A comparison of the gas phase acidities of phospholipid headgroups: Experimental and computational studies

Proton-bound dimers consisting of two glycerophospholipids with different headgroups were prepared using negative ion electrospray ionization and dissociated in a triple quadrupole mass spectrometer. Analysis of the tandem mass spectra of the dimers using the kinetic method provides, for the first time, an order of acidity for the phospholipid classes in the gas phase of PE < PA << PG < PS < PI. Hybrid density functional calculations on model phospholipids were used to predict the absolute deprotonation enthalpies of the phospholipid classes from isodesmic proton transfer reactions with phosphoric acid. The computational data largely support the experimental acidity trend, with the exception of the relative acidity ranking of the two most acidic phospholipid species. Possible causes of the discrepancy between experiment and theory are discussed and the experimental trend is recommended. The sequence of gas phase acidities for the phospholipid headgroups is found to (1) have little correlation with the relative ionization efficiencies of the phospholipid classes observed in the negative ion electrospray process, and (2) correlate well with fragmentation trends observed upon collisional activation of phospholipid \[M - H](-) anions. (c) 2005 American Society for Mass Spectrometry.

The implementation of a guideline of care for patients with a Sengstaken-Blakemore tube in situ in a general intensive care unit using transitional change theory

The use of the Sengstaken–Blakemore tube as a life-saving treatment for bleeding oesophageal varices is slowly becoming the least preferred method possibly due to the potential complications associated with its placement. Nursing practice pertaining to the care of this patient group appears ad hoc and reliant on local knowledge and experience as opposed to recognised evidence of best practice. Therefore, this paper focuses on the application of Lewin's transitional change theory used to introduce a change in nursing practice with the application of a guideline to enhance the care of patients with a Sengstaken–Blakemore tube in situ within a general intensive care unit. This method identified some of the complexities surrounding the change process including the driving and restraining forces that must be harnessed and minimised in order for the adoption of change to be successful.

Assessing exposure to polybrominated diphenyl ethers (PBDEs) for workers in the vicinity of a large recycling facility

Increased levels of polybrominated diphenyl ethers (PBDEs) can occur particularly in dust and soil surrounding facilities that recycle products containing PBDEs. This may be the source of increased exposure for nearby workers and residents. To investigate, we measured PBDE levels in soil, office dust and blood of workers at the closest workplace (i.e. within 100m) to a large automotive shredding and metal recycling facility in Brisbane, Australia. The workplace investigated in this study was independent of the automotive shredding facility and was one of approximately 50 businesses of varying types within a relatively large commercial/industrial area surrounding the recycling facility. Concentrations of PBDEs in soils were at least an order of magnitude greater than background levels in the area. Congener profiles were dominated by larger molecular weight congeners; in particular BDE-209. This reflected the profile in outdoor air samples previously collected at this site. Biomonitoring data from blood serum indicated no differential exposure for workers near the recycling facility compared to a reference group of office workers, also in Brisbane. Unlike air, indoor dust and soil sample profiles, serum samples from both worker groups were dominated by congeners BDE-47, BDE-153, BDE-99, BDE-100 and BDE-183 and was similar to the profile previously reported in the general Australian population. Estimated exposures for workers near the industrial point source suggested indoor workers had significantly higher exposure than outdoor workers due to their exposure to indoor dust rather than soil. However, no relationship was observed between blood PBDE levels and different roles and activity patterns of workers on-site. These comparisons of PBDE levels in serum provide additional insight into the inter-individual variability within Australia. Results also indicate congener patterns in the workplace environment did not match blood profiles of workers. This was attributed to the relatively high background exposures for the general Australian population via dietary intake and the home environment.

The salt dependence of DNA recognition by NF-kappaB p50 : a detailed kinetic analysis of the effects on affinityand specificity

The binding kinetics of NF-kappaB p50 to the Ig-kappaB site and to a DNA duplex with no specific binding site were determined under varying conditions of potassium chloride concentration using a surface plasmonresonance biosensor. Association and dissociation rate constants were measured enabling calculation of the dissociation constants. Under previously established high affinity buffer conditions, the k a for both sequences was in the order of 10(7) M-1s-1whilst the k d values varied 600-fold in a sequence-dependent manner between 10(-1) and 10(-4 )s-1, suggesting that the selectivity of p50 for different sequences is mediated primarily through sequence-dependent dissociation rates. The calculated K D value for the Ig-kappaB sequence was 16 pM, whilst the K D for the non-specific sequence was 9.9 nM. As the ionic strength increased to levels which are closer to that of the cellular environment, the binding of p50 to the non-specific sequence was abolished whilst the specific affinity dropped to nanomolar levels. From these results, a mechanism is proposed in which p50 binds specific sequences with high affinity whilst binding non-specific sequences weakly enough to allow efficient searching of the DNA.

