Hydrogen bonding interactions in poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone)/poly(hydroxyether of bisphenol A) triblock copolymer/homopolymer blends and the effect on crystallization, microphase separation and self-assembly

This study investigated the self-assembled microphase separated morphologies that are obtained in bulk, by the complexation of a semicrystalline poly(ε-caprolactone-dimethyl siloxane-ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer and a homopolymer, poly(hydroxyether of bisphenol A) (PH) in tetrahydrofuran (THF). In these blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically, the homopolymer interacts with PCL blocks through hydrogen bonding interactions. The crystallization, microphase separation and crystalline structures of a triblock copolymer/homopolymer blends were investigated. The phase behavior of the complexes was investigated using small-angle X-ray scattering and transmission electron microscopy. At low PH concentrations, PCL interacts relatively weakly with PH, whereas in complexes containing more than 50 wt% PH, the PCL block interacts significantly with PH, leading to the formation of composition-dependent nanostructures. SAXS and TEM results indicate that the lamellar morphology of neat PCL-PDMS-PCL triblock copolymer changes into disordered structures at 40-60 wt% PH. Spherical microdomains were obtained in the order of 40-50 nm in complexes with 80 wt% PH. At this concentration, the complexes show a completely homogenous phase of PH/PCL, with phase-separated spherical PDMS domains. The formation of these nanostructures and changes in morphology depends on the strength of hydrogen bonding between PH/PCL blocks and also the phase separated PDMS blocks.

Enhancement of ‘dry’ proton conductivity by self-assembled nanochannels in all-solid polyelectrolytes

Proton transport has been recognized as an essential process in many biological systems, as well as electrochemical devices including fuel cells and redox flow batteries. In the present study, we address the pressing need for solvent-free proton conducting polymer electrolytes for high-temperature PEM fuel cell applications by developing a novel all-solid polyelectrolyte membrane with a self-assembled proton-channel structure. We show that this self-assembled nanostructure endows the material with exciting ‘dry’ proton conductivity at elevated temperatures, as high as 0.3 mS cm−1 at 120 °C, making it an attractive candidate for high-temperature PEM fuel cell applications. Based on the combined investigation of solid-state NMR, FTIR and conductivity measurements, we propose that both molecular design and nano-scale structures are essential for obtaining highly conductive anhydrous proton conductors.

A facile method to fabricate carbon nanostructures via the self-assembly of polyacrylonitrile/poly (methyl methacrylate-b-polyacrylonitrile) AB/B' type block copolymer/homopolymer blends

The self-assembly and high temperature behavior of AB/B′ type block copolymer/homopolymer blends containing polyacrylonitrile (PAN) polymers were studied for the first time. Here, microphase separated nanostructures were formed in the poly(methyl methacrylate-b-polyacrylonitrile) (PMMAN) block copolymer and their blends with homopolymer PAN at various blend ratios. Additionally, these nanostructures were transformed into porous carbon nanostructures by sacrificing PMMA blocks via pyrolysis. Spherical and worm like morphologies were observed in both TEM and AFM images at different compositions. The thermal and phase behavior examinations showed good compatibility between the blend components in all studied compositions. The PAN homopolymer (B′) with a comparatively higher molecular weight than the corresponding block (B) of the block copolymer is expected to exhibit ‘dry brush’ behavior in this AB/B′ type system. This study provides a basic understanding of the miscibility and phase separation in the PMMAN/PAN system, which is important in the nanostructure formation of bulk PAN based materials with the help of block copolymers to develop advanced functional materials.

Synthesis and self-assembly behaviour of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan)

We report for the first time the use of Nα-Boc-l-tryptophan for the synthesis of amphiphilic BAB triblock copolymers for potential drug delivery applications. A library of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan) (PBoclTrp-b-PEG-b-PBoclTrp) amphiphilic copolymers were synthesized through the ring opening polymerization of Nα-Boc-l-tryptophan Nα-carboxy anhydride as initiated by diamino-terminated PEG of fixed molecular weight (Mn 3350). The influence of the hydrophobic block length over self-assembly was investigated for 4 of the BAB copolymers of molecular weights varying between Mn 5000 and Mn 17000. It was found that an increase in hydrophobic block length led to an increase in hydrodynamic size of aggregates in solution, as well as a decrease in critical micelle concentration. TEM analysis showed the formation of spherical micelles with the largest of the copolymers forming interconnected networks of spherical micelles. The influence of hydrophobic block length over the formation of secondary structure was analyzed using circular dichroism and infrared spectroscopy. Collectively we found that the presence of t-Boc protected l-tryptophan leads to the preferential formation of α-helix secondary structure through hydrogen bonding, which, in a drug delivery vehicle context, could help in controlling drug release. Also, it is believed that the use of novel Nα-Boc-l-tryptophan could improve drug stabilization in the hydrophobic core via π-π interactions between indole rings.

