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1.
Front Psychiatry ; 15: 1377433, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39114738

RESUMO

In 2009, Massachusetts General Hospital and the Red Sox Foundation launched Home Base, a nonprofit dedicated to providing care to veterans, service members, and their loved ones who struggle with the invisible wounds of war free of charge. Significant needs exist for mental health services in each of these populations, and a need for innovative approaches to address shortcomings in existing treatment models. Three inventive components of our programming are highlighted herein: a Veteran Outreach Team, which helps to engage patients in care, programming, and services specifically for family members, and an intensive outpatient substance use treatment program. More than 4,000 patients, 3,031 veterans and service members, and 1,025 family members have engaged in treatment at Home Base. Patients were asked to complete post-treatment self-measures, including a satisfaction questionnaire via an electronic data collection system. The vast majority of individuals who engaged in our treatment model were satisfied with the care they received (>92%) and would refer their peers to the Home Base program (>75%). Data from 78 individuals who completed the dual diagnosis services demonstrated large effect sizes in reductions in alcohol use and comorbid mental health symptoms. These data suggest that novel components to the standard outpatient mental health model might provide substantive benefits for the patients served. While internal data is prone to a lack of generalizability, these additional offerings help ameliorate patients' expressed shortcomings with existing models; present literature that describes the benefits that these additions provide is also reviewed. The lessons learned and limitations are discussed.

2.
Child Adolesc Ment Health ; 29(1): 33-42, 2024 02.
Artigo em Inglês | MEDLINE | ID: mdl-37431157

RESUMO

BACKGROUND: Screen media activity (SMA) can negatively affect youth behavioral health. Sleep may mediate this association but has not been previously explored. We examined whether sleep mediated the association between SMA and youth behavioral health among a community sample. METHOD: Parents completed questions about their child (N = 564) ages 3-17 at Wave 1, Wave 2 (4-8 months later), and Wave 3 (12 months later). Path analyses were conducted to examine links between Wave 1 SMA and Wave 3 behavioral health problems (i.e., internalizing, externalizing, attention, peer problems) through Wave 2 sleep disturbance and duration. RESULTS: SMA was significantly associated with greater sleep disturbance, ß = .11, 95% CI [.01, .21] and shorter sleep duration, ß = -.16 [-.25, -.06], and greater sleep disturbance was associated with worse youth behavioral health across internalizing, ß = .14 [.04, .24], externalizing, B = .23 [.12, .33], attention, ß = .24 [.15, .34], and peer problems, ß = .25 [.15, .35]. Longer sleep duration was associated with more externalizing, ß = .13 [.04, .21], and attention problems, ß = .12 [.02, .22], and fewer peer problems, ß = -.09 [-.17, -.01], but not with internalizing problems. Lastly, there was a direct effect of SMA on peer problems, ß = -.15 [-.23, -.06] such that higher SMA that does not impact sleep may have a positive impact on reducing peer problems. CONCLUSIONS: Sleep (i.e., disturbances and shorter duration) may partially account for the small associations observed between SMA and worse behavioral health in youth. To continue expanding our understanding, future research should utilize more diverse representative samples, use objective measures of SMA and sleep, and examine other relevant aspects of SMA, including content, device type, and timing of use.


Assuntos
Comportamento Problema , Transtornos do Sono-Vigília , Adolescente , Criança , Humanos , Pais , Sono , Duração do Sono , Transtornos do Sono-Vigília/epidemiologia , Pré-Escolar
3.
Psychol Trauma ; 14(S1): S4-S12, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-34591535

