Teaching Old Polymers New Tricks: Improved Synthesis and Anomalous Crystallinity for a Lost Semi-Fluorinated Polyaryl Ether via Interfacial Polymerization of Hexafluoroacetone Hydrate and Diphenyl Ether.

A practical and direct electrophilic polymerization of hexafluoroacetone hydrate with diphenyl ether toward the preparation of semi-fluorinated polyaryl ethers (PAE) is reported. Electrophilic aromatic substitution (EAS) polymerization under interfacial conditions with phase transfer catalyst (Aliquat 336) proceeds in trifluoromethanesulfonic anhydride by generation of trifluoromethanesulfonic acid and the protonated hexafluoroacetone (HFA) in situ affording 1,1,1,3,3,3-hexafluoroisopropylidene (6F) PAE with high regioselectivity (4,4'-DPE) and high molecular weight (≈60 kDa). Although first reported in a 1966 US Patent by DuPont using harsh conditions, improved synthetic methods or modern characterization has not been disclosed until now. Despite the presence of the 6F group, known to impart disordered morphology, this simple semi-fluorinated PAE exhibits anomalous crystallinity with polymorphic melting points (Tm ) ranging from 230-309 °C, high solubility in common organic solvents, a glass transition (Tg ) of 163 °C, and thermo-oxidative stability above 500 °C. Tough optically clear films prepared from solution give transmittance higher than 90% throughout the visible region. Synthesis, mechanistic aspects, and characterization including surface and dielectric properties are discussed.

Ring-Forming Polymerization toward Perfluorocyclobutyl and Ortho-Diynylarene-Derived Materials: From Synthesis to Practical Applications.

Many desirable characteristics of polymers arise from the method of polymerization and structural features of their repeat units, which typically are responsible for the polymer's performance at the cost of processability. While linear alternatives are popular, polymers composed of cyclic repeat units across their backbones have generally been shown to exhibit higher optical transparency, lower water absorption, and higher glass transition temperatures. These specifically include polymers built with either substituted alicyclic structures or aromatic rings, or both. In this review article, we highlight two useful ring-forming polymer groups, perfluorocyclobutyl (PFCB) aryl ether polymers and ortho-diynylarene- (ODA) based thermosets, both demonstrating outstanding thermal stability, chemical resistance, mechanical integrity, and improved processability. Different synthetic routes (with emphasis on ring-forming polymerization) and properties for these polymers are discussed, followed by their relevant applications in a wide range of aspects.

Return to the Primary Acute Care Service Among Patients With Multiple Myeloma on an Acute Inpatient Rehabilitation Unit.

BACKGROUND: Pancytopenia, immunosuppression, and other factors may place patients with multiple myeloma at risk for medical complications. These patients often require inpatient rehabilitation. No previous studies have looked at risk factors for return to the primary acute care service of this patient population. OBJECTIVE: To determine the percentage of and factors associated with return to the primary acute care service of multiple myeloma rehabilitation inpatients. DESIGN: Retrospective review. SETTING: Acute inpatient rehabilitation unit within a National Cancer Institute Comprehensive Cancer Center. PARTICIPANTS: All patients with multiple myeloma admitted to the inpatient rehabilitation unit between March 1, 2004, and February 28, 2015. MAIN OUTCOME MEASURES: Return to the primary acute care service was analyzed with demographic information, multiple myeloma characteristics, medications, laboratory values, and hospital admission characteristics. RESULTS: One hundred forty-three inpatient rehabilitation admissions were found during the study period. After we removed multiple admissions of the same patients and planned transfers to the primary acute care service, 122 admissions were analyzed. Thirty-two (26%) patients transferred back to the primary acute care service for unplanned reasons. Multivariate analysis revealed male gender and thrombocytopenia as significantly associated with return to the primary acute care service. The median survival of patients who transferred back to the inpatient primary acute care service was 180 days versus 550 days for those who did not (P < .001). CONCLUSION: Because of their medical fragility, clinicians caring for rehabilitation inpatients with multiple myeloma should maintain close contact with the primary oncology service. Factors associated with an increased risk of transfer back to the primary acute care service include male gender and thrombocytopenia. LEVEL OF EVIDENCE: IV.

