Modulating the nonlinear absorption response of SnOx thin films via phase engineering.

Phase (composition) is known to play a key role in determining the electronic and optical properties of amorphous oxide semiconductors. In this work, modulating the ultrafast nonlinear optical (NLO) response of SnO2 and SnO thin films by tuning oxygen partial pressure during film sputtering is explored. Femtosecond Z-scan results demonstrate that intermediate phases have no profound impact on the two-photon absorption (TPA) response of SnO2 and SnO films. Interestingly, the magnitude of the effective nonlinear absorption coefficient (ßeff) of both intermediate SnO2-x and SnOx are enhanced after the change of Sn2+/Sn4+ composition ratio, as measured by picosecond Z-scan technique. Femtosecond degenerate pump-probe measurements show that intermediate phases accelerate the carrier trapping and improve the defect-related carrier absorption in SnOx (SnO-rich) film, while intermediate phase suppress the TPA response of SnO2-x (SnO2-rich) films, therefore carrier-induced absorption dominates the NLO behavior of SnO2-x film on picosecond regime. Our results indicate a simple and effective way to modulate the NLO response of transparent conductive oxide SnO2 and SnO.

Broadband optical nonlinearity and all-optical switching features in low-defect GaN.

GaN is a one of promising materials for nonlinear optical applications. In this work, the broadband nonlinear optical response and potential applications for all-optical switching (AOS) are evaluated in low-defect GaN. In the pump-probe experiments, the ultrafast optical switching times are consistent with pulse widths accompanied with relative weak free-carrier absorption response, and the modulation contrast can reach ∼60% by varying the polarization orientations between the pump and probe lights. In the visible region, the broadband two-photon absorption effect exhibits excellent values for the imaginary part of figure of merit (FOM), providing the possibility of AOS based on nonlinear absorption (magnitude). While in the near-infrared region and under the presence of three-photon absorption, not only the real part of FOM based on Kerr effect is evaluated, but also the maximum light intensity for the usage of AOS based on nonlinear refraction (phase) is determined. The broadband nonlinear optical and AOS features in low-defect GaN will be highly favorable for the applications in the field of integrated nonlinear photonics and photonic circuits.

Enhancement of Two-Photon Absorption in Boron-Dipyrromethene (BODIPY) Derivatives.

The linear and nonlinear optical properties of two BODIPY derivatives, 1,7-Diphenyl-3,5-bis(9,9-dimethyl-9H-fluoren-2-yl)-boron-diuoride-azadipyrromethene (ZL-61) and 1,7-Diphenyl-3,5-bis(4-(1,2,2-triphenylvinyl)phenyl)-boron-diuoride-azadipyrromethene (ZL-22), were comprehensively investigated based on experimental and theoretical studies. It was found that both compounds show a strong two-photon absorption response in the near-infrared regime, and the two-photon-absorption cross-section values of ZL-61 and ZL-22 were determined to be 8321 GM and 1864 GM at 800 nm, respectively. The improvement of the two-photon absorption cross section in ZL-61 was attributed to the enhancement of the donor group, which was confirmed by transient absorption measurements and DFT calculation. Our results indicate that these BODIPY derivatives are a promising candidate for optical limiting and two-photon imaging applications.

Visualizing the impact of chloride addition on the microscopic carrier dynamics of MAPbI3 thin films using femtosecond transient absorption microscopy.

The spatial heterogeneity of carrier dynamics in mixed halide perovskite CH3NH3PbI3-xClx thin films with a range of different chloride additions is mapped using femtosecond transient absorption microscopy (TAM). The comparison of TAM images of fibrous and granular polycrystalline CH3NH3PbI3-xClx films indicates that the impact of chloride addition on the local heterogeneity of carrier dynamics is highly dependent on the film preparation method and the resulting morphology. In addition to signals of pristine CH3NH3PbI3, CH3NH3PbI3-xClx films with a fibrous structure show long-lived excited state absorption (ESA) signals in localized, microscopic regions. The ESA signal exhibits transient absorption with a rise time of about 5 ps after the excitation pulse, indicating that these distinct micrograins have preferential carrier trapping properties. The chemical composition of these micrograins does not differ detectably from their surroundings. In contrast, in CH3NH3PbI3-xClx films with a granular structure, Cl addition does not seem to affect the charge carrier dynamics. These results provide insight into the localized effects of halide mixing and on the resulting photophysical properties of mixed halide perovskite materials on the micrometer length scale.

