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1.
Manag Sport Leis ; 29(3): 433-444, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38550353

RESUMO

Rationale/Purpose: 1.Mass gathering events have resumed with the availability of SARS-CoV-2 vaccines. However, the pandemic is ongoing and such events potentially contribute to upsurges in COVID-19 cases. There is mounting evidence that public health mitigation strategies such as mask requirements, capacity restrictions, and physical distancing reduce transmission risk. However, evidence suggests imperfect compliance with these strategies. This study aimed to quantify spectators' masking behaviors and identify correlates of mask-wearing during a major sporting event. Design/Methodology/Approach: 2.This study used a repeated cross-sectional design, in which trained observers used a web-based application to record counts of mask-wearing. Findings: 3.Overall, 74% of spectators observed correctly wore masks. Mask-wearing behavior was associated with presumed sex, location of the spectator, game competitiveness, and whether the teams playing originated from a state with an active mask mandate. Implications: 4.Understanding the factors associated with masking behavior may help venues prepare for future events and identify innovative and targeted strategies to promote compliance with public health mitigation measures. Contribution: 5.This study makes contributions to understanding how to manage public health risks during a high-profile sporting event, specifically by identifying spectator-, game-, venue-, and state-level factors associated with mask-wearing.

2.
Soft Matter ; 19(27): 5169-5178, 2023 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-37401445

RESUMO

We report on the delamination of thin (≈µm) hydrogel films grafted to silicon substrates under the action of swelling stresses. Poly(dimetylacrylamide) (PDMA) films are synthesized by simultaneously cross-linking and grafting preformed polymer chains onto the silicon substrate using a thiol-ene reaction. The grafting density at the film/substrate interface is tuned by varying the surface density of reactive thiol-silane groups on the silicon substrate. Delamination of the films from well controlled line defects with low adhesion is monitored under a humid water vapor flow ensuring full saturation of the polymer network. A propagating delamination of the film is observed under the action of differential swelling stresses at the debonding front. A threshold thickness for the onset of this delamination is evidenced which is increasing with grafting density while the debonding velocity is also observed to decrease with an increase in grafting density. These observations are discussed within the framework of a nonlinear fracture mechanics model which assumes that the driving force for crack propagation is the difference between the swelling state of the bonded and delaminated parts of the film. Using this model, the threshold energy for crack initiation was determined from the measured threshold thickness and discussed in relation to the surface density of reactive thiol groups on the substrate.

3.
Gerontol Geriatr Med ; 9: 23337214231163438, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36968120

RESUMO

Avoidable hospitalizations among nursing home residents result in poorer health outcomes and excess costs. Consequently, efforts to reduce avoidable hospitalizations have been a priority over the recent decade. However, many potential interventions are time-intensive and require dedicated clinical staff, although nursing homes are chronically understaffed. The OPTIMISTIC project was one of seven programs selected by CMS as "enhanced care & coordination providers" and was implemented from 2012 to 2020. This qualitative study explores the perceptions of the nurses that piloted a virtual care support project developed to expand the program's reach through telehealth, and specifically considered how nurses perceived the effectiveness of this program. Relationships, communication, and access to information were identified as common themes facilitating or impeding the perceived effectiveness of the implementation of virtual care support programs within nursing homes.

4.
Polymers (Basel) ; 14(3)2022 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-35160488

RESUMO

Natural cellulose-based Caesalpinia sappan L. wood fiber (CSWF) has been demonstrated to have significant promise as a new untreated bio-reinforcement of the polybutylene succinate (PBS) composite film. The morphology, mechanical characteristics, and biodegradation were investigated. The morphology, the fiber distribution, and the fiber aggregation has been discussed. The properties of the composite have been improved by the addition of CSWF from 5 phr to 10 phr, while with the addition of 15 phr, the properties were dropped. The result showed that CSWF could be used as a new reinforcement without any treatment, and 10 phr of CSWF was the best formulation of a new biocomposite film. The PBS/CSWF10 composite film had the highest mechanical strength, with a tensile strength of 12.21 N/mm2 and an elongation at break of 21.01%, respectively. It was completely degraded by soil bury in three months. Therefore, the PBS/CSWF10 composite film has the potential to be a green with a promising short-term degradation.