Effectiveness of an Educational Intervention on Reducing Misconceptions Among Ethnic Minorities With Complicated Mild to Severe Traumatic Brain Injury.

OBJECTIVE: To evaluate the effectiveness of an educational intervention designed to reduce traumatic brain injury (TBI)-related misconceptions among blacks and Latinos with complicated mild to severe TBI. DESIGN: Randomized controlled trial with masked 1-month follow-up. SETTING: Community. PARTICIPANTS: Persons (N=52) with complicated mild to severe TBI (mean best day 1 Glasgow Coma Scale score, 11.27±3.89) were randomly recruited from 141 eligible participants (mean age, 37.71±13.88y; age range, 19-66y; mean months postinjury, 24.69±11.50); 25 participants (48.1%) of participants were black and 27 (51.9%) were Hispanic/Latino. Of the Hispanic/Latino participants, 18 (66.7%) were non-U.S. born and 12 (44.4%) spoke Spanish as their primary language. Twenty-seven individuals were randomized to the educational intervention group and 25 were randomized to the wait-list control group. INTERVENTIONS: Single-session educational intervention with written materials provided in English or Spanish. MAIN OUTCOME MEASURES: Forty-item Common Misconceptions about Traumatic Brain Injury Questionnaire administered at baseline and 1-month follow-up. RESULTS: After controlling for ethnic and language differences, a significant between-group main effect (P=.010) and a significant time-group interaction for the Common Misconceptions about Traumatic Brain Injury Questionnaire were noted (Wilks Λ=.89; F1,46=6.00; P=.02). The intervention group showed a decrease in TBI misconception percentages, whereas the wait-list control group maintained similar percentages. At 1-month follow-up, the wait-list control group reported more misconceptions than did the intervention group (P=.019). CONCLUSIONS: An educational intervention developed to address the recovery process, common symptoms, and ways to handle the symptoms provides promise as a tool to decrease TBI misconceptions among persons from ethnically and educationally diverse backgrounds. The effects of therapist characteristics and the client-therapist relation on outcomes should be further explored.

Utilization of a Meldrum's acid towards functionalized fluoropolymers possessing dual reactivity for thermal crosslinking and post-polymerization modification.

New thermally cross-linkable and/or post-functionalizable perfluorocyclobutyl (PFCB) polymers containing Meldrum's acid moieties have been successfully prepared via the thermal cyclopolymerization of a new Meldrum's acid functionalized aromatic trifluorovinyl ether (TFVE) monomer.

Symptom Burden and Functional Gains in a Cancer Rehabilitation Unit.

BACKGROUND/AIMS: To determine if there is a relationship between patient symptoms and functional improvement on inpatient rehabilitation. METHODS: Retrospective review of medical records at an American tertiary referral-based cancer center of all patients admitted to an inpatient rehabilitation unit between 3/1/2013-5/20/2013. Main outcome measures included the Edmonton Symptom and Assessment Scale (ESAS) and Functional Independence Measure (FIM). FINDINGS: The medical records for 71 unique cancer rehabilitation inpatients were analyzed. Statistical analysis of total admission ESAS on total FIM change found no significant relationships. The symptom burden of the patients was mild. Patients demonstrated statistically significant improvements in function and symptoms during inpatient rehabilitation. The mean change in total FIM and total ESAS were an increase of 19.20 and decrease of 7.41 respectively. Statistically significant changes occurred in fatigue, sleep, pain, and anxiety. CONCLUSION: Both symptom and functional scores improved significantly during inpatient rehabilitation. However, no significant relationships were found between symptoms at admission and improvement in FIM.

Association between the summer season and body fatness and aerobic fitness among Hispanic children.

BACKGROUND: Few studies have investigated changes in adiposity and fitness during the academic year (AY) and summer season (SS) in minority children. This study aimed to assess if adiposity indicators and fitness change during the school AY and SS in Hispanic children. METHODS: One hundred nineteen low-income Hispanic children (9.2 ± 0.8) participated in the study. Demographic, body weight and height, percent body fat (% BF), and aerobic endurance were assessed at 3 time points: measurement 1 (M1), beginning of AY; M2, end of AY; and M3, end of SS. Using weight and height, body mass index (BMI) was calculated and normalized (BMI z-scores). Mixed effects between-within-subjects analysis of variance (ANOVA) design was used to examine changes in selected variables. RESULTS: A significant decrease of BMI z-scores in overweight children (p = .024) was observed during the AY only, but not during the SS. Percent BF increased significantly over the AY and SS (p < .001), particularly in girls. Aerobic endurance showed a significant increase over the AY (p < .001), but it did not change over the SS (p = .552). CONCLUSIONS: Results indicated that the SS might place Hispanic children at increased risk for additional adiposity and lower fitness.

