Rearrangement of α-pinene oxide using a surface catalysed spinning disc reactor (SDR)

Isomerisation of α-pinene oxide to campholenic aldehyde was performed by immobilising zinc triflate based catalysts on the surface of a spinning disc reactor (SDR). Two types of catalyst have been studied and the influence of operating parameters such as rotational speed, feed flow rate and reaction temperature on conversion and selectivity towards campholenic aldehyde has been investigated in considerable detail. The findings of the study suggest that immobilising the catalyst on the reactor surface and performing the reaction in continuous mode has potential for achieving benefits of Green Chemical Technology (GCT).

A new non-contact optical device for ocular biometry

Background: A new commercially available device (IOLMaster, Zeiss Instruments) provides high resolution non-contact measurements of axial length (using partial coherent interferometry), anterior chamber depth, and corneal radius (using image analysis). The study evaluates the validity and repeatability of these measurements and compares the findings with those obtained from instrumentation currently used in clinical practice. Method: Measurements were taken on 52 subjects (104 eyes) aged 18-40 years with a range of mean spherical refractive error from +7.0 D to -9.50 D. IOLMaster measurements of anterior chamber depth and axial length were compared with A-scan applanation ultrasonography (Storz Omega) and those for corneal radius with a Javal-Schiötz keratometer (Topcon) and an EyeSys corneal videokeratoscope. Results: Axial length: the difference between IOLMaster and ultrasound measures was insignificant (0.02 (SD 0.32) mm, p = 0.47) with no bias across the range sampled (22.40-27.99 mm). Anterior chamber depth: significantly shorter depths than ultrasound were found with the IOLMaster (-0.06 (0.25) mm, p <0.02) with no bias across the range sampled (2.85-4.40 mm). Corneal radius: IOLMaster measurements matched more closely those of the keratometer than those of the videokeratoscope (mean difference -0.03 v -0.06 mm respectively), but were more variable (95% confidence 0.13 v 0.07 mm). The repeatability of all the above IOLMaster biometric measures was found to be of a high order with no significant bias across the measurement ranges sampled. Conclusions: The validity and repeatability of measurements provided by the IOLMaster will augment future studies in ocular biometry.

Poly(methyl methacrylate) model study of optical surface quality after excimer laser photorefractive keratectomy

Purpose: To evaluate lenses produced by excimer laser ablation of poly(methyl methacrylate) (PMMA) plates. Setting: University research laboratory. Methods: Two Nidek EC-5000 scanning-slit excimer laser systems were used to ablate plane-parallel plates of PMMA. The ablated lenses were examined by focimetry, interferometry, and mechanical surface profiling. Results: The spherical optical powers of the lenses matched the expected values, but the cylindrical powers were generally lower than intended. Interferometry revealed marked irregularity in the surface of negative corrections, which often had a positive “island” at their center. Positive corrections were generally smoother. These findings were supported by the results of mechanical profiling. Contrast sensitivity measurements carried out when observing through ablated lenses whose power had been neutralized with a suitable spectacle lens of opposite sign confirmed that the surface irregularities of the ablated lenses markedly reduced contrast sensitivity over a range of spatial frequencies. Conclusion: Improvements in beam delivery systems seem desirable.

Abnormal systemic and ocular vascular response to temperature provocation in primary open-angle glaucoma patients:a case for autonomic failure?

PURPOSE. To assess systemic and ocular vascular reactivity in response to warm and cold provocation in untreated patients with primary open-angle glaucoma and normal control subjects. METHODS. Twenty-four patients with primary open-angle glaucoma and 22 normal control subjects were subjected to a modified cold pressor test involving immersion of the right hand in 40°C warm water followed by 4°C cold water exposure, and finger and ocular blood flow were assessed by means of peripheral laser Doppler flowmetry and retinal flowmetry, respectively. Finger and body temperature as well as intraocular pressure, systemic blood pressure, systemic pulse pressure, heart rate, and ocular perfusion pressure were also monitored. RESULTS. The patients with glaucoma demonstrated an increase in diastolic blood pressure (P = 0.023), heart rate (P = 0.010), and mean ocular perfusion pressure (P = 0.039) during immersion of the tested hand in 40°C water. During cold provocation, the patients demonstrated a significant decrease in finger (P = 0.0003) and ocular blood flow (the parameter velocity measured at the temporal neuroretinal rim area; P = 0.021). Normal subjects did not demonstrate any blood flow or finger temperature changes during immersion of the tested hand in 40°C water (P > 0.05); however, they exhibited increases in systolic blood pressure (P = 0.034) and pulse pressure (P = 0.0009) and a decrease in finger blood flow (P = 0.0001) during cold provocation. In normal subjects, the ocular blood flow was unchanged during high- and low-temperature challenge. CONCLUSIONS. Cold provocation elicits a different blood pressure, and ocular blood flow response in patients with primary open-angle glaucoma compared with control subjects. These findings suggest a systemic autonomic failure and ocular vascular dysregulation in POAG patients.

