior to and at various points during incubation, and lumen diameter was measured. Mean ± SD percentage of lumen closure for all groups of ameroid ring constrictors combined was 85.2 ± 1.6% at day 0 (prior to plasma incubation) and 95.4 ± 0.8% at day 27. Mean lumen area was 3.64 ± 0.43 mm(2) (95% confidence interval, 2.67 to 4.77 mm(2)) at day 0 and 1.32 ± 0.25 mm(2) (95% confidence interval, 0.76 to 2.04 mm(2)) at day 27. None of the ameroid ring constrictors had closed completely by day 27. Overall closure rates for ameroid ring constrictors appeared to be unaffected by repeated gas sterilization up to 10 times. Findings suggested that veterinary surgeons can resterilize ameroid ring constrictors up to 10 times with confidence that ring properties would remain suitable for clinical use.

Protein Phosphatase 1ß Limits Ring Canal Constriction during Drosophila Germline Cyst Formation

PubMed Central

Yamamoto, Shinya; Bayat, Vafa; Bellen, Hugo J.; Tan, Change

2013-01-01

Germline cyst formation is essential for the propagation of many organisms including humans and flies. The cytoplasm of germline cyst cells communicate with each other directly via large intercellular bridges called ring canals. Ring canals are often derived from arrested contractile rings during incomplete cytokinesis. However how ring canal formation, maintenance and growth are regulated remains unclear. To better understand this process, we carried out an unbiased genetic screen in Drosophila melanogaster germ cells and identified multiple alleles of flapwing (flw), a conserved serine/threonine-specific protein phosphatase. Flw had previously been reported to be unnecessary for early D. melanogaster oogenesis using a hypomorphic allele. We found that loss of Flw leads to over-constricted nascent ring canals and subsequently tiny mature ring canals, through which cytoplasmic transfer from nurse cells to the oocyte is impaired, resulting in small, non-functional eggs. Flw is expressed in germ cells undergoing incomplete cytokinesis, completely colocalized with the Drosophila myosin binding subunit of myosin phosphatase (DMYPT). This colocalization, together with genetic interaction studies, suggests that Flw functions together with DMYPT to negatively regulate myosin activity during ring canal formation. The identification of two subunits of the tripartite myosin phosphatase as the first two main players required for ring canal constriction indicates that tight regulation of myosin activity is essential for germline cyst formation and reproduction in D. melanogaster and probably other species as well. PMID:23936219

Relaxed open mouth as a playful signal in wild ring-tailed lemurs.

PubMed

Palagi, Elisabetta; Norscia, Ivan; Spada, Giulia

2014-11-01

Play signals are commonly used by animals to communicate their playful motivation and to limit the risk that rough acts are misunderstood by playmates. The relaxed open mouth is the most common facial expression performed during play in many mammals and represents the ritualized version of the movement anticipating a play bite. The signaling nature of this expression has been proven in many haplorrhine species but never demonstrated in strepsirrhines. Our purpose was assessing whether, also in strepsirrhines, the relaxed open mouth has an actual communicative function. We studied wild ring-tailed lemurs (Lemur catta), characterized by highly social habits including intense playful interactions. They largely use playful signals, mostly performed with the black and white tail. The signaling function of the tail (tail play) has been widely demonstrated. We analyzed both tail play and the relaxed open mouth to verify how their distribution is affected by different play variables (e.g., play session symmetry, number of play mates, previous use of the same pattern). Indeed, ring-tailed lemurs use the relaxed open mouth as a communicative signal during play. Relaxed open mouth was more frequent during unbalanced interactions showing the highest asymmetry in the patterns performed by the two players (offensive/neutral). Compared to tail play, relaxed open mouth was more frequent during dyadic than polyadic interactions and, as a highly directional signal, it was more frequently replicated by the play mate. Therefore, the relaxed open mouth needs to be performed face-to-face so that signal detection can be optimized. Similar to previous findings in monkeys and apes, the relaxed open mouth in lemurs seems to be a ritualized signal used to engage and, perhaps, sustain playful interaction. © 2014 Wiley Periodicals, Inc.

Mechanistic Study on Electronic Excitation Dissociation of the Cellobiose-Na+ Complex

NASA Astrophysics Data System (ADS)

Huang, Yiqun; Pu, Yi; Yu, Xiang; Costello, Catherine E.; Lin, Cheng

2016-02-01

The recent development of electron activated dissociation (ExD) techniques has opened the door for high-throughput, detailed glycan structural elucidation. Among them, ExD methods employing higher-energy electrons offer several advantages over low-energy electron capture dissociation (ECD), owing to their applicability towards chromophore-labeled glycans and singly charged ions, and ability to provide more extensive structural information. However, a lack of understanding of these processes has hindered rational optimization of the experimental conditions for more efficient fragmentation as well as the development of informatics tools for interpretation of the complex glycan ExD spectra. Here, cellobiose-Na+ was used as the model system to investigate the fragmentation behavior of metal-adducted glycans under irradiation of electrons with energy exceeding their ionization potential, and served as the basis on which a novel electronic excitation dissociation (EED) mechanism was proposed. It was found that ionization of the glycan produces a mixture of radical cations and ring-opened distonic ions. These distonic ions then capture a low-energy electron to produce diradicals with trivial singlet-triplet splitting, and subsequently undergo radical-induced dissociation to produce a variety of fragment ions, the abundances of which are influenced by the stability of the distonic ions from which they originate.

Releasing the cohesin ring: A rigid scaffold model for opening the DNA exit gate by Pds5 and Wapl.

PubMed

Ouyang, Zhuqing; Yu, Hongtao

2017-04-01

The ring-shaped ATPase machine, cohesin, regulates sister chromatid cohesion, transcription, and DNA repair by topologically entrapping DNA. Here, we propose a rigid scaffold model to explain how the cohesin regulators Pds5 and Wapl release cohesin from chromosomes. Recent studies have established the Smc3-Scc1 interface as the DNA exit gate of cohesin, revealed a requirement for ATP hydrolysis in ring opening, suggested regulation of the cohesin ATPase activity by DNA and Smc3 acetylation, and provided insights into how Pds5 and Wapl open this exit gate. We hypothesize that Pds5, Wapl, and SA1/2 form a rigid scaffold that docks on Scc1 and anchors the N-terminal domain of Scc1 (Scc1N) to the Smc1 ATPase head. Relative movements between the Smc1-3 ATPase heads driven by ATP and Wapl disrupt the Smc3-Scc1 interface. Pds5 binds the dissociated Scc1N and prolongs this open state of cohesin, releasing DNA. We review the evidence supporting this model and suggest experiments that can further test its key principles. © 2017 WILEY Periodicals, Inc.

Finite spaces and schemes

NASA Astrophysics Data System (ADS)

Sancho de Salas, Fernando

2017-12-01

A ringed finite space is a ringed space whose underlying topological space is finite. The category of ringed finite spaces contains, fully faithfully, the category of finite topological spaces and the category of affine schemes. Any ringed space, endowed with a finite open covering, produces a ringed finite space. We introduce the notions of schematic finite space and schematic morphism, showing that they behave, with respect to quasi-coherence, like schemes and morphisms of schemes do. Finally, we construct a fully faithful and essentially surjective functor from a localization of a full subcategory of the category of schematic finite spaces and schematic morphisms to the category of quasi-compact and quasi-separated schemes.

Ring dark and antidark solitons in nonlocal media.

PubMed

Horikis, Theodoros P; Frantzeskakis, Dimitrios J

2016-02-01

Ring dark and antidark solitons in nonlocal media are found. These structures have, respectively, the form of annular dips or humps on top of a stable CW background, and exist in a weak or strong nonlocality regime, defined by the sign of a characteristic parameter. It is demonstrated analytically that these solitons satisfy an effective cylindrical Kadomtsev-Petviashvili (aka Johnson's) equation and, as such, can be written explicitly in closed form. Numerical simulations show that they propagate undistorted and undergo quasi-elastic collisions, attesting to their stability properties.

Remarkable regioselective position-10 bromination of bacteriopyropheophorbide-a and ring-B reduced pyropheophorbide-a.

PubMed

Ethirajan, Manivannan; Joshi, Penny; William, White H; Ohkubo, Kei; Fukuzumi, Shunichi; Pandey, Ravindra K

2011-04-15

Both bacteriopyropheophorbide-a and ring-B reduced pyropheophorbide-a on reacting with NBS (N-bromosuccinamide) undergo electrophilic bromination to provide 10-bromo analogs. The electronic nature of the substituents present at position-3 did not make any difference in the regioselective outcome of the brominated products. These relatively stable brominated chlorins and bacteriochlorins provide an easy way of introducing a wide variety of functionalities, which could be extremely useful in developing improved agents for biomedical applications and supramolecular chemistry. © 2011 American Chemical Society

Activation of a Carbon-Oxygen Bond of Benzofuran by Precoordination of Manganese to the Carbocyclic Ring: A Model for Hydrodeoxygenation.

PubMed

Zhang; Watson; Dullaghan; Gorun; Sweigart

1999-08-01

Stable unsaturated heterocycles such as benzofuran are difficult to remove from petroleum by conventional catalytic hydrotreating. However, in a model system, coordination of Mn(CO)(3)(+) to the aromatic ring of benzofuran activates the C-O bond towards insertion of [Pt(PPh(3))(2)] [Eq. (1)]. The insertion is preceded by precoordination to the furan C=C bond; thus, the 2,3-dihydro analogue of 1, which lacks this double bond, does not undergo insertion of the Pt moiety.

Revisiting the Fully Automated Double-Ring Infiltrometer Using Open-Source Electronics

EPA Science Inventory

The double-ring infiltrometer (DRI) is commonly used for measuring soil hydraulic conductivity. However, constant-head DRI tests typically involve the use of Mariotte tubes, which can be problematic to set-up, and time-consuming to maintain and monitor during infiltration tests....

CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings

DOE PAGES

Schmidt, Joel E.; Xie, Dan; Rea, Thomas; ...

2015-01-23

A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [4 25 46 2] mtw building unit and a previously unreported [4 45 2] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected withmore » oval 8-rings (2.9 Å × 5.5 Å opening) through medium-sized cavities (~7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants.« less

Incorporating 3D laparoscopy for the management of locally advanced cervical cancer: a comparison with open surgery.

PubMed

Raspagliesi, Francesco; Bogani, Giorgio; Martinelli, Fabio; Signorelli, Mauro; Chiappa, Valentina; Scaffa, Cono; Sabatucci, Ilaria; Adorni, Marco; Lorusso, Domenica; Ditto, Antonino

2016-08-03

To test the effects of the implementation of 3D laparoscopic technology for the execution of nerve-sparing radical hysterectomy. Thirty patients undergoing nerve-sparing radical hysterectomy via 3D laparoscopic (3D-LNSRH, n = 10) or open surgery (NSRH, n = 20) were studied prospectively. No significant differences were observed in baseline patient characteristics. Operative times were similar between groups. We compared the first 10 patients undergoing 3D-LNSRH with the last 20 patients undergoing NSRH. Baseline characteristics were similar between groups (p>0.2). Patients undergoing 3D-LNSRH had longer operative time (264.4 ± 21.5 vs 217.2 ± 41.0 minutes; p = 0.005), lower blood loss (53.4 ± 26.1 vs 177.7 ± 96.0 mL; p<0.001), and shorter length of hospital stay (4.3 ± 1.2 vs 5.4 ± 0.7 days; p = 0.03) in comparison to patients undergoing open abdominal procedures. No intraoperative complication occurred. One (10%) patient had conversion to open surgery due to technical difficulties and the inability to insert the uterine manipulator. A trend towards higher complication (grade 2 or worse) rate was observed for patients undergoing NSRH in comparison to 3D-LNSRH (p = 0.06). Considering only severe complications (grade 3 or worse), no difference was observed (0/10 vs 2/20; p = 0.54). 3D-laparoscopic nerve-sparing radical hysterectomy is a safe and effective procedure. The implementation of 3D laparoscopic technology allows the execution of challenging operations via minimally invasive surgery, thus reducing open abdominal procedure rates. Further large prospective studies are warranted.

Prospective evaluation of short-term impact and recovery of health related quality of life in men undergoing robotic assisted laparoscopic radical prostatectomy versus open radical prostatectomy.

PubMed

Miller, Javier; Smith, Angela; Kouba, Erik; Wallen, Eric; Pruthi, Raj S

2007-09-01

In the last few years there have been increasing claims that robotic assisted laparoscopic radical prostatectomy decreases short-term morbidity in patients undergoing surgical treatment for prostate cancer. However, there is surprisingly little objective evidence to support this point, which is often used to market the procedure to patients. To address this issue we prospectively evaluated patients undergoing open and robotic assisted laparoscopic radical prostatectomy at baseline and weekly through the postoperative period using a validated questionnaire. A total of 162 men undergoing radical prostatectomy, including open radical prostatectomy in 120 and robotic assisted laparoscopic radical prostatectomy in 42, for clinically localized prostate cancer completed the SF-12, version 2 Physical and Mental Health Survey Acute Form preoperatively and each week postoperatively for 6 weeks. Physical and Mental Component Scores were calculated from the questionnaires at each time point. Comparisons between the 2 surgical approaches were made at each time point. No significant differences were seen between the open and robotic assisted laparoscopic radical prostatectomy groups with regard to patient age, clinical stage or preoperative prostate specific antigen. Mean surgical blood loss was significantly higher in the open group compared to that in the robotic assisted laparoscopic group. Physical Component Scores in the robotic assisted laparoscopic group were significantly higher than those in the open cohort beginning postoperative week 1 and extending through week 6. On statistical extrapolation Physical Component Scores returned to baseline between weeks 5 and 6 postoperatively in the robotic assisted laparoscopic group and between weeks 6 and 7 in the open group. Mental Component Score scores were not statistically different between the groups except preoperatively. This study helps prospectively define short-term health related quality of life in patients undergoing robotic assisted laparoscopic vs open radical prostatectomy. Higher physical scores were seen in the robotic assisted laparoscopic group than the open group beginning postoperative week 1 and continuing weekly throughout the 6-week study period. Physical Component Score scores returned to baseline sooner in the robotic assisted laparoscopic group than in the open group.

A numerical investigation into the dynamics of Uranus' mu-ring

NASA Astrophysics Data System (ADS)

Kumar, K.; De Pater, I.; Showalter, M.

2017-12-01

Showalter and Lissauer (2006) reported the discovery of the nu-ring and mu-ring, located beyond Uranus' main ring system. Both faint, dusty rings are located interior to the large classical moons and were observed by co-adding Hubble Space Telescope (HST) images. The peak radial brightness of the mu-ring coincides with the orbit of Mab, a small moon discovered in 2003 by Showalter and Lissauer. Observations of the Mab/mu-ring system indicate a highly dynamic environment. The motion of Mab was determined to be anomalous over short time scales, with large position deviations computed with respect to a fitted precessing Keplerian ellipse. Numerical simulations to survey the possible cause of this anomalous motion hint at the possibility of interactions with a distribution of tens of bodies, below the HST detection threshold, in the neighborhood of Mab (Kumar, et al., 2016). Analysis of the mu-ring data has led to the discovery of peculiar features, leading to open questions about dust dynamics in the associated region around Uranus. Observations obtained using the HST and Keck telescopes reveal that the μ-ring is blue, indicative of a pre-dominance of sub-micron-sized particles (de Pater, et al., 2006). The only other blue ring detected in the Solar System is Saturn's E-ring, generated by plumes on Enceladus' south pole. The origin of the mu-ring however remains an open area of research. Mab is thought to be the likely source of the material in the mu-ring, with micrometeoroid impacts releasing material into orbit around Uranus, much like Jupiter's faint rings are regenerated by companion (small) moons (Burns et al. 1999). The mu-ring's blue color suggests however that there is an unknown mechanism at play that hides or removes large particles from the expected size distribution. We present results from a numerical investigation into the effects of gravitational and non-gravitational forces on the evolution of mu-ring dust particles. Following on from previous studies (Sfair and Giuliatti Winter, 2009; Sfair and Giuliatti Winter, 2012; Sfair, 2013; Hsu, et al., 2014), we generate statistics to provide insight into the lifetime of mu-ring dust. We utilize these results to analyze the possibility that the steep size distribution results from size-based sorting effects due to the natural environment.

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

PubMed

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Catalysts for CO2/epoxide ring-opening copolymerization

PubMed Central

Trott, G.; Saini, P. K.; Williams, C. K.

2016-01-01

This article summarizes and reviews recent progress in the development of catalysts for the ring-opening copolymerization of carbon dioxide and epoxides. The copolymerization is an interesting method to add value to carbon dioxide, including from waste sources, and to reduce pollution associated with commodity polymer manufacture. The selection of the catalyst is of critical importance to control the composition, properties and applications of the resultant polymers. This review highlights and exemplifies some key recent findings and hypotheses, in particular using examples drawn from our own research. PMID:26755758

Method of polymerizing exo-methylene cyclic organic compounds using homogeneous ring-opening catalysts

DOEpatents

Marks, Tobin J.; Yang, Xinmin; Jia, Li

1994-01-01

The regiospecific (1,2-Me.sub.2 C.sub.5 H.sub.3).sub.2 ZrMe.sup.+ MeB(C.sub.6 F.sub.5).sub.3.sup.- mediated ring-opening polymerization of methylenecyclobutane and its copolymerization with ethylene to polyolefins of microstructure--{CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.2)]--.sub.n and {--[CH.sub.2 CHR]--.sub.x [CH.sub.2 CH.sub.2 CH.sub.2 C(CH.sub.2)]--.sub.y }.sub.n' respectively, is disclosed.

Chemical Sensors Based on Optical Ring Resonators

NASA Technical Reports Server (NTRS)

Homer, Margie; Manfreda, Allison; Mansour, Kamjou; Lin, Ying; Ksendzov, Alexander

2005-01-01

Chemical sensors based on optical ring resonators are undergoing development. A ring resonator according to this concept is a closed-circuit dielectric optical waveguide. The outermost layer of this waveguide, analogous to the optical cladding layer on an optical fiber, is a made of a polymer that (1) has an index of refraction lower than that of the waveguide core and (2) absorbs chemicals from the surrounding air. The index of refraction of the polymer changes with the concentration of absorbed chemical( s). The resonator is designed to operate with relatively strong evanescent-wave coupling between the outer polymer layer and the electromagnetic field propagating along the waveguide core. By virtue of this coupling, the chemically induced change in index of refraction of the polymer causes a measurable shift in the resonance peaks of the ring. In a prototype that has been used to demonstrate the feasibility of this sensor concept, the ring resonator is a dielectric optical waveguide laid out along a closed path resembling a racetrack (see Figure 1). The prototype was fabricated on a silicon substrate by use of standard techniques of thermal oxidation, chemical vapor deposition, photolithography, etching, and spin coating. The prototype resonator waveguide features an inner cladding of SiO2, a core of SixNy, and a chemical-sensing outer cladding of ethyl cellulose. In addition to the ring Chemical sensors based on optical ring resonators are undergoing development. A ring resonator according to this concept is a closed-circuit dielectric optical waveguide. The outermost layer of this waveguide, analogous to the optical cladding layer on an optical fiber, is a made of a polymer that (1) has an index of refraction lower than that of the waveguide core and (2) absorbs chemicals from the surrounding air. The index of refraction of the polymer changes with the concentration of absorbed chemical( s). The resonator is designed to operate with relatively strong evanescent-wave coupling between the outer polymer layer and the electromagnetic field propagating along the waveguide core. By virtue of this coupling, the chemically induced change in index of refraction of the polymer causes a measurable shift in the resonance peaks of the ring. In a prototype that has been used to demonstrate the feasibility of this sensor concept, the ring resonator is a dielectric optical waveguide laid out along a closed path resembling a racetrack (see Figure 1). The prototype was fabricated on a silicon substrate by use of standard techniques of thermal oxidation, chemical vapor deposition, photolithography, etching, and spin coating. The prototype resonator waveguide features an inner cladding of SiO2, a core of SixNy, and a chemical-sensing outer cladding of ethyl cellulose. In addition to the ring res

Density Waves in Saturn's Rings from Cassini Radio Occultations

NASA Astrophysics Data System (ADS)

French, R. G.; Rappaport, N. J.; Marouf, E. A.; McGhee, C. A.

2005-12-01

The Cassini Radio Science Team conducted a set of optimized diametric occultations by Saturn and its rings from May to September 2005, providing 11 separate probes of Saturn's ionosphere and atmosphere, and 12 optical depth profiles of the complete ring system. Each event was observed by the stations of the Deep Space Net (DSN) at three radio frequencies (S, X, Ka bands, with corresponding wavelengths of ? = 13, 3.6, and 0.9 cm). Very accurate pointing by the spacecraft and ground antennas resulted in stable baseline signal levels, and the relatively large ring opening angle (B=19-25°) permitted us to probe even quite dense ring regions with excellent SNR. The RSS occultation technique enables us to recover very fine detailed radial structure by correcting for diffraction effects. Multiple occultation chords, covering a variety of ring longitudes and ring opening angles, reveal the structure of the rings in remarkable detail, including density and bending waves, satellite wakes, and subtle variations at the 100-m radius scale. Janus and Epimetheus are responsible for a particularly rich set of density waves, and their coorbital interactions result in a complex interplay of time-variable ring structure over the 8-year libration period of the two satellites. We compare the first-order 2:1, 4:3, 5:4, and 6:5 coorbital density waves from multiple occultation chords to linear density wave models based on a dynamical model of the orbital exchange between the moons. From the observed dispersion relation of the wave crests, we infer the surface mass density and eccentricity gradient of particle streamlines, and match the detailed shapes of the wave crests using a non-linear analysis. Second-order coorbital features are also evident, and there are even hints of third-order density waves in the high SNR radio occultation data.

Eosinophilic esophagitis prevalence in an adult population undergoing upper endoscopy in southeastern Mexico.

PubMed

De la Cruz-Patiño, E; Ruíz Juárez, I; Meixueiro Daza, A; Grube Pagola, P; Roesch-Dietlen, F; Remes-Troche, J M

2015-01-01

Eosinophilic esophagitis (EoE) prevalence fluctuates according to the population studied and varies from 0.4% in an open population to 6.5% in subjects with esophageal symptoms. Even though this entity has been described in North American and European populations, it is still considered an 'unusual' condition in Latin America. The study aimed to determine EoE prevalence in patients undergoing elective endoscopy in a tertiary referral center in southeastern Mexico. Consecutive patients were evaluated that had been referred to the Medical and Biological Research Institute, Veracruz, Mexico, for upper endoscopy due to gastrointestinal symptoms. Demographic variables and symptoms were analyzed in all the cases. Eight mucosal biopsies of the esophagus (four proximal and four distal) were obtained and were reviewed by a blinded pathologist. Histological diagnosis was established when the mean eosinophil count at a large magnification was ≥15. A total of 235 subjects (137 women, 51.16 years) were evaluated, and EoE prevalence was 1.7% (4/235 95% confidence interval 0.2-3.6%). In all four cases, pH test were normal. Among patients with histological diagnosis of EoE, a greater number of patients with a past history of asthma (50% vs. 19.3%, P = 0.04) and a tendency for a greater frequency of dysphagia (50% vs. 25%, P = 0.10). There were no differences in the endoscopic findings (rings, grooves, plaques, or stricture) when compared with the patients presenting with erosive esophagitis. EoE prevalence among patients undergoing upper endoscopy from southeastern Mexico was 1.7%, which can be regarded as intermediate to low. © 2014 International Society for Diseases of the Esophagus.

Development of a small prototype for a proof-of-concept of OpenPET imaging

NASA Astrophysics Data System (ADS)

Yamaya, Taiga; Yoshida, Eiji; Inaniwa, Taku; Sato, Shinji; Nakajima, Yasunori; Wakizaka, Hidekatsu; Kokuryo, Daisuke; Tsuji, Atsushi; Mitsuhashi, Takayuki; Kawai, Hideyuki; Tashima, Hideaki; Nishikido, Fumihiko; Inadama, Naoko; Murayama, Hideo; Haneishi, Hideaki; Suga, Mikio; Kinouchi, Shoko

2011-02-01

The OpenPET geometry is our new idea to visualize a physically opened space between two detector rings. In this paper, we developed the first small prototype to show a proof-of-concept of OpenPET imaging. Two detector rings of 110 mm diameter and 42 mm axial length were placed with a gap of 42 mm. The basic imaging performance was confirmed through phantom studies; the open imaging was realized at the cost of slight loss of axial resolution and 24% loss of sensitivity. For a proof-of-concept of PET image-guided radiation therapy, we carried out the in-beam tests with 11C radioactive beam irradiation in the heavy ion medical accelerator in Chiba to visualize in situ distribution of primary particles stopped in a phantom. We showed that PET images corresponding to dose distribution were obtained. For an initial proof-of-concept of real-time multimodal imaging, we measured a tumor-inoculated mouse with 18F-FDG, and an optical image of the mouse body surface was taken during the PET measurement by inserting a digital camera in the ring gap. We confirmed that the tumor in the gap was clearly visualized. The result also showed the extension effect of an axial field-of-view (FOV); a large axial FOV of 126 mm was obtained with the detectors that originally covered only an 84 mm axial FOV. In conclusion, our initial imaging studies showed promising performance of the OpenPET.

A Study of Small Satellites Captured in Corotation Resonance

NASA Astrophysics Data System (ADS)

Santos Araújo, Nilton Carlos; Vieira Neto, E.

2013-05-01

Abstract (2,250 Maximum Characters): Currently we find in the solar system several types of celestial objects such as planets, satellites, rings, etc.. The dynamics of these objects have always been interesting for studies, mainly the satellites and rings of Saturn. We have the knowledge that these satellites and rings undergo various types of orbital resonances. These resonances are responsible for the formation of numerous structures in the rings such as, for example, almost the entire structure of A ring. Thus we see how important it is to examine the nature of these resonant interactions in order to understand the characteristics observed in the satellites and rings of Saturn. In this work we highlight the corotation resonance, which occurs when the velocity pattern of the potential disturbing frequency is equal to the orbital frequency of a satellite. In the Saturnian system there are three satellites, Aegaeon, Anthe and Methone that are in corotation resonance with Mimas. In this paper we study, through numerical simulations, corotation resonance of the G ring arc of Saturn with Tethys and Mimas, while Mimas is migrating. Ours initial results show that no particles escape from the corotational resonance while Mimas migrate, that is, it is very robust. We also show the effects and consequences of Tethys migration on Mimas and de G arc.

A Handheld Open-Field Infant Keratometer (An American Ophthalmological Society Thesis)

PubMed Central

Miller, Joseph M.

2010-01-01

Purpose: To design and evaluate a new infant keratometer that incorporates an unobstructed view of the infant with both eyes (open-field design). Methods: The design of the open-field infant keratometer is presented, and details of its construction are given. The design incorporates a single-ring keratoscope for measurement of corneal astigmatism over a 4-mm region of the cornea and includes a rectangular grid target concentric within the ring to allow for the study of higher-order aberrations of the eye. In order to calibrate the lens and imaging system, a novel telecentric test object was constructed and used. The system was bench calibrated against steel ball bearings of known dimensions and evaluated for accuracy while being used in handheld mode in a group of 16 adult cooperative subjects. It was then evaluated for testability in a group of 10 infants and toddlers. Results: Results indicate that while the device achieved the goal of creating an open-field instrument containing a single-ring keratoscope with a concentric grid array for the study of higher-order aberrations, additional work is required to establish better control of the vertex distance. Conclusion: The handheld open-field infant keratometer demonstrates testability suitable for the study of infant corneal astigmatism. Use of collimated light sources in future iterations of the design must be incorporated in order to achieve the accuracy required for clinical investigation. PMID:21212850

A handheld open-field infant keratometer (an american ophthalmological society thesis).

PubMed

Miller, Joseph M

2010-12-01

To design and evaluate a new infant keratometer that incorporates an unobstructed view of the infant with both eyes (open-field design). The design of the open-field infant keratometer is presented, and details of its construction are given. The design incorporates a single-ring keratoscope for measurement of corneal astigmatism over a 4-mm region of the cornea and includes a rectangular grid target concentric within the ring to allow for the study of higher-order aberrations of the eye. In order to calibrate the lens and imaging system, a novel telecentric test object was constructed and used. The system was bench calibrated against steel ball bearings of known dimensions and evaluated for accuracy while being used in handheld mode in a group of 16 adult cooperative subjects. It was then evaluated for testability in a group of 10 infants and toddlers. Results indicate that while the device achieved the goal of creating an open-field instrument containing a single-ring keratoscope with a concentric grid array for the study of higher-order aberrations, additional work is required to establish better control of the vertex distance. The handheld open-field infant keratometer demonstrates testability suitable for the study of infant corneal astigmatism. Use of collimated light sources in future iterations of the design must be incorporated in order to achieve the accuracy required for clinical investigation.

Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Chia, Mei

The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value-added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally-observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Bronsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to gamma-valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range of chemical intermediates and end products can be obtained using heterogeneous catalysts or by thermal decomposition. Mechanistic insights from experimentally-observed reactivity trends and results from DFT calculations indicate that 2-pyrones undergo reactions unique to their structure such as keto-enol tautomerization, retro Diels-Alder, and nucleophilic attack by water. Ring-opening and decarboxylation reactions were found to be governed by key structural features such as the degree of saturation in the ring (e.g., C4=C5 bond), nature of the solvent, and presence of an acid catalyst.

A Simple and Novel Approach to Delineating Stereochemistry of Electrocyclic Reactions

ERIC Educational Resources Information Center

Mandal, Dipak K.

2012-01-01

The dynamic stereochemistry of electrocyclic reactions (a class of pericyclic reactions) stems from the operation of either conrotatory (con) or disrotatory (dis) mode of ring-closing and ring-opening processes. Difficulty is often encountered in depicting product stereochemistry resulting from such movements of substituents. A novel, simple,…

Synthesis and structural studies of heterobimetallic alkoxide complexes supported by bis(phenolate) ligands: efficient catalysts for ring-opening polymerization of L-lactide.

PubMed

Chen, Hsuan-Ying; Liu, Mei-Yu; Sutar, Alekha Kumar; Lin, Chu-Chieh

2010-01-18

A series of heterobimetallic titanium(IV) complexes [LTi(O(i)Pr)(mu-O(i)Pr)(2)Li(THF)(2)], [LTi(O(i)Pr)(mu-O(i)Pr)(2)Na(THF)(2)], [LTi(mu-O(i)Pr)(2)Zn(O(i)Pr)(2)], and [LTi(mu-O(i)Pr)(2)Mg(O(i)Pr)(2)] (where L = bidentate bisphenol ligands) have been synthesized and characterized including a structural determination of [L(1)Ti(mu(2)-O(i)Pr)(2)(O(i)Pr)Li(THF)(2)] (1a). These complexes were investigated for their utility in the ring-opening polymerization (ROP) of l-lactide (LA). Polymerization activities have been shown to correlate with the electronic properties of the substituent within the bisphenol ligand. In contrast to monometallic titanium initiator 1e, all the heterobimetallic titanium initiators (Ti-Li, Ti-Na, Ti-Zn, and Ti-Mg) show enhanced catalytic activity toward ring-opening polymerization (ROP) of l-LA. In addition, the use of electron-donating methoxy or methylphenylsulfonyl functional ligands reveals the highest activity. The bisphenol bimetallic complexes give rise to controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number-average molecular weight. The polymerization kinetics using 2c as an initiator were also studied, and the experimental results indicate that the reaction rate is first-order with respect to both monomer and catalyst concentration with a polymerization rate constant, k = 81.64 M(-1) min(-1).

Laparoscopic-assisted extracorporeal ovarian cystectomy: a new technique.

PubMed

Ikuma, Kenichino; Amin, Magdy; Yukio, Yamada; Hisato, Okuo; Yoshihiro, Ito; Shintaro, Ueda; Masako, Tanaka; Yasuki, Koyasu

2004-01-01

An increasing number of adnexal masses are currently managed laparoscopically, which has hampered progress regarding the different techniques of laparoscopic surgery. In this chapter, a modified application of surgical instrument was described in laparoscopic ovarian cystectomy-we named this device, Lap-Disc Mini. This new instrument has three rings, an inner flexible ring fixed to a middle ring by a rubber corset, and an additional dynamic outer ring that has a rubbery-like iris opening, which allows the application of different-sized trocars and extracorporeal ovarian cystectomy. This technique has proved to be effective and safe, especially in removing large ovarian cyst.

Reactive simulation of the chemistry behind the condensed-phase ignition of RDX from hot spots.

PubMed

Joshi, Kaushik L; Chaudhuri, Santanu

2015-07-28

Chemical events that lead to thermal initiation and spontaneous ignition of the high-pressure phase of RDX are presented using reactive molecular dynamics simulations. In order to initiate the chemistry behind thermal ignition, approximately 5% of RDX crystal is subjected to a constant temperature thermal pulse for various time durations to create a hot spot. After application of the thermal pulse, the ensuing chemical evolution of the system is monitored using reactive molecular dynamics under adiabatic conditions. Thermal pulses lasting longer than certain time durations lead to the spontaneous ignition of RDX after an incubation period. For cases where the ignition is observed, the incubation period is dominated by intermolecular and intramolecular hydrogen transfer reactions. Contrary to the widely accepted unimolecular models of initiation chemistry, N-N bond dissociations that produce NO2 species are suppressed in the condensed phase. The gradual temperature and pressure increase in the incubation period is accompanied by the accumulation of short-lived, heavier polyradicals. The polyradicals contain intact triazine rings from the RDX molecules. At certain temperatures and pressures, the polyradicals undergo ring-opening reactions, which fuel a series of rapid exothermic chemical reactions leading to a thermal runaway regime with stable gas-products such as N2, H2O and CO2. The evolution of the RDX crystal throughout the thermal initiation, incubation and thermal runaway phases observed in the reactive simulations contains a rich diversity of condensed-phase chemistry of nitramines under high-temperature/pressure conditions.

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

PubMed

Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

2016-09-29

The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

The origin of the eccentricities of the rings of Uranus

NASA Technical Reports Server (NTRS)

Goldreich, P.; Tremaine, S.

1981-01-01

The effect of gravitational perturbations from a nearby satellite on the eccentricity e of a narrow particulate ring is considered. The perturbations near a resonance in an eccentric ring may be divided into corotation and Lindblad terms. For small e, the corotation terms damp e, whereas the Lindblad terms excite e. In the absence of saturation the corotation terms win by a small margin, and e damps. However, if the perturbations open gaps at the strongest resonances, then the Lindblad terms win, and e grows. This result offers an explanation for the existence of both circular and eccentric rings around Uranus. It is also shown that eccentricity changes induced by circular rings on eccentric satellite orbits are similar to those induced by satellites with circular orbits on eccentric rings.

Developments in the use of rare earth metal complexes as efficient catalysts for ring-opening polymerization of cyclic esters used in biomedical applications

NASA Astrophysics Data System (ADS)

Cota, Iuliana

2017-04-01

Biodegradable polymers represent a class of particularly useful materials for many biomedical and pharmaceutical applications. Among these types of polyesters, poly(ɛ-caprolactone) and polylactides are considered very promising for controlled drug delivery devices. These polymers are mainly produced by ring-opening polymerization of their respective cyclic esters, since this method allows a strict control of the molecular parameters (molecular weight and distribution) of the obtained polymers. The most widely used catalysts for ring-opening polymerization of cyclic esters are tin- and aluminium-based organometallic complexes; however since the contamination of the aliphatic polyesters by potentially toxic metallic residues is particularly of concern for biomedical applications, the possibility of replacing organometallic initiators by novel less toxic or more efficient organometallic complexes has been intensively studied. Thus, in the recent years, the use of highly reactive rare earth initiators/catalysts leading to lower polymer contamination has been developed. The use of rare earth complexes is considered a valuable strategy to decrease the polyester contamination by metallic residues and represents an attractive alternative to traditional organometallic complexes.

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

DOE PAGES

Bühler, Christine C.; Minitti, Michael P.; Deb, Sanghamitra; ...

2011-01-01

The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the well-known ring opening to 1,3,5-hexatriene, while a 5.99 eV photon lifts the molecule directly into the 3p-Rydberg state. Excitation to 3p does not induce ring opening. In both experiments, time-dependent shifts of the Rydberg electron binding energy reflect the structural dynamics of the molecular core. Structural distortions associated with 3p-excitation cause a dynamical shift in the -more » and -binding energies by 10 and 26 meV/ps, respectively, whereas after excitation into 1B, more severe structural transformations along the ring-opening coordinate produce shifts at a rate of 40 to 60 meV/ps. The experiment validates photoionization-photoelectron spectroscopy via Rydberg states as a powerful technique to observe structural dynamics of polyatomic molecules.« less

Modeling of lipase catalyzed ring-opening polymerization of epsilon-caprolactone.

PubMed

Sivalingam, G; Madras, Giridhar

2004-01-01

Enzymatic ring-opening polymerization of epsilon-caprolactone by various lipases was investigated in toluene at various temperatures. The determination of molecular weight and structural identification was carried out with gel permeation chromatography and proton NMR, respectively. Among the various lipases employed, an immobilized lipase from Candida antartica B (Novozym 435) showed the highest catalytic activity. The polymerization of epsilon-caprolactone by Novozym 435 showed an optimal temperature of 65 degrees C and an optimum toluene content of 50/50 v/v of toluene and epsilon-caprolactone. As lipases can degrade polyesters, a maximum in the molecular weight with time was obtained due to the competition of ring opening polymerization and degradation by specific chain end scission. The optimum temperature, toluene content, and the variation of molecular weight with time are consistent with earlier observations. A comprehensive model based on continuous distribution kinetics was developed to model these phenomena. The model accounts for simultaneous polymerization, degradation and enzyme deactivation and provides a technique to determine the rate coefficients for these processes. The dependence of these rate coefficients with temperature and monomer concentration is also discussed.

Rugged Iris Mechanism

NASA Technical Reports Server (NTRS)

Ferragut, Nelson J.

2005-01-01

A rugged iris mechanism has been designed to satisfy several special requirements, including a wide aperture in the "open" position, full obscuration in the "closed" position, ability to function in a cryogenic or other harsh environment, and minimization of friction through minimization of the number of components. An important element of the low-friction aspect of the design is maximization of the flatness of, and provision of small gaps between, adjacent iris blades. The tolerances of the design can be very loose, accommodating thermal expansions and contractions associated with large temperature excursions. The design is generic in that it is adaptable to a wide range of aperture sizes and can be implemented in a variety of materials to suit the thermal, optical, and mechanical requirements of various applications. The mechanism (see figure) includes an inner flat ring, an outer flat ring, and an even number of iris blades. The iris blades shown in front in the figure are denoted as "upper," and the iris blades shown partly hidden behind the front ones are denoted as "lower." Each iris blade is attached to the inner ring by a pivot assembly and to the outer ring by a roller/slider assembly. The upper and lower rings are co-centered and are kept in sliding contact. The iris is opened or closed by turning the outer ring around the center while holding the inner ring stationary. The mechanism is enclosed in a housing (not shown in the figure) that comprises an upper and a lower housing shell. The housing provides part of the sliding support for the outer ring and keeps the two rings aligned as described above. The aforementioned pivot assemblies at the inner ring also serve as spacers for the housing. The lower housing shell contains part of the lower sliding surface and features for mounting the overall mechanism and housing assembly. The upper housing shell contains part of the upper sliding surface.

Preliminary engineering study: Quick opening valve MSFC high Reynolds number wind tunnel

NASA Technical Reports Server (NTRS)

1983-01-01

FluiDyne Engineering Corporation has conducted a preliminary engineering study of a quick-opening valve for the MSFC High Reynolds Number Wind Tunnel under NASA Contract NAS8-35056. The subject valve is intended to replace the Mylar diaphragm system as the flow initiation device for the tunnel. Only valves capable of opening within 0.05 sec. and providing a minimum of 11.4 square feet of flow area were considered. Also, the study focused on valves which combined the quick-opening and tight shutoff features in a single unit. A ring sleeve valve concept was chosen for refinement and pricing. Sealing for tight shutoff, ring sleeve closure release and sleeve actuation were considered. The resulting cost estimate includes the valve and requisite modifications to the facility to accommodate the valve as well as the associated design and development work.

PHYSICAL CHARACTERISTICS AND NON-KEPLERIAN ORBITAL MOTION OF 'PROPELLER' MOONS EMBEDDED IN SATURN'S RINGS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tiscareno, Matthew S.; Burns, Joseph A.; Hedman, Matthew M.

2010-08-01

We report the discovery of several large 'propeller' moons in the outer part of Saturn's A ring, objects large enough to be followed over the 5 year duration of the Cassini mission. These are the first objects ever discovered that can be tracked as individual moons, but do not orbit in empty space. We infer sizes up to 1-2 km for the unseen moonlets at the center of the propeller-shaped structures, though many structural and photometric properties of propeller structures remain unclear. Finally, we demonstrate that some propellers undergo sustained non-Keplerian orbit motion.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stephenson, Casey J.; Hassan Beyzavi, M.; Klet, Rachel C.

Reaction of styrene oxide with sodium cyanoborohydride and a catalytic amount of Hf-NU-1000 yields the anti-Markovnikov product, 2-phenylethanol, with over 98% regioselectivity. On the other hand, propylene oxide is ring opened in a Markovnikov fashion to form 2-propanol with 95% regioselectivity. Both styrene oxide and propylene oxide failed to react with sodium cyanoborohydride without the addition of Hf-NU-1000 indicative of the crucial role of Hf-NU-1000 as a catalyst in this reaction. To the best of our knowledge, this is the first report of the use of a metal-organic framework material as a catalyst for ring-opening of epoxides with hydrides.

Polymersome nanoreactors for enzymatic ring-opening polymerization.

