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At least 217 records · Page 12

Polyhydroxybutyrate laminated trilayer films with enhanced barrier and mechanical properties for active food packaging

Polysaccharides such as starch and chitosan have been explored for sustainable food packaging films. However, their inherent hydrophilicity and brittleness cause poor water vapor barrier performance and limited mechanical properties. To address these issues, starch was first functionalized with acetoacetate groups and subsequently blended with chitosan. Dynamic cross-linking occurred between the acetoacetate groups and the primary amine groups of chitosan, forming vinylogous urethane linkages that reduced the water solubility of the films while preserving high mechanical strength. With 30 wt% of glycerol as a plasticizer, the resulting films showed a tensile strength of up to 24.68 MPa and an elongation at break of up to 83.96%. To improve the barrier properties, poly(3-hydroxybutyrate) (PHB), plasticized with 5-15 wt% epoxidized vegetable oil, was laminated on top of the chitosan/modified starch films, resulting in a significantly reduced water vapor transmission rate (WVTR) of 66%. Additional components, such as food colors like β-carotene were incorporated into this layer to make UV-protective films. A third layer of PHB without active additives was then coated to further reduce WVTR by 99%. Therefore, this multilayer lamination strategy effectively enhanced the barrier and mechanical properties of the polysaccharide-based packaging films.

Active packaging↗

Regulation of adult cardiocyte growth: effects of active and passive mechanical loading

Fluctuations in hemodynamic load have been documented to modulate contractile protein turnover and myofibrillar structure in the heart; however, the relative importance of active and passive loading in regulating adult cardiocyte growth remains unresolved. To address this issue at the cellular level, adult feline cardiocytes were cultured either on Silastic membranes or plastic surfaces. Cardiocyte-laden membranes were stretched 10% of their rest length to enhance passive loading, whereas heart cells cultured on plastic or Silastic were field stimulated at 1 Hz to mimic active loading. Turnover of contractile proteins and structural integrity of the contractile-cytoskeletal apparatus were monitored for periods ranging from 4 to 72 h. Active and passive loading elevated contractile protein synthesis nearly equally (approximately 50%) and promoted the attachment of remodeled myofibrils to vinculin-positive focal contacts and/or costameres during the first 24 h of loading. Thereafter, rates of contractile protein synthesis returned to control values in passively stretched heart cells but remained elevated in field-stimulated cultures. The fractional rate of growth was increased significantly (approximately 8%/day) in electrically paced cells, whereas in passively stretched cardiocytes the growth rate rose only modestly (approximately 2%/day). Changes in the rate of myocyte growth appeared more closely correlated with the development of focal contacts and myofibril remodeling than with changes in myofibrillar protein turnover per se. 2,3-Butanedione monoxime, nifedipine, and, to a lesser extent, ryanodine blocked field-stimulated contractile protein synthesis and myofibrillar remodeling but had no impact on protein turnover or myofibril reassembly in passively loaded cardiocytes. The results of these experiments imply that both active and passive loading stimulate contractile protein turnover and myofibril remodeling, but the generation of active tension accelerates cardiocyte growth to a greater extent than passive loading. Furthermore, pharmacological interventions suggest that unique pathways may mediate these cellular events in actively and passively loaded adult cardiocytes.

NASA Discipline Cell Biology↗

Properties and reaction mechanism of phosphoric acid activated metakaolin geopolymer at varied curing temperatures

Reaction mechanism of phosphoric activated metakaolin is studied by techniques of calorimetry, ICP-OES, FTIR and NMR taking curing temperature and [H{sub 3}PO{sub 4}] as variables. A two-stage curing method including pre-curing at 40 °C for 24 h and second curing at 60/80 °C for another 24 h effectively mitigates thermal-cracking of the obtained silico-aluminate phosphate (SAP) samples, whose maximum compressive strength reaches 120 MPa. Dealumination of metakaolin in H{sub 3}PO{sub 4} solution produces low aluminate-containing silicate units and subsequently condensation of silicate tetrahedrons occurs. Higher temperature and H{sub 3}PO{sub 4} concentration accelerate the two processes. After complete reaction, A{sub VI} structure from metakaolin disappears and the dissolved Al preferably forms Al{sub VI}-O-P units. During reaction, metastable P-O-P intermediate appears in SAPs with higher P/Al ratio and finally transforms into Al-O-P structure upon PO{sub 4}{sup 3−} consumption. Phosphate units as P(OAl){sub x}(H{sub 2}O){sub 4-x} are connected with Si or Al structure units. Major structural units of the SAPs include Al-O-P, Si-O-P, Si-O-Si, and Si-O-Al.

