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1.
Ann Behav Med ; 57(3): 227-236, 2023 04 05.
Artigo em Inglês | MEDLINE | ID: mdl-36356036

RESUMO

BACKGROUND: Racial/ethnic discrimination has been linked to poor health outcomes. Effects of discrimination on health behaviors, including patterns of food consumption, may contribute to health outcomes. PURPOSE: We examined relations of discrimination to consumption of healthy and unhealthy foods in two diverse samples. Structural equation modeling was used to examine variations in associations of discrimination to consumption by the timing and type of discrimination, for healthy vs. unhealthy food, and by sample. METHODS: Study 1 included a racially and ethnically diverse sample of adults from New York City (NYC: N = 157); Study 2 included a sample of American Indian and Alaska Native (AI/AN) adults from the Denver metro area (N = 303), many of whom also identified with other racial/ethnic groups. Participants completed self-report measures of racial/ethnic discrimination, food consumption, life stressors, and sociodemographic variables. RESULTS: Structural equation models indicated discrimination was associated with food consumption. Tests of model invariance indicated that the model of discrimination to food consumption can be applied to both samples. Discrimination within the past-week was associated with more frequent consumption of both unhealthy and healthy foods, whereas lifetime discrimination was associated with more frequent consumption only of unhealthy foods. CONCLUSIONS: The data were limited to self-report measures and only the frequency of consumption was assessed. The findings suggest discrimination may contribute to health disparities through effects on food consumption. Differential effects for past-week and lifetime discrimination suggest that multiple mechanisms may be involved.


Experiencing racial discrimination may undermine health through effects on health behavior, including patterns of food consumption. In two studies, we tested whether racial discrimination was linked with food consumption, specifically the frequency with which people ate healthy and unhealthy foods. We investigated both lifetime exposure to discrimination as well as more recent (past-week) exposure as predictors of food consumption. Study 1 focused on racially and ethnically diverse adults from New York City (NYC); Study 2 focused on American Indian and Alaska Native (AI/AN) adults from the Denver metro area. Overall, we found that higher levels of discrimination were associated with more frequent consumption of both unhealthy and healthy food. The timing of discrimination mattered. Higher levels of discrimination within the past-week were associated with more frequent consumption of healthy and unhealthy foods. In contrast, higher levels of lifetime discrimination were associated only with more frequent consumption of unhealthy food. The links between discrimination and food consumption remained significant controlling for socioeconomic status. The relations of discrimination to food consumption were similar across the diverse sample from NYC and the AI/AN sample from Denver. These findings may help researchers understand how discrimination may contribute to health disparities.


Assuntos
Racismo , Adulto , Humanos , Comportamentos Relacionados com a Saúde , Grupos Raciais , Autorrelato , Cidade de Nova Iorque/epidemiologia
2.
J Chem Phys ; 154(22): 220401, 2021 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-34241199

RESUMO

This Editorial reports how the depletion force theory was originally developed by Sho Asakura and Fumio Oosawa and how their one-page paper was "rediscovered" about 20 years after the paper was published. The first part of this Editorial is mostly based on the lecture by Oosawa and his autobiographies, and the second part is written by one of two scientists who found the paper. The aim of this Editorial is to record the background of the discovery of the depletion force. We believe that this Editorial presents an interesting story showing how science develops. The story reminds us of the importance of basic education and continuous interests in unknown phenomena and interactions between people of different disciplines, although they are sometimes considered as separate elements of research.

3.
J Colloid Interface Sci ; 658: 639-647, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38134672

RESUMO

Whilst bottlebrush polymers have been studied in aqueous media for their conjectured role in biolubrication, surface forces and friction mediated by bottlebrush polymers in non-polar media have not been previously reported. Here, small-angle neutron scattering (SANS) showed that a diblock bottlebrush copolymer (oligoethyleneglycol acrylate/ethylhexyl acrylate; OEGA/EHA) formed spherical core-shell aggregates in n-dodecane (a model oil) in the polymer concentration range 0.1-2.0 wt%, with a radius of gyration Rg âˆ¼ 7 nm, comprising 40-65 polymer molecules per aggregate. The surface force apparatus (SFA) measurements revealed purely repulsive forces between surfaces bearing inhomogeneous polymer layers of thickness L âˆ¼ 13-23 nm, attributed to adsorption of a mixture of polymer chains and surface-deformed micelles. Despite the surface inhomogeneity, the polymer layers could mediate effective lubrication, demonstrating superlubricity with the friction coefficient as low as µ ∼ 0.003. The analysis of velocity-dependence of friction using the Eyring model shed light on the mechanism of the frictional process. That is, the friction mediation was consistent with the presence of nanoscopic surface aggregates, with possible contributions from a gel-like network formed by the polymer chains on the surface. These unprecedented results, correlating self-assembled polymer micelle structure with the surface forces and friction the polymer layers mediate, highlight the potential of polymers with the diblock bottlebrush architecture widespread in biological living systems, in tailoring desired surface interactions in non-polar media.