RESUMO

OBJECTIVE: Caregivers with a history of trauma exposure may struggle to parent effectively, particularly when symptoms of PTSD are prominent. Consequently, identifying factors that buffer associations between PTSD and poor parental functioning is critical to help trauma-exposed families thrive. One important source of resilience may spring from being part of a socially cohesive neighborhood that offers positive social connections and resources. The purpose of this study was to examine whether greater neighborhood cohesion buffers associations between PTSD and perceived parental functioning. METHOD: A diverse national sample of 563 Black and White veterans raising children in single or dual parent households completed questionnaires assessing PTSD symptoms and neighborhood cohesion at baseline, as well as parental functioning four months later. RESULTS: Multigroup moderation analyses that controlled for crime index, income, and sex revealed that among single Black veterans, but not other groups, the relationship between higher PTSD and poorer parental functioning was weakened for veterans who reported higher neighborhood cohesion. CONCLUSIONS: Findings suggest that PTSD symptoms and neighborhood cohesion affect parenting differently across racial and family makeup configurations, and that higher neighborhood cohesion might be particularly useful in buffering the association between PTSD and parenting among single Black veterans. (PsycInfo Database Record (c) 2022 APA, all rights reserved).


Assuntos
Transtornos de Estresse Pós-Traumáticos , Veteranos , Criança , Humanos , Poder Familiar , Pais , Características de Residência
4.
Artigo em Inglês | MEDLINE | ID: mdl-34474510

RESUMO

The Psychiatric Consultation Service at Massachusetts General Hospital sees medical and surgical inpatients with comorbid psychiatric symptoms and conditions. During their twice-weekly rounds, Dr Stern and other members of the Consultation Service discuss diagnosis and management of hospitalized patients with complex medical or surgical problems who also demonstrate psychiatric symptoms or conditions. These discussions have given rise to rounds reports that will prove useful for clinicians practicing at the interface of medicine and psychiatry.


Assuntos
Transtornos Mentais , Psiquiatria , Veteranos , Hospitais Gerais , Humanos , Transtornos Mentais/diagnóstico , Transtornos Mentais/epidemiologia , Transtornos Mentais/terapia , Encaminhamento e Consulta
5.
J Trauma Stress ; 32(5): 724-732, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31433527

RESUMO

It has been well established that warfare-related stress puts service members at risk for a range of mental health problems after they return from deployment. Less is known about service members' experience of family stressors during deployment. The aims of this study were to (a) evaluate whether family stressors would contribute unique variance to posttraumatic stress disorder (PTSD) and depressive symptoms above and beyond combat threat during deployment and (b) examine whether family stressors would amplify the negative effects of combat threat on postmilitary mental health 5 years postdischarge. Study participants reported their experience of objective and subjective family stressors and combat threat during deployment. Objective family stressors demonstrated unique associations with PTSD and depression symptoms and remained significant after accounting for ongoing family stressors reported at follow-up. A significant interaction was found between objective family stressors and combat threat on PTSD symptoms, r = -.10. Although the association between combat threat and PTSD was significant for participants who reported high, B = 0.04; and low, B = 0.09, exposure to family stressors, the steeper slope for those exposed to fewer family stressors indicates a stronger effect of combat threat. Follow-up analyses revealed that veterans who experienced high amounts of family stress and high levels of combat threat reported significantly worse PTSD symptoms than those who reported low family stress, t(256) = 3.98, p < .001. Findings underscore the importance of attending to the role that family stressors experienced during deployment play in service members' postmilitary mental health.


