Direct iminization of PEEK

Semi-crystalline poly(ether ketone)s are important high-temperature engineering thermoplastics, but are difficult to characterize at the molecular level because of their insolubility in conventional organic solvents. Here we report that polymers of this type, including PEEK, react cleanly at high temperatures with low-volatility aralkyl amines to afford stable, noncrystalline poly(ether-imine)s, which are readily soluble in solvents such as chloroform, THF and DMF and so characterizable by conventional size-exclusion chromatography

Limits of sensing temporal concentration changes by single cells

Berg and Purcell [Biophys. J. 20, 193 (1977)] calculated how the accuracy of concentration sensing by single-celled organisms is limited by noise from the small number of counted molecules. Here we generalize their results to the sensing of concentration ramps, which is often the biologically relevant situation (e.g. during bacterial chemotaxis). We calculate lower bounds on the uncertainty of ramp sensing by three measurement devices: a single receptor, an absorbing sphere, and a monitoring sphere. We contrast two strategies, simple linear regression of the input signal versus maximum likelihood estimation, and show that the latter can be twice as accurate as the former. Finally, we consider biological implementations of these two strategies, and identify possible signatures that maximum likelihood estimation is implemented by real biological systems.Comment: 11 pages, 2 figure

Conformational modulation of sequence recognition in synthetic macromolecules

The different triplet sequences in high molecular weight aromatic copolyimides comprising pyromellitimide units ("I") flanked by either ether-ketone ("K") or ether-sulfone residues ("S") show different binding strengths for pyrene-based tweezer-molecules. Such molecules bind primarily to the diimide unit through complementary π-π-stacking and hydrogen bonding. However, as shown by the magnitudes of 1H NMR complexation shifts and tweezer-polymer binding constants, the triplet "SIS" binds tweezer-molecules more strongly than "KIS" which in turn bind such molecules more strongly than "KIK". Computational models for tweezer-polymer binding, together with single-crystal X-ray analyses of tweezer-complexes with macrocyclic ether-imides, reveal that the variations in binding strength between the different triplet sequences arise from the different conformational preferences of aromatic rings at diarylketone and diarylsulfone linkages. These preferences determine whether or not chain-folding and secondary π−π-stacking occurs between the arms of the tweezermolecule and the 4,4'-biphenylene units which flank the central diimide residue

B-meson decay constants: a more complete picture from full lattice QCD

We extend the picture of $B$-meson decay constants obtained in lattice QCD beyond those of the $B$, $B_s$ and $B_c$ to give the first full lattice QCD results for the $B^*$, $B^*_s$ and $B^*_c$. We use improved NonRelativistic QCD for the valence $b$ quark and the Highly Improved Staggered Quark (HISQ) action for the lighter quarks on gluon field configurations that include the effect of $u/d$, $s$ and $c$ quarks in the sea with $u/d$ quark masses going down to physical values. For the ratio of vector to pseudoscalar decay constants, we find $f_{B^*}/f_B$ = 0.941(26), $f_{B^*_s}/f_{B_s}$ = 0.953(23) (both $2\sigma$ less than 1.0) and $f_{B^*_c}/f_{B_c}$ = 0.988(27). Taking correlated uncertainties into account we see clear indications that the ratio increases as the mass of the lighter quark increases. We compare our results to those using the HISQ formalism for all quarks and find good agreement both on decay constant values when the heaviest quark is a $b$ and on the dependence on the mass of the heaviest quark in the region of the $b$. Finally, we give an overview plot of decay constants for gold-plated mesons, the most complete picture of these hadronic parameters to date.Comment: 20 pages, 9 figures. Minor updates to the discussion in several places and some additional reference

Combination treatment with ionising radiation and gefitinib ('Iressa', ZD1839), an epidermal growth factor receptor (EGFR) inhibitor, significantly inhibits bladder cancer cell growth in vitro and in vivo

Purpose: External beam radiotherapy (EBRT) is the principal bladder-preserving monotherapy for muscle-invasive bladder cancer. Seventy percent of muscle-invasive bladder cancers express epidermal growth factor receptor (EGFR), which is associated with poor prognosis. Ionising radiation (IR) stimulates EGFR causing activation of cytoprotective signalling cascades and thus may be an underlying cause of radioresistance in bladder tumours. Materials and methods: We assessed the ability of IR to activate EGFR in bladder cancer cells and the effect of the anti-EGFR therapy, gefitinib on potential radiation-induced activation. Subsequently we assessed the effect of IR on signalling pathways downstream of EGFR. Finally we assessed the activity of gefitinib as a monotherapy, and in combination with IR, using clonogenic assay in vitro, and a murine model in vivo. Results: IR activated EGFR and gefitinib partially inhibited this activation. Radiation-induced activation of EGFR activated the MAPK and Akt pathways. Gefitinib partially inhibited activation of the MAPK pathway but not the Akt pathway. Treatment with combined gefitinib and IR significantly inhibited bladder cancer cell colony formation more than treatment with gefitinib alone (p = 0.001-0.03). J82 xenograft tumours treated with combined gefitinib and IR showed significantly greater growth inhibition than tumours treated with IR alone (p = 0.04). Conclusions: Combining gefitinib and IR results in significantly greater inhibition of invasive bladder cancer cell colony formation in vitro and significantly greater tumour growth inhibition in vivo. Given the high frequency of EGFR expression by bladder tumours and the low toxicity of gefitinib there is justification to translate this work into a clinical trial.Peer-reviewedPublisher Version1721