4.
Langmuir ; 27(8): 4362-70, 2011 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-21410203

RESUMO

A series of four hydrophobically modified, diphenylazo-based organic salts have been prepared and characterized. To achieve this a C(x) (x = 4, 6, 8, or 10) hydrocarbon chain was inserted between the diphenylazo moiety and the quaternary ammonium headgroup of the salt. The absorption of each of the four modified organic salts into anionic microgel particles of poly(N-isopropylacrylamide-co-acrylic acid) has been studied at pH 8. In addition, the hydrodynamic diameters and electrophoretic mobilities of the microgel particles have been studied as a function of the organic salt concentration, also at pH 8. In addition to the electrostatic attraction between the quaternary ammonium head groups of the organic salts and the anionic groups within the microgel particles, hydrophobic association between the chains of the organic salts within the microgel particles plays a role, with this effect increasing strongly from x=4 to 10. Desorption of the x=4 and 6 organic salts occurs readily on changing, in situ, the pH from 8 to 2.5 (and thereby eliminating the electrostatic interaction) but is only partially achieved for the x=8 and 10 organic salts. Indeed, for the x=10 organic salt, only about 80% of the organic salt is desorbed upon dilution of the microgel particles into a large excess of water.


Assuntos
Acrilamidas/química , Interações Hidrofóbicas e Hidrofílicas , Compostos de Amônio Quaternário/síntese química , Acrilatos , Géis/síntese química , Concentração de Íons de Hidrogênio , Tamanho da Partícula , Sais
5.
Langmuir ; 27(21): 12815-21, 2011 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-21882871

RESUMO

When aqueous suspensions of 1 µm, negatively charged polystyrene particles are subject to a 1 kHz alternating electric field of strength greater than 7 kV(rms) m(-1), dynamic elliptical clusters of particles spontaneously form. With potential applications in microchannel fluidics in mind, we characterize how cluster formation and particle circulation, driven by induced dipole-dipole interactions, is critically dependent on time, field strength, electrolyte concentration, and cell thickness. Logarithmic growth of cluster size is observed, and particle velocity within the clusters is found to be proportional to cluster length. Increasing cell thickness from 10 to 60 µm increases the projected cluster area but decreases cluster aspect ratio as the result of changing particle dispersal rates. Clusters are shown to generate significant fluid shear suitable for microchannel mixing applications. These clusters are observed to distort under transverse fluid flow and, above a critical flow rate, to undergo a transition to form regularly spaced particle streams, which may be suitable for two-dimensional visualization of fluid flow.

6.
Phys Chem Chem Phys ; 13(1): 110-3, 2011 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-20978687

RESUMO

Whilst binary colloid-polymer mixtures have been studied in detail over the past few decades, here the first results are presented on a ternary mixture involving two particle sizes. Novel and unusual phase separation kinetics are found, with a liquid phase separating from an aggregate phase.


Assuntos
Polímeros/química , Coloides/química , Cinética , Tamanho da Partícula , Propriedades de Superfície
7.
Langmuir ; 26(12): 9397-402, 2010 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-20232835

RESUMO

Depletion-induced phase separation in mixtures of charged silica particles and nonadsorbing polymer near theta conditions (polystyrene in dimethylformamide) was studied. The colloid-polymer size ratio q was varied through the particle size and the electrical double layer thickness (kappa(-1)) through addition of lithium chloride (LiCl). The dependence of the phase boundaries, and the nature of the separated phases, on q and kappa is reported and is found to be in good agreement with recent theoretical predictions (Gogelein, C.; Tuinier, R. Eur. Phys. J., E 2008, 27, 171-184).