5.
Pediatr Blood Cancer ; 69(5): e29546, 2022 05.
Artigo em Inglês | MEDLINE | ID: mdl-35107854

RESUMO

Despite treatment advancements and improved survival, approximately 1800 children in the United States will die of cancer annually. Survival may depend on nonclinical factors, such as economic stability, neighborhood and built environment, health and health care, social and community context, and education, otherwise known as social determinants of health (SDoH). Extant literature reviews have linked socioeconomic status (SES) and race to disparate outcomes; however, these are not inclusive of all SDoH. Thus, we conducted a systematic review on associations between SDoH and survival in pediatric cancer patients. Of the 854 identified studies, 25 were included in this review. In addition to SES, poverty and insurance coverage were associated with survival. More studies that include other SDoH, such as social and community factors, utilize prospective designs, and conduct analyses with more precise SDoH measures are needed.


Assuntos
Neoplasias , Determinantes Sociais da Saúde , Criança , Escolaridade , Humanos , Neoplasias/terapia , Pobreza , Estudos Prospectivos , Estados Unidos
6.
Langmuir ; 37(28): 8585-8593, 2021 07 20.
Artigo em Inglês | MEDLINE | ID: mdl-34236874

RESUMO

Surface-attached hydrogel films with well-controlled chemistry are a new approach of polymer thin layers and an actual alternative to polymer brushes and layer-by-layer assemblies. The advantage is that the thickness of hydrogel films can widely range from a few nanometers to several micrometers. Hydrogel films can also remarkably respond to stimuli such as temperature: (i) the thickness change is of great amplitude, fourfold and more, which could not be reached with the geometry of polymer brushes or layer-by-layer assemblies, (ii) the time response is very short (less than 1 s), and (iii) the swelling-to-collapse transition is narrow (a small temperature change of a few degrees may be enough). Poly(N-isopropylacrylamide) (PNIPAM) is the most temperature-responsive polymer investigated with a lower critical solution temperature (LCST) of around 32 °C. However, it is relevant to have the available polymers responding to various transition temperatures with the advantage of keeping the same chemistry. Poly[oligo(ethylene glycol) methacrylate] (PEGMA) meets these specifications since its transition temperature can be finely tuned with the number of oligo ethylene glycol units, while it attractively combines biocompatibility with PEG side chains. Here, we report the synthesis and the temperature-responsive properties of poly(PEGMA) hydrogel thin films. We used a simple, versatile, and well-controlled approach through thiol-ene click reaction, the so-called cross-linking and grafting, to synthesize surface-attached poly(PEGMA) hydrogel films with various thickness. We show that the transition temperature of poly(PEGMA) hydrogel films ranges from 15 to 60 °C if the number of PEG units is from 2 to 5. This transition temperature can also be finely adjusted for hydrogel films containing copolymers or mixing homopolymers of PEGMA with a suitable ratio. Moreover, the LCST properties, swelling-to-collapse amplitude and transition temperature, are not sensitive to salt. In particular, there is no effect on the LCST properties of surface-attached poly(PEGMA) hydrogel films in phosphate saline buffer, which is promising for applications in biology such as injectable hydrogels, drug delivery systems, hydrogel-based microfluidic valves, and flow switches for biotechnologies.


Assuntos
Hidrogéis , Polímeros , Metacrilatos , Transição de Fase , Temperatura
7.
Soft Matter ; 16(28): 6539-6548, 2020 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-32602511

RESUMO

We report on the transient frictional response of contacts between a rigid spherical glass probe and a micrometer-thick poly(dimethylacrylamide) hydrogel film grafted onto a glass substrate when a lateral relative motion is applied to the contact initially at rest. From dedicated experiments with in situ contact visualization, both the friction force and the contact size are observed to vary well beyond the occurrence of a full sliding condition at the contact interface. Depending on the imposed velocity and on the static contact time before the motion is initiated, either an overshoot or an undershoot in the friction force is observed. These observations are rationalized by considering that the transient is predominantly driven by the flow of water within the stressed hydrogel networks. From the development of a poroelastic contact model using a thin film approximation, we provide a theoretical description of the main features of the transient. We especially justify the experimental observation that the relaxation of friction force Ft(t) toward steady state is uniquely dictated by the time-dependence of the contact radius a(t), independently on the sliding velocity and on the applied normal load.