Optoelectronic Dichotomy of Mixed Halide CH3NH3Pb(Br1- xCl x)3 Single Crystals: Surface versus Bulk Photoluminescence.

In this work, the spatially dependent recombination kinetics of mixed-halide hybrid perovskite CH3NH3Pb(Br1- xCl x)3 (0 ≤ x ≤ 0.19) single crystals are investigated using time-resolved photoluminescence spectroscopy with one- and two-photon femtosecond laser excitation. The introduction of chloride by substituting a fraction of the bromide leads to a decreased lattice constant compared to pure bromide perovskite ( x = 0) and a higher concentration of surface defects. The measured kinetics under one-photon excitation (1PE) shows that increasing the chloride addition quenches the photoluminescence (PL) lifetimes, due to substitution-induced surface defects. In stark contrast, upon 2PE, the PL lifetimes measured deeper in the bulk become longer with increasing chloride addition, until the halide substitution reaches the critical concentration of ∼19%. At x = 19% Cl concentration, a significant reversal of this behavior is observed indicating a change in crystal structure beyond the continuous trends observed at lower percentages of halide substitution ( x ≤ 11%). The observed opposing trends, based on 1PE versus 2PE, highlight a dichotomy between extrinsic (surface) and intrinsic (bulk) effects of chloride substitution on the carrier dynamics in lead bromide perovskites. We discuss the physical relation between halide exchange and bulk carrier lifetimes in CH3NH3PbBr3 in terms of the Rashba effect. We propose that the latter is suppressed at the surface due to disorder in the alignment of the MA and that it increases in the bulk with Cl concentration because of the reduction in lattice parameters, which compresses the space available for the MA orientational degrees of freedom.

Stable 2D Bisthienoacenes: Synthesis, Crystal Packing, and Photophysical Properties.

Two novel 2D bisthienoacenes with annulated thiophene units at different positions were developed. Both 1,2- and 1,4-addition of the α,ß-unsaturated ketone moieties lead to the major formation of four-fold alkylsilylethynyl substituted 2D heteroacenes (namely BTT-4TIPS and BTP-4TIPS). The photophysical, electrochemical properties, crystal packing structures, and charge carrier transport performances were investigated in detail.

An analytical hierarchy process-based study on the factors affecting legislation on plastic bags in the USA.

Annually, a large number of used plastic shopping bags are released into the environment, posing significant threats to public health and wildlife. Owing to these concerns, many local, regional, and national governments around the world have passed legislation to ban or restrict the use of plastic shopping bags. However, in the USA there are only 18 states that have approved plastic bag bans/fees, and even within these states these regulations do not cover all cities or counties. There are many factors that could affect the development and implementation of these regulations. This article employs an analytical hierarchy process to analyse the factors that could impact the enactment of plastic bag regulations. Five impact factors are identified based on statistical data, that is, geographical location, interest of industry achievable, cost of living, level of economic development, and educational level of population. The weights of the five impact factors are determined and it is found that the possibility of banning or restricting plastic bags in general follows a certain pattern among all states.

Nonlinear optical properties tuning in meso-tetraphenylporphyrin derivatives substituted with donor/acceptor groups in picosecond and nanosecond regimes.

meso-Tetraphenylporphyrin (TPP) and its two substituted derivatives (meso-tetrakis(4-cyanophenyl)porphyrin [TPP(CN)4] and meso-tetrakis(4-methoxyphenyl)porphyrin [TPP(OMe)4]) were synthesized. Their nonlinear absorption and refraction properties were studied using the Z-scan technique in the picosecond (ps) and nanosecond (ns) regimes. The open aperture Z-scan results reveal that TPP and TPP(CN)4 display an identical reverse saturable absorption (RSA) character in the ps and ns regimes. While TPP(OMe)4 exhibits a transition from saturable absorption (SA) to RSA in the ps regime and a typical RSA character in the ns regime. The closed aperture Z-scan results show that TPP(CN)4 and TPP(OMe)4 have regular enhancement of the magnitude of nonlinear refraction as compared to their parent TPP in both the ps and ns regimes. In addition, the second-order molecular hyperpolarizabilities (γ) of these three porphyrins are calculated, and the γ values of TPP(CN)4 and TPP(OMe)4 are remarkable larger than that of TPP. The introduction of the electron-withdrawing group CN and the electron-donating group OMe into TPP has enhanced its nonlinear refraction and γ value, and tuned its nonlinear absorption (TPP(OMe)4), which could be useful for porphyrin-related applications based on the desired NLO properties.