PubMed

Nallani, Madhavan; de Hoog, Hans-Peter M; Cornelissen, Jeroen J L M; Palmans, Anja R A; van Hest, Jan C M; Nolte, Roeland J M

2007-12-01

Polystyrene-polyisocyanopeptide (PS-PIAT) polymersomes containing CALB in two different locations, one in the aqueous inner compartment and one in the bilayer, were investigated for enzymatic ring-opening polymerization of lactones in water. It is shown that the monomers 8-octanolactone and dodecalactone yield oligomers with this polymersome system. It is also observed that the polymerization activity is dependent on the position of the enzyme in the polymersome. SEM investigations show that the polymersome structures were destabilized during the polymerization. Further investigations show that the vesicular morphology of the polymersomes was destabilized only in the case of polymer product formation.

18,21-Anhydroaldosterone and derivatives.

PubMed

Harnik, M; Kashman, Y; Cojocaru, M; Lewicka, S; Vecsei, P

1989-07-01

18,21-Anhydroaldosterone 8, 18,21-anhydro-19-noraldosterone 9, and 3 alpha, 5 beta-tetrahydro-18,21-anhydro-19-noraldosterone 13, which may be present in acid-processed urine, were prepared by cleaving their 20-ketal derivatives 2, 3, and 12 with hot mineral acid. Compounds 8 and 9 were also made by direct dehydration of aldosterone 5 and 19-noraldosterone 10 in good yield. The reverse ring opening of 8 to 5 could be carried out in moderate yield with an acetic acid-acetic anhydride-perchloric acid mixture, while an analogous ring opening of 9 gave only a poor yield of 10.

Demonstration of an SOA-assisted open metro-access infrastructure for heterogeneous services.

PubMed

Schmuck, H; Bonk, R; Poehlmann, W; Haslach, C; Kuebart, W; Karnick, D; Meyer, J; Fritzsche, D; Weis, E; Becker, J; Freude, W; Pfeiffer, T

2014-01-13

An open converged metro-access network approach allows for sharing optical layer resources like fibers and optical spectrum among different services and operators. We demonstrated experimentally the feasibility of such a concept by the simultaneous operation of multiple services showing different modulation formats and multiplexing techniques. Flexible access nodes are implemented including semiconductor optical amplifiers to create a transparent and reconfigurable optical ring network. The impact of cascaded optical amplifiers on the signal quality is studied along the ring. In addition, the influence of high power rival signals in the same waveband and in the same fiber is analyzed.

Highly Z- and Enantioselective Ring-Opening/Cross-Metathesis Reactions Catalyzed by Stereogenic-at-Mo Adamantylimido Complexes

PubMed Central

Ibrahem, Ismail; Yu, Miao; Schrock, Richard R.; Hoveyda, Amir H.

2009-01-01

The first highly Z- and enantioselective class of ring-opening/cross-metathesis (ROCM) reactions is presented. Transformations are promoted in the presence of <2 mol % of chiral stereogenic-at-Mo monoaryloxide complexes, which bear an adamantylimido ligand and are prepared and used in situ. Reactions involve meso oxabicyclic substrates and afford the desired pyrans in 50–85% yield and in up to >98:<2 enantiomer ratio (er). Importantly, the desired chiral pyrans are thus obtained bearing a Z olefin either exclusively (>98:<2 Z:E) or predominantly (≥87:13 Z:E). PMID:19249833

Enzymatic preparation of novel thermoplastic di-block copolyesters containing poly[(R)-3-hydroxybutyrate] and poly(epsilon-caprolactone) blocks via ring-opening polymerization.

PubMed

Dai, Shiyao; Li, Zhi

2008-07-01

Enzymatic modification of a microbial polyester was achieved by the ring-opening polymerization of epsilon-caprolactone (CL) with low-molecular weight telechelic hydroxylated poly[( R)-3-hydroxybutyrate] (PHB-diol) as initiator and Novozym 435 (immobilized Candida antarctica Lipase B) as catalyst in anhydrous 1,4-dioxane or toluene. The ring-opening polymerization was investigated at different conditions with two different types of PHB-diols: PHB-diol(P), containing a primary OH and a secondary OH end groups, and PHB-diol(M), consisting of 91% PHB-diol(P) and 9% PHB-diol containing two secondary OH end groups. The reactions were followed by GPC analyses of the resulting polymers at different time points, and the optimal conditions were established to be 70 degrees C at a weight ratio of CL/enzyme/solvent of 8:1:24. The ring-opening polymerization of CL with PHB-diol(M) (Mn of 2380, NMR) at the molar ratio of 50:1 under the optimal conditions in 1,4-dioxane gave the corresponding poly[HB(56 wt %)-co-CL(44 wt %)] with Mn (NMR) of 3900 in 66% yield. Polymerization of CL and PHB-diol(P) ( Mn of 2010, NMR) at the same condition in toluene gave the corresponding poly[HB(28 wt %)-co-CL(72 wt %)] with Mn (NMR) of 7100 in 86% yield. Both polymers were characterized by (1)H and (13)C NMR and IR analyses as di-block copolyesters containing a PHB block with a secondary OH end group and a poly(epsilon-caprolactone) (PCL) block with a primary OH end group. NMR analyses and control experiments suggested no formation of random copolymers and no change of the PHB block during the reaction. The enzymatic ring-opening polymerization was selectively initiated by the primary OH group of PHB-diol, whereas the secondary OH group remained as an end group in the final polymers. The thermal properties of the di-block poly(HB-co-CL)s were analyzed by DSC, with excellent T g values for the elastomer domain: poly[HB(56 wt %)- co-CL(44 wt %)] with M n (NMR) of 3900 demonstrated a T g of -57 degrees C, Tm of 145, 123, and 53 degrees C; and poly[HB(28wt%)-co-CL(72wt%)] with Mn (NMR) of 7100 gave a Tg of -60 degrees C, Tm of 147 and 50 degrees C. Thus, the selective enzymatic ring-opening polymerization with PHB-diol as macro-initiator provides a new method for the preparation of PHB-based block copolymers as biomaterials with good thermoplastic properties and novel structures containing functional end groups.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daugherty, W.; Mcwilliams, A.; Skidmore, E.

The 9975 Type B shipping package is used within the DOE complex for shipping special nuclear materials. This package is re-certified annually in accordance with Safety Analysis Report requirements. The package is also used at the Savannah River Site as part of the long-term storage configuration of special nuclear materials. As such, the packages do not undergo annual recertification during storage, with uncertainty as to how long some of the package components will meet their functional requirements in the storage environment. The packages are currently approved for up to 15 years storage, and work continues to provide a technical basismore » to extend that period. This paper describes efforts by the Savannah River National Laboratory (SRNL) to extend the service life estimate of Viton® GLT and GLT-S fluoroelastomer O-rings used in the 9975 shipping package. O-rings of both compositions are undergoing accelerated aging at elevated temperature, and are periodically tested for compression stress relaxation (CSR) behavior and leak performance. The CSR behavior of O-rings was evaluated at temperatures from 79 °C to 177 °C. These collective data were used to develop predictive models for extrapolation of CSR behavior to relevant service temperatures (< 75 °C). O-rings were also aged in Primary Containment Vessel (PCV) fixtures at temperatures ranging from 79 °C to 232 °C. The fixtures are helium leak tested periodically to determine if they remain leak-tight. The PCV fixture tests demonstrate that the 9975 O-rings will remain leak-tight at temperatures up to 149 °C for 3 years or more, and no leak failures have been observed with up to 8 years aging at 93 °C. Significantly longer periods of leak-tight service are expected at the lower temperatures actually experienced in the storage environment. The predictive model developed from the CSR data conservatively indicates a service life of more than 20 years at the bounding temperature of 75 °C. Although the relationship between CSR behavior and leak-tight performance has not been established for this design, the CSR predictions for this O-ring are conservative relative to leak-tight performance to date.« less

Outcomes of ring versus suture annuloplasty for tricuspid valve repair in patients undergoing mitral valve surgery.

PubMed

Shinn, Sung Ho; Dayan, Victor; Schaff, Hartzell V; Dearani, Joseph A; Joyce, Lyle D; Lahr, Brian; Greason, Kevin L; Stulak, John M; Daly, Richard C

2016-08-01

There is controversy regarding the comparative effectiveness of methods of tricuspid valve (TV) repair-prosthetic ring versus suture annuloplasty-in patients undergoing operation for primary mitral valve (MV) disease. In this study, we analyzed factors associated with patient survival and recurrent tricuspid regurgitation (TR) following TV repair and focused on results stratified by method of tricuspid valve repair. We reviewed patients who underwent TV repair with suture (De Vega) or flexible ring annuloplasties at the time of MV surgery from 1995 to 2010. Patients with prior cardiac or concomitant aortic valve operations were excluded. Propensity matching was performed to account for potential differences in baseline characteristics between the groups. Primary outcomes were long-term mortality and postoperative TR grade. In the overall study, there were 415 patients with median age 72 years (range, 63-78 years), from which 148 matched pairs were identified by propensity score analysis. In the overall cohort, patients in the ring annuloplasty group more often had preoperative transvenous pacemakers (P = .05), lower ejection fractions (P = .028), and more recent years of operation (P < .001). For patients who had De Vega suture annuloplasty, long-term mortality was not different from that of patients who had ring annuloplasty (hazard ratio, 0.93; 95% confidence interval, 0.67-1.30). Older age, preoperative diabetes, and preoperative right ventricular dysfunction were predictors for long-term mortality. Durability of the annuloplasty methods was similar with no significant difference in trend of recurrent TR grades over follow-up (P = .807). Etiology of mitral regurgitation was not associated with recurrent TR during follow-up (P = .857). Late survival and TV durability following concomitant TV repair during MV surgery did not differ with respect to TV repair technique. In this series of patients with repaired tricuspid valves, etiology of MV disease did not influence postoperative changes in TR. Copyright © 2016 The American Association for Thoracic Surgery. Published by Elsevier Inc. All rights reserved.

[Plastic repair of tricuspid valve: Carpentier's ring annuloplasty versus De VEGA technique].

PubMed

Charfeddine, Salma; Hammami, Rania; Triki, Faten; Abid, Leila; Hentati, Mourad; Frikha, Imed; Kammoun, Samir

2017-01-01

Tricuspid valve disease has been neglected for a long time by cardiologists and surgeons, but for some years now leakage of tricuspid valve has been demonstrated as a prognostic factor in the evolution of patients with left heart valve disease undergoing surgery. Several techniques for plastic repair of tricuspid valve have been developed and the published studies differ on the results of these techniques; we conducted this study to assess the results of plastic repair of tricuspid valve in a population of patients with a high prevalence of rheumatic disease and to compare Carpentier's ring annuloplasty techniques with DEVEGA plasty. We conducted a retrospective study of patients undergoing plastic repair of tricuspid valve in the Department of Cardiology at the Medicine University of Sfax over a period of 25 years. We compared the results from the Group 1 (Carpentier's ring annuloplasty) with Group 2 (DeVEGA plasty). 91 patients were included in our study, 45 patients in the Group 1 and 46 patients in the Group 2. Most patients had mean or severe TI (83%) before surgery, ring dilation was observed in 90% of patients with no significant difference between the two groups. Immediate results were comparable between the two techniques but during monitoring recurrent, at least mean, insufficiency was significantly more frequent in the DeVEGA plasty Group. The predictive factors for significant recurring long term TI were DeVEGA technique (OR=3.26[1.12-9.28]) in multivariate study and preoperative pulmonary artery systolic pressure (OR=1.06 (1.01-1.12)). Plastic repair of tricuspid valve using Carpentier's ring seems to guarantee better results than DeVEGA plasty. On the other hand, preoperative high PASP is predictive of recurrent leakage of tricuspid valve even after plasty; hence the importance of surgery in the treatment of patients at an early stage of the disease.

Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle.

PubMed

Zanichelli, Valeria; Dallacasagrande, Luca; Arduini, Arturo; Secchi, Andrea; Ragazzon, Giulio; Silvi, Serena; Credi, Alberto

2018-05-11

Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle-the 'track' ring-endowed with two distinct recognition sites (a bipyridinium and an ammonium) for a calix[6]arene-the 'shuttle' ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site.

Asymmetric ring structure of Vps4 required for ESCRT-III disassembly

NASA Astrophysics Data System (ADS)

Caillat, Christophe; Macheboeuf, Pauline; Wu, Yuanfei; McCarthy, Andrew A.; Boeri-Erba, Elisabetta; Effantin, Gregory; Göttlinger, Heinrich G.; Weissenhorn, Winfried; Renesto, Patricia

2015-12-01

The vacuolar protein sorting 4 AAA-ATPase (Vps4) recycles endosomal sorting complexes required for transport (ESCRT-III) polymers from cellular membranes. Here we present a 3.6-Å X-ray structure of ring-shaped Vps4 from Metallosphera sedula (MsVps4), seen as an asymmetric pseudohexamer. Conserved key interface residues are shown to be important for MsVps4 assembly, ATPase activity in vitro, ESCRT-III disassembly in vitro and HIV-1 budding. ADP binding leads to conformational changes within the protomer, which might propagate within the ring structure. All ATP-binding sites are accessible and the pseudohexamer binds six ATP with micromolar affinity in vitro. In contrast, ADP occupies one high-affinity and five low-affinity binding sites in vitro, consistent with conformational asymmetry induced on ATP hydrolysis. The structure represents a snapshot of an assembled Vps4 conformation and provides insight into the molecular motions the ring structure undergoes in a concerted action to couple ATP hydrolysis to ESCRT-III substrate disassembly.

Pioneer 10 and 11 (Jupiter and Saturn) magnetic field experiments

NASA Technical Reports Server (NTRS)

Jones, D. E.

1986-01-01

Magnet field data obtained by the vector helium magnetometer (VHM) during the encounters of Jupiter (Pioneer 10 and 11) and Saturn (Pioneer 11) was analyzed and interpreted. The puzzling characteristics of the Jovian and Saturnian magnetospheric magnetic fields were studied. An apparent substorm (including thinning of the dayside tail current sheet) was observed at Jupiter, as well as evidence suggesting that at the magnetopause the cusp is at an abnormally low latitude. The characteristics of Saturn's ring current as observed by Pioneer 11 were dramatically different from those suggested by the Voyager observations. Most importantly, very strong perturbations in the azimuthal ring current magnetic field suggest that the plane of the ring was not in the dipole equatorial plane, being tilted 5 to 10 deg. relative to the dipole and undergoing significant changes during the encounter. When these changing currents were corrected for, an improved planetary field determination was obtained. In addition, the ring and azimuthal currents at Saturn displayed significantly different time dependences.

The importance of pelvic ring stabilization as a life-saving measure in pre-hospital - A case report commented by autopsy.

PubMed

Durão, Carlos; Alves, Magda; Barros, André; Pedrosa, Frederico

2017-08-01

Hip fractures with unstable pelvic ring have great morbidity and mortality rates. These fractures result from high energy trauma such as falls from heights, road accidents and collapsing structures or other similar mechanisms of action. We report the case of a 63 years old man, construction worker, who stood inside a ditch during a wall construction when he was surprised by this collapse, which resulted in direct trauma to the right thigh and pelvis. The autopsy revealed diaphysis fracture of the right femur with an open book pelvic fracture with severe hemorrhagic infiltration and hematoma of the pelvic muscles without arterial injury. Bone bleeding and the vascular damage associated with disruption of the sacroiliac ligaments promote a very significant bleeding. Simple maneuvers such as sheet circumferential compression to promote pelvic ring closure are effective on stabilizing and closure of the sacroiliac joint. Hip manipulation of the fracture was performed during the necropsy to demonstrate and prove how a simple sheet contention can promote stabilization of the pelvic ring by closing the sacroiliac joints in open book fractures.

Biodegradation of high-molecular-weight polycyclic aromatic hydrocarbons under anaerobic conditions: Overview of studies, proposed pathways and future perspectives.

PubMed

Nzila, Alexis

2018-05-07

The biodegradation of low- and high-molecular-weight polycyclic aromatic hydrocarbons (PAHs) (LWM-PAHs and HMW-PAHs, respectively) has been studied extensively under aerobic conditions. Molecular O 2 plays 2 critical roles in this biodegradation process. O 2 activates the aromatic rings through hydroxylation prior to ring opening and serves as a terminal electron acceptor (TEA). However, several microorganisms have devised ways of activating aromatic rings, leading to ring opening (and thus biodegradation) when TEAs other than O 2 are used (under anoxic conditions). These microorganisms belong to the sulfate-, nitrate-, and metal-ion-reducing bacteria and the methanogens. Although the anaerobic biodegradation of monocyclic aromatic hydrocarbons and LWM-PAH naphthalene have been studied, little information is available about the biodegradation of HMW-PAHs. This manuscript reviews studies of the anaerobic biodegradation of HMW-PAHs and identifies gaps that limit both our understanding and the efficiency of this biodegradation process. Strategies that can be employed to overcome these limitations are also discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Radar imaging of Saturn's rings

NASA Astrophysics Data System (ADS)

Nicholson, Philip D.; French, Richard G.; Campbell, Donald B.; Margot, Jean-Luc; Nolan, Michael C.; Black, Gregory J.; Salo, Heikki J.

2005-09-01

We present delay-Doppler images of Saturn's rings based on radar observations made at Arecibo Observatory between 1999 and 2003, at a wavelength of 12.6 cm and at ring opening angles of 20.1°⩽|B|⩽26.7°. The average radar cross-section of the A ring is ˜77% relative to that of the B ring, while a stringent upper limit of 3% is placed on the cross-section of the C ring and 9% on that of the Cassini Division. These results are consistent with those obtained by Ostro et al. [1982, Icarus 49, 367-381] from radar observations at |B|=21.4°, but provide higher resolution maps of the rings' reflectivity profile. The average cross-section of the A and B rings, normalized by their projected unblocked area, is found to have decreased from 1.25±0.31 to 0.74±0.19 as the rings have opened up, while the circular polarization ratio has increased from 0.64±0.06 to 0.77±0.06. The steep decrease in cross-section is at variance with previous radar measurements [Ostro et al., 1980, Icarus 41, 381-388], and neither this nor the polarization variations are easily understood within the framework of either classical, many-particle-thick or monolayer ring models. One possible explanation involves vertical size segregation in the rings, whereby observations at larger elevation angles which see deeper into the rings preferentially see the larger particles concentrated near the rings' mid-plane. These larger particles may be less reflective and/or rougher and thus more depolarizing than the smaller ones. Images from all four years show a strong m=2 azimuthal asymmetry in the reflectivity of the A ring, with an amplitude of ±20% and minima at longitudes of 67±4° and 247±4° from the sub-Earth point. We attribute the asymmetry to the presence of gravitational wakes in the A ring as invoked by Colombo et al. [1976, Nature 264, 344-345] to explain the similar asymmetry long seen at optical wavelengths. A simple radiative transfer model suggests that the enhancement of the azimuthal asymmetry in the radar images compared with that seen at optical wavelengths is due to the forward-scattering behavior of icy ring particles at decimeter wavelengths. A much weaker azimuthal asymmetry with a similar orientation may be present in the B ring.

Fracture of Colvin-Galloway-Future band in a patient with mitral valve annuloplasty.

PubMed

Bauer, S; Rosendahl, U; Pietrowski, D; Ennker, J

2006-08-01

Annuloplasty with various annuloplasty ring systems is a fundamental part of mitral valve repair and has been frequently performed since its introduction by Carpentier in 1969. Due to the different advantages or disadvantages of each system, some controversies exist regarding the best type of ring annuloplasty support. Here we describe, for the first time, the case of a female patient in which a fracture of a semi-rigid open annuloplasty ring occurred, leading to annular deformation and mitral regurgitation.

Genetic Mutations in Blood and Tissue Samples in Predicting Response to Treatment in Patients With Locally Advanced Rectal Cancer Undergoing Chemoradiation

ClinicalTrials.gov

2017-09-08

Mucinous Adenocarcinoma of the Rectum; Recurrent Rectal Cancer; Signet Ring Adenocarcinoma of the Rectum; Stage IIA Rectal Cancer; Stage IIB Rectal Cancer; Stage IIC Rectal Cancer; Stage IIIA Rectal Cancer; Stage IIIB Rectal Cancer; Stage IIIC Rectal Cancer

Reusable fast opening switch

DOEpatents

Van Devender, J.P.; Emin, D.

1983-12-21

A reusable fast opening switch for transferring energy, in the form of a high power pulse, from an electromagnetic storage device such as an inductor into a load. The switch is efficient, compact, fast and reusable. The switch comprises a ferromagnetic semiconductor which undergoes a fast transition between conductive and metallic states at a critical temperature and which undergoes the transition without a phase change in its crystal structure. A semiconductor such as europium rich europhous oxide, which undergoes a conductor to insulator transition when it is joule heated from its conductor state, can be used to form the switch.

Reusable fast opening switch

DOEpatents

Van Devender, John P.; Emin, David

1986-01-01

A reusable fast opening switch for transferring energy, in the form of a high power pulse, from an electromagnetic storage device such as an inductor into a load. The switch is efficient, compact, fast and reusable. The switch comprises a ferromagnetic semiconductor which undergoes a fast transition between conductive and insulating states at a critical temperature and which undergoes the transition without a phase change in its crystal structure. A semiconductor such as europium rich europhous oxide, which undergoes a conductor to insulator transition when it is joule heated from its conductor state, can be used to form the switch.

Automatic identification of land uses from ERTS-1 data obtained over Milwaukee, Wisconsin

NASA Technical Reports Server (NTRS)

Baumgardner, M. F.; Landgrebe, D. A. (Principal Investigator); Kramer, H. H.

1972-01-01

The author has identified the following significant results. Spectrally, thirteen classes of ground cover were identified within Milwaukee County: five classes of water, grassy open areas, beach, two classes of road, woods, suburban, inner city, and industry. A distinct concentric pattern of land use was identified in the county radiating outward from the central business district. The first ring has a principal feature, termed the inner city, which is indicative of the older part of the county. In the second ring, the land use becomes more complex, consisting of suburban areas, parks, and varied institutional features. The third general ring consists primarily of open, grassy land, with scattered residential subdivisions, wood lots, and small water bodies. The five classes of water identified suggest differences in depth, turbidity, and/or color. A number of major roads were identified. Other spectrally identifiable features included the larger county parks and larger cemeteries.

Efficacy, acceptability and tolerability of the combined contraceptive ring, NuvaRing, compared with an oral contraceptive containing 30 microg of ethinyl estradiol and 3 mg of drospirenone.

PubMed

Ahrendt, Hans-Joachim; Nisand, Israel; Bastianelli, Carlo; Gómez, Maria Angeles; Gemzell-Danielsson, Kristina; Urdl, Wolfgang; Karskov, Birgit; Oeyen, Luc; Bitzer, Johannes; Page, Geert; Milsom, Ian

2006-12-01

This randomized multicenter, open-label, trial compared efficacy, acceptability, tolerability and compliance of NuvaRing with a combined oral contraceptive (COC), containing 30 microg of ethinyl estradiol (EE) and 3 mg of drospirenone. In this 13-cycle study, 983 women were randomized and treated (intent-to-treat population) with NuvaRing or COC. One in-treatment pregnancy occurred with NuvaRing (Pearl Index=0.25) (95% confidence interval [CI]: 0.006, 1.363) and four with the COC (Pearl Index=0.99) (95% CI: 0.269, 2.530). For both groups, compliance (89.2% NuvaRing, 85.5% COC) and satisfaction (84% NuvaRing; 87% COC) were high; the vast majority of women found NuvaRing easy to insert (96%) and remove (97%). Tolerability was similar; the most frequent adverse events with NuvaRing were related to ring use, whereas estrogen-related events were more common with the COC. NuvaRing has comparable efficacy and tolerability to a COC containing 30 microg of EE and 3 mg drospirenone. User acceptability of both methods was high.

Inchworm movement of two rings switching onto a thread by biased Brownian diffusion represent a three-body problem.

PubMed

Benson, Christopher R; Maffeo, Christopher; Fatila, Elisabeth M; Liu, Yun; Sheetz, Edward G; Aksimentiev, Aleksei; Singharoy, Abhishek; Flood, Amar H

2018-05-07

The coordinated motion of many individual components underpins the operation of all machines. However, despite generations of experience in engineering, understanding the motion of three or more coupled components remains a challenge, known since the time of Newton as the "three-body problem." Here, we describe, quantify, and simulate a molecular three-body problem of threading two molecular rings onto a linear molecular thread. Specifically, we use voltage-triggered reduction of a tetrazine-based thread to capture two cyanostar macrocycles and form a [3]pseudorotaxane product. As a consequence of the noncovalent coupling between the cyanostar rings, we find the threading occurs by an unexpected and rare inchworm-like motion where one ring follows the other. The mechanism was derived from controls, analysis of cyclic voltammetry (CV) traces, and Brownian dynamics simulations. CVs from two noncovalently interacting rings match that of two covalently linked rings designed to thread via the inchworm pathway, and they deviate considerably from the CV of a macrocycle designed to thread via a stepwise pathway. Time-dependent electrochemistry provides estimates of rate constants for threading. Experimentally derived parameters (energy wells, barriers, diffusion coefficients) helped determine likely pathways of motion with rate-kinetics and Brownian dynamics simulations. Simulations verified intercomponent coupling could be separated into ring-thread interactions for kinetics, and ring-ring interactions for thermodynamics to reduce the three-body problem to a two-body one. Our findings provide a basis for high-throughput design of molecular machinery with multiple components undergoing coupled motion.

National Trends of Thoracic Endovascular Aortic Repair (TEVAR) Versus Open Repair in Blunt Thoracic Aortic Injury.

PubMed

Grigorian, Areg; Spencer, Dean; Donayre, Carlos; Nahmias, Jeffry; Schubl, Sebastian; Gabriel, Viktor; Barrios, Cristobal

2018-06-07

Blunt thoracic aortic injury (BTAI) occurs in <1% of all trauma admissions. Considering the advent of multiple thoracic endovascular aortic repair (TEVAR) devices over the past decade, improved outcomes of TEVAR supported in the literature, rapid diagnosis and improved preoperative planning of BTAI using computed tomography imaging, we hypothesized that the national incidence of TEVAR in BTAI has increased while open repair has decreased. In addition, we hypothesized that the mortality risk in BTAI patients undergoing TEVAR would be lower than open repair. This was a retrospective analysis of the National Trauma Data Bank from 2007-2015. The primary end-points of interest included the incidence of TEVAR and open repair, as well as mortality in BTAI patients undergoing intervention. Covariates were included in a multivariable analysis to determine risk for mortality in BTAI patients undergoing open repair versus TEVAR. We identified 3,628 BTAI patients undergoing intervention. Of these, 3,226 underwent TEVAR (87.9%) and 445 (12.1%) underwent open repair. Compared to open repair, TEVAR had a shorter mean length of stay (19.8 vs. 21.3 days, p<0.05) and lower rates of acute kidney injury (5.6% vs. 9.0%, p<0.05) and mortality (8.8% vs. 12.8%, p<0.05). Open repair had greater risk for mortality compared to TEVAR (OR=1.63, CI=1.19-2.23, p<0.05). The rate of open repair decreased from 7.4% in 2007 to 1.9% in 2015, while TEVAR increased from 12.1% to 25.7% during the same time-period. We confirmed previous findings that endovascular repair is associated with decreased mortality, length of stay and major complications including acute kidney injury. Future investigations should focus on identifying the ideal patient candidate for TEVAR and elucidate precise indications for TEVAR in BTAI. Copyright © 2018. Published by Elsevier Inc.

The RING-Type E3 Ligase XBAT35.2 Is Involved in Cell Death Induction and Pathogen Response1[OPEN

PubMed Central

Liu, Hongxia; Ravichandran, Sridhar; McVey, Sarah; Lilley, Carly; Teresinski, Howard J.; Gonzalez-Ferrer, Carmen; Prithiviraj, Balakrishnan

2017-01-01

XBAT35 belongs to a subfamily of Arabidopsis (Arabidopsis thaliana) RING-type E3s that are similar in domain architecture to the rice (Oryza sativa) XA21 Binding Protein3, a defense protein. The XBAT35 transcript undergoes alternative splicing to produce two protein isoforms, XBAT35.1 and XBAT35.2. Here, we demonstrate that XBAT35.2 localizes predominantly to the Golgi and is involved in cell death induction and pathogen response. XBAT35.2, but not XBAT35.1, was found to trigger cell death when overexpressed in tobacco (Nicotiana benthamiana) leaves and does so in a manner that requires its RING domain. Loss of XBAT35 gene function disrupts the plant’s ability to defend against pathogen attack, whereas overexpression of XBAT35.2 enhances resistance to pathogens. XBAT35.2 was found to be unstable and promotes its own degradation, suggesting self-regulation. Inoculation with virulent and avirulent strains of the bacterial pathogen Pseudomonas syringae pv tomato DC3000 results in a drastic reduction in the levels of ubiquitinated XBAT35.2 and an increase in the abundance of the E3. This implies that pathogen infection prohibits XBAT35.2 self-regulation and stabilizes the E3. In agreement with a role in defending against pathogens, XBAT35.2 interacts with defense-related Accelerated Cell Death11 (ACD11) in planta and promotes the proteasome-dependent turnover of ACD11 in cell-free degradation assays. In accordance with regulation by a stabilized XBAT35.2, the levels of ubiquitinated ACD11 increased considerably, and the abundance of ACD11 was reduced following pathogen infection. In addition, treatment of transgenic seedlings with a proteasome inhibitor results in the accumulation of ACD11, confirming proteasome-dependent degradation. Collectively, these results highlight a novel role for XBAT35.2 in cell death induction and defense against pathogens. PMID:28951488

Clinical feasibility of pre-operative neurodevelopmental assessment of infants undergoing open heart surgery.

PubMed

Campbell, Miranda; Rabbidge, Bridgette; Ziviani, Jenny; Sakzewski, Leanne

2017-08-01

Assessing the neurodevelopmental status of infants with congenital heart disease before surgery provides a means of identifying those at heightened risk of developmental delay. This study aimed to investigate factors impacting clinical feasibility of pre-operative neurodevelopmental assessment of infants undergoing early open heart surgery. Infants who underwent open heart surgery prior to 4 months of age participated in this cross-sectional study. The Test of Infant Motor Performance and Prechtl's Assessment of General Movements were undertaken on infants pre-operatively. When assessments could not be undertaken, reasons were ascribed to either infant or environmental circumstances. Demographic data and Aristotle scores were compared between groups of infants who did or did not undergo assessment. Binary logistic regression was used to explore associations. A total of 60 infants participated in the study. Median gestational age was 38.78 weeks (interquartile range: 36.93-39.72). Of these infants, 37 (62%) were unable to undergo pre-operative assessment. Twenty-four (40%) could not complete assessment due to infant-related factors and 13 (22%) due to environmental-related factors. For every point increase in the Aristotle Patient-Adjusted Complexity score, the infants likelihood of being unable to undergo assessment increased by 35% (odds ratio: 0.35; 95% confidence interval: 1.03-1.77, P = 0.03). Over half of the infants undergoing open heart surgery were unable to complete pre-operative neurodevelopmental assessment. The primary reason for this was infant-related medical instability. Findings suggest further research is warranted to investigate whether the Aristotle Patient-Adjusted Complexity score might serve as an indicator to inform developmental surveillance with this medically fragile cohort. © 2017 Paediatrics and Child Health Division (The Royal Australasian College of Physicians).

Combustor liner construction

NASA Technical Reports Server (NTRS)

Craig, H. M.; Wagner, W. B.; Strock, W. J. (Inventor)

1983-01-01

A combustor liner is fabricated from a plurality of individual segments each containing counter/parallel Finwall material and are arranged circumferentially and axially to define the combustion zone. Each segment is supported by a hook and ring construction to an opened lattice frame with sufficient tolerance between the hook and ring to permit thermal expansion with a minimum of induced stresses.

First uses of HAART 300 rings for aortic valve repair in Poland - 4 case studies.

PubMed

Juściński, Jacek H; Koprowski, Andrzej; Kołaczkowska, Magdalena; Kowalik, Maciej M; Rogowski, Jan A; Rankin, James S

2018-03-01

Aortic valve reconstructions using geometric annuloplasty rings HAART 300/200 open new era in aortic valve surgery. The HAART technology resizes, reshapes, stabilizes and simplifies aortic valve repair. The HAART aortic repair rings are designed to be implanted directly into aortic annulus (under aortic valve leaflets). We present first in Poland 4 cases of aortic valve reconstructions using geometric annuloplasty rings HAART 300. Two patients had type IA aortic insufficiency (due to El-Khoury classification) - they were treated by HAART 300 ring insertion and ascending aorta prosthesis implantation. Third patient, Marfan with type IB aortic insufficiency was repaired by HAART 300 ring implantation followed by remodeling (Yacoub) procedure. Fourth patient with type II aortic insufficiency (due to RCC prolapse) was repaired by HAART 300 implantation and cusp plication. All patients shows good results on 6 months postoperative 3D TTE examinations. Presented technique is reproducible and simplify aortic valve reconstructions.

Ring-Opening Polymerization of rac-Lactide with Aluminum Chiral Anilido-Oxazolinate Complexes

PubMed Central

2015-01-01

A series of dimethylaluminum complexes (L1a–i)AlMe2 (2a–i, where HL1a–i = 2-(2′-ArNH)phenyl-4-R1-oxazoline) bearing chiral, bidentate anilido-oxazolinate ligands have been prepared and characterized. Six of the complexes, in the presence of an alcohol cocatalyst, are shown to be active initiators for the stereoselective ring-opening polymerization of rac-lactide in toluene solution and under bulk conditions, yielding polylactides with a range of tacticity from slightly isotactic to moderately heterotactic. The reactivity and selectivity of these catalysts are discussed on the basis of the effect of their substituents. PMID:24891754

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

PubMed

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Epoxide reduction with hydrazine on graphene: a first principles study.

PubMed

Kim, Min Chan; Hwang, Gyeong S; Ruoff, Rodney S

2009-08-14

Mechanisms for epoxide reduction with hydrazine on a single-layer graphene sheet are examined using quantum mechanical calculations within the framework of gradient-corrected spin-polarized density-functional theory. We find that the reduction reaction is mainly governed by epoxide ring opening which is initiated by H transfer from hydrazine or its derivatives. In addition, our calculations suggest that the epoxide reduction by hydrazine may predominantly follow a direct Eley-Rideal mechanism rather than a Langmuir-Hinshelwood mechanism. We also discuss the generation of various hydrazine derivatives during the reduction of graphene oxide with hydrazine and their potential contribution to lowering the barrier height of epoxide ring opening.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barc, B.; Ryszka, M.; Spurrell, J.

Multi-photon ionization (MPI) of the RNA base uracil has been studied in the wavelength range 220–270 nm, coinciding with excitation to the S{sub 2}(ππ*) state. A fragment ion at m/z = 84 was produced by 2-photon absorption at wavelengths ≤232 nm and assigned to C{sub 3}H{sub 4}N{sub 2}O{sup +} following CO abstraction. This ion has not been observed in alternative dissociative ionization processes (notably electron impact) and its threshold is close to recent calculations of the minimum activation energy for a ring opening conical intersection to a σ(n-π)π* closed shell state. Moreover, the predicted ring opening transition leaves a COmore » group at one end of the isomer, apparently vulnerable to abstraction. An MPI mass spectrum of uracil-water clusters is presented for the first time and compared with an equivalent dry measurement. Hydration enhances certain fragment ion pathways (particularly C{sub 3}H{sub 3}NO{sup +}) but represses C{sub 3}H{sub 4}N{sub 2}O{sup +} production. This indicates that hydrogen bonding to water stabilizes uracil with respect to neutral excited-state ring opening.« less

Mechanistic studies aimed at the development of single site metal alkoxide catalysts for the production of polyoxygenates from renewable resources.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chisholm, Malcolm H.

2015-12-15

The work proposed herein follows on directly from the existing 3 year grant and the request for funding is for 12 months to allow completion of this work and graduation of current students supported by DOE. The three primary projects are as follows. 1.) A comparative study of the reactivity of LMg(OR) (solvent), where L= a β-diiminate or pyrromethene ligand, in the ring-opening of cyclic esters. 2.) The homopolymerization of expoxides, particularly propylene oxide and styrene oxide, and their copolymerizations with carbon dioxide or organic anhydrides to yield polycarbonates or polyesters, respectively. 3.) The development of well-defined bismuth (III) complexesmore » for ring-opening polymerizations that are tolerant of both air and water. In each of these topics special emphasis is placed on developing a detailed mechanistic understanding of the ring-opening event and how this is modified by the employment of specific metal and ligand combinations. This document also provides a report on findings of the past grant period that are not yet in the public domain/published and shows how the proposed work will bring the original project to conclusion.« less

Functionalization of multi-walled carbon nanotubes by epoxide ring-opening polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin Fanlong; Rhee, Kyong Yop; Park, Soo-Jin, E-mail: sjpark@inha.ac.kr

2011-12-15

In this study, covalent functionalization of carbon nanotubes (CNTs) was accomplished by surface-initiated epoxide ring-opening polymerization. FT-IR spectra showed that polyether and epoxide group covalently attached to the sidewalls of CNTs. TGA results indicated that the polyether was successfully grown from the CNT surface, with the final products having a polymer weight percentage of ca. 14-74 wt%. The O/C ratio of CNTs increased significantly from 5.1% to 29.8% after surface functionalization of CNTs. SEM and TEM images of functionalized CNTs exhibited that the tubes were enwrapped by polymer chains with thickness of several nanometers, forming core-shell structures with CNTs atmore » the center. - Graphical abstract: Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers, forming core-shell structures with CNTs at the center. Highlights: Black-Right-Pointing-Pointer CNTs were functionalized by epoxide ring-opening polymerization. Black-Right-Pointing-Pointer Polyether and epoxide group covalently attached to the sidewalls of CNTs. Black-Right-Pointing-Pointer Functionalized CNTs have a polymer weight percentage of ca. 14-74 wt%. Black-Right-Pointing-Pointer Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers.« less

Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, R.D.; Cortopassi, J.E.; Falloon, S.B.

1992-11-01

The reactions of 3,3-dimethylthietane, SCH{sub 2}CMe{sub 2}CH{sub 2} (3,3-DMT), and thietane, SCH{sub 2}CH{sub 2}CH{sub 2}, with Re{sub 3}(CO){sub 10}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}]({mu}-H){sub 3}, 2b. Compound 2a was characterized crystallographically and was found to consist of a trirhenium cluster with three bridging hydride ligands and a bridging thietane ligand coordinated through its sulfur atom. 2a and 2b react with halide ions by ring-opening additions to the 3,3-DMT ligand to yield the complex anions [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}x)({mu}-h){sub 3}]{sup -} 3A-6A, X = F (71%), Cl(71%), Br(84%), I(87%) and [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl)({mu}-H){sub 3}]{sup -}, 4b (67%). Similarly,more » addition of NMe{sub 3} to 2a and 2b yielded the ring-opened zwitterions Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}NMe{sub 3})({mu}-H){sub 3}, 7 a crystographically. They are zwitterions positively charged at the nitrogen atoms and negatively charged on the trirhenium clusters. Complex 7b was also obtained in a 48% yield from the reaction of Re{sub 3}(C){sub 12}({mu}-H){sub 3} with Me{sub 3}NO in the presence of thietane, but the corresponding reaction using 3,3-DMT yielded only 2a and Re{sub 3}(CO){sub 11}(SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}-H){sub 3}, 8. Attempts to obtain a ring-opening addition to 2a by reaction with PMe{sub 2}Ph yielded only Re{sub 3}(CO){sub 10}(PMe{sub 2}PH){sub 2}({mu}-H){sub 3} by ligand substitution. Attempts to obtain ring opening addition to 8 by reaction with I{sup -} yielded only [Re{sub 3}(CO){sub 11}I({mu}-H){sub 3}]{sup -} by ligand substitution. 20 refs., 3 figs., 10 tabs.« less

Initial mechanisms for the unimolecular decomposition of electronically excited bisfuroxan based energetic materials.

