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1.
Health Qual Life Outcomes ; 22(1): 7, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38221610

RESUMO

BACKGROUND: The Short Warwick and Edinburgh Mental Wellbeing Scale (SWEMWBS) is a widely used non-preference-based measure of mental health in the UK. The primary aim of this paper is to construct an algorithm to translate the SWEMWBS scores to utilities using the Recovering Quality of Life Utility Index (ReQoL-UI) measure. METHODS: Service users experiencing mental health difficulties were recruited in two separate cross-sectional studies in the UK. The following direct mapping functions were used: Ordinary Least Square, Tobit, Generalised Linear Models. Indirect (response) mapping was performed using seemingly unrelated ordered probit to predict responses to each of the ReQoL-UI items and subsequently to predict using UK tariffs of the ReQoL-UI from SWEMWBS. The performance of all models was assessed by the mean absolute errors, root mean square errors between the predicted and observed utilities and graphical representations across the SWEMWBS score range. RESULTS: Analyses were based on 2573 respondents who had complete data on the ReQoL-UI items, SWEMWBS items, age and sex. The direct mapping methods predicted ReQoL-UI scores across the range of SWEMWBS scores reasonably well. Very little differences were found among the three regression specifications in terms of model fit and visual inspection when comparing modelled and actual utility values across the score range of the SWEMWBS. However, when running simulations to consider uncertainty, it is clear that response mapping is superior. CONCLUSIONS: This study presents mapping algorithms from SWEMWBS to ReQoL as an alternative way to generate utilities from SWEMWBS. The algorithm from the indirect mapping is recommended to predict utilities from the SWEMWBS.


Assuntos
Saúde Mental , Qualidade de Vida , Humanos , Qualidade de Vida/psicologia , Estudos Transversais , Psicometria/métodos , Exame Físico , Inquéritos e Questionários
2.
Int J Equity Health ; 22(1): 254, 2023 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-38066530

RESUMO

BACKGROUND: Cancer causes a major disease burden worldwide. This is increasingly being realised in low and middle-income countries, which account disproportionately for preventable cancer deaths. Despite the World Health Organization calling for governments to develop policies to address this and alleviate cancer inequality, numerous challenges in executing effective cancer policies remain, which require consideration of the country-specific context. As this has not yet been considered in Ghana, the aim of this review was to bring together and critique the social-environmental, health policy and system factors to identifying opportunities for future health policies to reduce cancer burden in the Ghanian context. A critical policy-focused review was conducted to bring together and critique the current health systems context relating to cancer in Ghana, considering the unmet policy need, health system and social factors contributing to the burden and policy advances related to cancer. CONCLUSION: The findings highlight the changing burden of cancer in Ghana and the contextual factors within the socio-ecosystem that contribute to this. Policies around expanding access to and coverage of services, as well as the harmonization with medical pluralism have potential to improve outcomes and increase equity but their implementation and robust data to monitor their impact pose significant barriers.


Assuntos
Neoplasias , Humanos , Gana , Política de Saúde , Neoplasias/prevenção & controle , Política Pública
3.
Qual Life Res ; 31(11): 3283-3292, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-35796997

RESUMO

PURPOSE: To estimate the association between changes in BMI and changes in Health-Related Quality of Life (EQ-5D-3L). METHODS: The WRAP trial was a multicentre, randomised controlled trial with parallel design and recruited 1267 adults (BMI ≥ 28 kg/m2). Participants were allocated to Brief Intervention, a Commercial weight management Programme (WW, formerly Weight Watchers) for 12 weeks, or the same Programme for 52 weeks. Participants were assessed at 0, 3, 12, 24, and 60 months. We analysed the relationship between BMI and EQ-5D-3L, adjusting for age and comorbidities, using a fixed effects model. Test for attrition, model specification and missing data were conducted. Secondary analyses investigated a non-symmetric gradient for weight loss vs. regain. RESULTS: A unit increase in BMI was associated with a - 0.011 (95% CI - 0.01546, - 0.00877) change in EQ-5D-3L. A unit change in BMI between periods of observation was associated with - 0.016 017 (95% CI - 0.0077009, - 0.025086) change in EQ-5D-3L. The negative association was reduced during weight loss, as opposed to weight gain, but the difference was not statistically significant. CONCLUSIONS: We have identified a strong and statistically significant negative relationship between BMI changes and HRQoL. These estimates could be used in economic evaluations of weight loss interventions to inform policymaking. CLINICAL TRIAL REGISTRATION: This trial was registered with Current Controlled Trials, number ISRCTN82857232.