Frequency and reasons for return to the primary acute care service among patients with lymphoma undergoing inpatient rehabilitation.

OBJECTIVE: To assess the frequency and risk factors for return to the primary acute care service among patients with lymphoma undergoing inpatient rehabilitation. DESIGN: Retrospective study. SETTING: Tertiary referral-based cancer center. PATIENTS: All patients with a history of lymphoma admitted to an inpatient rehabilitation between October 1, 2003, and January 30, 2013. MAIN OUTCOME MEASURES: Items analyzed from patient records included return to the primary acute care service with demographic information, lymphoma characteristics, medications, hospital admission characteristics, and laboratory values. RESULTS: A total of 143 unique patient admissions were analyzed, and 54 of these 143 lymphoma inpatient rehabilitation admissions (38%) returned to the primary acute care service. However, 16 of 54 (30%) returned because they needed additional chemotherapy. Excluding patients who returned to the primary acute care service for chemotherapy, statistically significant or approaching statistically significant factors (P < .10) associated with return to the primary acute care service included a creatinine level ≥ 1.3 mg/dL (P = .0002), male gender (P = .001), history of hematopoietic stem cell transplantation (P = .0355), and presence of an intravenous antifungal agent (P = .0717). Of the patients transferred back to the primary acute care service, 13 of 38 (34%) were discharged directly home, 10 of 38 (26%) died in the hospital, 7 of 38 (18%) were transferred to a subacute rehabilitation facility, and 4 of 38 (11%) were transferred to inpatient rehabilitation. CONCLUSIONS: When excluding patients who returned for chemotherapy, patients with lymphoma who were male, had undergone hematopoietic stem cell transplantation, and had a creatinine level ≥ 1.3 mg/dL demonstrated increased risk for return to the primary acute care service.

A comparison of polymer substrates for photolithographic processing of flexible bioelectronics.

Flexible bioelectronics encompass a new generation of sensing devices, in which controlled interactions with tissue enhance understanding of biological processes in vivo. However, the fabrication of such thin film electronics with photolithographic processes remains a challenge for many biocompatible polymers. Recently, two shape memory polymer (SMP) systems, based on acrylate and thiol-ene/acrylate networks, were designed as substrates for softening neural interfaces with glass transitions above body temperature (37 °C) such that the materials are stiff for insertion into soft tissue and soften through low moisture absorption in physiological conditions. These two substrates, acrylate and thiol-ene/acrylate SMPs, are compared to polyethylene naphthalate, polycarbonate, polyimide, and polydimethylsiloxane, which have been widely used in flexible electronics research and industry. These six substrates are compared via dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and swelling studies. The integrity of gold and chromium/gold thin films on SMP substrates are evaluated with optical profilometry and electrical measurements as a function of processing temperature above, below and through the glass transition temperature. The effects of crosslink density, adhesion and cure stress are shown to play a critical role in the stability of these thin film materials, and a guide for the future design of responsive polymeric materials suitable for neural interfaces is proposed. Finally, neural interfaces fabricated on thiol-ene/acrylate substrates demonstrate long-term fidelity through both in vitro impedance spectroscopy and the recording of driven local field potentials for 8 weeks in the auditory cortex of laboratory rats.

Summer and follow-up interventions to affect adiposity with mothers and daughters.

