Rate Of Evolution Research Articles

Highly Active Photoreduction of Atmospheric‐Concentration CO2 into CH3COOH over Palladium Particles on Nb2O5 Nanosheets

AbstractThe endeavor to drive CO2 photoreduction towards the synthesis of C2 products is largely thwarted by the colossal energy hurdle inherent in C−C coupling. Herein, we load active metal particles on metal oxide nanosheets to build the dual metal pair sites for steering C−C coupling to form C2 products. Taking Pd particles anchored on the Nb2O5 nanosheets as an example, the high‐angle annular dark‐field image and X‐ray photoelectron spectroscopy demonstrate the presence of Pd−Nb metal pair sites on the Pd‐Nb2O5 nanosheets. Density functional theory calculations reveal these sites exhibit a low reaction energy barrier of only 1.02 eV for C−C coupling, implying that the introduction of Pd particles effectively tailors the reaction step to form C2 products. Therefore, the Pd‐Nb2O5 nanosheets achieve a CH3COOH evolution rate of 13.5 μmol g−1 h−1 in photoreduction of atmospheric‐concentration CO2, outshining all other single photocatalysts reported to date under analogous conditions.

P3HT/g-C3N4 composite fiber membranes for high-performance photocatalytic hydrogen evolution

As a superstar semiconducting polymer, poly(3-hexylthiophene) (P3HT) demonstrates high efficiency in carrier transport ability and wide absorption range. However, pristine P3HT exhibits minimal photocatalytic activity as a result of its short carrier transport distance and fast electron-hole recombination. Here, we strategically fabricated P3HT/g-C3N4 composites on polymethyl methacrylate (PMMA) fiber (PTCN) via electrospinning and the physicochemical properties were fully investigated. Raman spectroscopy, ultraviolet–visible (UV–Vis) absorption spectra and X-ray photoelectron spectroscopy (XPS) results demonstrated a well-defined p-n heterojunctions can be formed between P3HT and g-C3N4 molecules through π-π interaction and extended conjugated length of P3HT could be achieved by tuning the ratios of P3HT relative to g-C3N4. The presence of the heterojunctions facilitates the effective disconnection of the electron-hole pairs, resulting in a significantly enhanced photocatalytic hydrogen evolution rate of 7327 μ mol/(h·g) for the PTCN fiber membranes. This value exceeds that of P3HT fibers by 57.7 times and powder g-C3N4 by 6.8 times, respectively. The high photocatalytic hydrogen production activity of P3HT/g-C3N4 fiber membrane expands the application of P3HT. More importantly, these results indicate that the construction of heterojunction fiber materials is a promising approach for improving the photocatalytic ability of conjugated semiconducting polymers.

Dual Electric Field Coupling with Tunable Schottky Barrier Synergistically Regulating Electronic Configuration in CoP@Ni‐CdS Heterojunction for Efficient Photocatalytic H2 Evolution

AbstractDesigning and exploiting visible‐light‐responsive materials that converts solar into chemical energy is promising in achieving green energy sustainability, but addressing low electron–hole separation efficiency and sluggish surface kinetic process remains formidable challenges. Herein, a novel CoP@Ni‐CdS Schottky junction composed of Ni‐doped CdS nanorods and quasi‐metallic CoP nanoparticles is constructed via a simple hydrothermal–calcination method. Experiments and theoretical calculations demonstrate that magnetic Ni‐doping not only induces a spin‐polarized electric field and enhances the built‐in interfacial electric field strength, but also rises the Schottky barrier height at the heterointerface, which synergistically accelerates the separation efficiency of photoinduced charges and modulates the electronic configuration of the active site to optimize the adsorption–desorption behaviors for H2O molecules and H* intermediates. Therefore, the designed CoP@Ni‐CdS catalyst exhibits an exceptional photocatalytic performance with H2 evolution rate of 42.14 mmol g−1 h−1 with the apparent quantum efficiencies of 16.8% at 420 nm, which is 14.14 and 2.21 times higher than that of pristine CdS and Ni‐CdS, respectively. This work provides in‐depth insights into fabricating dual electric fields, tuning the Schottky barrier and modulating the electronic configuration of active sites in Schottky heterojunction for ameliorative photocatalytic activity.