Spanish Abstracts by Asociación Chilena de Estrés Traumático (ACET) Impactos a largo plazo de estresores familiares y amenazas de combate sobre la salud mental de los veteranos de guerra de Afganistán e Irak ESTRESORES FAMILIARES A LARGO PLAZO EN VETERANOS Ha sido bien establecido que el estrés relacionado con la guerra pone a los miembros del servicio en riesgo a una gama de problemas de salud mental después de su regreso del despliegue. Se sabe menos acerca de la experiencia de los miembros del servicio a estresores familiares durante su despliegue. Los objetivos de este estudio fueron (a) evaluar si los estresores familiares podrían contribuir de manera única a la varianza del trastorno de estrés postraumático (TEPT) y síntomas depresivos mucho mas allá de la amenaza de combate durante el despliegue y (b) examinar si los estresores familiares pueden amplificar los efectos negativos de la amenaza de combate en la salud mental postmilitar 5 años después del alta. Los participantes del estudio reportaron sus experiencias objetivas y subjetivas a estresores familiares y amenaza de combate durante el despliegue. Los estresores objetivos familiares demostraron asociaciones únicas con TEPT y síntomas depresivos y continuaron siendo significativos después de considerar los estresores familiares en curso, reportados en el seguimiento. Se encontró una interacción significativa entre los estresores familiares objetivos y la amenaza de combate en los síntomas de TEPT, r = -.10. Aunque la asociación entre la amenaza de combate y el TEPT fue significativa para los participantes que informaron una alta, B = 0.04; y una baja, B = 0.09 exposición a estresores familiares, la pendiente más pronunciada para aquellos expuestos a menos estresores familiares indica un efecto más fuerte de amenaza de combate. Los análisis de seguimiento revelaron que los veteranos que experimentaron grandes cantidades de estrés familiar y altos niveles de amenaza de combate informaron síntomas de TEPT significativamente peores que aquellos que informaron un bajo estrés familiar, t (256) = 3.98, p <.001. Los resultados subrayan la importancia de prestar atención al papel que los estresores familiares experimentados durante el despliegue en la salud mental post-militar de los miembros del servicio.


Assuntos
Depressão/etiologia , Família/psicologia , Transtornos de Estresse Pós-Traumáticos/etiologia , Estresse Psicológico/psicologia , Veteranos/psicologia , Exposição à Guerra , Adulto , Campanha Afegã de 2001- , Feminino , Humanos , Guerra do Iraque 2003-2011 , Masculino , Saúde Mental , Pessoa de Meia-Idade , Inquéritos e Questionários , Fatores de Tempo , Estados Unidos
6.
Psychiatry Res ; 271: 614-620, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30791333

RESUMO

Although symptom severity is a known predictor of treatment seeking, the role of functional impairment in this association is unclear. The purpose of this study was to examine the contribution of relationship and work impairment to service use among women and men with posttraumatic stress disorder (PTSD) and depression symptoms. Data from mailed surveys of 363 military veterans were examined longitudinally. Stratified regression analyses were applied to evaluate moderating and mediating effects of functional impairment in association between symptoms and mental health service use, with significant effects observed for relationship but not work impairment. For men, relationship impairment moderated the association between mental health and service use, such that the impact of depression symptoms on treatment seeking was reduced when accompanied by high impairment. For women, subsequently assessed relationship impairment acted as a mediator of the positive association between PTSD symptom severity and service use. The finding that relationship impairment interfered with treatment seeking for men but facilitated treatment seeking for women may help explain widely demonstrated sex differences in treatment seeking. Results underscore the importance of attending to the role of relationship impairment in veterans' treatment seeking and highlight the value of implementing sex-informed approaches to treatment promotion efforts.


Assuntos
Depressão/terapia , Serviços de Saúde Mental , Aceitação pelo Paciente de Cuidados de Saúde , Psicoterapia , Transtornos de Estresse Pós-Traumáticos/terapia , Veteranos/psicologia , Adulto , Depressão/psicologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Fatores Sexuais , Transtornos de Estresse Pós-Traumáticos/psicologia , Inquéritos e Questionários
7.
J Adolesc Health ; 63(4): 459-465, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-30286901

RESUMO

PURPOSE: To date, little is known about underlying psychophysiological contributions to the impact of media content and overall screen time on adolescent psychological functioning. In the present study we examine respiratory sinus arrhythmia (RSA) as a moderator of the link between specific types of media content use, overall media exposure, and the development of internalizing and aggressive symptoms in youth. METHODS: A sample of 374 adolescents (mean age = 15) reported on their media use, internalizing behavior, and aggressive behavior at time 1 (2011) and 1-year follow-up (2012). RSA reactivity was gathered during a challenging laboratory task. Path analyses were conducted to test the hypothesized three-way interaction model between media use, media content, and RSA reactivity, separately for internalizing and aggressive problems. RESULTS: Significant interactions were found for aggressive, but not prosocial, media content. For aggressive content, youth exhibiting RSA withdrawal reported significantly greater internalizing and aggressive symptoms when exposed to higher amounts of screen time and aggressive content. CONCLUSIONS: These findings suggest that profiles of heightened RSA withdrawal may place adolescents at greater risk to the negative impact of violent media, whereas prosocial media content may not significantly impact youth development of psychopathology. Implications for the role of psychophysiology in our understanding of media effects are discussed.


