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1.
Soc Sci Med ; 349: 116886, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38626503

RESUMO

Despite the well-established link between adolescent learning disabilities (LD) and mental health, little is known about its long-term consequences. This study examines the relationship between adolescent LD and adult depressive symptoms, with a focus on gender differences and underlying mechanisms. Using a sibling sample from the National Longitudinal Study of Adolescent to Adult Health (N = 3,414), this study estimated sibling fixed effects models to account for unobserved family-level characteristics such as genes and early childhood family and social context. Sobel mediation analyses were conducted to examine social-psychological mechanisms, including the student-teacher relationship, the student-student relationship, and a sense of school belonging. LD in adolescence was positively associated with depressive symptoms in adulthood (b = 0.823, p < 0.05). This association remained robust when controlling for unobserved family-level confounders as well as educational attainment in adulthood. Gender-stratified models showed that only the association for women is statistically significant (b = 1.935, p < 0.05), and its magnitude is nearly three times that of the association for men. Sobel mediation tests indicate that a decline in a sense of school belonging mediates approximately 17% of the association between adolescent LD and adult depressive symptoms. This study's findings suggest that LD in adolescence is associated with an increase in depressive symptoms in adulthood, particularly in women, and a low sense of school belonging may be a potential mediator. Implementing interventions to improve the school integration of girls with LD could be an effective means of improving their long-term mental health.


Assuntos
Depressão , Deficiências da Aprendizagem , Humanos , Masculino , Feminino , Adolescente , Depressão/psicologia , Depressão/epidemiologia , Deficiências da Aprendizagem/psicologia , Estudos Longitudinais , Fatores Sexuais , Adulto , Irmãos/psicologia , Estudantes/psicologia , Estudantes/estatística & dados numéricos
2.
Child Abuse Negl ; 151: 106718, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38431991

RESUMO

BACKGROUND: Despite existing literature on the link between bullying victimization and psychological well-being, little is known about the potential lasting negative effects of chronic bullying victimization, especially among children from multicultural families (CMF). OBJECTIVE: This study examined the longitudinal association between chronic bullying victimization and life satisfaction among CMF in Korea, and further investigated whether this association differs by immigrant mothers' country of origin. PARTICIPANTS AND SETTING: This study utilized data from the Multicultural Adolescents Panel Study (MAPS) 2011-2019, a nationally representative longitudinal study of CMF in Korea who were between the ages of 9 and 12 at baseline (N = 1375). METHODS: Fixed effects models were employed to address potential bias resulting from unobserved time-invariant confounders. Three theoretical models were proposed to examine the trajectory patterns of change in life satisfaction among chronically bullied children: cumulative effects, immediate-sustained effects, and short-lived effects models. RESULTS: The longitudinal trajectories of change in life satisfaction associated with chronic bullying victimization were consistent with an immediate-sustained effects model. Heterogeneous patterns in the association by mothers' country of origin were observed. A cumulative effects model was supported for children with Southeast Asian mothers, indicating that chronic bullying victimization leads to a cumulative decrease in life satisfaction. For children with Chinese and Japanese mothers, the results supported either immediate-sustained or short-lived effects models. CONCLUSIONS: Efforts to improve the psychological well-being of CMF should consider the potential long-term risk of chronic bullying victimization, particularly among youth with mothers from Southeast Asia.


Assuntos
Bullying , Vítimas de Crime , Emigrantes e Imigrantes , Criança , Feminino , Adolescente , Humanos , Estudos Longitudinais , Bullying/psicologia , República da Coreia/epidemiologia , Vítimas de Crime/psicologia , Satisfação Pessoal
3.
Cultur Divers Ethnic Minor Psychol ; 30(3): 415-424, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38407071

