Spiropyran Photoisomerization Dynamics in Multiresponsive Hydrogels

Light-responsive, spiropyran-functionalized hydrogels have been used to create reversibly photoactuated structures for applications ranging from microfluidics to nonlinear optics. Tailoring a spiropyran-functionalized hydrogel system for a particular application requires an understanding of how co-monomer composition affects the switching dynamics of the spiropyran chromophore. Such gels are frequently designed to be responsive to different stimuli such as light, temperature, and pH. The coupling of these influences can significantly alter spiropyran behavior in ways not currently well understood. To better understand the influence of responsive co-monomers on the spiropyran isomerization dynamics, we use UV-vis spectroscopy and time-dependent fluorescence intensity measurements to study spiropyran-modified hydrogels polymerized from four common hydrogel precursors of different pH and temperature responsivity: acrylamide, acrylic acid, N-isopropylacrylamide, and 2-(dimethylamino)ethyl methacrylate. In acidic and neutral gels, we observe unusual nonmonotonic, triexponential fluorescence dynamics under 405 nm irradiation that cannot be explicated by either the established spiropyran-merocyanine interconversion model or hydrolysis. To explain these results, we introduce an analytical model of spiropyran interconversions that includes H-aggregated merocyanine and its light-triggered disaggregation under 405 nm irradiation. This model provides an excellent fit to the observed fluorescence dynamics and elucidates exactly how creating an acidic internal gel environment promotes the fast and complete conversion of the hydrophilic merocyanine speciesto the hydrophobic spiropyran form, which is desired in most light-sensitive hydrogel actuators. This can be achieved by incorporating acrylic acid monomers and by minimizing the aggregate concentration. Beyond spiropyran-functionalized gel actuators, these conclusions are particularly critical for nonlinear optical computing applications

Survivorship care planning in gynecologic oncology perspectives from patients, caregivers, and health care providers

Purpose This qualitative study sought to describe the challenges following treatment and the preferences regarding survivorship care among patients treated for gynecological cancer, their caregivers, and health care providers. Methods Between July and August 2017, in-depth semi-structured interviews regarding survivorship were conducted at a large academic hospital in the USA among patients who recently completed treatment (< 12 months) for a gynecological cancer (ovarian, endometrial, cervical, and vulvar) and their primary caregivers. A focus group was conducted among health care providers (oncologists, nurses, and fellows). Main themes were identified using descriptive content analysis. Results A total of 30 individuals participated in this study (13 patients, 9 caregivers, 8 health care providers). Almost all participants reported a desire for more information on how to address survivorship needs, specifically as they related to side effects, follow-up schedule, and psychological assistance. Despite this uniformly identified need for more information, preferences for survivorship care planning differed across cancer types and individuals, with respect to content, timing, and mode of delivery. Health care providers expressed challenges in communicating with patients about survivorship, a desire to shift post-treatment conversations to the goal of improving quality of life as opposed to focusing on disease recurrence, and an unmet need for disease specific and individualized survivorship care planning. Conclusions Patients, caregivers, and health care providers each expressed a need for gynecologic cancer-tailored survivorship care resources

Longitudinal Course of Deficient Emotional Self-Regulation CBCL Profile in Youth with ADHD: Prospective Controlled Study

Background: While symptoms of deficient emotional self-regulation (DESR) have been long associated with attention-deficit/hyperactivity disorder (ADHD), there has been limited investigation of this aspect of the clinical picture of the disorder. The main aim of this study was to examine the predictive utility of DESR in moderating the course of ADHD children into adolescence. Methods: Subjects comprised 177 children with and 204 children without ADHD followed for an average of 4 years (aged 6–18 years at baseline, 54% male). Subjects were assessed with structured diagnostic interviews and measures of psychosocial functioning. DESR was defined by the presence (n = 79) or absence (n = 98) of Child Behavior Checklist (CBCL)-DESR profile (score ≥ 180 < 210 total of Attention, Aggression, and Anxious/Depressed subscales) at the baseline assessment. Results: Of subjects with DESR at baseline, 57% had DESR at follow-up. Persistent ADHD was significantly associated with DESR at follow-up (x$^{2}$$_{(1)}$ = 15.37, P < 0.001). At follow-up, ADHD + DESR subjects had significantly more comorbidities (z = 2.55, P = 0.01), a higher prevalence of oppositional defiant disorder (z = 3.01, P = 0.003), and more impaired CBCL social problems t-score (t$_{(227)}$ = 2.41, P = 0.02) versus ADHD subjects. Conclusion: This work suggests that a positive CBCL-DESR profile predicts subsequent psychopathology and functional impairments in children with ADHD suggesting that it has the potential to help identify children with ADHD at high risk for compromised outcomes