General self-efficacy influences affective task reactions during a work simulation : the temporal effects of changes in workload at different levels of control

This study investigated the effects of workload, control, and general self-efficacy on affective task reactions (i.e., demands-ability fit, active coping, and anxiety) during a work simulation. The main goals were: (1) to determine the extent general self-efficacy moderates the effects of demand and control on affective task reactions, and; (2) to determine if this varies as a function of changes in workload. Participants (N=141) completed an inbox activity under conditions of low or high control and within low and high workload conditions. The order of trials varied so that workload increased or decreased. Results revealed individuals with high general self-efficacy reported better demands-abilities fit and active coping as well as less anxiety. Three interactive effects were found. First, it was found that high control increased demands-abilities fit from trial 1 to trial 2, but only when workload decreased. Second, it was found that low efficacious individuals active coping increased in trial 2, but only under high control. Third, it was found that high control helped high efficacious individuals manage anxiety when workload decreased. However, for individuals with low general self-efficacy, neither high nor low control alleviated anxiety (i.e., whether workload increased or decreased over time).

The collision induced loss of carbon monoxide from deprotonated benzyl benzoate in the gas phase. An anionic 1,2-Wittig type rearrangement

The ion PhCO2--CHPh, upon collision activation, undergoes competitive losses of CO and CO2 of which the former process produces the base peak of the spectrum. Product ion and substituent effect (Hammett) studies indicate that PhCO2--CHPh cyclises to a deprotonated hydroxydiphenyloxirane which ring opens to PhCOCH(O-)Ph. This anion then undergoes an anionic 1,2-Wittig type rearrangement {through [PhCO- (PhCHO)]} to form Ph2CHO- and CO. The mechanism of the 1,2-rearrangement has been probed by an ab initio study [at MP4(SDTQ)/6-31++G(d,p) level] of the model system HCOCH2O- →; MeO- + CO The analogous system RCO2--CHPh (R = alkyl) similarly loses CO, and the migratory aptitudes of the alkyl R groups in this reaction are Bu′ > Me > Et ∼Pri). This trend correlates with the order of anion basicities (i.e. the order of ΔG○acid values of RH), supporting the operation of an anion migration process. The loss of CO2 from PhCO2--CHPh yields Ph2CH- as the anionic product: several mechanistic scenarios are possible, one of which involves an initial ipso nucleophilic substitution.

A biomechanical analysis of growing rods used in the management of early onset scoliosis

INTRODUCTION Managing spinal deformities in young children is challenging, particularly early onset scoliosis (EOS). Surgical intervention is often required if EOS has been unresponsive to conservative treatment particularly with rapidly progressive curves. An emerging treatment option for EOS is fusionless scoliosis surgery. Similar to bracing, this surgical option potentially harnesses growth, motion and function of the spine along with correcting spinal deformity. Dual growing rods are one such fusionless treatment, which aims to modulate growth of the vertebrae. The aim of this study was to ascertain the extent to which semiconstrained growing rods (Medtronic, Sofamor, Danek, Memphis, TN) with a telescopic sleeve component, reduce rotational constraint on the spine compared with standard "constrained / rigid" rods and hence potentially provide a more physiological mechanical environment for the growing spine. METHODS Six 40-60kg English Large White porcine spines served as a model for the paediatric human spine. Each spine was dissected into a 7 level thoracolumbar multi-segment unit (MSU), removing all non-ligamentous soft tissues and leaving 3cm of ribs either side. Pure nondestructive axial rotation moments of ±4Nm at a constant rotation rate of 8deg.s-1 were applied to the mounted MSU spines using a biaxial Instron testing machine. Displacement of each vertebral level was captured using a 3D motion tracking system (Optotrak 3020, Northern Digital Inc, Waterloo, ON). Each spine was tested in an un-instrumented state first and then with appropriately sized semi-constrained growing rods and rigid rods in alternating sequence. The rods were secured by multi-axial pedicle screws (Medtronic CD Horizon) at levels 2 and 6 of the construct. The range of motion (ROM), neutral zone (NZ) size and stiffness (Nm.deg-1) were calculated from the Instron load-displacement data and intervertebral ROM was calculated through a MATLAB algorithm from Optotrak data. RESULTS Irrespective of the order of testing, rigid rods significantly reduced the total ROM compared with semi-constrained rods (p<0.05) with in a significantly stiffer spine for both left and right axial rotation (p<0.05). Analysing the intervertebral motion within the instrumented levels 2-6, rigid rods showed reduced ROM compared with semi-constrained growing rods and compared with un-instrumented motion segments. CONCLUSION Semi-constrained growing rods maintain similar stiffness in axial rotation to un-instrumented spines, while dual rigid rods significantly reduce axial rotation. Clinically the effect of semi-constrained growing rods as observed in this study is that they would be expected to allow growth via the telescopic rod components while maintaining the axial flexibility of the spine, which may reduce occurrence of the crankshaft phenomenon.