Correlates of agreement between accelerometry and self-reported physical activity

PURPOSE: Understanding factors that influence accurate assessment of physical activity (PA) and sedentary behavior (SB) is important to measurement development, epidemiologic studies, and interventions. This study examined agreement between self-reported (International Physical Activity Questionnaire-Long Form [IPAQ-LF]) and accelerometry-based estimates of PA and SB across six countries and identified correlates of between-method agreement. METHODS: Self-report and objective (accelerometry-based) PA and SB data were collected in 2002-2011 from 3865 adult participants in eight cities from six countries (Belgium, Czech Republic, Denmark, Spain, United Kingdom, and United States). Between-method relative agreement (correlation) and absolute disagreement (mean difference between conceptually and intensity-matched IPAQ-LF and accelerometry-based PA and SB variables) were estimated. Also, sociodemographic characteristics and PA patterns were examined as correlates of between-method agreement. RESULTS: Observed relative agreement (relationships of IPAQ-LF with accelerometry-based PA and SB variables) was small to moderate (r = 0.05-0.37) and was moderated by sociodemographic (age, sex, weight status, and education) and behavioral (PA-type) factors. The absolute disagreement was large, with participants self-reporting higher PA intensity and total time in moderate-to-vigorous-intensity PA than accelerometry. Also, self-reported sitting time was lower than accelerometry-based sedentary behavior. After adjusting for sociodemographic and behavioral factors, the absolute disagreement between pairs of IPAQ-LF and accelerometry-based PA variables remained significantly different across cities/countries. CONCLUSIONS: Present findings suggest systematic cultural and/or linguistic and sociodemographic differences in absolute agreement between the IPAQ-LF and the accelerometry-based PA and SB variables. These results have implications for the interpretation of international PA and SB data and correlate/determinant studies. They call for further efforts to improve such measures.

Associations of objectively measured moderate-to-vigorous physical activity and sedentary behavior with quality of life and psychological well-being in prostate cancer survivors

PURPOSE: Although evidence is building on the positive effects of physical activity for prostate cancer survivors, less is known about the possible independent effects of sedentary behavior on quality of life and psychological well-being in this population. We determined the extent to which objectively measured moderate-to-vigorous physical activity (MVPA) and sedentary behavior were independently associated with quality of life, anxiety, and depressive symptoms in prostate cancer survivors.

METHODS: An exploratory cross-sectional analysis was undertaken on baseline data from a multicenter, cluster randomized controlled trial on the efficacy of a clinician referral and 12-week exercise program for men who had completed active treatment for prostate cancer. Multiple regression analyses were performed using data from 98 prostate cancer survivors who wore hip-mounted accelerometers (time spent sedentary defined as <100 counts per minute [CPM]; MVPA defined as >1,951 CPM) and completed self-report instruments on their quality of life, anxiety, and depressive symptoms. Results were compared with minimal clinically important differences for the quality of life scales.

RESULTS: Independent of sedentary behavior, increases in MVPA of between 15 and 33 min/day were associated with clinically important (but not statistically significant) improvements in three quality of life scales (insomnia, diarrhea, and financial difficulties). Independent of MVPA, decreases in sedentary behavior of 119 and 107 min/day were associated with clinically important (but not statistically significant) improvements in physical functioning and role functioning, respectively.

CONCLUSION: Within our exploratory study, modest increases in MVPA and more substantive decreases in sedentary behavior were independently associated with clinically important improvements in several quality of life scales. Further research, including prospective studies, is required to understand sedentary behavior across larger and more representative samples (in terms of their physical, psychological, and social functioning and their engagement in physical activity) of prostate cancer survivors.

