Adhesion between oppositely charged polyelectrolytes

The adhesion between a grafted polyelectrolyte layer (brush) and a gel of an oppositely charged polyelectrolyte has been measured as a function of applied pressure, and the interface has been traced using neutron reflectometry. The interface (in aqueous medium at pH 6) between the (polycationic) brush and the (polyanionic) gel has a limited pressure dependence, with a small amount of deformation of the interface at the brush–gel contact. Brushes with a dry thickness of up to 13 nm exhibit weak adhesion (measured using a mechanical force tester) with an adhesive failure when the gel is detached. Thicker brushes result in the gel exhibiting cohesive failure. Reversing the geometry, whereby a polycationic brush is replaced with a polyanion and the polyanionic gel is replaced with a polycation, reveals that the pH dependence of the adhesion is moderately symmetric about pH 6, but that the maximum force required to separate the polycation gel from the polyanion brush over the range of pH is greater than that for the polycation brush and polyanion gel. The polyanion used is poly(methacrylic acid) (PMAA) and polycations of poly[2-(diethylamino)ethyl methacrylate] (PDEAEMA) and poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) were used.     

Interdependence of Escherichia coli formate dehydrogenase and hydrogen-producing hydrogenases during mixed carbon sources fermentation at different pHs

The impact of the four membrane-bound [NiFe]-hydrogenases (Hyd) of Escherichia coli on total H₂-oxidizing activity during fermentation of a mixture of glucose, glycerol and formate at different pHs was examined. It was shown that Hyd-2 had a major contribution to total Hyd activity at pH 7.5 in early-stationary phase (24 h) cells, while the main contribution was made by Hyd-3 in late-stationary phase (72 h). Hyd-4-dependent Hyd activity could be demonstrated at pH 6.5 in cells lacking Hyd-1, Hyd-2 and Hyd-3. at pH 7.5 Hyd-4-dependent formate dehydrogenase (FDH-H) activity was demonstrated. Growth properties and fermentation end product patterns during 72 h demonstrated that the cells retained viability deep into stationary phase. Our findings emphasize the importance of formate in modulating H₂ metabolism, presumably by contributing to maintain redox, pH and pmf balance. This is important for regulating and enhancing H₂ production when a mixture of carbon sources is applied.     

Processing and electromechanical properties of high-coercive field ZnO-doped PIN-PZN-PT ceramics

This study explores sintering and piezoelectricity of ZnO-doped perovskite Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PZN-PT) ceramics. The enhanced densification of ZnO-doped PIN-PZN-PT is attributed to the formation of oxygen vacancies by the incorporation of Zn²⁺ into the perovskite B-site and increased rate of bulk diffusion relative to undoped PIN-PZN-PT. Incorporation of Zn²⁺ into the perovskite lattice increased the tetragonal character of PIN-PZN-PT as demonstrated by tetragonal peak splitting and increased Curie temperature. Sintering in flowing oxygen reduced the solubility of Zn²⁺ in the perovskite lattice and resulted in rhombohedral PIN-PZN-PT. Sintering in oxygen prevented secondary phase formation which resulted in a high-piezoelectric coefficient (d₃₃ – 550 pC/N), high-coercive field (E_c – 13 kV/cm), and high-rhombohedral to tetragonal phase transition temperature (T_r-t – 165°C). We conclude that ZnO-doped PIN-PZN-PT ceramics are excellent candidates for high-power transducer applications.     

Microstructure-properties relationship in two Al-Mg-Si alloys through a combination of extrusion and aging

Aluminum alloys containing magnesium and silicon as the major solutes are strengthened by precipitation of the metastable precursors (β″) of the equilibrium β (Mg₂Si) phase. In this study, dynamic aging of two Al-Mg-Si alloys—the 6061 (Al-1.34% Mg₂Si) and 6069 (Al-2.25% Mg₂Si) alloys—was conducted through equal channel angular extrusion (ECAE). Equal channel angular extrusion-assisted dynamic aging provides the potential for improving mechanical properties. The aging time scale is reduced from ∼1,000 min. for conventional static peak aging to ∼10 min. by using ECAE-assisted dynamic aging. Compared to the significant strengthening effect in static aging treatment, a notable further increase in ultimate tensile strength is achieved by dynamic aging: over 40 MPa for the 6061 alloy and 100 MPa for the 6069 alloy. Microstructures of both aged alloys were characterized using transmission electron microscopy; dislocation-assisted precipitation was observed to be the primary precipitate nucleation and growth mechanism during the dynamic aging process. It is concluded that ECAE-assisted dynamic aging is controllable and efficient in executing aging treatment that could result in superior mechanical properties of Al-Mg-Si alloys.     

