1,506 research outputs found
Application of density functional theory in the synthesis of electroactive polymers
A wide range of conjugated organic compounds undergo anodic electropolymerisation to produce polymers of high conductivity. However, electrooxidation does not always result in the formation of electroactive materials, since some reactions produce insulating films or soluble oligomers. Density functional theory (DFT) has been used to predict the outcome of electropolymerisation reactions by calculating the unpaired electron π-spin density distribution of monomeric radical cations, in order to determine coupling positions in the resultant polymers. π-Spin densities calculated for pyrrole, thiophene and (E)-stilbene are found to be in good agreement with experimental values. DFT has been used to investigate the low conductivity and redox inactivity of poly[(E)-3-styrylthiophenes] and poly[(E)-2-styrylheterocycles]. High positive spin densities at the alkene spacer linkage in the corresponding monomeric radical cations were found, suggesting crosslinking of the polymers via the double bond. In contrast, electroactive polymers of improved conductivity are formed from the electropolymerisation of some (Z)-2-α,β-diarylacrylonitriles. For these monomers, DFT calculations show the positions of highest spin density to be located at the α-positions of the heterocyclic rings, suggesting the presence of α,α′-linked monomeric couplings necessary for electroactivity
Term structure transmission of monetary policy
Under bond rate transmission of monetary policy, standard restrictions on policy responses to obtain determinate inflation need not apply. In periods of passive policy, bond rates may exhibit stable responses to inflation if future policy is anticipated to be active, or if time-varying term premiums incorporate inflation-dependent risk pricing. We derive a generalized Taylor Principle that requires a lower bound to the average anticipated path of forward rate responses to inflation. We also present a no-arbitrage term structure model with horizon-dependent policy and time-varying term premiums to explain mechanics and provide empirical results supporting these channels
Markers of mouse macrophage development detected by monoclonal antibodies
In this review, we present and discuss a selected panel of antibody-defined markers expressed during different stages of mouse macrophage d
Turbulent Supersonic/Hypersonic Heating Correlations for Open and Closed Cavities
Supersonic/hypersonic laminar heating correlations that were developed for damage assessment analysis of atmospheric re-entry vehicles have been modified and extended to cover fully-turbulent conditions over rectangular cavity geometries that are aligned with the local velocity. Turbulent boundary layer properties were computationally determined and used to develop the cavity geometry parametrics and to correlate experimental closed cavity heating data to yield new relationships for the floor-averaged and centerline endwall peak-heating augmentation. With the form of the closed-cavity correlations established, historical data were used to develop new correlations for turbulent open-cavity heating
Tiered Human Integrated Sequence Search Databases for Shotgun Proteomics.
The results of analysis of shotgun proteomics mass spectrometry data can be greatly affected by the selection of the reference protein sequence database against which the spectra are matched. For many species there are multiple sources from which somewhat different sequence sets can be obtained. This can lead to confusion about which database is best in which circumstances-a problem especially acute in human sample analysis. All sequence databases are genome-based, with sequences for the predicted gene and their protein translation products compiled. Our goal is to create a set of primary sequence databases that comprise the union of sequences from many of the different available sources and make the result easily available to the community. We have compiled a set of four sequence databases of varying sizes, from a small database consisting of only the ∼20,000 primary isoforms plus contaminants to a very large database that includes almost all nonredundant protein sequences from several sources. This set of tiered, increasingly complete human protein sequence databases suitable for mass spectrometry proteomics sequence database searching is called the Tiered Human Integrated Search Proteome set. In order to evaluate the utility of these databases, we have analyzed two different data sets, one from the HeLa cell line and the other from normal human liver tissue, with each of the four tiers of database complexity. The result is that approximately 0.8%, 1.1%, and 1.5% additional peptides can be identified for Tiers 2, 3, and 4, respectively, as compared with the Tier 1 database, at substantially increasing computational cost. This increase in computational cost may be worth bearing if the identification of sequence variants or the discovery of sequences that are not present in the reviewed knowledge base entries is an important goal of the study. We find that it is useful to search a data set against a simpler database, and then check the uniqueness of the discovered peptides against a more complex database. We have set up an automated system that downloads all the source databases on the first of each month and automatically generates a new set of search databases and makes them available for download at http://www.peptideatlas.org/thisp/
Andreev reflections in the pseudogap state of cuprate supercondcutors
We propose that, if the pseudogap state in the cuprate superconductors can be
described in terms of the phase-incoherent preformed pairs, there should exist
Andreev reflection from these pairs even above the superconducting transition
temperature, . After giving qualitative arguments for this effect, we
present more quantitative calculations based on the Bogoliubov--de Gennes
equation. Experimental observations of the effects of Andreev reflections above
---such as an enhanced tunneling conductance below the gap along the
copper oxide plane---could provide unambiguous evidence for the preformed pairs
in the pseudogap state.Comment: 5 pages, 1 figur
Comparison of case note review methods for evaluating quality and safety in health care
Objectives: To determine which of two methods of case note review – holistic (implicit) and criterion-based (explicit) – provides the most useful and reliable information for quality and safety of care, and the level of agreement within and between groups of health-care professionals when they use the two methods to review the same record. To explore the process–outcome relationship between holistic and criterion-based quality-of-care measures and hospital-level outcome indicators. © 2010 Crown Copyrigh
Effects of unidirectional flow shear stresses on the formation, fractal microstructure and rigidity of incipient whole blood clots and fibrin gels
Incipient clot formation in whole blood and fibrin gels was studied by the rheometric techniques of controlled stress
parallel superposition (CSPS) and small amplitude oscillatory shear (SAOS). The effects of unidirectional shear stress on incipient
clot microstructure, formation kinetics and elasticity are reported in terms of the fractal dimension (df ) of the fibrin network,
the gel network formation time (TGP ) and the shear elastic modulus, respectively. The results of this first haemorheological
application of CSPS reveal the marked sensitivity of incipient clot microstructure to physiologically relevant levels of shear
stress, these being an order of magnitude lower than have previously been studied by SAOS. CSPS tests revealed that exposure
of forming clots to increasing levels of shear stress produces a corresponding elevation in df , consistent with the formation of
tighter, more compact clot microstructures under unidirectional flow. A corresponding increase in shear elasticity was recorded.
The scaling relationship established between shear elasticity and df for fibrin clots and whole blood confirms the fibrin network
as the dominant microstructural component of the incipient clot in terms of its response to imposed stress. Supplementary studies
of fibrin clot formation by rheometry and microscopy revealed the substantial additional network mass required to increase df
and provide evidence to support the hypothesis that microstructural changes in blood clotted under unidirectional shear may be
attributed to flow enhanced thrombin generation and activation. CSPS also identified a threshold value of unidirectional shear
stress above which no incipient clot formation could be detected. CSPS was shown to be a valuable haemorheological tool for
the study of the effects of physiological and pathological levels of shear on clot properties
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