RESUMO

OBJECTIVES: Over the past three decades, the number of multicultural families in Korea, defined as a family consisting of a native Korean and a marriage immigrant, has increased significantly. Although bullying victimization among multicultural family youth is rightfully a growing concern, less is known about the effects bullying has on immigrant mothers of children who have been bullying victims. METHOD: Using data from the Multicultural Adolescents Panel Study, this study investigates whether children's bullying victimization is associated with immigrant mothers' acculturative stress and whether this association differs depending on mothers' country of origin (China, Japan, and Southeast Asian countries). RESULTS: Fixed effects estimates revealed that children's bullying victimization is positively associated with their immigrant mother's acculturative stress, and this association is robust to controlling for unobserved time-constant individual-level heterogeneity. When stratified by mother's country of origin, the association was larger and statistically significant only among Southeast Asian mothers. No associations were observed among Japanese and Chinese mothers. CONCLUSIONS: Our findings suggest that interventions aiming to support bullied children should be expanded to also support their immigrant mothers. Policymakers may wish to consider the specific backgrounds and contexts of immigrant mothers, with special attention to Southeast Asian women. (PsycInfo Database Record (c) 2024 APA, all rights reserved).


Assuntos
Aculturação , Bullying , Vítimas de Crime , Emigrantes e Imigrantes , Mães , Humanos , Emigrantes e Imigrantes/psicologia , Feminino , Bullying/psicologia , República da Coreia/etnologia , Mães/psicologia , Vítimas de Crime/psicologia , Adulto , Masculino , Adolescente , Criança , Estresse Psicológico/etnologia , Estresse Psicológico/psicologia , China/etnologia , Japão/etnologia , Sudeste Asiático/etnologia
4.
J Adolesc Health ; 74(4): 828-836, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38069939

RESUMO

PURPOSE: This study aims to examine the association between bullying victimization and depressive symptoms among youth from multicultural families in Korea, while distinguishing between the effects of entering and exiting bullying victimization. This study also investigates whether parental education moderates this association. METHODS: Using data from the Multicultural Adolescent Panel Survey, a nationally representative sample of children from multicultural families in Korea, this study employed novel asymmetric fixed-effects models that separately assess the effects of entering and exiting bullying victimization. Interaction models were conducted to consider the moderating roles of maternal and paternal college attainment. RESULTS: Conventional fixed-effects models showed that bullying victimization is significantly associated with an increase in depressive symptoms (b = 0.261). Asymmetric fixed-effects models suggest that the magnitude of the entry effect (b = 0.299) was significantly larger than that of the exit effect (b = -0.237). Furthermore, maternal college education amplified the mental health benefits of exiting from bullying victimization but did not buffer the harmful effects of entering bullying victimization. Gender-stratified analyses indicate that this protective effect of maternal college education was only significant for girls. Paternal college education, on the other hand, did not moderate either the entry or exit effects of bullying victimization. DISCUSSION: The study's findings on the asymmetric effects of bullying victimization on depressive symptoms emphasize the importance of providing follow-up care and mental health support for multicultural family youth who have experienced bullying, with particular attention to those with a history of victimization.


Assuntos
Bullying , Vítimas de Crime , Criança , Feminino , Adolescente , Humanos , Depressão/psicologia , Inquéritos e Questionários , Pais
5.
Soc Sci Med ; 341: 116545, 2024 01.
Artigo em Inglês | MEDLINE | ID: mdl-38160609

RESUMO

RATIONALE: Children from multicultural families in Korea are vulnerable to bullying victimization. Despite growing evidence on the mental health consequences of bullying victimization for victims, little is known about the spillover effects on their immigrant mothers. OBJECTIVE: This study examined the association between children's bullying victimization and their immigrant mothers' suicidal ideation. The potential moderating role of family socioeconomic status was also investigated. METHODS: Using nine waves of the Multicultural Adolescents Panel Study spanning from 2011 to 2019 (N = 1466), this study estimated individual fixed effects models to control for unobserved individual-level heterogeneity. Interaction models were used to investigate potential heterogeneity by family socioeconomic status, including maternal education, household income, and maternal occupational status. RESULTS: Fixed effects estimates revealed that children's bullying victimization is associated with an increased likelihood of suicidal ideation among marriage migrant mothers (b = 0.012, p < 0.05), even after controlling for unobserved time-invariant confounders as well as a set of time-varying covariates. Family socioeconomic status moderated this association. The association between children's bullying victimization and immigrant mothers' suicidal ideation was stronger for those with low levels of education and household income. No such moderating effects were observed for maternal occupation. CONCLUSIONS: The findings of this study suggest that efforts to address the mental health consequences of bullying victimization among multicultural family children should extend beyond the victim to their immigrant mothers. When developing interventions to reduce suicidal ideation among immigrant mothers whose children have been victimized, policymakers may wish to consider the moderating role of family socioeconomic status.


