Heterogeneous Reactions of Chlorine Nitrate and Dinitrogen Pentoxide on Sulfuric Acid Surfaces Representative of Global Stratospheric Aerosol Particles

Increasing evidence from field measurements, modeling studies, and laboratory experiments suggests that heterogeneous reactions on stratospheric sulfate aerosol particles can change the partitioning in the nitrogen and chlorine families and thereby affect global ozone levels. In this study, a Knudsen cell flow reactor was used to measure the uptake of ClONO₂ and N₂O₅ by sulfuric acid solutions representative of background and volcanic stratospheric aerosol particles. The uptake coefficient (γ) of chlorine nitrate on 50–75 wt% H₂SO₄ at 223 K was found to be markedly dependent on the acid concentration, with γ ranging from about 1 × 10⁻² to 1 × 10⁻⁴. These results are in good agreement with literature reports and the data fit the expression log γ= 1.87 – 0.074 × (wt% H₂SO₄). This reaction will thus have its largest impact when stratospheric temperatures are low and sulfuric acid aerosols are most dilute. Uptake of N₂O₅ was studied on solutions with compositions in the range 58–96 wt% H₂SO₄ at temperatures from 193 to 303 K. N₂O₅ reacted readily on sulfuric acid surfaces with uptake coefficients of about 0.06. The uptake coefficient was found to be independent of the sulfuric acid concentration and the solution temperature over the ranges studied. These results suggest that the reaction of N₂O₅ with H₂O will occur readily on sulfuric acid aerosol particles for most stratospheric conditions.     

Atmospheric Chemistry of 2-Ethyl Acrolein

The atmospheric oxidation of the unsaturated aldehyde 2-ethyl acrolein, CH₂=C(C₂H₅)CHO, has been studied in laboratory experiments involving the reaction of ozone with 2-ethyl acrolein in the dark (with cyclohexane added to scavenge the hydroxyl radical), and the sunlight irradiation of 2-ethyl acrolein with NO in air. The major carbonyl products of the 2-ethyl acrolein reaction with ozone are formaldehyde, acetaldehyde, and the dicarbonyl ethylglyoxal, CH₃CH₂COCHO. Sunlight irradiation of 2-ethyl acrolein and NO led to the formation of three carbonyls (formaldehyde, acetaldehyde, and ethylglyoxal) and three peroxyacyl nitrates, (RC(O)OONO₂), including PAN (R = CH₃), PPN (R = C₂H₅), and the unsaturated compound EPAN (R = CH₂=C(C₂H₅)). Mechanisms are outlined for the reactions of ozone and of the hydroxyl radical with 2-ethyl acrolein. These mechanisms are consistent with the observed carbonyl and peroxyacyl nitrate products. Thermal decomposition, a major atmospheric removal process for peroxyacyl nitrates, has been studied for EPAN. The decomposition rate of EPAN relative to that of PAN is 0.59–0.73 at 292–294 K and 1 atm of air. Atmospheric implications of these results are discussed.     

A Charged-Particle Detector Based on Proportional Tubes with a Segmented Cathode and Cathode Readout

A charged-particle detector based on proportional tubes with cathode readout is described. The cathode is sectionalized into 2.2 × 2.2-cm pads. The detector was tested on high-energy particle beams. At an anode-to-cathode distance of 1.1 cm, the spatial resolution was 1.25 mm along the anode wire. A simulation model of the detector on the basis of the measured pad-response function was proposed, compared to the experimental data, and used to calculate the two-track resolution. The detector can be used in various experiments as a large-area multiparticle two-coordinate detector.     

Metal-on-metal hip simulator study of increased wear particle surface area due to 'severe' patient activity

This study investigated changes in metal-on-metal (MOM) hip wear and wear particle characteristics arising from a more aggressive patient activity level compared with normal walking. The test hypothesis was that 'severe'-gait conditions will change wear, wear particle sizes, and morphology owing to a decline in joint lubrication. Four carbon MOM hip bearings 40 mm high were subjected to normal-walking and fast-jogging simulations in an orbital hip joint simulator with 25 per cent alpha-calf serum as a lubricant. Co-Cr-Mo wear particles were extracted using an enzymatic method, and prolate ellipsoid equations were used to estimate particle volume and surface area. Fast-jogging simulations generated a sevenfold increase in volumetric wear, a 33 per cent increase in mean wear particle size, and a threefold increase in the number of larger (needle) particles compared with walking. This resulted in a twentyfold increase in total wear particle surface area per 10(6) cycles compared with walking, thereby confirming our hypothesis. The clinical significance of this result suggests that highly active MOM patients may exhibit greater ion release than less active patients.     