8.
Polymers (Basel) ; 12(1)2020 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-31936092

RESUMO

We investigate the adsorption of pH- or temperature-responsive polymer systems by ellipsometry and neutron reflectivity. To this end, temperature-responsive poly (N-isopropylacrylamide) (PNIPAM) brushes and pH-responsive poly (acrylic acid) (PAA) brushes have been prepared using the "grafting onto" method to investigate the adsorption process of polymers and its reversibility under controlled environment. To that purpose, macromolecular brushes were designed with various chain lengths and a wide range of grafting density. Below the transition temperature (LCST), the characterization of PNIPAM brushes by neutron reflectivity shows that the swelling behavior of brushes is in good agreement with the scaling models before they collapse above the LCST. The reversible adsorption on PNIPAM brushes was carried out with linear copolymers of N-isopropylacrylamide and acrylic acid, P(NIPAM-co-AA). While these copolymers remain fully soluble in water over the whole range of temperature investigated, a quantitative adsorption driven by solvophobic interactions was shown to proceed only above the LCST of the brush and to be totally reversible upon cooling. Similarly, the pH-responsive adsorption driven by electrostatic interactions on PAA brushes was studied with copolymers of NIPAM and N,N-dimethylaminopropylmethacrylamide, P(NIPAM-co-MADAP). In this case, the adsorption of weak polycations was shown to increase with the ionization of the PAA brush with interactions mainly located in the upper part of the brush at pH 7 and more deeply adsorbed within the brush at pH 9.

9.
Adv Mater ; 31(21): e1808179, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30924992

RESUMO

Sandcastle worms have developed protein-based adhesives, which they use to construct protective tubes from sand grains and shell bits. A key element in the adhesive delivery is the formation of a fluidic complex coacervate phase. After delivery, the adhesive transforms into a solid upon an external trigger. In this work, a fully synthetic in situ setting adhesive based on complex coacervation is reported by mimicking the main features of the sandcastle worm's glue. The adhesive consists of oppositely charged polyelectrolytes grafted with thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) chains and starts out as a fluid complex coacervate that can be injected at room temperature. Upon increasing the temperature above the lower critical solution temperature of PNIPAM, the complex coacervate transitions into a nonflowing hydrogel while preserving its volume-the water content in the material stays constant. The adhesive functions in the presence of water and bonds to different surfaces regardless of their charge. This type of adhesive avoids many of the problems of current underwater adhesives and may be useful to bond biological tissues.

10.
Langmuir ; 34(50): 15238-15244, 2018 12 18.
Artigo em Inglês | MEDLINE | ID: mdl-30452277

RESUMO

Hydrogel coatings absorb water vapor, or other solvents, and, as such, are good candidates for antifog applications. In the present study, the transfer of vapor from the atmosphere to hydrogel thin films is measured in a situation where water vapor flows alongside the coating which is set to a temperature lower than the ambient temperature. The effect of the physico-chemistry of the hydrogel film on the swelling kinetics is particularly investigated. By using model thin films of surface-grafted polymer networks with controlled thickness, varied cross-links density, and varied affinity for water, we were able to determine the effect of the film hygroscopy on the dynamics of swelling of the film. These experimental results are accounted for by a diffusion-advection model that is supplemented with a boundary condition at the hydrogel surface: we show that the latter can be determined from the equilibrium sorption isotherms of the polymer films. Altogether, this paper offers a predictive tool for the swelling kinetics of any hydrophilic hydrogel thin film.

11.
Langmuir ; 34(33): 9617-9626, 2018 08 21.
Artigo em Inglês | MEDLINE | ID: mdl-30028620

RESUMO

We report on the frictional behavior of thin poly(dimethylacrylamide) hydrogel films grafted on glass substrates in sliding contact with a glass spherical probe. Friction experiments are carried out at various velocities and normal loads applied with the contact fully immersed in water. In addition to friction force measurements, a novel optical setup is designed to image the shape of the contact under steady-state sliding. The velocity dependence of both friction force Ft and contact shape is found to be controlled by a Péclet number, Pe, defined as the ratio of the time τ needed to drain the water out of the contact region to a contact time a/ v, where v is the sliding velocity and a is the contact radius. When Pe < 1, the equilibrium circular contact achieved under static normal indentation remains unchanged during sliding. Conversely, for Pe > 1, a decrease in the contact area is observed together with the development of a contact asymmetry when the sliding velocity is increased. A maximum in Ft is also observed at Pe ≈1. These experimental observations are discussed in the light of a poroelastic contact model based on a thin-film approximation. This model indicates that the observed changes in contact geometry are due to the development of a pore pressure imbalance when Pe > 1. An order-of-magnitude estimate of the friction force and its dependence on normal load and velocity are also provided under the assumption that most of the frictional energy is dissipated by poroelastic flow at the leading and trailing edges of the sliding contact.