Assuntos
Bullying , Vítimas de Crime , Feminino , Criança , Adolescente , Humanos , Ideação Suicida , Vítimas de Crime/psicologia , Mães/psicologia , Classe Social , República da Coreia , Bullying/psicologia
6.
J Adolesc Health ; 72(6): 914-922, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-36809865

RESUMO

PURPOSE: The purpose of this study is to examine the association between classmates' discrimination experiences and an individual student's depressive symptoms. A set of social-psychological and behavioral variables were considered as potential mechanisms underlying this association. METHODS: The data came from the Gyeonggi Education Panel Study of seventh graders in South Korea. This study leveraged quasi-experimental variation generated from random assignment of students to classes within schools to address the endogenous school selection problem and account for the unobserved school-level confounders. To formally test for mediation, Sobel tests were conducted and peer attachment, school satisfaction, smoking, and drinking were explored as mechanism variables. RESULTS: An increase in classmates' discrimination experiences was positively associated with an individual student's depressive symptoms. This association remained statistically significant even after adjusting for personal discrimination experience, a myriad of individual- and class-level covariates, as well as school fixed effects (b = 0.325, p < .05). Classmates' discrimination experiences were also associated with a decline in peer attachment and school satisfaction (b = -0.386, p < .01 and b = -0.399, p < .05, respectively). These psychosocial factors explained about one-third of the association between classmates' discrimination experiences and individual students' depressive symptoms. DISCUSSION: The findings of this study suggest that exposure to peer-level discrimination experience leads to friend detachment and school dissatisfaction, which in turn increases an individual student's depressive symptoms. This study reaffirms the importance of fostering a more cohesive and nondiscriminatory school environment to promote adolescents' psychological health and well-being.


Assuntos
Depressão , Estudantes , Humanos , Adolescente , Depressão/epidemiologia , Estudantes/psicologia , Instituições Acadêmicas , República da Coreia , Grupo Associado
7.
Eur Child Adolesc Psychiatry ; 32(1): 167-176, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-35881194

RESUMO

The aim of the study was to investigate the association between adolescent delinquency and sleep deficiency. A comprehensive set of potential mechanisms underlying this association were also examined. Using data from the National Longitudinal Study of Adolescent to Adult Health, the present study employed sibling fixed effects models to account for unobservable family-level confounders, such as genetic predisposition, parenting style, parental ability, and school and neighborhood environments. In Sobel mediation tests, the following mechanism variables were explored: substance use, school-based relationships, and parent-child relationships. An increase in delinquency (measured by the total number of types of delinquent behavior engaged) was associated with an increased risk of sleep deficiency one year later. Sibling fixed effects models with a lagged dependent variable revealed that this association is robust to adjustment for family-level heterogeneity as well as prior sleep deficiency. Substance use was the most salient pathway linking delinquency to sleep deficiency (17% for binge drinking and 26% for marijuana use), followed by student-teacher relationships (17%) and father-child relationships (16%). The results of this study suggest that policymakers and practitioners may consider developing interventions to help delinquent adolescents avoid substance use and restore disruptions of student-teacher and father-child relationships.