Cooperative Active Learning-Based Dual Control for Exploration and Exploitation in Autonomous Search.

In this article, a multi-estimator based computationally efficient algorithm is developed for autonomous search in an unknown environment with an unknown source. Different from the existing approaches that require massive computational power to support nonlinear Bayesian estimation and complex decision-making process, an efficient cooperative active-learning-based dual control for exploration and exploitation (COAL-DCEE) is developed for source estimation and path planning. Multiple cooperative estimators are deployed for environment learning process, which is helpful to improving the search performance and robustness against noisy measurements. The number of estimators used in COAL-DCEE is much smaller than that of the particles required for Bayesian estimation in information-theoretic approaches. Consequently, the computational load is significantly reduced. As an important feature of this study, the convergence and performance of COAL-DCEE are established in relation to the characteristics of sensor noises and turbulence disturbances. Numerical and experimental studies have been carried out to verify the effectiveness of the proposed framework. Compared with the existing approaches, COAL-DCEE not only provides convergence guarantee but also yields comparable search performance using much less computational power.

Distributed Fixed-Time Control for Leader-Steered Rigid Shape Formation With Prescribed Performance.

Resorting to the principle of rigid body kinematics, a novel framework for a multirobot network is proposed to form and maintain an invariant rigid geometric shape. Unlike consensus-based formation, this approach can perform both translational and rotational movements of the formation geometry, ensuring that the entire formation motion remains consistent with the leader. To achieve the target formation shape and motion, a distributed control protocol for multiple Euler-Lagrange robotic vehicles subject to nonholonomic constraints is developed. The proposed protocol includes a novel prescribed performance control (PPC) algorithm that addresses the second-order dynamics of the robotic vehicles by employing a combination of nonsingular sliding manifold and adaptive law. Finally, the effectiveness of the proposed formation framework and control protocol is demonstrated through the numerical simulations and practical experiments with a team of four robotic vehicles.

A Predictive Model for Graft Failure in Femtosecond Laser-Assisted Penetrating Keratoplasty Among Chinese Patients: A 2-Year Study.

INTRODUCTION: Graft failure is a major challenge in femtosecond laser-assisted penetrating keratoplasty (Fs-PKP). This study focuses on the development and validation of a clinical predictive model aimed at identifying the risk of graft failure in individuals undergoing Fs-PKP in China, offering a tailored approach to improve surgical outcomes. METHODS: This retrospective cohort study at Nanjing First Hospital involved 238 patients and followed the TRIPOD statement. The cohort was divided into a training set (n = 166) and a validation set (n = 72) in a 7:3 ratio. It analyzed 23 predictor variables related to recipient, donor, and surgical factors, defining graft failure as "visually significant and irreversible corneal stromal edema, haze, or scarring." A comprehensive nomogram was created using univariate and multivariate Cox regression analyses and assessed by concordance index (C-index), time-dependent receiver operating characteristics (ROC) curve, calibration plots, and decision curve analysis (DCA). RESULTS: Five critical risk factors were identified: recipients' history of systemic autoimmune disorders, ocular trauma, prior penetrating keratoplasty (PKP) history, donors' diabetes history, and the endothelial cell density of the donor cornea. The nomogram showed a C-index of 0.72 (95% CI 0.65-0.79) in the training group and 0.66 (95% CI 0.55-0.76) in the validation group, indicating robust predictive accuracy. Time-dependent ROC curves, calibration plots, and DCA consistently validated the model's reliability, predictive power, and clinical utility across both training and validation cohorts. CONCLUSIONS: Our study developed and validated a model incorporating five key factors, enhancing preoperative prediction and management for Chinese patients with Fs-PKP graft failure.

Water storage capacity is inversely associated with xylem embolism resistance in tropical karst tree species.