Binary Iron-Manganese Cocatalyst for Simultaneous Activation of C-C and C-O Bonds to Maximally Utilize Lignin for Syngas Generation over InGaN.

Solar-powered lignin reforming offers a carbon-neutral route for syngas production. This study explores a dual non-precious iron-manganese cocatalyst to simultaneously activate both C-C and C-O bonds for maximizing the utilization of various substituents of native lignin to yield syngas. By assembling with InGaN nanowires on a Si wafer, the as-designed dual FeMn cocatalyst affords a measurable syngas evolution rate of 42.4 mol·gcat-1·h-1 from native lignin in distilled water with a high selectivity of 93% and tunable H2/CO ratios under concentrated light, leading to a considerable light-to-fuel efficiency of 11.8%. The high FeMn atom efficiency arising from the 1-dimensional nanostructure of InGaN enables the achievement of a high turnover frequency (TOF) of 220896 mol syngas per mol FeMn per hour. By correlating explorationexperiments,the critical role of the dual FeMn cocatalyst in the evolving mechanism of lignin and water toward syngas is disclosed at the atomic level. It is discovered that the synergetic iron-manganese cocatalyst supported by InGaN nanowires enables simultaneous activation of C-C and C-O bonds with comparable minimized dissociation energies.This work demonstrates a new and earth-abundant bifunctional cocatalyst for utilizing various substituents of lignin to produce syngas powered by sunlight beyond fossil fuels.

Binary Iron‐Manganese Cocatalyst for Simultaneous Activation of C‐C and C‐O Bonds to Maximally Utilize Lignin for Syngas Generation over InGaN

Solar‐powered lignin reforming offers a carbon‐neutral route for syngas production. This study explores a dual non‐precious iron‐manganese cocatalyst to simultaneously activate both C‐C and C‐O bonds for maximizing the utilization of various substituents of native lignin to yield syngas. By assembling with InGaN nanowires on a Si wafer, the as‐designed dual FeMn cocatalyst affords a measurable syngas evolution rate of 42.4 mol·gcat‐1·h‐1 from native lignin in distilled water with a high selectivity of 93% and tunable H2/CO ratios under concentrated light, leading to a considerable light‐to‐fuel efficiency of 11.8%. The high FeMn atom efficiency arising from the 1‐dimensional nanostructure of InGaN enables the achievement of a high turnover frequency (TOF) of 220896 mol syngas per mol FeMn per hour. By correlating exploration experiments, the critical role of the dual FeMn cocatalyst in the evolving mechanism of lignin and water toward syngas is disclosed at the atomic level. It is discovered that the synergetic iron‐manganese cocatalyst supported by InGaN nanowires enables simultaneous activation of C‐C and C‐O bonds with comparable minimized dissociation energies. This work demonstrates a new and earth‐abundant bifunctional cocatalyst for utilizing various substituents of lignin to produce syngas powered by sunlight beyond fossil fuels.

Number of human protein interactions correlates with structural, but not regulatory conservation of the respective genes.

