Conformal and conductive biofilm-bridged artificial Z-scheme system for visible light-driven overall water splitting.

Semi-artificial Z-scheme systems offer promising potential toward efficient solar-to-chemical conversion, yet sustainable and stable designs are currently lacking. Here, we developed a sustainable hybrid Z-scheme system capable for visible light-driven overall water splitting by integrating the durability of inorganic photocatalysts with the interfacial adhesion and regenerative property of bacterial biofilms. The Z-scheme configuration is fabricated by drop casting a mixture of photocatalysts onto a glass plate, followed by the growth of biofilms for conformal conductive paste through oxidative polymerization of pyrrole molecules. Notably, the system exhibited scalability indicated by consistent catalytic efficiency across various sheet areas, resistance observed by remarkable maintaining of photocatalytic efficiency across a range of background pressures, and high stability as evidenced by minimal decay of photocatalytic efficiency after 100-hour reaction. Our work thus provides a promising avenue toward sustainable and high-efficiency artificial photosynthesis, contributing to the broader goal of sustainable energy solutions.

A Visible Light-Responsive TiO2 Photocathode Achieved by a Rh Dopant.

Developing an efficient and stable photocathode material for photoelectrochemical solar water splitting remains challenging. Herein, we demonstrate the potential of rutile TiO2 as a photocathode by Rh doping with visible light absorption up to 640 nm and an onset potential of 0.9 V versus the reversible hydrogen electrode. The dopant transforms the rutile host from an n-type semiconductor to a p-type one, as confirmed by the Mott-Schottky curve and kelvin probe force microscopy. Physical and photoelectrochemical analyses further suggest that the doping mechanism is dependent on concentration. Lower levels of dopants generate localized Rh3+, while higher levels favor Rh4+ that interacts more strongly with the O 2p orbitals. The latter is found not only to extend the visible light absorption range but also to facilitate charge transport. This work elucidates the role of the Rh dopant in adjusting the photoelectrochemical behavior of TiO2, and it provides a promising photocathode material for solar energy conversion.

Emergence and Causality in Complex Systems: A Survey of Causal Emergence and Related Quantitative Studies.

Emergence and causality are two fundamental concepts for understanding complex systems. They are interconnected. On one hand, emergence refers to the phenomenon where macroscopic properties cannot be solely attributed to the cause of individual properties. On the other hand, causality can exhibit emergence, meaning that new causal laws may arise as we increase the level of abstraction. Causal emergence (CE) theory aims to bridge these two concepts and even employs measures of causality to quantify emergence. This paper provides a comprehensive review of recent advancements in quantitative theories and applications of CE. It focuses on two primary challenges: quantifying CE and identifying it from data. The latter task requires the integration of machine learning and neural network techniques, establishing a significant link between causal emergence and machine learning. We highlight two problem categories: CE with machine learning and CE for machine learning, both of which emphasize the crucial role of effective information (EI) as a measure of causal emergence. The final section of this review explores potential applications and provides insights into future perspectives.

Anisotropic Charge Migration on Perovskite Oxysulfide for Boosting Photocatalytic Overall Water Splitting.

The synthesis of photocatalysts with both broad light absorption and efficient charge separation is significant for a high solar energy conversion, which still remains to be a challenge. Herein, a narrow-bandgap Y2Ti2O5S2 (YTOS) oxysulfide nanosheet coexposed with defined {101} and {001} facets synthesized by a flux-assisted solid-state reaction was revealed to display the character of an anisotropic charge migration. The selective photodeposition of cocatalysts demonstrated that the {101} and {001} surfaces of YTOS nanosheets were the reduction and oxidation regions during photocatalysis, respectively. Density functional theory (DFT) calculations indicated a band energy level difference between the {101} and {001} facets of YTOS, which contributes to the anisotropic charge migration between them. The exposed Ti atoms on the {101} surface and S atoms on the {001} surface were identified, respectively, as reducing and oxidizing centers of YTOS nanosheets. This anisotropic charge migration generated a built-in electric field between these two facets, quantified by spatially resolved surface photovoltage microscopy, the intensity of which was found to be highly correlated with photocatalytic H2 production activity of YTOS, especially exhibiting a high apparent quantum yield of 18.2% (420 nm) after on-site modification of a Pt@Au cocatalyst assisted by Na2S-Na2SO3 hole scavengers. In conjunction with an oxygen-production photocatalyst and a [Co(bpy)3]2+/3+ redox shuttle, the YTOS nanosheets achieved a solar-to-hydrogen conversion efficiency of 0.15% via a Z-scheme overall water splitting. Our work is the first to confirm anisotropic charge migration in a perovskite oxysulfide photocatalyst, which is crucial for enhancing charge separation and surface catalytic efficiency in this material.