Assuntos
Comportamento do Adolescente , Delinquência Juvenil , Transtornos Relacionados ao Uso de Substâncias , Adulto , Humanos , Adolescente , Irmãos , Estudos Longitudinais , Poder Familiar , Transtornos Relacionados ao Uso de Substâncias/epidemiologia
8.
Sci Rep ; 12(1): 15371, 2022 09 13.
Artigo em Inglês | MEDLINE | ID: mdl-36100619

RESUMO

In lymphedema, proinflammatory cytokine-mediated progressive cascades always occur, leading to macroscopic fibrosis. However, no methods are practically available for measuring lymphedema-induced fibrosis before its deterioration. Technically, CT can visualize fibrosis in superficial and deep locations. For standardized measurement, verification of deep learning (DL)-based recognition was performed. A cross-sectional, observational cohort trial was conducted. After narrowing window width of the absorptive values in CT images, SegNet-based semantic segmentation model of every pixel into 5 classes (air, skin, muscle/water, fat, and fibrosis) was trained (65%), validated (15%), and tested (20%). Then, 4 indices were formulated and compared with the standardized circumference difference ratio (SCDR) and bioelectrical impedance (BEI) results. In total, 2138 CT images of 27 chronic unilateral lymphedema patients were analyzed. Regarding fibrosis segmentation, the mean boundary F1 score and accuracy were 0.868 and 0.776, respectively. Among 19 subindices of the 4 indices, 73.7% were correlated with the BEI (partial correlation coefficient: 0.420-0.875), and 13.2% were correlated with the SCDR (0.406-0.460). The mean subindex of Index 2 [Formula: see text] presented the highest correlation. DL has potential applications in CT image-based lymphedema-induced fibrosis recognition. The subtraction-type formula might be the most promising estimation method.


Assuntos
Aprendizado Profundo , Linfedema , Estudos Transversais , Fibrose , Humanos , Linfedema/diagnóstico por imagem , Linfedema/etiologia , Tomografia Computadorizada por Raios X/métodos
9.
Life (Basel) ; 11(1)2021 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-33477822

RESUMO

The tricarboxylic acid cycle (TCA) is a series of chemical reactions used in aerobic organisms to generate energy via the oxidation of acetylcoenzyme A (CoA) derived from carbohydrates, fatty acids and proteins. In the eukaryotic system, the TCA cycle occurs completely in mitochondria, while the intermediates of the TCA cycle are retained inside mitochondria due to their polarity and hydrophilicity. Under cell stress conditions, mitochondria can become disrupted and release their contents, which act as danger signals in the cytosol. Of note, the TCA cycle intermediates may also leak from dysfunctioning mitochondria and regulate cellular processes. Increasing evidence shows that the metabolites of the TCA cycle are substantially involved in the regulation of immune responses. In this review, we aimed to provide a comprehensive systematic overview of the molecular mechanisms of each TCA cycle intermediate that may play key roles in regulating cellular immunity in cell stress and discuss its implication for immune activation and suppression.

10.
J Exerc Nutrition Biochem ; 23(1): 1-6, 2019 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-31010268

RESUMO

PURPOSE: To date, there have been no studies on the response of wrist tremor to increased muscle activity during exercise. This study aimed to evaluate the wrist tremor response with increasing muscle activity during bench press exercise. METHODS: Triceps muscle activity and wrist tremor response were measured by electromyography and an accelerometer, respectively, during bench press exercise in 11 healthy men without weight-training experience. Subjects performed bench press at 30% repetition maximum (RM), and the rating of perceived exertion (RPE) and lactate concentration were measured before and after exercise. One week later, an equivalent number of bench presses at 30% RM was performed without weight load as a control trial (CT). RESULTS: RPEs and lactate concentrations significantly increased after resistance exercise (30% RM) from 7.4 to 14.3 and 1.7 to 4.9, respectively (P<.01), but no such difference was observed in the CT. Muscle activity linearly increased during the 30% RM exercise, and wrist tremors were shown to linearly decrease. A strong negative correlation was observed between the two variables (r=-0.88, P<.001). CONCLUSION: We found that wrist tremors during resistance exercise, as measured using an accelerometer, can be used to predict muscle activity.