Tropical karst habitats are characterized by limited and patchy soil, large rocky outcrops and porous substrates, resulting in high habitat heterogeneity and soil moisture fluctuations. Xylem hydraulic efficiency and safety can determine the drought adaptation and spatial distribution of woody plants growing in karst environments. In this study, we measured sapwood-specific hydraulic conductivity (Ks), vulnerability to embolism, wood density, saturated water content, and vessel and pit anatomical characteristics in the branch stems of 12 evergreen tree species in a tropical karst seasonal rainforest in southwestern China. We aimed to characterize the effects of structural characteristics on hydraulic efficiency and safety. Our results showed that there was no significant correlation between Ks and hydraulic safety across the tropical karst woody species. Ks was correlated with hydraulic vessel diameter (r = 0.80, P < 0.05) and vessel density (r = -0.60, P < 0.05), while the stem water potential at 50 and 88% loss of hydraulic conductivity (P50 and P88) were both significantly correlated with wood density (P < 0.05) and saturated water content (P = 0.052 and P < 0.05, respectively). High stem water storage capacity was associated with low cavitation resistance possibly because of its buffering the moisture fluctuations in karst environments. However, both Ks and P50/P88 were decoupled from the anatomical traits of pit and pit membranes. This may explain the lack of tradeoff between hydraulic safety and efficiency in tropical karst evergreen tree species. Our results suggest that diverse hydraulic trait combination may facilitate species coexistence in karst environments with high spatial heterogeneity.

Dicoumarin with dimethyl thiocarbamate in the fluorescent detecting for Au3+ in water and cells.

Gold ions have high activity and cytotoxicity completely different from elemental gold. It is necessary and critical to develop Au3+ detection tools that are easy to operate, intuitive, inexpensive, and non-destructive testing. Here, we propose a novel two-photon fluorescent probe named DA for detecting Au3+, which is a rare combination of dicoumarin with dimethylthiocarbamate for the first time. Based on the PET mechanism, DA turns-on the fluorescence to yellow-green after specifically binds to Au3+, and the reaction is completed within 5 min. The detection limit is as low as 27.60 nM. Simultaneously, DA achieved qualitative and quantitative detection of Au3+ in environmental water samples, and fluorescence imaging of Au3+ in biological cells.

Distributed Generalized Nash Equilibrium Seeking and Its Application to Femtocell Networks.

In this article, distributed algorithms are developed to search the generalized Nash equilibrium (NE) with global constraints. Relations between the variational inequality and the NE are investigated via the Karush-Kuhn-Tucker (KKT) optimal conditions, which provide the underlying principle for developing the distributed algorithms. Two time-varying consensus schemes are proposed for each agent to estimate the actions of others, by which a distributed framework is established. The algorithm with fixed-gains is designed with certain system knowledge, while the adaptive algorithm is proposed to address the problem when the system parameters are not available. The asymptotic convergence to the NE is established through the Lyapunov theory and the consensus theory. The power control problem in a femtocell network is formulated as a Nash game and is solved by the proposed algorithms. The simulation results are provided to verify the effectiveness of theoretical development.

Consensus-Based Cooperative Algorithms for Training Over Distributed Data Sets Using Stochastic Gradients.

In this article, distributed algorithms are proposed for training a group of neural networks with private data sets. Stochastic gradients are utilized in order to eliminate the requirement for true gradients. To obtain a universal model of the distributed neural networks trained using local data sets only, consensus tools are introduced to derive the model toward the optimum. Most of the existing works employ diminishing learning rates, which are often slow and impracticable for online learning, while constant learning rates are studied in some recent works, but the principle for choosing the rates is not well established. In this article, constant learning rates are adopted to empower the proposed algorithms with tracking ability. Under mild conditions, the convergence of the proposed algorithms is established by exploring the error dynamics of the connected agents, which provides an upper bound for selecting the constant learning rates. Performances of the proposed algorithms are analyzed with and without gradient noises, in the sense of mean square error (MSE). It is proved that the MSE converges with bounded errors determined by the gradient noises, and the MSE converges to zero if the gradient noises are absent. Simulation results are provided to validate the effectiveness of the proposed algorithms.

A ratiometric fluorescent probe based on two-isophorone fluorophore for detecting cysteine.

The key biological thiol, cysteine (Cys), which can participate in many physiological and pathological processes in the human body, has also been proved to have considerable effects on redox homeostasis and the regulation of cell activity in vivo. A large number of studies have shown that abnormal Cys concentration is inseparable from the occurrence of many diseases. Therefore, it is of considerable research value to develop a method to specifically detect Cys. In this study, a new ratiometric fluorescent probe of two-isophorone fluorophore, TIFC, was proposed to successfully detect intracellular Cys by ratiometric fluorescence signals and the results showed that TIFC has good selectivity and sensitivity. The results of biological imaging experiments also demonstrated that probe TIFC can exhibit a rapid ratiometric response to Cys in vivo and has low cytotoxicity, enabling high biocompatible fluorescence imaging in osteoblasts. Therefore, TIFC has the potential of rapid ratio-response to Cys for the preliminary diagnosis of related diseases.