The m6A reader ECT1 drives mRNA sequestration to dampen salicylic acid-dependent stress responses in Arabidopsis.

N 6-methyladenosine (m6A) is a common epitranscriptional mRNA modification in eukaryotes. Thirteen putative m6A readers, mostly annotated as EVOLUTIONARILY CONSERVED C-TERMINAL REGION (ECT) proteins, have been identified in Arabidopsis (Arabidopsis thaliana), but few have been characterized. Here, we show that the Arabidopsis m6A reader ECT1 modulates salicylic acid (SA)-mediated plant stress responses. ECT1 undergoes liquid-liquid phase separation in vitro, and its N-terminal prion-like domain is critical for forming in vivo cytosolic biomolecular condensates in response to SA or bacterial pathogens. Fluorescence-activated particle sorting coupled with quantitative PCR analyses unveiled that ECT1 sequesters SA-induced m6A modification-prone mRNAs through its conserved aromatic cage to facilitate their decay in cytosolic condensates, thereby dampening SA-mediated stress responses. Consistent with this finding, ECT1 overexpression promotes bacterial multiplication in plants. Collectively, our findings unequivocally link ECT1-associated cytosolic condensates to SA-dependent plant stress responses, advancing the current understanding of m6A readers and the SA signaling network.

Correction: Zhang, J.; Liu, K. Neural Information Squeezer for Causal Emergence. Entropy 2023, 25, 26.

There was an error in the original publication [...].

Rhodium-Doped Barium Titanate Perovskite as a Stable p-Type Photocathode in Solar Water Splitting.

Solar water splitting from a p-n-conjugated photoelectrochemical (PEC) system is a promising way to produce hydrogen sustainably. At present, finding a compatible p-type photocathode material for the p-n system remains a great challenge in consideration of the photocurrent and stability. This paper highlighted a promising candidate, Rh/BaTiO3, by switching BaTiO3 from an n-type photoanode to a p-type photocathode upon Rh doping. The dopant activated visible light absorption up to 550 nm and an onset potential as high as 1.0 V (vs RHE). Using surface photovoltage spectroscopy as a powerful characterization tool, the n- to p-type transition of the semiconductor was studied and explained microscopically by which we quantitatively isolated the cathodic contribution caused by the Rh dopant. Unbiased overall solar water splitting was accomplished by serially connecting the Pt/Rh/BaTiO3 photocathode to a CoOx/Mo/BiVO4 photoanode, which produced a solar to hydrogen conversion efficiency of 0.1% and an excellent stability over 100 h of operation at ambient pressure. This work revealed the key role that the Rh dopant played in the n- to p-type adjustment of titanate semiconductors and demonstrated its great potential for application in PEC water splitting.

Matrix transformation of lunar regolith and its use as a feedstock for additive manufacturing.