Integrated optimisation of surface roughness and tool performance when face milling 416 SS

Tool life is an important factor to be considered during the optimisation of a machining process since cutting parameters can be adjusted to optimise tool changing, reducing cost and time of production. Also the performance of a tool is directly linked to the generated surface roughness and this is important in cases where there are strict surface quality requirements. The prediction of tool life and the resulting surface roughness in milling operations has attracted considerable research efforts. The research reported herein is focused on defining the influence of milling cutting parameters such as cutting speed, feed rate and axial depth of cut, on three major tool performance parameters namely, tool life, material removal and surface roughness. The research is seeking to define methods that will allow the selection of optimal parameters for best tool performance when face milling 416 stainless steel bars. For this study the Taguchi method was applied in a special design of an orthogonal array that allows studying the entire parameter space with only a number of experiments representing savings in cost and time of experiments. The findings were that the cutting speed has the most influence on tool life and surface roughness and very limited influence on material removal. By last tool life can be judged either from tool life or volume of material removal.

CD4+ T cell surface alpha enolase is lower in older adults

To identify novel cell ageing markers in order to gain insight into ageing mechanisms, we adopted membrane enrichment and comparison of the CD4+ T cell membrane proteome (purified by cell surface labelling using Sulfo-NHS-SS-Biotin reagent) between healthy young (n=9, 20-25y) and older (n=10; 50-70y) male adults. Following two-dimensional gel electrophoresis (2DE) to separate pooled membrane proteins in triplicates, the identity of protein spots with age-dependent differences (p<0.05 and >1.4 fold difference) was determined using liquid chromatography-mass spectrometry (LC-MS/MS). Seventeen protein spot density differences (ten increased and seven decreased in the older adult group) were observed between young and older adults. From spot intensity analysis, CD4+ T cell surface α-enolase was decreased in expression by 1.5 fold in the older age group; this was verified by flow cytometry (n=22) and qPCR with significantly lower expression of cellular α-enolase mRNA and protein compared to young adult CD4+ T cells (p<0.05). In an independent age-matched case-control study, lower CD4+ T cell surface α-enolase expression was observed in age-matched patients with cardiovascular disease (p<0.05). An immune-modulatory role has been proposed for surface α-enolase and our findings of decreased expression suggest that deficits in surface α-enolase merit investigation in the context of immune dysfunction during ageing and vascular disease.

Investigating ocular allergy:can we determine a better measurement?

Objective: Ocular allergy is a broad group of allergic conditions involving inflammation of the conjunctiva and the most common forms are seasonal allergic conjunctivitis (SAC; 90% of cases) and perennial allergic conjunctivitis (PAC; 5% of cases). The main symptom is ocular itching caused by mast cell degranulation leading to the release of histamine and other mediators such as tryptase. Tryptase is a neutral protease that is selectively concentrated in the secretory granules of human mast cells and has been shown to be a sensitive and specific marker of type I hypersensitivity reaction. The objective was to ascertain the best assay method for determining the tryptase levels in tear samples and whether this can be used to determine the efficacy of non-pharmacological treatments compared to no treatment or their combined effect with anti-allergic medication for SAC and PAC. Method: Thirty patients with a history of SAC were recruited into a randomised blind study during winter months when all the patients were asymptomatic. Suitability was determined by skin prick and conjunctival provocation tests. Patients were randomly assigned to either a non-pharmacological or a pharmacological Intervention group and received each test condition assigned to their group in a randomly assigned order. Symptoms were provoked by exposure to pollen in an environmental test chamber where the temperature, humidity and grass pollen levels were set to a high pollen count day. Tear samples were taken set intervals during the visit and then processed by enzyme linked immunosorbent assay (ELISA) for the detection of tryptase levels. Preliminary results: Results are still being analysed but the preliminary optimisation experiments tested four different ELISA systems; two indirect assays and two capture ‹sandwich› assays. The results suggest that in both sandwich assay systems non-specific binding occurred which could not be easily overcome. The indirect assay systems both showed specific reactions, and the sensitivity achieved was greater with the monoclonal than the polyclonal antibody. Using these findings the indirect assay system was optimised to provide a standardised system for measuring tryptase. Initial trials using human tear samples displayed tryptase levels between 23.1 and 175.1 ng/ml; levels which fall within the anticipated range for patients with SAC. Further statistical work is needed to determine whether tryptase levels vary between the treatments 75.