Energy Transfer and Trapping in Red-Chlorophyll-Free Photosystem I from Synechococcus WH 7803

We report for the first time steady-state and time-resolved emission properties of photosystem I (PSI) complexes isolated from the cyanobacterial strain Synechococcus WH 7803. The PSI complexes from this strain display an extremely small fluorescence emission yield at 77 K, which we attribute to the absence of so-called red antenna chlorophylls, chlorophylls with absorption maxima at wavelengths longer than those of the primary electron donor P700. Emission measurements at room temperature with picosecond time resolution resulted in two main decay components with lifetimes of about 7.5 and 18 ps and spectra peaking at about 685 nm. Especially in the red flanks, these spectra show consistent differences, which means that earlier proposed models for the primary charge separation reactions based on ultrafast (∼1 ps) excitation equilibration processes cannot describe the data. We show target analyses of a number of alternative models and conclude that a simple model (Ant2)* (Ant1/RC)* → RP2 can explain the time-resolved emission data very well. In this model, (Ant2)* represents chlorophylls that spectrally equilibrate in about 7.5 ps and in which RP2 represents the "final" radical pair P70

Coupling Modes and Stoichiometry of Cl−/HCO3− Exchange by slc26a3 and slc26a6

The SLC26 transporters are a family of mostly luminal Cl− and HCO3− transporters. The transport mechanism and the Cl−/HCO3− stoichiometry are not known for any member of the family. To address these questions, we simultaneously measured the HCO3− and Cl− fluxes and the current or membrane potential of slc26a3 and slc26a6 expressed in Xenopus laevis oocytes and the current of the transporters expressed in human embryonic kidney 293 cells. slc26a3 mediates a coupled 2Cl−/1HCO3− exchanger. The membrane potential modulated the apparent affinity for extracellular Cl− of Cl−/HCO3− exchange by slc26a3. Interestingly, the replacement of Cl− with NO3− or SCN− uncoupled the transport, with large NO3− and SCN− currents and low HCO3− transport. An apparent uncoupled current was also developed during the incubation of slc26a3-expressing oocytes in HCO3−-buffered Cl−-free media. These findings were used to develop a turnover cycle for Cl− and HCO3− transport by slc26a3. Cl− and HCO3− flux measurements revealed that slc26a6 mediates a 1Cl−/2HCO3− exchange. Accordingly, holding the membrane potential at 40 and −100 mV accelerated and inhibited, respectively, Cl−-mediated HCO3− influx, and holding the membrane potential at −100 mV increased HCO3−-mediated Cl− influx. These findings indicate that slc26a6 functions as a coupled 1Cl−/2HCO3− exchanger. The significance of isoform-specific Cl− and HCO3− transport stoichiometry by slc26a3 and slc26a6 is discussed in the context of diseases of epithelial Cl− absorption and HCO3− secretion

Topological wave functions and heat equations

It is generally known that the holomorphic anomaly equations in topological string theory reflect the quantum mechanical nature of the topological string partition function. We present two new results which make this assertion more precise: (i) we give a new, purely holomorphic version of the holomorphic anomaly equations, clarifying their relation to the heat equation satisfied by the Jacobi theta series; (ii) in cases where the moduli space is a Hermitian symmetric tube domain $G/K$, we show that the general solution of the anomaly equations is a matrix element \IP{\Psi | g | \Omega} of the Schr\"odinger-Weil representation of a Heisenberg extension of $G$, between an arbitrary state $\bra{\Psi}$ and a particular vacuum state $\ket{\Omega}$. Based on these results, we speculate on the existence of a one-parameter generalization of the usual topological amplitude, which in symmetric cases transforms in the smallest unitary representation of the duality group $G'$ in three dimensions, and on its relations to hypermultiplet couplings, nonabelian Donaldson-Thomas theory and black hole degeneracies.Comment: 50 pages; v2: small typos fixed, references added; v3: cosmetic changes, published version; v4: typos fixed, small clarification adde