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1.
J Hered ; 114(2): 152-164, 2023 04 06.
Artigo em Inglês | MEDLINE | ID: mdl-36477342

RESUMO

Inferences made from molecular data support regional stock assessment goals by providing insights into the genetic population dynamics of enigmatic species. Population genomics metrics, such as genetic diversity and population connectivity, serve as useful proxies for species health and stability. Sleeper sharks (genus Somniosus) are ecologically important deep-sea predators, estimated to reach ages of 250 to 300 yr and taking decades to reach sexual maturity. The subgenus Somniosus (Somniosus) is comprised of 3 species: S. pacificus, S. microcephalus, and S. antarcticus. Given the life history strategy of somniosids, they are vulnerable to overfishing and population declines. Further, data to assess the stocks of these species are limited. To address this deficiency, we used the reduced representation library method Restriction-site Associated DNA sequencing (RADseq) to conduct phylogenomic and population genomics analyses, providing novel information for use in stock assessments. Our results strongly support the species status of S. microcephalus (N = 79), but recover S. antarcticus (N = 2) intermixed within the S. pacificus (N = 170) clade. Population genomics analyses reveal genetic homogeneity within S. pacificus and S. microcephalus, and estimates of effective population size were in the hundreds for both species. Kinship analysis identified 2 first-degree relative pairs within our dataset (1 within each species). Our results contribute new information for stock assessments of these uniquely long-lived species by providing the strongest molecular evidence to date for the synonymization of S. antarcticus and S. pacificus, as well as estimating population genomic metrics for each supported species within the Somniosus (Somniosus) subgenus.


Assuntos
Conservação dos Recursos Naturais , Tubarões , Animais , Tubarões/genética , Pesqueiros , Ecologia
2.
Molecules ; 28(3)2023 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-36771173

RESUMO

The development of biobased antioxidant active packaging has been valued by the food industry for complying with environmental and food waste concerns. In this work, physicochemical properties for chitosan composite films as a potential active food packaging were investigated. Chitosan films were prepared by solution casting, plasticized with a 1:2 choline chloride: glycerol mixture as a deep eutectic solvent (DES) and incorporated with 0-10% of optimized açaí oil polyelectrolyte complexes (PECs). Scanning electron microscopy and confocal laser scanning microscopy revealed that the chitosan composite films were continuous and contained well-dispersed PECs. The increased PECs content had significant influence on the thickness, water vapor permeability, crystallinity (CrD) and mechanical and dynamic behavior of the films, as well as their antioxidant properties. The tensile strength was reduced in the following order: 11.0 MPa (control film) > 0.74 MPa (5% DES) > 0.63 MPa (5% DES and 5% PECs). Films containing 2% of PECs had an increased CrD, ~6%, and the highest elongation at break, ~104%. Films with 1% of PECs displayed the highest antioxidant properties against the ABTS and DPPH radicals, ~6 and ~17 mg TE g-1, respectively, and highest equivalent polyphenols content (>0.5 mg GAE g-1). Films with 2% of particles were not significantly different. These results suggested that the chitosan films that incorporated 1-2% of microparticles had the best combined mechanical and antioxidant properties as a potential material for food packaging.


Assuntos
Quitosana , Eliminação de Resíduos , Antioxidantes/química , Quitosana/química , Embalagem de Alimentos/métodos , Solventes Eutéticos Profundos , Cápsulas , Alimentos , Permeabilidade
3.
Molecules ; 28(19)2023 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-37836719

RESUMO

Conventionally, methanol is the solvent of choice in the synthesis of gamma-cyclodextrin metal-organic frameworks (γ-CD-MOFs), but using ethanol as a replacement could allow for a more food-grade synthesis condition. Therefore, the aim of the study was to compare the γ-CD-MOFs synthesised with both methanol and ethanol. The γ-CD-MOFs were characterised by scanning electron microscopy (SEM), surface area and pore measurement, Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD). The encapsulation efficiency (EE) and loading capacity (LC) of the γ-CD-MOFs were also determined for curcumin, using methanol, ethanol and a mixture of the two as encapsulation solvent. It was found that γ-CD-MOFs synthesised by methanol and ethanol do not differ greatly, the most significant difference being the larger crystal size of γ-CD-MOFs crystallised from ethanol. However, the change in solvent significantly influenced the EE and LC of the crystals. The higher solubility of curcumin in ethanol reduced interactions with the γ-CD-MOFs and resulted in lowered EE and LC. This suggests that different solvents should be used to deliberately manipulate the EE and LC of target compounds for better use of γ-CD-MOFs as their encapsulating and delivery agents.