Sonogashira cross-coupling and homocoupling on a silver surface:chlorobenzene and phenylacetylene on Ag(100)

Scanning tunneling microscopy, temperature-programmed reaction, near-edge X-ray absorption fine structure spectroscopy, and density functional theory calculations were used to study the adsorption and reactions of phenylacetylene and chlorobenzene on Ag(100). In the absence of solvent molecules and additives, these molecules underwent homocoupling and Sonogashira cross-coupling in an unambiguously heterogeneous mode. Of particular interest is the use of silver, previously unexplored, and chlorobenzene—normally regarded as relatively inert in such reactions. Both molecules adopt an essentially flat-lying conformation for which the observed and calculated adsorption energies are in reasonable agreement. Their magnitudes indicate that in both cases adsorption is predominantly due to dispersion forces for which interaction nevertheless leads to chemical activation and reaction. Both adsorbates exhibited pronounced island formation, thought to limit chemical activity under the conditions used and posited to occur at island boundaries, as was indeed observed in the case of phenylacetylene. The implications of these findings for the development of practical catalytic systems are considered.

Development of thresholds for surface preparation in repair systems with wet lay -up fiber reinforced polymers

Bonded repair of concrete structures with fiber reinforced polymer (FRP) systems is increasingly being accepted as a cost-efficient and structurally viable method of rapid rehabilitation of concrete structures. However, the relationships between long-term performance attributes, service-life, and details of the installation process are not easy to quantify. Accordingly, there is currently a lack of generally accepted construction specifications, making it difficult for the field engineer to certify the adequacy of the construction process. ^ The objective of the present study, as part of the National Cooperative Highway Research Program (NCHRP) Project 10-59B, was to investigate the effect of surface preparation on the behavior of wet lay-up FRP repair systems and consequently develop rational thresholds that provide sufficient performance. ^ The research program was comprised of both experimental and analytical work for wet lay-up FRP applications. The experimental work included flexure testing of sixty-seven (67) reinforced concrete beams and bond testing of ten (10) reinforced concrete blocks. Four different parameters were studied: surface roughness, surface flatness, surface voids and bug holes, and surface cracks/cuts. The findings were analyzed from various aspects and compared with the data available in the literature. As part of the analytical work, finite element models of the flexural specimens with surface flaws were developed using ANSYS. The purpose of this part was to extend the parametric study on the effects of concrete surface flaws and verify the experimental results based on nonlinear finite element analysis. ^ Test results showed that surface roughness does not appear to have a significant influence on the overall performance of the wet lay-up FRP systems with or without adequate anchorage, and whether failure was by debonding or rupture of FRP. Both experimental and analytical results for surface flatness proved that peaks on concrete surface, in the range studied, do not have a significant effect on the performance of wet lay-up FRP systems. However, valleys of particular size could reduce the strength of wet lay-up FRP systems. Test results regarding surface voids and surface cracks/cuts revealed that previously suggested thresholds for these flaws appear to be conservative, as also confirmed by analytical study. ^

Evidence of Recent Phosphorus Enrichment in Surface Soils of Taylor Slough and Northeast Everglades National Park

Everglades National Park (ENP) is the last hydrologic unit in the series of impounded marsh units that make up the present-day Everglades. The ENP receives water from upstream Water Conservation Areas via canals and water control structures that are highly regulated for flood control, water supply, wildlife management, concerns about poor water quality and the potential for downstream ecosystem degradation. Recent surveys of surface soils in ENP, designed for random sampling for spatial analysis of soil nutrients, did not sample proximate to inflow structures and thus did not detect increased soil phosphorus associated with these water conveyances. This study specifically addressed these areas in a focused sampling effort at three key inflow points in northeast ENP which revealed elevated soil TP proximate to inflows. Two transects extending down Shark River Slough and one down Taylor Slough (a natural watershed of particular ecological value) were found to have soil TP levels in excess of 500 mg kg−1—a threshold above which P enrichment is indicated. These findings suggest the negative impact of elevated water (P) from surface flows and support the assertion that significant soil TP enrichment is occurring in Taylor Slough and other areas of northeastern ENP.