PubMed

Yuan, Bing; Bernstein, Elliot R

2017-01-07

Unimolecular decomposition of energetic molecules, 3,3'-diamino-4,4'-bisfuroxan (labeled as A) and 4,4'-diamino-3,3'-bisfuroxan (labeled as B), has been explored via 226/236 nm single photon laser excitation/decomposition. These two energetic molecules, subsequent to UV excitation, create NO as an initial decomposition product at the nanosecond excitation energies (5.0-5.5 eV) with warm vibrational temperature (1170 ± 50 K for A, 1400 ± 50 K for B) and cold rotational temperature (<55 K). Initial decomposition mechanisms for these two electronically excited, isolated molecules are explored at the complete active space self-consistent field (CASSCF(12,12)/6-31G(d)) level with and without MP2 correction. Potential energy surface calculations illustrate that conical intersections play an essential role in the calculated decomposition mechanisms. Based on experimental observations and theoretical calculations, NO product is released through opening of the furoxan ring: ring opening can occur either on the S 1 excited or S 0 ground electronic state. The reaction path with the lowest energetic barrier is that for which the furoxan ring opens on the S 1 state via the breaking of the N1-O1 bond. Subsequently, the molecule moves to the ground S 0 state through related ring-opening conical intersections, and an NO product is formed on the ground state surface with little rotational excitation at the last NO dissociation step. For the ground state ring opening decomposition mechanism, the N-O bond and C-N bond break together in order to generate dissociated NO. With the MP2 correction for the CASSCF(12,12) surface, the potential energies of molecules with dissociated NO product are in the range from 2.04 to 3.14 eV, close to the theoretical result for the density functional theory (B3LYP) and MP2 methods. The CASMP2(12,12) corrected approach is essential in order to obtain a reasonable potential energy surface that corresponds to the observed decomposition behavior of these molecules. Apparently, highly excited states are essential for an accurate representation of the kinetics and dynamics of excited state decomposition of both of these bisfuroxan energetic molecules. The experimental vibrational temperatures of NO products of A and B are about 800-1000 K lower than previously studied energetic molecules with NO as a decomposition product.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elsasser, Brigitta M.; Schoenen, Iris; Fels, Gregor

Candida antarctica lipase B (CALB) efficiently catalyzes the ring-opening polymerization of lactones to high molecular weight products in good yield. In contrast, an efficient enzymatic synthesis of polyamides has so far not been described in the literature. This obvious difference in enzyme catalysis is the subject of our comparative study of the initial steps of a CALB catalyzed ring-opening polymerization of ε- caprolactone and ε-caprolactam. We have applied docking tools to generate the reactant state complex and performed quantum mechanical/molecular mechanical (QM/MM) calculations at the density functional theory (DFT) PBE0 level of theory to simulate the acylation of Ser105 bymore » the lactone and the lactam, respectively, via the corresponding first tetrahedral intermediates. We could identify a decisive difference in the accessibility of the two substrates in the ring-opening to the respective acyl enzyme complex as the attack of ε-caprolactam is hindered because of an energetically disfavored proton transfer during this part of the catalytic reaction while ε-caprolactone is perfectly processed along the widely accepted pathway using the catalytic triade of Ser105, His224, and Asp187. Since the generation of an acylated Ser105 species is the crucial step of the polymerization procedure, our results give an explanation for the unsatisfactory enzymatic polyamide formation and opens up new possibilities for targeted rational catalyst redesign in hope of an experimentally useful CALB catalyzed polyamide synthesis.« less

Passive Capture Joint with Three Degrees of Freedom

NASA Technical Reports Server (NTRS)

Cloyd, Richard A. (Inventor); Weddendorf, Bruce (Inventor)

2001-01-01

A passive capture joint with three degrees of freedom is presented wherein two structural elements are joined together solely by moving the two elements into position, and which when joined together have rotation in all three axes. The inventive apparatus is comprised of two halves: (1) a joint ball mounted on a stem as in a common trailer hitch, and; (2) a socket. The socket consists of a base having an exterior wall and forming an interior chamber, the chamber having a top end and a bottom end, and an interior wall. The chamber is open at the top end, and forms a spherical cup at the bottom end. The socket base's interior chamber is sized to accept the joint ball. The base also forms at least one bore at an acute angle away from the interior chamber's open end. The bores have a first opening in the interior wall of the chamber, and a second opening in the exterior wall of the base. Retaining balls sized to fit within the bores, but to only partially pass through the first opening, are moveably housed within the bores. The retaining balls are moveably held in the first opening by a compression spring housed in the bore. As the joint ball is inserted in the chamber it forces the retaining balls back into the bore until the equator of the joint ball passes. Because the bore is at an acute angle to the chamber the joint ball cannot exit the chamber without the joint being unlocked. The joint is unlocked by rotating a locking ring which encircles the base and covers the second opening. The locking ring has a radial slot for each retaining ball, disposed angularly from the base, and sized to allow passage of the retaining ball in the radial direction when the locking ring is rotated to align the radial slot with the second opening.

Quantum optimal control of isomerization dynamics of a one-dimensional reaction-path model dominated by a competing dissociation channel

NASA Astrophysics Data System (ADS)

Kurosaki, Yuzuru; Artamonov, Maxim; Ho, Tak-San; Rabitz, Herschel

2009-07-01

Quantum wave packet optimal control simulations with intense laser pulses have been carried out for studying molecular isomerization dynamics of a one-dimensional (1D) reaction-path model involving a dominant competing dissociation channel. The 1D intrinsic reaction coordinate model mimics the ozone open→cyclic ring isomerization along the minimum energy path that successively connects the ozone cyclic ring minimum, the transition state (TS), the open (global) minimum, and the dissociative O2+O asymptote on the O3 ground-state A1' potential energy surface. Energetically, the cyclic ring isomer, the TS barrier, and the O2+O dissociation channel lie at ˜0.05, ˜0.086, and ˜0.037 hartree above the open isomer, respectively. The molecular orientation of the modeled ozone is held constant with respect to the laser-field polarization and several optimal fields are found that all produce nearly perfect isomerization. The optimal control fields are characterized by distinctive high temporal peaks as well as low frequency components, thereby enabling abrupt transfer of the time-dependent wave packet over the TS from the open minimum to the targeted ring minimum. The quick transition of the ozone wave packet avoids detrimental leakage into the competing O2+O channel. It is possible to obtain weaker optimal laser fields, resulting in slower transfer of the wave packets over the TS, when a reduced level of isomerization is satisfactory.

COOLANT STABILIZED WITH KETONE

DOEpatents

Burr, J.G.; Strong, J.D.

1961-11-21

sion). U. S. Patent 3,009.88l. Nov. 2l, l06l. A method is given for inhibiting radiolytic damage to a polyphenyl composition undergoing nuclear irradiation, the polyphenyl composition initially consisting essentially of polyphenyls having 2 to 4 phenyl rings. The method comprises adding approximately 5 mole% anthraquinone to the polyphenyl composition. (AEC)

Understanding the Reaction Chemistry of 2,2':5',2''-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Understanding the Reaction Chemistry of 2,2':5',2"-Terthiophene Films with Vapor-Deposited Ag, Al, and Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sang, Lingzi; Matz, Dallas L.; Pemberton, Jeanne E.

The reaction chemistry of vapor-deposited 2,2':5',2''-terthiophene (α-3T) solid-state thin films with postdeposited Ag, Al, and Ca is investigated in ultrahigh vacuum using Raman spectroscopy. Vapor-deposited Ag forms nanoparticles on these films and induces considerable surface enhanced Raman scattering (SERS) along with a change in molecular symmetry of adjacent α-3T and formation of Ag–S bonds; no other reaction chemistry is observed. Vapor-deposited Al and Ca undergo chemical reaction with α-3T initiated by metal-to-α-3T electron transfer. For Al, the resulting product is predominantly amorphous carbon through initial radical formation and subsequent decomposition reactions. For Ca, the spectral evidence suggests two pathways: onemore » leading to α-3T polymerization and the other resulting in thiophene ring opening, both initiated by radical formation through Ca-to-α-3T electron transfer. These interfacial reactions reflect the complex chemistry that can occur between low work function metals and thiophene-based oligomers. This reactivity is strongly correlated with metal work function.« less

Diastereoselective addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones

NASA Astrophysics Data System (ADS)

Uteuliyev, Maulen M.; Nguyen, Thien T.; Coltart, Don M.

2015-12-01

The α-alkylation of ketones and their derivatives by the addition of their corresponding enolates to alkyl halides is a fundamental synthetic transformation, but its utility is limited because the key bond-forming step proceeds in a bimolecular nucleophilic substitution fashion. Here we describe how an umpolung strategy that involves the addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones—directed by the alkoxide of the 1-azo-3-alkoxy propenes formed in situ via base-induced ring opening of the epoxide—leads to the syn-selective production of α-alkyl-β-hydroxy N-sulfonyl hydrazones with α-quaternary centres. This transformation is remarkable in its ability to incorporate an unprecedented range of carbon-based substituents, which include primary, secondary and tertiary alkyl, as well as alkenyl, aryl, allenyl and alkynyl groups. Subsequent hydrolysis of the β-hydroxy N-sulfonyl hydrazone products produces the corresponding β-hydroxy ketones. In addition to hydrolysis, the hydrazone products are poised to undergo numerous different known synthetic transformations via well-established chemistry, which would provide access to a wide array of useful structures.

On the formation of the ·CH 2CH 2CH=NH 2+ distonic radical cation upon ionization of cyclopropylamine and allylamine

NASA Astrophysics Data System (ADS)

Nguyen, Minh Tho; Creve, Steven; Ha, Tae-Kyu

1998-08-01

Ab initio molecular orbital and density functional theory calculations have been applied to determine the relative stability of the cyclopropylamine 1 and allylamine (CH 2=CHCH 2NH 2+·2) radical cations and their isomers. It is confirmed that, upon ionization, 1 undergoes barrier-free ring-opening giving the distonic species ·CH 2CH 2CH=NH 2+3. 2 also rearranges by a 1,2-H-shift to the more stable 3 (by 70 kJ/mol) which is, however, less stable than the 1-aminopropene ion (CH 3-CH=CH-NH 2+·4) by 60 kJ/mol. The transition structure TS 2/3 lies 40 kJ/mol higher in energy than TS 3/4. Although QCISD and B3LYP calculations of isotropic hyperfine coupling constants agree reasonably with observed values, supporting the presence of the distonic 3 in ESR matrix experiments, the exclusive observation of 3, but not 4, is intriguing. This emphasizes the role of the matrix in stabilizing 3.

Arctic tree rings as recorders of variations in light availability

PubMed Central

Stine, A. R.; Huybers, P.

2014-01-01

Annual growth ring variations in Arctic trees are often used to reconstruct surface temperature. In general, however, the growth of Arctic vegetation is limited both by temperature and light availability, suggesting that variations in atmospheric transmissivity may also influence tree-ring characteristics. Here we show that Arctic tree-ring density is sensitive to changes in light availability across two distinct phenomena: explosive volcanic eruptions (P<0.01) and the recent epoch of global dimming (P<0.01). In each case, the greatest response is found in the most light-limited regions of the Arctic. Essentially no late 20th century decline in tree-ring density relative to temperature is seen in the least light-limited regions of the Arctic. Consistent results follow from analysis of tree-ring width and from individually analysing each of seven tree species. Light availability thus appears an important control, opening the possibility for using tree rings to reconstruct historical changes in surface light intensity. PMID:24805143

Self-organized formation of GaSb/GaAs quantum rings.

PubMed

Timm, R; Eisele, H; Lenz, A; Ivanova, L; Balakrishnan, G; Huffaker, D L; Dähne, M

2008-12-19

Ring-shaped GaSb/GaAs quantum dots, grown by molecular beam epitaxy, were studied using cross-sectional scanning tunneling microscopy. These quantum rings have an outer shape of a truncated pyramid with baselengths around 15 nm and heights of about 2 nm but are characterized by a clear central opening extending over about 40% of the outer baselength. They form spontaneously during the growth and subsequent continuous capping of GaSb/GaAs quantum dots due to the large strain and substantial As-for-Sb exchange reactions leading to strong Sb segregation.

Lone Propeller

NASA Image and Video Library

2017-09-15

This view of Saturn's A ring features a lone "propeller" -- one of many such features created by small moonlets embedded in the rings as they attempt, unsuccessfully, to open gaps in the ring material. The image was taken by NASA's Cassini spacecraft on Sept. 13, 2017. It is among the last images Cassini sent back to Earth. The view was taken in visible light using the Cassini spacecraft wide-angle camera at a distance of 420,000 miles (676,000 kilometers) from Saturn. Image scale is 2.3 miles (3.7 kilometers). https://photojournal.jpl.nasa.gov/catalog/PIA21894

Development of an Inflatable Head/Neck Restraint System for Ejection Seats

DTIC Science & Technology

1977-02-28

crewman’s head . It has been observed that low pressures, about 2 psi (1.38 nt/cm2 ) to 4 psi (2.76 nt/cm2 ), create some "spring back" or trampoline ...neck ring Neck injury Head rotation 210 ABSTRACT (Continue on rev’erse side If necessary end identify by block number) 4A ringý-shaped inflatable head ...injuries due to violent forward head rotation at the time of ejection thrust and parachute opening shock. Inflation of the neck ring will,’ be conducted by a

The occultation of 28 Sgr by Saturn - Saturn pole position and astrometry

NASA Technical Reports Server (NTRS)

Hubbard, W. B.; Porco, C. C.; Hunten, D. M.; Rieke, G. H.; Rieke, M. J.; Mccarthy, D. W.; Haemmerle, V.; Clark, R.; Turtle, E. P.; Haller, J.

1993-01-01

Saturn's ring plane-defined pole position is presently derived from the geometry of Saturn's July 3, 1989 occultation of 28 Sgr, as indicated by the timings of 12 circular edges in the Saturn C-ring as well as the edges of the Encke gap and the outer edge of the Keeler gap. The edge timings are used to solve for the position angle and opening angle of the apparent ring ellipses; the internal consistency of the data set and the redundancy of stations indicates an absolute error of the order of 5 km. The pole position thus obtained is consistent with the pole and ring radius scale derived from Voyager occultation observations.

Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products.

PubMed

Schmidt, Bernd; Kunz, Oliver

2013-01-01

Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

Open Source Initiative Powers Real-Time Data Streams

NASA Technical Reports Server (NTRS)

2014-01-01

Under an SBIR contract with Dryden Flight Research Center, Creare Inc. developed a data collection tool called the Ring Buffered Network Bus. The technology has now been released under an open source license and is hosted by the Open Source DataTurbine Initiative. DataTurbine allows anyone to stream live data from sensors, labs, cameras, ocean buoys, cell phones, and more.

Designing efficient photochromic dithienylethene dyads.

PubMed

Fihey, Arnaud; Jacquemin, Denis

2015-06-01

Aiming at designing more efficient multiphotochromes, we investigate with the help of ab initio tools the impact of the substitution on a series of dimers constituted of two dithienylethene (DTE) moieties, strongly coupled to each other through an ethynyl linker. The electronic structure and the optical properties of a large panel of compounds, substituted on different positions by various types of electroactive groups, have been compared with the aim of designing a dyad in which the three possible isomers (open-open, closed-open, closed-closed) can be reached. We show that appending the reactive carbons atoms of the DTE core with electroactive groups on one of the two photochromes allows cyclisation to be induced on a specific moiety, which leads to the formation of the desired closed-open isomer. Substituting the lateral positions of the thiophene rings provides further control of the topology of the frontier molecular orbitals, so that the electronic transition inducing the second ring closure stands out in the spectrum of the intermediate isomer.

Experimental Study of Shock Generated Compressible Vortex Ring

NASA Astrophysics Data System (ADS)

Das, Debopam; Arakeri, Jaywant H.; Krothapalli, Anjaneyulu

2000-11-01

Formation of a compressible vortex ring and generation of sound associated with it is studied experimentally. Impulse of a shock wave is used to generate a vortex ring from the open end of a shock-tube. Vortex ring formation process has been studied in details using particle image Velocimetry (PIV). As the shock wave exits the tube it diffracts and expands. A circular vortex sheet forms at the edge and rolls up into a vortex ring. Far field microphone measurement shows that the acoustic pressure consists of a spike due to shock wave followed by a low frequency pressure wave of decaying nature, superimposed with high frequency pressure wave. Acoustic waves consist of waves due to expansion, waves formed in the tube during diaphragm breakage and waves associated with the vortex ring and shear-layer vortices. Unsteady evolution of the vortex ring and shear-layer vortices in the jet behind the ring is studied by measuring the velocity field using PIV. Corresponding vorticity field, circulation around the vortex core and growth rate of the vortex core is calculated from the measured velocity field. The velocity field in a compressible vortex ring differs from that of an incompressible ring due to the contribution from both shock and vortex ring.

Molecular insights into RBR E3 ligase ubiquitin transfer mechanisms.

PubMed

Dove, Katja K; Stieglitz, Benjamin; Duncan, Emily D; Rittinger, Katrin; Klevit, Rachel E

2016-08-01

RING-in-between-RING (RBR) ubiquitin (Ub) ligases are a distinct class of E3s, defined by a RING1 domain that binds E2 Ub-conjugating enzyme and a RING2 domain that contains an active site cysteine similar to HECT-type E3s. Proposed to function as RING/HECT hybrids, details regarding the Ub transfer mechanism used by RBRs have yet to be defined. When paired with RING-type E3s, E2s perform the final step of Ub ligation to a substrate. In contrast, when paired with RBR E3s, E2s must transfer Ub onto the E3 to generate a E3~Ub intermediate. We show that RBRs utilize two strategies to ensure transfer of Ub from the E2 onto the E3 active site. First, RING1 domains of HHARI and RNF144 promote open E2~Ubs. Second, we identify a Ub-binding site on HHARI RING2 important for its recruitment to RING1-bound E2~Ub. Mutations that ablate Ub binding to HHARI RING2 also decrease RBR ligase activity, consistent with RING2 recruitment being a critical step for the RBR Ub transfer mechanism. Finally, we demonstrate that the mechanism defined here is utilized by a variety of RBRs. © 2016 The Authors.

Deletion of cytosolic gating ring decreases gate and voltage sensor coupling in BK channels.

PubMed

Zhang, Guohui; Geng, Yanyan; Jin, Yakang; Shi, Jingyi; McFarland, Kelli; Magleby, Karl L; Salkoff, Lawrence; Cui, Jianmin

2017-03-06

Large conductance Ca 2+ -activated K + channels (BK channels) gate open in response to both membrane voltage and intracellular Ca 2+ The channel is formed by a central pore-gate domain (PGD), which spans the membrane, plus transmembrane voltage sensors and a cytoplasmic gating ring that acts as a Ca 2+ sensor. How these voltage and Ca 2+ sensors influence the common activation gate, and interact with each other, is unclear. A previous study showed that a BK channel core lacking the entire cytoplasmic gating ring (Core-MT) was devoid of Ca 2+ activation but retained voltage sensitivity (Budelli et al. 2013. Proc. Natl. Acad. Sci. USA http://dx.doi.org/10.1073/pnas.1313433110). In this study, we measure voltage sensor activation and pore opening in this Core-MT channel over a wide range of voltages. We record gating currents and find that voltage sensor activation in this truncated channel is similar to WT but that the coupling between voltage sensor activation and gating of the pore is reduced. These results suggest that the gating ring, in addition to being the Ca 2+ sensor, enhances the effective coupling between voltage sensors and the PGD. We also find that removal of the gating ring alters modulation of the channels by the BK channel's β1 and β2 subunits. © 2017 Zhang et al.

Deletion of cytosolic gating ring decreases gate and voltage sensor coupling in BK channels

PubMed Central

Zhang, Guohui; Shi, Jingyi; McFarland, Kelli; Magleby, Karl L.; Salkoff, Lawrence

2017-01-01

Large conductance Ca2+-activated K+ channels (BK channels) gate open in response to both membrane voltage and intracellular Ca2+. The channel is formed by a central pore-gate domain (PGD), which spans the membrane, plus transmembrane voltage sensors and a cytoplasmic gating ring that acts as a Ca2+ sensor. How these voltage and Ca2+ sensors influence the common activation gate, and interact with each other, is unclear. A previous study showed that a BK channel core lacking the entire cytoplasmic gating ring (Core-MT) was devoid of Ca2+ activation but retained voltage sensitivity (Budelli et al. 2013. Proc. Natl. Acad. Sci. USA. http://dx.doi.org/10.1073/pnas.1313433110). In this study, we measure voltage sensor activation and pore opening in this Core-MT channel over a wide range of voltages. We record gating currents and find that voltage sensor activation in this truncated channel is similar to WT but that the coupling between voltage sensor activation and gating of the pore is reduced. These results suggest that the gating ring, in addition to being the Ca2+ sensor, enhances the effective coupling between voltage sensors and the PGD. We also find that removal of the gating ring alters modulation of the channels by the BK channel’s β1 and β2 subunits. PMID:28196879

Clinical acceptability of an ethylene-vinyl-acetate nonmedicated vaginal ring.

PubMed

Roumen, F J; Dieben, T O

1999-01-01

In an open study the acceptability of a newly designed vaginal ring was evaluated. The ring being developed for contraceptive purposes was made of ethylene-vinyl-acetate copolymer (EVA). In this study the ring did not contain active medication. Three groups of 20 healthy female volunteers were asked to use rings--with a diameter of 54 mm--for 21 consecutive days; each group was assigned rings with a different cross-sectional thickness of 3, 3.5, or 4 mm. Subjects were given diary cards to report on insertion and removal of the ring and on complaints. Of the 65 women who participated, 59 completed the study and used the ring for at least 21 days, giving an acceptability of 91% (59/65). No major differences were found between the three types of rings except for a sensation of expulsion, which was reported more often in the group assigned the smallest cross-sectional-thickness ring. Expulsion was reported once during intercourse in the 3.5-mm group. Insertion and removal of the rings were judged to be easy by the overall majority of the women. The ring was felt by the partner during intercourse in 35%-50% of couples. Further development of an active combined contraceptive EVA ring with a cross-sectional thickness of 4 mm seems a reasonable option. In future studies with the active ring, allowance for temporary removal of the ring during intercourse, if preferred, may be suggested.

Endoscopic versus open bursectomy of lateral malleolar bursitis.

PubMed

Choi, Jae Hyuck; Lee, Kyung Tai; Lee, Young Koo; Kim, Dong Hyun; Kim, Jeong Ryoul; Chung, Woo Chull; Cha, Seung Do

2012-06-01

Compare the result of endoscopic versus open bursectomy in lateral malleolar bursitis. Prospective evaluation of 21 patients (22 ankles) undergoing either open or endoscopic excision of lateral malleolar bursitis. The median age was 64 (38-79) years old. The median postoperative follow-up was 15 (12-18) months. Those patients undergoing endoscopic excision showed a higher satisfaction rate (excellent 9, good 2) than open excision (excellent 4, good 3, fair 1). The wounds also healed earlier in the endoscopic group although the operation time was slightly longer. One patient in the endoscopic group had recurrence of symptoms but complications in the open group included one patient with skin necrosis, one patient with wound dehiscence, and two patients of with superficial peroneal nerve injury. Endoscopic resection of the lateral malleolar bursitis is a promising technique and shows favorable results compared to the open resection. Therapeutic studies-Investigating the result of treatment, Level II.

Inherent conformational flexibility of F1-ATPase α-subunit.

PubMed

Hahn-Herrera, Otto; Salcedo, Guillermo; Barril, Xavier; García-Hernández, Enrique

2016-09-01

The core of F1-ATPase consists of three catalytic (β) and three noncatalytic (α) subunits, forming a hexameric ring in alternating positions. A wealth of experimental and theoretical data has provided a detailed picture of the complex role played by catalytic subunits. Although major conformational changes have only been seen in β-subunits, it is clear that α-subunits have to respond to these changes in order to be able to transmit information during the rotary mechanism. However, the conformational behavior of α-subunits has not been explored in detail. Here, we have combined unbiased molecular dynamics (MD) simulations and calorimetrically measured thermodynamic signatures to investigate the conformational flexibility of isolated α-subunits, as a step toward deepening our understanding of its function inside the α3β3 ring. The simulations indicate that the open-to-closed conformational transition of the α-subunit is essentially barrierless, which is ideal to accompany and transmit the movement of the catalytic subunits. Calorimetric measurements of the recombinant α-subunit from Geobacillus kaustophilus indicate that the isolated subunit undergoes no significant conformational changes upon nucleotide binding. Simulations confirm that the nucleotide-free and nucleotide-bound subunits show average conformations similar to that observed in the F1 crystal structure, but they reveal an increased conformational flexibility of the isolated α-subunit upon MgATP binding, which might explain the evolutionary conserved capacity of α-subunits to recognize nucleotides with considerable strength. Furthermore, we elucidate the different dependencies that α- and β-subunits show on Mg(II) for recognizing ATP. Copyright © 2016 Elsevier B.V. All rights reserved.

Signatures of Young Planets in the Continuum Emission from Protostellar Disks

NASA Astrophysics Data System (ADS)

Isella, Andrea; Turner, Neal J.

2018-06-01

Many protostellar disks show central cavities, rings, or spiral arms likely caused by low-mass stellar or planetary companions, yet few such features are conclusively tied to bodies embedded in the disks. We note that even small features on the disk surface cast shadows, because the starlight grazes the surface. We therefore focus on accurately computing the disk thickness, which depends on its temperature. We present models with temperatures set by the balance between starlight heating and radiative cooling, which are also in vertical hydrostatic equilibrium. The planet has 20, 100, or 1000 M ⊕, ranging from barely enough to perturb the disk significantly, to clearing a deep tidal gap. The hydrostatic balance strikingly alters the appearance of the model disk. The outer walls of the planet-carved gap puff up under starlight heating, throwing a shadow across the disk beyond. The shadow appears in scattered light as a dark ring that could be mistaken for a gap opened by another more distant planet. The surface brightness contrast between outer wall and shadow for the 1000 M ⊕ planet is an order of magnitude greater than a model neglecting the temperature disturbances. The shadow is so deep that it largely hides the planet-launched outer arm of the spiral wave. Temperature gradients are such that outer low-mass planets undergoing orbital migration will converge within the shadow. Furthermore, the temperature perturbations affect the shape, size, and contrast of features at millimeter and centimeter wavelengths. Thus radiative heating and cooling are key to the appearance of protostellar disks with embedded planets.

On random pressure pulses in the turbine draft tube

NASA Astrophysics Data System (ADS)

Kuibin, P. A.; Shtork, S. I.; Skripkin, S. G.; Tsoy, M. A.

2017-04-01

The flow in the conical part of the hydroturbine draft tube undergoes various instabilities due to deceleration and flow swirling at off-design operation points. In particular, the precessing vortex rope develops at part-load regimes in the draft tube. This rope induces periodical low-frequency pressure oscillations in the draft tube. Interaction of rotational (asynchronous) mode of disturbances with the elbow can bring to strong oscillations in the whole hydrodynamical system. Recent researches on flow structure in the discharge cone in a regime of free runner had revealed that helical-like vortex rope can be unstable itself. Some coils of helix close to each other and reconnection appears with generation of a vortex ring. The vortex ring moves toward the draft tube wall and downstream. The present research is focused on interaction of vortex ring with wall and generation of pressure pulses.

Hydrochromic Approaches to Mapping Human Sweat Pores.

PubMed

Park, Dong-Hoon; Park, Bum Jun; Kim, Jong-Man

2016-06-21

Hydrochromic materials, which undergo changes in their light absorption and/or emission properties in response to water, have been extensively investigated as humidity sensors. Recent advances in the design of these materials have led to novel applications, including monitoring the water content of organic solvents, water-jet-based rewritable printing on paper, and hydrochromic mapping of human sweat pores. Our interest in this area has focused on the design of hydrochromic materials for human sweat pore mapping. We recognized that materials appropriate for this purpose must have balanced sensitivities to water. Specifically, while they should not undergo light absorption and/or emission transitions under ambient moisture conditions, the materials must have sufficiently high hydrochromic sensitivities that they display responses to water secreted from human sweat pores. In this Account, we describe investigations that we have carried out to develop hydrochromic substances that are suitable for human sweat pore mapping. Polydiacetylenes (PDAs) have been extensively investigated as sensor matrices because of their stimulus-responsive color change property. We found that incorporation of headgroups composed of hygroscopic ions such as cesium or rubidium and carboxylate counterions enables PDAs to undergo a blue-to-red colorimetric transition as well as a fluorescence turn-on response to water. Very intriguingly, the small quantities of water secreted from human sweat pores were found to be sufficient to trigger fluorescence turn-on responses of the hydrochromic PDAs, allowing precise mapping of human sweat pores. Since the hygroscopic ion-containing PDAs developed in the initial stage display a colorimetric transition under ambient conditions that exist during humid summer periods, a new system was designed. A PDA containing an imidazolium ion was found to be stable under all ambient conditions and showed temperature-dependent hydrochromism corresponding to a colorimetric change near body temperature. This feature enables the use of this technique to generate high-quality images of sweat pores. This Account also focuses on the results of the most recent phase of this investigation, which led to the development of a simple yet efficient and reliable technique for sweat pore mapping. The method utilizes a hydrophilic polymer composite film containing fluorescein, a commercially available dye that undergoes a fluorometric response as a result of water-dependent interconversion between its ring-closed spirolactone (nonfluorescent) and ring-opened fluorone (fluorescent) forms. Surface-modified carbon nanodots (CDs) have also been found to be efficient for hydrochromic mapping of human sweat pores. The results discovered by Lou et al. [ Adv. Mater. 2015 , 27 , 1389 ] are also included in this Account. Sweat pore maps obtained from fingertips using these materials were found to be useful for fingerprint analysis. In addition, this hydrochromism-based approach is sufficiently sensitive to enable differentiation between sweat-secreting active pores and inactive pores. As a result, the techniques can be applied to clinical diagnosis of malfunctioning sweat pores. The directions that future research in this area will follow are also discussed.

FOOD INTOLERANCES AND ASSOCIATED SYMPTOMS IN PATIENTS UNDERGOING FOBI-CAPELLA TECHNIQUE WITHOUT GASTRIC RING

PubMed Central

MOREIRA, Marcella de Arruda; ESPÍNOLA, Patrícia Ramos Maciel; de AZEVEDO, Camila Wanderley

2015-01-01

Background Bariatric surgery is considered the only effective method to treat refractory obesity, and especially for those in which clinical treatment was not successful. However, the appearance of food intolerances and clinical manifestations are quite common. Aim To identify food intolerances and associated them to symptoms in patients undergoing Fobi-Capella technique without gastric ring. Methods This was a cross-sectional study of adult patients who had more than one year after surgery. Demographic, anthropometric, weight and preoperative height data were investigated. Nutritional status was classified according to the criteria established by the World Health Organization. It was considered food intolerance the presence of nausea, vomiting, diarrhea or bloating after eating a particular food. Results The sample consisted of 61 patients who attended the nutritional consultation of which 26 (42.6%) had food intolerance, mostly related to red meat (n=12; 34.3%) during the first six months of operation; there was a significant difference between the periods between 0 and 6 months, and 7 to 12 (p=0.02). Among the symptoms reported by patients, nausea was the most recurrent until the 6th month, but without significant differences between the two periods (p=0.06). Conclusions The Fobi-Capella procedure without gastric ring promoted high frequency of intolerance to meat in general, especially for the red, chicken and fish, on this sequence; nausea was the most frequent symptom. These data suggest the need for adequate nutritional monitoring throughout the postoperative period. PMID:25861067

CLEARING MAGNET DESIGN FOR APS-U

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abliz, M.; Grimmer, J.; Jaski, Y.

2017-06-25

The Advanced Photon Source is in the process of developing an upgrade (APS-U) of the storage ring. The upgrade will be converting the current double bend achromat (DBA) lattice to a multi-bend achromat (MBA) lattice. In addition, the storage ring will be operated at 6 GeV and 200 mA with regular swap-out injection to keep the stored beam current constant [1]. The swap-out injection will take place with beamline shutters open. For radiation safety to ensure that no electrons can exit the storage ring, a passive method of protecting the beamline and containing the electrons inside the storage ring ismore » proposed. A clearing magnet will be located in all beamline front ends inside the storage ring tunnel. This article will discuss the features and design of the clearing magnet scheme for APS-U.« less

Structural and kinetic analysis of the COP9-Signalosome activation and the cullin-RING ubiquitin ligase deneddylation cycle

PubMed Central

Mosadeghi, Ruzbeh; Reichermeier, Kurt M; Winkler, Martin; Schreiber, Anne; Reitsma, Justin M; Zhang, Yaru; Stengel, Florian; Cao, Junyue; Kim, Minsoo; Sweredoski, Michael J; Hess, Sonja; Leitner, Alexander; Aebersold, Ruedi; Peter, Matthias; Deshaies, Raymond J; Enchev, Radoslav I

2016-01-01

The COP9-Signalosome (CSN) regulates cullin–RING ubiquitin ligase (CRL) activity and assembly by cleaving Nedd8 from cullins. Free CSN is autoinhibited, and it remains unclear how it becomes activated. We combine structural and kinetic analyses to identify mechanisms that contribute to CSN activation and Nedd8 deconjugation. Both CSN and neddylated substrate undergo large conformational changes upon binding, with important roles played by the N-terminal domains of Csn2 and Csn4 and the RING domain of Rbx1 in enabling formation of a high affinity, fully active complex. The RING domain is crucial for deneddylation, and works in part through conformational changes involving insert-2 of Csn6. Nedd8 deconjugation and re-engagement of the active site zinc by the autoinhibitory Csn5 glutamate-104 diminish affinity for Cul1/Rbx1 by ~100-fold, resulting in its rapid ejection from the active site. Together, these mechanisms enable a dynamic deneddylation-disassembly cycle that promotes rapid remodeling of the cellular CRL network. DOI: http://dx.doi.org/10.7554/eLife.12102.001 PMID:27031283

Use of the initial trauma CT scan to aid in diagnosis of open pelvic fractures.

PubMed

Scolaro, John A; Wilson, David J; Routt, Milton Lee Chip; Firoozabadi, Reza

2015-10-01

Open pelvic disruptions represent high-energy injuries. The prompt identification and management of these injuries decreases their associated morbidity and mortality. Computed tomography (CT) scans are routinely obtained in the initial evaluation of patients with pelvic injuries. The purpose of this study is to identify the incidence and source of air densities noted on computed tomography (CT) scans of the abdominal and pelvic region in patients with pelvic fractures and evaluate the use of initial CT imaging as an adjunctive diagnostic tool to identify open injuries. A retrospective review of a prospectively collected database was performed at a single institution. Seven hundred and twenty-two consecutive patients with a pelvic disruption over a two-year period were included. Review of initial injury CT scans was performed using bone and lung viewing algorithms to identify the presence of extra-luminal air. The primary outcome was the presence, location and source of air identified on pre-operative CT scans. Secondary measurements were identification of air by plain radiograph and correlation between identified air densities on CT and clinically diagnosed open pelvic fractures. Ninety-eight patients were identified as having extra-luminal air densities on CT scans. Eighty-one patients were included in the final analysis following application of inclusion and exclusion criteria. Air was noted by the radiologist in forty-five (55.6%) instances. Six patients (7.4%) were clinically diagnosed with an open pelvic ring disruption; in two patients (2.4%) this diagnosis was delayed. In all patients, the CT was able to track air from its origin. In patients with pelvic disruptions, the injury CT should also be evaluated for the presence and source of extra-luminal air. In some patients, this finding may represent an open pelvic ring disruption. A complete physical exam and CT evaluation should be used to decrease the missed or delayed diagnosis of an open pelvic ring injury. Copyright © 2015 Elsevier Ltd. All rights reserved.

Early Primary Care Provider Follow-up and Readmission After High-Risk Surgery

PubMed Central

Brooke, Benjamin S.; Stone, David H.; Cronenwett, Jack L.; Nolan, Brian; DeMartino, Randall R.; MacKenzie, Todd A.; Goodman, David C.; Goodney, Philip P.

2014-01-01

IMPORTANCE Follow-up with a primary care provider (PCP) in addition to the surgical team is routinely recommended to patients discharged after major surgery despite no clear evidence that it improves outcomes. OBJECTIVE To test whether PCP follow-up is associated with lower 30-day readmission rates after open thoracic aortic aneurysm (TAA) repair and ventral hernia repair (VHR), surgical procedures known to have a high and low risk of readmission, respectively. DESIGN, SETTING, AND PARTICIPANTS In a cohort of Medicare beneficiaries discharged to home after open TAA repair (n = 12 679) and VHR (n = 52 807) between 2003 to 2010, we compared 30-day readmission rates between patients seen and not seen by a PCP within 30 days of discharge and across tertiles of regional primary care use. We stratified our analysis by the presence of complications during the surgical (index) admission. MAIN OUTCOMES AND MEASURES Thirty-day readmission rate. RESULTS Overall, 2619 patients (20.6%) undergoing open TAA repair and 4927 patients (9.3%) undergoing VHR were readmitted within 30 days after surgery. Complications occurred in 4649 patients (36.6%) undergoing open TAA repair and 4528 patients (8.6%) undergoing VHR during their surgical admission. Early follow-up with a PCP significantly reduced the risk of readmission among open TAA patients who experienced perioperative complications, from 35.0% (without follow-up) to 20.4% (with follow-up) (P < .001). However, PCP follow-up made no significant difference in patients whose hospital course was uncomplicated (19.4% with follow-up vs 21.9% without follow-up; P = .31). In comparison, early follow-up with a PCP after VHR did not reduce the risk of readmission, regardless of complications. In adjusted regional analyses, undergoing open TAA repair in regions with high compared with low primary care use was associated with an 18% lower likelihood of 30-day readmission (odds ratio, 0.82; 95% CI, 0.71–0.96; P = .02), whereas no significant difference was found among patients after VHR. CONCLUSIONS AND RELEVANCE Follow-up with a PCP after high-risk surgery (eg, open TAA repair), especially among patients with complications, is associated with a lower risk of hospital readmission. Patients undergoing lower-risk surgery (eg, VHR) do not receive the same benefit from early PCP follow-up. Identifying high-risk surgical patients who will benefit from PCP integration during care transitions may offer a low-cost solution toward limiting readmissions. PMID:25074237

Nucleophilic ortho-Allylation of Pyrroles and Pyrazoles: An Accelerated Pummerer/Thio-Claisen Rearrangement Sequence

PubMed Central

2013-01-01

Arylsulfinyl groups direct the metal-free, regiospecific, nucleophilic ortho-allylation of pyrroles and pyrazoles. Mechanistic studies support the intermediacy of allylsulfonium salts that undergo facile thio-Claisen rearrangement onto the heterocyclic ring, giving products of coupling. The strategy has been adapted to allow regiospecific propargylation of the heterocyclic substrates. PMID:23855635

Substrate-Controlled Product Divergence: Conversion of CO2 into Heterocyclic Products.

PubMed

Rintjema, Jeroen; Epping, Roel; Fiorani, Giulia; Martín, Eddy; Escudero-Adán, Eduardo C; Kleij, Arjan W

2016-03-14

Substituted epoxy alcohols and amines allow substrate-controlled conversion of CO2 into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach results in an unusual scope of CO2-derived products by initial activation of CO2 through either the amine or alcohol unit, thus providing nucleophiles for intramolecular epoxy ring opening under mild reaction conditions. Control experiments support the crucial role of the amine/alcohol fragment in this process with the nucleophile-assisted ring-opening step following an SN i pathway, and a 5-exo-tet cyclization, thus leading to heterocyclic scaffolds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regioselective palladium-catalyzed ring-opening reactions of C1-substituted oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylates

PubMed Central

Edmunds, Michael; Raheem, Mohammed Abdul; Boutin, Rebecca; Tait, Katrina

2016-01-01

Summary Palladium-catalyzed ring-opening reactions of C1 substituted 7-oxanorbornadiene derivatives with aryl iodides were investigated. The optimal conditions for this reaction were found to be PdCl2(PPh3)2, ZnCl2, Et3N and Zn in THF. Both steric and electronic factors played a role in the outcome of the reaction as increasing the steric bulk on the bridgehead carbon decreased the yield. These reactions were found to be highly regioselective, giving only one of the two possible regioisomers in all cases. A diverse collection of novel, highly substituted biphenyl derivatives were obtained. PMID:26977182

Report on the ENIAC (Electronic Numerical Integrator and Computer)

DTIC Science & Technology

1946-06-01

3401070 •ra l!Oeelall Ia ~· C....te .. t ’ hla •ltsar ~nan •-•~an, four nl.,• uaoatat•d ’Clt’l ••ell dlllt, ’l’llet Ia, t<M>r nlaJtl npn .. ..,l...the· chronological order shDwn on PX-CJ.-306. • When the cyelinp, unit ring rcach~s stuge 11, · gate B27 opens t.e pass an on beat pulse, This...C(X;) ’ Stage clcv6n of’ the ring opens g~te B27 . This gate passes a pulsD f which sets the tlip-tlop E27. Thll negative output or the tUp-tlop

Plasma Sheet Injections into the Inner Magnetosphere: Two-way Coupled OpenGGCM-RCM model results

NASA Astrophysics Data System (ADS)

Raeder, J.; Cramer, W. D.; Toffoletto, F.; Gilson, M. L.; Hu, B.

2017-12-01

Plasma sheet injections associated with low flux tube entropy bubbles have been found to be the primary means of mass transport from the plasma sheet to the inner magnetosphere. A two-way coupled global magnetosphere-ring current model, where the magnetosphere is modeled by the OpenGGCM MHD model and the ring current is modeled by the Rice Convection Model (RCM), is used to determine the frequency of association of bubbles with injections and inward plasma transport, as well as typical injection characteristics. Multiple geomagnetic storms and quiet periods are simulated to track and characterize inward flow behavior. Dependence on geomagnetic activity levels or drivers is also examined.

Biocatalytic Synthesis of Poly(δ-Valerolactone) Using a Thermophilic Esterase from Archaeoglobus fulgidus as Catalyst

PubMed Central

Cao, Hong; Han, Haobo; Li, Guangquan; Yang, Jiebing; Zhang, Lingfei; Yang, Yan; Fang, Xuedong; Li, Quanshun

2012-01-01

The ring-opening polymerization of δ-valerolactone catalyzed by a thermophilic esterase from the archaeon Archaeoglobus fulgidus was successfully conducted in organic solvents. The effects of enzyme concentration, temperature, reaction time and reaction medium on monomer conversion and product molecular weight were systematically evaluated. Through the optimization of reaction conditions, poly(δ-valerolactone) was produced in 97% monomer conversion, with a number-average molecular weight of 2225 g/mol, in toluene at 70 °C for 72 h. This paper has produced a new biocatalyst for the synthesis of poly(δ-valerolactone), and also deeper insight has been gained into the mechanism of thermophilic esterase-catalyzed ring-opening polymerization. PMID:23202895

Structure of a helicase–helicase loader complex reveals insights into the mechanism of bacterial primosome assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bin; Eliason, William K.; Steitz, Thomas A.

