A Comprehensive Evaluation of Dioxins and Furans Occurrence in River Sediments from a Secondary Steel Recycling Craft Village in Northern Vietnam.

This first study investigated the presence of dioxins and furans in river sediments around a craft village in Vietnam, focusing on Secondary Steel Recycling. Sediment samples were collected from various locations along the riverbed near the Da Hoi Secondary Steel Recycling village in Bac Ninh province. The analysis was conducted using a HRGC/HRMS-DFS device, detecting a total of 17 dioxin/furan isomers in all samples, with an average total concentration of 288.86 ng/kg d.w. The concentrations of dioxin/furan congeners showed minimal variation among sediment samples, ranging from 253.9 to 344.2 ng/kg d.w. The predominant compounds in the dioxin group were OCDD, while in the furan group, they were 1,2,3,4,6,7,8-HpCDF and OCDF. The chlorine content in the molecule appeared to be closely related to the concentration of dioxins and their percentage distribution. However, the levels of furan isomers did not vary significantly. The distribution of these compounds was not dependent on the flow direction, as they were mainly found in solid waste and are not water-soluble. Although the hepta and octa congeners had high concentrations, when converted to TEQ values, the tetra and penta groups (for dioxins) and the penta and hexa groups (for furans) contributed more to toxicity. Furthermore, the source of dioxins in sediments at Da Hoi does not only originate from steel recycling production activities but also from other combustion sites. The average total toxicity was 10.92 ng TEQ/kg d.w, ranging from 4.99 to 17.88 ng TEQ/kg d.w, which did not exceed the threshold specified in QCVN 43:2017/BTNMT, the National Technical Regulation on Sediment Quality. Nonetheless, these levels are still concerning. The presence of these toxic substances not only impacts aquatic organisms in the sampled water environment but also poses potential health risks to residents living nearby.

Assessing the Effects of Orbital Relaxation and the Coherent-State Transformation in Quantum Electrodynamics Density Functional and Coupled-Cluster Theories.

Cavity quantum electrodynamics (QED) generalizations of time-dependent (TD) density functional theory (DFT) and equation-of-motion (EOM) coupled-cluster (CC) theory are used to model small molecules strongly coupled to optical cavity modes. We consider two types of calculations. In the first approach (termed "relaxed"), we use a coherent-state-transformed Hamiltonian within the ground- and excited-state portions of the calculations, and cavity-induced orbital relaxation effects are included at the mean-field level. This procedure guarantees that the energy is origin-invariant in post-self-consistent-field calculations. In the second approach (termed "unrelaxed"), we ignore the coherent-state transformation and the associated orbital relaxation effects. In this case, ground-state unrelaxed QED-CC calculations pick up a modest origin dependence but otherwise reproduce relaxed QED-CC results within the coherent-state basis. On the other hand, a severe origin dependence manifests in ground-state unrelaxed QED mean-field energies. For excitation energies computed at experimentally realizable coupling strengths, relaxed and unrelaxed QED-EOM-CC results are similar, while significant differences emerge for unrelaxed and relaxed QED-TDDFT. First, QED-EOM-CC and relaxed QED-TDDFT both predict that electronic states that are not resonant with the cavity mode are nonetheless perturbed by the cavity. Unrelaxed QED-TDDFT, on the other hand, fails to capture this effect. Second, in the limit of large coupling strengths, relaxed QED-TDDFT tends to overestimate Rabi splittings, while unrelaxed QED-TDDFT underestimates them, given splittings from relaxed QED-EOM-CC as a reference, and relaxed QED-TDDFT generally does the better job of reproducing the QED-EOM-CC results.

Co-occurrence of phthalic acid esters (PAEs) and cyclic volatile methylsiloxanes (cVMSs) in fine particulate matter (PM0.5 and PM0.1) collected from an industrial area in Vietnam.