12.
PLoS One ; 12(12): e0189604, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29281693

RESUMO

Efficient deconstruction of plant biomass is a major barrier to the development of viable lignocellulosic biofuels. Pretreatment with ionic liquids reduces lignocellulose recalcitrance to enzymatic hydrolysis, increasing yields of sugars for conversion into biofuels. However, commercial cellulases are not compatible with many ionic liquids, necessitating extensive water washing of pretreated biomass prior to hydrolysis. To circumvent this issue, previous research has demonstrated that several thermophilic bacterial cellulases can efficiently deconstruct lignocellulose in the presence of the ionic liquid, 1-ethyl-3-methylimadizolium acetate. As promising as these enzymes are, they would need to be produced at high titer in an industrial enzyme production host before they could be considered a viable alternative to current commercial cellulases. Aspergillus niger has been used to produce high titers of secreted enzymes in industry and therefore, we assessed the potential of this organism to be used as an expression host for these ionic liquid-tolerant cellulases. We demonstrated that 29 of these cellulases were expressed at detectable levels in a wild-type strain of A. niger, indicating a basic level of compatibility and potential to be produced at high levels in a host engineered to produce high titers of enzymes. We then profiled one of these enzymes in detail, the ß-glucosidase A5IL97, and compared versions expressed in both A. niger and Escherichia coli. This comparison revealed the enzymatic activity of A5IL97 purified from E. coli and A. niger is equivalent, suggesting that A. niger could be an excellent enzyme production host for enzymes originally characterized in E. coli, facilitating the transition from the laboratory to industry.


Assuntos
Aspergillus niger/enzimologia , Celulases/metabolismo , Líquidos Iônicos/metabolismo , Biomassa , Celulases/genética , Escherichia coli/genética , Fermentação , Hidrólise , Proteínas Recombinantes/metabolismo
13.
ACS Appl Mater Interfaces ; 8(37): 24870-9, 2016 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-27560306

RESUMO

A new strategy for the fabrication of micropatterns of surface-attached hydrogels with well-controlled chemistry is reported. The "grafting onto" approach is preferred to the "grafting from" approach. It consists of cross-linking and grafting preformed and functionalized polymer chains through thiol-ene click chemistry. The advantage is a very good control without adding initiators. A powerful consequence of thiol-ene click reaction by UV irradiation is the facile fabrication of micropatterned hydrogel thin films by photolithography. It is achieved either with photomasks using common UV lamp or without photomasks by direct drawing due to laser technology. Our versatile approach allows the fabrication of various chemical polymer networks on various solid substrates. It is demonstrated here with silicon wafers, glass and gold surfaces as substrates, and two responsive hydrogels, poly(N-isopropylacrylamide) for its responsiveness to temperature and poly(acrylic acid) for its pH-sensitivity. We also demonstrate the fabrication of stable hydrogel multilayers (or stacked layers) in which each elementary layer height can widely range from a few nanometers to several micrometers, providing an additional degree of freedom to the internal architecture of hydrogel patterns. This facile route for the synthesis of micrometer-resolute hydrogel patterns with tailored architecture and multiresponsive properties should have a strong impact.

14.
ACS Appl Mater Interfaces ; 8(18): 11729-38, 2016 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-27008162

RESUMO

A facile route for the fabrication of surface-attached hydrogel thin films with well-controlled chemistry and tailored architecture on wide range of thickness from nanometers to micrometers is reported. The synthesis, which consists in cross-linking and grafting the preformed and ene-reactive polymer chains through thiol-ene click chemistry, has the main advantage of being well-controlled without the addition of initiators. As thiol-ene click reaction can be selectively activated by UV-irradiation (in addition to thermal heating), micropatterned hydrogel films are easily synthesized. The versatility of our approach is illustrated by the possibility to fabricate various chemical polymer networks, like stimuli-responsive hydrogels, on various solid substrates, such as silicon wafers, glass, and gold surfaces. Another attractive feature is the development of new complex hydrogel films with targeted architecture. The fabrication of various architectures for polymer films is demonstrated: multilayer hydrogel films in which single-networks are stacked one onto the other, interpenetrating networks films with mixture of two networks in the same layer, and nanocomposite hydrogel films where nanoparticles are stably trapped inside the mesh of the network. Thanks to its simplicity and its versatility this novel approach to surface-attached hydrogel films should have a strong impact in the area of polymer coatings.