Effects of a pre-workout energy drink supplement on upper body muscular endurance performance

International Journal of Exercise Science 9(5): 667-676, 2016. The use of pre-workout beverages is becoming an increasingly common method of improving performance during exercise in athletic and recreationally active populations. Therefore, the purpose of this study was to investigate the effects of a commercially available energy drink on exercise performance. Thirty-one healthy males (n=23) and females (n=8) participated in this study and were separated into two groups: supplement (SU; n=16) or placebo (PL; n=15). Subjects visited the laboratory on 2 occasions separated by no more than 7 days. The first visit consisted of completing a push up to fatigue protocol (PUFP) without ingesting the pre-workout energy drink supplement (PWEDS). The second visit consisted of ingesting either a placebo or the PWEDS 30 minutes prior to completing the PUFP. Rate of perceived exertion (RPE) was recorded following each set of push-ups on both testing days. Also, participant’s height, weight, and body composition were collected. There was no significant differences at baseline in any variable between groups (p = \u3e.05). After the second testing session, both groups significantly improved total push-ups (PL Pre: 133.3 ±39.4, PL Post: 155.3 ± 54.1; SU Pre: 139.3 ± 58.5, SU Post: 161.3 ± 79.4; p=\u3c.001), and push-ups completed in each of the 3 sets (p=\u3c.001), when compared to baseline. Post-testing revealed no significant difference between groups in total push-ups completed or RPE at any time point, when compared to baseline. In conclusion, the commercially available PWEDS offered no additional ergogenic effects when compared to the placebo

Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s

The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride

Exploring Constructions of Commitment for Women in Mid and Later Life Aged 50 to 65

This thesis explores the way women in mid and later life understand commitment to men in heterosexual relationships. Commitment in relationships is central to human experience but is greatly under-theorised in sociological literature. This lack of knowledge is even more pronounced in relation to women in mid and later life. To date there is no empirical research which specifically addresses this area of study and generational cohorts. Over the last 40 years the Office for National Statistics has recorded a steady increase in divorce, separation and the numbers of women living alone. This research is made more significant given the size of baby boomer and generation X cohorts. The overarching aim of this research is to explore how women in mid and later life understand commitment to men. I specifically explore the ways duty, obligation and personal choice impact women’s perceptions of commitment. I also consider the way women’s situatedness in time influences their perceptions of commitment. Situating myself as a baby boomer feminist I selected snowballing as the method of recruitment. The chosen methodology for the study was a combination of secondary-source research and semi-structured interviews of fourteen women. I found that commitment for women is undergoing a steady transformation, informed by what I argue is the gendered nature of commitment. Women in the study reached what I have termed ‘a pivotal moment’. This represents a time in the relationship where women participants made the decision that something must change for the relationship to continue. The pivotal moment can be aligned with a form of raised consciousness, where participants were able to recognise inequality and oppression within their relationship. Once reached, the pivotal moment leads onto a new form of commitment which I term ‘curated’, where women are more able to prioritise their own needs

Diffusive hidden Markov model characterization of DNA looping dynamics in tethered particle experiments

In many biochemical processes, proteins bound to DNA at distant sites are brought into close proximity by loops in the underlying DNA. For example, the function of some gene-regulatory proteins depends on such DNA looping interactions. We present a new technique for characterizing the kinetics of loop formation in vitro, as observed using the tethered particle method, and apply it to experimental data on looping induced by lambda repressor. Our method uses a modified (diffusive) hidden Markov analysis that directly incorporates the Brownian motion of the observed tethered bead. We compare looping lifetimes found with our method (which we find are consistent over a range of sampling frequencies) to those obtained via the traditional threshold-crossing analysis (which can vary depending on how the raw data are filtered in the time domain). Our method does not involve any time filtering and can detect sudden changes in looping behavior. For example, we show how our method can identify transitions between long-lived, kinetically distinct states that would otherwise be difficult to discern

Practice Feedback Interventions: 15 Suggestions for Optimizing Effectiveness

Electronic practice data are increasingly being used to provide feedback to encourage practice improvement. However, evidence suggests that despite decades of experience, the effects of such interventions vary greatly and are not improving over time. Guidance on providing more effective feedback does exist, but it is distributed across a wide range of disciplines and theoretical perspectives. Through expert interviews; systematic reviews; and experience with providing, evaluating, and receiving practice feedback, 15 suggestions that are believed to be associated with effective feedback interventions have been identified. These suggestions are intended to provide practical guidance to quality improvement professionals, information technology developers, educators, administrators, and practitioners who receive such interventions. Designing interventions with these suggestions in mind should improve their effect, and studying the mechanisms underlying these suggestions will advance a stagnant literature