11.
Annu Int Conf IEEE Eng Med Biol Soc ; 2018: 4198-4201, 2018 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30441280

RESUMO

By using the microfluidic spinning technology we generated tiny hydrogel tubular scaffolds. Fibroblast (NIH/3T3) cell cultures were performed for seventeen days to demonstrate the potential of cell attachment on surfaces and encapsulation in the wall of he microscopic scaffolds for blood vessel-like structure forming. Over theculture period, the NIH/3T3 confluence reached around 80\%, and 100\% on the inside and outside scaffolds' surface respectively while cells proliferated and coalesced in cell group in the hydrogel wall. These results could further be applied to endothelial co-culturing for forming engineered blood vessel.


Assuntos
Engenharia Tecidual , Alicerces Teciduais , Animais , Técnicas de Cocultura , Humanos , Masculino , Camundongos
12.
J Phys Chem B ; 120(36): 9723-31, 2016 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-27537433

RESUMO

Hydrogen bonds (H-bonds) play an important role in determining the structures and dynamics of molecular systems. In this work, we investigated the effect of H-bonds on the vibrational population relaxation and orientational relaxation dynamics of HN3 and N3(-) in methanol (CH3OH) and N,N-dimethyl sulfoxide (DMSO) using polarization-controlled infrared pump-probe spectroscopy and quantum chemical calculations. Our detailed analysis of experimental and computational results reveals that both vibrational population relaxation and orientational relaxation dynamics of HN3 and N3(-) in CH3OH and DMSO are substantially dependent on the strength of the H-bonds between the probing solute and its surrounding solvent. Especially in the case of N3(-) in CH3OH, the vibrational population relaxation of N3(-) is found to occur by a direct intermolecular vibrational energy transfer to CH3OH due to large vibrational coupling strength. The orientational relaxation dynamics of HN3 and N3(-), which are well fit by a biexponential function, are analyzed by the wobbling-in-a-cone model and extended Debye-Stokes-Einstein equation. Depending on the intermolecular interactions, the slow overall orientational relaxation occurs under slip, stick, and superstick boundary conditions. For HN3 and N3(-) in CH3OH and DMSO, the vibrational population relaxation becomes faster but the orientational relaxation becomes slower as the H-bond strength is increased. Our current results imply that H-bonds have significant effects on the vibrational population relaxation and orientational relaxation dynamics of a small solute whose size is comparable to the size of the solvent.

13.
Phys Chem Chem Phys ; 17(27): 17557-61, 2015 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-26080746

RESUMO

Two-dimensional infrared (2DIR) spectroscopy, which has been proven to be an excellent experimental method for studying thermally-driven chemical processes, was successfully used to investigate the acid dissociation equilibrium of HN3 in methanol (CH3OH) and dimethyl sulfoxide (DMSO) for the first time. Our 2DIR experimental results indicate that the acid-base equilibrium occurs on picosecond timescales in CH3OH but that it occurs on much longer timescales in DMSO. Our results imply that the different timescales of the acid-base equilibrium originate from different proton transfer mechanisms between the acidic (HN3) and basic (N3(-)) species in CH3OH and DMSO. In CH3OH, the acid-base equilibrium is assisted by the surrounding CH3OH molecules which can directly donate H(+) to N3(-) and accept H(+) from HN3 and the proton migrates through the hydrogen-bonded chain of CH3OH. On the other hand, the acid-base equilibrium in DMSO occurs through the mutual diffusion of HN3 and N3(-) or direct proton transfer. Our 2DIR experimental results corroborate different proton transfer mechanisms in the acid-base equilibrium in protic (CH3OH) and aprotic (DMSO) solvents.