Building a sustainable human habitat on the Moon requires advances in excavation, paving, and additive manufacturing to construct landing pads, surface transportation arteries, resilient shelters, and scientific outposts. Construction of infrastructure elements on the lunar surface necessitates exploration of the interfacial reactivity of locally sourced regolith and the adaptation of Earth-based construction techniques. Various crosslinking frameworks and sintering methods have been proposed as a means of consolidating lunar regolith into load-bearing structures but each have challenges related to incomplete understanding of reaction chemistry, excessive thermal budgets, and lack of universal applicability to different mineral components of regolith. We describe here a versatile experimental and computational study of the consolidation of a regolith simulant through formation of siloxane networks enmeshing mineral particles by surface dissolution-precipitation and polycondensation reactions. Furthermore, by tailoring the rheological properties of the formulation an additive manufacturing feedstock can be developed for the construction of lunar infrastructure.

Hierarchical regulatory module GENOMES UNCOUPLED1-GOLDEN2-LIKE1/2-WRKY18/40 modulates salicylic acid signaling.

Chloroplast-to-nucleus retrograde signaling (RS) pathways are critical in modulating plant development and stress adaptation. Among chloroplast proteins mediating RS pathways, GENOMES UNCOUPLED1 (GUN1) represses the transcription of the nuclear transcription factors GOLDEN2-LIKE1 (GLK1) and GLK2 that positively regulate chloroplast biogenesis. Given the extensive exploration of the function of GUN1 in biogenic RS carried out in previous years, our understanding of its role in plant stress responses remains scarce. Here, we revealed that GUN1 contributes to the expression of salicylic acid (SA)-responsive genes (SARGs) through transcriptional repression of GLK1/2 in Arabidopsis (Arabidopsis thaliana). Loss of GUN1 significantly compromised the SA responsiveness in plants, concomitant with the upregulation of GLK1/2 transcripts. In contrast, knockout of GLK1/2 potentiated the expression of SARGs and led to enhanced stress responses. Chromatin immunoprecipitation, coupled with quantitative PCR and related reverse genetic approaches, unveiled that in gun1, GLK1/2 might modulate SA-triggered stress responses by stimulating the expression of WRKY18 and WRKY40, transcriptional repressors of SARGs. In summary, we demonstrate that a hierarchical regulatory module, consisting of GUN1-GLK1/2-WRKY18/40, modulates SA signaling, opening a research avenue regarding a latent GUN1 function in plant-environment interactions.

Proportioning Factors of Alkali-Activated Materials and Interaction Relationship Revealed by Response Surface Modeling.

Alkali-activated fly-ash-slag blending materials (AA-FASMs) are gradually being studied and applied more because of their good performance. There are many factors affecting the alkali-activated system, and the effect of single-factor variation on the performance of AA-FASM has been mostly reported; however, there is a lack of unified understanding of the mechanical properties and microstructure of AA-FASM under curing conditions and multiple-factor interaction. Therefore, this study investigated the compressive strength development and reaction products of alkali-activated AA-FASM under three curing conditions including seal (S), dry (D) and water saturation (W). Based on the response surface model, the relationship between the interaction of slag content (WSG), activator modulus (M) and activator dosage (RA) on its strength was established. The results showed that the maximum compressive strength of AA-FASM after 28 days of sealed curing was about 59 MPa, while the strengths of dry- and water-saturation-cured specimens decreased by 9.8% and 13.7%, respectively. The seal-cured samples also had the smallest mass change rate and linear shrinkage and the most compact pore structure. Due to the adverse effects from a too-high or too-low modulus and dosage of the activators, the shapes of upward convex, slope and inclined convex were under the interaction of WSG/M, WSG/RA and M/RA, respectively. The correlation coefficient R2 > 0.95 and p-value < 0.05 indicated that the proposed model could be used to predict strength development given the complex factors. Optimal proportioning and curing conditions were found to be WSG = 50%, M = 1.4, RA = 50% and sealed curing.

Cooperative role of AtRsmD and AtRimM proteins in modification and maturation of 16S rRNA in plastids.

