240 research outputs found
Phenalene-phosphazene complexes: effect of exocyclic charge densities on the cyclotriphosphazene ring system
The synthesis and properties of a new series of 1,9-diamino-substituted phenalene complexes of the cyclotriphosphazene ring system is described. One of the compounds is shown to be amphoteric, and this behavior allows an examination of the response of the phosphazene linkage to variations in exocyclic charge density at the spiro center in a plane perpendicular to the cyclotriphosphazene ring system. ^(31)P NMR spectroscopy indicates that substituent lone pairs with this orientation are not effective in long-range delocalization within the phosphazene linkage (in accord with our theoretical model of spiro delocalization). An X-ray crystal structure of one compound (7) identifies the presence of clathrated molecules of chloroform together with doubly hydrogen-bonded pairs of the phenalene-phosphazene complexes in the lattice. Crystal data for 7 (C_(13)H_8Cl_4N_5P_3ā¢CHCl_3): monoclinic space group P2_1/c, a = 12.401 (4) Ć
, b = 28.404 (6) Ć
, c = 12.962 (3) Ć
, Ī² = 91.76 (2)Ā°, V = 4564 (2) Ć
^3, Z = 8, R = 0.050 for 4525 reflections
A Brief Review of Past INL Work Assessing Radionuclide Content in TMI-2 Melted Fuel Debris: The Use of 144Ce as a Surrogate for Pu Accountancy
This report serves as a literature review of prior work performed at Idaho National Laboratory, and its predecessor organizations Idaho National Engineering Laboratory (INEL) and Idaho National Engineering and Environmental Laboratory (INEEL), studying radionuclide partitioning within the melted fuel debris of the reactor of the Three Mile Island 2 (TMI-2) nuclear power plant. The purpose of this review is to document prior published work that provides supporting evidence of the utility of using 144Ce as a surrogate for plutonium within melted fuel debris. When the TMI-2 accident occurred no quantitative nondestructive analysis (NDA) techniques existed that could assay plutonium in the unconventional wastes from the reactor. However, unpublished work performed at INL by D. W. Akers in the late 1980s through the 1990s demonstrated that passive gamma-ray spectrometry of 144Ce could potentially be used to develop a semi-quantitative correlation for estimating plutonium content in these materials. The fate and transport of radioisotopes in fuel from different regions of the core, including uranium, fission products, and actinides, appear to be well characterized based on the maximum temperature reached by fuel in different parts of the core and the melting point, boiling point, and volatility of those radioisotopes. Also, the chemical interactions between fuel, fuel cladding, control elements, and core structural components appears to have played a large role in determining when and how fuel relocation occurred in the core; perhaps the most important of these reaction appears to be related to the formation of mixed-material alloys, eutectics, in the fuel cladding. Because of its high melting point, low volatility, and similar chemical behavior to plutonium, the element cerium appears to have behaved similarly to plutonium during the evolution of the TMI-2 accident. Anecdotal evidence extrapolated from open-source literature strengthens this logical feasibility for using cerium, which is rather easy to analyze using passive nondestructive analysis gamma-ray spectrometry, as a surrogate for plutonium in the final analysis of TMI-2 melted fuel debris. The generation of this report is motivated by the need to perform nuclear material accountancy measurements on the melted fuel debris that will be excavated from the damaged nuclear reactors at the Fukushima Daiichi nuclear power plant in Japan, which were destroyed by the Tohoku earthquake and tsunami on March 11, 2011. Lessons may be taken from prior U.S. work related to the study of the TMI-2 core debris to support the development of new assay methods for use at Fukushima Daiichi. While significant differences exist between the two reactor systems (pressurized water reactor (TMI-2) versus boiling water reactor (FD), fresh water post-accident cooing (TMI-2) versus salt water (FD), maintained containment (TMI-2) versus loss of containment (FD)) there remain sufficient similarities to motivate these comparisons
In Vitro and In Vivo Evidence for Lack of Endovascular Remodeling by Third Trimester Trophoblasts
The placentalādecidual interaction through invading trophoblasts determines whether a physiological transformation of the uterine spiral arteries is established or not. Trophoblast-orchestrated artery remodeling is central to normal placentation. Dysregulated uteroplacental interaction and vascular remodeling are thought to be associated with the molecular events underlying the pathology of late pregnancy anomalies including preeclampsia. Although the exact gestational age at which trophoblast invasion ceases is not known, it remains unclear whether late pregnancy trophoblasts retain the ability to transform the uterine arteries. Here, we have developed a dual cell, in vitro culture system that mimics the vascular remodeling events during normal pregnancy. We demonstrate that first and third trimester trophoblasts respond differentially to interactive signals from endothelial cells when cultured on matrigel. Term primary trophoblasts or immortalized third trimester extravillous TCL1 trophoblasts not only fail to respond to signals from endothelial cells but also inhibit endothelial cell tube formation. In contrast, HTR8 cells, representing a first trimester trophoblast cell line with invasive properties, undergo spontaneous migration and synchronize with the endothelial cells in a capillary network. This disparity in behavior was confirmed in vivo using a matrigel plug assay. Poor expression of VEGF C and VEGF receptors coupled with high E-cadherin expression by term primary trophoblasts and TCL1 cells contributed to their restricted interactive and migratory properties. We further show that the kinase activity of VEGF R2 is essential for proactive crosstalk by HTR8 cells. This unique behavior of first trimester trophoblasts in the presence of endothelial cells offers a potential approach to study cellācell interactions and to decipher modulatory components in the serum samples from adverse pregnancy outcomes
Direct Amination of 9-Hydroxy-1-oxophenalene to Produce 9-Amino-1-oxophenalene and Related Compounds
In connection with our studies of organo-non-metallic complexes of the 1,9-disubstituted phenalene unit 1 we required access to compounds possessing a total of just two ionizable hydrogen atoms in the A,B groups of 1. The prototypical compound in this series, 9-amino-1-oxophenalene (2), is not known although 9-hydroxy-l-oxophenalene (3) was first prepared in 1941 and a number