Bioactivity evaluation of collagen-based scaffolds containing a series of Sr-doped melt-quench derived phosphate-based glasses

Phosphate-based glasses have been attracting attention due to their possible medical applications arising from unique dissolution characteristics in the human body leading to the possibility of new tissue regeneration. In this study, the leaching kinetics of a series of melt-quenched Sr-doped phosphate glasses are presented. Regardless of the presence of Sr, all the glasses have an initial linear and sustained release of the ions followed by a plateau. To guarantee proper nutritional support to the growing tissue during regeneration and to mimic the 3-dimensional architecture of tissues, organic scaffold systems have been developed. However, their poor mechanical strength has limited their application. To overcome this problem, cross-linkers can be used although this then limits the solubility of the materials. To succeed in dealing with such a limitation, in this paper, by freeze-drying, the aforementioned soluble melt-quenched phosphate glasses were combined as powders with collagen fibres from bovine achilles tendon to make degradable scaffolds. The scaffolds were characterized by SEM, EDX and BET. Changes to the dissolution behaviour of the glasses arising from the presence of collagen interacting with the ions leached were reported. Furthermore, the ability of the scaffolds to induce hydroxyapatite (HA) formation was evaluated: one the elaborated scaffold could grow an HA-like layer after a week in SBF. Based on the results obtained, a possible application in restorative dentistry is proposed for one or more materials.

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Aggregation‐Induced Nonlinear Optical Effects of AIEgen Nanocrystals for Ultradeep In Vivo Bioimaging

Nonlinear optical microscopy has become a powerful tool in bioimaging research due to its unique capabilities of deep optical sectioning, high‐spatial‐resolution imaging, and 3D reconstruction of biological specimens. Developing organic fluorescent probes with strong nonlinear optical effects, in particular third‐harmonic generation (THG), is promising for exploiting nonlinear microscopic imaging for biomedical applications. Herein, a simple method for preparing organic nanocrystals based on an aggregation‐induced emission (AIE) luminogen (DCCN) with bright near‐infrared emission is successfully demonstrated. Aggregation‐induced nonlinear optical effects, including two‐photon fluorescence (2PF), three‐photon fluorescence (3PF), and THG, of DCCN are observed in nanoparticles, especially for crystalline nanoparticles. The nanocrystals of DCCN are successfully applied for 2PF microscopy at 1040 nm NIR‐II excitation and THG microscopy at 1560 nm NIR‐II excitation, respectively, to reconstruct the 3D vasculature of the mouse cerebral vasculature. Impressively, the THG microscopy provides much higher spatial resolution and brightness than the 2PF microscopy and can visualize small vessels with diameters of ≈2.7 µm at the deepest depth of 800 µm in a mouse brain. Thus, this is expected to inspire new insights into the development of advanced AIE materials with multiple nonlinearity, in particular THG, for multimodal nonlinear optical microscopy.     

A numerical analysis of the elastic-plastic peel test

The adhesive fracture energy, G_c, is determined from two types of elastic-plastic peel tests (i.e. the single-arm 90° and T-peel methods) and a linear-elastic fracture-mechanics (LEFM) test method (i.e. the tapered double-cantilever beam, TDCB method). A rubber-toughened epoxy adhesive, with both aluminium-alloy and steel substrates, has been used in the present work to manufacture the bonded joints. The peel tests are then modelled using numerical methods. The overall approach to modelling the elastic-plastic peel tests is to employ a finite-element analysis (FEA) approach and to model the crack advance through the adhesive layer via a node-release technique, based upon attaining a critical plastic strain in the element immediately ahead of the crack tip. It is shown that this ‘critical plastic strain fracture model (CPSFM)’ results in predicted values of the steady-state peel loads which are in excellent agreement with the experimentally-measured values. Also, the resulting values of G_c, as determined using the FEA CPSFM approach, have been found to be in excellent agreement with values from previously-reported analytical and direct-measurement methods. Further, it has been found that the calculated values of G_c are independent of whether a standard LEFM test or an elastic-plastic peel test method is employed. Therefore, it has been demonstrated that the value of the adhesive fracture energy, G_c, is independent of the geometric parameters studied and the value of G_c is indeed a characteristic of the joint, in this case for cohesive fracture through the adhesive layer. Finally, it is noted that the FEA CPSFM approach promises considerable potential for the analysis of peel tests which involve very extensive plastic deformation of the peeling arm and for analysing, and predicting, the performance of more complex adhesively-bonded geometries which involve extensive plastic deformation of the substrates.