Assuntos
Qualidade de Vida , Redução de Peso , Adulto , Índice de Massa Corporal , Análise Custo-Benefício , Humanos , Qualidade de Vida/psicologia , Inquéritos e Questionários
4.
BMC Cancer ; 21(1): 1237, 2021 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-34794404

RESUMO

BACKGROUND: The types of outcomes measured collected in clinical studies and those required for cost-effectiveness analysis often differ. Decision makers routinely use quality adjusted life years (QALYs) to compare the benefits and costs of treatments across different diseases and treatments using a common metric. QALYs can be calculated using preference-based measures (PBMs) such as EQ-5D-3L, but clinical studies often focus on objective clinician or laboratory measured outcomes and non-preference-based patient outcomes, such as QLQ-C30. We model the relationship between the generic, preference-based EQ-5D-3L and the cancer specific quality of life questionnaire, QLQ-C30 in patients with breast cancer. This will result in a mapping that allows users to convert QLQ-C30 scores into EQ-5D-3L scores for the purposes of cost-effectiveness analysis or economic evaluation. METHODS: We use data from a randomized trial of 602 patients with HER2-positive advanced breast cancer provided 3766 EQ-5D-3L observations. Direct mapping using adjusted, limited dependent variable mixture models (ALDVMM) is compared to a random effects linear regression and indirect mapping using seemingly unrelated ordered probit models. EQ-5D-3L was estimated as a function of the summary scales of the QLQ-C30 and other patient characteristics. RESULTS: A four component mixture model outperformed other models in terms of summary fit statistics. A close fit to the observed data was observed across the range of disease severity. Simulated data from the model closely aligned to the original data and showed that mapping did not significantly underestimate uncertainty. In the simulated data, 22.15% were equal to 1 compared to 21.93% in the original data. Variance was 0.0628 in the simulated data versus 0.0693 in the original data. The preferred mapping is provided in Excel and Stata files for the ease of users. CONCLUSION: A four component adjusted mixture model provides reliable, non-biased estimates of EQ-5D-3L from the QLQ-C30, to link clinical studies to economic evaluation of health technologies for breast cancer. This work adds to a growing body of literature demonstrating the appropriateness of mixture model based approaches in mapping.


Assuntos
Neoplasias da Mama/tratamento farmacológico , Qualidade de Vida , Anos de Vida Ajustados por Qualidade de Vida , Inquéritos e Questionários , Ado-Trastuzumab Emtansina/uso terapêutico , Antineoplásicos Imunológicos/uso terapêutico , Ensaios Clínicos Fase III como Assunto , Análise Custo-Benefício/métodos , Feminino , Humanos , Modelos Lineares , Pessoa de Meia-Idade , Ensaios Clínicos Controlados Aleatórios como Assunto , Índice de Gravidade de Doença , Incerteza
5.
Value Health ; 21(12): 1399-1405, 2018 12.
Artigo em Inglês | MEDLINE | ID: mdl-30502783

