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A new heteronuclear EuII–MnII complex with high photoluminescence quantum yield is designed and synthesized, which represents the first example of f → d molecular sensitization.

In this paper, we model the trajectory of the cumulative confirmed cases and deaths of COVID-19 (in log scale) via a piecewise linear trend model. The model naturally captures the phase transitions of the epidemic growth rate via change-points and further enjoys great interpretability due to its semiparametric nature. On the methodological front, we advance the nascent self-normalization (SN) technique (Shao, 2010) to testing and estimation of a single change-point in the linear trend of a nonstationary time series. We further combine the SN-based change-point test with the NOT algorithm (Baranowski et al., 2019) to achieve multiple change-point estimation. Using the proposed method, we analyze the trajectory of the cumulative COVID-19 cases and deaths for 30 major countries and discover interesting patterns with potentially relevant implications for effectiveness of the pandemic responses by different countries. Furthermore, based on the change-point detection algorithm and a flexible extrapolation function, we design a simple two-stage forecasting scheme for COVID-19 and demonstrate its promising performance in predicting cumulative deaths in the U.S.

We synthesized three efficient blue emitting Eu(ii) complexes with narrow full width at half maximums and fabricated the first deep blue OLEDs based on an Eu(ii) complex.

We propose a novel and unified framework for change-point estimation in multivariate time series. The proposed method is fully non-parametric, robust to temporal dependence and avoids the demanding consistent estimation of long-run variance. One salient and distinct feature of the proposed method is its versatility, where it allows change-point detection for a broad class of parameters (such as mean, variance, correlation and quantile) in a unified fashion. At the core of our method, we couple the self-normalisation- (SN) based tests with a novel nested local-window segmentation algorithm, which seems new in the growing literature of change-point analysis. Due to the presence of an inconsistent long-run variance estimator in the SN test, non-standard theoretical arguments are further developed to derive the consistency and convergence rate of the proposed SN-based change-point detection method. Extensive numerical experiments and relevant real data analysis are conducted to illustrate the effectiveness and broad applicability of our proposed method in comparison with state-of-the-art approaches in the literature.

Luminescent cerium(III) complexes based on the d-f transition have characteristics of broad emission spectra, tunable emission colors, and short excited state lifetimes, showing potential applications in display, lighting, and other fields. Thus it is important to construct luminescent Ce(III) complexes with high photoluminescence efficiency and good stability. In this work, five Ce(III) complexes with dihydrobis(pyrazolyl)borate or diphenylbis(pyrazolyl)borate ligands, where pyrazolyl stands for pyrazolyl, 3-methylpyrazolyl, or 3,5-dimethylpyrazolyl, were designed and synthesized, showing emission colors from deep blue to yellow with a maximum wavelength in the range of 390-560 nm, short excited state lifetimes of 30-80 ns, and photoluminescence quantum yields exceeding 75% in solid powder. By comparing these complexes, it is found that higher photoluminescence efficiency and better thermal/air stability could be achieved in the complexes with dihydrobis(pyrazolyl)borate ligands.

During tumor initiation and progression, the complicated role of immune cells in the tumor immune microenvironment remains a concern. Myeloid-derived suppressor cells (MDSCs) are a group of immune cells that originate from the bone marrow and have immunosuppressive potency in various diseases, including cancer. In recent years, the key role of cancer stemness has received increasing attention in cancer development and therapy. Several studies have demonstrated the important regulatory relationship between MDSCs and cancer stem cells (CSCs). However, there is still no clear understanding regarding the complex interacting regulation of tumor malignancy, and current research progress is limited. In this review, we summarize the complicated role of MDSCs in the modulation of cancer stemness, evaluate the mechanism of the relationship between CSCs and MDSCs, and discuss potential strategies for eradicating CSCs with respect to MDSCs.

Organic light-emitting diodes (OLEDs) have gained widespread commercial use, yet there is a continuous need to identify innovative emitters that offer higher efficiency and broader color gamut. To effectively screen out promising OLED molecules that are yet to be synthesized, we perform a representation learning aided high throughput virtual screening (HTVS) over millions of Ir(III) complexes, a prototypical type of phosphorescent OLED material, constructed via a random combination of 278 reported ligands. We successfully screen out a decent amount of promising candidates for both display and lighting purposes, which are worth further experimental investigation. The high efficiency and accuracy of our model are largely attributed to the pioneering attempt of using representation learning to organic luminescent molecules, which is initiated by a pre-training procedure with over 1.6 million 3D molecular structures and frontier orbital energies predicted via semi-empirical methods, followed by a fine-tune scheme via the quantum mechanical computed properties over around 1500 candidates. Such workflow enables an effective model construction process that is otherwise hindered by the scarcity of labeled data, and can be straightforwardly extended to the discovery of other novel materials.