36 MATERIALS SCIENCE↗

Decoupling the catalytic and degradation mechanisms of cobalt active sites during acidic water oxidation

Advancement of iridium-free catalysts for the low-pH oxygen evolution reaction (OER) is required to enable multi-gigawatt-scale proton-exchange water electrolysis. Cobalt-based materials might address this requirement, but little is known about the mechanism of operation of these OER catalysts at low pH. Here we investigate the nature and evolution of the active cobalt sites along with charge- and mass-transfer processes that support their catalytic function within a cobalt–iron–lead oxide material using in situ spectroscopic, gravimetric and electrochemical techniques. We demonstrate that corrosion of the cobalt sites and their reformation through electrooxidation of dissolved Co 2+ do not affect the catalytic mechanism and are decoupled from the OER. The OER-coupled charge transfer is supported by Co (3+δ)+ -oxo-species, which are structurally different from those reported for alkaline/near-neutral conditions and are formed on a relatively slow timescale of minutes. These mechanistic insights might assist in developing genuinely practical catalysts for this vital technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural insights into the mechanism of oxidative activation of heme-free H-NOX from Vibrio cholerae

Bacterial heme nitric oxide/oxygen (H-NOX) domains are nitric oxide (NO) or oxygen sensors. This activity is mediated through binding of the ligand to a heme cofactor. However, H-NOX from Vibrio cholerae (Vc H-NOX) can be easily purified in a heme-free state that is capable of reversibly responding to oxidation, suggesting a heme-independent function as a redox sensor. This occurs by oxidation of Cys residues at a zinc-binding site conserved in a subset of H-NOX homologs. Remarkably, zinc is not lost from the protein upon oxidation, although its ligation environment is significantly altered. Using a combination of computational and experimental approaches, we have characterized localized structural changes that accompany the formation of specific disulfide bonds between Cys residues upon oxidation. Furthermore, the larger-scale structural changes accompanying oxidation appear to mimic those changes observed upon NO binding to the heme-bound form. Thus, Vc H-NOX and its homologs may act as both redox and NO sensors by completely separate mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identification of crystal plasticity model parameters by multi-objective optimization integrating microstructural evolution and mechanical data

Crystal plasticity models evolve a polycrystalline yield surface using meso-scale descriptions of deformation mechanisms. The activation of deformation mechanisms is governed by crystallography and a set of model parameters, which are typically calibrated through the fitting of mechanical data such as stress–strain curves and elastic lattice strains. Microstructural data such as phase fractions and texture evolution are used for verifying crystal plasticity parameters. In this study, we use a multi-objective genetic algorithm to identify hardening parameters from flow stress curves with an option to incorporate texture into the optimization approach. Robust, generalized objective functions are developed and used to identify sets of parameters pertaining to dislocation density-based hardening laws in visco-plastic and elasto-plastic self-consistent (VPSC and EPSC) homogenization models. First, the parameters are identified for pure Nb directly from texture using an objective function based on generalized spherical harmonics. Since texture evolution is driven by the relative contribution of active slip systems, the parameters governing the evolution of slip resistance ratios can be recovered from fitting discrete textures at a series of strains. Next, a comprehensive set of load reversal data for dual phase (DP) 780 steel is used to fit a hardening law and a back-stress law in EPSC. Finally, parameters pertaining to a complex hardening law for the evolution of slip and twinning in pure α-Ti are identified. Remarkably, using texture as an objective in combination with stress–strain objectives constrains the model of Ti to fully reproduce not only stress–strain and texture evolution but also hierarchical twinning measurements as a function of initial grain size and texture. Furthermore, given an appropriate model fit to representative experimental texture evolution, underlying twin volume fractions contributing to texture evolution can be predicted.

42 ENGINEERING↗

Structural mechanism of allosteric activation of TRPML1 by PI(3,5)P 2 and rapamycin

Transient receptor potential mucolipin 1 (TRPML1) is a Ca 2+ -permeable, nonselective cation channel ubiquitously expressed in the endolysosomes of mammalian cells and its loss-of-function mutations are the direct cause of type IV mucolipidosis (MLIV), an autosomal recessive lysosomal storage disease. TRPML1 is a ligand-gated channel that can be activated by phosphatidylinositol 3,5-bisphosphate [PI(3,5)P 2 ] as well as some synthetic small-molecule agonists. Recently, rapamycin has also been shown to directly bind and activate TRPML1. Interestingly, both PI(3,5)P 2 and rapamycin have low efficacy in channel activation individually but together they work cooperatively and activate the channel with high potency. To reveal the structural basis underlying the synergistic activation of TRPML1 by PI(3,5)P 2 and rapamycin, we determined the high-resolution cryoelectron microscopy (cryo-EM) structures of the mouse TRPML1 channel in various states, including apo closed, PI(3,5)P 2 -bound closed, and PI(3,5)P 2 /temsirolimus (a rapamycin analog)-bound open states. These structures, combined with electrophysiology, elucidate the molecular details of ligand binding and provide structural insight into how the TRPML1 channel integrates two distantly bound ligand stimuli and facilitates channel opening.