Chloroplast pre-ribosomal RNA (rRNA) undergoes maturation, which is critical for ribosome assembly. While the central and auxiliary factors in rRNA maturation have been elucidated in bacteria, their mode of action remains largely unexplored in chloroplasts. We now reveal chloroplast-specific factors involved in 16S rRNA maturation, Arabidopsis thaliana orthologs of bacterial RsmD methyltransferase (AtRsmD) and ribosome maturation factor RimM (AtRimM). A forward genetic screen aimed to find suppressors of the Arabidopsis yellow variegated 2 (var2) mutant defective in photosystem II quality control found a causal nonsense mutation in AtRsmD. The substantially impaired 16S rRNA maturation and translation due to the mutation rescued the leaf variegation phenotype by lowering the levels of chloroplast-encoded proteins, including photosystem II core proteins, in var2. The subsequent co-immunoprecipitation coupled with mass spectrometry analyses and bimolecular fluorescence complementation assay found that AtRsmD interacts with AtRimM. Consistent with their interaction, loss of AtRimM also considerably impairs 16S rRNA maturation with decelerated m2 G915 modification in 16S rRNA catalyzed by AtRsmD. The atrimM mutation also rescued var2 mutant phenotypes, corroborating the functional interplay between AtRsmD and AtRimM towards modification and maturation of 16S rRNA and chloroplast proteostasis. The maturation and post-transcriptional modifications of rRNA are critical to assembling ribosomes responsible for protein translation. Here, we revealed that the cooperative regulation of 16S rRNA m2 G915 modifications by AtRsmD methyltransferase and ribosome assembly factor AtRimM contributes to 16S rRNA maturation, ribosome assembly, and proteostasis in chloroplasts.

Effect of the Moisture Content of Recycled Aggregate on the Mechanical Performance and Durability of Concrete.

Wasted concrete was often used as a recycled aggregate instead natural stone in fresh concrete to reduce the environmental impact in a decade. However, because of the residual mortar interface, the performance of recycled aggregate was weaker. In this paper, the recycled aggregate was prewetted, and the effects of prewetted degree on the workability, strength, and durability of concrete were studied. The properties of the interfacial transition zone (ITZ), including microhardness, pore structure, and width, were also investigated. The results show that the workability intensity increased with the increase in prewetted degree from 0% to 100%, while the strength was first increased and then decreased with the optimal value of 43.3 MPa when the prewetted degree was 50-65%. The water absorption and chloride ion diffusion coefficient were also decreased by approximately 10% at minimum with the prewetted degree around 55% because of the declined fraction of pores larger than 50 µm and smaller porosity. The width of ITZ was first sharply decreased with a prewetted degree of 50-65%, then increased again with higher moisture, while microhardness of the ITZ showed the opposite trend and reached 82.7 MPa at maximum, at 50%. The appropriate moisture (50-65%) improved the pore structure and hydration products with an internal curing effect. When the moisture content was too high, the excess water was released from aggregate to the matrix, causing a higher water-cement ratio at ITZ; the porosity and the number of macrospores were increased to weaken the performance of concrete.

Insight into the Light-Driven Hydrogen Production over Pure and Rh-Doped Rutile in the Presence of Ascorbic Acid: Impact of Interfacial Chemistry on Photocatalysts.

The surface states of a semiconductor photocatalyst are essential for interfacial charge transfer in heterogeneous photocatalytic reactions. Here, we report that the light-driven hydrogen evolution reaction (HER) activity of 0.5 mol % Rh-doped rutile increases by more than 30 times compared with that of rutile when ascorbic acid is used as a sacrificial agent. Intensity-modulated photocurrent spectroscopy and surface photovoltage spectroscopy are employed to reveal the impact of surface states on the photo-oxidation reactions. It is found that the adsorption of ascorbic acid molecules dramatically reduces the activity of rutile due to coverage of the HER-active Ti sites. Nevertheless, for Rh-doped rutile, ascorbic acid neutralizes the Rh(IV) sites that would otherwise cause severe recombination of electron-hole pairs and resurrects its photocatalytic performance. This work demonstrates the key role of interfacial chemistry in photocatalytic reactions and provides a strategy for excavating the potential of various photocatalysts.