4.
Langmuir ; 37(2): 827-840, 2021 01 19.
Artigo em Inglês | MEDLINE | ID: mdl-33395302

RESUMO

It is possible that Pickering emulsions can optimize the transport of nutraceuticals, pharmaceuticals, and other bioactive compounds in human physiology. So-called ultrastable Pickering emulsions are often destabilized in the gastric digestion regime if the particles are proteinaceous in nature. The present study seeks to test how the interfacial structure can be engineered via synergistic particle-particle interactions to impact the gastric coalescence of Pickering emulsions. In this study, we designed plant-based protein-particle-stabilized oil-in-water emulsions (PPM-E, with 20 wt % sunflower oil) via pea protein microgels (PPM at 1 wt %). The PPM hydrodynamic diameter is ∼250 nm. In vitro gastric digestion of PPM-E confirmed droplet coalescence within 30 min of pepsin addition. Supposedly surface-active cellulose nanocrystals (CNCs, 1-3 wt %) were added to PPM-E at pH 3.0 to determine if they could act as a barrier to interfacial pepsinolysis due to the CNC and PPM being oppositely charged at this gastric pH value. A combination of confocal microscopy, zeta potential, and Langmuir trough measurements suggested that CNCs and PPMs might form a combined layer at the O/W interface, owing to the electrostatic attraction between them. CNCs at >2 wt % inhibited the pepsinolyis of the adsorbed PPM film and thus droplet coalescence. However, increasing concentrations of CNC also increased the bulk viscosity of the PPM-E and eventually caused gelation of the emulsions, which would also delay their gastric breakdown. In conclusion, tuning the bulk and interfacial structure of Pickering emulsions via synergistic interactions between two types of particles could be an effective strategy to modify the enzymatic breakdown of such emulsions, which would have important applications in pharmaceuticals, foods, and other soft-matter applications.


Assuntos
Microgéis , Nanopartículas , Celulose , Digestão , Emulsões , Humanos , Proteínas de Plantas
5.
Langmuir ; 35(29): 9493-9503, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31240936

RESUMO

We have computed the free energy per unit area (i.e., interfacial tension) between a solid surface and two coexisting polymer solutions, where there is no specific interaction between the particles and either polymer, via self-consistent field calculations. Several different systems have been studied, including those where the two polymers differ in molecular weight (Mw) by a factor of ∼2 or where the polymers have the same Mw, but one set of chains is branched with the other linear. In the absence of any enthalpic contribution resulting from adsorption on the solid particle surface, the differences in the free energy per unit area resulting from the polymer-depleted regions around the particles in the two coexisting phases are found to be ∼1 µN m-1. Although this value may seem rather small, this difference is more than capable of inducing the partitioning of particles of 100 nm in size (or larger) into the phase with the lower interfacial free energy at the solid surface. By examining the density profile variation of the polymers close to the surface, we can also infer information about the wettability and contact angle (θ) of solid particles at the interface between the two coexisting phases. This leads to the conclusion that for all systems of this type, when the incompatibility between the two polymers is sufficiently large, θ will be close to 90°.