We compute the value-at-risk of financial losses by fitting a generalized Pareto distribution to exceedances over a threshold. Following the common practice of setting the threshold as high sample quantiles, we show that, for both independent observations and time-series data, the asymptotic variance for the maximum likelihood estimation depends on the choice of threshold, unlike the existing study of using a divergent threshold. We also propose a random weighted bootstrap method for the interval estimation of VaR, with critical values computed by the empirical distribution of the absolute differences between the bootstrapped estimators and the maximum likelihood estimator. While our asymptotic results unify the inference with nondivergent and divergent thresholds, the finite sample studies via simulation and application to real data show that the derived confidence intervals well cover the true VaR in insurance and finance.

Quartz glass shows superior physicochemical properties and is used in modern high technology. Due to its hard and brittle characteristics, traditional polishing slurry mostly uses strong acid, strong alkali, and potent corrosive additives, which cause environmental pollution. Furthermore, the degree of damage reduces service performance of the parts due to the excessive corrosion. Therefore, a novel quartz glass green and efficient non-damaging chemical mechanical polishing slurry was developed, consisting of cerium oxide (CeO2), Lanthanum oxyfluoride (LaOF), potassium pyrophosphate (K4P2O7), sodium N-lauroyl sarcosinate (SNLS), and sodium polyacrylate (PAAS). Among them, LaOF abrasive showed hexahedral morphology, which increased the cutting sites and uniformed the load. The polishing slurry was maintained by two anionic dispersants, namely SNLS and PAAS, to maintain the suspension stability of the slurry, which makes the abrasive in the slurry have a more uniform particle size and a smoother sample surface after polishing. After the orthogonal test, a surface roughness (Sa) of 0.23 nm was obtained in the range of 50 × 50 μm2, which was lower than the current industry rating of 0.9 nm, and obtained a material removal rate (MRR) of 530.52 nm/min.

We consider a high-dimensional dynamic pricing problem under non-stationarity, where a firm sells products to $T$ sequentially arriving consumers that behave according to an unknown demand model with potential changes at unknown times. The demand model is assumed to be a high-dimensional generalized linear model (GLM), allowing for a feature vector in $\mathbb R^d$ that encodes products and consumer information. To achieve optimal revenue (i.e., least regret), the firm needs to learn and exploit the unknown GLMs while monitoring for potential change-points. To tackle such a problem, we first design a novel penalized likelihood-based online change-point detection algorithm for high-dimensional GLMs, which is the first algorithm in the change-point literature that achieves optimal minimax localization error rate for high-dimensional GLMs. A change-point detection assisted dynamic pricing (CPDP) policy is further proposed and achieves a near-optimal regret of order $O(s\sqrt{\Upsilon_T T}\log(Td))$, where $s$ is the sparsity level and $\Upsilon_T$ is the number of change-points. This regret is accompanied with a minimax lower bound, demonstrating the optimality of CPDP (up to logarithmic factors). In particular, the optimality with respect to $\Upsilon_T$ is seen for the first time in the dynamic pricing literature, and is achieved via a novel accelerated exploration mechanism. Extensive simulation experiments and a real data application on online lending illustrate the efficiency of the proposed policy and the importance and practical value of handling non-stationarity in dynamic pricing.

A new heteronuclear Eu

Organic light-emitting diodes (OLEDs) have had commercial success in displays and lighting. Compared to red and green OLEDs, blue OLEDs are still the bottleneck because the high-energy and long-lived triplet exciton in traditional blue OLEDs causes the short operational lifetime of the device. As a new type emitter, lanthanide complexes with a 5d-4f transition could have short excited-state lifetimes on the order of nanoseconds. To achieve a high-efficiency 5d-4f transition, we systematically tuned the steric and electronic effects of tripodal tris(pyrazolyl)borate ligands and drew a full picture of their Ce(III) complexes. Intriguingly, all of these complexes show bright blue emission with high photoluminescence quantum yields exceeding 95% and short decay lifetimes of 35-73 ns both in the solid powder and in dichloromethane solutions. Using the Ce(III) complex emitter, we show a blue OLED with a maximum external quantum efficiency of 14.1% and a maximum luminance of 33,160 cd m-2, and the specific electroluminescence mechanism of direct exciton formation on the Ce(III) ion with a near-unity exciton utilization efficiency is also confirmed. The discovered photoluminescence and electroluminescence property-structure relationships may shed new light on the rational design of highly efficient lanthanide-based blue emitters and their optoelectronic devices such as OLEDs.

By CFD-DEM simulations, the present work is aimed to investigate the transient gas-solid bubbling mechanisms along a whole bubble lifecycle in a 2D fluidized bed from a micro perspective. Systemic comparisons with CCD measurements confirm the validity of current simulations. Afterward, the manner of particle motion and its driving mechanisms at various stages are investigated. In order to do that, external forces are analyzed at an individual particle level, including the drag, pressure gradient force, and their resultant acceleration together with gravity. Many interesting findings have been achieved. For example, a switch in directions of drag and pressure gradient forces at the root of an initial bubble enables its detachment. And, regarding their contributions to the burst of a bubble, the drag force is several times of the pressure gradient forces. Present efforts help to offer a novel view of particle dynamics during the bubbling fluidization.

