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The Rouse dynamics of polymer chains in model nanocomposite polyethylene oxide/silica nanoparticles (NPs) was investigated using quasielastic neutron scattering. The apparent Rouse rate of the polymer chains decreases as the particle loading increases. However, there is no evidence of an immobile segment population on the probed time scale of tens of ps. The slowing down of the dynamics is interpreted in terms of modified Rouse models for the chains in the NP interphase region. Thus, two chain populations, one bulk-like and the other characterized by a suppression of Rouse modes, are identified. The spatial extent of the interphase region is estimated to be about twice the adsorbed layer thickness, or ≈2 nm. These findings provide a detailed description of the suppression of the chain dynamics on the surface of NPs. These results are relevant insights on surface effects and confinement and provide a foundation for the understanding of the rheological properties of polymer nanocomposites with well-dispersed NPs.
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Monoclonal antibodies (mAbs) form viscoelastic gel-like layers at the air-water interface due to their amphiphilic nature, and this same protein characteristic can lead to undesired aggregation of proteins in therapeutic formulations. We hypothesize that the interfacial viscoelasticity and surface pressure of mAbs at the air-water interface will correlate with their long-term stability. To test this hypothesis, the interfacial viscoelastic rheology and surface pressure of five different antibodies with varying visible particle counts from a three-year stability study were measured. We find that both the surface pressures and interfacial elastic moduli correlate well with the long-time mAb solution stability within a class of mAbs with the interfacial elastic moduli being particularly sensitive to discriminate between stable and unstable mAbs across a range of formulations. Furthermore, X-ray reflectivity was used to gain insight into the interfacial structure of mAbs at the air-water interface, providing a possible molecular mechanism to explain the relationship between interfacial elastic moduli and the long-term stability.
Assuntos
Anticorpos Monoclonais , Água , Módulo de Elasticidade , Anticorpos Monoclonais/química , Água/química , ReologiaRESUMO
Understanding the interfacial structure-property relationship of complex fluid-fluid interfaces is increasingly important for guiding the formulation of systems with targeted interfacial properties, such as those found in multiphase complex fluids, biological systems, biopharmaceuticals formulations, and many consumer products. Mixed interfacial flow fields, typical of classical Langmuir trough experiments, introduce a complex interfacial flow history that complicates the study of interfacial properties of complex fluid interfaces. In this article, we describe the design, implementation, and validation of a new instrument capable of independent application of controlled interfacial dilation and shear kinematics on fluid interfaces. Combining the Quadrotrough with both in situ Brewster angle microscopy and neutron reflectometry provides detailed structural measurements of the interface at the mesoscale and nanoscale in relationship to interfacial material properties under controlled interfacial deformation histories.
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Produtos Biológicos , Dilatação , Propriedades de SuperfícieRESUMO
Hydrogels of biopolymers such as agar and gelatin are widely used in many applications, and in many cases, the gels are loaded with nanoparticles. The polymer chains in these gels are cross-linked by physical bonds into three-dimensional networks, with the mesh size of these networks typically being 10-100 nm. One class of "soft" nanoparticles are liposomes, which have an aqueous core surrounded by a lipid bilayer. Solutes encapsulated in the liposomal core can be delivered externally over time. In this paper, we create liposomes with diameters â¼150 nm from an unsaturated phospholipid (lecithin) and embed them in agar gels (the aqueous phase also contains 0-50% of glycerol, which is an active ingredient in cosmetic products). Upon placing this gel in quiescent water, we find that the liposomes release out of the gel into the water over a period of 1-3 days, even though the gel remains intact. This is a surprising result that runs contrary to our expectation that the liposomes would simply remain immobilized in the gel. We show that the release rate of liposomes can be tuned by several variables: for example, the release rate increases as the agar concentration is lowered and the rate increases steadily with temperature. In addition to agar, release of liposomes also occurs out of other physical gels including those of agarose and gelatin. However, liposomes made from a saturated phospholipid do not release out of any gels. We discuss a possible mechanism for liposomal release, which involves intact liposomes deforming and squeezing through transient large pores that arise in physical networks such as agar. Our findings have relevance to transdermal delivery: they suggest the possibility of systematically delivering liposomes loaded with actives out of an intact matrix.