Assuntos
Dimetil Sulfóxido/química , Metanol/química , Equilíbrio Ácido-Base , Azidas/química , Ligação de Hidrogênio , Espectrofotometria Infravermelho , Ácidos Sulfúricos/química
14.
J Phys Chem B ; 117(43): 13604-13, 2013 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-24073894

RESUMO

Ultrafast two-dimensional infrared (2DIR) spectroscopy was used to study H-bond exchange dynamics in aqueous NaPF6 solutions. Interestingly, there are two spectrally distinct hydrogen-bond (H-bond) configurations in aqueous NaPF6 solutions: water molecules that are H-bonded to PF6(-) (ODA) or other water molecules (ODW). These two spectrally distinct subsets of water in aqueous NaPF6 solutions provide an opportunity to study the individual dynamics of water in two H-bond configurations as well as interconversion dynamics between them. Most significantly, we have successfully measured H-bond exchange dynamics between two spectrally distinct H-bond configurations in real time by ultrafast 2DIR spectroscopy. In aqueous 5.0 M NaPF6 solution, water molecules switch their H-bond partners from PF6(-) to water molecule (ODA → ODW) with a time constant of 12.0 ps and from water molecule to PF6(-) (ODW → ODA) with a time constant of 21.6 ps at room temperature. H-bond exchange dynamics in aqueous NaPF6 solution were found to be relatively slower than those in aqueous NaBF4 and NaClO4 solutions which were studied previously, which was attributed to the asymmetric potential energy curve for the H-bond exchange process based on the orientational jump mechanism.

15.
J Phys Chem B ; 117(9): 2748-56, 2013 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-23409952

RESUMO

Azide ion is an excellent vibrational probe for studying ion-ion and ion-dipole interactions in solutions because its frequency is sensitively dependent on its local environments. When azide ion forms contact ion pairs with cations in dimethylsulfoxide (DMSO), free azide ion and contact ion pairs are spectrally well distinguished in FTIR spectra. Here, we investigated vibrational population relaxation, P(t), and orientational relaxation dynamics, r(t), of free azide ion and contact ion pairs (LiN3, NaN3, NH4N3, MgN3(+), and CaN3(+)) in DMSO by IR pump-probe spectroscopy. For metal azide ion pairs, the metal ion slowed down the vibrational relaxation of azide ion by acting like a thermal insulator. Biexponential behavior of r(t) was analyzed in the wobbling-in-a-cone model. The long time component of r(t) of free azide ion was found to be viscosity-dependent. The wobbling motion of azide ion within the frame of metal azide ion pairs was weakly dependent on the countercation. When the overall orientational relaxation of metal azide ion pairs was analyzed by the extended Debye-Stokes-Einstein equation, it was well described under stick or superstick boundary conditions due to a strong interaction between the metal ion and DMSO molecules. Our experimental results provide important insight in understanding the rotational dynamics of small ionic species in polar solvents when the size of the ionic species is smaller than or comparable to that of the solvent molecule.


Assuntos
Azidas/química , Dimetil Sulfóxido/química , Metais/química , Soluções , Espectroscopia de Infravermelho com Transformada de Fourier
16.
J Phys Chem B ; 116(30): 9152-9, 2012 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-22746977