A quantification of the interaction and spatial ordering in nano-arrays

This paper reports on the use of a local order measure to quantify the spatial ordering of a quantum dot array (QDA). By means of electron ground state energy analysis in a quantum dot pair, it is demonstrated that the length scale required for such a measure to characterize the opto-electronic properties of a QDA is of the order of a few QD radii. Therefore, as local order is the primary factor that affects the opto-electronic properties of an array of quantum dots of homogeneous size, this order was quantified through using the standard deviation of the nearest neighbor distances of the quantum dot ensemble. The local order measure is successfully applied to quantify spatial order in a range of experimentally synthesized and numerically generated arrays of nanoparticles. This measure is not limited to QDAs and has wide ranging applications in characterizing order in dense arrays of nanostructures.

Third harmonic generation of the surface wave in the semiconductor-metal slowing-down structure

A nonlinear process is considered of the surface wave third harmonics generation in a slowing-down semiconductor-metal structure. The process is conditioned by non-parabolicity of the charge carrier dispersion law. It is shown that in narrow-gap semiconducting materials it is necessary to account for the process together with the surface wave second harmonics generation conditioned by nonlinearity of quasi-hydrodynamics and the Maxwell equations. The conclusion is made that the third harmonies amplitude in narrow-gap semiconductors may exceed substantially the signal amplitude at the 3w frequency in a gas plasma and be of the same order with the surface waves second harmonies amplitude.

Metal artifacts from titanium and steel screws in CT, 1.5T and 3T MR images of the tibial Pilon: A quantitative assessment in 3D

Radiographs are commonly used to assess articular reduction of the distal tibia (pilon) fractures postoperatively, but may reveal malreductions inaccurately. While Magnetic Resonance Imaging (MRI) and Computed Tomography (CT) are potential 3D alternatives they generate metal-related artifacts. This study aims to quantify the artifact size from orthopaedic screws using CT, 1.5T and 3T MRI data. Three screws were inserted into one intact human cadaver ankle specimen proximal to and along the distal articular surface, then CT, 1.5T and 3T MRI scanned. Four types of screws were investigated: titanium alloy (TA), stainless steel (SS) (Ø = 3.5 mm), cannulated TA (CTA) and cannulated SS (CSS)(Ø = 4.0 mm, Ø empty core = 2.6 mm). 3D artifact models were reconstructed using adaptive thresholding. The artifact size was measured by calculating the perpendicular distance from the central screw axis to the boundary of the artifact in four anatomical directions with respect to the distal tibia. The artifact sizes (in the order of TA, SS, CTA and CSS) from CT were 2.0 mm, 2.6 mm, 1.6 mm and 2.0 mm; from 1.5T MRI they were 3.7 mm, 10.9 mm, 2.9 mm, and 9 mm; and 3T MRI they were 4.4 mm, 15.3 mm, 3.8 mm, and 11.6 mm respectively. Therefore, CT can be used as long as the screws are at a safe distance of about 2 mm from the articular surface. MRI can be used if the screws are at least 3 mm away from the articular surface except SS and CSS. Artifacts from steel screws were too large thus obstructed the pilon from being visualised in MRI. Significant differences (P < 0.05) were found in the size of artifacts between all imaging modalities, screw types and material types, except 1.5T versus 3T MRI for the SS screws (P = 0.063). CTA screws near the joint surface can improve postoperative assessment in CT and MRI. MRI presents a favourable non-ionising alternative when using titanium hardware. Since these factors may influence the quality of postoperative assessment, potential improvements in operative techniques should be considered.

Force-deformation properties of the human heel pad during barefoot walking

Introduction: The plantar heel pad is a specialized fibroadipose tissue that attenuates and, in part, dissipates the impact energy associated with heel strike. Although near maximal deformation of the heel pad has been shown during running, in vivo measurement of the deformation and structural properties of the heel pad during walking remains largely unexplored. This study employed a fluoroscope, synchronized with a pressure platform, to obtain force–deformation data for the heel pad during walking. Methods: Dynamic lateral foot radiographs were acquired from 6 male and 10 female adults (age, 45 ± 10 yrs; height, 1.66 ± 0.10 m; and weight, 80.7 ± 10.8 kg), while walking barefoot at preferred speeds. The inferior aspect of the calcaneus was digitized and the sagittal thickness and deformation of the heel pad relative to the support surface calculated. Simultaneous measurement of the peak force beneath the heel was used to estimate the principal structural properties of the heel pad. Results: Transient loading profiles associated with walking induced rapidly changing deformation rates in the heel pad and resulted in irregular load–deformation curves. The initial stiffness (32 ± 11 N.mm-1) of the heel pad was an order of magnitude lower than its final stiffness (212 ± 125 N.mm-1) and on average, only 1.0 J of energy was dissipated by the heel pad with each step during walking. Peak deformation (10.3 mm) approached that predicted for the limit of pain tolerance (10.7 mm). Conclusion: These findings suggest the heel pad operates close to its pain threshold even at speeds encountered during barefoot walking and provides insight as to why barefoot runners may adopt ‘forefoot’ strike patterns that minimize heel loading.