Assuntos
Desenvolvimento do Adolescente/fisiologia , Agressão/fisiologia , Arritmia Sinusal Respiratória/fisiologia , Tempo de Tela , Adolescente , Feminino , Humanos , Estudos Longitudinais , Masculino , Plasticidade Neuronal
8.
Dev Psychol ; 54(9): 1661-1673, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-30148394

RESUMO

A burgeoning literature supports the role of autonomic nervous system (ANS) functioning as an index of physiologic sensitivity to the environment, but extant research is limited in its focus on single branches of the ANS, childhood samples, and solely negative environmental factors. This study seeks to address these limitations by exploring whether reactivity in the parasympathetic (PNS) and sympathetic (SNS) nervous systems jointly moderate the prospective contributions of both positive (maternal involvement) and negative (maternal psychological control) aspects of the family environment to developmentally relevant outcomes in adolescence (depressive symptoms and emotion regulation). At Wave 1, adolescents (n = 352, 52% female, M age = 15.27, SD = 1.04; 65% White) and their parents completed a problem-solving discussion task, during which adolescent ANS activation was continuously monitored, and reports of maternal involvement, maternal psychological control, adolescent depressive symptoms, and adolescent emotion regulation were obtained. Adolescent depressive symptoms and emotion regulation were assessed again 1 year later (Wave 2). Results indicated that PNS and SNS reactivity jointly moderated the prospective contributions of maternal involvement and maternal psychological control to depressive symptoms and emotion regulation. Specifically, adolescents who exhibited reciprocal SNS activation appeared to be most sensitive to both positive and negative parenting environments. Adolescents exhibiting coinhibition or coactivation profiles of autonomic reactivity were comparatively unreactive to parenting. This study corroborates the notion that consideration of multiple physiological systems is critical to our understanding of biological processes in the development of emotional functioning in adolescence. (PsycINFO Database Record


Assuntos
Ajustamento Emocional , Relações Mãe-Filho/psicologia , Mães/psicologia , Sistema Nervoso Parassimpático/fisiologia , Poder Familiar/psicologia , Sistema Nervoso Simpático/fisiologia , Adolescente , Depressão/fisiopatologia , Ajustamento Emocional/fisiologia , Inteligência Emocional/fisiologia , Feminino , Resposta Galvânica da Pele , Humanos , Estudos Longitudinais , Masculino , Resolução de Problemas/fisiologia , Estudos Prospectivos , Testes Psicológicos , Psicologia do Adolescente , Arritmia Sinusal Respiratória
9.
Fam Process ; 57(1): 181-194, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-27988925

RESUMO

This research examined the longitudinal association between parent socialization of coping and child adjustment, as well as the moderating role of children's skin conductance level reactivity (SCLR). Participants were a community sample of children (n = 64, M age = 9.02, 54.5% females, 93.2% Caucasian) and their parent(s). Parent coping suggestions were observed while their child engaged in a stressful challenge task, during which the child's SCLR, a measure of children's physiological reactivity to stress, was also measured. Parent(s) completed the Child Behavior Checklist (Achenbach & Rescorla, 2001) at baseline and a 6-month follow-up to assess internalizing and externalizing problems. Results revealed that secondary control engagement suggestions predicted fewer internalizing problems over time. In addition, disengagement suggestions predicted fewer externalizing problems over time among children with high SCLR. This study provides evidence that parent coping suggestions serve as a resource that protects youth from developing adjustment problems.


