Modeling the dynamics of tamponade multicomponent gases during retina reattachment surgery

Vitrectomy and pneumatic retinopexy are common surgical procedures used to treat retinal detachment. To reattach the retina, gases are used to inflate the vitreous space allowing the retina to attach by surface tension and buoyancy forces that are superior to the location of the bubble. These procedures require the injection of either a pure tamponade gas, such as C₃F₈ or SF₆, or mixtures of these gases with air. The location of the retinal detachment, the anatomical spread of the retinal defect, and the length of time the defect has persisted, will determine the suggested volume and duration of the gas bubble to allow reattachment. After inflation, the gases are slowly absorbed by the blood allowing the vitreous to be refilled by aqueous. We have developed a model of the mass transfer dynamics of tamponade gases during pneumatic retinopexy or pars plana vitrectomy procedures. The model predicts the expansion and persistence of intraocular gases (C₃F₈, SF₆), oxygen, nitrogen, and carbon dioxide, as well as the intraocular pressure. The model was validated using published literature in rabbits and humans. In addition to correlating the mass transfer dynamics by surface area, permeability, and partial pressure driving forces, the mass transfer dynamics are affected by the percentage of the tamponade gases. Rates were also correlated with the physical properties of the tamponade and blood gases. The model gave accurate predictions in humans. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3651–3662, 2017     

Iterative Antimicrobial Candidate Selection from Informed D‐/L‐Peptide Dimer Libraries

Growing resistance to antibiotics, as well as newly emerging pathogens, stimulate the investigation of antimicrobial peptides (AMPs) as therapeutic agents. Here, we report a new library design concept based on a stochastic distribution of natural AMP amino acid sequences onto half‐length synthetic peptides. For these compounds, a non‐natural motif of alternating D ‐ and L ‐backbone stereochemistry of the peptide chain predisposed for β‐helix formation was explored. Synthetic D ‐/L ‐peptides with permuted half‐length sequences were delineated from a full‐length starter sequence and covalently recombined to create two‐dimensional compound arrays for antibacterial screening. Using the natural AMP magainin as a seed sequence, we identified and iteratively optimized hit compounds showing high antimicrobial activity against Gram‐positive and Gram‐negative bacteria with low hemolytic activity. Cryo‐electron microscopy characterized the membrane‐associated mechanism of action of the new D ‐/L ‐peptide antibiotics.     

The TRAPS Apparatus: Enhancing Target Density of Nanoparticle Beams in Vacuum for X-ray and Optical Spectroscopy

We present an experimental setup that allows the injection of charged nanoparticles in a diameter range of 3–15 nm into a vacuum chamber and their storage there in an electrodynamic cage. The nanoparticle density in the trap is limited by space charge and can be several orders of magnitude higher than in a free nanoparticle beam. The setup provides for the first time a tool for the application of advanced techniques of spectroscopy to free nanoparticles in this size range. It consists of a combination of (1) a plasma discharge nanoparticle source that generates a high density of nanoparticles of various composition suspended in helium carrier gas at a pressure of about 10–150 mbar, (2) an aerodynamic lens optimized for small particles (diameter 3–15 nm) that forms a well-collimated beam of charged nanoparticles and focuses it into (3) an octopole ion trap operated at low frequencies and filled with helium buffer gas at 10^?2 mbar in order to moderate and store the nanoparticles at densities of more than 10⁷ cm^?3.     

Strength degradation and failure limits of dense and porous ceramic membrane materials

Thin dense membrane layers, mechanically supported by porous substrates, are considered as the most efficient designs for oxygen supply units used in Oxy-fuel processes and membrane reactors. Based on the favorable permeation properties and chemical stability, several materials were suggested as promising membrane and substrate materials: Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ, La_0.6?xSr_0.4Co_0.2Fe_0.8O_3?δ (x = 0, 0.02) and Ce_0.9Gd_0.1O_1.95?δ. Although membranes operate at elevated temperatures, the ends of tubes in certain three-end concepts remain almost at room temperature. The current work concentrates on the failure potential of these membrane parts, where in a complex device also the highest residual stresses should arise due to differences in thermal expansion. In particular, sensitivity of the materials to subcritical crack growth was assessed since the long-term reliability of the component does not only depend on its initial strength, but also on strength degradation effects. The results were subsequently used as a basis for a strength–probability–time lifetime prediction.     

Development of a metallic/ceramic composite for the deposition of thin-film oxygen transport membrane

Asymmetric perovskite membranes have an attractive potential in the application of O₂/N₂ gas separation for future membrane-based power plants using oxyfuel technology. In this study – a metal-supported membrane structure with a thin-film perovskite layer and porous ceramic interlayers was developed. Porous NiCoCrAlY sintered at 1225 °C in H₂ was selected as the substrate based on a sufficient permeability and corrosion resistance in co-firing conditions. According to the oxidation behaviour of NiCoCrAlY, the temperature for co-firing of the substrate and the interlayers was defined as 1100 °C for 5 h in air. Two interlayers of La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ were applied by screen printing. The top layer was deposited by magnetron sputtering with a thickness of 3.8 μm. While gas-tightness was improved considerably, significant air-leakage was still detected. In summary, the successful development of a metal-perovskite-composite is shown, which acts as a basis for further development of a gas-tight metal-supported oxygen transport membrane structure.     