6.
Langmuir ; 35(40): 13078-13089, 2019 10 08.
Artigo em Inglês | MEDLINE | ID: mdl-31525933

RESUMO

Here, we report a novel "double Pickering stabilization" of water-in-oil (W/O) emulsions, where complex formation at the interface between Pickering polyphenol particles adsorbing from the oil side and whey protein microgel (WPM) particles coadsorbing from the aqueous side of the interface is investigated. The interfacial complex formation was strongly dependent on the concentration of WPM particles. At low WPM concentrations, both polyphenol crystals and WPM particles are present at the interface and the water droplets were stabilized through their synergistic action, while at higher concentrations, the WPM particles acted as "colloidal glue" between the water droplets and polyphenol crystals, enhancing the water droplet stability for more than 90 days and prevented coalescence. Via this mechanism, the addition of WPM up to 1 wt % gave a significant improvement in the stability of the W/O emulsions, allowing an increase to a 20 wt % water droplet fraction. The evidence suggests that the complex was probably formed due to electrostatic attraction between oppositely charged polyphenol Pickering particles on the oil side of the interface and WPM Pickering particles mainly on the aqueous side of the interface. Interfacial shear viscosity measurements and monolayer (Langmuir trough) experiments at the air-water interface provided further evidence of this strengthening of the film due to the synergistic particle-particle complex formation at the interface.

7.
Langmuir ; 34(34): 10001-10011, 2018 08 28.
Artigo em Inglês | MEDLINE | ID: mdl-30074808

RESUMO

In recent years, there has been a resurgence of interest in Pickering emulsions because of the recognition of the unique high steric stabilization provided by particles at interfaces. This interest is particularly keen for water-in-oil (W/O) emulsions because of the limited range of suitable Pickering stabilizers available. We demonstrate for the first time that W/O emulsions can be stabilized by using crystals from naturally occurring polyphenols (curcumin and quercetin particles). These particles were assessed based on their size, microstructure, contact angle, interfacial tension, and ζ-potential measurements in an attempt to predict the way that they act as Pickering stabilizers. Static light-scattering results and microstructural analysis at various length scales [optical microscopy, confocal laser scanning microscopy (CLSM), and scanning electron microscopy (SEM)] confirmed that the quercetin particles has a nearly perfect crystalline rod shape with a high aspect ratio; that is, the ratio of length to diameter ( L/ D) was ca. 2.5:1-7:1. On the other hand, the curcumin particles ( d3,2 = 0.2 µm) had a polyhedral shape. Droplet sizing and CLSM revealed that there was an optimum concentration (0.14 and 0.25 wt % for quercetin and curcumin, respectively) where smaller water droplets were formed ( d3,2 ≈ 6 µm). Interfacial shear viscosity (η i) measurements confirmed that a stronger film was formed at the interface with quercetin particles (η i ≈ 25 N s m-1) rather than with curcumin particles (η i ≈ 1.2 N s m-1) possibly because of the difference in the shape and size of the two crystals. This study provides new insights into the creation of Pickering W/O emulsions with polyphenol crystals and may lead to various soft matter applications where Pickering stabilization using biocompatible particles is a necessity.

8.
J Sci Food Agric ; 98(5): 2002-2010, 2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-28940205

RESUMO

BACKGROUND: Blueberry juice powder was developed via foam-mat freeze-drying (FMFD) and spray-drying (SD) via addition of maltodextrin (MD) and whey protein isolate (WPI) at weight ratios of MD/WPI = 0.4 to 3.2 (with a fixed solids content of 5 wt% for FMFD and 10 wt% for SD). Feed rates of 180 and 360 mL h-1 were tested in SD. The objective was to evaluate the effect of the drying methods and carrier agents on the physical properties of the corresponding blueberry powders and reconstituted products. RESULTS: Ratios of MD/WPI = 0.4, 1.0 and 1.6 produced highly stable foams most suitable for FMFD. FMFD gave high yields and low bulk density powders with flake-like particles of large size that were also dark purple with high red values. SD gave low powder recoveries. The powders had higher bulk density and faster rehydration times, consisting of smooth, spherical and smaller particles than in FMFD powders. The SD powders were bright purple but less red than FMFD powders. Solubility was greater than 95% for both FMFD and SD powders. CONCLUSION: The FMFD method is a feasible method of producing blueberry juice powder and gives products retaining more characteristics of the original juice than SD. © 2017 Society of Chemical Industry.