Assuntos
Adaptação Psicológica/fisiologia , Resposta Galvânica da Pele , Pais/psicologia , Socialização , Estresse Psicológico/fisiopatologia , Adulto , Criança , Comportamento Infantil/fisiologia , Comportamento Infantil/psicologia , Humanos , Estudos Longitudinais , Masculino , Relações Pais-Filho , Estresse Psicológico/psicologia
10.
J Dev Behav Pediatr ; 39(1): 46-54, 2018 01.
Artigo em Inglês | MEDLINE | ID: mdl-28937450

RESUMO

OBJECTIVE: Excessive screen time has been associated with a multitude of child health problems. This pilot study examined the feasibility and preliminary outcome of a novel 1-session intervention designed to help parents reduce their child's screen time. METHODS: Thirty-nine parents of 5- to 12-year-old children were randomized to the intervention (a combined didactics and hands-on approach focused on technology-specific parenting) or waitlist control group. RESULTS: The findings suggested that a sample could be recruited in a reasonable time (6 wk) at a reasonable cost, randomized, and retained at 6 weeks postintervention. Preliminary evidence suggested the intervention, which was implemented with fidelity, was associated with change in technology-specific parenting and 1 of 2 measures of child screen time. Parents reported satisfaction with the intervention and confidence in managing their child's screen time. CONCLUSION: The results of this pilot study suggest that this 1-session intervention is a promising approach to managing child screen time.


Assuntos
Educação Infantil , Computadores de Mão , Educação não Profissionalizante/métodos , Poder Familiar , Televisão , Jogos de Vídeo , Adulto , Criança , Pré-Escolar , Estudos de Viabilidade , Feminino , Humanos , Masculino , Projetos Piloto , Resultado do Tratamento
11.
J Appl Dev Psychol ; 44: 28-38, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-27795603

RESUMO

In the present study we propose a model linking parental perceptions of technology to technology-related parenting strategies to youth screen time, and, finally, to internalizing and externalizing problem behaviors. Participants were 615 parents drawn from three community samples of families with children across three developmental stages: young childhood, middle childhood, and adolescence. The model was tested at each stage with the strongest support emerging in the young childhood sample. One component of parental perceptions of technology, perceived efficacy, was related to technology-related parenting strategies across developmental stages. However, the association of these strategies to child screen time and, in turn, problem behaviors, diminished as children increased in age. Implications for intervention are considered.

12.
J Dev Behav Pediatr ; 37(4): 277-84, 2016 05.
Artigo em Inglês | MEDLINE | ID: mdl-26890562

RESUMO

OBJECTIVE: The purpose of this study was to examine the indirect effect of youth screen time (e.g., television, computers, smartphones, video games, and tablets) on behavioral health problems (i.e., internalizing, externalizing, and peer problems) through sleep duration and disturbances. METHODS: The authors assessed a community sample of parents with a child in one of the following three developmental stages: young childhood (3-7 yrs; N = 209), middle childhood (8-12 yrs; N = 202), and adolescence (13-17 yrs; N = 210). Path analysis was used to test the hypothesized indirect effect model. RESULTS: Findings indicated that, regardless of the developmental stage of the youth, higher levels of youth screen time were associated with more sleep disturbances, which, in turn, were linked to higher levels of youth behavioral health problems. CONCLUSION: Children who have increased screen time are more likely to have poor sleep quality and problem behaviors.


Assuntos
Comportamento do Adolescente , Comportamento Infantil , Computadores de Mão , Comportamento Problema , Transtornos do Sono-Vigília/etiologia , Televisão , Jogos de Vídeo/efeitos adversos , Adolescente , Criança , Pré-Escolar , Feminino , Humanos , Masculino
13.
J Fam Psychol ; 30(5): 641-646, 2016 08.
Artigo em Inglês | MEDLINE | ID: mdl-26751759

RESUMO

This study examines the associations of 2 types of parenting practices-general adaptive parenting and technology-related strategies-with youth screen time. We hypothesized that technology-related parenting focused on behavioral control would relate directly to screen time and serve to link general parenting to screen time. Participants were 615 parents drawn from 3 community samples of families with children across 3 development stages: young childhood (3-7 years; n = 210), middle childhood (8-12 years; n = 200), and adolescents (13-17 years; n = 205). Using structural equation modeling, we found that general adaptive parenting was not related to child screen time but was positively related to technology-related parenting strategies for all 3 samples. For the young and, to some extent, middle childhood samples, but not for the adolescent sample, general adaptive parenting was positively linked to youth screen time through technology-related parenting strategies. (PsycINFO Database Record


