Recent attention surrounds bisphenol‐A (BPA) due to potential estrogen mimicry and human health hazards. The public's negative reactions to these concerns threaten the commercial use of BPA requiring the global polymer community to investigate suitable replacements for commercial products that demand very good thermal and mechanical properties from BPA. This review highlights four classes of polymers that often utilize BPA for enhancing specific properties: polycarbonates, polyesters, epoxies and polyimides. A compilation of recent efforts involving the design of BPA‐free polymers is provided. Alternative monomers include 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol and isosorbide, and emerging polymers that exhibit acceptable thermal and mechanical properties are discussed. Copyright © 2012 Society of Chemical Industry
A one-pot melt polymerization of plant oil-based monomers and diamines afforded film-forming, isocyanate-free poly(amide-hydroxyurethane)s with processability and mechanical integrity.
The present study examined changes in sleep quality following hematopoietic stem cell transplantation (HSCT) and investigated associations with biobehavioral factors. Individuals undergoing HSCT for hematologic malignancies (N = 228) completed measures of sleep quality and psychological symptoms pre-transplant and 1, 3, 6 and 12 months post transplant. Circulating inflammatory cytokines (IL-6, TNF-α) were also assessed. Sleep quality was poorest at 1 month post transplant, improving and remaining relatively stable after 3 months post transplant. However, approximately half of participants continued to experience significant sleep disturbance at 6 and 12 months post transplant. Mixed-effects linear regression models indicated that depression and anxiety were associated with poorer sleep quality, while psychological well-being was associated with better sleep. Higher circulating levels of IL-6 were also linked with poorer sleep. Subject-level fixed effects models demonstrated that among individual participants, changes in depression, anxiety and psychological well-being were associated with corresponding changes in sleep after covarying for the effects of time since transplant. Sleep disturbance was most severe when depression and anxiety were greatest and psychological well-being was lowest. Findings indicate that sleep disturbance is a persistent problem during the year following HSCT. Patients experiencing depression or anxiety and those with elevated inflammation may be at particular risk for poor sleep.
Despite the well-established foundation of polyurethane chemistry in both industry and academia, research continues at a vigorous pace to refi ne synthetic processes and discover new functional materials. Incorporating ionic groups into polymers is a synthetic parameter capable of tailoring polymer properties and enabling emerging technologies. This review focuses on recent effort in the fi eld of ion-containing segmented polyurethane copolymers. Multiple synthetic strategies to incorporate both cationic and anionic sites, including a particular focus on waterborne polyurethane dispersions and green synthetic methods, are examined. Fundamental structure-property relationships based on ionic structure, content, and placement are explored and many applications, including biomedical products and polymer electrolytes for energy devices are discussed.(PEG) or poly(tetramethylene oxide) (PTMO), to the polyurethane reaction. The hydrogen bonding, depicted in Figure 1 , between the urethane carbonyl oxygen and urethane hydrogen, coupled with crystallization, constructs the hard segment (HS) domains, while the functionalized fl exible spacers comprise the soft segments (SSs) in an alternating fashion. The microphase-separated morphology of segmented polyurethanes is the foundation for their versatility, with the ability to further tune materials for a specifi c application with other synthetic parameters such as chemical composition and molecular weight. Yilgör and co-workers, [ 5 ] Yurtsever and co-workers, [ 6 ] and Wilkes and co-workers [ 7 ] extensively studied various model segmented polyurethane systems to further understand the morphology and factors infl uencing morphology on a fundamental structure-property level.Many comprehensive reviews and peer-reviewed journal articles focus on fundamental structure-property relationships of segmented polyurethanes.
Macrophage antibody dependent cellular phagocytosis (ADCP) is a major cytotoxic mechanism for both therapeutic unconjugated monoclonal antibodies (mAb) such as rituximab, and antibody induced hemolytic anemia and immune thrombocytopenia. Here, we studied the mechanisms controlling the rate and capacity of macrophages to carry out ADCP in settings of high target to effector cell ratio such as that seen in patients with circulating tumor burden in leukemic phase disease. Using quantitative live-cell imaging of primary human and mouse macrophages we found that, upon initial challenge with mAb-opsonized lymphocytes, macrophages undergo a brief burst (<1hr) of rapid phagocytosis which is then invariably followed by a sharp reduction in phagocytic activity that can persist for days. This previously unknown refractory period of ADCP, or "hypophagia," was observed in all macrophage/mAb/target cell conditions tested in vitro, and was also seen in vivo in Kupffer cells from mice induced to undergo successive rounds of ⍺CD20 mAb-dependent clearance of circulating B cells. Importantly, hypophagia had no effect on antibody-independent phagocytosis and did not alter macrophage viability. In mechanistic studies we found that the rapid loss of activating Fc receptors from the surface and their subsequent proteolytic degradation is the primary mechanism responsible for the loss of ADCP activity in hypophagia. These data suggest hypophagia is a critical limiting step in macrophage-mediated clearance of cells via ADCP and that understanding such limitations to innate immune system cytotoxic capacity will aid in the development of mAb regimens that could optimize ADCP and improve patient outcome.
Despite a high prevalence of sleep disruption among hematopoietic cell transplant (HCT) recipients, relatively little research has investigated its relationships with modifiable cognitive or behavioral factors or used actigraphy to characterize sleep disruption in this population. Autologous HCT recipients who were 6 to 18 months post-transplant completed self-report measures of cancer-related distress, fear of cancer recurrence, dysfunctional sleep cognitions, and inhibitory sleep behaviors upon enrollment. Patients then wore an actigraph for seven days and completed a self-report measure of sleep disruption on day seven of the study. Among the 84 participants (age M=60, 45% female), 41% reported clinically-relevant sleep disruption. Examination of actigraph data confirmed that, on average, sleep was disrupted (wake after sleep onset M=66 minutes) and sleep efficiency was less than recommended (sleep efficiency M=78%). Cancer-related distress, fear of recurrence, dysfunctional sleep cognitions, and inhibitory sleep behaviors were related to self-reported sleep disruption (p’s < .05) but not objective sleep indices. Results suggest that many HCT recipients experience sleep disruption after transplant. Cancer-related distress, fear of recurrence, dysfunctional sleep cognitions, and maladaptive sleep behaviors are related to self-reported sleep disruption and should be considered targets for cognitive behavioral intervention in this population.
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