BACKGROUND: The development of effective obesity interventions to reduce adiposity indicators in Latina girls is a public health priority because of their increased risk for becoming overweight. Research indicates that the summer season may be a critical time to intervene because summer exacerbates children's risk for excessive weight gain and increased body fat development. PURPOSE: The purpose of this study was twofold: (1) to determine if summer and follow-up interventions reduce adiposity in Latina girls; (2) to assess if such interventions reduce adiposity in Latina girls after controlling for their mothers' adiposity measures. DESIGN: This study had a non-experimental (one-group pre- and multiple post-intervention assessment) design. Following a 4-week healthy-lifestyle summer program, each mother-daughter pair participated in 12 weekly follow-up sessions. SETTING/PARTICIPANTS: The sample consisted of 61 pairs of Latina girls and their mothers (N=122). Daughters' average age was 10.9 years (± 1.6 years) and mothers' average age was 38.0 years (± 1.6 years). All daughters and 92% of the mothers were categorized as overweight/obese. MAIN OUTCOME MEASURES: Percent body fat (%BF), abdominal fat, and height and weight measurements to calculate BMI were conducted at pre-intervention (M1 [baseline]) and three post-intervention time points (M2 [Month 2]; M3 [Month 3]; and M4 [Month 6]). Paired sample t-tests were used to assess the differences in adiposity among the daughters from M1 to M4. Repeated-measures ANCOVA tests were used to control for mother's adiposity. RESULTS: Reductions of %BF (p<0.001); abdominal fat (p<0.05); and BMI (p<0.001) at M2 were found for the summer intervention, but no effects were found at M4. Maternal %BF, abdominal fat, and BMI did not have an impact on the daughters' adiposity indicators. CONCLUSIONS: Results from this study revealed that a summer intervention appears to be effective in reducing adiposity in Latina girls, but the follow-up sessions did not result in sustaining continued reductions. Maternal measures did not influence their daughters' adiposity measures.

Frequency and reasons for return to acute care in patients with leukemia undergoing inpatient rehabilitation: a preliminary report.

OBJECTIVE: The aim of this study was to assess the frequency and reasons for return to the primary acute care service among patients with leukemia undergoing inpatient rehabilitation. DESIGN: This is a retrospective study of all patients with leukemia, myelodysplastic syndrome, aplastic anemia, or myelofibrosis admitted to inpatient rehabilitation at a tertiary referral-based cancer center between January 1, 2005, and April 10, 2012. Items analyzed from patient records included return to the primary acute care service with demographic information, leukemia characteristics, medications, hospital admission characteristics, and laboratory values. RESULTS: Two hundred twenty-five patients were admitted a total of 255 times. Ninety-three (37%) of the 255 leukemia inpatient rehabilitation admissions returned to the primary acute care service. Eighteen (19%) and 42 (45%) of the 93 patients died in the hospital and were discharged home, respectively. Statistically significant factors (P < 0.05) associated with return to the primary acute care service include peripheral blast percentage and the presence of an antifungal agent on the day of the inpatient rehabilitation transfer. Using additional two factors (platelet count and the presence of an antiviral agent, both P < 0.11), the Return to Primary-Leukemia Index was formulated. CONCLUSIONS: Patients with leukemia with the presence of circulating peripheral blasts and/or an antifungal agent may be at increased risk for return to the primary acute care service. The Return to Primary-Leukemia Index should be tested in prospective studies to determine its usefulness.

Return to primary service among bone marrow transplant rehabilitation inpatients: an index for predicting outcomes.

OBJECTIVE: To assess rehabilitation inpatient risk of return to primary (RTP) service in patients with bone marrow transplant (BMT). DESIGN: Retrospective review. SETTING: Inpatient rehabilitation unit within a tertiary referral-based cancer center. PARTICIPANTS: All patients with BMT (131) who were admitted a total of 147 times to inpatient rehabilitation between January 1, 2002, and April 30, 2010. INTERVENTIONS: None. MAIN OUTCOME MEASURES: We analyzed RTP service and demographic information, cancer characteristics, medications, hospital admission characteristics, and laboratory values. RESULTS: A total of 61 (41%) of 147 of BMT admissions were transferred from the inpatient rehabilitation unit back to the primary service. Of those transferred back, 23 (38%) of 61 died after being transferred back to the primary service. Significant or near-significant relationships were found for a platelet count of <43,000 per microliter (P<.01); a creatinine level of >0.9 milligrams/deciliter (P<.01); the presence of an antiviral agent (P=.0501); the presence of an antibacterial agent (P=.0519); the presence of an antifungal agent (P<.05); and leukemia, lymphoma, or multiple myeloma diagnosis (P<.05). Using 5 of these factors, the RTP-BMT index was formulated to determine the likelihood of return to the primary team. CONCLUSIONS: Patients with BMT have a high rate of transfer from the inpatient rehabilitation unit back to the primary service. The RTP-BMT index score can be a useful tool to help clinicians predict the likelihood of return to the primary acute care service.

