969 resultados para Reversible Addition Fragmentation Chain Transfer (raft)
Resumo:
Current recipes for learning across business sectors too often fail to recognize the embedded and contextual nature of management practice. The existing literature gives little emphasis to the symbiotic relationship between supply chain management and the broader dynamics of context. The aerospace and construction sectors are selected for comparison on the basis that they are so different. The UK aerospace sector has undergone extensive consolidation as a result of the imperatives of global competitive pressures. In contrast, the construction industry has experienced decades of fragmentation and remains highly localized. An increasing proportion of output in the aerospace sector occurs within a small number of large, globally orientated firms. In contrast, construction output is dominated by a plethora of small firms with high levels of subcontracting and a widespread reliance on self-employment. These differences have fundamental implications for the way that supply chain management is understood and implemented in the two sectors. Semi-structured interviews with practitioners from both sectors support the contention that supply chain management is more established in aerospace than construction. The introduction of prime contracting and the increasing use of framework agreements within the construction sector potentially provide a much more supportive climate for supply chain management than has traditionally prevailed. However, progress depends upon an improved continuity of workload under such arrangements.
Resumo:
Hypothesis: The aim of this study was to measure the mass loading effect of an active middle-ear implant (the Vibrant Soundbridge) in cadaver temporal bones. Background: Implantable middle ear hearing devices such as Vibrant Soundbridge have been used as an alternative to conventional hearing aids for the rehabilitation of sensorineural hearing loss. Other than the obvious disadvantage of requiring implantation middle ear surgery, it also applies a direct weight on the ossicular chain which, in turn, may have an impact on residual hearing. Previous studies have shown that applying a mass directly on the ossicular chain has a damping effect on its response to sound. However, little has been done to investigate the magnitude and the frequency characteristics of the mass loading effect in devices such as the Vibrant Soundbridge. Methods: Five fresh cadaver temporal bones were used. The stapes displacement was measured using laser Doppler vibrometry before and after the placement of a Vibrant Sound-bridge floating mass transducer. The effects of mass and attachment site were compared with the unloaded response. Measurements were obtained at frequencies between 0.1 and 10 kHz and at acoustic input levels of 100 dB sound pressure level. Each temporal bone acted as its own control. Results: Placement of the floating mass transducer caused a reduction of the stapes displacement. There were variations between the bones. The change of the stapes displacement varied from 0 dB to 28 dB. The effect was more prominent at frequencies above 1,000 Hz. Placing the floating mass transducer close to the incudostapedial joint reduced the mass loading effect. Conclusion: The floating mass transducer produces a measurable reduction of the stapes displacement in the temporal bone model. The effect is more prominent at high frequencies.
Resumo:
This study probed the possible effects of type III resistant starch (RS) crystalline polymorphism on RS fermentability by human gut microbiota and the short chain fatty acids production in vitro. Human fecal pH-controlled batch cultures showed RS induces an ecological shift in the colonic microbiota with polymorph B inducing Bifidobacterium spp. and polymorph A inducing Atopobium spp. Interestingly, polymorph B also induced higher butyrate production to levels of 0.79 mM. In addition, human gut simulation demonstrated that polymorph B promotes the growth of bifidobacteria in the proximal part of the colon and double their relative proportion in the microbiota in the distal colon. These findings suggest that RS polymorph B may promote large bowel health. While the findings are limited by study constraints, they do raise the possibility of using different thermal processing to delineate differences in the prebiotic capabilities of RS, especially its butryrogenicity in the human colon.
Resumo:
The first example of an intramolecular enantioselective Michael addition of nitronates onto conjugated systems utilizing a chiral phase-transfer catalyst is described. A range of five-membered gamma-nitro esters with up to three stereocentres have been prepared and the relative and absolute configurations proven by chemical and crystallographic methods. The products are rapidly obtained and are precursors to five-membered cyclic gamma-amino acids.