Exchanging the substrate specificities of pyruvate decarboxylase from Zymomonas mobilis and benzoylformate decarboxylase from Pseudomonas putida

Pyruvate decarboxylase from Zymomonas mobilis (PDC) and benzoylformate decarboxylase from Pseudomonas putida (BFD) are thiamine diphosphate-dependent enzymes that decarboxylate 2-keto acids. Although they share a common homotetrameric structure they have relatively low sequence similarity and different substrate spectra. PDC prefers short aliphatic substrates whereas BFD favours aromatic 2-keto acids. These preferences are also reflected in their carboligation reactions. PDC catalyses the conversion of benzaldehyde and acetaldehyde to (R)-phenylacetylcarbinol and predominantly (S)-acetoin, whereas (R)-benzoin and mainly (S)-2-hydroxypropiophenone are the products of BFD catalysis. Comparison of the X-ray structures of both enzymes identified two residues in each that were likely to be involved in determining substrate specificity. Site-directed mutagenesis was used to interchange these residues in both BFD and PDC. The substrate range and kinetic parameters for the decarboxylation reaction were studied for each variant. The most successful variants, PDCI472A and BFDA460I, catalysed the decarboxylation of benzoylformate and pyruvate, respectively, although both variants now preferred the long-chain aliphatic substrates, 2-ketopentanoic and 2-ketohexanoic acid. With respect to the carboligase activity, PDCI472A proved to be a real chimera between PDC and BFD whereas BFDA460I/F464I provided the most interesting result with an almost complete reversal of the stereochemistry of its 2-hydroxypropiophenone product.     

Creep behavior and its correlation with defect chemistry of La0.58Sr0.4Co0.2Fe0.8O3−δ

The creep behavior of La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) perovskite was studied in the temperature range 750–950 °C in air and vacuum (P_O2 ≈ 4 mbar). A transition in the apparent activation energy was found between 800 and 850 °C for both oxygen partial pressures. The apparent activation energy is ～250 kJ mol^?1 for the temperature range 700–800 °C under vacuum (P_O2 ≈ 4 mbar) and ～480 kJ mol^?1 for 850–950 °C in both atmospheres. Above 850 °C, the creep rate of LSCF is higher in vacuum than in air although the same cubic structure exists. The stress exponent of the creep law is in the range 1.9–2.5 for all temperatures, which excludes a transition of creep mechanism. It is suggested that, below 800 °C, cation vacancies originate from the necessary balance with the substituted cations in LSCF, and the determined activation energy reflects the energy barrier for cation migration via these vacancies. Above 850 °C, additional vacancies appear to be formed intrinsically, and the activation energy represents the sum of the thermally activated formation energy of cation vacancies and migration energy of cations.     

Evaluation and simulation of the peel behavior of polyethylene/polybutene‐1 peel systems

The peel characteristics of sealed low‐density polyethylene/isotactic polybutene‐1 (PE‐LD/iPB‐1) films, with different contents of iPB‐1 up to 20 m.‐% (mass percentage), were evaluated and simulated in dependence on the iPB‐1 content, and in dependence on the peel rate. Sealing involves close contact and localized melting of two films for a few seconds. The required force, to separate the local adhered films, is the peel force, which is influenced, among others, by the content of iPB‐1. The peel force decreases exponentially with increasing iPB‐1 content. Transmission electron microscopy studies reveal a favorable dispersion of the iPB‐1 particles within the seal area, for iPB‐1 concentrations ≥6 m.‐%. Here, the iPB‐1 particles form continuous belt‐like structures, which lead to a stable and reproducible peel process. The investigation of the peel rate‐dependency on the peel characteristics is of important interest for practical applications. The peel force increases with increasing peel rate by an exponential law. A numerical simulation of the present material system proves to be useful to comprehend the peel process, and to understand the peel behavior in further detail. Peel tests of different peel samples were simulated, using a two‐dimensional finite element model, including cohesive zone elements. The established finite element model of the peel process was used to simulate the influence of the modulus of elasticity on the peel behavior. The peel force is independent of the modulus of elasticity, however, the peel initiation value increases with increasing modulus of elasticity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of the Spray Angle on the Properties of HVOF Sprayed WC–Co Coatings Using (−10 + 2 μm) Fine Powders

The application of fine powders in thermal spray technology represents an innovative approach to apply dense and smooth near-net shape coatings on tools with complex geometry. However, this aim can only be achieved as long as the influence of the handling parameters of the spray process, such as the spray angle, is sufficiently understood. In this study, the influence of the spray angle on the deposition rate as well as on the coating properties (microhardness, roughness, and porosity) of HVOF-sprayed, fine-structured coatings are investigated. A fine, agglomerated, and sintered WC-12Co powder (agglomerate size: 2-10 μm, WC-particle Fisher sub-sieve size = 400 nm) was used as feedstock material. It has been shown that HVOF spraying of fine powders is less susceptible to an alteration of the spray angle than most other thermal spray processes such as plasma- or arc-spraying. The reduction of the spray angle results in a decrease in the deposition rate, while no significant degradation of the coating properties is found up to 30°. However, at spray angles below 30° the coating strength is negatively affected by the formation of pores and cracks.