Neural correlates of impaired self-awareness of apathy, disinhibition and dysexecutive deficits in cocaine-dependent individuals

Cocaine addiction is characterized by impaired self-awareness about cognitive and motivational deficits, leading to poor treatment outcomes. However, there is still limited understanding of the neurophysiological underpinnings of this impairment. We aimed to establish if impaired self-awareness is underpinned by brain structural phenotypes among cocaine-dependent individuals (CDI). Sixty-five CDI and 65 designated informants completed the Frontal Systems Behavior Scale, and a subsample of 40 CDI were scanned via magnetic resonance imaging. We applied multiple regression models to establish the association between levels of self-awareness indexed by Frontal Systems Behavior Scale's discrepancy scores (i.e. informant ratings minus self-reports of apathy, disinhibition and dysexecutive deficits) and gray matter volumes indexed by magnetic resonance imaging voxel-based measures within five brain regions of interest: anterior cingulate cortex, orbitofrontal cortex (OFC), striatum, insula and dorsolateral prefrontal cortex (DLPFC). We also examined the neural underpinnings of underestimation versus overestimation of deficits, by splitting the CDI group according to the positive or negative value of their discrepancy scores. We found that poorer self-awareness of apathy deficits was associated with greater gray matter volume in the dorsal striatum, and poorer self-awareness of disinhibition deficits was associated with greater gray matter volume in the OFC in the whole sample. More underestimation and more overestimation of executive deficits were linked to lower DLPFC volume. We show that impaired self-awareness of cognitive and motivational deficits in cocaine addiction has a neural underpinning, implicating striatum, OFC and DLPFC structural phenotypes.

DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

Gender Differences in the Influence of Protective Factors, Risk Factors, and Health Risk Behaviors on HIV Risk Behaviors Among Youth in South Florida

Adolescents engage in a range of risk behaviors during their transition from childhood to adulthood. Identifying and understanding interpersonal and socio-environmental factors that may influence risk-taking is imperative in order to meet the Healthy People 2020 goals of reducing the incidence of unintended pregnancies, HIV, and other sexually transmitted infections among youth. The purpose of this study was to investigate gender differences in the predictors of HIV risk behaviors among South Florida youth. More specifically, this study examined how protective factors, risk factors, and health risk behaviors, derived from a guiding framework using the Theory of Problem Behavior and Theory of Gender and Power, were associated with HIV risk behavior. A secondary analysis of 2009 Youth Risk Behavior Survey data sets from Miami-Dade, Broward, and Palm Beach school districts tested hypotheses for factors associated with HIV risk behaviors. The sample consisted of 5,869 high school students (mean age 16.1 years), with 69% identifying as Black or Hispanic. Logistic regression analyses revealed gender differences in the predictors of HIV risk behavior. An increase in the health risk behaviors was related to an increase in the odds that a student would engage in HIV risk behavior. An increase in risk factors was also found to significantly predict an increase in the odds of HIV risk behavior, but only in females. Also, the probability of participation in HIV risk behavior increased with grade level. Post-hoc analyses identified recent sexual activity (past 3 months) as the strongest predictor of condom nonuse and having four or more sexual partners for both genders. The strongest predictors of having sex under the influence of drugs/alcohol were alcohol use in both genders, marijuana use in females, and physical fighting in males. Gender differences in the predictors of unprotected sex, multiple sexual partners, and having sex under the influence were also found. Additional studies are warranted to understand the gender differences in predictors of HIV risk behavior among youth in order to better inform prevention programming and policy, as well as meet the national Healthy People 2020 goals.

The effectiveness of an online workshop on behavior management as a professional development tool for teachers

The current study examines the effects of an online workshop pertaining to classroom behavior management on teacher self-efficacy, attitudes, motivation, knowledge, and practices. In addition, information about teacher utilization of the Internet, their opinions about professional development, and experiences with classroom management were collected. Participants included 57 1 st through 5th grade special and regular education teachers. Eligible teachers were those who teach an academic subject and had at least one child in the classroom they considered as disruptive. Teachers were randomized to either a training or waitlist group. Classroom observations of teacher practices and questionnaires were utilized. Teachers in the training group participated in two assessment points, baseline and post-workshop, and received access to the online course immediately following the baseline assessment. Teachers in the waitlist group participated in three assessment points, baseline, post-workshop, and follow-up, and received access to the online course immediately following the post-workshop assessment. Findings show that all teachers had access to the Internet at home and at school and used it on a daily basis. The majority of teachers indicated having some past training on all the techniques that were presented in the online workshop. All teachers expressed satisfaction with the workshop, indicating that it should be offered again. Post-workshop, findings showed significant group differences in knowledge with a large effect for the training group scoring higher than the waitlist group on a quiz. Secondly, group differences in self-efficacy, knowledge, and attitudes with teachers’ past-training as a moderator, was examined. Past-training was not found to be a significant moderator of self-efficacy, knowledge, or attitudes. However, the main effect for training group was significant for attitudes. In addition, teacher attitudes, but not knowledge and self-efficacy, significantly predicted motivation to implement. Next, the moderating effect of barriers on motivation and classroom management skill implementation was examined. Barriers were not found to be a significant moderator. Lastly, the training group was observed to be significantly more effective at giving commands compared to the waitlist group. The current study demonstrates the potential of a low-intensity online workshop on classroom management to enhance the accessibility of teacher professional development. ^

