Fundamentals of gas sorption and transport in thermally rearranged polyimides

textThermally rearranged polymers are formed from the solid-state thermal reaction of polyimides and polyamides that contain reactive groups ortho position to their diamine. These polymers have shown outstanding transport properties for gas separation applications. The thrust of this work is to critically examine the chemical and morphological structure of these polymers and to identify the fundamental contributions of gas sorption to permeability. To accomplish this goal, a series of TR polymers and TR polymer precursors have been synthesized and investigated for transport properties. As a function of conversion, diffusivity increases more dramatically than sorption, which explains the outstanding permeabilities observed for these samples. Modifications to the polymer backbone structure, which can be achieved by adding rigid functional groups such as hexafluoroisopropylidene-functional linking groups, can further be used to improve permeabilities. The precursor used to form TR polymers has dramatic effects on the final polymer transport properties. Despite having nearly identical polymer structure, TR polymers formed from polyamide precursors have lower combinations of permeability and selectivity than TR polymers formed from polyimide precursors. In addition to structure-property studies with TR polymers, this thesis also present comparisons of permeability, diffusivity, and sorption of sparingly soluble gases (i.e., hydrogen and helium) for hydrocarbon-based polymer, highly fluorinated polymers, perfluoropolymers, and a silicon-based polymer. An explanation for the unique transport properties of perfluoropolymers is presented from the standpoint of the solution-diffusion model, whereby perfluoropolymers have uniquely different solubility selectivities than hydrocarbon-based polymers. Additionally, a large database of sorption, diffusion, and permeability coefficients is used to determine the contributions of free volume on solubility selectivity in polymers.Chemical Engineerin

Resistance Exercise, Muscle Strength, Physical Function and Quality of Life in Head and Neck Cancer Patients Undergoing Chemoradiation

Chemoradiation therapy (CRT) is the standard of care treatment for Head and Neck Cancer (HNCa) patients. Despite its established therapeutic efficacy, adverse effects accompanying CRT result in clinically-meaningful declines in muscle strength, physical function and quality of life (QOL). The adverse effects observed during CRT place HNCa patients at heightened risk for functional decline, mortality, and morbidity. Accordingly, there is a pressing need to evaluate the utility of supportive care interventions, such as resistance exercise (RE), to attenuate the deleterious effects observed during CRT. PURPOSE: Determine the utility of implementing a group-mediated cognitive behavioral (GMCB) RE intervention in the treatment of HNCa patients undergoing CRT. In the current study, we evaluated the effects of the RE intervention for attenuating the typical declines observed in satisfaction with life (SWL), quality of life (QOL), muscle strength, and physical function. METHODS: The HNCaRE study was a single-arm, pilot trial in 20 HNCa patients undergoing CRT. Assessment of outcomes were obtained at baseline, 3-months, and 6-month follow-up visits. RESULTS: Results of a completer’s (n=11) repeated measures ANOVA analysis yielded a non-significant effect for satisfaction with life (p=0.19), upper body strength (p=0.57), and physical function (p=0.38). Significant results were found for QOL (p=0.04). Although the results of the ANOVA analysis were non-significant for muscular strength, physical function, and SWL, the effect size calculations revealed meaningful declines in SWL from baseline to 3-months (d = -.373) and 6-months (d = -.138). Significant decrease in QOL ratings from baseline to 3-months (d = -1.632) and 6-months (d = -1.162). Small increase in chest press from baseline to 3-months (d = .237) and a large decrease from baseline to 6-months (d = -.080). Small increase in 400 meter walk from baseline to 3-months (d = .156) and a slight decrease from baseline to 6-months (d = -.206). CONCLUSION: Findings from the HNCaRE pilot trial support the feasibility of implementing a GMBC-based RE intervention among HNCa patients undergoing CRT and provide evidence of the preliminary efficacy of this approach for meaningfully attenuating the magnitude of the declines in strength, physical function, QOL, and SWL. These promising results underscore the potential utility of integrating the GMCB RE intervention in the supportive care of HNCa patients undergoing CRT

SDSS-IV MaNGA: Variations in the N/O -- O/H relation bias metallicity gradient measurements

In this paper we use strong line calibrations of N/O and O/H in MaNGA spaxel data to explore the systematics introduced by variations in N/O on various strong-line metallicity diagnostics. We find radial variations in N/O at fixed O/H which correlate with total galaxy stellar-mass; and which can induce $\sim 40 \%$ systematic uncertainties in oxygen abundance gradients when nitrogen-dependent abundance calibrations are used. Empirically, we find that these differences are associated with variation in the local star formation efficiency, as predicted by recent chemical evolution models for galaxies, but we cannot rule out other processes such as radial migration and the accretion of passive dwarf galaxies also playing a role.Comment: 8 pages, 4 figures. Submitted to ApJL. All comments are welcom

SDSS-IV MaNGA: Evidence for enriched accretion onto satellite galaxies in dense environments

We investigate the environmental dependence of the local gas-phase metallicity in a sample of star-forming galaxies from the MaNGA survey. Satellite galaxies with stellar masses in the range $910^{10.5} \, \mathrm{M_{\odot}}$) centrals are $\sim 0.1 \, \mathrm{dex}$ more metal rich than satellites of low-mass ($M_{*} < 10^{10} \, \mathrm{M_{\odot}}$) centrals, controlling for local stellar mass surface density and gas fraction. Fitting a gas-regulator model to the spaxel data, we are able to account for variations in the local gas fraction, stellar mass surface density and local escape velocity-dependent outflows. We find that the best explanation for the metallicity differences is the variation in the average metallicity of accreted gas between different environments that depends on the stellar mass of the dominant galaxies in each halo. This is interpreted as evidence for the exchange of enriched gas between galaxies in dense environments that is predicted by recent simulations

Epidemiology and Outcomes of Vertebral Artery Injury in 16 582 Cervical Spine Surgery Patients: An AOSpine North America Multicenter Study.