RESUMO

BACKGROUND: Preference-based measures of health, such as the three-level EuroQol five-dimensional questionnaire (EQ-5D-3L), are required to calculate quality-adjusted life-years for use in cost-effectiveness analysis, but are often not recorded in clinical studies. In these cases, mapping can be used to estimate preference-based measures. OBJECTIVES: To model the relationship between the EQ-5D-3L and the Functional Assessment of Cancer Therapy-Breast Cancer (FACT-B) instrument, comparing indirect and direct mapping methods, and the use of FACT-B summary score versus FACT-B subscale scores. METHODS: We used data from three clinical studies for advanced breast cancer providing 11,958 observations with full information on FACT-B and the EQ-5D-3L. We compared direct mapping using adjusted limited dependent variable mixture models (ALDVMMs) with indirect mapping using seemingly unrelated ordered probit models. The EQ-5D-3L was estimated as a function of FACT-B and other patient-related covariates. RESULTS: The use of FACT-B subscale scores was better than using the total FACT-B score. A good fit to the observed data was observed across the entire range of disease severity in all models. ALDVMMs outperformed the indirect mapping. The breast cancer-specific scale had a strong influence in predicting the pain/discomfort and self-care dimensions of the EQ-5D-3L. CONCLUSIONS: This article adds to the growing literature that demonstrates the performance of the ALDVMM method for mapping. Regardless of which model is used, the subscales of FACT-B should be included as independent variables wherever possible. The breast cancer-specific subscale of FACT-B is important in predicting the EQ-5D-3L. This suggests that generic cancer measures should not be used for utility mapping in patients with breast cancer.


Assuntos
Algoritmos , Neoplasias da Mama , Qualidade de Vida , Inquéritos e Questionários , Atividades Cotidianas , Adulto , Análise Custo-Benefício , Feminino , Nível de Saúde , Humanos , Pessoa de Meia-Idade , Anos de Vida Ajustados por Qualidade de Vida
6.
Value Health ; 21(6): 748-757, 2018 06.
Artigo em Inglês | MEDLINE | ID: mdl-29909881

RESUMO

BACKGROUND: Studies have shown that methods based on mixture models work well when mapping clinical to preference-based methods. OBJECTIVES: To develop these methods in different ways and to compare performance in a case study. METHODS: Data from 856 patients with asthma allowed mapping between the Asthma Quality of Life Questionnaire and both the five-level EuroQol five-dimensional questionnaire (EQ-5D-5L) and the health utilities index mark 3 (HUI3). Adjusted limited dependent variable mixture models and beta-based mixture models were estimated. Optional inclusion of the gap between full health and the next value as well as a mass point at the next feasible value were explored. RESULTS: In all cases, model specifications formally modeling the gap between full health and the next feasible value were an improvement on those that did not. Mapping to the HUI3 required more components in the mixture models than did mapping to the EQ-5D-5L because of its uneven distribution. The optimal beta-based mixture models mapping to the HUI3 included a probability mass at the utility value adjacent to full health. This is not the case when estimating the EQ-5D-5L, because of the low proportion of observations at this point. CONCLUSIONS: Beta-based mixture models marginally outperformed adjusted limited dependent variable mixture models with the same number of components in this data set. Nevertheless, they require a larger number of parameters and longer estimation time. Both mixture model types closely fit both EQ-5D-5L and HUI data. Standard mapping approaches typically lead to biased estimates of health gain. The mixture model approaches exhibit no such bias. Both can be used with confidence in applied cost-effectiveness studies. Future mapping studies in other disease areas should consider similar methods.


Assuntos
Antiasmáticos/uso terapêutico , Asma/tratamento farmacológico , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Algoritmos , Asma/psicologia , Feminino , Nível de Saúde , Humanos , Masculino , Pessoa de Meia-Idade , Modelos Estatísticos , Preferência do Paciente , Probabilidade , Qualidade de Vida , Anos de Vida Ajustados por Qualidade de Vida , Inquéritos e Questionários , Resultado do Tratamento , Adulto Jovem
7.
BMC Public Health ; 18(1): 500, 2018 04 16.
Artigo em Inglês | MEDLINE | ID: mdl-29807535