High Performance and Multipurpose Triarylamine-Enchained Semifluorinated Polymers.

Transparent, film-forming fluorinated arylene vinylene ether (FAVE) polymers with enchained triarylamine (TAA) moieties were prepared and characterized. Control over fluoro-olefin content within the backbone, as a function of base, was confirmed and postpolymerization dehydrofluorination was shown to increase fluoroolefin content from 5 to 31 mol %. Thermal cross-linking was found to occur approximately 100 °C lower than in traditional FAVE polymers (ca. 160 °C). Electrochemical analysis demonstrated the enchained TAA retained its established electrochemical character. The latent reactivity of the TAA was explored via electrophilic aromatic substitution and formylation reactions toward precise functionalization for specific electro-optic applications and others.

An exploration of transactional states and cessation-related social variables within adolescent smokers.

BACKGROUND: Given the high rate of adolescent smoking, cessation remains a vital public health priority. This study explored archival data using a structured phenomenological framework known as Reversal Theory (RT). In order to better understand aspects of adolescent tobacco use we compared the transactional, psychological states described by RT to the factor structure of adolescents' self-reported social environment influencing tobacco use. METHODS: In a two step analysis of questions about self-reported tobacco use cognitions, attitudes, and behaviors from youth enrolled during the 2003-2004 period in a Texas, state-wide, mandated tobacco cessation program (N=1807), four factors and 11 items were identified as significantly related to the influence of social context and adolescents' tobacco use. These first step results guided the items to be selected for further analysis. In step two the variables were subjected to a factor analysis using principal components extraction and varimax rotation. The resulting factor structure was compared and interpreted within the context of descriptions of RT transactional states. RESULTS: The analysis indicated that four factors were closely aligned to descriptions of the Reversal Theory transactional states and could be reinterpreted from within the framework of RT. The first factor included feelings of self-efficacy for quitting (autic mastery). The second and third transactional factors diverged between one factor to quit, and an opposing transactional factor to continue to smoke. Both of these transactional states are variants of the autocentric state where one wants to experience feelings of gain with the help of others. The fourth factor could be interpreted as 'confidence' or 'optimism'. CONCLUSIONS: This intra-individual conflict revealed by the opposition of factors two and three clarifies a paradoxical issue where an adolescent wants to quit smoking with social support in one setting yet in another social environment chooses to smoke to gain or retain peer acceptance. These data illustrate that adolescent' self-identified quit skills and social support structures are important to the quitting process. This exploratory investigation has important implications for addressing RT state reversals in youth cessation programming activities.

Grafting of chain-end-functionalized perfluorocyclobutyl (PFCB) aryl ether ionomers onto mesoporous carbon supports.

Water-soluble perfluorocyclobutyl (PFCB) aryl ether ionomers bearing sulfonic acid groups in the main chain and phosphonic acid end groups were prepared and used to modify the surfaces of mesoporous carbon materials containing dispersed zirconia nanoparticles. Ionomer surface grafting occurred via phosphonate bonding onto the zirconia particle surfaces.

Perfluorinated polymer colloids: controlling the size, shape, and surface charge.

The first report of perfluorocyclobutyl (PFCB) aryl ether polymer colloids is presented herein. The biphenyl rings were post-functionalized with chlorosulfonic acid modification in the backbone of the perfluoropolymer, thereby changing the zeta potential (ζ) of the colloids across the pH range (2-12). Self-assembly of the colloids was observed by scanning electron microscopy (SEM) on four separate surfaces which led to different morphological changes for each surface; spherical on Al substrate, clover-like on Cr substrate, flower-like on carbon substrate, and "squalloid" on Si substrate.

Hispanic maternal and children's perceptions of neighborhood safety related to walking and cycling.

This study examined neighborhood safety as perceived by children (mean age=10 years) and their mothers, and its association with children's physical activity. For all eight safety items examined, children perceived their environment as less dangerous than mothers (p<0.05). None of the multiple regression models predicting children's physical activity by safety perceptions were significant (p>0.10). The maternal perception model explained the highest percentage of variance (R(2)=0.26), compared to the children's perception model (R(2)=0.22). Findings suggest that future studies should explore relations between self-reported and objectively measured safety barriers to Hispanic youth walking and cycling.