2013-09-19

During the assembly of the bacterial loader-dependent primosome, helicase loader proteins bind to the hexameric helicase ring, deliver it onto the oriC DNA and then dissociate from the complex. Here, to provide a better understanding of this key process, we report the crystal structure of the ~570-kDa prepriming complex between the Bacillus subtilis loader protein and the Bacillus stearothermophilus helicase, as well as the helicase-binding domain of primase with a molar ratio of 6:6:3 at 7.5 Å resolution. The overall architecture of the complex exhibits a three-layered ring conformation. Moreover, the structure combined with the proposed model suggests that themore » shift from the ‘open-ring’ to the ‘open-spiral’ and then the ‘closed-spiral’ state of the helicase ring due to the binding of single-stranded DNA may be the cause of the loader release.« less

Synthesis of modified cyclic and acyclic dextrins and comparison of their complexation ability

PubMed Central

Jicsinszky, László; Sohajda, Tamás; Puskás, István; Fenyvesi, Éva

2014-01-01

Summary We compared the complex forming ability of α-, β- and γ-cyclodextrins (α-CD, β-CD and γ-CD) with their open ring analogs. In addition to the native cyclodextrins also modified cyclodextrins and the corresponding maltooligomers, functionalized with neutral 2-hydroxypropyl moieties, were synthesized. A new synthetic route was worked out via bromination, benzylation, deacetylation and debenzylation to obtain the 2-hydroxypropyl maltooligomer counterparts. The complexation properties of non-modified and modified cyclic and acyclic dextrins were studied and compared by photon correlation spectroscopy (PCS) and capillary electrophoresis (CE) using model guest compounds. In some cases cyclodextrins and their open-ring analogs (acyclodextrins) show similar complexation abilities, while with other guests considerably different behavior was observed depending on the molecular dimensions and chemical characteristics of the guests. This was explained by the enhanced flexibility of the non-closed rings. Even the signs of enantiorecognition were observed for the chloropheniramine/hydroxypropyl maltohexaose system. Further studies are planned to help the deeper understanding of the interactions. PMID:25550750

Computational Analysis on Performance of Thermal Energy Storage (TES) Diffuser

NASA Astrophysics Data System (ADS)

Adib, M. A. H. M.; Adnan, F.; Ismail, A. R.; Kardigama, K.; Salaam, H. A.; Ahmad, Z.; Johari, N. H.; Anuar, Z.; Azmi, N. S. N.

2012-09-01

Application of thermal energy storage (TES) system reduces cost and energy consumption. The performance of the overall operation is affected by diffuser design. In this study, computational analysis is used to determine the thermocline thickness. Three dimensional simulations with different tank height-to-diameter ratio (HD), diffuser opening and the effect of difference number of diffuser holes are investigated. Medium HD tanks simulations with double ring octagonal diffuser show good thermocline behavior and clear distinction between warm and cold water. The result show, the best performance of thermocline thickness during 50% time charging occur in medium tank with height-to-diameter ratio of 4.0 and double ring octagonal diffuser with 48 holes (9mm opening ~ 60%) acceptable compared to diffuser with 6mm ~ 40% and 12mm ~ 80% opening. The conclusion is computational analysis method are very useful in the study on performance of thermal energy storage (TES).

Interaction of Vortex Rings and Steady Jets with Permeable Screens of Varied Porosity

NASA Astrophysics Data System (ADS)

Musta, Mustafa

2013-11-01

Vortex ring and steady jet interaction with a porous matrix formed from several parallel, transparent permeable screens with the same grid geometry for open area ratios (φ) 49.5% - 83.8% was studied previously using digital particle image velocimetry (DPIV) at jet Reynolds number (Re) of 1000-3000. Vortex ring results showed that unlike the experiments with thin screens, a transmitted vortex ring, which has a similar diameter to the primary one, wasn't formed. Instead a centerline vortex ring like structure formed and its diameter, circulation, and dissipation time decreased as φ decreased. However, for the case of screens φ = 55.7% with large screen spacing, reformation of large scale weak vortex rings was observed downstream of the first screen. The present work experimentally investigates the interaction of vortex rings and steady jets with screens of decreasing φ (83.8%-49.5%) in the flow direction. A piston type vortex ring generator was used and measurements were made using DPIV. The vortex ring results show that the size and circulation of the vortex ring like flow structure was changed based on the screen φ within the permeable screen matrix. Similarly, steady jet flow structure and the local turbulent kinetic energy was changed based on the local screen φ.

New 'Molecular Movie' Reveals Ultrafast Chemistry in Motion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minitti, Michael

2015-06-22

Scientists for the first time tracked ultrafast structural changes, captured in quadrillionths-of-a-second steps, as ring-shaped gas molecules burst open and unraveled. Ring-shaped molecules are abundant in biochemistry and also form the basis for many drug compounds. The study points the way to a wide range of real-time X-ray studies of gas-based chemical reactions that are vital to biological processes.

Thermoset polymers via ring opening metathesis polymerization of functionalized oils

DOEpatents

Larock, Richard C; Henna, Phillip H; Kessier, Michael R

2012-11-27

The invention provides a method for producing a thermosetting resin from renewable oils, the method comprising supplying renewable oil molecules containing strained ring alkene moieties; reacting the alkene moieties with cyclic alkenes to create a polymer; and repeating the above two steps until the resin having desired characteristics are obtained. Also provided is a thermoset resin comprising functionalized renewable oil polymerized with a co-monomer.

New 'Molecular Movie' Reveals Ultrafast Chemistry in Motion

ScienceCinema

Minitti, Michael

2018-02-14

Scientists for the first time tracked ultrafast structural changes, captured in quadrillionths-of-a-second steps, as ring-shaped gas molecules burst open and unraveled. Ring-shaped molecules are abundant in biochemistry and also form the basis for many drug compounds. The study points the way to a wide range of real-time X-ray studies of gas-based chemical reactions that are vital to biological processes.

Optimal control of quantum rings by terahertz laser pulses.

PubMed

Räsänen, E; Castro, A; Werschnik, J; Rubio, A; Gross, E K U

2007-04-13

Complete control of single-electron states in a two-dimensional semiconductor quantum-ring model is established, opening a path into coherent laser-driven single-gate qubits. The control scheme is developed in the framework of optimal-control theory for laser pulses of two-component polarization. In terms of pulse lengths and target-state occupations, the scheme is shown to be superior to conventional control methods that exploit Rabi oscillations generated by uniform circularly polarized pulses. Current-carrying states in a quantum ring can be used to manipulate a two-level subsystem at the ring center. Combining our results, we propose a realistic approach to construct a laser-driven single-gate qubit that has switching times in the terahertz regime.

Feasibility of a ring FEL at low emittance storage rings

NASA Astrophysics Data System (ADS)

Agapov, I.

2015-09-01

A scheme for generating coherent radiation at latest generation low emittance storage rings such as PETRA III at DESY (Balewski et al., 2004 [1]) is proposed. The scheme is based on focusing and subsequent defocusing of the electron beam in the longitudinal phase space at the undulator location. The expected performance characteristics are estimated for radiation in the wavelength range of 500-1500 eV. It is shown that the average brightness is increased by several orders of magnitude compared to spontaneous undulator radiation, which can open new perspectives for photon-hungry soft X-ray spectroscopy techniques.

Comparable perioperative mortality outcomes in younger patients undergoing elective open and endovascular abdominal aortic aneurysm repair.

PubMed

Liang, Nathan L; Reitz, Katherine M; Makaroun, Michel S; Malas, Mahmoud B; Tzeng, Edith

2018-05-01

Evidence for benefit of endovascular aneurysm repair (EVAR) over open surgical repair for de novo infrarenal abdominal aortic aneurysms (AAAs) in younger patients remains conflicting because of heterogeneous study populations and small sample sizes. The objective of this study was to compare perioperative and short-term outcomes for EVAR and open surgery in younger patients using a large national disease and procedure-specific data set. We identified patients 65 years of age or younger undergoing first-time elective EVAR or open AAA repair from the Vascular Quality Initiative (2003-2014). We excluded patients with pararenal or thoracoabdominal aneurysms, those medically unfit for open repair, and those undergoing EVAR for isolated iliac aneurysms. Clinical and procedural characteristics were balanced using inverse propensity of treatment weighting. A supplemental analysis extended the study to those younger than 70 years. We identified 2641 patients, 73% (n = 1928) EVAR and 27% (n = 713) open repair. The median age was 62 years (interquartile range, 59-64 years), and 13% were female. The median follow-up time was 401 days (interquartile range, 357-459 days). Unadjusted perioperative survival was 99.6% overall (open repair, 99.1%; EVAR, 99.8%; P < .001), with 97.4% 1-year survival overall (open repair, 97.3%; EVAR, 97.4%; P = .9). Unadjusted reintervention rates were five (open repair) and seven (EVAR) reinterventions per 100 person-years (P = .8). After propensity weighting, the absolute incidence of perioperative mortality was <1% in both groups (open repair, 0.9%, EVAR, 0.2%; P < .001), and complication rates were low. Propensity-weighted survival (hazard ratio, 0.88; 95% confidence interval, 0.56-1.38; P = .6) and reintervention rates (open repair, 6; EVAR, 8; reinterventions per 100 person-years; P = .8) did not differ between the two interventions. The analysis of those younger than 70 years showed similar results. In this study of younger patients undergoing repair of infrarenal AAA, 30-day morbidity and mortality for both open surgery and EVAR are low, and the absolute mortality difference is small. The prior published perioperative mortality and 1-year survival benefit of EVAR over open AAA repair is not observed in younger patients. Further studies of long-term durability are needed to guide decision-making for open repair vs EVAR in this population. Copyright © 2017 Society for Vascular Surgery. Published by Elsevier Inc. All rights reserved.

Suicide Inhibition of Cytochrome P450 Enzymes by Cyclopropylamines via a Ring-opening Mechanism: Proton-Coupled Electron Transfer Makes a Difference

NASA Astrophysics Data System (ADS)

Zhang, Xiaoqian; Li, Xiao-Xi; Liu, Yufang; Wang, Yong

2017-01-01

N-benzyl-N-cyclopropylamine (BCA) has been attracting great interests for decades for its partial suicide inactivation role to cytochrome P450 (P450) via a ring-opening mechanism besides acting as a role of normal substrates. Understanding the mechanism of such partial inactivation is vital to the clinical drug design. Thus, density functional theoretical (DFT) calculations were carried out on such P450-catalyzed reactions, not only on the metabolic pathway, but on the ring-opening inactivation one. Our theoretical results demonstrated that, in the metabolic pathway, besides the normal carbinolamine, an unexpected enamine was formed via the dual hydrogen abstraction (DHA) process, in which the competition between rotation of the H-abstracted substrate radical and the rotation of hydroxyl group of the protonated Cpd II moiety plays a significant role in product branch; In the inactivation pathway, the well-noted single electron transfer (SET) mechanism-involved process was invalidated for its high energy barrier, a proton-coupled electron transfer (PCET(ET)) mechanism plays a role. Our results are consistent with other related theoretical works on heteroatom-hydrogen (X-H, X = O, N) activation and revealed new features. The revealed mechanisms will play a positive role in relative drug design.

Enzymatic catalysis of anti-Baldwin ring closure in polyether biosynthesis.

PubMed

Hotta, Kinya; Chen, Xi; Paton, Robert S; Minami, Atsushi; Li, Hao; Swaminathan, Kunchithapadam; Mathews, Irimpan I; Watanabe, Kenji; Oikawa, Hideaki; Houk, Kendall N; Kim, Chu-Young

2012-03-04

Polycyclic polyether natural products have fascinated chemists and biologists alike owing to their useful biological activity, highly complex structure and intriguing biosynthetic mechanisms. Following the original proposal for the polyepoxide origin of lasalocid and isolasalocid and the experimental determination of the origins of the oxygen and carbon atoms of both lasalocid and monensin, a unified stereochemical model for the biosynthesis of polyether ionophore antibiotics was proposed. The model was based on a cascade of nucleophilic ring closures of postulated polyepoxide substrates generated by stereospecific oxidation of all-trans polyene polyketide intermediates. Shortly thereafter, a related model was proposed for the biogenesis of marine ladder toxins, involving a series of nominally disfavoured anti-Baldwin, endo-tet epoxide-ring-opening reactions. Recently, we identified Lsd19 from the Streptomyces lasaliensis gene cluster as the epoxide hydrolase responsible for the epoxide-opening cyclization of bisepoxyprelasalocid A to form lasalocid A. Here we report the X-ray crystal structure of Lsd19 in complex with its substrate and product analogue to provide the first atomic structure-to our knowledge-of a natural enzyme capable of catalysing the disfavoured epoxide-opening cyclic ether formation. On the basis of our structural and computational studies, we propose a general mechanism for the enzymatic catalysis of polyether natural product biosynthesis. © 2012 Macmillan Publishers Limited. All rights reserved

In vitro eye irritation testing using the open source reconstructed hemicornea - a ring trial.

PubMed

Mewes, Karsten R; Engelke, Maria; Zorn-Kruppa, Michaela; Bartok, Melinda; Tandon, Rashmi; Brandner, Johanna M; Petersohn, Dirk

2017-01-01

The aim of the present ring trial was to test whether two new methodological approaches for the in vitro classification of eye irritating chemicals can be reliably transferred from the developers' laboratories to other sites. Both test methods are based on the well-established open source reconstructed 3D hemicornea models. In the first approach, the initial depth of injury after chemical treatment in the hemicornea model is derived from the quantitative analysis of histological sections. In the second approach, tissue viability, as a measure for corneal damage after chemical treatment, is analyzed separately for epithelium and stroma of the hemicornea model. The three independent laboratories that participated in the ring trial produced their own hemicornea models according to the test producer's instructions, thus supporting the open source concept. A total of 9 chemicals with different physicochemical and eye-irritating properties were tested to assess the between-laboratory reproducibility (BLR), the predictive performance, as well as possible limitations of the test systems. The BLR was 62.5% for the first and 100% for the second method. Both methods enabled to discriminate Cat. 1 chemicals from all non-Cat. 1 substances, which qualifies them to be used in a top-down approach. However, the selectivity between No Cat. and Cat. 2 chemicals still needs optimization.

Updates on Software development for a RICH detector

NASA Astrophysics Data System (ADS)

Voloshin, Andrew; Benmokhtar, Fatiha; Lendacky, Andrew; Goodwill, Justin

2017-01-01

The CLAS12 detector at Thomas Jefferson National Accelerator Facility (TJNAF) is undergoing an upgrade. One of the improvements is the addition of a Ring Imaging Cherenkov (RICH) detector to improve particle identification in the 3-8 GeV/c momentum range. Approximately 400 multi anode photomultiplier tubes (MAPMTs) are going to be used to detect Cherenkov Radiation in the single photoelectron spectra (SPS). Software development for slow control as well as online monitoring is under development. I will be presenting my work on the development of a java based programs for a monitor and explain its interaction with a Mysql database where the MAPMTs information is stored as well as the techniques used to visualize Cherenkov rings.

Ring Imaging Cerenkov Detector for CLAS12

NASA Astrophysics Data System (ADS)

Muhoza, Mireille; Aaron, Elise; Smoot, Waymond; Benmokhtar, Fatiha

2017-09-01

The CLAS12 detector at Thomas Jefferson National Accelerator Facility (TJNAF) is undergoing an upgrade. One of the additions to this detector is a Ring Imaging Cherenkov (RICH) detector to improve particle identification in the 3-8 GeV/c momentum range. Approximately 400 multi anode photomultiplier tubes (MAPMTs) will be used to detect Cherenkov Radiation in the single photoelectron spectra (SPS). Detector tests are taking place at Jefferson Lab, while analysis software development is ongoing at Duquesne. I will be summarizing the work done at Duquesne on the Database development and the analysis of the ADC and TDCs for the Hamamatsu Multi-Anode PMTs that are used for Cerenkov light radiation. National Science Foundation, Award 1615067.

Pseudoephedrine-Directed Asymmetric α-Arylation of α-Amino Acid Derivatives.

PubMed

Atkinson, Rachel C; Fernández-Nieto, Fernando; Mas Roselló, Josep; Clayden, Jonathan

2015-07-27

Available α-amino acids undergo arylation at their α position in an enantioselective manner on treatment with base of N'-aryl urea derivatives ligated to pseudoephedrine as a chiral auxiliary. In situ silylation and enolization induces diastereoselective migration of the N'-aryl group to the α position of the amino acid, followed by ring closure to a hydantoin with concomitant explulsion of the recyclable auxiliary. The hydrolysis of the hydantoin products provides derivatives of quaternary amino acids. The arylation avoids the use of heavy-metal additives, and is successful with a range of amino acids and with aryl rings of varying electronic character. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectral properties and structure of unsymmetrical diarylethenes based on thiazole ring with hydrogen at the reactive carbon.

PubMed

Lvov, Andrey G; Alexeeva, Anna M; Lvova, Evgeniya A; Krayushkin, Mikhail M; Shirinian, Valerii Z

2018-05-31

Six new photoactive unsymmetrical diarylethenes bearing thiazole ring with hydrogen at the reactive carbon atom have been synthesized. Their structures have been studied by DFT calculations and X-ray crystallography. All compounds undergo irreversible photochemical transformations under irradiation with ultraviolet light, proceeding through the photocyclization stage. It has been found that only some normal (thiophene, imidazole and pyrazole derivatives) and inverse type (oxazole derivative) diarylethenes form colored photoinduced isomers under UV. In polar acetonitrile these intermediates show relatively fast irreversible thermal reaction, while in nonpolar toluene slow cycloreversion to initial diarylethenes is the predominant process of these species. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparing the locking threshold for rings and chains of oscillators.

PubMed

Ottino-Löffler, Bertrand; Strogatz, Steven H

2016-12-01

We present a case study of how topology can affect synchronization. Specifically, we consider arrays of phase oscillators coupled in a ring or a chain topology. Each ring is perfectly matched to a chain with the same initial conditions and the same random natural frequencies. The only difference is their boundary conditions: periodic for a ring and open for a chain. For both topologies, stable phase-locked states exist if and only if the spread or "width" of the natural frequencies is smaller than a critical value called the locking threshold (which depends on the boundary conditions and the particular realization of the frequencies). The central question is whether a ring synchronizes more readily than a chain. We show that it usually does, but not always. Rigorous bounds are derived for the ratio between the locking thresholds of a ring and its matched chain, for a variant of the Kuramoto model that also includes a wider family of models.

Comparing the locking threshold for rings and chains of oscillators

NASA Astrophysics Data System (ADS)

Ottino-Löffler, Bertrand; Strogatz, Steven H.

2016-12-01

We present a case study of how topology can affect synchronization. Specifically, we consider arrays of phase oscillators coupled in a ring or a chain topology. Each ring is perfectly matched to a chain with the same initial conditions and the same random natural frequencies. The only difference is their boundary conditions: periodic for a ring and open for a chain. For both topologies, stable phase-locked states exist if and only if the spread or "width" of the natural frequencies is smaller than a critical value called the locking threshold (which depends on the boundary conditions and the particular realization of the frequencies). The central question is whether a ring synchronizes more readily than a chain. We show that it usually does, but not always. Rigorous bounds are derived for the ratio between the locking thresholds of a ring and its matched chain, for a variant of the Kuramoto model that also includes a wider family of models.

Contractile responses of human deferential artery and vas deferens to vasopressin.

PubMed

Medina, P; Martínez, M C; Aldasoro, M; Vila, J M; Chuan, P; Lluch, S

1996-04-11

We studied the effects of vasopressin on isolated rings of human deferential artery and vas deferens (prostatic portion) obtained from patients undergoing radical cystectomy (n = 11) or prostatectomy (n = 10). Ring segments of artery or vas deferens were studied in organ bath experiments at optimal resting tension. In artery rings, vasopressin produced concentration-dependent, endothelium-independent contractions with an EC50 of 4.5 x 10(-10) M. The presence of NG-nitro-L-arginine methyl ester hydrochloride (10(-4) M), an inhibitor of nitric oxide synthase, did not change significantly (P > 0.05) the vasopressin-induced contraction. In ring preparations of the prostatic part of the vas deferens, vasopressin induced phasic contractions with an EC50 of 7.0 x 10(-9) M. The vasopressin V1 receptor antagonist, d(CH2)5Tyr(Me)AVP (10(-8) and 10(-6)), displaced to the right in parallel the control curve to vasopressin in artery and vas deferens rings. These results indicate that vasopressin exerts a powerful constrictor action on human deferential artery and vas deferens by direct stimulation of V1 receptors. It is concluded that the deferential artery may dampen the passage of blood to the vas deferens in circumstances characterized by increased plasma vasopressin levels.

Ring Current Response to Different Storm Drivers. Van Allen Probes and Cluster Observations.

NASA Astrophysics Data System (ADS)

Bingham, S.; Mouikis, C.; Kistler, L. M.; Spence, H. E.; Gkioulidou, M.; Claudepierre, S. G.; Farrugia, C. J.

2015-12-01

The ring current responds differently to the different solar and interplanetary storm drivers such as coronal mass injections, (CME's), co-rotating interaction regions (CIR's), high-speed streamers and other structures. The resulting changes in the ring current particle pressure change the global magnetic field, which affects the transport of the radiation belts. In order to determine the field changes during a storm it is necessary to understand the transport, sources and losses of the particles that contribute to the ring current. The source population of the storm time ring current is the night side plasma sheet. However, it is not clear how these convecting particles affect the storm time ring current pressure development. We use Van Allen Probes and Cluster observations together with the Volland-Stern and dipole magnetic field models to determine the contribution in the ring current pressure of the plasma sheet particles convecting from the night side that are on open drift paths, during the storm evolution. We compare storms that are related to different interplanetary drivers, CME and CIR, as observed at different local times.

Perioperative outcomes and complications of open vs laparoscopic extraperitoneal inguinal hernia repair in a mature surgical practice.

PubMed

Winslow, E R; Quasebarth, M; Brunt, L M

2004-02-01

Although the laparoscopic totally extraperitoneal (TEP) approach to hernia repair has been associated with less pain and a faster postoperative recovery than traditional open repair, many practicing surgeons have been reluctant to adopt this technique because of the lengthy operative times and the learning curve for this procedure. Data from all patients undergoing TEP repair since 1997 and open mesh repair (OPEN) since 1999 were collected prospectively. Selection of surgical approach was based on local hernia factors, anesthetic risk, previous abdominal surgery, and patient preference. Statistical analyses were performed using unpaired t-tests and chi-squared tests. Data are mean +/- SD. TEP repairs were performed in 147 patients and open repairs in 198 patients. Patients in the OPEN group were significantly older (59 +/- 19 years OPEN vs 51 +/- 13 years TEP) and had a higher ASA (1.9 +/- 0.7 OPEN vs 1.5 +/- 0.6 TEP; p < 0.01). TEP repairs were more likely to be carried out for bilateral (33% TEP, 5% OPEN) or recurrent hernias (31% TEP, 11% OPEN) than were open repairs ( p < 0.01). Concurrent procedures accompanied 31% of TEP and 12% of OPEN repairs ( p < 0.01). Operative times (min) were significantly shorter in the TEP group for both unilateral (63 +/- 22 TEP, 70 +/- 20 OPEN; p = 0.02) and bilateral (78 +/- 27 TEP, 102 +/- 27 OPEN; p = 0.01) repairs. Mean operative times decreased over time in the TEP group for both unilateral and bilateral repairs ( p < 0.01). Patients undergoing TEP were more likely ( p < 0.01) to develop urinary retention (7.9% TEP, 1.1% OPEN), but were less likely ( p < 0.01) to have skin numbness (2.8% TEP, 35.8% OPEN) or prolonged groin discomfort (1.4% TEP, 5.3% OPEN). Despite a higher proportion of patients undergoing bilateral repairs, recurrent hernia repair, and concurrent procedures, operative times are shorter for laparoscopic TEP repair than for open mesh repair. TEP repairs can be performed efficiently and without major complications, even when the learning curve is included.

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

DOE PAGES

Theis, Daniel; Ivanic, Joseph; Windus, Theresa L.; ...

2016-03-10

The metastable ring structure of the ozone 1 1A 1 ground state, which theoretical calculations have shown to exist, has so far eluded experimental detection. An accurate prediction for the energy difference between this isomer and the lower open structure is therefore of interest, as is a prediction for the isomerization barrier between them, which results from interactions between the lowest two 1A 1 states. In the present work, valence correlated energies of the 1 1A 1 state and the 2 1A 1 state were calculated at the 1 1A 1 open minimum, the 1 1A 1 ring minimum, themore » transition state between these two minima, the minimum of the 2 1A 1 state, and the conical intersection between the two states. The geometries were determined at the full-valence multi-configuration self-consistent-field level. Configuration interaction (CI) expansions up to quadruple excitations were calculated with triple-zeta atomic basis sets. The CI expansions based on eight different reference configuration spaces were explored. To obtain some of the quadruple excitation energies, the method of CorrelationEnergy Extrapolation by Intrinsic Scaling was generalized to the simultaneous extrapolation for two states. This extrapolation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 11A1 state, the present calculations yield the estimates of (ring minimum—open minimum) ~45–50 mh and (transition state—open minimum) ~85–90 mh. For the (2 1A 1– 1A 1) excitation energy, the estimate of ~130–170 mh is found at the open minimum and 270–310 mh at the ring minimum. At the transition state, the difference (2 1A 1– 1A 1) is found to be between 1 and 10 mh. The geometry of the transition state on the 11A1 surface and that of the minimum on the 2 1A 1 surface nearly coincide. More accurate predictions of the energydifferences also require CI expansions to at least sextuple excitations with respect to the valence space. Furthermore, for every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about ±10 mh with respect to the energy differences.« less

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Theis, Daniel; Ivanic, Joseph; Windus, Theresa L.

The metastable ring structure of the ozone 1 1A 1 ground state, which theoretical calculations have shown to exist, has so far eluded experimental detection. An accurate prediction for the energy difference between this isomer and the lower open structure is therefore of interest, as is a prediction for the isomerization barrier between them, which results from interactions between the lowest two 1A 1 states. In the present work, valence correlated energies of the 1 1A 1 state and the 2 1A 1 state were calculated at the 1 1A 1 open minimum, the 1 1A 1 ring minimum, themore » transition state between these two minima, the minimum of the 2 1A 1 state, and the conical intersection between the two states. The geometries were determined at the full-valence multi-configuration self-consistent-field level. Configuration interaction (CI) expansions up to quadruple excitations were calculated with triple-zeta atomic basis sets. The CI expansions based on eight different reference configuration spaces were explored. To obtain some of the quadruple excitation energies, the method of CorrelationEnergy Extrapolation by Intrinsic Scaling was generalized to the simultaneous extrapolation for two states. This extrapolation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 11A1 state, the present calculations yield the estimates of (ring minimum—open minimum) ~45–50 mh and (transition state—open minimum) ~85–90 mh. For the (2 1A 1– 1A 1) excitation energy, the estimate of ~130–170 mh is found at the open minimum and 270–310 mh at the ring minimum. At the transition state, the difference (2 1A 1– 1A 1) is found to be between 1 and 10 mh. The geometry of the transition state on the 11A1 surface and that of the minimum on the 2 1A 1 surface nearly coincide. More accurate predictions of the energydifferences also require CI expansions to at least sextuple excitations with respect to the valence space. Furthermore, for every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about ±10 mh with respect to the energy differences.« less

Better Object Recognition and Naming Outcome With MRI-Guided Stereotactic Laser Amygdalohippocampotomy for Temporal Lobe Epilepsy

PubMed Central

Drane, Daniel L.; Loring, David W.; Voets, Natalie L.; Price, Michele; Ojemann, Jeffrey G.; Willie, Jon T.; Saindane, Amit M.; Phatak, Vaishali; Ivanisevic, Mirjana; Millis, Scott; Helmers, Sandra L.; Miller, John W.; Meador, Kimford J.; Gross, Robert E.

2015-01-01

SUMMARY OBJECTIVES Temporal lobe epilepsy (TLE) patients experience significant deficits in category-related object recognition and naming following standard surgical approaches. These deficits may result from a decoupling of core processing modules (e.g., language, visual processing, semantic memory), due to “collateral damage” to temporal regions outside the hippocampus following open surgical approaches. We predicted stereotactic laser amygdalohippocampotomy (SLAH) would minimize such deficits because it preserves white matter pathways and neocortical regions critical for these cognitive processes. METHODS Tests of naming and recognition of common nouns (Boston Naming Test) and famous persons were compared with nonparametric analyses using exact tests between a group of nineteen patients with medically-intractable mesial TLE undergoing SLAH (10 dominant, 9 nondominant), and a comparable series of TLE patients undergoing standard surgical approaches (n=39) using a prospective, non-randomized, non-blinded, parallel group design. RESULTS Performance declines were significantly greater for the dominant TLE patients undergoing open resection versus SLAH for naming famous faces and common nouns (F=24.3, p<.0001, η2=.57, & F=11.2, p<.001, η2=.39, respectively), and for the nondominant TLE patients undergoing open resection versus SLAH for recognizing famous faces (F=3.9, p<.02, η2=.19). When examined on an individual subject basis, no SLAH patients experienced any performance declines on these measures. In contrast, 32 of the 39 undergoing standard surgical approaches declined on one or more measures for both object types (p<.001, Fisher’s exact test). Twenty-one of 22 left (dominant) TLE patients declined on one or both naming tasks after open resection, while 11 of 17 right (non-dominant) TLE patients declined on face recognition. SIGNIFICANCE Preliminary results suggest 1) naming and recognition functions can be spared in TLE patients undergoing SLAH, and 2) the hippocampus does not appear to be an essential component of neural networks underlying name retrieval or recognition of common objects or famous faces. PMID:25489630

Atropisomerization in N-aryl-2(1H)-pyrimidin-(thi)ones: a ring-opening/rotation/ring-closure process in place of a classical rotation around the pivot bond.

PubMed

Najahi, Ennaji; Vanthuyne, Nicolas; Nepveu, Françoise; Jean, Marion; Alkorta, Ibon; Elguero, José; Roussel, Christian

2013-12-20

Uncatalyzed racemization processes in atropisomeric diphenyl-like frameworks are classically described as the result of the rotation around the pivotal single bond linking two planar frameworks. Severe constraints leading to more or less distorted transition states account for the experimental barrier to atropenantiomerization. In 1988, one of us hypothesized that, in N-aryl-2(1H)-pyrimidin-(thi)ones, a ring-opening/ring-closure process was contributing to the observed racemization process accounting for the lower barriers in the sulfur analogues than in oxygen analogues. Now, a series of six novel 6-amino-5-cyano-1,4-disubstituted-2(1H)-pyrimidinones 5a-5f and two 6-amino-5-cyano-4-p-tolyl-1-substituted-2(1H)-pyrimidinethiones 6a and 6b were synthesized and characterized through spectroscopic and X-ray diffraction studies. Semipreparative HPLC chiral separation was achieved, and enantiomerization barriers were obtained by thermal racemization. The rotational barriers of 6-amino-5-cyano-1-o-tolyl-4-p-tolyl-2(1H)-pyrimidinone (5b) and 6-amino-5-cyano-1-(naphthalen-1-yl)-4-p-tolyl-2(1H)-pyrimidinone (5e) were found to be 120.4 and 125.1 kJ·mol(-1) (n-BuOH, 117 °C), respectively, and those of the corresponding thiones were 116.8 and 109.6 kJ·mol(-1) (EtOH, 78 °C), respectively. DFT calculations of the rotational barriers clearly ruled out the classical rotation around the pivotal bond with distorted transition states in the case of the sulfur derivatives. Instead, the ranking of the experimental barriers (sulfur versus oxygen, and o-tolyl versus 1-naphthyl in both series) was nicely reproduced by calculations when the rotation occurred via a ring-opened form in N-aryl-2(1H)-pyrimidinethiones.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Transport electron through a quantum wire by side-attached asymmetric quantum-dot rings

NASA Astrophysics Data System (ADS)

Rostami, A.; Zabihi, S.; Rasooli S., H.; Seyyedi, S. K.

2011-12-01

The electronic conductance at zero temperature through a quantum wire with side-attached asymmetric quantum ring (as a scatter system) is theoretically studied using the non-interacting Anderson tunneling Hamiltonian method. We show that the asymmetric configuration of QD- scatter system strongly impresses the amplitude and spectrum of quantum wire nanostructure transmission characteristics. It is shown that whenever the balanced number of quantum dots in two rings is substituted by unbalanced scheme, the number of forbidden mini-bands in quantum wire conductance increases and QW-nanostructure electronic conductance contains rich spectral properties due to appearance of the new anti-resonance and resonance points in spectrum. Considering the suitable gap between nano-rings can strengthen the amplitude of new resonant peaks in the QW conductance spectrum. The proposed asymmetric quantum ring scatter system idea in this paper opens a new insight on designing quantum wire nano structure for given electronic conductance.

The stresses in stiffener openings

NASA Technical Reports Server (NTRS)

Marguerre, K

1942-01-01

The present study treats as a typical example a ring the center line of which is produced by the intersection of two circular cylinders of different diameter. Three load cases are analyzed: (1) Axial and circumferential stresses in both cylinders, the cylinder stresses themselves to be in the ratio conformal to the cylinders loaded under internal pressure. (2) Pure longitudinal tension in the large cylinder. (3) Pure shear (torsion) in the large cylinder. To simplify the calculation, it is assumed that the ring, compared to the shell, is very strong, so that its deformations have no perceptible effect on the stress condition in the shell. This provides an upper limit for the ring stresses actually produced in a shell design, for, according to the theory of stressed skin statics the shells, by elastic flexibility of the ring, regroup the forces deposited on it in such a manner that the ring is relieved.

Large fully retractable telescope enclosures still closable in strong wind

NASA Astrophysics Data System (ADS)

Bettonvil, Felix C. M.; Hammerschlag, Robert H.; Jägers, Aswin P. L.; Sliepen, Guus

2008-07-01

Two prototypes of fully retractable enclosures with diameters of 7 and 9 m have been built for the high-resolution solar telescopes DOT (Dutch Open Telescope) and GREGOR, both located at the Canary Islands. These enclosures protect the instruments for bad weather and are fully open when the telescopes are in operation. The telescopes and enclosures also operate in hard wind. The prototypes are based on tensioned membrane between movable but stiff bows, which fold together to a ring when opened. The height of the ring is small. The prototypes already survived several storms, with often snow and ice, without any damage, including hurricane Delta with wind speeds up to 68 m/s. The enclosures can still be closed and opened with wind speeds of 20 m/s without any problems or restrictions. The DOT successfully demonstrated the open, wind-flushing concept for astronomical telescopes. It is now widely recognized that also large future telescopes benefit from wind-flushing and retractable enclosures. These telescopes require enclosures with diameters of 30 m until roughly 100 m, the largest sizes for the ELTs (Extreme Large Telescopes), which will be built in the near future. We discuss developments and required technology for the realization of these large sizes.

Switching from Controlled Ring-Opening Polymerization (cROP) to Controlled Ring-Closing Depolymerization (cRCDP) by Adjusting the Reaction Parameters That Determine the Ceiling Temperature

PubMed Central

2016-01-01

Full control over the ceiling temperature (Tc) enables a selective transition between the monomeric and polymeric state. This is exemplified by the conversion of the monomer 2-allyloxymethyl-2-ethyl-trimethylene carbonate (AOMEC) to poly(AOMEC) and back to AOMEC within 10 h by controlling the reaction from conditions that favor ring-opening polymerization (Tc > T0) (where T0 is the reaction temperature) to conditions that favor ring-closing depolymerization (Tc < T0). The ring-closing depolymerization (RCDP) mirrors the polymerization behavior with a clear relation between the monomer concentration and the molecular weight of the polymer, indicating that RCDP occurs at the chain end. The Tc of the polymerization system is highly dependent on the nature of the solvent, for example, in toluene, the Tc of AOMEC is 234 °C and in acetonitrile Tc = 142 °C at the same initial monomer concentration of 2 M. The control over the monomer to polymer equilibrium sets new standards for the selective degradation of polymers, the controlled release of active components, monomer synthesis and material recycling. In particular, the knowledge of the monomer to polymer equilibrium of polymers in solution under selected environmental conditions is of paramount importance for in vivo applications, where the polymer chain is subjected to both high dilution and a high polarity medium in the presence of catalysts, that is, very different conditions from which the polymer was formed. PMID:27783494

In vitro Drug Metabolism Investigation of 7-Ethoxycoumarin in Human, Monkey, Dog and Rat Hepatocytes by High Resolution LC-MS/MS.

PubMed

Feng, Wan-Yong; Wen, Jenny; Stauber, Kathe

2018-04-18

Recently, it has been an increasing concern on the bioactivation and adverse reactions associated with consumption of herbal and nature products such as coumarin family. 7-ethoxycoumarin is one of coumarin family compounds, but little information is available regarding its potential reactive metabolites. In this study, we investigated its metabolism in cryopreserved male/female mixed human, male Cynomolgus monkey, male Beagle dog and male Sprague Dawley rat hepatocytes. Following the incubation of 7-ethoxylcoumarin in the hepatocytes for 2 hr, 28 metabolites were detected and identified using high resolution LC-Q-Exactive system in the positive ion and negative ion modes. O-deethylation, glucuronidation, sulfation, oxygenation, oxidative ring-opening, hydrogenation, glutathionation, dehydrogenation, cysteination, glucosidation, methylation, and hydrolysis were observed. At least sixteen metabolites were newly identified. M1 (O-deethylation, mono-oxygenation and glucuronidation), M3 (O-deethylation and glucuronidation), M5 (hydrolysis and mono-oxygenation), M14 (Odeethylation), M16 (hydrolysis), M22 (oxidative ring-opening and oxygenation) and M27 (mono-oxygenation) appeared to be major metabolites in human hepatocytes. M3, M5, M8, M13 (mono-oxygenation), M14, M16, M18 (O-deethylation and sulfation), M22 and M27 appeared to be major metabolites in monkey hepatocytes. M14, M16, M18, M20 (glutathionation and dehydrogenation) and M27 appeared to be major metabolites in dog hepatocytes. M1 (O-deethylation, mono-oxygenation and glucuronidation), M3, M5, M13, M14, M16, M17 (cysteination), M18, M20, and M22 appeared to be major metabolites in rat hepatocytes. Species differences in metabolism of 7-ethoxylcoumarin in hepatocytes were observed across humans, monkeys, dogs and rats. The analysis of metabolites suggests that 7-ethoxylcoumarin may undergo 3,4-epoxidation responsible for formation of glutathione and its derived cysteine conjugates, and carboxylic acid and its glucuronides, glucosides and sulfate, besides well-known 7-hydroxycoumarin, coumarin-7-O-glucuronide, and coumarin-7-O-glucuronide. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

The impact of exospheric neutral dynamics on ring current decay

NASA Astrophysics Data System (ADS)

Ilie, R.; Liemohn, M. W.; Skoug, R. M.; Funsten, H. O.; Gruntman, M.; Bailey, J. J.; Toth, G.

2015-12-01

The geocorona plays an important role in the energy budget of the Earth's inner magnetosphere since charge exchange of energetic ions with exospheric neutrals makes the exosphere act as an energy sink for ring current particles. Long-term ring current decay following a magnetic storm is mainly due to these electron transfer reactions, leading to the formation energetic neutral atoms (ENAs) that leave the ring current system on ballistic trajectories. The number of ENAs emitted from a given region of space depends on several factors, such as the energy and species of the energetic ion population in that region and the density of the neutral gas with which the ions undergo charge exchange. However, the density and structure of the exosphere are strongly dependent on changes in atmospheric temperature and density as well as charge exchange with the ions of plasmaspheric origin, which depletes the geocorona (by having a neutral removed from the system). Moreover, the radiation pressure exerted by solar far-ultraviolet photons pushes the geocoronal hydrogen away from the Earth in an anti-sunward direction to form a tail of neutral hydrogen. TWINS ENA images provide a direct measurement of these ENA losses and therefore insight into the dynamics of the ring current decay through interactions with the geocorona. We assess the influence of geocoronal neutrals on ring current formation and decay by analysis of the predicted ENA emissions using 6 different geocoronal models and simulations from the HEIDI ring current model during storm time. Comparison with TWINS ENA images shows that the location of the peak ENA enhancements is highly dependent on the distribution of geocoronal hydrogen density. We show that the neutral dynamics has a strong influence on the time evolution of the ring current populations as well as on the formation of energetic neutral atoms.

Modeling FtsZ ring formation in the bacterial cell-anisotropic aggregation via mutual interactions of polymer rods.

PubMed

Fischer-Friedrich, Elisabeth; Gov, Nir

2011-04-01

The cytoskeletal protein FtsZ polymerizes to a ring structure (Z ring) at the inner cytoplasmic membrane that marks the future division site and scaffolds the division machinery in many bacterial species. FtsZ is known to polymerize in the presence of GTP into single-stranded protofilaments. In vivo, FtsZ polymers become associated with the cytoplasmic membrane via interaction with the membrane-binding proteins FtsA and ZipA. The FtsZ ring structure is highly dynamic and undergoes constantly polymerization and depolymerization processes and exchange with the cytoplasmic pool. In this theoretical study, we consider a scenario of Z ring self-organization via self-enhanced attachment of FtsZ polymers due to end-to-end interactions and lateral interactions of FtsZ polymers on the membrane. With the assumption of exclusively circumferential polymer orientations, we derive coarse-grained equations for the dynamics of the pool of cytoplasmic and membrane-bound FtsZ. To capture stochastic effects expected in the system due to low particle numbers, we simulate our computational model using a Gillespie-type algorithm. We obtain ring- and arc-shaped aggregations of FtsZ polymers on the membrane as a function of monomer numbers in the cell. In particular, our model predicts the number of FtsZ rings forming in the cell as a function of cell geometry and FtsZ concentration. We also calculate the time of FtsZ ring localization to the midplane in the presence of Min oscillations. Finally, we demonstrate that the assumptions and results of our model are confirmed by 3D reconstructions of fluorescently-labeled FtsZ structures in E. coli that we obtained.