Assuntos
Mirtilos Azuis (Planta)/química , Manipulação de Alimentos/métodos , Frutas/química , Manipulação de Alimentos/instrumentação , Liofilização , Tamanho da Partícula , Pós/química
9.
Langmuir ; 33(51): 14699-14708, 2017 12 26.
Artigo em Inglês | MEDLINE | ID: mdl-29193975

RESUMO

Aqueous lubrication has emerged as an active research area in recent years due to its prevalence in nature in biotribological contacts and its enormous technological soft-matter applications. In this study, we designed aqueous dispersions of biocompatible whey-protein microgel particles (WPM) (10-80 vol %) cross-linked via disulfide bonding and focused on understanding their rheological, structural and biotribological properties (smooth polydimethylsiloxane (PDMS) contacts, Ra < 50 nm, ball-on-disk set up). The WPM particles (Dh = 380 nm) displayed shear-thinning behavior and good lubricating performance in the plateau boundary as well as the mixed lubrication regimes. The WPM particles facilitated lubrication between bare hydrophobic PDMS surfaces (water contact angle 108°), leading to a 10-fold reduction in boundary friction force with increased volume fraction (ϕ ≥ 65%), largely attributed to the close packing-mediated layer of particles between the asperity contacts acting as "true surface-separators", hydrophobic moieties of WPM binding to the nonpolar surfaces, and particles employing a rolling mechanism analogous to "ball bearings", the latter supported by negligible change in size and microstructure of the WPM particles after tribology. An ultralow boundary friction coefficient, µ ≤ 0.03 was achieved using WPM between O2 plasma-treated hydrophilic PDMS contacts coated with bovine submaxillary mucin (water contact angle 47°), and electron micrographs revealed that the WPM particles spread effectively as a layer of particles even at low ϕ∼ 10%, forming a lubricating load-bearing film that prevented the two surfaces from true adhesive contact. However, above an optimum volume fraction, µ increased in HL+BSM surfaces due to the interpenetration of particles that possibly impeded effective rolling, explaining the slight increase in friction. These effects are reflected in the highly shear thinning nature of the WPM dispersions themselves plus the tendency for the apparent viscosity to fall as dispersions are forced to very high volume fractions. The present work demonstrates a novel approach for providing ultralow friction in soft polymeric surfaces using proteinaceous microgel particles that satisfy both load bearing and kinematic requirements. These findings hold great potential for designing biocompatible particles for aqueous lubrication in numerous soft matter applications.


Assuntos
Proteínas do Soro do Leite/química , Animais , Bovinos , Fricção , Interações Hidrofóbicas e Hidrofílicas , Lubrificação , Reologia , Propriedades de Superfície , Viscosidade
10.
Langmuir ; 32(49): 13234-13243, 2016 12 13.
Artigo em Inglês | MEDLINE | ID: mdl-27951697

RESUMO

Nonspecific interactions of flavonoids with lipids can alter the membrane's features (e.g., thickness and fluctuations) as well as influence their therapeutic potentials. However, relatively little is known about the details of how flavonoids interact with lipid components. Structure-dependent interactions of a variety of flavonoids with phospholipid monolayers on a mercury (Hg) film electrode were established by rapid cyclic voltammetry (RCV). The data revealed that flavonoids adopting a planar configuration altered the membrane properties more significantly than nonplanar flavonoids. Quercetin, rutin, and tiliroside were selected for follow-up experiments with Langmuir monolayers, Brewster angle microscopy (BAM), and small-angle X-ray scattering (SAXS). Relaxation phenomena in DOPC monolayers and visualization of the surface with BAM revealed a pronounced monolayer stabilization effect with both quercetin and tiliroside, whereas rutin disrupted the monolayer structure rendering the surface entirely smooth. SAXS showed a monotonous membrane thinning for all compounds studied associated with an increase in the mean fluctuations of the membrane. Rutin, quercetin, and tiliroside decreased the bilayer thickness of DOPC by ∼0.45, 0.8, and 1.1 Šat 6 mol %, respectively. In addition to the novelty of using lipid monolayers to systematically characterize the structure-activity relationship (SAR) of a variety of flavonoids, this is the first report investigating the effect of tiliroside with biomimetic membrane models. All the flavonoids studied are believed to be localized in the lipid/water interface region. Both this localization and the membrane perturbations have implications for their therapeutic activity.