RESUMO

BACKGROUND: The prevalence of childhood obesity has been increasing but the causes are not fully understood. Recent public health interventions and guidance aiming to reduce childhood obesity have focused on the whole family, as opposed to just the child but there remains a lack of empirical evidence examining this relationship. METHODS: Using data from the longitudinal Millennium Cohort Study (MCS), we investigate the dynamic relationship between underlying family lifestyle and childhood obesity during early childhood. The MCS interviewed parents shortly after the birth of their child and follow up interviews were carried out when the child was 3, 5 and 7 years. We use a dynamic latent factor model, an approach that allows us to identify family lifestyle, its evolution over time (in this case between birth and 7 years) and its influence on childhood obesity and other observable outcomes. RESULTS: We find that family lifestyle is persistent, 87.43% of families which were above the 95th percentile on the lifestyle distribution, remained above the 95th percentile when the child was 7 years old. Family lifestyle has a significant influence on all outcomes in the study, including diet, exercise and parental weight status; family lifestyle accounts for 11.3% of the variation in child weight by age 7 years. CONCLUSION: The analysis suggests that interventions should therefore be prolonged and persuasive and target the underlying lifestyle of a family as early as possible during childhood in order to have the greatest cumulative influence. Our results suggest that children from advantaged backgrounds are more likely to be exposed to healthier lifestyles and that this leads to inequalities in the prevalence of obesity. To reduce inequalities in childhood obesity, policy makers should target disadvantaged families and design interventions specifically for these families.


Assuntos
Família/psicologia , Estilo de Vida , Obesidade Infantil/epidemiologia , Criança , Pré-Escolar , Feminino , Humanos , Estudos Longitudinais , Masculino , Prevalência , Reino Unido/epidemiologia
9.
Soft Matter ; 10(10): 1572-8, 2014 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-24652005

RESUMO

How stress or strain imparts mobility to glasses is a scientific issue linking ideas of jamming and the glass transition across colloids, granular materials, polymers, and molecular glasses. Here, we address for the first time how stress applied during vitrification, formation of the glassy state by a temperature quench, affects the subsequent stability of the glassy state, even after the stress has been removed. Using entangled polymers that are easily manipulated mechanically above the glass transition temperature, we find that the resulting polymer glasses become less stable, exhibiting a higher physical aging rate, when stress is applied while rapidly cooling the polymer films. The data show an initial plateau value at low stress, before transitioning rapidly to a higher aging rate at larger stress. These results are suggestive of the glassy system being left trapped in a less stable, higher energy state with faster physical aging rate when stressed above some minimum value during vitrification.

10.
PLoS One ; 19(6): e0305124, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38861509

RESUMO

BACKGROUND: Since the early 2000s, there have been marked trends in adolescent health and wellbeing indicators across Europe, North America and Australia. In particular, there have been substantial declines in youth drinking. We know little about how these trends are underpinned by co-occurring indicators within individuals. This paper aims to analyse change over time in how indicators cluster within individuals and differences in these patterns between five countries with different trends in youth drinking. METHODS: We analysed four waves of repeat cross-sectional survey data from 15-year-olds in England (n = 5942), Italy (n = 5234), the Netherlands (n = 5408), Hungary (n = 5274), and Finland (n = 7446), which were included in the Health Behaviours in School-aged Children (HBSC) study between 2001/02 and 2013/14. We defined clusters of individuals using multigroup latent class analyses which accounts for change over time. The class indicators included health behaviours, attitudes, wellbeing and relationships. We modelled associations between class membership, sex, and family affluence over time. RESULTS: We identified four classes in all countries: Overall unhealthy, Overall healthy, Moderately healthy and Substance abstainers with behaviour risk indicators. The proportion of adolescents in the Overall unhealthy class declined between 2001/02 and 2013/14 by between 22.8 percentage points (pp) in England and 3.2pp in Italy. The extent to which indicators of health and wellbeing changed as linked clusters differed across countries, but changes in alcohol consumption, smoking, drug use and sexual activity were typically concurrent. Adolescents with low family affluence were more likely to be in the Overall unhealthy class in all years. CONCLUSIONS: Improvements in indicators of adolescent health and well-being are due mainly to concurrent declines in drinking, smoking, sexual activity, and cannabis use, but these declines are not consistently associated with improvements in other domains. They have also not led to reductions in inequalities in indicators of health and well-being.