Global Myocardial Strain in Multisystem Inflammatory Syndrome in Children, Kawasaki Disease, and Healthy Children: A Network Meta-Analysis.

Background: Nearly 6,000 multisystem inflammatory syndrome in children (MIS-C) have been reported in the United States by November 2021. Left ventricular global myocardial strain has been proved to be one of the best evidence of the diagnostic and prognostic implications for cardiac dysfunction. The global myocardial strain change of MIS-C in the acute phase was still unclear. Methods: PubMed and other sources were searched. A network meta-analysis was conducted. MIS-C was divided into two groups according to left ventricular ejection fraction (LVEF): MIS-C with depressed ejection fraction (MIS-C dEF) and MIS-C with preserved ejection fraction (MIS-C pEF). Global longitudinal strain (GLS) and global circumferential strain (GCS) were compared among MIS-C, Kawasaki disease (KD), and healthy children. Results: In total, nine case-control studies were included, published between 2014 and 2021. These studies involved 107 patients with MIS-C, 188 patients with KD, and 356 healthy children. After Bayesian analysis, MIS-C dEF group was found to have a lower LVEF, higher GLS and GCS than the KD groups. Both MIS-C pEF and KD had similar GLS and GCS, which were higher than healthy controls. There was no difference of LVEF among MIS-C pEF, KD, and healthy controls. Conclusion: MIS-C dEF was more severe than KD, both in LVEF and global myocardial strain. MIS-C pEF and KD were similar with mild impaired left ventricular myocardial strain compared with the healthy children. Global myocardial strain may be a monitoring index for MIS-C. Systematic Review Registration: [https://www.crd.york.ac.uk/prospero/], identifier [CRD42021264760].

Facet Engineering on WO3 Mono-Particle-Layer Electrode for Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) performance of WO3 photoanodes for water splitting is heavily influenced by the orientation of crystal facets. In this work, mono-particle-layer electrodes, assembled by particulate WO3 square plates with highly uniform alignment along the (002) facet, improved PEC water oxidation kinetics and stability. Photo-deposition of Au along the cracks formed on the surface of the plates, which are the edges of {110} facets, was found to further enhance electron collection efficiency. Combination of these two strategies allowed the facet-engineered WO3 electrode to produce significantly higher efficiencies in charge separation and transfer than the electrode prepared without facet orientation. This work has provided a facile route for fabricating a structurally designed WO3 photoelectrode, which is also applicable to other regularly shaped semiconductor photocatalysts with anisotropic charge migration.

Association of epicardial adipose tissue with the severity and adverse clinical outcomes of COVID-19: A meta-analysis.

OBJECTIVES: Epicardial adipose tissue (EAT) has been proposed to be an independent predictor of visceral adiposity. EAT measures are associated with coronary artery disease, diabetes, and chronic obstructive pulmonary disease, which are risk factors for COVID-19 poor prognosis. Whether EAT measures are related to COVID-19 severity and prognosis is controversial. METHODS: We searched 6 databases for studies until January 7, 2022. The pooled effects are presented as the standard mean difference (SMD) or weighted mean difference with 95% confidence intervals (CIs). The primary end point was COVID-19 severity. Adverse clinical outcomes were also assessed. RESULTS: A total of 13 studies with 2482 patients with COVID-19 were identified. All patients had positive reverse transcriptase-polymerase chain reaction results. All quantitative EAT measures were based on computed tomography. Patients in the severe group had higher EAT measures compared with the nonsevere group (SMD = 0.74, 95% CI: 0.29-1.18, P = 0.001). Patients with hospitalization requirement, requiring invasive mechanical ventilation, admitted to intensive care unit, or with combined adverse outcomes had higher EAT measures compared to their controls (all P < 0.001). CONCLUSIONS: EAT measures were associated with the severity and adverse clinical outcomes of COVID-19. EAT measures might help in prognostic risk stratification of patients with COVID-19.