Assuntos
Flavonoides/química , Membranas/química , Fosfolipídeos/química , Microscopia , Quercetina , Rutina , Espalhamento a Baixo Ângulo , Propriedades de Superfície , Difração de Raios X
11.
Soft Matter ; 12(15): 3558-69, 2016 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-26959339

RESUMO

Emulsions stabilized by soft whey protein microgel particles have gained research interest due to their combined advantages of biocompatibility and a high degree of resistance to coalescence. We designed Pickering oil-in-water emulsions using whey protein microgels by a facile route of heat-set gel formation followed by mechanical shear and studied the influence of heat treatment on emulsions stabilized by these particles. The aim of this study was to compare the barrier properties of the microgel particles and heat-treated fused microgel particles at the oil-water interface in delaying the digestion of the emulsified lipids using an in vitro digestion model. A combination of transmission electron microscopy and surface coverage measurements revealed an increased coverage of heat-treated microgel particles at the interface. The heat-induced microgel particle aggregation and, therefore, a fused network at the oil-water interface were more beneficial to delay the rate of digestion in the presence of pure lipase and bile salts compared to intact whey protein microgel particles, as shown by the measurements of zeta potential and free fatty acid release, plus theoretical calculations. However, simulated gastric digestion with pepsin impacted significantly on such barrier effects, due to the proteolysis of the particle network at the interface irrespective of the heat treatment, as visualized using sodium dodecyl sulfate polyacryl amide gel electrophoresis measurements.


Assuntos
Temperatura Alta , Proteínas do Soro do Leite/química , Proteínas do Soro do Leite/metabolismo , Ácidos e Sais Biliares/química , Biomimética , Digestão , Emulsões , Ácidos Graxos não Esterificados/metabolismo , Géis , Mucosa Intestinal/metabolismo , Cinética , Lipase/metabolismo , Óleos/química , Tamanho da Partícula , Água/química
12.
Mol Biol Evol ; 31(7): 1803-15, 2014 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-24803641

RESUMO

The mountain pine beetle (MPB; Dendroctonus ponderosae Hopkins), a major pine forest pest native to western North America, has extended its range north and eastward during an ongoing outbreak. Determining how the MPB has expanded its range to breach putative barriers, whether physical (nonforested prairie and high elevation of the Rocky Mountains) or climatic (extreme continental climate where temperatures can be below -40 °C), may contribute to our general understanding of range changes as well as management of the current epidemic. Here, we use a panel of 1,536 single nucleotide polymorphisms (SNPs) to assess population genetic structure, connectivity, and signals of selection within this MPB range expansion. Biallelic SNPs in MPB from southwestern Canada revealed higher genetic differentiation and lower genetic connectivity than in the northern part of its range. A total of 208 unique SNPs were identified using different outlier detection tests, of which 32 returned annotations for products with putative functions in cholesterol synthesis, actin filament contraction, and membrane transport. We suggest that MPB has been able to spread beyond its previous range by adjusting its cellular and metabolic functions, with genome scale differentiation enabling populations to better withstand cooler climates and facilitate longer dispersal distances. Our study is the first to assess landscape-wide selective adaptation in an insect. We have shown that interrogation of genomic resources can identify shifts in genetic diversity and putative adaptive signals in this forest pest species.