Assuntos
Adaptação Psicológica , Computadores , Poder Familiar , Televisão , Jogos de Vídeo , Adolescente , Criança , Pré-Escolar , Feminino , Humanos , Masculino
14.
Bioresour Technol ; 102(1): 290-7, 2011 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-20663660

RESUMO

Shewanella-containing microbial fuel cells (MFCs) typically use the fresh water wild-type strain Shewanella oneidensis MR-1 due to its metabolic diversity and facultative oxidant tolerance. However, S. oneidensis MR-1 is not capable of metabolizing polysaccharides for extracellular electron transfer. The applicability of Shewanella japonica (an agar-lytic Shewanella strain) for power applications was analyzed using a diverse array of carbon sources for current generation from MFCs, cellular physiological responses at an electrode surface, biofilm formation, and the presence of soluble extracellular mediators for electron transfer to carbon electrodes. Critically, air-exposed S. japonica utilizes biosynthesized extracellular mediators for electron transfer to carbon electrodes with sucrose as the sole carbon source.


Assuntos
Fontes de Energia Bioelétrica/microbiologia , Shewanella/fisiologia , Biofilmes/crescimento & desenvolvimento , Carbono/metabolismo , Eletricidade , Eletrodos/microbiologia , Transporte de Elétrons , Espaço Extracelular/metabolismo , Água Doce/microbiologia , Oxirredução , Shewanella/metabolismo , Solubilidade
15.
J Colloid Interface Sci ; 342(2): 499-504, 2010 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-19906382

RESUMO

Electrochemical impedance spectroscopy and the quartz crystal microbalance measurements are used to examine the ability of potential applied to a substrate to create, in situ, conditions favorable for the electrostatic deposition of polyelectrolytes onto a gold substrate modified by the self-assembly of cysteine. Cysteine is a zwitterionic compound that, when confined to a substrate, has the ability to establish either a net positive or a net negative interfacial charge, depending on the conditions. As such, cysteine modified interfaces could possibly be used as a versatile substrate for deposition of either cationic or anionic polyelectrolytes. The potential of zero charge of a gold electrode modified by self-assembly with cysteine in the presence of 0.10molL(-1) KCl and buffered at pH 5 is found by differential capacitance measurement to be -0.12(+/-0.02)V vs. Ag/AgCl. When -0.05V vs. Ag/AgCl is applied to the substrate (a potential positive of the PZC) in the presence of different polyelectrolytes, both impedance spectroscopy and quartz crystal microbalance data suggest the accumulation of anionic poly(sodium styrenesulfonate) along the cysteine modified interface. Conversely, when -0.40V vs. Ag/AgCl is applied to the substrate (a potential negative of the PZC), experimental results suggest the accumulation of cationic poly(diallydimethylammonium chloride).

16.
J Colloid Interface Sci ; 331(2): 318-21, 2009 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-19108847

RESUMO

Electrochemical impedance spectroscopy and the quartz crystal microbalance are used to monitor the deposition of polyelectrolytes onto an interface modified with a monolayer of cysteine. When using an anionic redox probe, Fe(CN)(6)(-4), the impedance of the cysteine modified electrode is a function of the solution pH; the charge-transfer resistance being higher at basic pH, and smaller under acidic conditions relative to the value found when the solution is buffered near the pI for cysteine. This behavior is consistent with the electrostatic interaction between the anionic redox probe and the net charge of the interface. After exposure of the cysteine-modified interface to 0.10 mol L(-1) HCl solutions containing polystyrene sulfonate, the impedance of the modified interface increases. This behavior is consistent with the interface having a net negative charge, and suggests that the polyanion is confined to the interface. Quartz crystal microbalance measurements also show that 700+/-20 ng of the PSS is deposited under the acidic conditions. After exposure to 0.10 mol L(-1) NaOH solutions containing poly(diallyldimethyl)ammonium chloride, the impedance of the modified interface decreases, consistent with the electrostatic assembly of the polycation to the cysteine monolayer under these conditions. Quartz crystal microbalance measurements indicate that 770+/-40 ng of the poly(diallyldimethylammonium chloride) are deposited under the basic conditions.