Resumo:
A Bayesian Model Averaging approach to the estimation of lag structures is introduced, and applied to assess the impact of R&D on agricultural productivity in the US from 1889 to 1990. Lag and structural break coefficients are estimated using a reversible jump algorithm that traverses the model space. In addition to producing estimates and standard deviations for the coe¢ cients, the probability that a given lag (or break) enters the model is estimated. The approach is extended to select models populated with Gamma distributed lags of di¤erent frequencies. Results are consistent with the hypothesis that R&D positively drives productivity. Gamma lags are found to retain their usefulness in imposing a plausible structure on lag coe¢ cients, and their role is enhanced through the use of model averaging.
Resumo:
Side chain liquid crystal polymers and elastomers exhibit a rich phase behaviour which arises from the antagonistic influences of the entropically disordered polymer chain configuration and the long range orientational ordering of the mesogenic units. This competition arises since the natural macroscopic phase separation is inhibited by the inherent chemical connectivity of the system. At the heart of this connectivity is the spacer link and we consider here its influence on the phase behaviour. In particular we consider a series of elastomers in which the number of alkyl units in the spacer is systematically varied from 2 to 6. The lengthening of the coupling spacer is accompanied by an alternation of the sign of coupling between the polymer chain and the mesogenic unit. These results demonstrate the dominating influence of the so-called hinge effect in determining the phase behaviour. In addition to the alternation of the sign there is some decrease in the magnitude of the coupling with increasing spacer length.
Resumo:
Stimulation of platelets by the extracellular matrix protein collagen leads to activation of a tyrosine kinase-dependent mechanism resulting in secretion and aggregation. Tyrosine phosphorylation of the tyrosine kinase Syk and phospholipase Cgamma2 are early events in collagen-induced activation. We recently proposed that collagen-signaling in platelets involves a receptor or a receptor-associated protein containing an immunoreceptor tyrosine-based activation motif (ITAM) enabling interaction with Syk. In this report we show that collagen stimulation of platelets causes rapid tyrosine phosphorylation of the ITAM containing Fc receptor gamma-chain and that this is precipitated by the tandem Src homology 2 (SH2) domains of Syk expressed as a fusion protein. In addition we demonstrate an association between the Fc receptor gamma-chain with endogenous Syk in collagen-stimulated platelets. The Fc receptor gamma-chain undergoes tyrosine phosphorylation in platelets stimulated by a collagen-related peptide which does not bind the integrin alpha2beta1 and by the lectin wheat germ agglutinin. In contrast, cross-linking of the platelet low affinity receptor for immune complexes, FcgammaRIIA, or stimulation by thrombin does not induce phosphorylation of the Fc receptor gamma-chain. The present results provide a molecular basis for collagen activation of platelets which is independent of the integrin alpha2beta1 and involves phosphorylation of the Fc receptor gamma-chain, its association with Syk and subsequent phosphorylation of phospholipase Cgamma2. Collagen is the first example of a nonimmune receptor stimulus to signal through a pathway closely related to signaling by immune receptors.
Resumo:
Knowledge is recognised as an important source of competitive advantage and hence there has been increasing academic and practitioner interest in understanding and isolating the factors that contribute to effective knowledge transfer between supply chain actors. The literature identifies power as a salient contributor to the effective operation of a supply chain partnership. However, there is a paucity of empirical research examining how power among actors influences knowledge acquisition and in turn the performance of supply chain partners. The aim of this research is to address this gap by examining the relationship between power, knowledge acquisition and supply chain performance among the supply chain partners of a focal Chinese steel manufacturer. A structured survey was used to collect the necessary data. Two conceptually independent variables – ‘availability of alternatives’ and ‘restraint in the use of power’ – were used to assess actual and realised power, respectively. Controlling for contingencies, we found that the flow of knowledge increased when supply chain actors had limited alternatives and when the more powerful actor exercised restraint in the use of power. Moreover, we found a positive relationship between knowledge acquisition and supply chain performance. This paper enriches the literature by empirically extending our understanding of how power affects knowledge acquisition and performance.