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Hidrogéis , Lipossomos , Biopolímeros , Gelatina , Géis , FosfatidilcolinasRESUMO
We report the use of a temperature insensitive, food-grade hydrogel to reduce the caloric density of pancakes that were prepared at temperatures much higher than the boiling point of water. This cheap, facile method utilises a mixed agar-methylcellulose hydrogel, which was blended to produce a slurry of hydrogel microbeads. The pancake batter was mixed with a controlled volume percentage of slurry of hydrogel beads and cooked. From bomb calorimetry experiments, the composites were found to have a reduced caloric density that reflects the volume percentage of hydrogel beads mixed with the batter. Using this procedure, we were able to reduce the caloric density of pancakes by up to 23 ± 3% when the volume percentage of hydrogel beads initially used was 25%. The method is not limited to pancakes and could potentially be applied to various other food products. The structure and morphology of the freeze-dried pancakes and pancake-hydrogel composites were investigated and pores of a similar size to the hydrogel beads were found, confirming that the gel beads maintained their structure during the cooking process. There is scope for further development of this method by the encapsulation of nutritionally beneficial or flavour enhancing ingredients within the hydrogel beads.
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Aditivos Alimentares/química , Hidrogel de Polietilenoglicol-Dimetacrilato/química , Testes Calóricos , Culinária , Farinha/análise , Análise de Alimentos , Temperatura Alta , Metilcelulose/químicaRESUMO
BACKGROUND: Random monoallelic expression defines an unusual class of genes displaying random choice for expression between the maternal and paternal alleles. Once established, the allele-specific expression pattern is stably maintained and mitotically inherited. Examples of random monoallelic genes include those found on the X-chromosome and a subset of autosomal genes, which have been most extensively studied in humans. Here, we report a genome-wide analysis of random monoallelic expression in the mouse. We used high density mouse genome polymorphism mapping arrays to assess allele-specific expression in clonal cell lines derived from heterozygous mouse strains. RESULTS: Over 1,300 autosomal genes were assessed for allele-specific expression, and greater than 10% of them showed random monoallelic expression. When comparing mouse and human, the number of autosomal orthologs demonstrating random monoallelic expression in both organisms was greater than would be expected by chance. Random monoallelic expression on the mouse autosomes is broadly similar to that in human cells: it is widespread throughout the genome, lacks chromosome-wide coordination, and varies between cell types. However, for some mouse genes, there appears to be skewing, in some ways resembling skewed X-inactivation, wherein one allele is more frequently active. CONCLUSIONS: These data suggest that autosomal random monoallelic expression was present at least as far back as the last common ancestor of rodents and primates. Random monoallelic expression can lead to phenotypic variation beyond the phenotypic variation dictated by genotypic variation. Thus, it is important to take into account random monoallelic expression when examining genotype-phenotype correlation.
Assuntos
Alelos , Desequilíbrio Alélico/genética , Cromossomos/genética , Expressão Gênica/genética , Animais , Estudos de Associação Genética , Genoma , Genótipo , Humanos , Camundongos , Análise de Sequência com Séries de Oligonucleotídeos , Polimorfismo de Nucleotídeo Único , Cromossomo X/genéticaRESUMO
Monoallelic expression with random choice between the maternal and paternal alleles defines an unusual class of genes comprising X-inactivated genes and a few autosomal gene families. Using a genome-wide approach, we assessed allele-specific transcription of about 4000 human genes in clonal cell lines and found that more than 300 were subject to random monoallelic expression. For a majority of monoallelic genes, we also observed some clonal lines displaying biallelic expression. Clonal cell lines reflect an independent choice to express the maternal, the paternal, or both alleles for each of these genes. This can lead to differences in expressed protein sequence and to differences in levels of gene expression. Unexpectedly widespread monoallelic expression suggests a mechanism that generates diversity in individual cells and their clonal descendants.