59 BASIC BIOLOGICAL SCIENCES↗

Structure of the phosphoinositide 3-kinase (PI3K) p110γ-p101 complex reveals molecular mechanism of GPCR activation

The class IB phosphoinositide 3-kinase (PI3K), PI3Kγ, is a master regulator of immune cell function and a promising drug target for both cancer and inflammatory diseases. Critical to PI3Kγ function is the association of the p110γ catalytic subunit to either a p101 or p84 regulatory subunit, which mediates activation by G protein–coupled receptors. Here, we report the cryo–electron microscopy structure of a heterodimeric PI3Kγ complex, p110γ-p101. This structure reveals a unique assembly of catalytic and regulatory subunits that is distinct from other class I PI3K complexes. p101 mediates activation through its Gβγ-binding domain, recruiting the heterodimer to the membrane and allowing for engagement of a secondary Gβγ-binding site in p110γ. Mutations at the p110γ-p101 and p110γ–adaptor binding domain interfaces enhanced Gβγ activation. A nanobody that specifically binds to the p101-Gβγ interface blocks activation, providing a novel tool to study and target p110γ-p101–specific signaling events in vivo.

59 BASIC BIOLOGICAL SCIENCES↗

New Insights on Plasmin Long Term Stability and the Mechanism of Its Activity Inhibition Analyzed by Quartz Crystal Microbalance

We used the research quartz crystal microbalance (RQCM) to monitor regulatory effects of plasmin and trypsin in the presence of their inhibitor α2-antiplasmin. The gold surface of quartz crystals was modified with a β-casein layer that served as a substrate for protease digestion. The addition of plasmin or trypsin as well as their mixtures with α2-antiplasmin resulted in an increase of resonant frequency, f, and in a decrease of motional resistance, Rm, depending on the molar ratio of protease: antiplasmin. At equimolar concentrations of protease and α2-antiplasmin (5 nM:5 nM) full inhibition of protease activity took place. Monitoring of plasmin activity on an hourly and daily basis revealed a prominent effect of autolysis and decrease of plasmin activity in freshly activated samples. The degree of inhibition as well as plasmin half-life (t1/2 = 2.48 ± 0.28 days) connected with its degradation was determined.

36 MATERIALS SCIENCE↗

The structure of host galaxies of radio-loud quasars and possible triggering mechanisms for quasar activity

An image modeling program is used to analyze optical imaging data for a sample of radio-loud quasars with redshifts between 0.2 and 0.7. It is found that the host galaxies of these quasars tend to be more compact than normal ellipticals. The cooling flow cluster elliptical galaxies near these host galaxies are studied. It is suggested that these cooling flow galaxies are also compact due to star formation in their central regions. Two populations of quasars are identified. One, in which activity is triggered by galaxy mergers of interactions has predominately spiral galaxies and are radio quiet. The other, in which activity is triggered by star formation bursts induced by cooling flows, has predominately elliptical hosts and may be radio loud.

Romanishin, W.↗

Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

Zhang, Renyi↗

Mechanotransduction through Integrins

The goal of this project was to characterize the molecular mechanism by which cells recognize and respond to physical forces in their local environment. The project was based on the working hypothesis that cells sense mechanical stresses through cell surface integrin receptors and through their interconnections with the underlying cytoskeleton. Work completed and published in past funding period had provided direct support for this hypothesis. In particular, we demonstrated that application of mechanical stresses to activated integrin receptors (but not inactive integrins or other control transmembrane receptors) resulted in stress-dependent activation of the CAMP signaling pathway leading to gene transcription. We also showed that this form of mechanotransduction requires activation of heterotrimeric G proteins. In this grant, our specific aims included: 1) to characterize the signal processing capabilities of different integrins and other cell surface receptors, 2) to identify heterotrimeric G proteins that mediate CAMP signaling by stresses applied to integrins, 3) to identify molecules that mediate transmembrane mechanochemical coupling between integrins and G proteins, and 4) to use genome-wide gene expression profiling techniques to identify other genes and signaling pathways that are activated by mechanical forces transmitted over specific cell surface receptors. Elucidation of the mechanism by which cells sense mechanical stresses through integrins and translate them into a biochemical response should help us to understand the molecular basis of the cellular response to gravity as well as many other forms of mechanosensation and tissue regulation.

Ingber, Donald↗