A randomised trial of a contraceptive vaginal ring in women at risk of HIV infection in Rwanda: Safety of intermittent and continuous use

PubMed Central

Van Nuil, Jennifer Ilo; Uwineza, Mireille; Umulisa, Marie Michelle; Mwambarangwe, Lambert; Ndagijimana, Jean Claude; De Baetselier, Irith; Buyze, Jozefien; Delvaux, Thérèse; Crucitti, Tania; Jespers, Vicky

2018-01-01

Background Contraceptive vaginal rings could play a role in expanding the contraceptive method mix and in preparing communities for the introduction of HIV prevention and multipurpose rings. Methods We conducted an open label single-centre randomised clinical trial of intermittent versus continuous use of NuvaRing® in Kigali, Rwanda, in 2013–2014. We randomised 120 HIV-negative women 1:1 to intermittent use (three rings with a ring-free week in between rings) or continuous use (four rings without ring-free weeks). Women underwent an interview, counselling, and a speculum examination, and were tested for pregnancy, bacterial vaginosis (BV) by Nugent scoring, yeasts and trichomonads on wet mount, and sexually transmitted infections. Findings Only one woman withdrew early. Deliberate ring removals were rare, but spontaneous ring expulsions occurred during 14% of ring use periods. There were no incident pregnancies, serious adverse events, serious social harms, or early discontinuations for safety reasons. Systemic side effects were uncommon, and local side effects were not significantly differently distributed between groups except for lower abdominal pain (P = 0.013). The incidence of vaginal yeasts during ring use was high: 22% of intermittent users and 27% of continuous users had incident vaginal yeasts at one or multiple ring removal visits (P = 0.666), and symptomatic vaginal yeast cases were more common in the continuous than intermittent users (P = 0.031). In contrast, mean Nugent scores improved over time in both groups. Conclusions Intermittent and continuous NuvaRing® use were safe in Rwandan women and improved Nugent scores over time. However, attention should be paid to ring expulsions and to a potential increased risk of vaginal candidiasis. PMID:29856848

Modeling the near-Earth interaction between ring current ions and exospheric neutrals: escape through energetic neutral atoms (ENAs)

NASA Astrophysics Data System (ADS)

LLera, K.; Goldstein, J.; McComas, D. J.; Valek, P. W.

2016-12-01

The two major loss processes for ring current decay are precipitation and energetic neutral atoms (ENAs). Since the exospheric neutral density increases with decreasing altitudes, precipitating ring current ions (reaching down to 200 - 800 km in altitude) also produce low-altitude ENA signatures that can be stronger than the ring current emission at equatorial distances ( 2 - 9 Re). The higher density results in multiple collisions between the ring current ions and exospheric oxygen. The affect on hydrogen ions is the focus of this study. Since the H particle sustains energy loss ( 36 eV) at each neutralizing or re-ionizing interaction, the escaped ENAs do not directly reflect the ring current properties. We model the energy loss due to multiple charge exchange and electron stripping interactions of 1 - 100 keV precipitating ring current ions undergo before emerging as low-altitude ENAs. The H particle is either an ion or an ENA throughout the simulation. Their lifetime is analytically determined by the length of one mean free path. We track the ion state with Lorentz motion while the ENA travels ballistically across the geomagnetic field. Our simulations show the energy loss is greater than 20% for hydrogen ring current ions below 30 keV (60 keV for the simulations that wander equatorward). This is the first quantification of the energy loss associated with the creation of low-altitude ENAs. Our model (currently constrained in the meridional plane) has revealed characteristics on how precipitation is affected by the near-Earth neutral exosphere. This ion-neutral interaction removes particles from the loss cone but promotes loss through ENA generation. These findings should be implemented in models predicting the ring current decay and used as an analysis tool to reconstruct the ring current population from observed low-altitude ENAs.

The Shapers

NASA Image and Video Library

2015-01-26

Two masters of their craft are caught at work shaping Saturn's rings. Pandora (upper right) sculpts the F ring, as does nearby Prometheus (not seen in this image). Meanwhile, Daphnis is busy holding open the Keeler gap (bottom center), its presence revealed here by the waves it raises on the gap's edge. The faint moon is located where the inner and outer waves appear to meet. Also captured in this image, shining through the F ring above the image center, is a single star. Although gravity is by its very nature an attractive force, moons can interact with ring particles in such a way that they effectively push ring particles away from themselves. Ring particles experience tiny gravitational "kicks" from these moons and subsequently collide with other ring particles, losing orbital momentum. The net effect is for moons like Pandora (50 miles or 81 kilometers across) and Daphnis (5 miles or 8 kilometers across) to push ring edges away from themselves. The Keeler gap is the result of just such an interaction. This view looks toward the unilluminated side of the rings from about 50 degrees below the ringplane. The image was taken in visible light with the Cassini spacecraft narrow-angle camera on Jan. 30, 2013. http://photojournal.jpl.nasa.gov/catalog/PIA18298

Analysis of radially cracked ring segments subject to forces and couples

NASA Technical Reports Server (NTRS)

Gross, B.; Srawley, J. E.

1977-01-01

Results of planar boundary collocation analysis are given for ring segment (C-shaped) specimens with radial cracks, subjected to combined forces and couples. Mode I stress intensity factors and crack mouth opening displacements were determined for ratios of outer to inner radius in the range 1.1 to 2.5 and ratios of crack length to segment width in the range 0.1 to 0.8.

Analysis of radially cracked ring segments subject to forces and couples

NASA Technical Reports Server (NTRS)

Gross, B.; Strawley, J. E.

1975-01-01

Results of planar boundary collocation analysis are given for ring segment (C shaped) specimens with radial cracks, subjected to combined forces and couples. Mode I stress intensity factors and crack mouth opening displacements were determined for ratios of outer to inner radius in the range 1.1 to 2.5, and ratios of crack length to segment width in the range 0.1 to 0.8.

Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Junming; Karim, Ayman M.; Zhang, He

2013-10-01

Abstract Carbon supported metal catalysts (Cu/C, Fe/C, Pd/C, Pt/C, PdFe/C and Ru/C) have been prepared, characterized and tested for vapor-phase hydrodeoxygenation (HDO) of guaiacol (GUA) at atmospheric pressure. Phenol was the major intermediate on all catalysts. Over the noble metal catalysts saturation of the aromatic ring was the major pathway observed at low temperature (250 °C), forming predominantly cyclohexanone and cyclohexanol. Substantial ring opening reaction was observed on Pt/C and Ru/C at higher reaction temperatures (e.g., 350 °C). Base metal catalysts, especially Fe/C, were found to exhibit high HDO activity without ring-saturation or ring-opening with the main products being benzene,more » phenol along with small amounts of cresol, toluene and trimethylbenzene (TMB). A substantial enhancement in HDO activity was observed on the PdFe/C catalysts. Compared with Fe/C, the yield to oxygen-free aromatic products (i.e., benzene/toluene/TMB) on PdFe/C increased by a factor of four at 350 °C, and by approximately a factor of two (83.2% versus 43.3%) at 450 °C. The enhanced activity of PdFe/C is attributed to the formation of PdFe alloy as evidenced by STEM, EDS and TPR.« less

An event database for rotational seismology

NASA Astrophysics Data System (ADS)

Salvermoser, Johannes; Hadziioannou, Celine; Hable, Sarah; Chow, Bryant; Krischer, Lion; Wassermann, Joachim; Igel, Heiner

2016-04-01

The ring laser sensor (G-ring) located at Wettzell, Germany, routinely observes earthquake-induced rotational ground motions around a vertical axis since its installation in 2003. Here we present results from a recently installed event database which is the first that will provide ring laser event data in an open access format. Based on the GCMT event catalogue and some search criteria, seismograms from the ring laser and the collocated broadband seismometer are extracted and processed. The ObsPy-based processing scheme generates plots showing waveform fits between rotation rate and transverse acceleration and extracts characteristic wavefield parameters such as peak ground motions, noise levels, Love wave phase velocities and waveform coherence. For each event, these parameters are stored in a text file (json dictionary) which is easily readable and accessible on the website. The database contains >10000 events starting in 2007 (Mw>4.5). It is updated daily and therefore provides recent events at a time lag of max. 24 hours. The user interface allows to filter events for epoch, magnitude, and source area, whereupon the events are displayed on a zoomable world map. We investigate how well the rotational motions are compatible with the expectations from the surface wave magnitude scale. In addition, the website offers some python source code examples for downloading and processing the openly accessible waveforms.

Outcomes of complex robot-assisted extravesical ureteral reimplantation in the pediatric population.

PubMed

Arlen, Angela M; Broderick, Kristin M; Travers, Curtis; Smith, Edwin A; Elmore, James M; Kirsch, Andrew J

2016-06-01

While open ureteral reimplantation remains the gold standard for surgical treatment of vesicoureteral reflux (VUR), minimally invasive approaches offer potential benefits. This study evaluated the outcomes of children undergoing complex robot-assisted laparoscopic ureteral reimplantation (RALUR) for failed previous anti-reflux surgery, complex anatomy, or ureterovesical junction obstruction (UVJO), and compared them with patients undergoing open extravesical repair. Children undergoing complex RALUR or open extravesical ureteral reimplantation (OUR) were identified. Reimplantation was classified as complex if ureters: 1) had previous anti-reflux surgery, 2) required tapering and/or dismembering, or 3) had associated duplication or diverticulum. Seventeen children underwent complex RALUR during a 24-month period, compared with 41 OUR. The mean follow-up was 16.6 ± 6.5 months. The RALUR children were significantly older (9.3 ± 3.7 years) than the OUR patients (3.1 ± 2.7 years; P < 0.001). All RALUR patients were discharged on postoperative day one, while 24.4% of children in the open group required longer hospitalization (mean 1.3 ± 0.7 days; P = 0.03). Adjusting for age, there was no significant difference in inpatient analgesic usage between the two cohorts. Three OUR patients (7.3%) developed postoperative febrile urinary tract infection compared with a single child (5.9%) undergoing RALUR (P = 1.00). There was no significant difference in complication rate between the two groups (12.2% OUR versus 11.8% RALUR; P = 1.00). A postoperative cystogram was performed in the majority of RALUR patients, with no persistent VUR detected, and one child (6.7%) was diagnosed with contralateral reflux. Reported VUR resolution rates following robot-assisted ureteral reimplantation are varied. In the present series, children undergoing RALUR following failed previous anti-reflux surgery, with complex anatomy, or UVJO experienced a shorter length of stay but had similar analgesic requirements to those undergoing open repair. Radiographic, clinical success rates and complication risk were comparable. This study had several limitations, aside from lack of randomization. Analgesic use was limited to an inpatient setting, and pain scores were not assessed. Not all children underwent a postoperative VCUG, so the true radiographic success rate is unknown. A larger patient cohort with longer follow-up is necessary to determine predictors of radiographic and clinical failure. Older children with a previous history of anti-reflux surgery were more likely to undergo RALUR. These children had success and complication rates comparable to younger patients following complex open extravesical reimplantation, which underscores the expanding role of robot-assisted lower urinary tract reconstructive surgery in the pediatric population. Copyright © 2015 Journal of Pediatric Urology Company. Published by Elsevier Ltd. All rights reserved.

Understanding extractive bleed : wood extractives: distribution, properties, and classes

Treesearch

Edward Burke; Norm Slavik; Tony Bonura; Dennis Connelly; Tom Faris; Arnie Nebelsick; Brent Stuart; Sam Williams; Alex C. Wiedenhoeft

2010-01-01

Color, odor, and natural durability of heartwood are characteristics imparted by a class of chemicals in wood known collectively extractives. Wood is converted by the tree from sapwood to heartwood by the deposition of extractives, typically many years after the growth ring undergoing this change was formed by the tree. Extractives are thus not a part of the wood...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo

In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ε-caprolactam will be discussed in the viewpoint of increasing manufacturing speedmore » and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.« less

Theoretical study on the ring-opening hydrolysis reactions of N-alkylmaleimide dimers

NASA Astrophysics Data System (ADS)

Tan, Xue-Jie; Wang, Chao; Guo, Xian-Kun

2018-01-01

On the basis of our previous experimental results, the ring-opening hydrolysis reaction mechanisms of two kinds of N-alkylmaleimide dimers without or with the assistance of one and two water molecules have been theoretically investigated in detail. All possible geometries were optimized using the B3LYP/6-311+G(d,p)//B3LYP/6-31+G(d) method in the gas phase and ethanol solution. Calculated results show that every pathway is a four-step hydrolytic degradation process and every step could occur in a concerted way, instead of previously suggested asynchronous stepwise mechanism. Extra H2O or ethanol could act as carriers of proton. The results are consistent with experimental observations.

[Effects of elevated ozone on Pinus armandii growth: a simulation study with open-top chamber].

PubMed

Liu, Chang-Fu; Liu, Chen; He, Xing-Yuan; Ruan, Ya-Nan; Xu, Sheng; Chen, Zhen-Ju; Peng, Jun-Jie; Li, Teng

2013-10-01

By using open-top chamber (OTC) and the techniques of dendrochronology, this paper studied the growth of Pinus armandii under elevated ozone, and explored the evolution dynamics and adaptation mechanisms of typical forest ecosystems to ozone enrichment. Elevated ozone inhibited the stem growth of P. armandii significantly, with the annual growth of the stem length and diameter reduced by 35.0% and 12.9%, respectively. The annual growth of tree-ring width and the annual ring cells number decreased by 11.5% and 54.1%, respectively, but no significant change was observed in the diameter of tracheid. At regional scale, the fluctuation of ozone concentration showed significant correlation with the variation of local vegetation growth (NDVI).

Zirconium(IV)-Catalyzed Ring Opening of on-DNA Epoxides in Water.

PubMed

Fan, Lijun; Davie, Christopher P

2017-05-04

DNA-encoded library technology (ELT) has spurred wide interest in the pharmaceutical industry as a powerful tool for hit and lead generation. In recent years a number of "DNA-compatible" chemical modifications have been published and used to synthesize vastly diverse screening libraries. Herein we report a newly developed, zirconium tetrakis(dodecyl sulfate) [Zr(DS) 4 ] catalyzed ring-opening of on-DNA epoxides in water with amines, including anilines. Subsequent cyclization of the resulting on-DNA β-amino alcohols leads to a variety of biologically interesting, nonaromatic heterocycles. Under these conditions, a library of 137 million on-DNA β-amino alcohols and their cyclization products was assembled. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis.

PubMed

Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien

2014-02-01

Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin-dependent heat and thermoelectric currents in a Rashba ring coupled to a photon cavity

NASA Astrophysics Data System (ADS)

Abdullah, Nzar Rauf; Tang, Chi-Shung; Manolescu, Andrei; Gudmundsson, Vidar

2018-01-01

Spin-dependent heat and thermoelectric currents in a quantum ring with Rashba spin-orbit interaction placed in a photon cavity are theoretically calculated. The quantum ring is coupled to two external leads with different temperatures. In a resonant regime, with the ring structure in resonance with the photon field, the heat and the thermoelectric currents can be controlled by the Rashba spin-orbit interaction. The heat current is suppressed in the presence of the photon field due to contribution of the two-electron and photon replica states to the transport while the thermoelectric current is not sensitive to changes in parameters of the photon field. Our study opens a possibility to use the proposed interferometric device as a tunable heat current generator in the cavity photon field.

Male factor infertility and lack of openness about infertility as risk factors for depressive symptoms in males undergoing assisted reproductive technology treatment in Italy.

PubMed

Babore, Alessandra; Stuppia, Liborio; Trumello, Carmen; Candelori, Carla; Antonucci, Ivana

2017-04-01

To investigate the association between male factor infertility and openness to discussing assisted reproductive technology (ART) treatment with levels of depression among men undergoing infertility treatment. Cross-sectional. Not applicable. Three hundred forty participants (170 men and their partners) undergoing ART treatments. Administration of a set of questionnaires. Depressive symptoms were detected by means of the Zung Depression Self-Rating Scale. Participants' willingness to share their infertility treatment experience with other people was assessed by means of self-report questionnaires. In this study, 51.8% of males chose not to discuss their ART treatments with people other than their partner. In addition, the decision to discuss or not discuss the ART treatments with others was significantly associated with men's depressive symptoms. Male factor infertility was significantly associated with depression when considered together with the decision not to discuss ART treatments with others. A general disposition characterized by a lack of openness with others seemed to be a significant predictor of depression. There is a need for routine fertility care to pay greater attention to men's emotional needs. Before commencing reproductive treatment, male patients may benefit from undergoing routine screening for variables (i.e., male factor infertility and openness to others about ART) that may affect their risk of depression. Copyright © 2017 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights reserved.

Parkin, A Top Level Manager in the Cell’s Sanitation Department

PubMed Central

Rankin, Carolyn A; Roy, Ambrish; Zhang, Yang; Richter, Mark

2011-01-01

Parkin belongs to a class of multiple RING domain proteins designated as RBR (RING, in between RING, RING) proteins. In this review we examine what is known regarding the structure/function relationship of the Parkin protein. Parkin contains three RING domains plus a ubiquitin-like domain and an in-between-RING (IBR) domain. RING domains are rich in cysteine amino acids that act as ligands to bind zinc ions. RING domains may interact with DNA or with other proteins and perform a wide range of functions. Some function as E3 ubiquitin ligases, participating in attachment of ubiquitin chains to signal proteasome degradation; however, ubiquitin may be attached for purposes other than proteasome degradation. It was determined that the C-terminal most RING, RING2, is essential for Parkin to function as an E3 ubiquitin ligase and a number of substrates have been identified. However, Parkin also participates in a number of other fiunctions, such as DNA repair, microtubule stabilization, and formation of aggresomes. Some functions, such as participation in a multi-protein complex implicated in NMDA activity at the post synaptic density, do not require ubiquitination of substrate molecules. Recent observations of RING proteins suggest their function may be regulated by zinc ion binding. We have modeled the three RING domains of Parkin and have identified a new set of RING2 ligands. This set allows for binding of two rather than just one zinc ion, opening the possibility that the number of zinc ions bound acts as a molecular switch to modulate Parkin function. PMID:21633666

CHEMISTRY OF OXIDATION OF POLYCYCLIC AROMATIC HYDROCARBONS BY SOIL PSEUDOMONADS

PubMed Central

Rogoff, Martin H.

1962-01-01

Rogoff, Martin H. (U.S. Bureau of Mines, Pittsburgh, Pa.). Oxidation of polycyclic aromatic hydrocarbons by soil pseudomonads. J. Bacteriol. 83:998–1004. 1962.—Substitution of phenanthrene by a methyl group at the 9-carbon blocks oxidation of the compound by a resting-cell suspension of a phenanthrene-grown soil pseudomonad. When 2-methylphenanthrene is provided, the oxidation rate is considerably higher; 3-methylphenanthrene is oxidized at a rate intermediate between the other two, even though the methyl group is attached to a carbon directly involved in ring splitting. Cells grown on naphthalene or anthracene oxidize phenanthrene at a much lower rate than cells grown with phenanthrene or 2-methylnaphthalene as the source of carbon. Naphthalene-grown cells also absorb less phenanthrene from aqueous solution than do their phenanthrene-grown counterparts. The data are in keeping with the hypothesis that polynuclear aromatic hydrocarbons attach to the relevant bacterial enzymes at carbon-carbon bonds of high electron density (K regions; localized double bonds), and that the ring-splitting reactions then occur at other bonds on the substrate molecule. The actual bond that undergoes fission is determined by the electronic and steric configurations of the enzyme-substrate complex. When linearly arranged aromatic compounds such as naphthalene or anthracene are attacked, attachment to an enzyme and ring splitting may take place on the same ring; angular aromatic compounds such as phenanthrene afford attachment to an enzyme at a bond in a ring other than the one containing the ring-splitting site. PMID:14493381

Perspectives on micropole undulators in synchrotron radiation technology

NASA Astrophysics Data System (ADS)

Tatchyn, Roman; Csonka, Paul; Toor, Arthur

1989-07-01

Micropole undulators promise to advance synchrotron radiation (SR) technology in two distinct ways. The first is in the development of economical, low-energy storage rings, or linacs, as soft x-ray sources, and the second is in the opening up of gamma-ray spectral ranges on high-energy storage rings. In this paper the promise and current status of micropole undulator (MPU) technology are discussed, and a review of some practical obstacles to the implementation of MPU's on present-day storage rings is given. Some successful results of recent performance measurements of micropole undulators on the Lawrence Livermore National Laboratory linac are briefly summarized.

GPS Tracking of Free-Ranging Pigs to Evaluate Ring Strategies for the Control of Cysticercosis/Taeniasis in Peru.

PubMed

Pray, Ian W; Swanson, Dallas J; Ayvar, Viterbo; Muro, Claudio; Moyano, Luz M; Gonzalez, Armando E; Garcia, Hector H; O'Neal, Seth E

2016-04-01

Taenia solium, a parasitic cestode that affects humans and pigs, is the leading cause of preventable epilepsy in the developing world. T. solium eggs are released into the environment through the stool of humans infected with an adult intestinal tapeworm (a condition called taeniasis), and cause cysticercosis when ingested by pigs or other humans. A control strategy to intervene within high-risk foci in endemic communities has been proposed as an alternative to mass antihelminthic treatment. In this ring strategy, antihelminthic treatment is targeted to humans and pigs residing within a 100 meter radius of a pig heavily-infected with cysticercosis. Our aim was to describe the roaming ranges of pigs in this region, and to evaluate whether the 100 meter radius rings encompass areas where risk factors for T. solium transmission, such as open human defecation and dense pig activity, are concentrated. In this study, we used Global Positioning System (GPS) devices to track pig roaming ranges in two rural villages of northern Peru. We selected 41 pigs from two villages to participate in a 48-hour tracking period. Additionally, we surveyed all households to record the locations of open human defecation areas. We found that pigs spent a median of 82.8% (IQR: 73.5, 94.4) of their time roaming within 100 meters of their homes. The size of home ranges varied significantly by pig age, and 93% of the total time spent interacting with open human defecation areas occurred within 100 meters of pig residences. These results indicate that 100 meter radius rings around heavily-infected pigs adequately capture the average pig's roaming area (i.e., home range) and represent an area where the great majority of exposure to human feces occurs.

Surgical Outcomes After Open, Laparoscopic, and Robotic Gastrectomy for Gastric Cancer.

PubMed

Yang, Seung Yoon; Roh, Kun Ho; Kim, You-Na; Cho, Minah; Lim, Seung Hyun; Son, Taeil; Hyung, Woo Jin; Kim, Hyoung-Il

2017-07-01

In contrast to the significant advantages of laparoscopic versus open gastrectomy, robotic gastrectomy has shown little benefit over laparoscopic gastrectomy. This study aimed to compare multi-dimensional aspects of surgical outcomes after open, laparoscopic, and robotic gastrectomy. Data from 915 gastric cancer patients who underwent gastrectomy by one surgeon between March 2009 and May 2015 were retrospectively reviewed. Perioperative parameters were analyzed for short-term outcomes. Surgical success was defined as the absence of conversion to open surgery, major complications, readmission, positive resection margin, or fewer than 16 retrieved lymph nodes. This study investigated 241 patients undergoing open gastrectomy, 511 patients undergoing laparoscopic gastrectomy, and 173 patients undergoing robotic gastrectomy. For each approach, the respective incidences were as follows: conversion to open surgery (not applicable, 0.4%, and 0%; p = 0.444), in-hospital major complications (5.8, 2.7, and 1.2%; p = 0.020), delayed complications requiring readmission (2.9, 2.0, and 1.2%; p = 0.453), positive resection margin (1.7, 0, and 0%; p = 0.003), and inadequate number of retrieved lymph nodes (0.4, 4.1, and 1.7%; p = 0.010). Compared with open and laparoscopic surgery, robotic gastrectomy had the highest surgical success rate (90, 90.8, and 96.0%). Learning-curve analysis of success using cumulative sum plots showed success with the robotic approach from the start. Multivariate analyses identified age, sex, and gastrectomy extent as significant independent parameters affecting surgical success. Surgical approach was not a contributing factor. Open, laparoscopic, and robotic gastrectomy exhibited different incidences and causes of surgical failure. Robotic gastrectomy produced the best surgical outcomes, although the approach method itself was not an independent factor for success.

DNA bases ring-expanded with a cyclopentadiene free radical: a theoretical investigation of building blocks with diradical character.

PubMed

Zhao, Peiwen; Bu, Yuxiang

2016-01-14

In this work, we computationally design radical nucleobases which possess improved electronic properties, especially diradical properties through introducing a cyclopentadiene radical. We predict that the detailed electromagnetic features of base assemblies are based on the orientation of the extra five-membered cyclopentadiene ring. Broken symmetry DFT calculations take into account the relevant structures and properties. Our results reveal that both the radicalized DNA bases and the base pairs formed when they combine with their counterparts remain stable and display larger spin delocalization. The mode of embedding the cyclopentadiene free radical in the structures has some influence on the degree of π-conjugation, which results in various diradical characteristics. Single-layered radical base pairs all have an open-shell singlet ground state, but the energy difference between singlet and triplet is not significant. For two-layered radical base pairs, the situation is more complex. All of them have an open-shell state as their ground state, including an open-shell singlet state and an open-shell triplet state. That is, the majority of radical base pairs possess anti-ferromagnetic or ferromagnetic characteristics. We present here a more in-depth discussion and analyses to study the magnetic characteristics of radical bases and base pairs. As an important factor, two-layered radical base pairs also have been carefully analyzed. We hope that all the measurements and results presented here will stimulate further detailed insights into the related mechanisms in modified DNA bases and the design of better ring-expanded DNA magnetic materials.

Biopsy system guided by positron emission tomography in real-time

NASA Astrophysics Data System (ADS)

Moliner, L.; Álamo, J.; Hellingman, D.; Peris, J. L.; Gomez, J.; Tattersall, P.; Carrilero, V.; Orero, A.; Correcher, C.; Benlloch, J. M.

2016-03-01

In this work we present the MAMMOCARE prototype, a biopsy guided system based on PET. The system is composed by an examination table where the patient is situated in prone position, a PET detector and a biopsy device. The PET detector is composed by two rings. These rings can be separated mechanically in order to allow the needle insertion. The first acquisition is performed with the closed ring configuration in order to obtain a high quality image to locate the lesion. Then, the software calculates the optimum path for the biopsy and moves the biopsy and PET systems to the desired position. At this point, two compression pallets are used to hold the breast. Then, the PET system opens and the biopsy procedure starts. The images are obtained at several steps to ensure the correct location of the needle during the procedure. The performance of the system is evaluated measuring the spatial resolution and sensitivity according the NEMA standard. The uniformity of the reconstructed images is also estimated. The radial resolution is 1.62mm in the center of the FOV and 3.45mm at 50mm off the center in the radial direction using the closed configuration. In the open configuration the resolution reaches 1.85mm at center and 3.65mm at 50mm. The sensitivity using an energy window of 250keV-750keV is 3.6% for the closed configuration and 2.5% for the open configuration. The uniformity measured in the center of the FOV is 14% and 18% for the closed and open configurations respectively.

Synthesis and antibacterial evaluation of new, unsymmetrical triaryl bisamidine compounds

PubMed Central

Nguyen, Son T.; Williams, John D.; Butler, Michelle M.; Ding, Xiaoyuan; Mills, Debra M.; Tashjian, Tommy F.; Panchal, Rekha G.; Weir, Susan K.; Moon, Chaeho; Kim, Hwa-Ok; Marsden, Jeremiah; Peet, Norton P.; Bowlin, Terry L.

2014-01-01

Herein we describe the synthesis and antibacterial evaluation of a new, unsymmetrical triaryl bisamidine compound series, [Am]-[indole]-[linker]-[HetAr/Ar]-[Am], in which [Am] is an amidine or amino group, [linker] is a benzene, thiophene or pyridine ring, and [HetAr/Ar] is a benzimidazole, imidazopyridine, benzofuran, benzothiophene, pyrimidine or benzene ring. When the [HetAr/Ar] unit is a 5,6-bicyclic heterocycle, it is oriented such that the 5-membered ring portion is connected to the [linker] unit and the 6-membered ring portion is connected to the [Am] unit. Among the 34 compounds in this series, compounds with benzofuran as the [HetAr/Ar] unit showed the highest potencies. Introduction of a fluorine atom or a methyl group to the triaryl core led to the more potent analogs. Bisamidines are more active toward bacteria while the monoamidines are more active toward mammalian cells (as indicated by low CC50 values). Importantly, we identified compound P12a (MBX 1887) with a relatively narrow spectrum against bacteria and a very high CC50 value. Compound P12a has been scaled up and is currently undergoing further evaluations for therapeutic applications. PMID:24969013

Inheritance of a Ring Chromosome 21 in a Couple Undergoing In Vitro Fertilization (IVF): A Case Report

PubMed Central

Mazzaschi, Roberto L. P.; Love, Donald R.; Hayes, Ian; George, Alice

2011-01-01

An amniotic fluid sample from an in vitro fertilized pregnancy was referred for cytogenetic analysis based on a Down syndrome screening risk of 1 : 21. Routine cytogenetic analysis showed a nonmosaic karyotype of 46,XX,r(21)(p11.2q22.3), with partial monosomy for chromosome 21 due to a ring chromosome replacing one of the normal homologues. Detailed ultrasound scanning for the remainder of the pregnancy did not reveal any unusual findings. Parental bloods showed that the mother was mosaic for the ring 21 with a karyotype of 46,XX,r(21)(p11.2q22.3)/46,XX and the father had an unrelated Robertsonian translocation, with a karyotype of 45,XY,rob(13;14)(q10;q10). Microarray analysis of cultured amniocytes determined the extent of the deletion of chromosome 21 material in the ring. The parents were given genetic counselling, and a phenotypically normal female baby was delivered at term. This case highlights the importance of karyotyping as an initial step in the management of couples referred for in vitro fertilization. PMID:23074672

Cryo-EM structure of the gasdermin A3 membrane pore.

PubMed

Ruan, Jianbin; Xia, Shiyu; Liu, Xing; Lieberman, Judy; Wu, Hao

2018-05-01

Gasdermins mediate inflammatory cell death after cleavage by caspases or other, unknown enzymes. The cleaved N-terminal fragments bind to acidic membrane lipids to form pores, but the mechanism of pore formation remains unresolved. Here we present the cryo-electron microscopy structures of the 27-fold and 28-fold single-ring pores formed by the N-terminal fragment of mouse GSDMA3 (GSDMA3-NT) at 3.8 and 4.2 Å resolutions, and of a double-ring pore at 4.6 Å resolution. In the 27-fold pore, a 108-stranded anti-parallel β-barrel is formed by two β-hairpins from each subunit capped by a globular domain. We identify a positively charged helix that interacts with the acidic lipid cardiolipin. GSDMA3-NT undergoes radical conformational changes upon membrane insertion to form long, membrane-spanning β-strands. We also observe an unexpected additional symmetric ring of GSDMA3-NT subunits that does not insert into the membrane in the double-ring pore, which may represent a pre-pore state of GSDMA3-NT. These structures provide a basis that explains the activities of several mutant gasdermins, including defective mutants that are associated with cancer.

Stirling cycle engine

DOEpatents

Lundholm, Gunnar

1983-01-01

In a Stirling cycle engine having a plurality of working gas charges separated by pistons reciprocating in cylinders, the total gas content is minimized and the mean pressure equalization among the serial cylinders is improved by using two piston rings axially spaced at least as much as the piston stroke and by providing a duct in the cylinder wall opening in the space between the two piston rings and leading to a source of minimum or maximum working gas pressure.

Working with the superabrasives industry to optimize tooling for grinding brittle materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, J.S.; Piscotty, M.A.; Blaedel, K.L.

1996-05-01

The optics manufacturing industry is undertaking a significant modernization, as computer-numeric-controlled (CNC) equipment is joining or replacing open-loop equipment and hand lapping/polishing on the shop floor. Several prototype CNC lens grinding platforms employing ring tools are undergoing development and demonstration at the Center for Optics Manufacturing in Rochester, NY, and several machine tool companies have CNC product lines aimed at the optics industry. Benefits to using CNC ring tool grinding equipment include: essentially unlimited flexibility in selecting radii of curvature without special radiused tooling, the potential for CIM linkages to CAD workstations, and the cultural shift from craftsmen with undocumentedmore » procedures to CNC machine operators employing computerized routines for process control. In recent years, these developments, have inspired a number of US optics companies to invest in CNC equipment and participate in process development activities involving bound diamond tooling. This modernization process,extends beyond large optics companies that have historically embraced advanced equipment, to also include smaller optical shops where a shift to CNC equipment requires a significant company commitment. This paper addresses our efforts to optimize fine grinding wheels to support the new generation of CNC equipment. We begin with a discussion of how fine grinding fits into the optical production process, and then describe an initiative for improving the linkage between optics industry and the grinding wheel industry. For the purposes of this paper, we define fine wheels to have diamond sizes below 20 micrometers, which includes wheels used for what is sometimes called medium grinding (e.g. 10-20 micrometers diamond) and for fine grinding (e.g. 2-4 micrometers diamond).« less

Double Purse-String Telescoped Pancreaticogastro stomy using an Atraumatic Self-retaining Ring Retractor in a Subtotal Stomach-Preserving Pancreaticoduodenectomy.

PubMed

Narita, Masato; Matsusue, Ryo; Hata, Hiroaki; Yamaguchi, Takashi; Otani, Tetsushi; Ikai, Iwao

2016-03-01

Pancreatoenteric anastomotic failure is the main cause of pancreatic fistula after pancreaticoduodenectomy (PD). Double purse-string telescoped pancreaticogastrostomy, reported by Addeo et al., is an easy and safe procedure.1 The aim of this article was to introduce our technique of pancreaticogastrostomy using an atraumatic self-retaining ring retractor (Alexis Wound Retractor) in a patient undergoing subtotal stomach-preserving PD (SSPPD). An 82-year-old woman presented with pancreatic cancer located in the uncinate process of pancreas. She underwent SSPPD with resection of the superior mesenteric vein (SMV) and double purse-string telescoped pancreaticogastrostomy using an Alexis wound retractor. The pancreas was transected on the portal vein and the remnant pancreas was separated from the splenic vein and artery. After extirpation of specimens and reconstruction of the SMV, two seromuscular purse-string sutures were placed on the posterior wall of the upper stomach. The anterior wall of the upper stomach was incised and opened using an Alexis wound retractor. The remnant pancreas was inserted into the gastric cavity through the posterior wall of the stomach and sutured circumferentially with running stitches to fix on the gastric muco-muscular layer. After closure of the anterior wall of the stomach, purse-string sutures were tightened and pancreaticogastrostomy was completed. The patient's postoperative course was uneventful and a computed tomography imaging study revealed no fluid collection around the pancreaticogastrostomy. This patient was discharged on the 14th postoperative day. Use of an Alexis wound retractor makes it easier to perform a double purse-string telescoped pancreaticogastrostomy by a self-expanding property to allow a wide operative view.

Femtosecond Laser in situ Keratomileusis Flap Creation in Narrow Palpebral Fissure Eyes without Suction.

PubMed

Chang, John S M; Law, Antony K P; Ng, Jack C M; Cheng, May S Y

2017-01-01

To evaluate a surgical technique used in eyes with narrow palpebral fissure undergoing femtosecond laser flap creation without suction during laser in situ keratomileusis (LASIK). All data of 2 patient groups were collected through chart review. Group 1 consisted of 6 eyes with narrow palpebral fissure in which the suction ring was manually fixated and femtosecond laser was applied accordingly. Thirty comparison cases were randomly drawn from among eyes that underwent a standard LASIK procedure matched for age and preoperative refraction (group 2). Only 1 eye of each patient was selected to compare the refractive and visual outcomes between groups. In all group 1 eyes, the flaps were created successfully with manual fixation of the suction ring without suction. No eyes lost 2 or more lines of vision. No significant difference was found in the safety and refractive outcomes between groups. Manual fixation of the suction ring in eyes with narrow palpebral fissure without suction was feasible for flap creation during LASIK.

Femtosecond Laser in situ Keratomileusis Flap Creation in Narrow Palpebral Fissure Eyes without Suction

PubMed Central

Chang, John S.M.; Law, Antony K.P.; Ng, Jack C.M.; Cheng, May S.Y.

2017-01-01

Purpose To evaluate a surgical technique used in eyes with narrow palpebral fissure undergoing femtosecond laser flap creation without suction during laser in situ keratomileusis (LASIK). Methods All data of 2 patient groups were collected through chart review. Group 1 consisted of 6 eyes with narrow palpebral fissure in which the suction ring was manually fixated and femtosecond laser was applied accordingly. Thirty comparison cases were randomly drawn from among eyes that underwent a standard LASIK procedure matched for age and preoperative refraction (group 2). Only 1 eye of each patient was selected to compare the refractive and visual outcomes between groups. Results In all group 1 eyes, the flaps were created successfully with manual fixation of the suction ring without suction. No eyes lost 2 or more lines of vision. No significant difference was found in the safety and refractive outcomes between groups. Conclusion Manual fixation of the suction ring in eyes with narrow palpebral fissure without suction was feasible for flap creation during LASIK. PMID:28690535

In vivo structure of the E. coli FtsZ-ring revealed by photoactivated localization microscopy (PALM).

PubMed

Fu, Guo; Huang, Tao; Buss, Jackson; Coltharp, Carla; Hensel, Zach; Xiao, Jie

2010-09-13

The FtsZ protein, a tubulin-like GTPase, plays a pivotal role in prokaryotic cell division. In vivo it localizes to the midcell and assembles into a ring-like structure-the Z-ring. The Z-ring serves as an essential scaffold to recruit all other division proteins and generates contractile force for cytokinesis, but its supramolecular structure remains unknown. Electron microscopy (EM) has been unsuccessful in detecting the Z-ring due to the dense cytoplasm of bacterial cells, and conventional fluorescence light microscopy (FLM) has only provided images with limited spatial resolution (200-300 nm) due to the diffraction of light. Hence, given the small sizes of bacteria cells, identifying the in vivo structure of the Z-ring presents a substantial challenge. Here, we used photoactivated localization microscopy (PALM), a single molecule-based super-resolution imaging technique, to characterize the in vivo structure of the Z-ring in E. coli. We achieved a spatial resolution of ∼35 nm and discovered that in addition to the expected ring-like conformation, the Z-ring of E. coli adopts a novel compressed helical conformation with variable helical length and pitch. We measured the thickness of the Z-ring to be ∼110 nm and the packing density of FtsZ molecules inside the Z-ring to be greater than what is expected for a single-layered flat ribbon configuration. Our results strongly suggest that the Z-ring is composed of a loose bundle of FtsZ protofilaments that randomly overlap with each other in both longitudinal and radial directions of the cell. Our results provide significant insight into the spatial organization of the Z-ring and open the door for further investigations of structure-function relationships and cell cycle-dependent regulation of the Z-ring.

ALS superbend magnet performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marks, Steve; Zbasnik, John; Byrne, Warren

2001-12-10

The Lawrence Berkeley National Laboratory has been engaged in the design, construction and testing of four superconducting dipoles (Superbends) that are installed in three arcs of the Advanced Light Source (ALS), with the fourth magnet as a spare. This represents a major upgrade to the ALS providing an enhanced flux and brightness at photon energies above 10 keV. In preparation for installation, an extensive set of tests and measurements have been conducted to characterize the magnetic and cryogenic performance of the Superbends and to fiducialize them for accurate placement in the ALS storage ring. The magnets are currently installed, andmore » the storage ring is undergoing final commissioning. This paper will present the results of magnetic and cryogenic testing.« less

Partial-Vacuum-Gasketed Electrochemical Corrosion Cell

NASA Technical Reports Server (NTRS)

Bonifas, Andrew P.; Calle, Luz M.; Hintze, Paul E.

2006-01-01

An electrochemical cell for making corrosion measurements has been designed to prevent or reduce crevice corrosion, which is a common source of error in prior such cells. The present cell (see figure) includes an electrolyte reservoir with O-ring-edged opening at the bottom. In preparation for a test, the reservoir, while empty, is pressed down against a horizontal specimen surface to form an O-ring seal. A purge of air or other suitable gas is begun in the reservoir, and the pressure in the reservoir is regulated to maintain a partial vacuum. While maintaining the purge and partial vacuum, and without opening the interior of the reservoir to the atmosphere, the electrolyte is pumped into the reservoir. The reservoir is then slowly lifted a short distance off the specimen. The level of the partial vacuum is chosen such that the differential pressure is just sufficient to keep the electrolyte from flowing out of the reservoir through the small O-ring/specimen gap. Electrochemical measurements are then made. Because there is no gasket (and, hence, no crevice between the specimen and the gasket), crevice corrosion is unlikely to occur.

Effects on cycle control and bodyweight of the combined contraceptive ring, NuvaRing, versus an oral contraceptive containing 30 microg ethinyl estradiol and 3 mg drospirenone.

PubMed

Milsom, I; Lete, I; Bjertnaes, A; Rokstad, K; Lindh, I; Gruber, C J; Birkhäuser, M H; Aubeny, E; Knudsen, T; Bastianelli, C

2006-09-01

The objective of this study was to compare cycle control, cycle-related characteristics and bodyweight effects of NuvaRing with those of a combined oral contraceptive (COC) containing 30 microg of ethinyl estradiol and 3 mg of drospirenone. A randomized, multicentre, open-label trial in which 983 women were treated (intent-to-treat population) with NuvaRing or the COC for 13 cycles. Breakthrough bleeding or spotting during cycles 2-13 was in general less frequent with NuvaRing than that with the COC (4.7-10.4%) and showed a statistically significant odds ratio of 0.61 (95% confidence interval: 0.46, 0.80) with longitudinal analysis. Intended bleeding was significantly better for all cycles with NuvaRing (55.2-68.5%) than that with the COC (35.6-56.6%) (P < 0.01). Changes from baseline in mean bodyweight and body composition parameters were relatively small for both groups with no notable between-group differences. NuvaRing was associated with better cycle control than the COC, and there was no clinically relevant difference between the two groups in bodyweight.

The efficacy of tolvaptan in the perioperative management of chronic kidney disease patients undergoing open-heart surgery.