Distribution patterns of 10 phthalic acid diesters (PAEs) and four cyclic volatile methylsiloxanes (cVMSs) were investigated in fine particulate matter (PM0.1 and PM0.5) collected from Bac Ninh, an industrial province in Vietnam during September-October in 2021. Total concentrations of PAEs found in PM0.1 and PM0.5 were in the ranges of 1.76-372 (median: 34.0 ng/m3) and 2.23-895 ng/m3 (median: 15.4 ng/m3), respectively. Among PAEs, di-n-butyl phthalate (DBP) was the most abundant compound found in PM0.1, whereas, di-2-(ethyl)hexyl phthalate (DEHP) was measured at the highest concentration in PM0.5. Total concentrations of cVMSs measured in PM0.1 and PM0.5 were in the ranges of method quantification limit (MQL)-203 (median: 2.10 ng/m3) and MQL-537 ng/m3 (median: 0.389 ng/m3), respectively. Among cVMSs, decamethylcyclopentasiloxane (D5) was found at the highest concentration in both PM0.1 and PM0.5 fractions of particulate matter. The concentration ratios between PAEs and cVMSs in PM0.1/PM0.5 were greater than 1 (except di-n-octyl phthalate: DnOP), suggesting that these chemicals tend to sorb to PM0.1 more preferentially than PM0.5. Among sampling locations, high concentrations of PAEs and cVMSs were found at traffic intersections (Que Vo district) and a craft village (Tu Son city). Relatively stronger correlations existed between cVMSs pairs in PM0.1 and PM0.5 (correlation coefficient: 0.73-1) than those of PAEs (-0.83-0.90). The human exposure doses to PAEs and cVMSs through inhalation of particulate matter were estimated based on the measured concentrations in PM0.1 and PM0.5 fractions. The estimated exposure doses of PAEs and cVMSs for infants (7.1 ng/kg-bw/d and 2.5 ng/kg-bw/d) were higher than those for adults (2.6 ng/kg-bw/d and 0.9 ng/kg-bw/d).

Enhanced Diastereocontrol via Strong Light-Matter Interactions in an Optical Cavity.

The enantiopurification of racemic mixtures of chiral molecules is important for a range of applications. Recent work has shown that chiral group-directed photoisomerization is a promising approach to enantioenrich racemic mixtures of BINOL, but increased control of the diasteriomeric excess (de) is necessary for its broad utility. Here we develop a cavity quantum electrodynamics (QED) generalization of time-dependent density functional theory and demonstrate computationally that strong light-matter coupling can alter the de of the chiral group-directed photoisomerization of BINOL. The relative orientation of the cavity mode polarization and the molecules in the cavity dictates the nature of the cavity interactions, which either enhance the de of the (R)-BINOL diasteriomer (from 17% to ≈40%) or invert the favorability to the (S)-BINOL derivative (to ≈34% de). The latter outcome is particularly remarkable because it indicates that the preference in diasteriomer can be influenced via orientational control, without changing the chirality of the directing group. We demonstrate that the observed effect stems from cavity-induced changes to the Kohn-Sham orbitals of the ground state.

Distribution and ecological risk assessment of phthalic acid esters in surface sediments of three rivers in Northern Vietnam.

Pollution status and distribution characteristics of ten typical phthalic acid esters (PAEs) were investigated in 36 sediment samples collected from three rivers in Northern Vietnam from June to October 2020. The total concentrations of PAEs in sediment samples collected from the To Lich River (n = 9), the Nhue River (n = 12), and the Day River (n = 15) were in ranges of 11,000-125,000 ng/g-dwt (mean/median: 50,000/42,200 ng/g-dwt), 2140-89,900 ng/g-dwt (mean/median: 29,300/20,700 ng/g-dwt), and 1140-43,100 ng/g-dwt (mean/median: 13,800/10,400 ng/g-dwt), respectively. Among ten PAEs studied, di-(2-ethylhexyl) phthalate (DEHP) was found at the highest levels in all samples meanwhile dimethyl phthalate (DMP), diethyl phthalate (DEP), and dipropyl phthalate (DPP) were detected at low frequency and concentration. Significant correlations have existed between the median-chain (C4-C7) PAE pairs in sediment samples. Due to the high accumulation in the sediments, the median-chain PAEs had a higher ecological risk than the short-chain (C1-C3) PAEs. These contaminants may present a longstanding influence on organisms and ecosystems.

Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment.

The electron attachment variant of equation-of-motion coupled-cluster theory (EOM-EA-CC) is generalized to the case of strong light-matter coupling within the framework of cavity quantum electrodynamics (QED). The resulting EOM-EA-QED-CC formalism provides an ab initio, correlated, and non-perturbative description of cavity-induced effects in many-electron systems that complements other recently proposed cavity-QED-based extensions of CC theory. Importantly, this work demonstrates that QED generalizations of EOM-CC theory are useful frameworks for exploring particle-non-conserving sectors of Fock space, thereby establishing a path forward for the simultaneous description of both strong electron-electron and electron-photon correlation effects.

Transcriptional Stress Memory and Transgenerational Inheritance of Drought Tolerance in Plants.