The differential ratio of nonsynonymous to synonymous nucleotide substitutions (dN/dS) is a common measure of the rate of structural evolution in proteincoding genes. In addition, we recently suggested that the proportion of transposable elements in gene promoters that host functional genomic sites serves as a marker of the rate of regulatory evolution of genes. Such functional genomic regions may include transcription factor binding sites and modified histone binding loci. Here, we constructed a model of the human interactome based on 600,136 documented molecular interactions and investigated the overall relationship between the number of interactions of each protein and the rate of structural and regulatory evolution of the corresponding genes. By evaluating a total of 4,505 human genes and 1,936 molecular pathways we found a general correlation between structural and regulatory evolution rate metrics (Spearman 0.08-0.16 and 0.25-0.37 for gene and pathway levels, respectively, p < 0.01). Further exploration revealed in the established human interactome model lack of correlation between the rate of gene regulatory evolution and the number of protein interactions on gene level, and weak negative correlation (∼0.15) on pathway level. We also found a statistically significant negative correlation between the rate of gene structural evolution and the number of protein interactions (Spearman -0.11 and -0.3 for gene and pathway levels, respectively, p < 0.01). Our result suggests stronger structural rather than regulatory conservation of genes whose protein products have multiple interaction partners.

Study on the causes and coping strategies of adolescent mental illness

In recent years, especially since the epidemic, there has been an explosive increase in the incidence of adolescent mental disorders, which has aroused the attention of the whole society. From the perspectives of evolution, humanism, and psychodynamics, this paper analyzes the deep-rooted causes of the increasing incidence of psychological disorders in adolescents and explores various dilemmas adolescents face. From an evolutionary point of view, the current rate of social progress exceeds the rate of human evolution and the rate of cognitive improvement of young people, making it difficult for young people to adapt to complex social environments. In humanitarian terms, excessive academic pressure places a heavy burden on young people. From the perspective of psychodynamics, the conflict between standard, ego, and superego can cause mental illness in adolescents. In addition, this paper points out that adolescent mental illness marks the evolution of social awareness of mental health, and all parties in society need to build a supportive policy framework to foster widespread awareness of mental health.

An updated phylogeography and population dynamics of porcine circovirus 2 genotypes: are they reaching an equilibrium?

Porcine circovirus 2 (PCV2) emerged more than three decades ago as one of the most impactful pathogens in the swine industry. Despite being a DNA virus, one of the hallmarks of PCV2 is its high evolutionary rate, which has led to the emergence of different genotypes, each exhibiting varying degrees of evolutionary success. Current knowledge suggests the occurrence of three main waves of genotype dominance, alternating over time (i.e., PCV2a, PCV2b, and PCV2d), alongside less prevalent genotypes. However, although PCV2d is currently the most common genotype nowadays, the others continue being circulating in the pig population. The present study reconsidered the epidemiological and evolutionary patterns of PCV2 genotypes using phylodynamic analyses, benefiting from an almost 10-fold increase in ORF2 sequence availability compared to previous studies. Additionally, a phylogeographic analysis was performed to investigate viral dispersal patterns and frequency, and the selective pressures acting on the capsid protein were estimated and compared among genotypes. While successive emergence of major genotypes was confirmed, this study extends previous findings by revealing subsequent prevalence fluctuations of PCV2a and PCV2b after their initial decline. This evolutionary process may represent an example of balancing selection, specifically negative frequency-dependent selection, where a genotype fitness diminishes as it becomes more common, and vice versa. Variations in genotype- or clade-specific immunity-affected by the local prevalence of viral groups-combined with the periodic introduction of strains that have independently evolved in different regions, may have led to fluctuations in the population dynamics of major genotypes over time. These fluctuations were associated with ongoing evolution and variations in the capsid amino acid profile. These findings have profound implications for future control strategies. Although PCV2d remains the most prevalent and widespread genotype, other genotypes should not be neglected. Control strategies should thus target the entire PCV2 population, with a focus on fostering broader and more cross-protective immunity.

A Supramolecular‐Nanocage‐Based Framework Stabilized by π‐π Stacking Interactions with Enhanced Photocatalysis

Abstractπ frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π‐π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular‐nanocage‐based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π‐π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π‐2). π‐2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π‐2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co‐catalyst, the hydrogen evolution rate reaches a record‐high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π‐2 to the highly active Pt upon illumination. π‐2 represents the unique stable supramolecular‐cage‐based π framework with excellent photocatalytic activity.

A Supramolecular-Nanocage-Based Framework Stabilized by π-π Stacking Interactions with Enhanced Photocatalysis.

π frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π-π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular-nanocage-based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π-π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π-2). π-2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π-2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co-catalyst, the hydrogen evolution rate reaches a record-high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π-2 to the highly active Pt upon illumination. π-2 represents the unique stable supramolecular-cage-based π framework with excellent photocatalytic activity.

Absence of heterosis for hypoxia tolerance in F1 hybrids of Tigriopus californicus.

Hybridization produces a range of outcomes from advantageous to disadvantageous, and a goal of genetic research is to understand the gene interactions that generate these outcomes. Interactions between cytoplasmic elements, such as mitochondria, and the nucleus may be particularly vulnerable to accruing disadvantageous combinations as a result of their different rates of evolution. However, mitonuclear incompatibilities often do not have an observable effect until the F2 and later generations. We used Tigriopus californicus, a model system for mitonuclear incompatibilities that is also known for exhibiting heterosis in the F1 generation, to test whether hypoxia was more stressful for mitonuclear interactions than other environmental stressors. We generated 284 parental and 436 F1 hybrids from four population crosses (720 total) and compared parental and F1 populations for hypoxia tolerance. We observed that, on average, F1 hybrids were less likely to survive a hypoxia stress test than parental populations (Parental:F1 coefficients ranged from -0.04 to 0.14 with none significantly different from 0). This suggests that hypoxia may be a particularly intense stressor for mitonuclear coordination, and that hybridization outcomes vary by trait.

Drug-use-associated infective endocarditis in Denmark

Abstract Introduction Infective endocarditis (IE) has high mortality and the incidence is rising. Intravenous drug use is a risk factor for IE and poses challenges in clinical care. Amid the opioid crisis in many countries, rates of drug-use-associated IE (DU-IE) are increasing. While drug use in Denmark has remained stable the last decade, little is understood about the features and prognostic impact of DU-IE in developed nations not facing a current opioid crisis. Further, with multiple preventive measures deployed in local Danish regions, data on the evolution of DU-IE are warranted. Purpose To examine the temporal evolution, baseline characteristics, and long-term rates of all-cause mortality and IE recurrence in patients with DU-IE compared with patients with non-DU-IE. Methods This nationwide cohort study identified all first-time IE-patients (1999-2018) and categorized them in 1) patients with DU-IE, and 2) patients with non-DU-IE. Drug use was defined using ICD-8/10 codes or treatment for opioid use disorder. Patients were followed from the date of discharge, and absolute one-year rates of mortality and IE recurrence were examined with Kaplan-Meier estimates and the cumulative incidence function, respectively. Outcomes were compared with a multivariable adjusted Cox model. Results We identified 8,843 patients with IE: 407 (4.6%) with DU-IE (61% male, median age 44 years) and 8,436 (95.4%) with non-DU-IE (66% male, median age 72 years). While the absolute number of DU-IE increased, the proportion of DU-IE decreased from 5.9% in 1999-2003 (n=87) to 3.8% in 2014-2018 (n=114). Patients with DU-IE had a higher proportion of bloodstream infection with Staphylococcus aureus (49.4% vs 26.7%, p&amp;lt;0.001); conversely, they had a lower proportion of bloodstream infections with Streptococcusspecies (14.4% vs. 26.2%, p&amp;lt;0.011). Patient with DU-IE had lower in-hospital mortality compared with non-DU-IE (15.5% vs. 20.9%, p&amp;lt;0.001). Among those surviving admission, the one-year cumulative incidence of all-cause mortality was 16.9% in DU-IE and 17.3% in non-DU-IE (p=0.82), yet in adjusted analysis, DU-IE was associated with a higher one-year mortality rate (HR 1.64 [95% CI:1.23-2.21]) (Figure). The one-year cumulative incidence of IE recurrence was 12.8% in DU-IE and 4.3% in non-DU-IE, which corresponded to an adjusted HR of 3.39 (95% CI:2.35-4.88) in DU-IE. Conclusion While an increase in the absolute number of patients with DU-IE was observed, the proportion among all IE-patients was on the decline in Denmark until 2018—which contrasts with other countries where physicians currently battle collateral damage of the opioid crisis. Although drug use was associated with lower in-hospital mortality, it was striking that even though patient with DU-IE was almost 30 years younger, they still had higher rates of all-cause mortality and a more than three-fold increase in IE recurrence one year following discharge.