PubMed

Yamada, Mitsutomo; Nishi, Hiroyuki; Sekiya, Naosumi; Horikawa, Kohei; Takahashi, Toshiki; Sawa, Yoshiki

2017-04-01

The perioperative management of chronic kidney disease (CKD) patients undergoing open-heart surgery is challenging. In this study, we evaluated the effects of tolvaptan in CKD patients after open-heart surgery. Between 2010 to 2015, 731 patients underwent open-heart surgery in our hospital. We consecutively selected 71 patients with stage IIIa-IV CKD and divided them into two groups. Those who received tolvaptan postoperatively were defined as the "Tolvaptan group" (n = 25) and those who did not were defined as the "Non-tolvaptan group" (n = 46). We compared the urine volume of postoperative days (POD) 1 and 2, the number of days to return to preoperative body weight (BW), and the change in the postoperative estimated glomerular filtration rate (eGFR). In the tolvaptan group, the urine volume was significantly larger (P = .04) and the duration to preoperative BW tended to be shorter. Overall, the postoperative change in the eGFR tended to be better in the tolvaptan group (P = .008). In particular, we found a significantly better trend in CKD stage IV (P = .04) patients and in the patients, whose cardiopulmonary bypass (CPB) time was longer than 120 min (P = .03). Tolvaptan can safely be used for CKD patients undergoing open-heart surgery and can provide a feasible urine volume without leading to a deterioration of their renal function.

Developing new methods for the mono-end functionalization of living ring opening metathesis polymers.

PubMed

Kilbinger, Andreas F M

2012-01-01

In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer-protein conjugates are two examples for the former and polymer-β-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

PubMed

Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

2017-08-10

Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

Enzymatic catalysis of anti-Baldwin ring closure in polyether biosynthesis

PubMed Central

Hotta, Kinya; Chen, Xi; Paton, Robert S.; Minami, Atsushi; Li, Hao; Swaminathan, Kunchithapadam; Mathews, Irimpan I.; Watanabe, Kenji; Oikawa, Hideaki; Houk, Kendall N.; Kim, Chu-Young

2012-01-01

Polycyclic polyether natural products have fascinated chemists and biologists alike owing to their useful biological activity, highly complex structure and intriguing biosynthetic mechanisms. Following the original proposal for the polyepoxide origin of lasalocid and isolasalocid1 and the experimental determination of the origins of the oxygen and carbon atoms of both lasalocid and monensin, a unified stereochemical model for the biosynthesis of polyether ionophore antibiotics was proposed2. The model was based on a cascade of nucleophilic ring closures of postulated polyepoxide substrates generated by stereospecific oxidation of all-trans polyene polyketide intermediates2. Shortly thereafter, a related model was proposed for the biogenesis of marine ladder toxins, involving a series of nominally disfavoured anti-Baldwin, endo-tet epoxide-ring-opening reactions3–5. Recently, we identified Lsd19 from the Streptomyces lasaliensis gene cluster as the epoxide hydrolase responsible for the epoxide-opening cyclization of bisepoxyprelasalocid A6 to form lasalocid A7,8. Here we report the X-ray crystal structure of Lsd19 in complex with its substrate and product analogue9 to provide the first atomic structure—to our knowledge—of a natural enzyme capable of catalysing the disfavoured epoxide-opening cyclic ether formation. On the basis of our structural and computational studies, we propose a general mechanism for the enzymatic catalysis of polyether natural product biosynthesis. PMID:22388816

UV-tunable laser induced phototransformations of matrix isolated anethole.

PubMed

Krupa, Justyna; Wierzejewska, Maria; Nunes, Cláudio M; Fausto, Rui

2014-03-14

A matrix isolation study of the infrared spectra and structure of anethole (1-methoxy-4-(1-propenyl)benzene) has been carried out, showing the presence of two E conformers (AE1, AE2) of the molecule in the as-deposited matrices. Irradiation using ultraviolet-tunable laser light at 308-307 nm induced conformationally selective phototransformations of these forms into two less stable Z conformers (AZ1, AZ2). The back reactions were also detected upon irradiation at 301 nm. On the whole, the obtained results allow for full assignment of the infrared spectra of all the four experimentally observed anethole isomers and showed that the narrowband UV-induced E-Z photoisomerization is an efficient and selective way to interconvert the two isomers of anethole into each other, with conformational discrimination. Photolysis of anethole was observed as well, with initial methoxyl O-C bond cleavage and formation of CH3 and p-propenylphenoxy (AR) radicals, followed by radical recombination to form 2-methyl-4-propenyl-2,4-cyclohexadienone, which subsequently undergoes ring-opening generating several conformers of long-chain conjugated ketenes. Interpretation of the experimental observations was supported by density functional theory (B3LYP and B2PLYD) calculations.

Robot-Assisted Versus Open Liver Resection in the Right Posterior Section

PubMed Central

Cipriani, Federica; Ratti, Francesca; Bartoli, Alberto; Ceccarelli, Graziano; Casciola, Luciano; Aldrighetti, Luca

2014-01-01

Background: Open liver resection is the current standard of care for lesions in the right posterior liver section. The objective of this study was to determine the safety of robot-assisted liver resection for lesions located in segments 6 and 7 in comparison with open surgery. Methods: Demographics, comorbidities, clinicopathologic characteristics, surgical treatments, and outcomes from patients who underwent open and robot-assisted liver resection at 2 centers for lesions in the right posterior section between January 2007 and June 2012 were reviewed. A 1:3 matched analysis was performed by individually matching patients in the robotic cohort to patients in the open cohort on the basis of demographics, comorbidities, performance status, tumor stage, and location. Results: Matched patients undergoing robotic and open liver resections displayed no significant differences in postoperative outcomes as measured by blood loss, transfusion rate, hospital stay, overall complication rate (15.8% vs 13%), R0 negative margin rate, and mortality. Patients undergoing robotic liver surgery had significantly longer operative time (mean, 303 vs 233 minutes) and inflow occlusion time (mean, 75 vs 29 minutes) compared with their open counterparts. Conclusions: Robotic and open liver resections in the right posterior section display similar safety and feasibility. PMID:25516700

Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

NASA Astrophysics Data System (ADS)

Xu, Tiwen; Jia, Zhixin; Luo, Yuanfang; Jia, Demin; Peng, Zheng

2015-02-01

The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress-strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

Cdt1 stabilizes an open MCM ring for helicase loading.

PubMed

Frigola, Jordi; He, Jun; Kinkelin, Kerstin; Pye, Valerie E; Renault, Ludovic; Douglas, Max E; Remus, Dirk; Cherepanov, Peter; Costa, Alessandro; Diffley, John F X

2017-06-23

ORC, Cdc6 and Cdt1 act together to load hexameric MCM, the motor of the eukaryotic replicative helicase, into double hexamers at replication origins. Here we show that Cdt1 interacts with MCM subunits Mcm2, 4 and 6, which both destabilizes the Mcm2-5 interface and inhibits MCM ATPase activity. Using X-ray crystallography, we show that Cdt1 contains two winged-helix domains in the C-terminal half of the protein and a catalytically inactive dioxygenase-related N-terminal domain, which is important for MCM loading, but not for subsequent replication. We used these structures together with single-particle electron microscopy to generate three-dimensional models of MCM complexes. These show that Cdt1 stabilizes MCM in a left-handed spiral open at the Mcm2-5 gate. We propose that Cdt1 acts as a brace, holding MCM open for DNA entry and bound to ATP until ORC-Cdc6 triggers ATP hydrolysis by MCM, promoting both Cdt1 ejection and MCM ring closure.

Cdt1 stabilizes an open MCM ring for helicase loading

PubMed Central

Frigola, Jordi; He, Jun; Kinkelin, Kerstin; Pye, Valerie E.; Renault, Ludovic; Douglas, Max E.; Remus, Dirk; Cherepanov, Peter; Costa, Alessandro; Diffley, John F. X.

2017-01-01

ORC, Cdc6 and Cdt1 act together to load hexameric MCM, the motor of the eukaryotic replicative helicase, into double hexamers at replication origins. Here we show that Cdt1 interacts with MCM subunits Mcm2, 4 and 6, which both destabilizes the Mcm2–5 interface and inhibits MCM ATPase activity. Using X-ray crystallography, we show that Cdt1 contains two winged-helix domains in the C-terminal half of the protein and a catalytically inactive dioxygenase-related N-terminal domain, which is important for MCM loading, but not for subsequent replication. We used these structures together with single-particle electron microscopy to generate three-dimensional models of MCM complexes. These show that Cdt1 stabilizes MCM in a left-handed spiral open at the Mcm2–5 gate. We propose that Cdt1 acts as a brace, holding MCM open for DNA entry and bound to ATP until ORC–Cdc6 triggers ATP hydrolysis by MCM, promoting both Cdt1 ejection and MCM ring closure. PMID:28643783

O-Ring Installation for Underwater Components and Applications

DTIC Science & Technology

1982-04-15

cure is effected and the heat source removed. AGING -- To undergo changes in physical properties with age or lapse of time. AIR CHECKS -- Surface...the use of heat and pressure, resulting in greatly increased strength and elasticity of rubber -like materials. VULCANIZING AGENT -- A material that...Cross Section Dia -- Diameter EP, EPM, EPDM -- Ethylene-Propylene Rubber F or ’F -- Degrees Fahrenheit FED -- Federal Specification FPM -- Fluorocarbon

C–H Functionalization of Cyclic Amines: Redox-Annulations with α,β-Unsaturated Carbonyl Compounds

PubMed Central

Kang, YoungKu; Richers, Matthew T.; Sawicki, Conrad H.; Seidel, Daniel

2015-01-01

Cyclic amines such as pyrrolidine and 1,2,3,4-tetrahydroisoquinoline undergo redox-annulations with α,β-unsaturated aldehydes and ketones. Carboxylic acid promoted generation of a conjugated azomethine ylide is followed by 6π-electrocylization, and, in some cases, tautomerization. The resulting ring-fused pyrrolines are readily oxidized to the corresponding pyrroles or reduced to pyrrolidines. PMID:26051897

Nursing care of the patient undergoing coronary artery bypass grafting.

PubMed

Martin, Caron G; Turkelson, Sandra L

2006-01-01

The role of the professional nurse in the perioperative care of the patient undergoing open heart surgery is beneficial for obtaining a positive outcome for the patient. This article focuses on the preoperative and postoperative nursing care of patients undergoing coronary artery bypass graft surgery. Risk assessment, preoperative preparation, current operative techniques, application of the nursing process immediately after surgery, and common postoperative complications will be explored.

REVIEW OF AGING DATA ON EPDM O-RINGS IN THE H1616 SHIPPING PACKAGE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skidmore, E.

Currently, all H1616 shipping package containers undergo annual re-verification testing, including containment vessel leak testing to verify leak-tightness (<1 x 10{sup -7} ref cc/sec air) as per ANSI N14.5. The purpose of this literature review is to supplement aging studies currently being performed by SRNL on the EPDM O-rings to provide the technical basis for extending annual re-verification testing for the H1616 shipping package and to predict the life of the seals at bounding service conditions. The available data suggest that the EPDM O-rings can retain significant mechanical properties and sealing force at or below bounding service temperatures (169 Fmore » or 76 C) beyond the 1 year maintenance period. Interpretation of available data suggests that a service life of at least 2 years and potentially 4-6 years may be possible at bounding temperatures. Seal lifetimes at lower, more realistic temperatures will likely be longer. Being a hydrocarbon elastomer, EPDM O-rings may exhibit an inhibition period due to the presence of antioxidants. Once antioxidants are consumed, mechanical properties and seal performance could decline at a faster rate. Testing is being performed to validate the assumptions outlined in this report and to assess the long-term performance of O-ring seals under actual service conditions.« less

UVIT observations of the star-forming ring in NGC 7252: Evidence of possible AGN feedback suppressing central star formation

NASA Astrophysics Data System (ADS)

George, K.; Joseph, P.; Mondal, C.; Devaraj, A.; Subramaniam, A.; Stalin, C. S.; Côté, P.; Ghosh, S. K.; Hutchings, J. B.; Mohan, R.; Postma, J.; Sankarasubramanian, K.; Sreekumar, P.; Tandon, S. N.

2018-05-01

Context. Some post-merger galaxies are known to undergo a starburst phase that quickly depletes the gas reservoir and turns it into a red-sequence galaxy, though the details are still unclear. Aims: Here we explore the pattern of recent star formation in the central region of the post-merger galaxy NGC 7252 using high-resolution ultraviolet (UV) images from the UVIT on ASTROSAT. Methods: The UVIT images with 1.2 and 1.4 arcsec resolution in the FUV and NUV are used to construct a FUV-NUV colour map of the central region. Results: The FUV-NUV pixel colour map for this canonical post-merger galaxy reveals a blue circumnuclear ring of diameter 10'' (3.2 kpc) with bluer patches located over the ring. Based on a comparison to single stellar population models, we show that the ring is comprised of stellar populations with ages ≲300 Myr, with embedded star-forming clumps of younger age (≲150Myr). Conclusions: The suppressed star formation in the central region, along with the recent finding of a large amount of ionised gas, leads us to speculate that this ring may be connected to past feedback from a central super-massive black hole that has ionised the hydrogen gas in the central 4'' 1.3 kpc.

Blow-out protector and fire control system for petroleum exploration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caraway, M.F.; Caraway, B.L.

1987-10-06

A blow-out protector is described for an oil well comprising a housing having a vertical passageway therethrough for a Kelly. The housing has a lower end adapter flange to be connected to a well casing, an elastomeric body having an opening for the Kelly and carried on the Kelly for providing sealing contact with the Kelly and housing passageway, a catch ring secured to the Kelly and having a surface defined by a given diameter, a compressor ring plate positioned below the elastomeric body on the Kelly, means on an interior of the housing having a given diameter and preventingmore » the compressor ring plate from falling down and yet providing engagement with the surface of the catch ring, the compressor ring plate having a hole for passage of the Kelly drive-mechanism for the drill pipe, the catch ring on the Kelly positioned below the compressor plate. The diameter of the catch ring is smaller than the diameter of the interior means on the housing so that when the Kelly is pulled up the catch ring will contact and force the compressor ring plate against the elastomeric body and force the elastomeric body into tight contact with both the Kelly and the housing thus sealing the space between the Kelly and the housing against a blow-out.« less

Novel Use of Active Leptospermum Honey for Ringed Fixator Pin Site Care in Diabetic Charcot Deformity Patients.

PubMed

Lazarides, Alexander L; Hamid, Kamran S; Kerzner, Michael S

2018-04-01

Open reduction with external fixation (OREF) utilizing fine wire ringed fixators for correction of Charcot deformity has gained popularity over the past decade. Pin site infections are a well-documented complication of external fixation as well as a driver of escalating health care costs. We aimed to demonstrate the safety and efficacy of a novel method of pin site care utilizing active Leptospermum honey-impregnated dressings (MediHoney) in diabetic patients undergoing deformity correction with OREF. Twenty-one diabetic patients with Charcot deformities of the lower extremity were prospectively enrolled and followed for pin site complications following OREF for deformity correction. Active Leptospermum honey dressings were applied at metal-cutaneous interfaces at the end of the OREF procedure and replaced weekly for a total of 8 weeks. Patients were monitored for pin site infections from the time of surgery until external fixator removal. Sixteen consecutive patients receiving standard OREF for Charcot deformities were evaluated retrospectively to serve as a control group. Of the 21 enrolled patients, 19 underwent OREF and followed up throughout the study period. Treated patients had a mean age of 58.5 years and mean body mass index measuring 33.3 kg/m 2 as documented prior to surgery. The 15 patients with hemoglobin A1c labs drawn in the 3 months preceding surgery averaged 7.5. Fixators were removed at an average of 12.1 weeks after adequate bony healing. Of the 244 pin sites in 19 patients, 3 pin sites (1.2% of pins) in 2 patients (10.5% of patients) showed evidence of superficial infection. All infections resolved with oral antibiotics. Infection rates were significantly reduced when compared to the standard care control group. Pilot data in a prospectively collected case series demonstrate safety and efficacy of active Leptospermum honey-impregnated dressings when used for fine wire ringed fixator pin site care in diabetic Charcot deformity patients. Further investigation in the form of a prospective randomized controlled study is warranted to demonstrate the potential value of this novel intervention. Level IV.

Design, synthesis and biological evaluation of novel ring-opened cromakalim analogues with relaxant effects on vascular and respiratory smooth muscles and as stimulators of elastin synthesis.

PubMed

Bouhedja, Mourad; Peres, Basile; Fhayli, Wassim; Ghandour, Zeinab; Boumendjel, Ahcène; Faury, Gilles; Khelili, Smail

2018-01-20

Two new series of ring-opened analogues of cromakalim bearing sulfonylurea moieties (series A: with N-unmethylated sulfonylureas, series B: with N-methylated sulfonylureas) were synthesized and tested as relaxants of vascular and respiratory smooth muscles (rat aorta and trachea, respectively). Ex vivo biological evaluations indicated that the most active compounds, belonging to series B, displayed a marked vasorelaxant activity on endothelium-intact aortic rings and the trachea. A majority of series B compounds exhibited a higher vasorelaxant activity (EC 50  < 22 μM) than that of the reference compound diazoxide (EC 50  = 24 μM). Interestingly, several tested compounds of series B also presented stronger relaxant effects on the trachea than the reference compound cromakalim (EC 50  = 124 μM), in particular compounds B4, B7 and B16 (EC 50  < 10 μM). By contrast, series A derivatives were poorly active on aortic rings (EC 50  > 57 μM for all, and EC 50  > 200 μM for a majority of them), but some of them showed an interesting relaxing effect on trachea (i.e. A15 and A33, EC 50  = 30 μM). The most potent compounds of both series, i.e. A15, A33 and B16, tested on aortic rings in the presence of glibenclamide or 80 mM KCl, suggested that they acted as voltage-gated Ca 2+ channel blockers, like verapamil, instead of being ATP-potassium channel activators, as is cromakalim, the parent molecule. Further investigations on cultured vascular smooth muscle cells showed a strong stimulating effect on elastin synthesis, especially compound B16, which was more active at 20 μM than diazoxide, a reference ATP-sensitive potassium channel activator. Taken together, our results show that the N-methylation of the sulfonylurea moieties of ring-opened cromakalim analogues led to new compounds blocking calcium-gated channels, which had a major impact on the arterial and tracheal activities as well as selectivity. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Theis, Daniel; Windus, Theresa L.; Ruedenberg, Klaus

The metastable ring structure of the ozone 1{sup 1}A{sub 1} ground state, which theoretical calculations have shown to exist, has so far eluded experimental detection. An accurate prediction for the energy difference between this isomer and the lower open structure is therefore of interest, as is a prediction for the isomerization barrier between them, which results from interactions between the lowest two {sup 1}A{sub 1} states. In the present work, valence correlated energies of the 1{sup 1}A{sub 1} state and the 2{sup 1}A{sub 1} state were calculated at the 1{sup 1}A{sub 1} open minimum, the 1{sup 1}A{sub 1} ring minimum,more » the transition state between these two minima, the minimum of the 2{sup 1}A{sub 1} state, and the conical intersection between the two states. The geometries were determined at the full-valence multi-configuration self-consistent-field level. Configuration interaction (CI) expansions up to quadruple excitations were calculated with triple-zeta atomic basis sets. The CI expansions based on eight different reference configuration spaces were explored. To obtain some of the quadruple excitation energies, the method of Correlation Energy Extrapolation by Intrinsic Scaling was generalized to the simultaneous extrapolation for two states. This extrapolation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 1{sup 1}A{sub 1} state, the present calculations yield the estimates of (ring minimum—open minimum) ∼45–50 mh and (transition state—open minimum) ∼85–90 mh. For the (2{sup 1}A{sub 1}–{sup 1}A{sub 1}) excitation energy, the estimate of ∼130–170 mh is found at the open minimum and 270–310 mh at the ring minimum. At the transition state, the difference (2{sup 1}A{sub 1}–{sup 1}A{sub 1}) is found to be between 1 and 10 mh. The geometry of the transition state on the 1{sup 1}A{sub 1} surface and that of the minimum on the 2{sup 1}A{sub 1} surface nearly coincide. More accurate predictions of the energy differences also require CI expansions to at least sextuple excitations with respect to the valence space. For every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about ±10 mh with respect to the energy differences.« less

CLOSURE DEVICE

DOEpatents

Linzell, S.M.; Dorcy, D.J.

1958-08-26

A quick opening type of stuffing box employing two banks of rotatable shoes, each of which has a caraming action that forces a neoprene sealing surface against a pipe or rod where it passes through a wall is presented. A ring having a handle or wrench attached is placed eccentric to and between the two banks of shoes. Head bolts from the shoes fit into slots in this ring, which are so arranged that when the ring is rotated a quarter turn in one direction the shoes are thrust inwardly to cramp the neopnrene about the pipe, malting a tight seal. Moving the ring in the reverse direction moves the shoes outwardly and frees the pipe which then may be readily removed from the stuffing box. This device has particular application as a closure for the end of a coolant tube of a neutronic reactor.

The effect of ring distortions on buckling of blunt conical shells. [Viking mission aeroshell

NASA Technical Reports Server (NTRS)

Heard, W. L., Jr.; Anderson, M. S.; Stephens, W. B.

1975-01-01

A rigorous analytical study of cones stiffened by many thin-gage, open-section rings is presented. The results are compared with data previously obtained from uniform pressure tests of the Viking mission flight aeroshell and of the Viking structural prototype aeroshells. A conventional analysis, in which the rings are modeled as discrete rigid cross sections, is shown to lead to large, unconservative strength predictions. A more sophisticated technique of modeling the rings as shell branches leads to much more realistic strength predictions and more accurately predicts the failure modes. It is also shown that if a small initial imperfection proportional to the shape of the buckling mode is assumed, the critical buckling modes from analysis and test are in agreement. However, the reduction in buckling strength from the perfect-shell predictions is small.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akparov, V V; Dmitriev, Valentin G; Duraev, V P

A semiconductor ring laser (SRL) with a radiation wavelength of 1540 nm and a fibre ring cavity is developed and studied in several main lasing regimes. An SRL design based on a semiconductor optical travelling-wave amplifier and a ring cavity, composed of a single-mode polarisation-maintaining fibre, is considered. The SRL is studied in the regime of a rotation speed sensor, in which the frequency shift of counterpropagating waves in the SRL is proportional to its rotation speed. The minimum rotation speed that can be detected using the SRL under consideration depends on the cavity length; in our experiment it turnedmore » to be 1deg s{sup -1}. The changes in the threshold current, emission spectrum, and fundamental radiation wavelength upon closing and opening the SRL ring cavity and with a change in its radius are also investigated. (lasers)« less

The Mechanics of Peak-Ring Impact Crater Formation from the IODP-ICDP Expedition 364

NASA Astrophysics Data System (ADS)

Melosh, H.; Collins, G. S.; Morgan, J. V.; Gulick, S. P. S.

2017-12-01

The Chicxulub impact crater is one of very few peak-ring impact craters on Earth. While small (less than 3 km on Earth) impact craters are typically bowl-shaped, larger craters exhibit central peaks, which in still larger (more than about 100 km on Earth) craters expand into mountainous rings with diameters close to half that of the crater rim. The origin of these peak rings has been contentious: Such craters are far too large to create in laboratory experiments and remote sensing of extraterrestrial examples has not clarified the mechanics of their formation. Two principal models of peak ring formation are currently in vogue, the "nested crater" model, in which the peak ring originates at shallow depths in the target, and the "dynamic collapse" model in which the peak ring is uplifted at the base of a collapsing, over-steepened central peak and its rocks originate at mid-crustal depths. IODP-ICDP Expedition 364 sought to elucidate, among other important goals, the mechanics of peak ring formation in the young (66 Myr), fresh, but completely buried Chicxulub impact crater. The cores from this borehole now show unambiguously that the rocks in the Chicxulub peak ring originated at mid-crustal depths, apparently ruling out the nested crater model. These rocks were shocked to pressures on the order of 10-35 GPa and were so shattered that their densities and seismic velocities now resemble those of sedimentary rocks. The morphology of the final crater, its structure as revealed in previous seismic imaging, and the results from the cores are completely consistent with modern numerical models of impact crater excavation and collapse that incorporate a model for post-impact weakening. Subsequent to the opening of a ca. 100 km diameter and 30 km deep transient crater, this enormous hole in the crust collapsed over a period of about 10 minutes. Collapse was enabled by movement of the underlying rocks, which briefly behaved in the manner of a high-viscosity fluid, a brittle deformation state described by the process of "acoustic" fluidization initiated by strong elastic vibrations accompanying the opening and collapse of the crater. The shattered core, cut by both melt rock and clastic dikes, is consistent with the block model of acoustic fluidization supporting its application to crater collapse both on the Earth and on other planets.

Cassini RSS occultation observations of density waves in Saturn's rings

NASA Astrophysics Data System (ADS)

McGhee, C. A.; French, R. G.; Marouf, E. A.; Rappaport, N. J.; Schinder, P. J.; Anabtawi, A.; Asmar, S.; Barbinis, E.; Fleischman, D.; Goltz, G.; Johnston, D.; Rochblatt, D.

2005-08-01

On May 3, 2005, the first of a series of eight nearly diametric occultations by Saturn's rings and atmosphere took place, observed by the Cassini Radio Science (RSS) team. Simultaneous high SNR measurements at the Deep Space Network (DSN) at S, X, and Ka bands (λ = 13, 3.6, and 0.9 cm) have provided a remarkably detailed look at the radial structure and particle scattering behavior of the rings. By virtue of the relatively large ring opening angle (B=-23.6o), the slant path optical depth of the rings was much lower than during the Voyager epoch (B=5.9o), making it possible to detect many density waves and other ring features in the Cassini RSS data that were lost in the noise in the Voyager RSS experiment. Ultimately, diffraction correction of the ring optical depth profiles will yield radial resolution as small as tens of meters for the highest SNR data. At Ka band, the Fresnel scale is only 1--1.5 km, and thus even without diffraction correction, the ring profiles show a stunning array of density waves. The A ring is replete with dozens of Pandora and Prometheus inner Lindblad resonance features, and the Janus 2:1 density wave in the B ring is revealed with exceptional clarity for the first time at radio wavelengths. Weaker waves are abundant as well, and multiple occultation chords sample a variety of wave phases. We estimate the surface mass density of the rings from linear density wave models of the weaker waves. For stronger waves, non-linear models are required, providing more accurate estimates of the wave dispersion relation, the ring surface mass density, and the angular momentum exchange between the rings and satellite. We thank the DSN staff for their superb support of these complex observations.

Annular dynamics after mitral valve repair with different prosthetic rings: A real-time three-dimensional transesophageal echocardiography study.

PubMed

Nishi, Hiroyuki; Toda, Koichi; Miyagawa, Shigeru; Yoshikawa, Yasushi; Fukushima, Satsuki; Kawamura, Masashi; Yoshioka, Daisuke; Saito, Tetsuya; Ueno, Takayoshi; Kuratani, Toru; Sawa, Yoshiki

2016-09-01

We assessed the effects of different types of prosthetic rings on mitral annular dynamics using real-time three-dimensional echocardiography (RT3DE). RT3DE was performed in 44 patients, including patients undergoing mitral annuloplasty using the Cosgrove-Edwards flexible band (Group A, n = 10), the semi-rigid Sorin Memo 3D ring (Group B, n = 17), the semi-rigid Edwards Physio II ring (Group C, n = 7) and ten control subjects. Various annular diameters were measured throughout the cardiac cycle. We observed flexible anterior annulus motion in all of the groups except Group C. A flexible posterior annulus was only observed in Group B and the Control group. The mitral annular area changed during the cardiac cycle by 8.4 ± 3.2, 6.3 ± 2.0, 3.2 ± 1.3, and 11.6 ± 5.0 % in Group A, Group B, Group C, and the Control group, respectively. The dynamic diastolic to systolic change in mitral annular diameters was lost in Group C, while it was maintained in Group A, and to a good degree in Group B. In comparison to the Control group, the mitral annulus shape was more ellipsoid in Group B and Group C, and more circular in Group A. Although mitral regurgitation was well controlled by all of the types of rings that were utilized in the present study, we demonstrated that the annulus motion and annulus shape differed according to the type of prosthetic ring that was used, which might provide important information for the selection of an appropriate prosthetic ring.

Near--Infrared Imaging of the Starburst Ring in UGC12815

NASA Astrophysics Data System (ADS)

Smith, D. A.; Herter, T.; Haynes, M. P.; Neff, S. G.

1995-05-01

Starburst galaxies define an enigmatic class of objects undergoing a brief, intense episode of star formation. In order to investigate the nature of nearby starbursts, we have analyzed the 20 starburst galaxies with the highest 4.85 GHz luminosities from the survey of Condon, Frayer, & Broderick (1991, AJ, 101, 362) at infrared and optical wavelengths. As part of our study, we recently used the Cassegrain Infrared Camera at the Hale 5 m telescope to obtain high spatial resolution near--infrared images of the cores of 17 of these galaxies in order to better understand the starburst triggering mechanism. We find that one galaxy, UGC12815 (NGC7771), possesses a nucleus surrounded by a bright starburst ring. We present 1.25, 1.65, and 2.2 microns (J, H, and K band) images of the nuclear region of UGC12815 and a preliminary analysis of the properties of the starburst ring. The resolution of our K band image is 0.6('') FWHM. The ring is ~ 1.6 kpc (6('') ) in diameter assuming H_0=75 km/s/Mpc; several knots are detected in the ring at 2.2 microns. The spatial distribution of these knots is compared to that observed at 6 cm. The luminosities of the ring and nucleus, as mapped in the near--infrared and radio, are also discussed. Color maps (H-K and J-H) constructed from the near--infrared images trace the relative roles of extinction, and emission from evolved red stars, blue stars, thermal gas, and hot dust in the nucleus and starburst ring. A comparison between UGC12815 and other systems with circumnuclear starbursts is also made.

Minimally invasive versus open fusion for Grade I degenerative lumbar spondylolisthesis: analysis of the Quality Outcomes Database.

PubMed

Mummaneni, Praveen V; Bisson, Erica F; Kerezoudis, Panagiotis; Glassman, Steven; Foley, Kevin; Slotkin, Jonathan R; Potts, Eric; Shaffrey, Mark; Shaffrey, Christopher I; Coric, Domagoj; Knightly, John; Park, Paul; Fu, Kai-Ming; Devin, Clinton J; Chotai, Silky; Chan, Andrew K; Virk, Michael; Asher, Anthony L; Bydon, Mohamad

2017-08-01

OBJECTIVE Lumbar spondylolisthesis is a degenerative condition that can be surgically treated with either open or minimally invasive decompression and instrumented fusion. Minimally invasive surgery (MIS) approaches may shorten recovery, reduce blood loss, and minimize soft-tissue damage with resultant reduced postoperative pain and disability. METHODS The authors queried the national, multicenter Quality Outcomes Database (QOD) registry for patients undergoing posterior lumbar fusion between July 2014 and December 2015 for Grade I degenerative spondylolisthesis. The authors recorded baseline and 12-month patient-reported outcomes (PROs), including Oswestry Disability Index (ODI), EQ-5D, numeric rating scale (NRS)-back pain (NRS-BP), NRS-leg pain (NRS-LP), and satisfaction (North American Spine Society satisfaction questionnaire). Multivariable regression models were fitted for hospital length of stay (LOS), 12-month PROs, and 90-day return to work, after adjusting for an array of preoperative and surgical variables. RESULTS A total of 345 patients (open surgery, n = 254; MIS, n = 91) from 11 participating sites were identified in the QOD. The follow-up rate at 12 months was 84% (83.5% [open surgery]; 85% [MIS]). Overall, baseline patient demographics, comorbidities, and clinical characteristics were similarly distributed between the cohorts. Two hundred fifty seven patients underwent 1-level fusion (open surgery, n = 181; MIS, n = 76), and 88 patients underwent 2-level fusion (open surgery, n = 73; MIS, n = 15). Patients in both groups reported significant improvement in all primary outcomes (all p < 0.001). MIS was associated with a significantly lower mean intraoperative estimated blood loss and slightly longer operative times in both 1- and 2-level fusion subgroups. Although the LOS was shorter for MIS 1-level cases, this was not significantly different. No difference was detected with regard to the 12-month PROs between the 1-level MIS versus the 1-level open surgical groups. However, change in functional outcome scores for patients undergoing 2-level fusion was notably larger in the MIS cohort for ODI (-27 vs -16, p = 0.1), EQ-5D (0.27 vs 0.15, p = 0.08), and NRS-BP (-3.5 vs -2.7, p = 0.41); statistical significance was shown only for changes in NRS-LP scores (-4.9 vs -2.8, p = 0.02). On risk-adjusted analysis for 1-level fusion, open versus minimally invasive approach was not significant for 12-month PROs, LOS, and 90-day return to work. CONCLUSIONS Significant improvement was found in terms of all functional outcomes in patients undergoing open or MIS fusion for lumbar spondylolisthesis. No difference was detected between the 2 techniques for 1-level fusion in terms of patient-reported outcomes, LOS, and 90-day return to work. However, patients undergoing 2-level MIS fusion reported significantly better improvement in NRS-LP at 12 months than patients undergoing 2-level open surgery. Longer follow-up is needed to provide further insight into the comparative effectiveness of the 2 procedures.

Ab initio multiple spawning on laser-dressed states: a study of 1,3-cyclohexadiene photoisomerization via light-induced conical intersections

NASA Astrophysics Data System (ADS)

Kim, Jaehee; Tao, Hongli; Martinez, Todd J.; Bucksbaum, Phil

2015-08-01

We extend the ab initio multiple spawning method to include both field-free and field-induced nonadiabatic transitions. We apply this method to describe ultrafast pump-probe experiments of the photoinduced ring-opening of gas phase 1,3-cyclohexadiene. In the absence of a control field, nonadiabatic transitions mediated by a conical intersection (CoIn) lead to rapid ground state recovery with both 1,3-cyclohexadiene and ring-opened hexatriene products. However, application of a control field within the first 200 fs after photoexcitation results in suppression of the hexatriene product. We demonstrate that this is a consequence of population dumping prior to reaching the CoIn and further interpret this in terms of light-induced CoIns created by the control field.

Hydraulically actuated gas exchange valve assembly and engine using same

DOEpatents

Carroll, Thomas S.; Taylor, Gregory O.

2002-09-03

An engine comprises a housing that defines a hollow piston cavity that is separated from a gas passage by a valve seat. The housing further defines a biasing hydraulic cavity and a control hydraulic cavity. A gas valve member is also included in the engine and is movable relative to the valve seat between an open position at which the hollow piston cavity is open to the gas passage and a closed position in which the hollow piston cavity is blocked from the gas passage. The gas valve member includes a ring mounted on a valve piece and a retainer positioned between the ring and the valve piece. A closing hydraulic surface is included on the gas valve member and is exposed to liquid pressure in the biasing hydraulic cavity.

Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers

DOE PAGES

McGrath, Alaina J.; Shi, Weichao; Rodriguez, Christina G.; ...

2014-12-11

Here, we report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic ( R or S) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [ mm]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small anglemore » x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties.« less

Fusion of Renewable Ring Resonator Lasers and Ultrafast Laser Inscribed Photonic Waveguides

PubMed Central

Chandrahalim, Hengky; Rand, Stephen C.; Fan, Xudong

2016-01-01

We demonstrated the monolithic integration of reusable and wavelength reconfigurable ring resonator lasers and waveguides of arbitrary shapes to out-couple and guide laser emission on the same fused-silica chip. The ring resonator hosts were patterned by a single-mask standard lithography, whereas the waveguides were inscribed in the proximity of the ring resonator by using 3-dimensional femtosecond laser inscription technology. Reusability of the integrated ring resonator – waveguide system was examined by depositing, removing, and re-depositing dye-doped SU-8 solid polymer, SU-8 liquid polymer, and liquid solvent (toluene). The wavelength reconfigurability was validated by employing Rhodamine 6G (R6G) and 3,3′-Diethyloxacarbocyanine iodide (CY3) as exemplary gain media. In all above cases, the waveguide was able to couple out and guide the laser emission. This work opens a door to reconfigurable active and passive photonic devices for on-chip coherent light sources, optical signal processing, and the investigation of new optical phenomena. PMID:27600872

Fusion of Renewable Ring Resonator Lasers and Ultrafast Laser Inscribed Photonic Waveguides.

PubMed

Chandrahalim, Hengky; Rand, Stephen C; Fan, Xudong

2016-09-07

We demonstrated the monolithic integration of reusable and wavelength reconfigurable ring resonator lasers and waveguides of arbitrary shapes to out-couple and guide laser emission on the same fused-silica chip. The ring resonator hosts were patterned by a single-mask standard lithography, whereas the waveguides were inscribed in the proximity of the ring resonator by using 3-dimensional femtosecond laser inscription technology. Reusability of the integrated ring resonator - waveguide system was examined by depositing, removing, and re-depositing dye-doped SU-8 solid polymer, SU-8 liquid polymer, and liquid solvent (toluene). The wavelength reconfigurability was validated by employing Rhodamine 6G (R6G) and 3,3'-Diethyloxacarbocyanine iodide (CY3) as exemplary gain media. In all above cases, the waveguide was able to couple out and guide the laser emission. This work opens a door to reconfigurable active and passive photonic devices for on-chip coherent light sources, optical signal processing, and the investigation of new optical phenomena.

Imaging electron wave functions inside open quantum rings.

PubMed

Martins, F; Hackens, B; Pala, M G; Ouisse, T; Sellier, H; Wallart, X; Bollaert, S; Cappy, A; Chevrier, J; Bayot, V; Huant, S

2007-09-28

Combining scanning gate microscopy (SGM) experiments and simulations, we demonstrate low temperature imaging of the electron probability density |Psi|(2)(x,y) in embedded mesoscopic quantum rings. The tip-induced conductance modulations share the same temperature dependence as the Aharonov-Bohm effect, indicating that they originate from electron wave function interferences. Simulations of both |Psi|(2)(x,y) and SGM conductance maps reproduce the main experimental observations and link fringes in SGM images to |Psi|(2)(x,y).

The potential complications of open carpal tunnel release surgery to the ulnar neurovascular bundle and its branches: A cadaveric study.

PubMed

Boughton, O; Adds, P J; Jayasinghe, J A P

2010-07-01

This study investigated the ulnar artery and the ulnar nerve and its branches in the palm to assess how frequently they may be at risk of damage during open carpal tunnel release surgery. Twenty-one formalin-embalmed cadaveric hands were dissected, and the proximity of the ulnar neurovascular bundle to two different lines of incision, the 3rd and 4th interdigital web space axis and the ring finger axis, was assessed and compared. It was found that an incision in the latter (ring finger) axis put the ulnar artery at risk in 12 of 21 specimens, whereas an incision in the former axis (3rd/4th interdigital web space) put the ulnar artery at risk in only two specimens. In 15 hands at least one structure (the ulnar artery or a branch of the ulnar nerve) was at risk in the ring finger axis compared to only seven hands in the axis of the 3rd/4th interdigital web space. We conclude that the ulnar artery and branches of the ulnar nerve are at increased risk of damage with an incision in the axis of the ring finger. The importance of using a blunt dissection technique under direct vision during surgery to identify and preserve these structures and median nerve branches is emphasized. (c) 2010 Wiley-Liss, Inc.

Better object recognition and naming outcome with MRI-guided stereotactic laser amygdalohippocampotomy for temporal lobe epilepsy.

PubMed

Drane, Daniel L; Loring, David W; Voets, Natalie L; Price, Michele; Ojemann, Jeffrey G; Willie, Jon T; Saindane, Amit M; Phatak, Vaishali; Ivanisevic, Mirjana; Millis, Scott; Helmers, Sandra L; Miller, John W; Meador, Kimford J; Gross, Robert E

2015-01-01

Patients with temporal lobe epilepsy (TLE) experience significant deficits in category-related object recognition and naming following standard surgical approaches. These deficits may result from a decoupling of core processing modules (e.g., language, visual processing, and semantic memory), due to "collateral damage" to temporal regions outside the hippocampus following open surgical approaches. We predicted that stereotactic laser amygdalohippocampotomy (SLAH) would minimize such deficits because it preserves white matter pathways and neocortical regions that are critical for these cognitive processes. Tests of naming and recognition of common nouns (Boston Naming Test) and famous persons were compared with nonparametric analyses using exact tests between a group of 19 patients with medically intractable mesial TLE undergoing SLAH (10 dominant, 9 nondominant), and a comparable series of TLE patients undergoing standard surgical approaches (n=39) using a prospective, nonrandomized, nonblinded, parallel-group design. Performance declines were significantly greater for the patients with dominant TLE who were undergoing open resection versus SLAH for naming famous faces and common nouns (F=24.3, p<0.0001, η2=0.57, and F=11.2, p<0.001, η2=0.39, respectively), and for the patients with nondominant TLE undergoing open resection versus SLAH for recognizing famous faces (F=3.9, p<0.02, η2=0.19). When examined on an individual subject basis, no SLAH patients experienced any performance declines on these measures. In contrast, 32 of the 39 patients undergoing standard surgical approaches declined on one or more measures for both object types (p<0.001, Fisher's exact test). Twenty-one of 22 left (dominant) TLE patients declined on one or both naming tasks after open resection, while 11 of 17 right (nondominant) TLE patients declined on face recognition. Preliminary results suggest (1) naming and recognition functions can be spared in TLE patients undergoing SLAH, and (2) the hippocampus does not appear to be an essential component of neural networks underlying name retrieval or recognition of common objects or famous faces. Wiley Periodicals, Inc. © 2014 International League Against Epilepsy.

Ultrasound-guided transversus abdominis plane block in patients undergoing open inguinal hernia repair: 0.125% bupivacaine provides similar analgesic effect compared to 0.25% bupivacaine.