Plants respond to drought stress by producing abscisic acid, a chemical messenger that regulates gene expression and thereby expedites various physiological and cellular processes including the stomatal operation to mitigate stress and promote tolerance. To trigger or suppress gene transcription under drought stress conditions, the surrounding chromatin architecture must be converted between a repressive and active state by epigenetic remodeling, which is achieved by the dynamic interplay among DNA methylation, histone modifications, loop formation, and non-coding RNA generation. Plants can memorize chromatin status under drought conditions to enable them to deal with recurrent stress. Furthermore, drought tolerance acquired during plant growth can be transmitted to the next generation. The epigenetically modified chromatin architectures of memory genes under stressful conditions can be transmitted to newly developed cells by mitotic cell division, and to germline cells of offspring by overcoming the restraints on meiosis. In mammalian cells, the acquired memory state is completely erased and reset during meiosis. The mechanism by which plant cells overcome this resetting during meiosis to transmit memory is unclear. In this article, we review recent findings on the mechanism underlying transcriptional stress memory and the transgenerational inheritance of drought tolerance in plants.

Multi-task learning neural networks for breath sound detection and classification in pervasive healthcare.

With the emergence of many grave Chronic obstructive pulmonary diseases (COPDs) and the COVID-19 pandemic, there is a need for timely detection of abnormal respiratory sounds, such as deep and heavy breaths. Although numerous efficient pervasive healthcare systems have been proposed for tracking patients, few studies have focused on these breaths. This paper presents a method that supports physicians in monitoring in-hospital and at-home patients by monitoring their breath. The proposed method is based on three deep neural networks in audio analysis: RNNoise for noise suppression, SincNet - Convolutional Neural Network, and Residual Bidirectional Long Short-Term Memory for breath sound analysis at edge devices and centralized servers, respectively. We also developed a pervasive system with two configurations: (i) an edge architecture for in-hospital patients; and (ii) a central architecture for at-home ones. Furthermore, a dataset, named BreathSet, was collected from 27 COPD patients being treated at three hospitals in Vietnam to verify our proposed method. The experimental results demonstrated that our system efficiently detected and classified breath sounds with F1-scores of 90% and 91% for the tiny model version on low-cost edge devices, and 90% and 95% for the full model version on central servers, respectively. The proposed system was successfully implemented at hospitals to help physicians in monitoring respiratory patients in real time.

Size-extensive seniority-zero energy functionals derived from configuration interaction with double excitations.

The doubly occupied configuration interaction (DOCI) approach can provide an accurate black-box description of nondynamic electron correlation at a computational cost that increases combinatorially with the system size. Remarkably, a pair coupled-cluster doubles (pCCD) approach (also known as the antisymmetrized product of one-reference orbital geminals) can reproduce DOCI energies with only a quadratic number of wave function parameters, and, when neglecting the cost associated with any two-electron integral transformations, these parameters can be determined at a cubic computational cost. Other simpler seniority-zero approaches derived from size-extensive modified configuration interaction doubles functionals can also provide approximations to DOCI energies at similar computational costs. We develop seniority-zero formulations of the coupled-electron pair approximation, the averaged coupled-pair functional, averaged quadratic coupled-cluster, and the parametric two-electron reduced density matrix (p2RDM) approach. These methods are Hermitian and thus offer several potential advantages over pCCD theory, including a reduction in the number of variable parameters and simplified definitions of reduced density matrices. Of the methods investigated, only the pair p2RDM (pp2RDM) approach yields energies that are comparable in quality to pCCD and DOCI. For the molecular systems investigated, pp2RDM-derived RDMs are found to be better approximations to DOCI ones than those obtained from pCCD.

An adiabatic connection for doubly-occupied configuration interaction wave functions.

An adiabatic connection (AC) is developed as an electron correlation correction for doubly occupied configuration interaction (DOCI) wave functions. Following the work of Pernal [Phys. Rev. Lett. 120, 013001 (2018)], the working equations of the approach, termed AC-DOCI, are rooted in the extended random phase approximation (ERPA) and require knowledge of only the ground-state two-electron reduced density matrix (2RDM) from the DOCI. As such, the AC is naturally suited to modeling electron correlation in variational 2RDM (v2RDM)-based approximations to the DOCI. The v2RDM-driven AC-DOCI is applied to the dissociation of molecular nitrogen and the double dissociation of water; the approach yields energies that are similar in quality to those from second-order multireference perturbation theory near equilibrium, but the quality of the AC-DOCI energy degrades at stretched geometries. The exact adiabatic connection path suggests the assumption that the one-electron reduced-density matrix is constant along the AC path is invalid at stretched geometries, but this deficiency alone cannot explain the observed behavior. Rather, it appears that the ERPA's single-particle-transition ansatz cannot, in general, provide good approximations to the 2RDM along the AC path. The AC-DOCI is also applied to a set of 45 reaction energies; for these systems, the approach has an average accuracy that is comparable to that of single-reference second-order many-body perturbation theory.