Basic measurements of radiation from the Baseline Surface Radiation Network (BSRN) in the years 1992 to 2012, reference list of 6378 datasets

In the framework of the global energy balance, the radiative energy exchanges between Sun, Earth and space are now accurately quantified from new satellite missions. Much less is known about the magnitude of the energy flows within the climate system and at the Earth surface, which cannot be directly measured by satellites. In addition to satellite observations, here we make extensive use of the growing number of surface observations to constrain the global energy balance not only from space, but also from the surface. We combine these observations with the latest modeling efforts performed for the 5th IPCC assessment report to infer best estimates for the global mean surface radiative components. Our analyses favor global mean downward surface solar and thermal radiation values near 185 and 342 Wm**-2, respectively, which are most compatible with surface observations. Combined with an estimated surface absorbed solar radiation and thermal emission of 161 Wm**-2 and 397 Wm**-2, respectively, this leaves 106 Wm**-2 of surface net radiation available for distribution amongst the non-radiative surface energy balance components. The climate models overestimate the downward solar and underestimate the downward thermal radiation, thereby simulating nevertheless an adequate global mean surface net radiation by error compensation. This also suggests that, globally, the simulated surface sensible and latent heat fluxes, around 20 and 85 Wm**-2 on average, state realistic values. The findings of this study are compiled into a new global energy balance diagram, which may be able to reconcile currently disputed inconsistencies between energy and water cycle estimates.

Biogenic components, major, trace and rare earth elements of equatorial Pacific Ocean surface sediments (Table 1)

We have analyzed the major, trace, and rare earth element composition of surface sediments collected from a transect across the Equator at 135°W longitude in the Pacific Ocean. Comparing the behavior of this suite of elements to the CaCO3, opal, and Corg fluxes (which record sharp maxima at the Equator, previously documented at the same sampling stations) enables us to assess the relative significance of the various pathways by which trace elements are transported to the equatorial Pacific seafloor. The 1. (1) high biogenic source at the Equator, associated with equatorial divergence of surface water and upwelling of nutrient-rich water, and 2. (2) high aluminosilicate flux at 4°N, associated with increased terrigenous input from elevated rainfall at the Intertropical Convergence Zone (ITCZ) of the tradewinds, are the two most important fluxes with which elemental transport is affiliated. The biogenic flux at the Equator transports Ca and Sr structurally bound to carbonate tests and Mn primarily as an adsorbed component. Trace elements such as Cr, As, Pb, and the REEs are also influenced by the biogenic flux at the Equator, although this affiliation is not regionally dominant. Normative calculations suggest that extremely large fluxes of Ba and P at the Equator are carried by only small proportions of barite and apatite phases. The high terrigenous flux at the ITCZ has a profound effect on chemical transport to the seafloor, with elemental fluxes increasing tremendously and in parallel with Ti. Normative calculations, however, indicate that these fluxes are far in excess of what can be supplied by lattice-bound terrigenous phases. The accumulation of Ba is greater than is affiliated with biogenic transport at the Equator, while the P flux at the ITCZ is only 10% less than at the Equator. This challenges the common view that Ba and P are essentially exclusively associated with biogenic fluxes. Many other elements (including Mn, Pb, As, and REEs) also record greater accumulation beneath the ITCZ than at the Equator. Thus, adsorptive scavenging by terrigenous paniculate matter, or phases intimately associated with them, appears to be an extremely important process regulating elemental transport to the equatorial Pacific seafloor. These findings emphasize the role of vertical transport to the sediment, and provide additional constraints on the paleochemical use of trace elements to track biogenic and terrigenous fluxes.

