Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold.

Supramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga4L612- on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies

Improved Eye Tracking with Hardware-generated Multi-Polarized Images

Eye tracking is performed in augmented reality, virtual reality, or extended reality (AR/VR/XR) applications to determine the gaze direction of the user. However, eye tracking based on a captured image of the eye can be inaccurate when the image contains saturated pixels due to high reflection from the user’s eye. This disclosure describes techniques to generate multi-polarized images (images with different polarization angles) simultaneously. A metalens is provided in the imaging apparatus to generate multiple images with different polarization. The images are partitioned on the same sensor. The image that is relatively free of saturation can be used to perform eye tracking, thus improving eye tracking accuracy

Comparing statistical methods in assessing the prognostic effect of biomarker variability on time-to-event clinical outcomes

BACKGROUND: In recent years there is increasing interest in modeling the effect of early longitudinal biomarker data on future time-to-event or other outcomes. Sometimes investigators are also interested in knowing whether the variability of biomarkers is independently predictive of clinical outcomes. This question in most applications is addressed via a two-stage approach where summary statistics such as variance are calculated in the first stage and then used in models as covariates to predict clinical outcome in the second stage. The objective of this study is to compare the relative performance of various methods in estimating the effect of biomarker variability. METHODS: A joint model and 4 different two-stage approaches (naïve, landmark analysis, time-dependent Cox model, and regression calibration) were illustrated using data from a large multi-center randomized phase III trial, the Ocular Hypertension Treatment Study (OHTS), regarding the association between the variability of intraocular pressure (IOP) and the development of primary open-angle glaucoma (POAG). The model performance was also evaluated in terms of bias using simulated data from the joint model of longitudinal IOP and time to POAG. The parameters for simulation were chosen after OHTS data, and the association between longitudinal and survival data was introduced via underlying, unobserved, and error-free parameters including subject-specific variance. RESULTS: In the OHTS data, joint modeling and two-stage methods reached consistent conclusion that IOP variability showed no significant association with the risk of POAG. In the simulated data with no association between IOP variability and time-to-POAG, all the two-stage methods (except the naïve approach) provided a reliable estimation. When a moderate effect of IOP variability on POAG was imposed, all the two-stage methods underestimated the true association as compared with the joint modeling while the model-based two-stage method (regression calibration) resulted in the least bias. CONCLUSION: Regression calibration and joint modelling are the preferred methods in assessing the effect of biomarker variability. Two-stage methods with sample-based measures should be used with caution unless there exists a relatively long series of longitudinal measurements and/or strong effect size (NCT00000125)

Evidence of Spin-Filtering in Quantum Constrictions with Spin-Orbit Interaction

A new type of blockade effect - spin-orbit blockade (SOB) - is found in the conduction of a quantum dot (QD) made of a material with spin-orbit interaction. The blockade arises from spin-filtering effect in a quantum point contact (QPC), which is a component of the QD. Hence the appearance of the blockade itself evidences the spin-filtering effect in the QPC. The lower bound of filtering efficiency is estimated to be above 80%.Comment: 4 pages, 4 figure

Time Asymmetric Quantum Mechanics and Shock Waves: Exploring the Irreversibility in Nonlinear Optics

The description of irreversible phenomena is a still debated topic in quantum mechanics. Still nowadays, there is no clear procedure to distinguish the coupling with external baths from the intrinsic irreversibility in isolated systems. In 1928 Gamow introduced states with exponentially decaying observables not belonging to the conventional Hilbert space. These states are named Gamow vectors, and they belong to rigged Hilbert spaces. This review summarizes the contemporary approach using Gamow vectors and rigged Hilbert space formalism as foundations of a generalized “time asymmetric” quantum mechanics. We study the irreversible propagation of specific wave packets and show that the topic is surprisingly related to the problem of irreversibility of shock waves in classical nonlinear evolution. We specifically consider the applications in the field of nonlinear optics. We show that it is possible to emulate irreversible quantum mechanical process by the nonlinear evolution of a laser beam and we provide experimental tests by the generation of dispersive shock waves in highly nonlocal regimes. We demonstrate experimentally the quantization of decay rates predicted by the time-asymmetric quantum mechanics. This work furnishes support to the idea of intrinsically irreversible wave propagation, and to novel tests of the foundations of quantum mechanics

Expression of the IL-11 Gene in Metastatic Cells Is Supported by Runx2-Smad and Runx2-cJun Complexes Induced by TGFβ1.

In tumor cells, two factors are abnormally increased that contribute to metastatic bone disease: Runx2, a transcription factor that promotes expression of metastasis related and osteolytic genes; and IL-11, a secreted osteolytic cytokine. Here, we addressed a compelling question: Does Runx2 regulate IL-11 gene expression? We find a positive correlation between Runx2, IL-11 and TGFβ1, a driver of the vicious cycle of metastatic bone disease, in prostate cancer (PC) cell lines representing early (LNCaP) and late (PC3) stage disease. Further, like Runx2 knockdown, IL-11 knockdown significantly reduced expression of several osteolytic factors. Modulation of Runx2 expression results in corresponding changes in IL-11 expression. The IL-11 gene has Runx2, AP-1 sites and Smad binding elements located on the IL-11 promoter. Here, we demonstrated that Runx2-c-Jun as well as Runx2-Smad complexes upregulate IL-11 expression. Functional studies identified a significant loss of IL-11 expression in PC3 cells in the presence of the Runx2-HTY mutant protein, a mutation that disrupts Runx2-Smad signaling. In response to TGFβ1 and in the presence of Runx2, we observed a 30-fold induction of IL-11 expression, accompanied by increased c-Jun binding to the IL-11 promoter. Immunoprecipitation and in situ co-localization studies demonstrated that Runx2 and c-Jun form nuclear complexes in PC3 cells. Thus, TGFβ1 signaling induces two independent transcriptional pathways - AP-1 and Runx2. These transcriptional activators converge on IL-11 as a result of Runx2-Smad and Runx2-c-Jun interactions to amplify IL-11 gene expression that, together with Runx2, supports the osteolytic pathology of cancer induced bone disease