Assuntos
Besouros/genética , Variação Genética , Adaptação Biológica , Alelos , Animais , Canadá , Besouros/fisiologia , Florestas , Frequência do Gene , Genoma de Inseto , Polimorfismo de Nucleotídeo Único , Seleção Genética
13.
J Hered ; 105(2): 188-202, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24381183

RESUMO

North Atlantic right whales have one of the lowest levels of genetic variation at minisatellite loci, microsatellite loci, and mitochondrial control region haplotypes among mammals. Here, adaptive variation at the peptide binding region of class I and class II DRB-like genes of the major histocompatibility complex was assessed. Amplification of a duplicated region in 222 individuals revealed at least 11 class II alleles. Six alleles were assigned to the locus Eugl-DRB1 and 5 alleles were assigned to the locus Eugl-DRB2 by assessing segregation patterns of alleles from 81 parent/offspring pedigrees. Pedigree analysis indicated that these alleles segregated into 12 distinct haplotypes. Genotyping a smaller subset of unrelated individuals (n = 5 and 10, respectively) using different primer sets revealed at least 2 class II pseudogenes (with ≥ 4 alleles) and at least 3 class I loci (with ≥ 6 alleles). Class II sequences were significantly different from neutrality at peptide binding sites suggesting loci may be under the influence of balancing selection. Trans-species sharing of alleles was apparent for class I and class II sequences. Characterization of class II loci represents the first step in determining the relationship between major histocompatibility complex variability and factors affecting health and reproduction in this species.


Assuntos
Genes MHC da Classe II/genética , Genes MHC Classe I/genética , Loci Gênicos , Linhagem , Baleias/genética , Alelos , Sequência de Aminoácidos , Animais , Feminino , Variação Genética , Haplótipos , Masculino , Repetições de Microssatélites , Dados de Sequência Molecular , Filogenia , Seleção Genética
14.
J Chem Phys ; 140(20): 204713, 2014 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-24880317

RESUMO

The degree of shrinkage of particle stabilised bubbles of various sizes, in a polydisperse bubble dispersion, has been investigated in the light of the finite adsorption times for the particles and the disproportionation kinetics of the bubbles. For the case where the system contains an abundance of particles we find a threshold radius, above which bubbles are stabilised without any significant reduction in their size. Bubbles with an initial radius below this threshold on the other hand undergo a large degree of shrinkage prior to stabilisation. As the ratio of the available particles to the bubbles is reduced, it is shown that the final bubble size, for the larger bubbles in the distribution, becomes increasingly governed by the number of particles, rather than their adsorption time per se. For systems with "adsorption controlled" shrinkage ratio, the final bubble distribution is found to be wider than the initial one, while for a "particle number controlled" case it is actually narrower. Starting from a unimodal bubble size distribution, we predict that at intermediate times, prior to the full stabilisation of all bubbles, the distribution breaks up into a bimodal one. However, the effect is transient and a unimodal final bubble size distribution is recovered, when all the bubbles are stabilised by the particles.


Assuntos
Adsorção , Nanopartículas/química , Termodinâmica , Difusão , Cinética , Tamanho da Partícula , Temperatura
15.
Food Funct ; 15(8): 3959-3979, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38568171

RESUMO

The majority of known peptides with high bioactivity (BAPs) such as antihypertensive, antidiabetic, antioxidant, hypocholesterolemic, anti-inflammatory and antimicrobial actions, are short-chain sequences of less than ten amino acids. These short-chain BAPs of varying natural and synthetic origin must be bioaccessible to be capable of being adsorbed systemically upon oral administration to show their full range of bioactivity. However, in general, in vitro and in vivo studies have shown that gastrointestinal digestion reduces BAPs bioactivity unless they are protected from degradation by encapsulation. This review gives a critical analysis of short-chain BAP encapsulation and performance with regard to the oral delivery route. In particular, it focuses on short-chain BAPs with antihypertensive and antidiabetic activity and encapsulation methods via nanoparticles and microparticles. Also addressed are the different wall materials used to form these particles and their associated payloads and release kinetics, along with the current challenges and a perspective of the future applications of these systems.