Dinocyst-derived sea-surface characteristics, palynomorph abundances, ice-rafted debris, and planktonic foraminifera abundances and d18O of the 35-41 ka BP interval of core MD99-2285

The last glacial millennial climatic events (i.e. Dansgaard-Oeschger and Heinrich events) constitute outstanding case studies of coupled atmosphere-ocean-cryosphere interactions. Here, we investigate the evolution of sea-surface and subsurface conditions, in terms of temperature, salinity and sea ice cover, at very high-resolution (mean resolution between 55 and 155 years depending on proxies) during the 35-41 ka cal BP interval covering three Dansgaard-Oeschger cycles and including Heinrich event 4, in a new unpublished marine record, i.e. the MD99-2285 core (62.69°N; -3.57s°E). We use a large panel of complementary tools, which notably includes dinocyst-derived sea-ice cover duration quantifications. The high temporal resolution and multiproxy approach of this work allows us to identify the sequence of processes and to assess ocean-cryosphere interactions occurring during these periodic ice-sheet collapse events. Our results evidence a paradoxical hydrological scheme where (i) Greenland interstadials are marked by a homogeneous and cold upper water column, with intensive winter sea ice formation and summer sea ice melting, and (ii) Greenland and Heinrich stadials are characterized by a very warm and low saline surface layer with iceberg calving and reduced sea ice formation, separated by a strong halocline from a less warm and saltier subsurface layer. Our work also suggests that this stadial surface/subsurface warming started before massive iceberg release, in relation with warm Atlantic water advection. These findings thus support the theory that upper ocean warming might have triggered European ice-sheet destabilization. Besides, previous paleoceanographic studies conducted along the Atlantic inflow pathways close to the edge of European ice-sheets suggest that such a feature might have occurred in this whole area. Nonetheless, additional high resolution paleoreconstructions are required to confirm such a regional scheme.

Microparticle surface layering through dry coating:impact of moisture content and process parameters on the properties of orally disintegrating tablets

OBJECTIVES: The aim of this study was to investigate the influence of process parameters during dry coating on particle and dosage form properties upon varying the surface adsorbed moisture of microcrystalline cellulose (MCC), a model filler/binder for orally disintegrating tablets (ODTs). METHODS: The moisture content of MCC was optimised using the spray water method and analysed using thermogravimetric analysis. Microproperty/macroproperty assessment was investigated using atomic force microscopy, nano-indentation, scanning electron microscopy, tablet hardness and disintegration testing. KEY FINDINGS: The results showed that MCC demonstrated its best flowability at a moisture content of 11.2% w/w when compared to control, comprising of 3.9% w/w moisture. The use of the composite powder coating process (without air) resulted in up to 80% increase in tablet hardness, when compared to the control. The study also demonstrated that surface adsorbed moisture can be displaced upon addition of excipients during dry processing circumventing the need for particle drying before tabletting. CONCLUSIONS: It was concluded that MCC with a moisture content of 11% w/w provides a good balance between powder flowability and favourable ODT characteristics.

Charge compensation and Ce3+ formation in trivalent doping of the CeO2(110) surface: The key role of dopant ionic radius

In this paper, we use density functional theory corrected for on-site Coulomb interactions (DFT + U) and hybrid DFT (HSE06 functional) to study the defects formed when the ceria (110) surface is doped with a series of trivalent dopants, namely, Al3+, Sc3+, Y3+, and In 3+. Using the hybrid DFT HSE06 exchange-correlation functional as a benchmark, we show that doping the (110) surface with a single trivalent ion leads to formation of a localized MCe / + O O • (M = the 3+ dopant), O- hole state, confirming the description found with DFT + U. We use DFT + U to investigate the energetics of dopant compensation through formation of the 2MCe ′ +VO ̈ defect, that is, compensation of two dopants with an oxygen vacancy. In conjunction with earlier work on La-doped CeO2, we find that the stability of the compensating anion vacancy depends on the dopant ionic radius. For Al3+, which has the smallest ionic radius, and Sc3+ and In3+, with intermediate ionic radii, formation of a compensating oxygen vacancy is stable. On the other hand, the Y3+ dopant, with an ionic radius close to that of Ce4+, shows a positive anion vacancy formation energy, as does La3+, which is larger than Ce4+ (J. Phys.: Condens. Matter 2010, 20, 135004). When considering the resulting electronic structure, in Al3+ doping, oxygen hole compensation is found. However, Sc 3+, In3+, and Y3+ show the formation of a reduced Ce3+ cation and an uncompensated oxygen hole, similar to La3+. These results suggest that the ionic radius of trivalent dopants strongly influences the final defect formed when doping ceria with 3+ cations. In light of these findings, experimental investigations of these systems will be welcome.