RESUMO

Spectroscopic properties (i.e., peak positions and widths) of vibrational probes are sensitively dependent on their local environments in liquids. Such spectroscopic sensitivities can be utilized for studying the structures and dynamics of a variety of molecular systems. Here, we have studied the ion pairing equilibrium and dynamics of SeCN(-) ion pairs with Li(+) and Mg(2+) cations in N,N-dimethylformamide (DMF). SeCN(-) ion is an excellent vibrational probe for studying ion dynamics in electrolyte solutions, not only because the vibrational lifetime of the CN stretch is substantially long but also because the CN stretch frequency is very sensitive to its local environment. When SeCN(-) ion forms contact ion pairs (CIPs) with Li(+) (Mg(2+)) ion in DMF solutions, the CN stretch frequency is found to be significantly blue-shifted such that free SeCN(-) ion is spectrally well distinguished from Li-SeCN CIP and Mg-SeCN(+) CIP. This fact allows us to study the ion pairing equilibrium between SeCN(-) ion and metal ions as well as the dynamics of metal-SeCN(-) ion pairs. Ion pairing equilibrium between SeCN(-) ion and Li(+) (or Mg(2+)) was studied by temperature-dependent Fourier transform infrared (FTIR) spectroscopy. The formation of CIPs in DMF was found to be entropically favored. Time-resolved IR pump-probe spectroscopy was used to study the vibrational population relaxation and orientational relaxation dynamics. Vibrational lifetimes of free SeCN(-) ion, Li-SeCN CIP, and Mg-SeCN(+) CIP were determined to be 83.6, 72.3, and 55.6 ps, respectively. Orientational relaxation dynamics were found to get slower in the order free SeCN(-) ion, Li-SeCN CIP, and Mg-SeCN(+) CIP. The orientational anisotropy decays of the CIPs, which were well fit by a biexponential function, were explained by two orientational relaxation processes, that is, a restricted (tethered) orientational relaxation of SeCN(-) within the CIPs followed by the overall orientational diffusion of the whole CIPs. The orientational relaxation time constants of Li-SeCN CIP and Mg-SeCN(+) CIP in DMF were twice different but the orientational diffusion radii calculated by the Debye-Stokes-Einstein equation were found to be almost identical within experimental error. The biexponential decay of the orientational anisotropy was analyzed by the wobbling-in-a-cone model. As a vibrational probe, SeCN(-) ion and SeCN group can be potentially used for measuring the molecular dynamics on a relatively long time scale because of their long lifetimes.


Assuntos
Cianatos/química , Dimetilformamida/química , Metais/química , Compostos de Selênio/química , Íons/química , Soluções/química , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura
17.
J Chem Phys ; 134(6): 064506, 2011 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-21322704

RESUMO

Ultrafast two-dimensional infrared (2DIR) spectroscopy has been proven to be an exceptionally useful method to study chemical exchange processes between different vibrational chromophores under thermal equilibria. Here, we present experimental results on the thermal equilibrium ion pairing dynamics of Li(+) and SCN(-) ions in N,N-dimethylformamide. Li(+) and SCN(-) ions can form a contact ion pair (CIP). Varying the relative concentration of Li(+) in solution, we could control the equilibrium CIP and free SCN(-) concentrations. Since the CN stretch frequency of Li-SCN CIP is blue-shifted by about 16 cm(-1) from that of free SCN(-) ion, the CN stretch IR spectrum is a doublet. The temperature-dependent IR absorption spectra reveal that the CIP formation is an endothermic (0.57 kJ∕mol) process and the CIP state has larger entropy by 3.12 J∕(K mol) than the free ion states. Since the two ionic configurations are spectrally distinguishable, this salt solution is ideally suited for nonlinear IR spectroscopic investigations to study ion pair association and dissociation dynamics. Using polarization-controlled IR pump-probe methods, we first measured the lifetimes and orientational relaxation times of these two forms of ionic configurations. The vibrational population relaxation times of both the free ion and CIP are about 32 ps. However, the orientational relaxation time of the CIP, which is ∼47 ps, is significantly longer than that of the free SCN(-), which is ∼7.7 ps. This clearly indicates that the effective moment of inertia of the CIP is much larger than that of the free SCN(-). Then, using chemical exchange 2DIR spectroscopy and analyzing the diagonal peak and cross-peak amplitude changes with increasing the waiting time, we determined the contact ion pair association and dissociation time constants that are found to be 165 and 190 ps, respectively. The results presented and discussed in this paper are believed to be important, not only because the ion-pairing dynamics is one of the most fundamental physical chemistry problems but also because such molecular ion-ion interactions are of critical importance in understanding Hofmeister effects on protein stability.


Assuntos
Dimetilformamida/química , Lítio/química , Termodinâmica , Tiocianatos/química , Soluções , Espectrofotometria Infravermelho
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