Assuntos
Saúde do Adolescente , Análise de Classes Latentes , Humanos , Adolescente , Estudos Transversais , Masculino , Feminino , Inglaterra , Itália/epidemiologia , Comportamentos Relacionados com a Saúde , Países Baixos/epidemiologia , Comportamento do Adolescente/psicologia , Hungria , Finlândia , Consumo de Bebidas Alcoólicas/epidemiologia
11.
Obesity (Silver Spring) ; 31(3): 823-831, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36746761

RESUMO

OBJECTIVE: This study aims to understand long-term trends in obesity and overweight in England by estimating life-course transitions as well as historical and birth cohort trends for both children and adults. METHODS: Data on individuals aged 5 to 85 years old from the Health Survey for England were used, covering the period 1992 to 2019 and birth cohorts born between 1909 and 2013. Individual BMI values were classified as healthy weight, overweight, or obesity. Trends were compared, and an age-period-cohort model was estimated using logistic regression and categorical age, period, and cohort groups. RESULTS: There was significant variation in age trajectories by birth cohorts for healthy weight and obesity prevalence. The odds of having obesity compared with a healthy weight increased consistently with age, increased throughout the study period (but faster between 1992 and 2001), and were higher for birth cohorts born between 1989 and 2008. The odds of having overweight showed an inverted U-shape among children, increased through adulthood, have been stable since 2012, and were considerably higher for the youngest birth cohort (2009-2013). CONCLUSIONS: Younger generations with higher overweight prevalence coupled with increasing obesity prevalence with age suggest that obesity should remain a high priority for public health policy makers in England.


Assuntos
Obesidade , Sobrepeso , Adulto , Criança , Feminino , Humanos , Pré-Escolar , Adolescente , Adulto Jovem , Pessoa de Meia-Idade , Idoso , Idoso de 80 Anos ou mais , Sobrepeso/epidemiologia , Índice de Massa Corporal , Estudos de Coortes , Obesidade/epidemiologia , Inglaterra/epidemiologia , Prevalência
12.
Prev Med Rep ; 36: 102481, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37881177

RESUMO

In England, the proportion of 13-15 year-olds who have ever drunk alcohol fell from 71% in 1999 to 35% in 2019. Despite substantial research literature studying this decline, we know little about connections with concurrent shifts in wider aspects of health and wellbeing. This paper aims to identify how indicators of health and wellbeing cluster within 15-year-olds in England, identify changes in clustering over time, and explore associations with sex and family affluence. We used latent class analysis of cross-sectional data from the Health Behaviours in School-aged Children study (n = 5,942; four waves 2001/02-2013/14). Classes were defined by indicators of substance use, sexual activity, diet, exercise, school-related measures, e-media use, parental relationships, and wellbeing. We identified three classes, which we labelled Overall unhealthy, Substance abstainers with behavioural risk indicators, and Overall healthy. The probability of being in the Overall unhealthy class fell (2001/02: 0.39; 2013/14: 0.18) while the probability of being in the Overall healthy class increased (0.21 to 0.41). The probability of weekly alcohol use fell in all classes (e.g. Overall unhealthy: 0.71 to 0.28). Females (female vs male OR: 1.74 95%CI: 1.30 - 2.34) and those with low family affluence (high vs low family affluence OR: 0.18 95%CI: 0.08 - 0.44) had significantly higher odds of being in the Overall unhealthy class. Overall, adolescents became more likely to have co-occurring indicators of good health and wellbeing, including reduced alcohol consumption, sexual activity and cigarette smoking. However, girls and those from poorer families remained more likely to have poor health and wellbeing.