STUDY DESIGN: A multicenter retrospective case series was compiled involving 21 medical institutions. Inclusion criteria included patients who underwent cervical spine surgery between 2005 and 2011 and who sustained a vertebral artery injury (VAI). OBJECTIVE: To report the frequency, risk factors, outcomes, and management goals of VAI in patients who have undergone cervical spine surgery. METHODS: Patients were evaluated on the basis of condition-specific functional status using the Neck Disability Index (NDI), modified Japanese Orthopaedic Association (mJOA) score, the Nurick scale, and the 36-Item Short-Form Health Survey (SF-36). RESULTS: VAIs were identified in a total of 14 of 16 582 patients screened (8.4 per 10 000). The mean age of patients with VAI was 59 years (±10) with a female predominance (78.6%). Patient diagnoses included myelopathy, radiculopathy, cervical instability, and metastatic disease. VAI was associated with substantial blood loss (770 mL), although only 3 cases required transfusion. Of the 14 cases, 7 occurred with an anterior-only approach, 3 cases with posterior-only approach, and 4 during circumferential approach. Fifty percent of cases of VAI with available preoperative imaging revealed anomalous vessel anatomy during postoperative review. Average length of hospital stay was 10 days (±8). Notably, 13 of the 14 (92.86%) cases resolved without residual deficits. Compared to preoperative baseline NDI, Nurick, mJOA, and SF-36 scores for these patients, there were no observed changes after surgery (P = .20-.94). CONCLUSIONS: Vertebral artery injuries are potentially catastrophic complications that can be sustained from anterior or posterior cervical spine approaches. The data from this study suggest that with proper steps to ensure hemostasis, patients recover function at a high rate and do not exhibit residual deficits

Rare Complications of Cervical Spine Surgery: Pseudomeningocoele.

STUDY DESIGN: This study was a retrospective, multicenter cohort study. OBJECTIVES: Rare complications of cervical spine surgery are inherently difficult to investigate. Pseudomeningocoele (PMC), an abnormal collection of cerebrospinal fluid that communicates with the subarachnoid space, is one such complication. In order to evaluate and better understand the incidence, presentation, treatment, and outcome of PMC following cervical spine surgery, we conducted a multicenter study to pool our collective experience. METHODS: This study was a retrospective, multicenter cohort study of patients who underwent cervical spine surgery at any level(s) from C2 to C7, inclusive; were over 18 years of age; and experienced a postoperative PMC. RESULTS: Thirteen patients (0.08%) developed a postoperative PMC, 6 (46.2%) of whom were female. They had an average age of 48.2 years and stayed in hospital a mean of 11.2 days. Three patients were current smokers, 3 previous smokers, 5 had never smoked, and 2 had unknown smoking status. The majority, 10 (76.9%), were associated with posterior surgery, whereas 3 (23.1%) occurred after an anterior procedure. Myelopathy was the most common indication for operations that were complicated by PMC (46%). Seven patients (53%) required a surgical procedure to address the PMC, whereas the remaining 6 were treated conservatively. All PMCs ultimately resolved or were successfully treated with no residual effects. CONCLUSIONS: PMC is a rare complication of cervical surgery with an incidence of less than 0.1%. They prolong hospital stay. PMCs occurred more frequently in association with posterior approaches. Approximately half of PMCs required surgery and all ultimately resolved without residual neurologic or other long-term effects

C5 Palsy After Cervical Spine Surgery: A Multicenter Retrospective Review of 59 Cases.

STUDY DESIGN: A multicenter, retrospective review of C5 palsy after cervical spine surgery. OBJECTIVE: Postoperative C5 palsy is a known complication of cervical decompressive spinal surgery. The goal of this study was to review the incidence, patient characteristics, and outcome of C5 palsy in patients undergoing cervical spine surgery. METHODS: We conducted a multicenter, retrospective review of 13 946 patients across 21 centers who received cervical spine surgery (levels C2 to C7) between January 1, 2005, and December 31, 2011, inclusive. P values were calculated using 2-sample t test for continuous variables and χ(2) tests or Fisher exact tests for categorical variables. RESULTS: Of the 13 946 cases reviewed, 59 patients experienced a postoperative C5 palsy. The incidence rate across the 21 sites ranged from 0% to 2.5%. At most recent follow-up, 32 patients reported complete resolution of symptoms (54.2%), 15 had symptoms resolve with residual effects (25.4%), 10 patients did not recover (17.0%), and 2 were lost to follow-up (3.4%). CONCLUSION: C5 palsy occurred in all surgical approaches and across a variety of diagnoses. The majority of patients had full recovery or recovery with residual effects. This study represents the largest series of North American patients reviewed to date