Properties and Microstructure of Na2CO3-Activated Binders Modified with Ca(OH)2 and Mg(OH)2.

Delayed strength development and long setting times are the main disadvantageous properties of Na2CO3-activated slag cements. In this work, combined auxiliary activators of Ca(OH)2 and Mg(OH)2 were incorporated in one-part Na2CO3-activated slag binders to accelerate the kinetics of alkali activation. The properties and microstructure evolution were investigated to clarify the reaction mechanism. The results showed that the additions of auxiliary activators promoted the hardening of the pastes within 2 h. The 28 days compressive strengths were in the range of 39.5-45.5 MPa, rendering the binders practical cementitious materials in general construction applications. Ca(OH)2 was more effective than Mg(OH)2 in accelerating the kinetics of alkali activation. The dissolution of Ca(OH)2 released more OH- and Ca2+ ions in the aqueous phase to increase alkalinity in the aqueous phase and promote the formation of the main binding gel phase of calcium-aluminosilicate hydrate (C-A-S-H). An increase in the Ca(OH)2/Mg(OH)2 ratios increased autogenous shrinkage and decreased drying shrinkage of the binders. The formation of a compact pore structure restricted the water evaporation from the binders during the drying procedure.

Generating multiple optical vortices in orange beams induced by selectively pumped frequency-doubled solid-state Raman lasers with mode conversion.

We employ a selectively pumped solid-state laser with stimulated Raman scattering and second-harmonic generation to generate frequency-doubled lasing modes (FDLMs) at 588 nm. The FDLMs are transformed by using an external cylindrical mode converter to generate various structured beams with multiple optical vortices. Theoretical analyses clearly reveal the relationship between the mode components in the laser emission and the transverse displacement of the off-center pumping. We further verify that the experimental results for the transformed FDLMs can be numerically reconstructed with a theoretical model. By analyzing the phase structures of the converted beams, it can be demonstrated that the number of vortices rises from 2 to 19 with increasing off-center displacement.

Neural Information Squeezer for Causal Emergence.

Conventional studies of causal emergence have revealed that stronger causality can be obtained on the macro-level than the micro-level of the same Markovian dynamical systems if an appropriate coarse-graining strategy has been conducted on the micro-states. However, identifying this emergent causality from data is still a difficult problem that has not been solved because the appropriate coarse-graining strategy can not be found easily. This paper proposes a general machine learning framework called Neural Information Squeezer to automatically extract the effective coarse-graining strategy and the macro-level dynamics, as well as identify causal emergence directly from time series data. By using invertible neural network, we can decompose any coarse-graining strategy into two separate procedures: information conversion and information discarding. In this way, we can not only exactly control the width of the information channel, but also can derive some important properties analytically. We also show how our framework can extract the coarse-graining functions and the dynamics on different levels, as well as identify causal emergence from the data on several exampled systems.

Bayesian and E-Bayesian Estimations of Bathtub-Shaped Distribution under Generalized Type-I Hybrid Censoring.

For the purpose of improving the statistical efficiency of estimators in life-testing experiments, generalized Type-I hybrid censoring has lately been implemented by guaranteeing that experiments only terminate after a certain number of failures appear. With the wide applications of bathtub-shaped distribution in engineering areas and the recently introduced generalized Type-I hybrid censoring scheme, considering that there is no work coalescing this certain type of censoring model with a bathtub-shaped distribution, we consider the parameter inference under generalized Type-I hybrid censoring. First, estimations of the unknown scale parameter and the reliability function are obtained under the Bayesian method based on LINEX and squared error loss functions with a conjugate gamma prior. The comparison of estimations under the E-Bayesian method for different prior distributions and loss functions is analyzed. Additionally, Bayesian and E-Bayesian estimations with two unknown parameters are introduced. Furthermore, to verify the robustness of the estimations above, the Monte Carlo method is introduced for the simulation study. Finally, the application of the discussed inference in practice is illustrated by analyzing a real data set.