Electroluminescence of f-f transition lanthanide complex is a traditional topic for display over decades. Here we report highly efficient organic light-emitting diodes based on a new terbium(III) complex with novel ligand CPMIP (1-(4-cyanophenyl)-3-methyl-4-isobutyryl-pyrazoline-5-one). The high triplet energy level of CPMIP (3.0 eV) and inhibited quenching effects in the solid-state lead to a nearly 100% photoluminescent quantum efficiency of Tb(CPMIP)3. The best Tb(CPMIP)3 device exhibited maximum external quantum efficiency up to 19.7%, setting a new record of OLEDs based on f-f transition lanthanide complexes.

We propose a piecewise linear quantile trend model to analyse the trajectory of the COVID-19 daily new cases (i.e. the infection curve) simultaneously across multiple quantiles. The model is intuitive, interpretable and naturally captures the phase transitions of the epidemic growth rate via change-points. Unlike the mean trend model and least squares estimation, our quantile-based approach is robust to outliers, captures heteroscedasticity (commonly exhibited by COVID-19 infection curves) and automatically delivers both point and interval forecasts with minimal assumptions. Building on a self-normalized (SN) test statistic, this paper proposes a novel segmentation algorithm for multiple change-point estimation. Theoretical guarantees such as segmentation consistency are established under mild and verifiable assumptions. Using the proposed method, we analyse the COVID-19 infection curves in 35 major countries and discover patterns with potentially relevant implications for effectiveness of the pandemic responses by different countries. A simple change-adaptive two-stage forecasting scheme is further designed to generate short-term prediction of COVID-19 cumulative new cases and is shown to deliver accurate forecast valuable to public health decision-making.

Purpose To evaluate a new non-contact instrument (OA-2000) measuring the ocular biometry parameters of silicone oil (SO)-filled aphakia eyes, as compared with IOLMaster 700. Methods Forty SO-filled aphakia eyes of 40 patients were enrolled in this cross-sectional clinical trial. The axial length (AL), central corneal thickness (CCT), keratometry (Kf [flattest keratometry] and Ks [steep keratometry, 90° apart from Kf]), and axis of the Kf (Ax1) measured with OA-2000 were compared with those measured with IOLMaster 700. The agreements of the results between the two devices were evaluated by Bland-Altman analysis. The differences of measurement results were evaluated by paired t test, and the correlation was evaluated by the Pearson coefficient. Results The mean AL obtained with the OA-2000 was 23.57 ± 0.93mm (range: 21.50 to 25.68mm), and that obtained with the IOLMaster 700 was 23.69 ± 0.94mm (range: 21.85 to 25.86mm), resulting in a mean offset of 0.124 ± 0.125mm (p t test of the Kf, Ks and Ax1. The CCT obtained with the OA-2000 was 530.7 ± 30.9µm (range: 470 to 578µm), and that obtained with the IOLMaster 700 was 545.3 ± 33.9µm (range: 479 to 600µm). The average offset was 14.6 ± 7.5µm, p

The circadian clock confers daily rhythmicity to many crucial biological processes and behaviors and its disruption is closely associated with carcinogenesis in several types of cancer. Brain and muscle arnt-like protein 1 (BMAL1) is a core circadian rhythm component in mammals and its dysregulation has been shown to contribute to aberrant metabolism in human diseases. However, the biological functions of BMAL1, especially its involvement in aberrant lipid metabolism in hepatocellular carcinoma (HCC), remain elusive. In the present study, we found that BMAL1 was frequently down-regulated in HCC cells mainly due to the up-regulation of miR-494-3p. Down-regulation of BMAL1 was significantly associated with poor survival in HCC patients. BMAL1 down-regulation promoted HCC cell growth and metastasis both

Eight nonplanar terdentate cyclometalated Pt(II) complexes (Pt1–Pt8) have been designed and synthesized with the general formula [Pt(N∧C∧N)Cl], where N∧C∧N represents 1,3-bis(N-methyl-N′-(pyridin-2...

Luminescent EuII complexes with a characteristic 5d-4f transition have potential applications in many fields. However, their instability in ambient conditions impedes further exploration and application. Herein, we report two new EuII complexes, bis[hydrotris(3-trifluoromethylpyrazolyl)borate]europium(II) (Eu-1) and bis[hydrotris(3-methylpyrazolyl)borate]europium(II) (Eu-2). Intriguingly, the blue emissive Eu-1 showed high air stability arising from fluorine protection and close molecular packing, as maintaining a photoluminescence quantum yield (PLQY) of 91 % (initial 96 %) upon exposure to air over 2200 hours. While the orange emissive Eu-2 showed a maximum luminance of 30620 cd m-2 , and a maximum external quantum efficiency (EQE) of 6.5 %, corresponding to an exciton utilization efficiency around 100 % in organic light-emitting diodes (OLEDs). These results could inspire further research on stable and efficient EuII complexes and their application in OLEDs.

We propose a novel dynamic bivariate peak over threshold (PoT) model to study the time-varying behavior of joint tail risk in financial markets. The proposed framework provides simultaneous modelin...