Resumo:
We present new radiative transfer simulations to support determination of sea surface temperature (SST) from Along Track Scanning Radiometer (ATSR) imagery. The simulations are to be used within the ATSR Reprocessing for Climate project. The simulations are based on the “Reference Forward Model” line-by-line model linked with a sea surface emissivity model that accounts for wind speed and temperature, and with a discrete ordinates scattering model (DISORT). Input to the forward model is a revised atmospheric profile dataset, based on full resolution ERA-40, with a wider range of high-latitude profiles to address known retrieval biases in those regions. Analysis of the radiative impacts of atmospheric trace gases shows that geographical and temporal variation of N2O, CH4, HNO3, and CFC-11 and CFC-12 have effects of order 0.05, 0.2, 0.1 K on the 3.7, 11, 12 μm channels respectively. In addition several trace gases, neglected in previous studies, are included using fixed profiles contributing ~ 0.04 K to top-of-atmosphere BTs. Comparison against observations for ATSR2 and AATSR indicates that forward model biases have been reduced from 0.2 to 0.5 K for previous simulations to ~ 0.1 K.
Resumo:
This article elucidates the Typological Primacy Model (TPM; Rothman, 2010, 2011, 2013) for the initial stages of adult third language (L3) morphosyntactic transfer, addressing questions that stem from the model and its application. The TPM maintains that structural proximity between the L3 and the L1 and/or the L2 determines L3 transfer. In addition to demonstrating empirical support for the TPM, this article articulates a proposal for how the mind unconsciously determines typological (structural) proximity based on linguistic cues from the L3 input stream used by the parser early on to determine holistic transfer of one previous (the L1 or the L2) system. This articulated version of the TPM is motivated by argumentation appealing to cognitive and linguistic factors. Finally, in line with the general tenets of the TPM, I ponder if and why L3 transfer might obtain differently depending on the type of bilingual (e.g. early vs. late) and proficiency level of bilingualism involved in the L3 process.
Resumo:
A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.
Resumo:
We present a detailed investigation of a magnetospheric flux transfer event (FTE) seen by the Active Magnetospheric Tracer Explorer (AMPTE) UKS and IRM satellites around 1046 UT on October 28, 1984. This event has been discussed many times previously in the literature and has been cited as support for a variety of theories of FTE formation. We make use of a model developed to reproduce ion precipitations seen in the cusp ionosphere. The analysis confirms that the FTE is well explained as a brief excursion into an open low-latitude boundary layer (LLBL), as predicted by two theories of magnetospheric FTEs: namely, that they are bulges in the open LLBL due to reconnection rate enhancements or that they are indentations of the magnetopause by magnetosheath pressure increases (but in the presence of ongoing steady reconnection). The indentation of the inner edge of the open LLBL that these two models seek to explain is found to be shallow for this event. The ion model reproduces the continuous evolution of the ion distribution function between the sheath-like population at the event center and the surrounding magnetospheric populations; it also provides an explanation of the high-pressure core of the event as comprising field lines that were reconnected considerably earlier than those that are draped over it to give the event boundary layer. The magnetopause transition parameter is used to isolate a field rotation on the boundaries of the core, which is subjected to the tangential stress balance test. The test identifies this to be a convecting structure, which is neither a rotational discontinuity (RD) nor a contact discontinuity, but could possibly be a slow shock. In addition, evidence for ion reflection off a weak RD on the magnetospheric side of this structure is found. The event structure is consistent in many ways with features predicted for the open LLBL by analytic MHD theories and by MHD and hybrid simulations. The de Hoffman-Teller velocity of the structure is significantly different from that of the magnetosheath flow, indicating that it is not an indentation caused by a high-pressure pulse in the sheath but is consistent with the motion of newly opened field lines (different from the sheath flow because of the magnetic tension force) deduced from the best fit to the ion data. However, we cannot here rule out the possibility that the sheath flow pattern has changed in the long interval between the two satellites observing the FTE and subsequently emerging into the magnetosheath; thus this test is not conclusive in this particular case. Analysis of the fitted elapsed time since reconnection shows that the core of the event was reconnected in one pulse and the event boundary layer was reconnected in a subsequent pulse. Between these two pulses is a period of very low (but nonzero) reconnection rate, which lasts about 14 mins. Thus the analysis supports, but does not definitively verify, the concept that the FTE is a partial passage into an open LLBL caused by a traveling bulge in that layer produced by a pulse in reconnection rate.