Improved Ultrafast Carrier Relaxation and Charge Transfer Dynamics in CuI Films and Their Heterojunctions via Sn Doping.

CuI is one of the promising hole transport materials for perovskite solar cells. However, its tendency to form defects is currently limiting its use for device applications. Here, we report the successful improvement of CuI through Sn doping and the direct measurement of the carrier relaxation and interfacial charge-transfer processes in Sn-doped CuI films and their heterostructures. Femtosecond-transient absorption (fs-TA) measurements reveal that Sn doping effectively passivates the trap states within the bandgap of CuI. The I-V characteristics of heterostructures demonstrate drastic improvement in transport characteristics upon Sn doping. Fs-TA measurements further confirm that the CuSnI/ZnO heterojunction has a type-II configuration with ultrafast charge transfer (<280 fs). The charge transfer time of a CuI/ZnO heterostructure is ∼2.8 times slower than that of the CuSnI/ZnO heterostructure, indicating that Sn doping suppresses the interfacial states that retard the charge transfer. These results elucidate the effect of Sn doping on the performance of CuI-based heterostructures.

LINC01006 and miR-3199 Serve as Novel Markers of Poor Prognosis in Colon Cancer and Regulate Cell Proliferation, Migration and Invasion.

PURPOSE: Colon cancer is the most commonly diagnosed gastrointestinal cancer. This research intended to evaluate the prognostic values of LINC01006 and miR-3199 for colon cancer and their effects on cell physiology. PATIENTS AND METHODS: LINC01006 and miR-3199 expression levels were determined by RT-qPCR. Patients' 5-year cumulative survival rate was analyzed by Kaplan-Meier curves with the Log rank test. Chi-square test and multivariate Cox regression analysis were used to access the clinical significance. CCK-8 assay, transwell assay, and TUNEL assays were used to monitor the change of cell proliferation, invasion, migration, and apoptosis. RESULTS: The expression level of LINC01006 was increased while miR-3199 was decreased in colon tissues and cells compared to normal ones. This dysregulated expression was correlated with T stage (P = 0.002) and N stage (P = 0.009). High LINC01006 level (HR = 4.048, 95%: 1.502-10.911, P = 0.006) or low miR-3199 level (HR = 3.421, 95% CI: 1.254-9.330, P = 0.016) was outstanding for predicting poor prognosis in patients with colon cancer. Downregulation of LINC01006 reduced cell proliferation, invasion, and migration but induced cell apoptosis (P < 0.05). CONCLUSION: LINC01006 knockdown showed anti-proliferative, anti-metastatic, and apoptotic-induced effects on colon cancer cells. This study contributes to research on promising prognostic biomarkers of colon cancer and might give way to further investigation of alternative tumor targets.

D-π-A type conjugated indandione derivatives: ultrafast broadband nonlinear absorption responses and transient dynamics.

The ultrafast nonlinear optical response of two 1,3-indandione derivatives (INB3 and INT3) was systematically investigated by the femtosecond Z-scan and pump-probe technique at multiple visible and near infrared wavelengths. Both compounds show strong broadband nonlinear absorption (NLA) and different wavelength-dependent two-photon absorption (TPA) characteristics in the range of 650-1100 nm. The TPA cross section of trithiophene-based compound INT3 was found to be larger than that of triphenylamine-based compound INB3 in the red region (650-800 nm), which is attributed to its longer π-conjugated structure and better molecular planarity. Interestingly, the effective NLA of INB3 was found to be larger than INT3 in the NIR region (800-1100 nm), which is related to the excited state absorption (ESA) induced by TPA. The ultrafast dynamics of both compounds were investigated by femtosecond transient absorption spectroscopy, which revealed a broadband ESA including several relaxation processes. This work extends nonlinear optical research on indandione derivatives, and the results suggest that these derivatives are promising candidates for optical limiting applications.

Correction: D-π-A type conjugated indandione derivatives: ultrafast broadband nonlinear absorption responses and transient dynamics.

[This corrects the article DOI: 10.1039/D2RA00349J.].