Self and other in communication and cognition : the role of auto-communication and intersubjectivity in autopoiesis of psychic systems

By referring to Niklas Luhmann's theory of self-referential systems, Aldo Mascareño (2008, submitted for publication) gives an account of system-environment interrelatedness, explaining how social and individual constitute each other through the process of communication and co-creation of meanings. Two possible extensions to his account are discussed. Firstly, auto-communication within the system that happens without any external reference needs to be taken into account while describing the existence and constant re-creation of psychic systems. Secondly, in order for the system and environment or two systems to communicate, an imagined and temporary intersubjectivity between the two needs to be assumed.

A vibrational spectroscopic study of the borate mineral ezcurrite Na4B10O17·7H2O – Implications for the molecular structure

We have studied the boron containing mineral ezcurrite Na4B10O17·7H2O using electron microscopy and vibrational spectroscopy. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm−1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1037 cm−1 is assigned to BO stretching vibration. Raman bands at 1129, 1163, 1193 cm−1 are attributed to BO stretching vibration of the tetrahedral units. The Raman band at 947 cm−1 is attributed to the antisymmetric stretching modes of tetrahedral boron. The sharp Raman peak at 1037 cm−1 is from the 11-B component such a mode, then it should have a smaller 10-B satellite near (1.03) × (1037) = 1048 cm−1, and indeed a small peak at 1048 is observed. The broad Raman bands at 3186, 3329, 3431, 3509, 3547 and 3576 cm−1 are assigned to water stretching vibrations. Broad infrared bands at 3170, 3322, 3419, 3450, 3493, 3542, 3577 and 3597 cm−1 are also assigned to water stretching vibrations. Infrared bands at 1330, 1352, 1389, 1407, 1421 and 1457 cm−1 are assigned to the antisymmetric stretching vibrations of trigonal boron. The observation of so many bands suggests that there is considerable variation in the structure of ezcurrite. Infrared bands at 1634, 1646 and 1681 cm−1 are assigned to water bending modes. The number of water bending modes is in harmony with the number of water stretching vibrations.

Structural characterization of the borate mineral inyoite – CaB3O3(OH)5⋅4(H2O)

We have studied the mineral Ca(H4B3O7)(OH)⋅4(H2O) or CaB3O3(OH)5⋅4(H2O) using electron microscopy and vibrational spectroscopy. The mineral has been characterized by a range of techniques including X-ray diffraction, thermal analysis, electron microscopy with EDX and vibrational spectroscopy. Electron microscopy shows a pure phase and the chemical analysis shows the presence of calcium only. The nominal resolution of the Raman spectrometer is of the order of 2 cm−1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. Raman and infrared bands are assigned to the stretching and bending modes of trigonal and tetrahedral boron and the stretching modes of the hydroxyl and water units. By using a combination of techniques we have characterized the borate mineral inyoite.

The molecular structure of the borate mineral szaibelyite MgBO2(OH): A vibrational spectroscopic study

We have studied the borate mineral szaibelyite MgBO2(OH) using electron microscopy and vibrational spectroscopy. EDS spectra show a phase composed of Mg with minor amounts of Fe. Both tetrahedral and trigonal boron units are observed. The nominal resolution of the Raman spectrometer is of the order of 2 cm−1 and as such is sufficient enough to identify separate bands for the stretching bands of the two boron isotopes. The Raman band at 1099 cm−1 with a shoulder band at 1093 cm−1 is assigned to BO stretching vibration. Raman bands at 1144, 1157, 1229, 1318 cm−1 are attributed to the BOH in-plane bending modes. Raman bands at 836 and 988 cm−1 are attributed to the antisymmetric stretching modes of tetrahedral boron. The infrared bands at 3559 and 3547 cm−1 are assigned to hydroxyl stretching vibrations. Broad infrared bands at 3269 and 3398 cm−1 are assigned to water stretching vibrations. Infrared bands at 1306, 1352, 1391, 1437 cm−1 are assigned to the antisymmetric stretching vibrations of trigonal boron. Vibrational spectroscopy enables aspects of the molecular structure of the borate mineral szaibelyite to be assessed.