8.
J Chem Phys ; 130(15): 154901, 2009 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-19388766

RESUMO

We compare the behavior of a new two-dimensional aqueous colloidal model system with a simple numerical treatment. To the first order the attractive interaction between the colloids induced by an in-plane rotating ac electric field is dipolar, while the charge stabilization leads to a shorter ranged, Yukawa-like repulsion. In the crystal-like "rafts" formed at sufficient field strengths, we find quantitative agreement between experiment and Monte Carlo simulation, except in the case of strongly interacting systems, where the well depth of the effective potential exceeds 250 times the thermal energy. The "lattice constant" of the crystal-like raft is located approximately at the minimum of the effective potential, resulting from the sum of the Yukawa and dipolar interactions. The experimental system has display applications, owing to the possibility of tuning the lattice spacing with the external electric field. Limitations in the applied field strength and relative range of the electrostatic interactions of the particles result in a reduction in tunable lattice spacing for small and large particles, respectively. The optimal particle size for maximizing the lattice spacing tunability was found to be around 1000 nm.

9.
J Phys Chem B ; 110(25): 12721-7, 2006 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-16800607

RESUMO

Microgel particles based on poly (N-isopropylacrylamide) have been shown to display an initial swelling behavior, followed by a collapse, with increasing concentration of added poly(ethylene oxide), PEO, chains. This paper considers the thermodynamic reasons for the observed expansion and subsequent shrinkage of the particles. At low concentrations of PEO, the free chains permeate into the microgel particles and cause an increase in osmotic pressure, expanding the particles. At higher concentrations of PEO, the particles are saturated and an increase in osmotic pressure in the external phase causes the particles to collapse again. The calculated magnitude of swelling and the effect of PEO molecular weight are, at least qualitatively, in agreement with the experimental observations reported elsewhere.

10.
Soft Matter ; 1(2): 160-165, 2005 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-32646086

RESUMO

A new method has been developed for the preparation of core-shell particles with thick, pH-responsive, polymer shells. In the first step, poly(vinylpyridine)(PVP) microgel particles are adsorbed onto oppositely-charged, ∼5 µm diameter silica spheres, to form "raspberry-like" structures. After separation, these "raspberries" are re-dispersed in water. A mixture of vinylpyridine and divinylbenzene (a cross-linking molecule), together with an oil-soluble initiator, are then added to the aqueous suspension. The added monomers and the initiator are absorbed into the sheath of PVP particles. Upon heating, the adsorbed PVP particles serve as the locus for further polymerisation, leading to seeded growth. The nature of the polymer shell formed is dependent on the level of surface coverage after the initial PVP particle adsorption step. A complete, irreversibly bound, polymer layer is only formed when the initial PVP particle surface coverage is high. The polymer shell possesses properties similar to those associated with microgel particles in solution, in that it was observed, using optical microscopy, to swell/de-swell in response to pH variation. Electron microscopy studies revealed that, in its de-swollen state, the polymer layer is thick and continuous. It is proposed that these types of core-shell particles could be of use for controlled release applications.

11.
Adv Colloid Interface Sci ; 106: 1-22, 2003 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-14672840

RESUMO

The phase behavior of mixtures of a cationic polyelectrolyte ('Jaguar') and an anionic surfactant (either sodium dodecyl sulfate or sodium lauryl ether sulfate) has been studied. For a given polyelectrolyte (and added NaCl) concentration, with increasing surfactant concentration, three phase regions were identified. The first region is a single homogeneous phase. Within this region, at some surfactant concentration, above the critical aggregation concentration, stable open-network 'particles' form, typically approximately 100 nm in size, which are net positively charged. However, as the surfactant concentration is increased further, these particles aggregate and form a two-phase system, i.e. a separated gel phase, containing a high percentage of water, co-existing with an aqueous surfactant phase. At some higher surfactant concentration still, the particles become sufficiently negatively charged that they re-stabilize. Beyond this surfactant concentration, therefore, the system reverts to being a single, homogeneous phase. Within the two-phase (aggregated particle) region an iso-electric point for the particles has been observed at a certain surfactant concentration, by electrophoresis. Furthermore, in this aggregated, gel-phase region, there appear to be typically approximately 2-4 surfactant molecules associated with each cationic site of the polymer chains. It is postulated that association of the anionic surfactant molecules occurs within the polyelectrolyte chains, binding them together, to form the particles referred to. These associated surfactant structures have been referred to here as 'internal' micelles. A crude estimate has been made, based on turbidity/time measurements, that there may be up to approximately 1000 polymer chains in each primary particle, bound together by the internal surfactant micelles. Small-angle light scattering studies of the aggregating particles indicate a fractal dimension for the aggregates, which would correspond to a diffusion-limited aggregation process.