13.
Obesity (Silver Spring) ; 30(9): 1898-1907, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35920148

RESUMO

OBJECTIVE: BMI is known to have an association with morbidities and mortality. Many studies have argued that identifying health risks using single BMI measures has limitations, particularly in older adults, and that changes in BMI can help to identify risks. This study identifies distinct BMI trajectories and their association with the risks of a range of morbidities and mortality. METHODS: The English Longitudinal Study of Aging provides data on BMI, mortality, and morbidities between 1998 and 2015, sampled from adults over 50 years of age. This study uses a growth-mixture model and discrete-time survival analysis, combined using a two-step approach, which is novel in this setting, to the authors' knowledge. RESULTS: This study identified four trajectories: "stable overweight," "elevated BMI," "increasing BMI," and "decreasing BMI." No differences in mortality, cancer, or stroke risk were found between these trajectories. BMI trajectories were significantly associated with the risks of diabetes, asthma, arthritis, and heart problems. CONCLUSIONS: These results emphasize the importance of looking at change in BMI alongside most recent BMI; BMI trajectories should be considered where possible when assessing health risks. The results suggest that established BMI thresholds should not be used in isolation to identify health risks, particularly in older adults.


Assuntos
Sobrepeso , Idoso , Índice de Massa Corporal , Humanos , Estudos Longitudinais , Pessoa de Meia-Idade , Morbidade , Sobrepeso/epidemiologia , Fatores de Risco , Análise de Sobrevida
14.
BMJ Open ; 12(10): e065153, 2022 10 05.
Artigo em Inglês | MEDLINE | ID: mdl-36198450

RESUMO

OBJECTIVES: Multiple social-cultural and contextual factors influence access to and acceptance of cancer treatment in Ghana. The aim of this research was to assess existing literature on how these factors interplay and could be susceptible to local and national policy changes. DESIGN: This study uses a critical interpretive synthesis approach to review qualitative and quantitative evidence about access to adult cancer treatment services in Ghana, applying the socioecological model and candidacy framework. RESULTS: Our findings highlighted barriers to accessing cancer services within each level of the socioecological model (intrapersonal, interpersonal community, organisational and policy levels), which are dynamic and interacting, for example, community level factors influenced individual perceptions and how they managed financial barriers. Evidence was lacking in relation to determinants of treatment non-acceptance across all cancers and in the most vulnerable societal groups due to methodological limitations. CONCLUSIONS: Future policy should prioritise multilevel approaches, for example, improving the quality and affordability of medical care while also providing collaboration with traditional and complementary care systems to refer patients. Research should seek to overcome methodological limitations to understand the determinants of accessing treatment in the most vulnerable populations.


Assuntos
Acessibilidade aos Serviços de Saúde , Neoplasias , Adulto , Custos e Análise de Custo , Gana , Humanos , Neoplasias/terapia , Pesquisa Qualitativa , Populações Vulneráveis
15.
PLoS One ; 17(9): e0271315, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36054087