PubMed

Erdoğan Arı, Dilek; Yıldırım Ar, Arzu; Karadoğan, Firdevs; Özcabı, Yetkin; Koçoğlu, Ayşegül; Kılıç, Fatih; Akgün, Fatma Nur

2016-02-01

To evaluate the effectiveness of 0.125% bupivacaine compared to 0.25% bupivacaine for ultrasound-guided transversus abdominis plane (TAP) block in patients undergoing open inguinal hernia repair. Randomized, double-blind study. Educational and research hospital. Forty adult patients of American Society of Anesthesiologists physical status I-III undergoing elective primary unilateral open inguinal hernia repair under spinal anesthesia. Patients in group I received 20 mL of 0.25% bupivacaine, whereas patients in group II received 20 mL of 0.125% bupivacaine for TAP block at the end of the surgery. Pain intensity was assessed at rest and during coughing using 10-cm visual analog scale score at 5, 15, 30, and 45 minutes and 1, 2, 4, 6, 12, and 24 hours after TAP block. Morphine consumption and time to first morphine requirement were recorded. Visual analog scale scores at rest and during coughing were not significantly different between groups at all time points measured. Twenty-four hours of morphine consumption (7.72±7.33 mg in group I and 6.06±5.20 mg in group II; P=.437) and time to first morphine requirement (182.35±125.16 minutes in group I and 143.21±87.28 minutes in group II; P=.332) were not different between groups. 0.125% Bupivacaine provides similar analgesic effect compared to 0.25% bupivacaine for ultrasound-guided TAP block in patients undergoing open inguinal hernia repair. Copyright © 2016 Elsevier Inc. All rights reserved.

Cassini Radio Occultations of Saturn's Rings: Scattered Signal and Particle Sizes

NASA Astrophysics Data System (ADS)

Thomson, F.; Wong, K.; Marouf, E.; French, R.; Rappaport, N.; McGhee, C.; Anabtawi, A.; Asmar, S.; Barbinis, E.; Fleischman, D.; Goltz, G.; Johnston, D.; Rochblatt, D.

2005-08-01

Eight Cassini radio occultations of Saturn's rings were conducted from May 3 to September 5, 2005. During any given occultation, Cassini transmits Ka-, X-, and S-band sinusoidal signals (0.94, 3.6, and 13 cm-wavelength) through the rings. Spectral analysis of the perturbed signals received at stations of the Deep Space Network (DSN) reveals two distinct signal components. The first is the direct signal, a narrowband component representing the incident sinusoid emerging from the rings reduced in amplitude and changed in phase. The second is the scattered signal, a broadband component, representing near-forward scattering by ring particles. After reconstruction to remove diffraction effects, time history of the direct signal yields profiles of ring structure at resolution approaching ˜50 m. Of primary concern here is the broadband component. For the first time ever, clearly detectable scattered signals were observed at all three (Ka/X/S) bands. A single X/S radio occultation by Voyager 1 in 1980 detected scattered signal at X-band only, primarily because of the small ring opening angle B=5.9o at the time, compared with 19.1 ≤ B ≤ 23.6o for Cassini. Time histories of the observed spectra (spectrograms) and their dependence on wavelength provide important information about physical ring properties, including abundance of meter-size particles, particle crowding, clustering, spatial anisotropy, vertical ring profile and thickness. Cassini occultation orbits were optimized to map scattering by individual ring features into nearly non-overlapping spectral bands, allowing unambiguous identification of the contribution of ring features to the computed spectrograms. We present Ka/X/S spectrograms over the full extent of the ring system and relate their behavior to observed ring structure. The spectrograms imply presence of meters-size particles throughout the ring system. Preliminary results regarding the particle size distribution and vertical ring profile of selected ring features are presented. Contributions of personnel of the DSN are gratefully acknowledged.

A high-speed, tunable silicon photonic ring modulator integrated with ultra-efficient active wavelength control.

PubMed

Zheng, Xuezhe; Chang, Eric; Amberg, Philip; Shubin, Ivan; Lexau, Jon; Liu, Frankie; Thacker, Hiren; Djordjevic, Stevan S; Lin, Shiyun; Luo, Ying; Yao, Jin; Lee, Jin-Hyoung; Raj, Kannan; Ho, Ron; Cunningham, John E; Krishnamoorthy, Ashok V

2014-05-19

We report the first complete 10G silicon photonic ring modulator with integrated ultra-efficient CMOS driver and closed-loop wavelength control. A selective substrate removal technique was used to improve the ring tuning efficiency. Limited by the thermal tuner driver output power, a maximum open-loop tuning range of about 4.5nm was measured with about 14mW of total tuning power including the heater driver circuit power consumption. Stable wavelength locking was achieved with a low-power mixed-signal closed-loop wavelength controller. An active wavelength tracking range of > 500GHz was demonstrated with controller energy cost of only 20fJ/bit.

Two dynamin-like proteins stabilize FtsZ rings during Streptomyces sporulation.

PubMed

Schlimpert, Susan; Wasserstrom, Sebastian; Chandra, Govind; Bibb, Maureen J; Findlay, Kim C; Flärdh, Klas; Buttner, Mark J

2017-07-25

During sporulation, the filamentous bacteria Streptomyces undergo a massive cell division event in which the synthesis of ladders of sporulation septa convert multigenomic hyphae into chains of unigenomic spores. This process requires cytokinetic Z-rings formed by the bacterial tubulin homolog FtsZ, and the stabilization of the newly formed Z-rings is crucial for completion of septum synthesis. Here we show that two dynamin-like proteins, DynA and DynB, play critical roles in this process. Dynamins are a family of large, multidomain GTPases involved in key cellular processes in eukaryotes, including vesicle trafficking and organelle division. Many bacterial genomes encode dynamin-like proteins, but the biological function of these proteins has remained largely enigmatic. Using a cell biological approach, we show that the two Streptomyces dynamins specifically localize to sporulation septa in an FtsZ-dependent manner. Moreover, dynamin mutants have a cell division defect due to the decreased stability of sporulation-specific Z-rings, as demonstrated by kymographs derived from time-lapse images of FtsZ ladder formation. This defect causes the premature disassembly of individual Z-rings, leading to the frequent abortion of septum synthesis, which in turn results in the production of long spore-like compartments with multiple chromosomes. Two-hybrid analysis revealed that the dynamins are part of the cell division machinery and that they mediate their effects on Z-ring stability during developmentally controlled cell division via a network of protein-protein interactions involving DynA, DynB, FtsZ, SepF, SepF2, and the FtsZ-positioning protein SsgB.

A Distinct Phenotype of Eyes Shut Homolog (EYS)-Retinitis Pigmentosa Is Associated With Variants Near the C-Terminus.

PubMed

Sengillo, Jesse D; Lee, Winston; Nagasaki, Takayuki; Schuerch, Kaspar; Yannuzzi, Lawrence A; Freund, K Bailey; Sparrow, Janet R; Allikmets, Rando; Tsang, Stephen H

2018-06-01

Mutations in the eyes shut homolog (EYS) gene are a frequent cause of autosomal recessive retinitis pigmentosa (arRP). This study used multimodal retinal imaging to elucidate genotype-phenotype correlations in EYS-related RP (EYS-RP). Cross-sectional study. Multimodal retinal imaging and electrophysiologic testing were assessed for 16 patients with genetic confirmation of EYS-RP. A total of 27 unique EYS variants were identified in 16 patients. Seven patients presented with an unusual crescent-shaped hyperautofluorescent (hyperAF) ring on fundus autofluorescence (FAF) imaging encompassing a large nasal-superior area of the posterior pole. Three patients had a typical circular or oval perifoveal hyperAF ring and 6 patients had no hyperAF ring. Spectral-domain (SD) and en face optical coherence tomography (OCT) showed preserved ellipsoid zone and retinal thickness spatially corresponding to areas within the hyperAF rings. Eleven patients presented with a rod-cone dystrophy on full-field electroretinogram (ffERG), 1 patient presented with cone-rod dystrophy, and 4 patients did not undergo ffERG testing. A significant spatial association was found between EYS variant position and FAF phenotype, with variants occurring at a nucleotide position greater than GRCh37 6:65300137 (c.5617C) being more associated with patients exhibiting hyperAF rings at presentation. EYS-RP is a heterogeneous manifestation. Variants occurring in positions closer to the C-terminus of EYS are more common in patients presenting with hyperAF rings on FAF imaging. Copyright © 2018 Elsevier Inc. All rights reserved.

First experiences with methods to measure ammonia emissions from naturally ventilated cattle buildings in the U.K.

NASA Astrophysics Data System (ADS)

Demmers, T. G. M.; Burgess, L. R.; Short, J. L.; Phillips, V. R.; Clark, J. A.; Wathes, C. M.

A method has been developed to measure the emission rate of ammonia from naturally ventilated U.K. livestock buildings. The method is based on measurements of ammonia concentration and estimates of the ventilation rate of the building by continuous release of carbon monoxide tracer within the building. The tracer concentration is measured at nine positions in openings around the perimeter of the building, as well as around a ring sampling line. Two criteria were evaluated to decide whether, at any given time, a given opening in the building acted as an air inlet or as an air outlet. Carbon monoxide concentration difference across an opening was found to be a better criterion than the temperature difference across the opening. Ammonia concentrations were measured continuously at the sampling points using a chemiluminescence analyser. The method was applied to a straw-bedded beef unit and to a slurry-based dairy unit. Both buildings were of space-boarded construction. Ventilation rates estimated by the ring line sample were consistently higher than by the perimeter samples. During calm weather, the ventilation estimates by both samples were similar (10-20 air changes h -1). However, during windy conditions (>5 m s -1) the ventilation rate was overestimated by the ring line sample (average 100 air changes h -1) compared to the perimeter samples (average 50 air changes h -1). The difference was caused by incomplete mixing of the tracer within the building. The ventilation rate estimated from the perimeter samples was used for the calculation of the emission rate. Preliminary estimates of the ammonia emission factor were 6.0 kg NH 3 (500 kg live-weight) -1 (190 d) -1 for the slurry-based dairy unit and 3.7 for the straw-bedded beef unit.

Photometric and spectroscopic evidence for a dense ring system around Centaur Chariklo

NASA Astrophysics Data System (ADS)

Duffard, R.; Pinilla-Alonso, N.; Ortiz, J. L.; Alvarez-Candal, A.; Sicardy, B.; Santos-Sanz, P.; Morales, N.; Colazo, C.; Fernández-Valenzuela, E.; Braga-Ribas, F.

2014-08-01

Context. A stellar occultation observed on 3rd June 2013 revealed the presence of two dense and narrow rings separated by a small gap around the Centaur object (10 199) Chariklo. The composition of these rings is not known. We suspect that water ice is present in the rings, as is the case for Saturn and other rings around the giant planets. Aims: In this work, we aim to determine if the variability in the absolute magnitude of Chariklo and the temporal variation of the spectral ice feature, even when it disappeared in 2007, can be explained by an icy ring system whose aspect angle changes with time. Methods: We explained the variations on the absolute magnitude of Chariklo and its ring by modeling the light reflected by a system as the one described above. Using X-shooter at VLT, we obtained a new reflectance spectra. We compared this new set of data with the ones available in the literature. We showed how the water ice feature is visible in 2013 in accordance with the ring configuration, which had an opening angle of nearly 34° in 2013. Finally, we also used models of light scattering to fit the visible and near-infrared spectra that shows different characteristics to obtain information on the composition of Chariklo and its rings. Results: We showed that absolute photometry of Chariklo from the literature and new photometric data that we obtained in 2013 can be explained by a ring of particles whose opening angle changes as a function of time. We used the two possible pole solutions for the ring system and found that only one of them, α = 151.30 ± 0.5, δ = 41.48 ± 0.2° (λ = 137.9 ± 0.5, β = 27.7 ± 0.2°), provides the right variation of the aspect angle with time to explain the photometry, whereas the other possible pole solution fails to explain the photometry. From spectral modeling, we derived the composition of the Chariklo surface and that of the rings using the result on the pole solution. Chariklo surface is composed with about 60% of amorphous carbon, 30% of silicates and 10% of organics; no water ice was found on the surface. The ring, on the other hand, contains 20% of water ice, 40-70% of silicates, and 10-30% of tholins and small quantities of amorphous carbon. Partially based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile. DDT 291.C-5035(A). Based on observations carried out at the Complejo Astronómico El Leoncito, which is operated under agreement between the Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina and the National Universities of La Plata, Córdoba, and San Juan.

Total Gastrectomy for Hereditary Diffuse Gastric Cancer at a Single Center: Postsurgical Outcomes in 41 Patients.

PubMed

Strong, Vivian E; Gholami, Sepideh; Shah, Manish A; Tang, Laura H; Janjigian, Yelena Y; Schattner, Mark; Selby, Luke V; Yoon, Sam S; Salo-Mullen, Erin; Stadler, Zsofia K; Kelsen, David; Brennan, Murray F; Coit, Daniel G

2017-12-01

The aim of this study was to describe postoperative outcomes of total gastrectomy at our institution for patients with hereditary diffuse gastric cancer (HDGC). HDGC, which is mainly caused by germline mutations in the E-cadherin gene (CDH1), renders a lifetime risk of gastric cancer of up to 70%, prompting a recommendation for prophylactic total gastrectomy. A prospective gastric cancer database identified 41 patients with CDH1 mutation who underwent total gastrectomy during 2005 to 2015. Perioperative, histopathologic, and long-term data were collected. Of the 41 patients undergoing total gastrectomy, median age was 47 years (range 20 to 71). There were 14 men and 27 women, with 25 open operations and 16 minimally invasive operations. Median length of stay was 7 days (range 4 to 50). In total, 11 patients (27%) experienced a complication requiring intervention, and there was 1 peri-operative mortality (2.5%). Thirty-five patients (85%) demonstrated 1 or more foci of intramucosal signet ring cell gastric cancer in the examined specimen. At 16 months median follow-up, the median weight loss was 4.7 kg (15% of preoperative weight). By 6 to 12 months postoperatively, weight patterns stabilized. Overall outcome was reported to be "as expected" by 40% of patients and "better than expected" by 45%. Patient-reported outcomes were similar to those of other patients undergoing total gastrectomy. Total gastrectomy should be considered for all CDH1 mutation carriers because of the high risk of invasive diffuse-type gastric cancer and lack of reliable surveillance options. Although most patients have durable weight loss after total gastrectomy, weights stabilize at about 6 to 12 months postoperatively, and patients report outcomes as being good to better than their preoperative expectations. No patients have developed gastric cancer recurrence after resections.

Export of Terrestrially-Derived Organic Matter from the Mississippi River to the Gulf of Mexico Sediments as Determined by Ultrahigh Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Hatcher, P.; Ware, S. A.; Vaughn, D.; Waggoner, D. C.; Bianchi, T. S.

2017-12-01

Sediment samples extending from the main channel of the Mississippi River to edge of the continental shelf of the Gulf of Mexico were extracted to recover humic acids from the organic matter and subjected to molecular level characterization by electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The data show that sedimentary organic matter at the river mouth contains humic substances with a predominantly terrestrial signature resembling those obtained from soils. Condensed aromatic molecules and carboxyl rich alicyclic molecules (CRAM) typify the major structures observed. The CRAM-like molecules persist progressing seaward into the Gulf while the condensed aromatic molecules diminish in relative abundance. This trend is characteristic of traditional mixing of allochthonous terrestrial with autochthonous source materials, consistent with published isotope and lignin phenol biomarker data. Alternatively, the trend could also be explained by oxidative degradation of mainly terrestrial organic matter whereby the condensed aromatic molecules would be selectively oxidized. CRAM molecules would then become selectively enriched as one progresses from the channel to the continental shelf. Laboratory studies show that aromatic molecules (like those in lignin) subjected to oxidative degradation mainly by hydroxyl radical attack, either biologically or non-biologically, undergo molecular rearrangement via ring-opening to form reactive species. These can interact with nucleophilic molecules such as peptides and sulfur-containing species and/or can undergo cycloaddition reactions to produce CRAM-like species. This latter explanation suggests that the main source of organic matter in this coastal depocenter is terrestrial and that autochthonous organic matter contributes little to sedimentary organic matter.

Synthesis of diazatricyclic core of Madangamines from cis-perhydroisoquinolines.

PubMed

Quirante, Josefina; Paloma, Laura; Diaba, Faïza; Vila, Xavier; Bonjoch, Josep

2008-01-18

Synthesis of the tricyclic core of madangamine alkaloids has been achieved in a 10-step sequence starting from a 4-(aminomethyl)anisole derivative. A Birch reduction and acylation with cyanoacetic acid followed by an intramolecular Michael process renders a polyfunctionalized cis-perhydroisoquinoline. A diastereoselective allylation and reduction of amide, nitrile, and ketone groups leads to a bicyclic alcohol, which undergoes aminocyclization through the nosyl derivative to the diazatricyclic ring.

The Ketene-Surrogate Coupling: Catalytic Conversion of Aryl Iodides to Aryl Ketenes via Ynol Ethers**

PubMed Central

Zhang, Wenhan; Ready, Joseph M.

2014-01-01

tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergoelectrocyclic ring closure to yield hydroxynaphthalenes and quinolines. PMID:24975840

Catalytic and mechanical cycles in F-ATP synthases. Fourth in the Cycles Review Series.

PubMed

Dimroth, Peter; von Ballmoos, Christoph; Meier, Thomas

2006-03-01

Cycles have a profound role in cellular life at all levels of organization. Well-known cycles in cell metabolism include the tricarboxylic acid and the urea cycle, in which a specific carrier substrate undergoes a sequence of chemical transformations and is regenerated at the end. Other examples include the interconversions of cofactors, such as NADH or ATP, which are present in the cell in limiting amounts and have to be recycled effectively for metabolism to continue. Every living cell performs a rapid turnover of ATP to ADP to fulfil various energetic demands and effectively regenerates the ATP from ADP in an energy-consuming process. The turnover of the ATP cycle is impressive; a human uses about its body weight in ATP per day. Enzymes perform catalytic reaction cycles in which they undergo several chemical and physical transformations before they are converted back to their original states. The ubiquitous F1F(o) ATP synthase is of particular interest not only because of its biological importance, but also owing to its unique rotational mechanism. Here, we give an overview of the membrane-embedded F(o) sector, particularly with respect to the recent crystal structure of the c ring from Ilyobacter tartaricus, and summarize current hypotheses for the mechanism by which rotation of the c ring is generated.

Piston-Skirt Lubrication System For Compressor

NASA Technical Reports Server (NTRS)

Schroeder, Edgar C.; Burzynski, Marion, Jr.

1994-01-01

Piston-skirt lubrication system provides steady supply of oil to piston rings of gas compressor. No need for oil-filled crankcase or external oil pump. Instead, part of each piston acts as its own oil pump circulating oil from reservoir. Annular space at bottom of piston and cylinder constitutes working volume of small oil pump. Depending on application, reservoir open to atmosphere, or sealed and pressurized in bellows to prevent contact between oil and atmosphere. Filter removes particles worn away from piston rings and cylinder wall during normal operation.

Chemical treatment for silica-containing glass surfaces

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1999-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Chemical treatment for silica-containing glass surfaces

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1998-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditions. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Chemical treatment for silica-containing glass surfaces

DOEpatents

Grabbe, Alexis; Michalske, Terry Arthur; Smith, William Larry

1999-01-01

Dehydroxylated, silica-containing, glass surfaces are known to be at least partially terminated by strained siloxane rings. According to the invention, a surface of this kind is exposed to a selected silane compound or mixture of silane compounds under reaction-promoting conditons. The ensuing reaction results in opening of the strained siloxane rings, and termination of surface atoms by chemical species, such as organic or organosilicon species, having desirable properties. These species can be chosen to provide qualities such as hydrophobicity, or improved coupling to a polymeric coating.

Cation induced electrochromism in 2,4-dinitrophenylhydrazine (DNPH): Tuning optical properties of aromatic rings

NASA Astrophysics Data System (ADS)

Sanader, Željka; Brunet, Claire; Broyer, Michel; Antoine, Rodolphe; Dugourd, Philippe; Mitrić, Roland; Bonačić-Koutecký, Vlasta

2013-05-01

We have theoretically investigated the influence of protons and noble metal cations on optical properties of 2,4-dinitrophenylhydrazine (DNPH). We show that optical properties of aromatic rings can be tuned by cation-induced electrochromism in DNPH due to binding to specific NO2 groups. Our findings on cation-induced electrochromism in DNPH may open new routes in two different application areas, due to the fact that DNPH can easily bind to biological molecules and surface materials through carbonyl groups.

Simple assembly of polysubstituted pyrazoles and isoxazoles via ring closure-ring opening domino reaction of 3-acyl-4,5-dihydrofurans with hydrazines and hydroxylamine.

PubMed

Chagarovskiy, Alexey O; Budynina, Ekaterina M; Ivanova, Olga A; Rybakov, Victor B; Trushkov, Igor V; Melnikov, Mikhail Ya

2016-03-14

A convenient general approach to 2-(pyrazol-4-yl)- and 2-(isoxazol-4-yl)ethanols based on the Brønsted acid-initiated reaction of 3-acyl-4,5-dihydrofurans with hydrazines or hydroxylamine was developed. Further transformation of the alcohol moiety in 2-(pyrazolyl)ethanols affording 2-(pyrazolyl)ethylamine as potent bioactive compounds as well as pyrazole-substituted derivatives of antitumor alkaloid crispine A was elaborated.

An x-ray diffraction study of some mesoionic 2,3-diphenyltetrazoles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luboradzki, R.; Kozminski, W.; Stefaniak, L.

1993-02-01

An X-my diffraction study is reported for four molecules of mesoionic 2,3-diphenyltetrazoles. The results confirm a dipolar [open quotes]mesoionic[close quotes] structure, aromatic character of the tetrazole ring and no conjugation between the phenyl and tetrazole rings. The geometry of the exocyclic group is discussed in detail. The molecular parameters of the compounds investigated are correlated with [sup 13]C and [sup 15]N nmr data. The results obtained are compared with similar structures which have already been studied.

3β,5α,6β-Trihy­droxy­androstan-17-one

PubMed Central

Andrade, L.C.R.; de Almeida, M.J.B.M.; Paixão, J.A.; Carvalho, J.F.S.; Sá e Melo, M.L.

2011-01-01

The title compound, C19H30O4, is an androstan-17-one derivative synthesized from the dehydro­epiandrosterone through a sequential addition of an oxidant, followed by a trans-diaxial opening of the epoxide generated, with Bi(OTf)3 (OTf is trifluoro­methane­sulfonate). The six-membered rings have a slightly flattened chair conformation, while the five-membered ring adopts a 14-α envelope conformation. All rings are trans fused. In the crystal, the mol­ecules are connected by O—H⋯O hydrogen bonds involving the hydroxyl and carbonyl groups, forming a three-dimensional network. A quantum mechanical ab initio Roothan Hartree–Fock calculation of the free mol­ecule gives bond lengths, valency angles and ring torsion angles of the free molecule at equilibrium geometry (energy minimum) close to the experimental values. PMID:21754383

Outcomes and Resource Utilization of Endoscopic Mass-Closure Technique for Laryngeal Clefts.

PubMed

Balakrishnan, Karthik; Cheng, Esther; de Alarcon, Alessandro; Sidell, Douglas R; Hart, Catherine K; Rutter, Michael J

2015-07-01

To compare resource utilization and clinical outcomes between endoscopic mass-closure and open techniques for laryngeal cleft repair. Case series with chart review. Tertiary academic children's hospital. Pediatric patients undergoing repair for Benjamin-Inglis type 1-3 laryngeal clefts over a 15-year period. All 20 patients undergoing endoscopic repair were included. Eight control patients undergoing open repair were selected using matching by age and cleft type. Demographic, clinical, and resource utilization data were collected. Twenty-eight patients were included (20 endoscopic, 8 open). Mean age, rates of tracheostomy and vocal fold immobility, and distribution of cleft types were not different between the 2 groups (all P > .2). Mean operative time (P = .004) and duration of hospital stay (P < .001) were significantly shorter in the endoscopic group. All repairs were intact in both groups at final postoperative endoscopy. Rates of persistent laryngeal penetration or aspiration on swallow study were not different between groups (P = 1.000), although results were available for only 11 patients. Endoscopic laryngeal cleft repair using a mass-closure technique provides a durable result while requiring significantly shorter operative times and hospital stays than open repair and avoiding the potential morbidity of laryngofissure. However, open repair may allow the simultaneous performance of other airway reconstructive procedures and may be a useful salvage technique when endoscopic repair fails. Postoperative swallowing results require further study. © American Academy of Otolaryngology—Head and Neck Surgery Foundation 2015.

A comparison of trends in operative approach and postoperative outcomes for colorectal cancer surgery.

PubMed

Addae, Jamin K; Gani, Faiz; Fang, Sandy Y; Wick, Elizabeth C; Althumairi, Azah A; Efron, Jonathan E; Canner, Joseph K; Euhus, David M; Schneider, Eric B

2017-02-01

Data-assessing trends and perioperative outcomes relative to surgical approach for colorectal cancer (CRC) surgery are lacking. We report national trends of CRC surgery and compare postoperative outcomes by surgical approach. A total of 261,886 patients undergoing surgery for CRC were identified using the Nationwide Inpatient Sample from 2009 to 2012. Trends in surgical approach were assessed using the Cochrane-Armitage test of trends. Multivariable logistic and linear regression analyses were performed to compare length of stay (LOS), postoperative complications, and cost by surgical approach. At the time of surgery, 57.5% underwent an open procedure, whereas 42.4% underwent either a laparoscopic (39.9%) or robotic (2.5%) colorectal surgery. The use of minimally invasive surgery increased over time (2009 versus 2012: 37.3% versus 46.8%; P < 0.001). Postoperative morbidity was 15.9% and was higher after open surgery (open versus laparoscopic versus robotic: 18.4% versus 12.4% versus 13.3%; P < 0.001). Patients who underwent a minimally invasive surgery had shorter LOS (laparoscopic: OR, 0.55, 95% CI, 0.52-0.58; robotic: OR, 0.58; 95% CI, 0.49-0.69; both P < 0.001). Robotic surgery was consistently associated with the highest mean costs followed by laparoscopic and open surgery (P < 0.001). Patients undergoing minimally invasive colorectal surgery had a lower postoperative morbidity and shorter LOS compared with patients undergoing open colorectal surgery. Copyright © 2016 Elsevier Inc. All rights reserved.

Compact structure and non-Gaussian dynamics of ring polymer melts.

PubMed

Brás, Ana R; Goossen, Sebastian; Krutyeva, Margarita; Radulescu, Aurel; Farago, Bela; Allgaier, Jürgen; Pyckhout-Hintzen, Wim; Wischnewski, Andreas; Richter, Dieter

2014-05-28

We present a neutron scattering analysis of the structure and dynamics of PEO polymer rings with a molecular weight 2.5 times higher than the entanglement mass. The melt structure was found to be more compact than a Gaussian model would suggest. With increasing time the center of mass (c.o.m.) diffusion undergoes a transition from sub-diffusive to diffusive behavior. The transition time agrees well with the decorrelation time predicted by a mode coupling approach. As a novel feature well pronounced non-Gaussian behavior of the c.o.m. diffusion was found that shows surprising analogies to the cage effect known from glassy systems. Finally, the longest wavelength Rouse modes are suppressed possibly as a consequence of an onset of lattice animal features as hypothesized in theoretical approaches.

Theoretical investigation on the chemoselective N-heterocyclic carbene-catalyzed cross-benzoin reactions.

PubMed

Liu, Tao; Han, Shu-Min; Han, Ling-Li; Wang, Lu; Cui, Xiang-Yang; Du, Chong-Yang; Bi, Siwei

2015-03-28

A density functional theory study was performed to understand the detailed mechanisms of the cross-benzoin reactions catalyzed by N-heterocyclic carbene (NHC) species. Our theoretical study predicted that the first H-transfer operates with water in solution as a mediator, and the second H-transfer undergoes a concerted mechanism rather than a stepwise one. In addition, the chemoselectivity of the reactions studied in this work has been explored. P1 was obtained as a major product mainly due to the more stable intermediate formed by reaction of NHC with reactant R1. Different steric effects resulting from the fused six-membered ring in transition state TS7 and the fused five-membered ring in transition state TS13 are the origin leading to the chemoselectivity.

Stellar Occultations by Saturn's Rings

NASA Astrophysics Data System (ADS)

Nicholson, Philip; Hedman, Matthew; French, Richard G.; Ansty, Todd

2018-04-01

On 15 September 2017 the Cassini mission came to an end when the spacecraft made a controlled entry into the planet's atmosphere. Over the preceding 13 years the Visual and Infrared Mapping Spectrometer (VIMS) instrument successfully observed over 170 stellar occultations by Saturn's rings, greatly increasing the available data set for high-resolution studies of the rings' structure and dynamics. Ring opening angles, B_\\ast ranged from 1.06° to 74.18°, while spacecraft ranges varied from 220,000 to 3,014,000 km. The effective radial resolution of the data is determined by a combination of Fresnel diffraction, stellar diameter and sampling rate, but is typically 150-300~m. We will briefly review the overall data set, before looking at examples of dynamical studies carried out with it over the past decade. These include modeling the geometry of self-gravity wakes in the A and B rings, evidence for viscous over-stability in the inner A ring, studies of eccentric, inclined and more complex orbital perturbations on the edges of isolated ringlets and narrow gaps, identification of density and bending waves in the C ring driven by both internal oscillations and gravity anomalies in Saturn, and the first reliable estimates of surface mass density in the central B ring.{\\bf References:} French \\etal\\ (2016a, 2016b, 2017), Hedman \\etal\\ (2007, 2010, 2014), Hedman \\& Nicholson (2013, 2014, 2016), Nicholson \\& Hedman (2010, 2016), Nicholson \\etal\\ (2014a, 2014b).

Rings of membrane sterols surround the openings of vesicles and fenestrae, in capillary endothelium.

PubMed

Simionescu, N; Lupu, F; Simionescu, M

1983-11-01

We investigated the distribution of sterols in the cell membrane of microvascular endothelium (mouse pancreas, diaphragm, brain, heart, lung, kidney, thyroid, adrenal, and liver) with the polyene antibiotic filipin, which reportedly has binding specificity for free 3-beta-hydroxysterols. In some experiments, concomitantly, cell-surface anionic sites were detected with cationized ferritin. Vessels were perfused in situ with PBS, followed by light fixation and filipin administration for 10 to 60 min. Tissues were further processed for thin-section and freeze-fracture electron microscopy. Short exposure (10 min) to filipin-glutaraldehyde solution resulted in the initial appearance, on many areas, of rings of characteristic filipin-sterol complexes within the rim surrounding stomata of most plasmalemmal vesicles, transendothelial channels, and fenestrae. Such rings were absent from the rims of the large openings of the sinusoid endothelium (liver, adrenal), coated pits and phagocytic vacuoles. After longer exposure (30-60 min), filipin-sterol complexes labeled randomly the rest of plasma membrane (except for coated pits, and partially the interstrand areas of junctions), and also marked most plasmalemmal vesicles. These peristomal rings of sterols were displayed mostly on the P face, and, at their full development, consisted of 6-8 units around a vesicle stoma, and 10-12 units around a fenestra. At their level, the intramembranous particles and the cell surface anionic sites were virtually excluded. Peristomal rings of sterols were also detected on the plasma membrane of pericytes and smooth muscle cells of the microvascular wall, which otherwise were poorly labeled with filipin-sterol complexes as compared to endothelial plasmalemma. It is presumed that the peristomal rings of cholesterol may represent important contributors to the local transient stabilization of plasma membrane and to the phase separation between cell membrane and vesicle membrane at a certain stage of their fusion/fission process.

PREFACE: Special section on vortex rings Special section on vortex rings

NASA Astrophysics Data System (ADS)

Fukumoto, Yasuhide

2009-10-01

This special section of Fluid Dynamics Research includes five articles on vortex rings in both classical and quantum fluids. The leading scientists of the field describe the trends in and the state-of-the-art development of experiments, theories and numerical simulations of vortex rings. The year 2008 was the 150th anniversary of 'vortex motion' since Hermann von Helmholtz opened up this field. In 1858, Helmholtz published a paper in Crelle's Journal which put forward the concept of 'vorticity' and made the first analysis of vortex motion. Fluid mechanics before that was limited to irrotational motion. In the absence of vorticity, the motion of an incompressible homogeneous fluid is virtually equivalent to a rigid-body motion in the sense that the fluid motion is determined once the boundary configuration is specified. Helmholtz proved, among other things, that, without viscosity, a vortex line is frozen into the fluid. This Helmholtz's law immediately implies the preservation of knots and links of vortex lines and its implication is enormous. One of the major trends of fluid mechanics since the latter half of the 20th century is to clarify the topological meaning of Helmholtz's law and to exploit it to develop theoretical and numerical methods to find the solutions of the Euler equations and to develop experimental techniques to gain an insight into fluid motion. Vortex rings are prominent coherent structures in a variety of fluid motions from the microscopic scale, through human and mesoscale to astrophysical scales, and have attracted people's interest. The late professor Philip G Saffman (1981) emphasized the significance of studies on vortex rings. One particular motion exemplifies the whole range of problems of vortex motion and is also a commonly known phenomenon, namely the vortex ring or smoke ring. Vortex rings are easily produced by dropping drops of one liquid into another, or by puffing fluid out of a hole, or by exhaling smoke if one has the skill. Their formation is a problem of vortex sheet dynamics, the steady state is a problem of existence, their duration is a problem of stability, and if there are several we have the problem of vortex interactions. Helmholtz himself, in the same paper (1858), devoted a few pages to an analysis of the motion of a vortex ring, and made substantial contributions. Since then, theoretical, experimental and numerical treatments of vortex rings have been developing continuously, yet we encounter mysteries and novel phenomena, with which vortex rings find new applications in, say, bio-fluid mechanics. Recently vortex rings have enlarged their scope beyond classical fluids to encompass super-fluids and Bose-Einstein condensates. On the occasion of the 150th anniversary of Helmholtz's theory on a vortex ring, it is worthwhile to bring together, in one issue, the latest understandings of and open problems in vortex rings from various aspects. The topics in this issue include development of theories and experiments for motion of vortex rings and their interaction with other vortex rings, flows and boundaries, with application to vortex-ring manipulation for flow control, original experiments on collision of vortex rings with a porous boundary, a novel numerical technique to simulate three-dimensional motion of vortex rings and new theories of dynamics of quantum vortex rings governed by nonlinear Schrödinger equations. I hope that this special section gives a sketch, in some proportion, of the current frontier of the field and provides a means to tackle future problems. References Saffman P G 1981 Dynamics of vorticity J. Fluid Mech. 106 49-58 von Helmholtz H 1858 Über Integrale der hydrodynamischen Gleichungen welche den Wirbelbewegungen entsprechen J. Reine Angew. Math. 55 25-55 (Engl. transl.: Tait P G 1867 On the integrals of the hydrodynamical equations which express vortex-motion Phil. Mag. 33 (4) 485-512)

Heating and cooling of the neutral ISM in the NGC 4736 circumnuclear ring

NASA Astrophysics Data System (ADS)

van der Laan, T. P. R.; Armus, L.; Beirao, P.; Sandstrom, K.; Groves, B.; Schinnerer, E.; Draine, B. T.; Smith, J. D.; Galametz, M.; Wolfire, M.; Croxall, K.; Dale, D.; Herrera Camus, R.; Calzetti, D.; Kennicutt, R. C.

2015-03-01

The manner in which gas accretes and orbits within circumnuclear rings has direct implications for the star formation process. In particular, gas may be compressed and shocked at the inflow points, resulting in bursts of star formation at these locations. Afterwards the gas and young stars move together through the ring. In addition, star formation may occur throughout the ring, if and when the gas reaches sufficient density to collapse under gravity. These two scenarios for star formation in rings are often referred to as the "pearls-on-a-string" and "popcorn" paradigms. In this paper, we use new Herschel/PACS observations, obtained as part of the KINGFISH open time key program, along with archival Spitzer and ground-based observations from the SINGS Legacy project, to investigate the heating and cooling of the interstellar medium in the nearby star-forming ring galaxy, NGC 4736. By comparing spatially resolved estimates of the stellar far-ultraviolet flux available for heating, with the gas and dust cooling derived from the far-infrared continuum and line emission, we show that while star formation is indeed dominant at the inflow points in NGC 4736, additional star formation is needed to balance the gas heating and cooling throughout the ring. This additional component most likely arises from the general increase in gas density in the ring over its lifetime. Our data provide strong evidence, therefore, for a combination of the two paradigms for star formation in the ring in NGC 4736.

Grooves and Kinks in the Rings

NASA Image and Video Library

2017-06-19

Many of the features seen in Saturn's rings are shaped by the planet's moons. This view from NASA's Cassini spacecraft shows two different effects of moons that cause waves in the A ring and kinks in a faint ringlet. The view captures the outer edge of the 200-mile-wide (320-kilometer-wide) Encke Gap, in the outer portion of Saturn's A ring. This is the same region features the large propeller called Earhart. Also visible here is one of several kinked and clumpy ringlets found within the gap. Kinks and clumps in the Encke ringlet move about, and even appear and disappear, in part due to the gravitational effects of Pan -- which orbits in the gap and whose gravitational influence holds it open. The A ring, which takes up most of the image on the left side, displays wave features caused by Pan, as well as the moons Pandora and Prometheus, which orbit a bit farther from Saturn on both sides of the planet's F ring. This view was taken in visible light with the Cassini spacecraft narrow-angle camera on March 22, 2017, and looks toward the sunlit side of the rings from about 22 degrees above the ring plane. The view was acquired at a distance of approximately 63,000 miles (101,000 kilometers) from Saturn and at a phase angle (the angle between the sun, the rings and the spacecraft) of 59 degrees. Image scale is 1,979 feet (603 meters) per pixel. https://photojournal.jpl.nasa.gov/catalog/PIA21333

Enhanced organic memory devices (OMEM) with a photochromic perhydro DTE as a transduction layer (Conference Presentation)

NASA Astrophysics Data System (ADS)

Cordes, Sandra; Kranz, Darius; Maibach, Eduard; Kempf, Maxim; Meerholz, Klaus

2016-09-01

In modern electronic systems memory elements are of fundamental importance for data storage. Especially solution-processable nonvolatile organic memories, which are inexpensive and can be manufactured on flexible substrates, are a promising alternative to brittle inorganic devices. Organic photochromic switchable compounds, mostly dithienylethenes (DTEs), are thermally stable, fatigue resistant and can undergo an electrically- or/and photo-induced ring-opening and -closing reaction which results in a change of energy levels. Due to the energetic difference in the highest occupied molecular orbital (HOMO) between the open and closed isomer, the DTE layer can be exploited as a switchable hole injection barrier that controls the electrical current in the diode. We demonstrated that a light-emitting organic memory (LE-OMEM) device with a perfluoro DTE transduction layer can be switched electrically via high current densities pulses and optically by irradiated light, with impressive current ON/OFF Ratios (OOR) of 10Λ2, 10Λ4 respectively. Currently we aim to minimize the barrier of the ON state and maximize the barrier of the OFF state by designing DTE molecules with larger differences in the HOMO energies of the two isomers yielding improved OOR values. By synthesizing perhydro derivates of DTE we achieved molecules with high HOMO levels and large ΔHOMO energies providing OMEM devices with excellent physical properties (OOR 1.4 x higher than perfluoro DTE). Due to the high HOMO level of the perhydro DTE utilization of hole transport layers (HTLs) is not necessary and thus manufacturing of OMEM devices is simplified.

Versatile Tandem Ring-Opening/Ring-Closing Metathesis Polymerization: Strategies for Successful Polymerization of Challenging Monomers and Their Mechanistic Studies.

PubMed

Park, Hyeon; Kang, Eun-Hye; Müller, Laura; Choi, Tae-Lim

2016-02-24

Tandem ring-opening/ring-closing metathesis (RO/RCM) results in extremely fast living polymerization; however, according to previous reports, only monomers containing certain combinations of cycloalkenes, terminal alkynes, and nitrogen linkers successfully underwent tandem polymerization. After examining the polymerization pathways, we proposed that the relatively slow intramolecular cyclization might lead to competing side reactions such as intermolecular cross metathesis reactions to form inactive propagating species. Thus, we developed two strategies to enhance tandem polymerization efficiency. First, we modified monomer structures to accelerate tandem RO/RCM cyclization by enhancing the Thorpe-Ingold effect. This strategy increased the polymerization rate and suppressed the chain transfer reaction to achieve controlled polymerization, even for challenging syntheses of dendronized polymers. Alternatively, reducing the reaction concentration facilitated tandem polymerization, suggesting that the slow tandem RO/RCM cyclization step was the main reason for the previous failure. To broaden the monomer scope, we used monomers containing internal alkynes and observed that two different polymer units with different ring sizes were produced as a result of nonselective α-addition and β-addition on the internal alkynes. Thorough experiments with various monomers with internal alkynes suggested that steric and electronic effects of the alkyne substituents influenced alkyne addition selectivity and the polymerization reactivity. Further polymerization kinetics studies revealed that the rate-determining step of monomers containing certain internal alkynes was the six-membered cyclization step via β-addition, whereas that for other monomers was the conventional intermolecular propagation step, as observed in other chain-growth polymerizations. This conclusion agrees well with all those polymerization results and thus validates our strategies.

Results from a survey of the dynamics shaping Uranus' Mab/μ-ring system

NASA Astrophysics Data System (ADS)

Kumar, Kartik; de Pater, Imke; Showalter, Mark R.