Sex-Positive Curricula: An Investigation of the Relationship Between Physical Fitness, Self-Concept and Sexual Functioning

Despite the well-recognized benefits of exercise, Americans are gaining weight in astounding proportions and levels of physical activity are on the decline. The purpose of this study was to investigate a relationship between physical fitness, self-concept and sexual health. There is a dearth of knowledge on this relationship specifically in the context of sex-negative curricula, which is the dominate discourse in the United States. One hundred and thirty-three participants between the ages of 18 - 50 volunteered for fitness testing and data collection. Physical fitness was assessed through body fat, resting metabolic rate, cardiovascular endurance, muscular strength, muscular endurance and flexibility. Self-reported exercise was measured using the International Physical Activity Questionnaire. Self-concept was measured by the Six Factor Self-Concept Scale, which presented a total self-concept score and as six individual concepts of self (likability, morality, task accomplishment, giftedness, power and vulnerability). Additionally, sexual function was measured by Derogatis Interview for Sexual Functioning and presented as both an aggregate score and five separate constructs of sexual functioning (fantasy/cognition, arousal, orgasm, behavior/experience, and drive/desire). Questions pertaining to sexual partners, sex education, and demographic information were also included. The results of the General Linear Model indicated significant relationships between physical fitness, self-concept and total sexual functioning. The sexual behavior/experience of men was predicted by body fat percentage and flexibility. In women, behavior/experience was predicted by body fat percentage and arousal was predicted by cardiovascular endurance. Total self-concept was related to muscular endurance. When men were isolated in the analysis, likability was positively related to sexual behavior/experience, and task accomplishment was inversely related to sexual behavior/experience. In women, giftedness was related to cognition/fantasy, arousal, orgasm and total sexual functioning. No relationships were found between physical fitness and the number of sexual partners in men; however, both muscular strength and the power self-concept were significantly related to number of sexual partners in women. As a result of these findings, women may be inclined to exercise to improve arousal and sexual functioning. Furthermore, educators should note the findings of a positive relationship between physical and psychological health and sexual well-being because they provide support for the development and adoption of sex-positive curricula that incorporate potential benefits of sexual activity.

Social Capital, HIV Risk Behavior and Substance Use among Recent Latino Immigrants in South Florida

Social capital, or social cohesion or group connectedness, can influence both HIV risk behavior and substance use. Because recent immigrants undergo a change in environment, one of the consequences can be a change in social capital. There may be an association among changes in social capital, and HIV risk behavior and substance use post immigration. The dissertation focused on the interface of these three variables among recent Latino immigrants (RLIs) in South Florida. The first manuscript is a systematic review of social capital and HIV risk behavior, and served as a partial background for the second and third manuscripts. Twelve papers with a measure of social capital as an independent variable and HIV risk as the dependent variable were included in the analysis. Eleven studies measured social capital at the individual level, and one study measured social capital at the group level. HIV risk was influenced by social capital, but the type of influence was dependent on the type of social capital and on the study population. Cognitive social capital, or levels of collective action, was protective against HIV in both men and women. The role of structural social capital, or levels of civic engagement/group participation, on HIV risk was dependent on the type of structural social capital and varied by gender. Microfinance programs and functional group participation were protective for women, while dysfunctional group participation and peer-level support may have increased HIV risk among men. The second manuscript was an original study assessing changes in social capital and HIV risk behavior pre to post immigration among RLIs in South Florida (n=527). HIV risk behavior was assessed through the frequency of vaginal-penile condom use, and the number of sexual partners. It was a longitudinal study using secondary data analysis to assess changes in social capital and HIV risk behavior pre immigration to two years post immigration, and to determine if there was a relationship between the two variables. There was an 8% decrease in total social capital (p ˂ .05). Reporting of ‘Never use’ of condoms in the past 90 days increased in all subcategories (p ˂ .05). Single men had a decrease in number of sexual partners (p ˂ .05). Lower social capital measured on the dimension of ‘friend and other’ was marginally associated with fewer sexual partners. The third manuscript was another original study looking at the association between social capital and substance use among RLIs in South Florida (n=527). Substance use with measured by frequency of hazardous alcoholic drinking, and illicit drug use. It was a longitudinal study of social capital and substance-use from pre to two years post immigration. Post-immigration, social capital, hazardous drinking and illicit drug use decreased (p˂.001). After adjusting for time, compared to males, females were less likely to engage in hazardous drinking (OR=.31, p˂.001), and less likely to engage in illicit drug use (OR=.67, p=.01). Documentation status was a moderator between social capital and illicit drug use. ‘Business’ and ‘Agency’ social capital were associated with changes in illicit drug use for documented immigrants. After adjusting for gender and marital status, on average, documented immigrants with a one-unit increase in ‘business’ social capital were 1.2 times more likely to engage in illicit drug use (p˂.01), and documented immigrants with one-unit increase in ‘agency’ social capital were 38% less likely to engage in illicit drug use (p˂.01). ‘Friend and other’ social capital was associated with a decrease in illicit drug use among undocumented immigrants. After adjusting for gender and marital status, on average, undocumented immigrants with a one-unit increase in ‘friend and other’ social capital were 45% less likely to engage in hazardous drinking and 44% less likely to use illicit drugs (p˂.01, p˂.05). Studying these three domains is relevant because HIV continues to be a public health issue, particularly in Miami-Dade County, which is ranked among other U.S. regions with high rates of HIV/AIDS prevalence. Substance use is associated with HIV risk behavior; in most studies, increased substance use is associated with increased chances of HIV risk behavior. Immigration, which is the hypothesized catalyst for the change in social capital, has an impact on the dynamic of a society. Greater immigration can be burdensome on the host country’s societal resources; however immigrants are also potentially a source of additional skilled labor for the workforce. Therefore, successful adaption of immigrants can have a positive influence on receiving communities. With Florida being a major receiver of immigrants to the U.S, this dissertation attempts to address an important public health issue for South Florida and the U.S. at large.