Assuntos
Trato Gastrointestinal , Peptídeos , Humanos , Peptídeos/química , Peptídeos/administração & dosagem , Trato Gastrointestinal/metabolismo , Animais , Sistemas de Liberação de Medicamentos/métodos , Nanopartículas/química , Administração Oral , Composição de Medicamentos , Digestão , Hipoglicemiantes/administração & dosagem , Hipoglicemiantes/química
16.
Cryst Growth Des ; 24(8): 3256-3268, 2024 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-38659660

RESUMO

The aim of this work is to shed light on the polymorphism of xanthones, a class of oxygenated molecules well known for their bioactivity, including antioxidant, anticancer, and anti-inflammatory effects. Understanding the polymorphism of xanthones can enable the design of novel solid products for pharmaceutical, nutraceutical, and agrochemical applications. Prior to this work, two entries accounting for different space groups were deposited for 9-xanthone in the Cambridge Structure Database (CSD): an orthorhombic P212121 and a monoclinic P21 structure solved at room and low temperatures, respectively. However, the very high similarity between these two structures and the lack of clear differences in their physical properties (e.g., thermal behavior) suggested the possibility of the existence of only one crystal structure. In fact, the differences shown in the literature data might be related to the chosen operating parameters, as well as the instrumental resolution of the single-crystal X-ray diffraction experiments. In the work presented here, the ambiguity in the polymorphism of xanthone is investigated using thermal analysis, powder and synchrotron single-crystal XRD, and optical microscopy. Additionally, a workflow for the correct identification of twinned crystal structures, which can be applied to other polymorphic systems, is presented. Such workflow combines the collection of a large data set of high-resolution diffraction patterns using synchrotron radiation with the use of principal component analysis, a dimensionality reduction technique, for a quick and effective identification of phase transitions happening during the data collection. Crystallization experiments were designed to promote the formation of different crystal structures of xanthone that were recrystallized based on past literature and beyond.

17.
Langmuir ; 29(31): 9841-8, 2013 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-23805874

RESUMO

The phase separation of a model system consisting of sodium caseinate + xanthan ± a low fraction (up to 3 wt %) of an oil-in-water emulsion was studied at room temperature (20-25 °C). The composition of the oil phase was either 100 wt % n-tetradecane (TD); 50% TD + 50% eicosane (EC) or 100% EC. The droplets in these three "emulsions" were therefore totally liquid, partially solid, and totally solid, respectively. In the presence of 22 mM CaCl2, the mixed TD+EC droplets were most effective at inhibiting phase separation, while the EC emulsions could not prevent phase separation at all. At 32 mM CaCl2 the emulsions tended to promote phase separation, possibly due to enhanced calcium ion-induced droplet aggregation. The apparent interfacial viscosity (ηi) between two macroscopically separated phases was also measured. In the presence of the semisolid mixed droplets ηi = 25 mN s m(-1), significantly higher than ηi with the pure (liquid) TD droplets (15 mN s m(-1)) or with the pure solid EC droplets (12 mN s m(-1)) or in the absence of droplets (<3 mN s m(-1)). Confocal microscopy showed that the microstructure of the phase separating regions also depended upon the composition of the oil droplets, and it is tentatively suggested that the more marked effects of the mixed emulsion droplets were due to them forming a stronger network at the interface via partial coalescence. Control of the extent of interfacial aggregation of droplets is therefore possibly one way to influence the course of phase separation in biopolymer mixtures.


Assuntos
Alcanos/química , Cloreto de Cálcio/química , Óleos/química , Polissacarídeos/química , Proteínas/química , Tamanho da Partícula , Propriedades de Superfície
18.
J Colloid Interface Sci ; 652(Pt A): 405-417, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37604052

RESUMO

HYPOTHESIS: Partial hydrolysis of large molecular weight (Mw), highly aggregated plant proteins is frequently used to improve their solubility. However, if this hydrolysis is extensive, random or nonselective, it is unlikely to improve functional properties such as surface activity, emulsion, or foam-stabilising capacity. EXPERIMENTS AND SIMULATION: Soy protein isolate (SPI) was hydrolysed by pepsin under optimal (pH 2.1) and non-optimal (pH 4.7) conditions. The surface activity and emulsion stabilising capacity of the resultant peptides were measured and compared. The colloidal interactions between a pair of emulsion droplets were modelled via Self-Consistent-Field Calculations (SCFC). FINDINGS: Hydrolysis at pH 2.1 and 4.7 resulted in a considerable increase in measured surface activity compared to the native (non-hydrolysed) SPI, but the hydrolysate from pH 2.1 was not as good an emulsion stabiliser as the hydrolysate (particularly the fraction Mw > 10 kDa) at pH 4.7. Furthermore, peptide analysis of the latter suggested it was dominated by a fragment of one of the major soy proteins ß-conglycinin, with Mw ≈ 25 kDa. SCFC calculations confirmed that interactions mediated by adsorbed layers of this peptide point to it being an excellent emulsion stabiliser.