Comparing high and low acculturated mothers and physical activity in Hispanic children.

BACKGROUND: Parents represent a key ecological component in influencing their child's physical activity. The aim of this exploratory study was to assess the relationship between maternal acculturation and physical activity in Hispanic children. METHODS: 102 Hispanic mothers (mean age 36.2 yrs; +SD 7.3 yrs) and their children (mean age 10.0 yrs, +SD 0.8 yrs) participated. Most of the mothers (74%) were foreign-born, with 62% classified as low acculturated and 38% high acculturated. Demographic, acculturation, and anthropometric measures were completed by mothers and children. Physical activity was measured using accelerometers. Relationships between maternal acculturation and demographic variables and children's physical activity were examined using chi-square, Analysis of Variance, and simple regression. RESULTS: Children had higher physical activity levels than their mothers (t(49) = -7.87, P < .0001). Significant correlations between maternal and child's physical activity levels were observed in moderate (r2 = 0.13, P = .001), vigorous (r2 = 0.08, P = .05), and moderate-to-vigorous physical activity (r2 = 0.17, P = .002). Low acculturated mothers were more likely to have active children compared with high acculturated mothers. Maternal BMI and other demographic characteristics were not significantly associated with child's physical activity. CONCLUSIONS: Findings from this study revealed an association among maternal acculturation, role modeling, and child's physical activity.

Synthesis of internal fluorinated alkenes via facile aryloxylation of substituted phenols with aryl trifluorovinyl ethers.

Nucleophilic addition-elimination of ortho- or para-substituted phenols to aryl trifluorovinyl ethers (TFVEs) in N,N-dimethylformamide was studied. Using sodium hydride as a base afforded vinyl substitution products R-Ar-O-CF=CF-O-Ar-R', where R or R' = H, Br, OMe, tert-Bu, or Ph. The vinyl substitution products produced mixtures of (Z)/(E)-isomers and this isomer ratio was influenced by substitution with more sterically encumbered phenol nucleophiles. Reactions using caesium carbonate afforded addition products R-Ar-O-CHFCF(2)-O-Ar-R' whereas upon dehydrofluorination using sodium hydride produced vinyl substitution products. The preparation of vinyl substituted and addition products proceeded in overall good isolated yields and were elucidated using (1)H and (19)F NMR, GC-MS, and X-ray analysis. Vinyl substituted products were inert to UV light and chemical reactivity using common polymerization promoters. Thermal activation of the (Z)/(E)-fluoroolefin (-CF=CF-) was observed at an onset of 310 °C in nitrogen using differential scanning calorimetry (DSC) producing insoluble network material. The synthesis, characterization, and mechanism for stereoselectivity are discussed.

Common misconceptions about traumatic brain injury among ethnic minorities with TBI.

OBJECTIVE: To investigate common TBI misconceptions among ethnic minorities with TBI. DESIGN: Cross-sectional study. SETTING: Level I trauma center. PARTICIPANTS: Fifty-eight persons with TBI (28 black and 30 Hispanic) discharged from the neurosurgery unit and living in the community. MAIN MEASURE: Forty-item Common Misconceptions about Traumatic Brain Injury Questionnaire (CM-TBI). RESULTS: Participants displayed misconceptions about approximately one-third of the 40 items, most regarding amnesia and recovery. Fewer misconceptions were found in the brain damage/injury and sequelae categories. A greater percentage of TBI misconceptions was associated with having lower education, actively practicing religion, being Spanish-speaking and non-US born. After controlling for education and actively practicing religion, Spanish-speaking Hispanics reported a greater percentage of misconceptions than English-speaking Hispanics and blacks. CONCLUSIONS AND IMPLICATIONS: Understanding common TBI misconceptions can assist rehabilitation staff in tailoring education programs for racial/ethnic minorities including those who are Spanish-speaking. Educational attainment and cultural factors should be considered when developing educational interventions for persons with TBI from diverse backgrounds. Inaccurate information regarding TBI, especially the recovery process, may hinder treatment planning by rehabilitation professionals and may result in disappointment and the setting of unrealistic goals for persons with injury and their families.