Assuntos
Polissacarídeos/química , Dodecilsulfato de Sódio/química , Suspensões/química , Ânions/química , Cátions/química , Eletrólitos/química , Floculação , Nefelometria e Turbidimetria , Transição de Fase , Soluções , Tensoativos/química
12.
J Colloid Interface Sci ; 262(2): 536-47, 2003 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-16256636

RESUMO

The solubilization of styrene by poly(butyl methacrylate-g-methoxypoly(ethylene glycol)) and poly(methyl methacrylate-g-methoxypoly(ethylene glycol)) graft copolymers has been examined. From turbidity measurements the solubility limit of the monomer in the micelles was obtained and the distribution coefficients were evaluated. Dynamic light scattering revealed that below the solubility limit, solubilization leads to a slight increase in micelle size, while above the solubility limit, there is a dramatic increase in particle size and turbidity as oil-in-water emulsions are formed through coalescence of monomer-swollen micelles. Polymerizations carried out below the solubility limit using the graft copolymer micelles as templates resembled microemulsion polymerizations in nature and led to very fine sterically stabilized polystyrene latex particles. Through careful control of the monomer concentration and the polymerization temperature it was possible to obtain spherical nanosize latex particles with similar size to those of the micelle precursors (10 nm) up to 11% monomer by weight. Polymerizations above the solubility limit, on the other hand, showed similarities with emulsion polymerizations and resulted in larger particles with higher polydispersity.


Assuntos
Nanoestruturas , Poliestirenos/química , Emulsões , Metacrilatos/química , Polietilenoglicóis/química , Ácidos Polimetacrílicos/química , Polimetil Metacrilato/química , Solubilidade
13.
J Colloid Interface Sci ; 274(1): 49-54, 2004 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-15120277

RESUMO

Aqueous dispersions of cross-linked poly(methylmethacrylate)-g-poly(ethylene oxide) [PMMA-g-PEO] microgel particles have been prepared from mixtures of methylmethacrylate [MMA] and MMA-PEO macromonomer, with ethylene glycol dimethacrylate [EGDM] as the cross-linking monomer (0.2-0.5% wt%). The hydrodynamic radius of these (unswollen) microgel particles ranged from 73 to 85 nm, and the particles were essentially monodisperse with regard to their size distribution. Their swelling behavior has been investigated in the presence of both water-miscible and water-immiscible organic solvents. In general, with the addition of a water-miscible solvent, deswelling behavior was observed. However, the microgel particles were swollen on addition of 1,4-dioxan, which is a good solvent for PMMA. With water-immiscible organic solvents, the extent of swelling depended on the solvency properties of the organic liquid for PMMA. In the presence of benzene, the somewhat large increases in particle size have been attributed to weak flocculation. This has been assumed from an estimate of the van der Waals attraction energy between the swollen microgel particles.

14.
J Colloid Interface Sci ; 264(2): 538-47, 2003 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-16256676

RESUMO

The diffusion behavior of core-shell latex particles with a liquid core of hexadecane and a solid polystyrene shell in water solution has been studied using the pulsed field gradient spin-echo (PFG-SE) NMR technique. The apparent diffusion coefficient and the root mean square displacement of oil were strongly dependent on the diffusion time Delta. With increasing diffusion time, the obstructing effect from the particle wall caused a decrease in the apparent oil diffusion coefficient. The root mean square displacement of oil inside the particle core was constant for all diffusion times and was used for the calculation of the particle radius. The volume fraction dependence of the apparent diffusion coefficient was found to be roughly consistent with the hard-sphere model. The diffraction pattern in the echo decay predicted from the q-space formalism for molecules diffusing inside a spherical cavity was almost completely smeared out due to polydispersity and wall relaxation effects. It was observed that 10-20% (w/w) of the particle shell consisted of hexadecane. This fact imparted a slow component to the echo decay, since the exchange time between oil in the shell and oil in the cavity was slow, which further contributed to the smearing out of the diffraction pattern. It was concluded that by using the core-shell concept very good signal-to-noise is obtained in the PFG-SE experiment, thus making possible studies of translational properties of colloidal particles in different environments to an extent that previously has been very difficult to perform.