Resumo:
The suggestion is discussed that characteristic particle and field signatures at the dayside magnetopause, termed “flux transfer events” (FTEs), are, in at least some cases, due to transient solar wind and/or magnetosheath dynamic pressure increases, rather than time-dependent magnetic reconnection. It is found that most individual cases of FTEs observed by a single spacecraft can, at least qualitatively, be explained by the pressure pulse model, provided a few rather unsatisfactory features of the predictions are explained in terms of measurement uncertainties. The most notable exceptions to this are some “two-regime” observations made by two satellites simultaneously, one on either side of the magnetopause. However, this configuration has not been frequently achieved for sufficient time, such observations are rare, and the relevant tests are still not conclusive. The strongest evidence that FTEs are produced by magnetic reconnection is the dependence of their occurrence on the north-south component of the interplanetary magnetic field (IMF) or of the magnetosheath field. The pressure pulse model provides an explanation for this dependence (albeit qualitative) in the case of magnetosheath FTEs, but this does not apply to magnetosphere FTEs. The only surveys of magnetosphere FTEs have not employed the simultaneous IMF, but have shown that their occurrence is strongly dependent on the north-south component of the magnetosheath field, as observed earlier/later on the same magnetopause crossing (for inbound/outbound passes, respectively). This paper employs statistics on the variability of the IMF orientation to investigate the effects of IMF changes between the times of the magnetosheath and FTE observations. It is shown that the previously published results are consistent with magnetospheric FTEs being entirely absent when the magnetosheath field is northward: all crossings with magnetosphere FTEs and a northward field can be attributed to the field changing sense while the satellite was within the magnetosphere (but close enough to the magnetopause to detect an FTE). Allowance for the IMF variability also makes the occurrence frequency of magnetosphere FTEs during southward magnetosheath fields very similar to that observed for magnetosheath FTEs. Conversely, the probability of attaining the observed occurrence frequencies for the pressure pulse model is 10−14. In addition, it is argued that some magnetosheath FTEs should, for the pressure pulse model, have been observed for northward IMF: the probability that the number is as low as actually observed is estimated to be 10−10. It is concluded that although the pressure model can be invoked to qualitatively explain a large number of individual FTE observations, the observed occurrence statistics are in gross disagreement with this model.
Resumo:
In vitro, the addition of lipids to a carbohydrate food has been found to increase the digestibility of starch. In contrast, in vivo studies have shown that the addition of fat to a food can reduce the glycaemic response (GR). The aim of this study was to assess if delayed gastric emptying (GE) causes reduced GR with the addition of lipids to a carbohydrate food and if a relationship between GR and in vitro digestion of starch exists for high fat foods. Ten healthy volunteers were tested on five occasions after consuming pancakes containing 50 g of available carbohydrate and 202 kcal of sunflower oil, olive oil, butter, medium chain triglyceride (MCT) oil or a control containing no oil. GR was measured using fingerpick blood samples, satiety using visual analogue scales and GE using the 13C octanoic acid breath test. There was a significant difference in GR between the different pancake breakfasts (p = 0.05). The highest GR was observed following the control pancakes and the lowest following the olive oil pancakes. There were significant differences in GE half time, lag phase and ascension time (p < 0.05) between the different pancakes with the control pancakes having the shortest GE time and the MCT pancakes the longest. There was a significant difference in satiety parameters fullness (p = 0.003) and prospective consumption (p = 0.050), with satiety being lowest following the control pancakes. There was a significant inverse correlation between the GR and all satiety parameters. A significant inverse correlation (p = 0.009) was also observed between the digestibility of starch in vitro and GR in vivo. The paper indicates that the digestibility of starch in vitro does not predict the GR for high fat containing foods