RESUMO

While all lower limb prosthesis walkers have a high risk of tripping and/or falling, above knee prosthesis users are reported to fall more frequently. Recognising this, engineers designed microprocessor knees (MPK) to help mitigate these risks, but to what extent these devices reduce this disparity between above and below knee users is unclear. A service review was carried out in a prosthetic limb centre regarding the frequency of trips and falls in the previous four weeks. Data from unilateral, community ambulators were extracted. Ordered logistic regressions were applied to investigate whether MPKs mitigated the increased risk of trips and falls for prosthetic knee users, compared to below knee prosthesis users. Socio-demographics (sex, age), prosthesis (prosthesis type, years of use), health (comorbidities, vision, contralateral limb status, medication), and physical function (use of additional walking aids, activity level) were included as covariates. Of the 315 participants in the analysis, 57.5% reported tripping and 20.3% reported falling. Non-microprocessor prosthetic knee (non-MPK) users were shown to trip significantly more than below knee prosthesis users (OR = 1.96, 95% CI = 1.17-3.28). Other covariates showing a significant association included contralateral limb injuries (OR = 1.91, 95% CI = 1.15-3.18) and using an additional walking aid (OR = 1.99, 95% CI = 1.13-3.50). Non-MPK users were also shown to fall significantly more than below knee prosthesis users (OR = 3.34, 95% CI = 1.73-6.45), with no other covariates showing a significant association. MPK users did not show an increased frequency of trips (OR = 0.74, 95% CI = 0.33-1.64) or falls (OR = 0.34, 95% CI = 0.18-2.62), compared to below knee prosthesis users. Of those who tripped at least once in the previous four weeks, those using a non-MPK (OR = 2.73, 95% CI = 1.30-5.74) presented an increased frequency of falling. These findings provide evidence to suggest that the use of MPKs reduces the difference in falls risk between above knee and below knee prosthesis users, providing justification for their provision.


Assuntos
Amputados , Membros Artificiais , Prótese do Joelho , Acidentes por Quedas/prevenção & controle , Humanos , Microcomputadores , Desenho de Prótese , Caminhada
16.
Macromolecules ; 52(14): 5399-5406, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31367064

RESUMO

Despite the growing application of nanostructured polymeric materials, there still remains a large gap in our understanding of polymer mechanics and thermal stability under confinement and near polymer-polymer interfaces. In particular, the knowledge of polymer nanoparticle thermal stability and mechanics is of great importance for their application in drug delivery, phononics, and photonics. Here, we quantified the effects of a polymer shell layer on the modulus and glass-transition temperature (T g) of polymer core-shell nanoparticles via Brillouin light spectroscopy and modulated differential scanning calorimetry, respectively. Nanoparticles consisting of a polystyrene (PS) core and shell layers of poly(n-butyl methacrylate) (PBMA) were characterized as model systems. We found that the high T g of the PS core was largely unaffected by the presence of an outer polymer shell, whereas the lower T g of the PBMA shell layer decreased with increasing PBMA thickness. The surface mobility was revealed at a temperature about 15 K lower than the T g of the PBMA shell layer. Overall, the modulus of the core-shell nanoparticles decreased with increasing PBMA shell layer thickness. These results suggest that the nanoparticle modulus and T g can be tuned independently through the control of nanoparticle composition and architecture.

17.
Macromolecules ; 51(21): 8522-8529, 2018 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-30906073

RESUMO

Advances in nanoparticle synthesis, self-assembly, and surface coating or patterning have enabled a diverse array of applications ranging from photonic and phononic crystal fabrication to drug delivery vehicles. One of the key obstacles restricting its potential is structural and thermal stability. The presence of a glass transition can facilitate deformation within nanoparticles, thus resulting in a significant alteration in structure and performance. Recently, we detected a glassy-state transition within individual polystyrene nanoparticles and related its origin to the presence of a surface layer with enhanced dynamics compared to the bulk. The presence of this mobile layer could have a dramatic impact on the thermal stability of polymer nanoparticles. Here, we demonstrate how the addition of a shell layer, as thin as a single polymer chain, atop the nanoparticles could completely eliminate any evidence of enhanced mobility at the surface of polystyrene nanoparticles. The ultrathin polymer shell layers were placed atop the nanoparticles via two approaches: (i) covalent bonding or (ii) electrostatic interactions. The temperature dependence of the particle vibrational spectrum, as recorded by Brillouin light scattering, was used to probe the surface mobility of nanoparticles with and without a shell layer. Beyond suppression of the surface mobility, the presence of the ultrathin polymer shell layers impacted the nanoparticle glass transition temperature and shear modulus, albeit to a lesser extent. The implication of this work is that the core-shell architecture allows for tailoring of the nanoparticle elasticity, surface softening, and glass transition temperature.

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