Assuntos
Proteínas de Plantas , Proteínas de Soja , Adsorção , Emulsões/química , Proteínas de Soja/química , Proteínas de Plantas/química , Hidrólise , Peptídeos , Concentração de Íons de Hidrogênio
19.
Adv Colloid Interface Sci ; 320: 102983, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37690329

RESUMO

This review discusses the current knowledge of interfacial and bulk interactions of biopolymeric microgels in relation to the well-established properties of synthetic microgels for applications as viscosity modifiers and Pickering stabilisers. We present a timeline showing the key milestones in designing microgels and their bulk/ interfacial performance. Poly(N-isopropylacrylamide) (pNIPAM) microgels have remained as the protagonist in the synthetic microgel domain whilst proteins or polysaccharides have been primarily used to fabricate biopolymeric microgels. Bulk properties of microgel dispersions are dominated by the volume fraction (ϕ) of the microgel particles, but ϕ is difficult to pinpoint, as addressed by many theoretical models. By evaluating recent experimental studies over the last five years, we find an increasing focus on the analysis of microgel elasticity as a key parameter in modulating their packing at the interfaces, within the provinces of both synthetic and biopolymeric systems. Production methods and physiochemical factors shown to influence microgel swelling in the aqueous phase can have a significant impact on their bulk as well as interfacial performance. Compared to synthetic microgels, biopolymer microgels show a greater tendency for polydispersity and aggregation and do not appear to have a core-corona structure. Comprehensive studies of biopolymeric microgels are still lacking, for example, to accurately determine their inter- and intra- particle interactions, whilst a wider variety of techniques need to be applied in order to allow comparisons to real systems of practical usage.


Assuntos
Microgéis , Géis/química , Tamanho da Partícula , Propriedades de Superfície , Água/química
20.
Mol Ecol ; 21(12): 2931-48, 2012 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-22554298

RESUMO

Environmental change has a wide range of ecological consequences, including species extinction and range expansion. Many studies have shown that insect species respond rapidly to climatic change. A mountain pine beetle epidemic of record size in North America has led to unprecedented mortality of lodgepole pine, and a significant range expansion to the northeast of its historic range. Our goal was to determine the spatial genetic variation found among outbreak population from which genetic structure, and dispersal patterns may be inferred. Beetles from 49 sampling locations throughout the outbreak area in western Canada were analysed at 13 microsatellite loci. We found significant north-south population structure as evidenced by: (i) Bayesian-based analyses, (ii) north-south genetic relationships and diversity gradients; and (iii) a lack of isolation-by-distance in the northernmost cluster. The north-south structure is proposed to have arisen from the processes of postglacial colonization as well as recent climate-driven changes in population dynamics. Our data support the hypothesis of multiple sources of origin for the outbreak and point to the need for population specific information to improve our understanding and management of outbreaks. The recent range expansion across the Rocky Mountains into the jack/lodgepole hybrid and pure jack pine zones of northern Alberta is consistent with a northern British Columbia origin. We detected no loss of genetic variability in these populations, indicating that the evolutionary potential of mountain pine beetle to adapt has not been reduced by founder events. This study illustrates a rapid range-wide response to the removal of climatic constraints, and the potential for range expansion of a regional population.


Assuntos
Besouros/genética , Variação Genética , Pinus , Alberta , Animais , Colúmbia Britânica , Mudança Climática , Repetições de Microssatélites , Dinâmica Populacional
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