Robust Organocatalysts for the Cleavage of Vegetable Oil Derivatives to Aldehydes through Retrobenzoin Condensation.

A series of thiazolium salts was prepared and tested for the cleavage of the α-hydroxyketone derived from methyl oleate. The robustness of these precatalysts was determined by dynamic thermogravimetric analyses (TGA). It has been shown that the stability of these species is mainly governed by the nature of the counter-anion and some of them were found to be stable until 350-400 °C. The α-hydroxyketone derived from methyl oleate was cleaved under reactive distillation conditions using optimized, thermally robust N-butylthiazolium triflate to give the cleavage product, namely, nonanal and methyl azelaaldehydate, with 85 and 70 % yields. A range of α-hydroxyketones derived from several fatty acids was cleaved to give the corresponding bio-based aldehydes with up to 98 % isolated yields. Finally, this protocol was successfully applied to a high-oleic sunflower oil derivative.

An Automated Mouse Tail Vascular Access System by Vision and Pressure Feedback.

This paper develops an automated vascular access system (A-VAS) with novel vision-based vein and needle detection methods and real-time pressure feedback for murine drug delivery. Mouse tail vein injection is a routine but critical step for preclinical imaging applications. Due to the small vein diameter and external disturbances such as tail hair, pigmentation, and scales, identifying vein location is difficult and manual injections usually result in poor repeatability. To improve the injection accuracy, consistency, safety, and processing time, A-VAS was developed to overcome difficulties in vein detection noise rejection, robustness in needle tracking, and visual servoing integration with the mechatronics system.

Exchange rate pass-through for European Union countries.

Exchange rate pass-through (ERPT) represents a degree to which changes in nominal exchange rates are transmitted into domestic prices. European Union (EU) countries have experienced the unprecedented inflationary pressure due to high geopolitical risk events. As such, understanding the ERPT plays a crucial role. This study provides a comprehensive and up-to-date analysis of ERPT to import prices for 16 EU countries from January 2006 to December 2022. Using the panel autoregressive distributed lag (ARDL) model, our findings confirm the linear, rather than nonlinear, ERPT pattern characterized by a diminishing trend over time in the EU countries. However, the degree of pass-through varies depending on country characteristics. Specifically, countries that are highly dependent on imports experience a larger ERPT. Furthermore, the degree of pass-through to import prices is more significant and persistent during periods of high uncertainty. These findings are robust across various robust analyses including sub periods. Our findings provide that help policymakers evaluate the trade-offs between exchange rate risks and macroeconomic stability during times of high uncertainty.

Computational Insights into Prostaglandin E2 Ligand Binding and Activation of G-Protein-Coupled Receptors.

G-protein coupled receptors (GPCRs) are eukaryotic integral membrane proteins that regulate signal transduction cascade pathways implicated in a variety of human diseases and are consequently of interest as drug targets. For this reason, it is of interest to investigate the way in which specific ligands bind and trigger conformational changes in the receptor during activation and how this in turn modulates intracellular signaling. In the present study, we investigate the way in which the ligand Prostaglandin E2 interacts with three GPCRs in the E-prostanoid family: EP1, EP2, and EP3. We examine information transfer pathways based on long-time scale molecular dynamics simulations using transfer entropy and betweenness centrality to measure the physical transfer of information among residues in the system. We monitor specific residues involved in binding to the ligand and investigate how the information transfer behavior of these residues changes upon ligand binding. Our results provide key insights that enable a deeper understanding of EP activation and signal transduction functioning pathways at the molecular level, as well as enabling us to make some predictions about the activation pathway for the EP1 receptor, for which little structural information is currently available. Our results should advance ongoing efforts in the development of potential therapeutics targeting these receptors.

Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory.

Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment of molecular polaritons requires the treatment of matter and photon degrees of freedom on equal quantum mechanical footing. In the limit of molecular electronic strong or ultrastrong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of ab initio quantum chemistry, yielding an approach we refer to as ab initio cavity quantum electrodynamics, where the photon degrees of freedom are treated at the level of cavity quantum electrodynamics. Here, we present an approach called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory to provide ground- and excited-state polaritonic surfaces with a balanced description of strong correlation effects among electronic and photonic degrees of freedom. This method provides a platform for ab initio cavity quantum electrodynamics when both strong electron correlation and strong light-matter coupling are important and is an important step toward computational approaches that yield multiple polaritonic potential energy surfaces and couplings that can be leveraged for ab initio molecular dynamics simulations of polariton chemistry.

From foreign direct investment to environmental regulations: Does a feedback effect ever exist?

This study revisits the feedback effect from foreign direct investments (FDI) on environmental regulations under the presence of the host country's political structure. Such a relationship may encounter the endogeneity problem due to the omitted variable bias and reverse causality. As such, the two-step system generalized method of moments is employed. Using data from 21 OECD countries from 1990 to 2019, we confirm that FDI flows influence environmental regulations, but such an effect is conditional on the host country's political constraints. Specifically, FDI increases (decreases) the stringency of environmental regulations if domestic political constraints are sufficiently high (low). Understanding the mechanisms of how FDI flows can affect environmental regulations allows countries to revise their policies to attract more FDI flows to support economic growth while simultaneously minimising their negative effects on the environment.

Dopant-Induced Charge Redistribution on the 3D Sponge-like Hierarchical Structure of Quaternary Metal Phosphides Nanosheet Arrays Derived from Metal-Organic Frameworks for Natural Seawater Splitting.

Dopant-induced electron redistribution on transition metal-based materials has long been considered an emerging new electrocatalyst that is expected to replace noble-metal-based electrocatalysts in natural seawater electrolysis; however, their practical applications remain extremely daunting due to their sluggish kinetics in natural seawater. In this work, we developed a facile strategy to synthesize the 3D sponge-like hierarchical structure of Ru-doped NiCoFeP nanosheet arrays derived from metal-organic frameworks with remarkable hydrogen evolution reaction (HER) performance in natural seawater. Based on experimental results and density functional theory calculations, Ru-doping-induced charge redistribution on the surface of metal active sites has been found, which can significantly enhance the HER activity. As a result, the 3D sponge-like hierarchical structure of Ru-NiCoFeP nanosheet arrays achieves low overpotentials of 52, 149, and 216 mV at 10, 100, and 500 mA cm-2 in freshwater alkaline, respectively. Notably, the electrocatalytic activity of the Ru-NiCoFeP electrocatalyst in simulated alkaline seawater and natural alkaline seawater is nearly the same as that in freshwater alkaline. This electrocatalyst exhibits superior catalytic properties with outstanding stability under a high current density of 85 mA cm-2 for more than 100 h in natural seawater, which outperforms state-of-the-art 20% Pt/C at high current density. Our work provides valuable guidelines for developing a low-cost and high-efficiency electrocatalyst for natural seawater splitting.

Simulating Chemistry on Bosonic Quantum Devices.

Bosonic quantum devices offer a novel approach to realize quantum computations, where the quantum two-level system (qubit) is replaced with the quantum (an)harmonic oscillator (qumode) as the fundamental building block of the quantum simulator. The simulation of chemical structure and dynamics can then be achieved by representing or mapping the system Hamiltonians in terms of bosonic operators. In this Perspective, we review recent progress and future potential of using bosonic quantum devices for addressing a wide range of challenging chemical problems, including the calculation of molecular vibronic spectra, the simulation of gas-phase and solution-phase adiabatic and nonadiabatic chemical dynamics, the efficient solution of molecular graph theory problems, and the calculations of electronic structure.

The long-run effects of financial development on income inequality: Evidence from the Asia-Pacific countries.

Income inequality is a vexing developmental challenge for governments and policymakers as it impedes social transformation and economic growth and development. Meanwhile, promoting financial development is generally regarded as an effective way to achieve inclusive and sustainable growth. This study examines the long-run effects of financial development, economic growth, and their combined effects on income inequality for 12 Asia-Pacific countries from 1990 to 2021. This paper employs various econometric techniques and different financial development proxies to ensure the findings' robustness. The paper also constructs a financial development index using the principal component analysis to fully capture the comprehensive effect of financial development on income inequality. Empirical results reveal that the impact of financial development on income inequality follows the inverted U-shaped relationship - financial development widens income inequality and only reduces income when surpassing its turning point. Findings further reveal that the nonlinear effect of financial development on income inequality is contingent upon the level of per capita income. Thus, policies promoting financial development to reduce income inequality should consider the existing level of per capita income.