15.
J Colloid Interface Sci ; 273(2): 435-41, 2004 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-15082378

RESUMO

Experiments on the kinetics of heteroaggregation between oppositely charged particles, using both dynamic light scattering and turbidity methods, are reported. The negatively charged particles were cross-linked poly( [Formula: see text] -isopropylacrylamide) [PNIPAM] microgel particles, prepared using a carboxylic-acid-based initiator; these particles are swollen at room temperature. The positive particles were poly(4-vinylpyridine) [P4VP] particles, prepared using an amidinium-based initiator; such particles do not respond to temperature changes but do swell below pH approximately 4, where the pyridine moieties become protonated. As expected, the rate of heteroaggregation was shown to be largely independent of added salt concentration (up to approximately 20 mM), for a variety of alkali metal chlorides (MCl, where M = Li, Na, K, or Rb). However, an unexpected, significant decrease in the aggregation rate was observed at certain specific sodium chloride concentrations (typically at approximately 1 and also approximately 4 mM). Similar effects were not seen with the other alkali metal chloride salts. This strange effect was eventually attributed to the fact that the net charge on the positively charged P4VP particles had been reduced by the adsorption of (anionic) silicate species leached from the glassware container. Sodium silicates are known to be significantly more soluble than those of the other alkali metal ions, particularly at high pH. Moreover, P4VP particles dispersed in water, ostensibly at neutral pH, do buffer the aqueous medium to pH values around 9 or higher. This mechanism was confirmed by determining the electrophoretic mobility of the P4VP particles as a function of pH in the presence of the various alkali metal chloride salts. The mobility remained positive in 1 mM salt solutions over the pH range 3 to 11 for all the salts, except for sodium chloride; in that case the mobility reversed sign at alkaline pH values. A similar effect was observed for a cationic polystyrene latex sample, prepared with the same amidinium-based initiator. These experiments demonstrate the importance of soluble silicates, leached from glass storage vessels, particularly in the presence of sodium ions. Needless to say, the "anomalous" effects disappeared when plastic storage vessels were used in place of the glass ones.

16.
J Colloid Interface Sci ; 262(2): 548-59, 2003 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-16256637

RESUMO

A series of water-soluble, amphiphilic graft copolymers has been prepared by free-radical copolymerization of methoxypoly(ethylene glycol) macromonomers, with either methyl methacrylate or butyl methacrylate as the comonomers, in water/ethanol solvent mixtures. Lower molecular weight copolymers were obtained by increasing the concentration of the initiator, azobisisobutyronitrile (AIBN), used in the polymerization reaction. However, the route used also led to the formation of significant quantities of tetramethylsuccinodinitrile, a toxic byproduct resulting from the cage reaction of AIBN. Static fluorescence measurements using pyrene as a probe, along with 1H NMR experiments, showed that the graft copolymers form aggregates in water at very low concentrations (approximately 0.01 g l(-1)) with the pendant hydrophilic graft chains forming a stabilizing shell around the hydrophobic backbone. An increase in the hydrophile-lipophile balance of the graft copolymers was found to lead to smaller aggregates with lower aggregation numbers and highly swollen hydrophilic shells, as revealed by small angle neutron scattering (SANS).


Assuntos
Polietilenoglicóis/química , Ácidos Polimetacrílicos/química , Metacrilatos/química , Micelas , Polimetil Metacrilato/química , Soluções , Água
18.
Adv Colloid Interface Sci ; 203: 51-4, 2014 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-24345732

RESUMO

In 1913, J.W. McBain introduced the word "micelle" into surface and colloid chemistry in the context of the association of surfactant molecules in aqueous solution. This article gives a biographic account of McBain, and reviews the early work on micellar aggregation, leading up to the pioneering ideas of G.S. Hartley who introduced the first model of the spherical micelle that we would recognise today.

19.
Adv Colloid Interface Sci ; 137(2): 144-9, 2008 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-18461698
20.
Adv Colloid Interface Sci ; 170(1-2): 56-67, 2012 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-22257683

RESUMO

The history of colloid science, from its modern foundations in the mid-nineteenth century, has been strongly concerned with studies of the aggregation of colloidal particles. It was Thomas Graham (1861) who defined the word "colloid" (from the Greek word for glue) for those materials which could not pass through membranes, unlike smaller, truly-dissolved materials. Subsequently, Graham (1864), following earlier studies, principally by Selmi and Faraday, described "the power possessed by salts for destroying colloidal solutions". Although numerous, quantitative studies of particle aggregation were made in the years that followed, in particular, the determination of minimum electrolyte concentrations for the onset of particle aggregation and aggregation rates, no general theoretical framework emerged to account for these quantitative findings until the middle of the twentieth century. It was during and immediately following the Second World War that two sets of authors, Derjaguin and Landau, in Russia, and Verwey and Overbeek, in the Netherlands, independently came up with the theory that is now universally referred to as the DLVO theory of particle interactions and aggregation. All modern developments of the theory of particle aggregation use the DLVO theory as the keystone. However, the DLVO theory itself was based on a large body of experimental data in regard to particle aggregation obtained over the previous hundred years or so. This article is an attempt to review that body of experimental data and to show how this guided the DLVO authors in their thinking.

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