15.
Langmuir ; 30(32): 9700-6, 2014 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-25099624

RESUMO

We investigated the effect of specific interactions on the structure of interfaces between a brush and a hydrogel on the polymer chain length scale. We used a model system for which the interactions between the brush and the gel are switchable. We synthesized weak polyelectrolyte brushes of poly(acrylic acid) and hydrogels of polyacrylamide and poly(N,N-dimethylacrylamide) which interact solely when the poly(acrylic acid) is mainly in its acidic form. The monomer density profiles of the poly(acrylic acid) brush immersed in pure deuterium oxide (D2O) or in contact with a D2O-swollen gel were determined by neutron reflectivity. At pH 2 when the brush is in its neutral form, it interacts with the gel by hydrogen bonds while at pH 9 when the brush is a polyelectrolyte it is not interacting with the gel. Our results show that the presence of interactions with the gel at pH 2 increases the swelling ratio of the brush relative to that in pure D2O, meaning that the brushes exhibit conformations which are more extended from the surface than in the absence of interactions.


Assuntos
Hidrogéis/química , Polímeros/química , Concentração de Íons de Hidrogênio , Nêutrons
16.
Langmuir ; 28(33): 12282-7, 2012 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-22823739

RESUMO

We investigated the surface structure of hydrogels of poly(N,N-dimethylacrylamide) (PDMA) hydrogels synthesized and cross-linked simultaneously by redox free radical polymerization. We demonstrate the existence of a less cross-linked layer at the surface of the gel at least at two different length scales characterized by shear rheology and by neutron reflectivity, suggesting the existence of a gradient in cross-linking. The composition of the layer is shown to depend on the degree of hydrophobicity of the mold surface and is weaker for more hydrophobic molds. While the macroscopic tests proved the existence of a relatively thick under-cross-linked layer, we also demonstrated by neutron reflectivity that the gel surface at the submicrometric scale (500 nm) was also affected by the surface treatment of the mold. These results should have important implications for the measurement of macroscopic surface properties of these hydrogels such as friction or adhesion.


Assuntos
Acrilamidas/química , Hidrogéis/química , Concentração de Íons de Hidrogênio , Reologia , Propriedades de Superfície , Temperatura
17.
Langmuir ; 27(3): 1232-40, 2011 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-21207954

RESUMO

Following the great success of traditional microfluidic devices across many disciplines, a new class of microfluidic systems emerged in recent years, which features finely tuned, localized surface modifications within the microstructures in order to keep up with the demand for devices of ever increasing complexity (lab on chip, assay on chip, etc.). Graft photopolymerization has become a powerful tool for such localized surface modifications particularly in combination with poly(dimethylsiloxane) (PDMS) devices, as it is compatible with many functional monomers and allows for high spatial resolution. However, application within enclosed PDMS microstructures and in particular well-controlled surface-directed polymerization remains challenging. Detailed understanding of the interaction between photoinitiator, benzophenone (BP), and polymer matrix is needed. We have developed a visualization technique, which allows for observation of reacted BP in situ within the PDMS matrix. We present a detailed study on solvent-driven BP diffusion providing results essential to successful surface treatment. We also identified and investigated photoinitiator inhibition by oxygen and provide appropriate mitigation strategies.


Assuntos
Benzofenonas/química , Dimetilpolisiloxanos/química , Polímeros/química , Absorção , Difusão
18.
Anal Chem ; 82(21): 8848-55, 2010 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-20919710

RESUMO

Many microfluidic applications require modified surface wettability of the microchannels. Patterning of wettability within enclosed microfluidic structures at high spatial resolution has been challenging in the past. In this paper, we report an improved method for altering the surface wettability in poly(dimethylsiloxane) (PDMS) microchannels by UV-induced graft polymerization of poly(acrylic acid). Our method presents significant improvements in terms of wettability contrast and spatial resolution of the patterned structures as compared to recent literature and is in particular applicable to complex microfluidic structures with a broad range of channel sizes and aspect ratios. A key part of our work is the clear description of the surface treatment process with the identification of key parameters, some of which have been overlooked, neglected, or misinterpreted in previous works. We have studied these key parameters in detail and provide recommended values for each parameter supported by experimental results. This detailed understanding of the treatment process and the effects of the critical parameters on it allowed us to significantly improve quality and reliability of the treatment process.

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