What Influences Information Security Behavior? A Study with Brazilian Users

The popularization of software to mitigate Information Security threats can produce an exaggerated notion about its full effectiveness in the elimination of any threat. This situation can result reckless users behavior, increasing vulnerability. Based on behavioral theories, a theoretical model and hypotheses were developed to understand the extent to which human perception of threat, stress, control and disgruntlement can induce responsible behavior. A self-administered questionnaire was created and validated. The data were collected in Brazil, and complementary results regarding similar studies conducted in USA were found. The results show that there is influence of information security orientations provided by organizations in the perception about severity of the threat. The relationship between threat, effort, control and disgruntlement, and the responsible behavior towards information security was verified through linear regression. The contributions also involve relatively new concepts in the field and a new research instrument.

Knowledge of and attitudes toward sexual and reproductive health among college students

Abstract Introduction: Knowledge provides the foundation for values, attitudes and behavior. Knowledge about sexual and reproductive health (SRH) and positive attitudes are essential for implementing protective behaviors. Objectives: The aim of this study was to evaluate SRH knowledge and attitudes in college students and their association with sexual and reproductive behaviors. Material and methods: A cross-sectional study was conducted in a sample of 1946 college students. The data were collected using a self-report questionnaire on the sociodemographics characteristics of the sample, an inventory on SRH knowledge and an attitude scale, and were analyzed with descriptive and inferential statistics (ANOVA and Pearson’s correlation). Results: The sample was 64% female and 36% male, with a mean age of 21 years. The majority were sexually active and used contraception. The SRH knowledge was moderate (22.27 ± 5.79; maximum score = 44), while the average SRH attitude score was more favorable (118.29 ± 13.92; maximum score = 140). Female and younger students studying life and health sciences had higher (P < .05) SRH knowledge and attitude scores. The consistent use of condom and health care surveillance were highly dependent on the students’ SRH knowledge and attitudes. Engagement in sexual risk behaviors was associated with lower scores for these variables. Conclusions: Strategies to increase SRH knowledge and attitudes are important tools for improving protective behaviors, especially with respect to contraception, health care surveillance and exposure to sexual risk. Older males studying topics other than life sciences should be a priority target for interventions due to their higher sexual risk

Foreign fighters, human rights and self-determination in Syria and Iraq: decoding the humanitarian impact of foreign fighters in practice

Foreign fighters have become inextricably linked to perceptions of human rights abuses in the Syria and Iraq wars, particularly since the Islamic State group founded its caliphate. This paper explores the human rights impact of foreign fighters in the conflicts, noting that while foreign fighters have been involved in grave human rights abuses, such behavior has not been uniform and must be differentiated by group and role. In this regard, it is argued that while foreign fighters have overwhelmingly had a negative impact on most human rights indicators, fighters in some groups have positively impacted the Right to Self-Determination. Further, the paper notes that while foreign fighters have been large-scale perpetrators of human rights abuses, one must also consider the propaganda value of such acts because foreign fighter-led violence is more newsworthy globally than local-led violence.