An All-Photonic Molecular Amplifier and Binary Flip-flop

A chemical system is proposed that is capable of amplifying small optical inputs into large changes in internal composition, based on a feedback interaction between switchable fluorescence and visible-light photoswitching. This system would demonstrate bifurcating reaction kinetics under irradiation and reach one of two stable photostationary states depending on the initial composition of the system. This behavior would allow the system to act as a chemical realization of the flip-flop circuit, the fundamental element in sequential logic and binary memory storage. We use detailed numerical modeling to demonstrate the feasibility of the proposed behavior based on known molecular phenomena and comment on some of the conditions required to realize this system

Electromechanical Response of Polycrystalline Barium Titanate Resolved at the Grain Scale

Ferroic materials are critical components in many modern devices. Polycrystalline states of these materials dominate the market due to their cost effectiveness and ease of production. Studying the coupling of ferroic properties across grain boundaries and within clusters of grains is therefore critical for understanding bulk polycrystalline ferroic behavior. Here, three-dimensional X-ray diffraction is used to reconstruct a 3D grain map (grain orientations and neighborhoods) of a polycrystalline barium titanate sample and track the grain-scale non-180° ferroelectric domain switching strains of 139 individual grains in situ under an applied electric field. The map shows that each grain is located in a very unique local environment in terms of intergranular misorientations, leading to local strain heterogeneity in the as-processed state of the sample. While primarily dependent on the crystallographic orientation relative to the field directions, the response of individual grains is also heterogeneous. These unique experimental results are of critical importance both when building the starting conditions and considering the validity of grain-scale modeling efforts, and provide additional considerations in the design of novel ferroic materials

Large, Tunable, and Reversible pH Changes by Merocyanine Photoacids

Molecular photoswitches capable of generating precise pH changes will allow pH-dependent processes to be controlled remotely and noninvasively with light. We introduce a series of new merocyanine photoswitches, which deliver reversible bulk pH changes up to 3.2 pH units (pH 6.5 to pH 3.3) upon irradiation with 450 nm light, displaying tunable and predictable timescales for thermal recovery. We present models to show that the key parameters for optimizing the bulk pH changes are measurable: the solubility of the photoswitch, the acidity of the merocyanine form, the thermal equilibrium position between the spiropyran and the merocyanine isomers, and the increased acidity under visible light irradiation. Using ultrafast transient absorption spectroscopy, we determined the quantum yields for the ring-closing reaction and found that the lifetimes of the transient cis-merocyanine isomers ranged from 30 to 550 ns. Quantum yields did not appear to be a limitation for bulk pH switching. The models we present use experimentally determined parameters and are, in principle, able to predict the change in pH obtained for any related merocyanine photoacid

Towards segmentation and spatial alignment of the human embryonic brain using deep learning for atlas-based registration

We propose an unsupervised deep learning method for atlas based registration to achieve segmentation and spatial alignment of the embryonic brain in a single framework. Our approach consists of two sequential networks with a specifically designed loss function to address the challenges in 3D first trimester ultrasound. The first part learns the affine transformation and the second part learns the voxelwise nonrigid deformation between the target image and the atlas. We trained this network end-to-end and validated it against a ground truth on synthetic datasets designed to resemble the challenges present in 3D first trimester ultrasound. The method was tested on a dataset of human embryonic ultrasound volumes acquired at 9 weeks gestational age, which showed alignment of the brain in some cases and gave insight in open challenges for the proposed method. We conclude that our method is a promising approach towards fully automated spatial alignment and segmentation of embryonic brains in 3D ultrasound

The Geography of Sexual Orientation: Structural Stigma and Sexual Attraction, Behavior, and Identity Among Men Who Have Sex with Men Across 38 European Countries.

: While the prevalence of sexual identities and behaviors of men who have sex with men (MSM) varies across countries, no study has examined country-level structural stigma toward sexual minorities as a correlate of this variation. Drawing on emerging support for the context-dependent nature of MSM's open sexual self-identification cross-nationally, we examined country-level structural stigma as a key correlate of the geographic variation in MSM's sexual attraction, behavior, and identity, and concordance across these factors. Data come from the European MSM Internet Survey, a multi-national dataset containing a multi-component assessment of sexual orientation administered across 38 European countries (N = 174,209). Country-level stigma was assessed using a combination of national laws and policies affecting sexual minorities and a measure of attitudes toward sexual minorities held by the citizens of each country. Results demonstrate that in more stigmatizing countries, MSM were significantly more likely to report bisexual/heterosexual attractions, behaviors, and identities, and significantly less likely to report concordance across these factors, than in less stigmatizing countries. Settlement size moderated associations between country-level structural stigma and odds of bisexual/heterosexual attraction and behavior, such that MSM living in sparsely populated locales within high-structural stigma countries were the most likely to report bisexual or heterosexual behaviors and attractions. While previous research has demonstrated associations between structural stigma and adverse physical and mental health outcomes among sexual minorities, this study was the first to show that structural stigma was also a key correlate not only of sexual orientation identification, but also of MSM's sexual behavior and even attraction. Findings have implications for understanding the ontology of MSM's sexuality and suggest that a comprehensive picture of MSM's sexuality will come from attending to the local contexts surrounding this important segment of the global population.<br/

Theory of quasiequilibrium nonlinear optical absorption in semiconductor superlattices

Quasiequilibrium nonlinear optical absorption spectra are computed for semiconductor superlattices. The theory generalizes the semiconductor Bloch equations to describe anisotropic structures. The equation for the interband polarization is solved numerically and the carrier‐density dependent optical nonlinearities are computed. Starting from excitonic absorption, with increasing density exciton saturation and the development of gain is observed. The dependence of the gain spectra on structural parameters of the superlattice is discussed

Singlet Fission in Concentrated TIPS-Pentacene Solutions: The Role of Excimers and Aggregates

The excited-state dynamics of 6,13-bis(triisopropylsilylethynyl)pentacene is investigated to determine the role of excimer and aggregate formation in singlet fission in high-concentration solutions. Photoluminescence spectra were measured by excitation with the evanescent wave in total internal reflection, in order to avoid reabsorption effects. The spectra over nearly two magnitudes of concentration were nearly identical, with no evidence for excimer emission. Time-correlated single-photon counting measurements confirm that the fluorescence lifetime shortens with concentration. The observed rate constant grows at high concentrations, and this effect is modeled in terms of the hard-sphere radial distribution function. NMR measurements confirm that aggregation takes place with a binding constant of between 0.14 and 0.43 M-1. Transient absorption measurements are consistent with a diffusive encounter mechanism for singlet fission, with hints of more rapid singlet fission in aggregates at the highest concentration measured. These data show that excimers do not play the role of an emissive intermediate in exothermic singlet fission in solution and that, while aggregation occurs at higher concentrations, the mechanism of singlet fission remains dominated by diffusive encounters