2014-11-01

Based on Hubble Space Telescope (HST) data, Showalter and Lissauer (2006) reported the discovery of two faint rings beyond Uranus’ main rings: the ν- and μ- rings. They constitute Uranus' outer ring system and are located beyond the ɛ-ring but interior to the large classical moons. After co-adding a series of HST images, Showalter and Lissauer (2006) obtained radial profiles for both new rings. They discovered that the peak radial intensity of the μ-ring aligns closely with the orbit of Mab. Along with numerous other observations, this points to the fact that the Mab/μ-ring system is highly coupled.The discovery of the μ-ring has led to open questions about dust dynamics beyond Uranus' main rings. Like Saturn's E-ring, observations reveal that the μ-ring is blue, indicative of a pre-dominance of sub-micron-sized particles (de Pater et al., 2006). The E-ring results from plumes on Enceladus' south pole, however the origin of the μ-ring remains a mystery. The latter is likely fed by ejecta from micro-meteorite impacts with Mab, much like Jupiter's faint rings are regenerated by companion (small) moons (Burns et al., 1999). The μ-ring's steep size-distribution suggests that there is an unknown mechanism at play that hides or removes large dust particles. We present results from an investigation into the forces shaping the μ-ring. To simulate the motion of dust in the Mab/μ-ring system, we developed a numerical toolbox (Dustsim; Kumar et al., 2015) that uses Tudat (Kumar et al., 2012). We performed integrations using Dustsim that included the effects of Uranus' gravity field, titled magnetic moment, solar radiation pressure, and collisions with a putative suite of large μ-ring bodies, hypothesized as the cause of Mab's anomalous orbital motion (Kumar et al., 2014). Following on from previous studies (e.g., Sfair and Giuliatti Winter, 2009; Sfair and Giuliatti Winter, 2012), we present a survey of the expected lifetime of μ-ring dust, as a function of particle size. Our results lay the basis for further research into the hypothesis that the blueness of the μ-ring is a manifestation of size-based sorting, resulting from the natural environment.

The Dewar Isomer of 1,2-Dihydro-1,2-azaborinines: Isolation, Fragmentation, and Energy Storage.

PubMed

Edel, Klara; Yang, Xinyu; Ishibashi, Jacob S A; Lamm, Ashley N; Maichle-Mössmer, Cäcilia; Giustra, Zachary X; Liu, Shih-Yuan; Bettinger, Holger F

2018-05-04

The photochemistry of 1,2-dihydro-1,2-azaborinine derivatives was studied under matrix isolation conditions and in solution. Photoisomerization occurs exclusively to the Dewar valence isomers upon irradiation with UV light (>280 nm) with high quantum yield (46 %). Further photolysis with UV light (254 nm) results in the formation of cyclobutadiene and an iminoborane derivative. The thermal electrocyclic ring-opening reaction of the Dewar valence isomer back to the 1,2-dihydro-1-tert-butyldimethylsilyl-2-mesityl-1,2-azaborinine has an activation barrier of (27.0±1.2) kcal mol -1 . In the presence of the Wilkinson catalyst, the ring opening occurs rapidly and exothermically (ΔH=(-48±1) kcal mol -1 ) at room temperature. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-activation of Single Molecule Magnet Behavior in a Manganese-based Complex

NASA Astrophysics Data System (ADS)

Fetoh, Ahmed; Cosquer, Goulven; Morimoto, Masakazu; Irie, Masahiro; El-Gammal, Ola; El-Reash, Gaber Abu; Breedlove, Brian K.; Yamashita, Masahiro

2016-03-01

A major roadblock to fully realizing molecular electronic devices is the ability to control the properties of each molecule in the device. Herein we report the control of the magnetic properties of single-molecule magnets (SMMs), which can be used in memory devices, by using a photo-isomerizable diarthylenthene ligand. Photo-isomerization of the diarylethene ligand bridging two manganese salen complexes with visible light caused a significant change in the SMM behavior due to opening of the six-membered ring of diarylethene ligand, accompanied by reorganization of the entire molecule. The ring-opening activated the frequency-dependent magnetization of the complex. Our results are a major step towards the realization of molecular memory devices composed of SMMs because the SMM behaviour can be turned on and off simply by irradiating the molecule.

Prediction of enhanced solvent-induced enantioselectivity for a ring opening with a bifurcating reaction path

DOE PAGES

Carpenter, Barry K.; Harvey, Jeremy N.; Glowacki, David R.

2014-12-11

Classical molecular dynamics simulations are reported for the deazetisation and ring opening of meso-2,3-difluoro-2,3-dimethyldiazocyclopropane in three solvents: CHCl 3, CHFClBr and CH 3CH(OH)CF 3 (TFIPA). In this study, the achiral reactant leads to enantiomeric allene products, and the question addressed in the study is whether either of the chiral, enantiomerically pure solvents can induce significant enantiomeric excess in the products. The direct dynamics calculations use an empirical valence bond potential for the solute, with empirical parameters optimised against M06-2X/cc-pVTZ density functional results. The results reveal that the exothermic N 2 loss and ring opening promote transient strong solvent–solute interactions withinmore » the first ~100 fs of the reaction. Because of the bifurcating reaction path, these interactions occur at time when the “decision” about which enantiomer of the product to form has yet to be made (at least for many of the trajectories). Hence, it is possible in principle that the solvent could exert a larger-than-normal influence on the course of the reaction. In fact, the results reveal no such effect for CHFClBr but do predict that TFIPA should induce 15.2 ± 2.1% enantiomeric excess. This is roughly an order of magnitude larger than solvent-induced enantiomeric excesses found experimentally in reactions where the conversion of reactant(s) to enantiomeric products occur over separate transition states.« less

Amphiphilic polymers formed from ring-opening polymerization: a strategy for the enhancement of gene delivery.

PubMed

Zhang, Yi-Mei; Huang, Zheng; Zhang, Ji; Wu, Wan-Xia; Liu, Yan-Hong; Yu, Xiao-Qi

2017-03-28

Cationic liposomes and polymers are both important candidates for use as non-viral gene vectors. However, both of them have special shortcomings and application limits. This work is devoted to the combination of advantages of liposomes and polymers. The ring-opening polymerization strategy was used for the preparation of amphiphilic polymers from cyclen-based cationic small lipids. The non-hydrophobic polymer and the corresponding lipids were also prepared for performing structure-activity relationship studies. Gel electrophoresis results reveal that both the lipopolymers and liposomes could effectively condense DNA into nanoparticles and protect DNA from degradation. Compared to polymers, the DNA binding ability of liposomes is more affected by hydrophobic tails. Under the same dosage, the synthetic polymers have stronger DNA binding ability than the liposomes. In vitro transfection experiments show that the polymers could give better transfection efficiency, which was much higher than those of the corresponding liposomes and non-hydrophobic polymer. The oleyl moiety is suitable for lipidic vectors, but things were different for polymers. Under optimized conditions, up to 14.2 times higher transfection efficiency than that for 25 kDa bPEI could be obtained. More importantly, the lipopolymers showed much better serum tolerance, which was further confirmed by protein adsorption, gel electrophoresis, flow cytometry, and CLSM assays. The results indicate that ring-opening polymerization is a promising strategy for the enhancement of the gene delivery efficiency and biocompatibility of cationic lipids.

Fabrication and Performance of MEMS-Based Pressure Sensor Packages Using Patterned Ultra-Thick Photoresists

PubMed Central

Chen, Lung-Tai; Chang, Jin-Sheng; Hsu, Chung-Yi; Cheng, Wood-Hi

2009-01-01

A novel plastic packaging of a piezoresistive pressure sensor using a patterned ultra-thick photoresist is experimentally and theoretically investigated. Two pressure sensor packages of the sacrifice-replacement and dam-ring type were used in this study. The characteristics of the packaged pressure sensors were investigated by using a finite-element (FE) model and experimental measurements. The results show that the thermal signal drift of the packaged pressure sensor with a small sensing-channel opening or with a thin silicon membrane for the dam-ring approach had a high packaging induced thermal stress, leading to a high temperature coefficient of span (TCO) response of −0.19% span/°C. The results also show that the thermal signal drift of the packaged pressure sensors with a large sensing-channel opening for sacrifice-replacement approach significantly reduced packaging induced thermal stress, and hence a low TCO response of −0.065% span/°C. However, the packaged pressure sensors of both the sacrifice-replacement and dam-ring type still met the specification −0.2% span/°C of the unpackaged pressure sensor. In addition, the size of proposed packages was 4 × 4 × 1.5 mm3 which was about seven times less than the commercialized packages. With the same packaging requirement, the proposed packaging approaches may provide an adequate solution for use in other open-cavity sensors, such as gas sensors, image sensors, and humidity sensors. PMID:22454580

Insulative laser shell coupler

DOEpatents

Arnold, Phillip A.; Anderson, Andrew T.; Alger, Terry W.

1994-01-01

A segmented coaxial laser shell assembly having at least two water jacket sections, two pairs of interconnection half rings, a dialectric break ring, and a pair of threaded ring sections. Each water jacket section with an inner tubular section that defines an inner laser cavity with water paths adjacent to at least a portion of the exterior of the inner tubular section, and mating faces at the end of the water jacket section through which the inner laser cavity opens and which defines at least one water port therethrough in communication with the water jackets. The water paths also define in their external surface a circumferential notch set back from and in close proximity to the mating face. The dielectric break ring has selected thickness and is placed between, and in coaxial alignment with, the mating faces of two of the adjacent water jacket sections. The break ring also defines an inner laser cavity of the same size and shape as the inner laser cavity of the water jacket sections and at least one water passage through the break ring to communicate with at least one water port through the mating faces of the water jacket sections.

Insulative laser shell coupler

DOEpatents

Arnold, P.A.; Anderson, A.T.; Alger, T.W.

1994-09-20

A segmented coaxial laser shell assembly having at least two water jacket sections, two pairs of interconnection half rings, a dielectric break ring, and a pair of threaded ring sections is disclosed. Each water jacket section with an inner tubular section that defines an inner laser cavity with water paths adjacent to at least a portion of the exterior of the inner tubular section, and mating faces at the end of the water jacket section through which the inner laser cavity opens and which defines at least one water port therethrough in communication with the water jackets. The water paths also define in their external surface a circumferential notch set back from and in close proximity to the mating face. The dielectric break ring has selected thickness and is placed between, and in coaxial alignment with, the mating faces of two of the adjacent water jacket sections. The break ring also defines an inner laser cavity of the same size and shape as the inner laser cavity of the water jacket sections and at least one water passage through the break ring to communicate with at least one water port through the mating faces of the water jacket sections. 4 figs.

The O+ contribution and role on the ring current pressure development for CMEs and CIRs using Van Allen Probes observations

NASA Astrophysics Data System (ADS)

Mouikis, C.; Bingham, S.; Kistler, L. M.; Farrugia, C. J.; Spence, H. E.; Gkioulidou, M.

2016-12-01

The ring current responds differently to the different solar and interplanetary storm drivers such as coronal mass injections, (CME's), co-rotating interaction regions (CIR's), high-speed streamers and other structures. The resulting changes in the ring current particle pressure change the global magnetic field, which affects the transport of the radiation belts. In order to determine the field changes during a storm, it is necessary to understand the transport, sources and losses of the particles that contribute to the ring current. The source population of the storm time ring current is the night side plasma sheet. We use Van Allen Probes observations to determine the ring current pressure contribution of the convecting plasma sheet H+ and O+ particles in the storm time development of the ring current. We compare storms that are related to different interplanetary drivers, CMEs and CIRs, as observed at different local times. We find that during the storm main phase most of the ring current pressure in the pre-midnight inner magnetosphere is contributed by particles on open drift paths that cause the development of a strong partial ring current that causes most of the main phase Dst drop. These particles can reach as deep as L 2 and their pressure compares to the local magnetic field pressure as deep as L 3. During the recovery phase, if these particles are not lost at the magnetopause, will become trapped and will contribute to the symmetric ring current. However, the largest difference between the CME and CIR ring current responses during the storm main and early recovery phases is caused by how the 15 - 60 keV O+ responds to these drivers.

Theoretical study on the mechanism of a ring-opening reaction of oxirane by the active-site aspartic dyad of HIV-1 protease.

PubMed

Kóna, Juraj

2008-01-21

Two possible mechanisms of the irreversible inhibition of HIV-1 protease by epoxide inhibitors are investigated on an enzymatic model using ab initio (MP2) and density functional theory (DFT) methods (B3LYP, MPW1K and M05-2X). The calculations predict the inhibition as a general acid-catalyzed nucleophilic substitution reaction proceeding by a concerted SN2 mechanism with a reaction barrier of ca. 15-21 kcal mol(-1). The irreversible nature of the inhibition is characterized by a large negative reaction energy of ca. -17-(-24) kcal mol(-1). A mechanism with a direct proton transfer from an aspartic acid residue of the active site onto the epoxide ring has been shown to be preferred compared to one with the proton transfer from the acid catalyst facilitated by a bridging catalytic water molecule. Based on the geometry of the transition state, structural data important for the design of irreversible epoxide inhibitors of HIV-1 protease were defined. Here we also briefly discuss differences between the epoxide ring-opening reaction in HIV-1 protease and epoxide hydrolase, and the accuracy of the DFT method used.

CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings† †Electronic supplementary information (ESI) available: Details of the synthesis and characterization of all materials as well as details on the synchrotron and RED data collection and structure determination, including the cif file. See DOI: 10.1039/c4sc03935a Click here for additional data file.

PubMed Central

Schmidt, Joel E.; Xie, Dan; Rea, Thomas

2015-01-01

A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [425462] mtw building unit and a previously unreported [4452] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected with oval 8-rings (2.9 Å × 5.5 Å opening) through medium-sized cavities (∼7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants. PMID:29163872

Sol-gel chemistry by ring-opening polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.

2000-02-07

Sol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. The authors have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits them to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solventmore » is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which they have successfully demonstrated.« less

Earhart Propeller in Saturn A Ring

NASA Image and Video Library

2017-03-30

The propeller informally named "Earhart" is seen in this view from NASA's Cassini spacecraft at much higher resolution than ever before. This view, obtained on March 22, 2017, is the second time Cassini has deliberately targeted an individual propeller for close-up viewing during its ring-grazing orbits, after its images of Santos-Dumont (PIA21433) a month earlier. The biggest known propeller, informally named "Bleriot," is slated for the third and final propeller close-up in April 2017. Propellers are disturbances in the ring caused by a central moonlet. The moonlet itself would be a few pixels wide in this view, but it is difficult to distinguish from (and may be obscured by) the disturbed ring material that surrounds it. (See PIA20525 for more info on propellers.) The detailed structure of the Earhart propeller, as seen here, differs from that of Santos-Dumont. It is not clear whether these differences have to do with intrinsic differences between Earhart and Santos-Dumont, or whether they have to do with different viewing angles or differences in where the propellers were imaged in their orbits around Saturn. Earhart is situated very close to the 200-mile-wide (320-kilometer-wide) Encke Gap, which is held open by the much larger moon Pan. In this view, half of the Encke Gap is visible as the dark region at right. The gap and the propeller are a study in contrasts. The propeller is nothing more than Earhart's attempt to open a gap like Encke using its gravity. However, Earhart's attempt is thwarted by the mass of the ring, which fills in the nascent gap before it can extend very far. Pan is a few thousand times more massive than Earhart, which enables it to maintain a gap that extends all the way around the ring. To the left of the propeller are wave features in the rings caused by the moons Pandora, Prometheus and Pan. The visible-light image was acquired by the Cassini narrow-angle camera at a distance of 69,183 miles (111,340 kilometers) from the propeller feature. Image scale is 0.4 mile (670 meters) per pixel in the radial, or outward-from-Saturn, direction. The view looks toward the sunlit side of the rings. https://photojournal.jpl.nasa.gov/catalog/PIA21437

Femtosecond electron diffraction and spectroscopic studies of a solid state organic chemical reaction

NASA Astrophysics Data System (ADS)

Jean-Ruel, Hubert

Photochromic diarylethene molecules are excellent model systems for studying electrocyclic reactions, in addition to having important technological applications in optoelectronics. The photoinduced ring-closing reaction in a crystalline photochromic diarylethene derivative was fully resolved using the complementary techniques of transient absorption spectroscopy and femtosecond electron crystallography. These studies are detailed in this thesis, together with the associated technical developments which enabled them. Importantly, the time-resolved crystallographic investigation reported here represents a highly significant proof-of-principle experiment. It constitutes the first study directly probing the molecular structural changes associated with an organic chemical reaction with sub-picosecond temporal and atomic spatial resolution---to follow the primary motions directing chemistry. In terms of technological development, the most important advance reported is the implementation of a radio frequency rebunching system capable of producing femtosecond electron pulses of exceptional brightness. The temporal resolution of this newly developed electron source was fully characterized using laser ponderomotive scattering, confirming a 435 +/- 75 fs instrument response time with 0.20 pC bunches. The ultrafast spectroscopic and crystallographic measurements were both achieved by exploiting the photoreversibility of diarylethene. The transient absorption study was first performed, after developing a novel robust acquisition scheme for thermally irreversible reactions in the solid state. It revealed the formation of an open-ring excited state intermediate, following photoexcitation of the open-ring isomer with an ultraviolet laser pulse, with a time constant of approximately 200 fs. The actual ring closing was found to occur from this intermediate with a time constant of 5.3 +/- 0.3 ps. The femtosecond diffraction measurements were then performed using multiple crystal orientations and a large number of different samples. To analyse the results, an innovative method was developed in which the apparently complex ring-closing reaction is distilled down to a small number of basic rotations. Immediately following photoexcitation, sub-picosecond structural changes associated with the formation of the intermediate are observed. The rotation of the thiophene rings is identified as the key motion. Subsequently, on the few picosecond time scale, the time-resolved diffraction patterns are observed to converge towards those associated with the closed-ring photoproduct. The formation of the closed-ring molecule is thus unambiguously witnessed.

Cerebroprotective effect of piracetam in patients undergoing open heart surgery.

PubMed

Holinski, Sebastian; Claus, Benjamin; Alaaraj, Nour; Dohmen, Pascal Maria; Neumann, Konrad; Uebelhack, Ralf; Konertz, Wolfgang

2011-01-01

Reduction of cognitive function is a possible side effect after the use of cardiopulmonary bypass (CPB) during cardiac surgery. Since it has been proven that piracetam is cerebroprotective in patients undergoing coronary bypass surgery, we investigated the effects of piracetam on the cognitive performance of patients undergoing open heart surgery. Patients scheduled for elective open heart surgery were randomized to the piracetam or placebo group in a double-blind study. Patients received 12 g of piracetam or placebo at the beginning of the operation. Six neuropsychological subtests from the Syndrom Kurz Test and the Alzheimer's Disease Assessment Scale were performed preoperatively and on day 3, postoperatively. To assess the overall cognitive function and the degree of cognitive decline across all tests after the surgery, we combined the six test-scores by principal component analysis. A total of 88 patients with a mean age of 67 years were enrolled into the study. The mean duration of CPB was 110 minutes. Preoperative clinical parameters and overall cognitive functions were not significantly different between the groups. The postoperative combined score of the neuropsychological tests showed deterioration of cognitive function in both groups (piracetam: preoperative 0.19 ± 0.97 vs. postoperative -0.97 ± 1.38, p <0.0005 and placebo: preoperative -0.14 ± 0.98 vs. postoperative -1.35 ± 1.23, p <0.0005). Patients taking piracetam did not perform better than those taking placebo, and both groups had the same decline of overall cognitive function (p = 0.955). Piracetam had no cerebroprotective effect in patients undergoing open heart surgery. Unlike the patients who underwent coronary surgery, piracetam did not reduce the early postoperative decline of neuropsychological abilities in heart valve patients.

A mechanical analysis of conduit arteries accounting for longitudinal residual strains.

PubMed

Wang, Ruoya; Gleason, Rudolph L

2010-04-01

Identification of an appropriate stress-free reference configuration is critically important in providing a reasonable prediction of the intramural stress distribution when performing biomechanical analyses on arteries. The stress-free state is commonly approximated as a radially cut ring that typically opens into a nearly circular sector, relieving much of the circumferential residual strains that exist in the traction-free configuration. An opening angle is often used to characterize this sector. In this study, we first present experimental results showing significant residual deformations in the longitudinal direction of two commonly studied arteries in the pig: the common carotid artery and the left anterior descending coronary artery. We concluded that a radially cut ring cannot completely describe the stress-free state of the arteries. Instead, we propose the use of a longitudinal opening angle, in conjunction with the traditional circumferential opening angle, to experimentally quantify the stress-free state of an artery. Secondly, we propose a new kinematic model to account for the addition of longitudinal residual strains through employing the longitudinal opening angle and performed a stress analysis. We found that with the inclusion of longitudinal residual strains in the stress analysis, the predicted circumferential stress gradient was decreased by 3-fold and the predicted longitudinal stress gradient was increased by 5.7-fold. Thus, inclusion of longitudinal residual strains has a significant effect on the predicted stress distribution in arteries.

Electric currents induced by twisted light in Quantum Rings.

PubMed

Quinteiro, G F; Berakdar, J

2009-10-26

We theoretically investigate the generation of electric currents in quantum rings resulting from the optical excitation with twisted light. Our model describes the kinetics of electrons in a two-band model of a semiconductor-based mesoscopic quantum ring coupled to light having orbital angular momentum (twisted light). We find the analytical solution, which exhibits a "circular" photon-drag effect and an induced magnetization, suggesting that this system is the circular analog of that of a bulk semiconductor excited by plane waves. For realistic values of the electric field and material parameters, the computed electric current can be as large as microA; from an applied perspective, this opens new possibilities to the optical control of the magnetization in semiconductors.

Theory of a ring laser. [electromagnetic field and wave equations

NASA Technical Reports Server (NTRS)

Menegozzi, L. N.; Lamb, W. E., Jr.

1973-01-01

Development of a systematic formulation of the theory of a ring laser which is based on first principles and uses a well-known model for laser operation. A simple physical derivation of the electromagnetic field equations for a noninertial reference frame in uniform rotation is presented, and an attempt is made to clarify the nature of the Fox-Li modes for an open polygonal resonator. The polarization of the active medium is obtained by using a Fourier-series method which permits the formulation of a strong-signal theory, and solutions are given in terms of continued fractions. It is shown that when such a continued fraction is expanded to third order in the fields, the familiar small-signal ring-laser theory is obtained.

Prophase pathway-dependent removal of cohesin from human chromosomes requires opening of the Smc3–Scc1 gate

PubMed Central

Buheitel, Johannes; Stemmann, Olaf

2013-01-01

Faithful transmission of chromosomes during eukaryotic cell division requires sister chromatids to be paired from their generation in S phase until their separation in M phase. Cohesion is mediated by the cohesin complex, whose Smc1, Smc3 and Scc1 subunits form a tripartite ring that entraps both DNA double strands. Whereas centromeric cohesin is removed in late metaphase by Scc1 cleavage, metazoan cohesin at chromosome arms is displaced already in prophase by proteolysis-independent signalling. Which of the three gates is triggered by the prophase pathway to open has remained enigmatic. Here, we show that displacement of human cohesin from early mitotic chromosomes requires dissociation of Smc3 from Scc1 but no opening of the other two gates. In contrast, loading of human cohesin onto chromatin in telophase occurs through the Smc1–Smc3 hinge. We propose that the use of differently regulated gates for loading and release facilitates unidirectionality of DNA's entry into and exit from the cohesin ring. PMID:23361318

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

PubMed

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization

PubMed Central

2016-01-01

The need for polymers for high-end applications, coupled with the desire to mimic nature’s macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design. PMID:26795940

Thermodynamic Presynthetic Considerations for Ring-Opening Polymerization.

PubMed

Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine

2016-03-14

The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

Do substorms energise the ring current?

NASA Astrophysics Data System (ADS)

Sandhu, J. K.; Rae, J.; Freeman, M. P.; Forsyth, C.; Jackman, C. M.; Lam, M. M.

2017-12-01

The substorm phenomenon is a highly dynamic and variable process that results in the global reconfiguration and redistribution of energy within the magnetosphere. There are many open questions surrounding substorms, particularly how the energy released during a substorm is distributed throughout the magnetosphere, and how the energy loss varies from one substorm to the next. In this study, we explore whether energy lost during the substorm plays a role in energising the ring current. Using observations of the particle energy flux from RBSPICE/RBSP, we are able to quantitatively observe how the energy is distributed spatially and across the different ion species (H+, He+, and O+). Furthermore, we can observe how the total energy content of the ring current changes during the substorm process, using substorm phases defined by the SOPHIE algorithm. This analysis provides information on how the energy released from a substorm is partitioned throughout the magnetosphere, and on the processes determining the energy provided to the ring current. Overall, our results show that the substorm-ring current coupling is more complex than originally thought, and we discuss the reasons behind this complex response.

Quasi-one-dimensional density of states in a single quantum ring.

PubMed

Kim, Heedae; Lee, Woojin; Park, Seongho; Kyhm, Kwangseuk; Je, Koochul; Taylor, Robert A; Nogues, Gilles; Dang, Le Si; Song, Jin Dong

2017-01-05

Generally confinement size is considered to determine the dimensionality of nanostructures. While the exciton Bohr radius is used as a criterion to define either weak or strong confinement in optical experiments, the binding energy of confined excitons is difficult to measure experimentally. One alternative is to use the temperature dependence of the radiative recombination time, which has been employed previously in quantum wells and quantum wires. A one-dimensional loop structure is often assumed to model quantum rings, but this approximation ceases to be valid when the rim width becomes comparable to the ring radius. We have evaluated the density of states in a single quantum ring by measuring the temperature dependence of the radiative recombination of excitons, where the photoluminescence decay time as a function of temperature was calibrated by using the low temperature integrated intensity and linewidth. We conclude that the quasi-continuous finely-spaced levels arising from the rotation energy give rise to a quasi-one-dimensional density of states, as long as the confined exciton is allowed to rotate around the opening of the anisotropic ring structure, which has a finite rim width.

GPS Tracking of Free-Ranging Pigs to Evaluate Ring Strategies for the Control of Cysticercosis/Taeniasis in Peru

PubMed Central

Pray, Ian W.; Swanson, Dallas J.; Ayvar, Viterbo; Muro, Claudio; Moyano, Luz M.; Gonzalez, Armando E.; Garcia, Hector H.; O’Neal, Seth E.

2016-01-01

Background Taenia solium, a parasitic cestode that affects humans and pigs, is the leading cause of preventable epilepsy in the developing world. T. solium eggs are released into the environment through the stool of humans infected with an adult intestinal tapeworm (a condition called taeniasis), and cause cysticercosis when ingested by pigs or other humans. A control strategy to intervene within high-risk foci in endemic communities has been proposed as an alternative to mass antihelminthic treatment. In this ring strategy, antihelminthic treatment is targeted to humans and pigs residing within a 100 meter radius of a pig heavily-infected with cysticercosis. Our aim was to describe the roaming ranges of pigs in this region, and to evaluate whether the 100 meter radius rings encompass areas where risk factors for T. solium transmission, such as open human defecation and dense pig activity, are concentrated. Methodology/Principal Findings In this study, we used Global Positioning System (GPS) devices to track pig roaming ranges in two rural villages of northern Peru. We selected 41 pigs from two villages to participate in a 48-hour tracking period. Additionally, we surveyed all households to record the locations of open human defecation areas. We found that pigs spent a median of 82.8% (IQR: 73.5, 94.4) of their time roaming within 100 meters of their homes. The size of home ranges varied significantly by pig age, and 93% of the total time spent interacting with open human defecation areas occurred within 100 meters of pig residences. Conclusions/Significance These results indicate that 100 meter radius rings around heavily-infected pigs adequately capture the average pig’s roaming area (i.e., home range) and represent an area where the great majority of exposure to human feces occurs. PMID:27035825

Amino acid-based dithiazines: synthesis and photofragmentation of their benzaldehyde adducts.

PubMed

Kurchan, Alexei N; Kutateladze, Andrei G

2002-11-14

Alpha-amino acids and GABA are functionalized with dithiazine rings via reaction with sodium hydrosulfide in aqueous formaldehyde. The resulting dithiazines are lithiated at -78 degrees C and reacted with benzaldehyde furnishing amino acid-based 2,5-bis-substituted dithiazines. These adducts undergo externally sensitized photofragmentation with quantum efficiency comparable to that of the parent dithiane adducts, thus offering a novel approach to amino acid-based photolabile tethers. [reaction: see text

p-TSA/Base-Promoted Propargylation/Cyclization of β-Ketothioamides for the Regioselective Synthesis of Highly Substituted (Hydro)thiophenes.

PubMed

Nandi, Ganesh Chandra; Singh, Maya Shankar

2016-07-15

Metal-free, p-toluenesulfonic acid (p-TSA)-mediated, straightforward propargylation of β-ketothioamides with aryl propargyl alcohol has been achieved at room temperature. In addition, the reaction also provided thiazole rings as byproducts. Furthermore, the propargylated thioamides undergo intramolecular 1,5-cyclization to afford fully substituted (hydro)thiophenes in the presence of base. Notably, the approach is pot, atom, and step economical (PASE).

Efficacy and safety of the contraceptive vaginal ring (NuvaRing) compared with a combined oral contraceptive in Chinese women: a 1-year randomised trial.

PubMed

Fan, Guang Sheng; Ren, Mulan; Di, Wen; Su, Ping; Chang, Qin; Wu, Shuying; Qin, Yun; Korver, Tjeerd; Marintcheva-Petrova, Maya; Yacik, Carol; McCrary Sisk, Christine; Wang, Guoqin

2016-08-01

The aim of the study was to assess the efficacy and tolerability of the monthly vaginal ring (NuvaRing; 15 μg ethinylestradiol [EE] and 120 μg etonogestrel per day) compared with a monophasic (21/7) combined oral contraceptive (COC) containing 30 μg EE and 3 mg drospirenone in healthy Chinese women aged 18-40 years. This was a phase III, open-label, randomised multicentre trial conducted in China. Participants received NuvaRing or COC for 13 cycles (3 weeks of ring/pill treatment followed by a 1-week ring-free/pill-free period). Contraceptive efficacy was assessed by in-treatment pregnancies and expressed by the Pearl Index (PI; number of pregnancies/100 woman-years of use). Cycle control was assessed by unscheduled (breakthrough) and absence of scheduled (withdrawal) bleeding events. Safety and tolerability were assessed throughout the study. Participants were randomised either to the NuvaRing (n = 732) or to the COC (n = 214); 588 (82.4%) and 182 (78.4%) participants, respectively, completed the study. There were 10 in-treatment pregnancies in the NuvaRing group (PI 1.92; 95% confidence interval [CI] 0.92, 3.53) and five in the COC group (PI 3.12; 95% CI 1.01, 7.29). Breakthrough bleeding/spotting ranged from 18.6% (Cycle 1) to 4.2% (Cycle 11) for NuvaRing and from 21.6% (Cycle 1) to 7.9% (Cycle 11) for COC. Absence of withdrawal bleeding ranged from 8.6% (Cycle 1) to 3.0% (Cycle 11) for NuvaRing and from 14.6% (Cycle 1) to 6.4% (Cycle 5) for COC. For NuvaRing and COC, respectively, 26.6% and 25.0% of participants had treatment-related adverse events, and 7.0% and 9.1% discontinued the study as a result. Once-monthly NuvaRing is efficacious and safe for use in Chinese women.

Radio Occultation Investigation of the Rings of Saturn and Uranus

NASA Technical Reports Server (NTRS)

Marouf, Essam A.

1997-01-01

The proposed work addresses two main objectives: (1) to pursue the development of the random diffraction screen model for analytical/computational characterization of the extinction and near-forward scattering by ring models that include particle crowding, uniform clustering, and clustering along preferred orientations (anisotropy). The characterization is crucial for proper interpretation of past (Voyager) and future (Cassini) ring, occultation observations in terms of physical ring properties, and is needed to address outstanding puzzles in the interpretation of the Voyager radio occultation data sets; (2) to continue the development of spectral analysis techniques to identify and characterize the power scattered by all features of Saturn's rings that can be resolved in the Voyager radio occultation observations, and to use the results to constrain the maximum particle size and its abundance. Characterization of the variability of surface mass density among the main ring, features and within individual features is important for constraining the ring mass and is relevant to investigations of ring dynamics and origin. We completed the developed of the stochastic geometry (random screen) model for the interaction of electromagnetic waves with of planetary ring models; used the model to relate the oblique optical depth and the angular spectrum of the near forward scattered signal to statistical averages of the stochastic geometry of the randomly blocked area. WE developed analytical results based on the assumption of Poisson statistics for particle positions, and investigated the dependence of the oblique optical depth and angular spectrum on the fractional area blocked, vertical ring profile, and incidence angle when the volume fraction is small. Demonstrated agreement with the classical radiative transfer predictions for oblique incidence. Also developed simulation procedures to generate statistical realizations of random screens corresponding to uniformly packed ring models, and used the results to characterize dependence of the extinction and near-forward scattering on ring thickness, packing fraction, and the ring opening angle.

Asymmetric processing of a substrate protein in sequential allosteric cycles of AAA+ nanomachines

NASA Astrophysics Data System (ADS)

Kravats, Andrea N.; Tonddast-Navaei, Sam; Bucher, Ryan J.; Stan, George

2013-09-01

Essential protein quality control includes mechanisms of substrate protein (SP) unfolding and translocation performed by powerful ring-shaped AAA+ (ATPases associated with various cellular activities) nanomachines. These SP remodeling actions are effected by mechanical forces imparted by AAA+ loops that protrude into the central channel. Sequential intra-ring allosteric motions, which underlie repetitive SP-loop interactions, have been proposed to comprise clockwise (CW), counterclockwise (CCW), or random (R) conformational transitions of individual AAA+ subunits. To probe the effect of these allosteric mechanisms on unfoldase and translocase functions, we perform Langevin dynamics simulations of a coarse-grained model of an all-alpha SP processed by the single-ring ClpY ATPase or by the double-ring p97 ATPase. We find that, in all three allosteric mechanisms, the SP undergoes conformational transitions along a common set of pathways, which reveals that the active work provided by the ClpY machine involves single loop-SP interactions. Nevertheless, the rates and yields of SP unfolding and translocation are controlled by mechanism-dependent loop-SP binding events, as illustrated by faster timescales of SP processing in CW allostery compared with CCW and R allostery. The distinct efficacy of allosteric mechanisms is due to the asymmetric collaboration of adjacent subunits, which involves CW-biased structural motions of AAA+ loops and results in CW-compatible torque applied onto the SP. Additional simulations of mutant ClpY rings, which render a subset of subunits catalytically-defective or reduce their SP binding affinity, reveal that subunit-based conformational transitions play the major role in SP remodeling. Based on these results we predict that the minimally functional AAA+ ring includes three active subunits, only two of which are adjacent.

Face-Sealing Butterfly Valve

NASA Technical Reports Server (NTRS)

Tervo, John N.

1992-01-01

Valve plate made to translate as well as rotate. Valve opened and closed by turning shaft and lever. Interactions among lever, spring, valve plate, and face seal cause plate to undergo combination of translation and rotation so valve plate clears seal during parts of opening and closing motions.

Comparison of lignocaine gel-soaked Falope rings vs rectal diclofenac suppository for pain relief in laparoscopic sterilization.

PubMed

Sharma, Jai Bhagwan; Ghosh, Bhaswati; Kumar, Praveen; Mittal, Suneeta; Kumar, Sunesh; Roy, Kallol Kumar

2011-01-01

To compare the analgesic efficacy of lignocaine gel-soaked Silastic bands compared with rectal diclofenac suppositories in patients undergoing interval laparoscopic sterilization under conscious sedation. Prospective, randomized, controlled, single-blinded, clinical trial. Day-case center in a tertiary care hospital in India. Ninety-six women undergoing interval laparoscopic sterilization using Silastic bands (Yoon rings) randomly allocated by computer-generated random numbers into 3 groups. All women received intravenous sedation with injection diazepam and pentazocine along with local infiltration lignocaine injected at the site of the incision meant for insertion of the single site laparocator. In group 1 (n = 32), the Silastic bands (Falope rings) were presoaked in 2% sterile lignocaine gel; in group 2 (n = 32), women received a 100-mg rectal diclofenac suppository while on the operating table; and women in group 3 received only conventional analgesic. Pain perception was assessed using an 11-point visual analog score just after the procedure while still on the table (zero minutes), at 30 minutes and 1 hour after the procedure, and at discharge. The women in all 3 groups were comparable insofar as age and parity. At zero minutes (while on the operating table), the pain score in all 3 groups was similar. However, the pain scores at 30 and 60 minutes, and at discharge were significantly lower in groups 1 and group 2 compared with group 3. However, 2 women (6.25%) in group 2 and 6 (18.75%) in group 3 required supplemental analgesia within 1 hour, and were administered a 500-mg oral dose of mefenamic acid. The need for further analgesia was significantly lower in groups 1 and 2 compared with group 3 (p = .02). Comparison of groups 1 and 3 revealed that in group 1, the pain scores were significantly lower at 30 minutes (p = .02), 1 hour (p = .005), and at discharge (p = .004). No patients in group 1 requested analgesia, whereas 6 women in group 3 asked for further analgesia within an hour postoperatively (p = .01). Similarly in groups 2 and 3, women who received diclofenac suppositories had significantly lower pain scores at the specified intervals (p = 0.02, 0.002, and 0.02, respectively). Application of lignocaine gel to Falope rings and preoperative insertion of a rectal diclofenac suppository are simple and effective measures for pain control in the early postoperative period in patients undergoing day-case laparoscopic sterilization under conscious sedation. Either method could be incorporated into routine practice, depending on patient and physician choice. Copyright © 2010 AAGL. Published by Elsevier Inc. All rights reserved.

High cleanliness globe valve with sine mechanism drive

NASA Astrophysics Data System (ADS)

Luo, Hu

2018-06-01

This paper gives a new type of quick-opening globe valve for life support pneumatic control system of the safety cabin at underground coal mine. The valve adopts the sine mechanism to transmit the rotating of the handle in the range of 90° to the reciprocating motion of the spool. The mechanism implements the quick-opening function of the valve through controlling the contact and separation between the O-ring and the end face of the valve. Since there is no relative sliding between the sealing interfaces, the valve solute uncontrollable disadvantage wear particles which produced by package ball valve, to ensure high cleanliness in flow path. Traditional transmission mechanism has a reinforcement effect and reduce handle open torque. By the finite element method, the relationship between the contact force and the compression of O-ring is analyzed to provide the boundary condition for the calculation of the rotational torque. Meanwhile the velocity field and pressure field along the flow path are simulated. The caliber size of the valve and the flow resistance coefficient are obtained. There is higher cleanliness, more reliable sealing, smaller handle open torque advantage compared with existing packing ball valve. The above work presents a new technical approach for the design of pneumatic control valve of the safety cabin.

Characterizing exo-ring systems around fast-rotating stars using the Rossiter-McLaughlin effect

NASA Astrophysics Data System (ADS)

de Mooij, Ernst J. W.; Watson, Christopher A.; Kenworthy, Matthew A.

2017-12-01

Planetary rings produce a distinct shape distortion in transit light curves. However, to accurately model such light curves the observations need to cover the entire transit, especially ingress and egress, as well as an out-of-transit baseline. Such observations can be challenging for long period planets, where the transits may last for over a day. Planetary rings will also impact the shape of absorption lines in the stellar spectrum, as the planet and rings cover different parts of the rotating star (the Rossiter-McLaughlin effect). These line-profile distortions depend on the size, structure, opacity, obliquity and sky-projected angle of the ring system. For slow-rotating stars, this mainly impacts the amplitude of the induced velocity shift; however, for fast-rotating stars the large velocity gradient across the star allows the line distortion to be resolved, enabling direct determination of the ring parameters. We demonstrate that by modelling these distortions we can recover ring system parameters (sky-projected angle, obliquity and size) using only a small part of the transit. Substructure in the rings, e.g. gaps, can be recovered if the width of the features (δW) relative to the size of the star is similar to the intrinsic velocity resolution (set by the width of the local stellar profile, γ) relative to the stellar rotation velocity (v sini, i.e. δW/R* ≳ vsini/γ). This opens up a new way to study the ring systems around planets with long orbital periods, where observations of the full transit, covering the ingress and egress, are not always feasible.

Acceptable short-term outcome of laparoscopic subtotal colectomy for inflammatory bowel disease.

PubMed

Frid, Natalie Lassen; Bulut, Orhan; Pachler, Jørn

2013-06-01

Laparoscopic colectomy for both benign and malignant disease, including inflammatory bowel disease (IBD), has recently been shown to have many advantages compared with open surgery. This study aimed to compare the effect of laparoscopic versus open subtotal colectomy (STC) for IBD on overall morbidity. A total of 99 patients undergoing STC for IBD at our institution from 2007 through 2011 were identified. Patients undergoing open STC were compared with patients undergoing laparoscopic STC. Outcomes included 30-day morbidity, conversion to laparotomy, intraoperative blood loss, operative time, admission time, late onset complications and 30-day mortality. Results are presented as median values. A total of 57 patients underwent open STC (Group 1) and 42 patients laparoscopic STC (Group 2). Group 1 comprised 26 males and 31 females, with a median age of 35 years and a body mass index (BMI) of 23.2 kg/m2. Group 2 comprised 18 males and 24 females, with a median age of 34 years and a BMI of 23.5 kg/m2. Group 2 had less morbidity (42.9% versus 75.4%, p < 0.002), reduced blood loss (100 ml versus 200 ml, p < 0.001), longer operative time (193.5 min. versus 128 min., p < 0.001), shorter length of hospital stay (six days versus 16 days, p < 0.001) than Group 1. One patient died (Group 1). There was no difference in late onset complications and no conversions to laparotomy in the laparoscopic group. Laparoscopic STC has a longer operative time, but improves short-term outcomes compared with open surgery. not relevant. not relevant.

THE ACTION OF ALKALIES ON PEPTIDES AND ON KETOPIPERAZINES

PubMed Central

Levene, P. A.; Pfaltz, M. H.

1925-01-01

1. The tripeptide glycyl-levo-alanyl-glycine in solution of either one or ten equivalents of alkali does not undergo racemization on standing. 2. The dipeptide levo-alanyl-glycine under the conditions given in (1) does not undergo racemization. 3. In ketopiperazines, levo-alanyl-glycine anhydride and in levo-prolyl-glycine anhydride under the influence of dilute alkalies, racemization takes place. 4. Racemization in the present experiments was never complete. The degree of racemization seems to depend, on the one hand, on the stability of the ketopiperazine ring; on the other, on the concentration of the alkali. 5. The significance of these observations will depend on the outcome of the work on a larger number of polypeptides and ketopiperazines. The work is now in progress in this laboratory. PMID:19872187