A review of rapid microwave fixation technology: Its expanding niche in morphologic studies

Microwave (MW) fixation methods are important because excellent preservation of both cell structure and antigenicity can be attained several orders of magnitude faster than by routine chemical fixation methods. However, because of the limitations of commercial MW ovens, fixation results are often irreproducible. We present a standardization protocol for MW fixation in household MW ovens that emphasizes magnetron warm-up; the use of a water load during sample irradiation, of an agar/saline/Giemsa model to evaluate uniformity of irradiation within the MW cavity, and of specimen containers with one dimension less than 1.5 cm; and fast specimen handling to prevent conductive heating artifacts after irradiation. We describe a prototypic MW device that improves the precision of sample irradiation and fixes blocks of tissue and cells in suspension in milliseconds. The solutions used to immerse the specimen during irradiation influence the specimen morphology. Aldehyde- or osmium-containing solutions used simultaneously with MW irradiation resulted in the best morphologic preservation of specimens up to 1 cm³. Using MW fixation methods and a postembedding, ultrastructural immunogold-labeling approach, we have localized granule chymase and histamine in rat mast cells and amylase in rat parotid acinar cells.     

Editorial: 50 Years of High Impact Research

Metallurgical and Materials Transactions A -     

Breeding birds and anurans of dynamic coastal wetlands in Green Bay,Lake Michigan

Breeding birds and anurans (frogs and toads) in coastal wetlands of Green Bay, Lake Michigan vary dynamically with changing water levels, habitat type, and geography. We describe species assemblages over a seven-year period (2011–2017) beginning with historic low water levels followed by an increase in average lake level of 0.85?m. In general, species richness and abundance of marsh-obligate species responded positively to increasing water levels, although several species of shallow wetlands (sandhill crane, sedge wren, swamp sparrow, and American toad) showed the opposite trend. Anuran assemblages were more diverse in the middle and upper bay, coinciding with a well-established nutrient gradient from the hypereutrophic lower bay to more oligotrophic waters of the upper bay. Three marsh-obligate bird species (black tern, sandhill crane, and sedge wren) were significantly more abundant in the middle or upper bay while sora, American coot, and common gallinule were more abundant in the eutrophic lower bay. Our findings have several important implications for conservation. Inland wetlands near the coast (including diked wetlands) might play a key ecological role by providing refugia for some species during low water years. However, the importance of shallow coastal wetlands and nearshore gradients of wetland habitat might be overlooked during low water years; when high water returns, these areas can become extremely productive and species-rich.     

Pond and Irrigation Model (PIM): a Tool for Simultaneously Evaluating Pond Water Availability and Crop Irrigation Demand

Agricultural ponds are an important alternative source of water for crop irrigation to conserve surface and ground water resources. In recent years more such ponds have been constructed in Mississippi and around the world. There is currently, however, a lack of a tool to simultaneously estimate crop irrigation demand and pond water availability. In this study, a Pond-Irrigation Model (PIM) was developed to meet this need using STELLA (Structural Thinking, Experiential Learning Laboratory with Animation) software. PIM simulated crop land and agricultural pond hydrological processes such as surface runoff, soil drainage, and evapotranspiration as well as crop irrigation demand and pond water availability. More importantly, PIM was able to decide when to conduct crop irrigation based on management allowable depletion (MAD) root zone soil water content and to determine optimal ratios of agricultural pond size to crop land with sufficient pond water available for crop irrigation. As a case demonstration, the model was applied to concomitantly estimate row crops (i.e., corn, cotton, and soybeans) water irrigation demand and pond water availability in a farm located at East-central Mississippi. Simulations revealed that corn used more soil water for growth than soybeans, whereas soybeans needed more irrigation water than corn and occurred due to less rainwater available for soybeans growth. We also found that there was one time for corn, zero time for cotton, and two times for soybeans when the pond water level was drawn to near zero for irrigation from 2005 to 2014. PIM developed in this study is a useful tool for estimating crop irrigation demand and pond water availability simultaneously.     

Ultrafast Laser Manufacture of Stable,Efficient Ultrafine Noble Metal Catalysts Mediated with MOF Derived High Density Defective Metal Oxides

Supported metal nanoparticles (MNPs) undergo severe aggregation, especially when the interaction between MNPs and their supports are limited and weak where their performance deteriorates dramatically. This becomes more severe when catalysts are operated under high temperature. Here, it is reported that MNPs including Pt, Au, Rh, and Ru, with sub‐2 nm size can be stabilized on densely packed defective CeO₂ nanoparticles with sub‐5 nm size via strong coupling by direct laser conversion of corresponding metal ions encapsulated cerous metal–organic frameworks (Ce‐MOFs). Ce‐MOF serves as an ideal dispersion precursor to uniformly encapsulate noble metal ions in their orderly arranged pores. Ultrafast laser vaporization and cooling forms uniform, ultrasmall, well‐mixed, and exceptionally dense nanoparticles of metal and metal oxide concurrently. The laser‐induced ultrafast reaction (within tens of nanoseconds) facilitates the precipitation of CeO₂ nanoparticles with abundant surficial defects. Due to the well‐mixed ultrasmall Pt and CeO₂ components with strong coupling, this catalyst exhibits exceptionally high stability and activity both at low and high temperatures (170–1100 °C) for CO oxidation in long‐term operation, significantly exceeding catalysts prepared by traditional methods. The scalable feature of laser and huge MOF family make it a versatile method for the production of MNP‐based nanocomposites in wide applications.