of derivatives of 1 possessing one or three ionizable hydrogen atoms in the A,B groups have recently become available. We have found that the high-pressure reaction between 9-hydroxy-1-oxophenalene (3) and aqueous ammonia
affords the desired 9-amino-1-oxophenalene (2) in high yield and good purity under relatively mild conditions. In addition 2 may be alkylated to produce the 9-amino-l-ethoxyphenalenylium salt which serves as a precursor
for the other derivatives in this series with two ionizable hydrogen atoms in the A,B groups of 1
Shaping Biological Knowledge: Applications in Proteomics
The central dogma of molecular biology has provided a meaningful principle
for data integration in the field of genomics. In this context, integration reflects
the known transitions from a chromosome to a protein sequence: transcription,
intron splicing, exon assembly and translation. There is no such clear principle for
integrating proteomics data, since the laws governing protein folding and interactivity
are not quite understood. In our effort to bring together independent pieces of
information relative to proteins in a biologically meaningful way, we assess the bias of
bioinformatics resources and consequent approximations in the framework of small-scale
studies. We analyse proteomics data while following both a data-driven (focus
on proteins smaller than 10 kDa) and a hypothesis-driven (focus on whole bacterial
proteomes) approach. These applications are potentially the source of specialized
complements to classical biological ontologies
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Measurement and Characterization of Nuclear Material at Idaho National Laboratory
A measurement plan and preliminary Monte Carlo simulations are presented for the investigation of well-defined mixed-oxide fuel pins. Measurement analysis including pulse-height distributions and time-dependent cross-correlation functions will be performed separately for neutrons and gamma rays. The utilization of Monte Carlo particle transport codes, specifically MCNP-PoliMi, is discussed in conjunction with the anticipated measurements. Four EJ-309 liquid scintillation detectors with an accurate pulse timing and digital, offline, optimized pulse-shape discrimination method will be used to prove the dependency of pulse-height distributions, cross-correlation functions, and material multiplicities upon fuel pin composition, fuel pin quantity, and detector geometry. The objective of the measurements and simulations is to identify novel methods for describing mixed-oxide fuel samples by relating measured quantities to fuel characteristics such as criticality, mass quantity, and material composition. This research has applications in nuclear safeguards and nonproliferation
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Neutron Emission Characteristics of Two Mixed-Oxide Fuels: Simulations and Initial Experiments
Simulations and experiments have been carried out to investigate the neutron emission characteristics of two mixed-oxide (MOX) fuels at Idaho National Laboratory (INL). These activities are part of a project studying advanced instrumentation techniques in support of the U.S. Department of Energy's Fuel Cycle Research and Development program and it's Materials Protection, Accounting, and Control for Transmutation (MPACT) campaign. This analysis used the MCNP-PoliMi Monte Carlo simulation tool to determine the relative strength and energy spectra of the different neutron source terms within these fuels, and then used this data to simulate the detection and measurement of these emissions using an array of liquid scintillator neutron spectrometers. These calculations accounted for neutrons generated from the spontaneous fission of the actinides in the MOX fuel as well as neutrons created via (alpha,n) reactions with oxygen in the MOX fuel. The analysis was carried out to allow for characterization of both neutron energy as well as neutron coincidences between multiple detectors. Coincidences between prompt gamma rays and neutrons were also analyzed. Experiments were performed at INL with the same materials used in the simulations to benchmark and begin validation tests of the simulations. Data was collected in these experiments using an array of four liquid scintillators and a high-speed waveform digitizer. Advanced digital pulse-shape discrimination algorithms were developed and used to collect this data. Results of the simulation and modeling studies are presented together with preliminary results from the experimental campaign
Social Value of Marine and Coastal Protected Areas in England and Wales.
The U.K. government is committed to establishing a coherent network of marine protected
areas by 2012 and the recentMarine and Coastal Access Act, 2009 will designate
marine conservation zones and provide wider access rights to the coast. To fulfill these
goals, this article argues the need for a clearer, shared understanding of the social
value of protected areas in creating new designations and managing existing ones. Although
marine and coastal environments attract many people and are vitally important
in terms of realized and potential social value, the majority of the public in the United
Kingdom lacks understanding and awareness regarding them. Combined with this, the
social value of marine and coastal protected areas (MCPAs) have been largely ignored
relative to conservation and economics, with the latter invariably taking precedence
in environmental policymaking. Social value reflects the complex, individual responses
that people experience in a given place. Many reasons determine why one area is valued
above another, and this research investigates the social value of MCPAs from a
practitionerās perspective through a series of interviews. Understanding why we āsociallyā
value MCPAs will ultimately equip managers with an informed understanding
of these spaces, influence management decisions, and, potentially, policymaking. This
article defines social value in the context of MCPAs in England and Wales from a
practitioner perspective, explores key concepts, and suggests possible improvements in
decision-making
Photophysics of the electronic states S0 and S1 for the coplanar molecular structures of the Ī±,Ļ-diphenylpolyenes DPH and DPO
Spectroscopy of the monoclinic and orthorhombic crystalline forms of all-trans-diphenylhexatriene (DPH) and all-trans-diphenyloctatetraene (DPO) show absorption and emission bands that do not generate the widely known Stokes shift of the polyene compounds, discovered by Hausser et al. in 1953 and repeatedly studied over the last 60 years. It can be concluded from our study that the crystallization system, whether in a monoclinic or orthorhombic system, does not significantly influence the photophysics of DPH and DPO in the crystal phas
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