Assuntos
Poliaminas/química , Polímeros/química , Eletricidade Estática , Cisteína/química , Eletrodos , Ouro/química , Polieletrólitos
17.
Langmuir ; 24(22): 12766-70, 2008 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-18947243

RESUMO

Electrochemical impedance spectroscopy (EIS) and quartz crystal microbalance (QCM) measurements are used to examine the ability of applied potential to drive the ionic self-assembly of poly(diallyldimethylammonium) chloride (PDDA) onto a substrate modified with a monolayer of 3-mercaptopropionic acid (3-MPA). The potential of zero charge (PZC) of the gold electrode modified with a monolayer of 3-MPA was found by differential capacitance measurements to be -0.12 (+/-0.01) V versus Ag-AgCl. Changing the substrate potential to values positive (-0.01 V vs Ag-AgCl) of the PZC induces interfacial conditions that are favorable for the electrostatic deposition of cationic polymers onto the surface of 3-MPA monolayers. This result is also consistent with experimental observations obtained when the 3-MPA-modified substrate is exposed to 0.10 mol L (-1) NaOH solutions. When potentials equal or negative to the PZC are applied to the substrate, no significant accumulation of the PDDA is found by either QCM or EIS measurement. This result is consistent with results obtained when the 3-MPA modified substrate is exposed to 0.10 mol L (-1) HCl solutions where no PDDA adsorption is expected because the monolayer is neutral under these conditions. Changes in the impedance and quartz crystal frequency obtained after potential is applied to the substrate are interpreted in terms of the applied potential creating interfacial conditions that are favorable for the deprotonation of the terminal carboxylic acid groups and the subsequent electrostatic assembly of the polycation onto the negatively charged monolayer.


Assuntos
Ácido 3-Mercaptopropiônico/química , Ouro/química , Polietilenos/química , Compostos de Amônio Quaternário/química , Adsorção , Ácidos Carboxílicos/química , Capacitância Elétrica , Impedância Elétrica , Eletroquímica/métodos , Eletrodos , Concentração de Íons de Hidrogênio , Íons , Prata/química , Compostos de Prata/química , Soluções , Propriedades de Superfície
18.
Langmuir ; 24(12): 6133-9, 2008 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-18494511

RESUMO

Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) are used to monitor changes in the ionization of monolayers of 11-mercaptoundecanoic acid. When using an anionic redox probe, Fe(CN)6(-4), the charge-transfer resistance of the 11-mercaptoundecanoic acid monolayer-modified interface increases in a sigmoidal fashion as the solution is made basic. The opposite effect is observed when using a cationic redox probe. The inflection points of these two titration curves, however, differ when using the different redox probes. This result is taken as being characteristic of the influence that applied potential has on the ionization of the monolayer. The role of substrate potential on the ionization of the monolayer is further investigated by SECM. The SECM measurement monitors the concentration of Ru(NH3)6(+3) as the potential of the substrate is varied about the potential of zero charge. For monolayers of 11-mercaptoundecanoic acid in solutions buffered near the pKa of the terminal carboxylic acid, potential excursions positive of the PZC cause an increase in the concentration of Ru(NH3)6(+3) local to the interface, and potential excursions negative of the PZC cause a decrease in the local concentration of Ru(NH3)6(+3). Similar experiments conducted with an interface modified with 11-undecanethiol had no impact on the local concentration of Ru(NH3)6(+3). These results are interpreted in terms of the influence that applied potential has on the pH of the solution local to the interface and the impact that this has on the ionization of the monolayer.

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