Graphdiyne‐Based Nickel–Cobalt Bimetallic Sulfide Cocatalyst for Efficient Photocatalytic Hydrogen Evolution

Initially, CoNiSx is synthesized on the graphdiyne (GDY) surface through a precipitation method, followed by the straightforward physical stirring approach to attach CoNiSx/GDY to the maple leaf CdS. This synthesis method significantly mitigates the accumulation of CoNiSx/GDY and concurrently augments the count of sites that are active for generating hydrogen. This three‐phase composite demonstrates exceptional performance in the area of photocatalytic hydrogen production, achieving a hydrogen evolution rate of 15.37 mmol·h−1 g−1. The employment of various characterization methodologies and density functional theory calculations have demonstrated the formation of a Z‐scheme heterojunction forms between GDY and CdS. This discovery indicates that the combination of GDY and CdS markedly improves the photogenerated carrier separation capability of the composite catalyst. The cocatalyst CoNiSx loaded on GDY effectively accelerates the electron transfer from the conduction band of GDY, thereby reducing the photogenerated carrier complexation of GDY. This phenomenon results in an increased quantity of photogenerated electron holes engaged in the redox reaction, ultimately achieving exceptional photocatalytic performance.

ZnIn2S4 nanosheets with geometric defects for enhanced solar-driven hydrogen evolution and wastewater treatment

The key to development of high-performance and low cost photocatalysts hydrogen evolution and waste degradation is to realize efficient photo-generated charge carrier separation and surface catalytic reaction simultaneously without noble metal co-catalyst. To achieve this goal, a noble metal free ZnIn2S4 photocatalyst with geometric defects has been constructed, in which [In-S]4 tetrahedral vacancies (named as (InS)v) on the surface are created by removing the In and S atoms. Further mechanistic investigation has revealed that the (InS)v not only works as the active sites for reductive reaction, but also improves photo-generated electron-hole separation. As a result, the solar-driven hydrogen evolution rate reaches 10.70 mmol/gh without co-catalyst after optimizing the densities of the (InS)v. The apparent quantum efficiency at 380 nm, 395 nm, 420 nm, 450 nm and 520 nm is as high as 14.0 %, 17.1 %, 12.1 %, 8.2 % and 2.4 %, respectively. In addition, these photocatalysts also achieve a rate of 97.78 % and 91.27 % of RhB and MO within 3 and 60 min, respectively. This work show-case a novel approach to develop dual functional and noble metal free photocatalysts for efficiently utilizing solar energy for hydrogen generation and wastewater treatment.

Stable Zinc Metal Battery Development: Using Fibrous Zirconia for Rapid Surface Conduction of Zinc Ions With Modified Water Solvation Structure.

The two most critical technical issues in Zn-based batteries, dendrite formation, and hydrogen evolution reaction, can be simultaneously addressed by introducing negatively charged fibrous ZrO2 as a separator. Electron redistribution between ZrO2 and Zn2+ ions renders the ZrO2 surface a preferred adsorption site for Zn2+ ions, making surface conduction the primary ion-transport mode. Surface conduction enables fibrous ZrO2 to exhibit a 6.54 times higher single-Zn-ion conductivity than that of conventional glass fiber, minimizing the concentration gradient of Zn2+ and suppressing dendrite formation. Additionally, strong Zr─O─Zn bonding stabilizes the Zn2+ ions with fewer solvated H2O molecules (≈2), preventing water molecules from approaching the electrode surface, as evidenced by a 58.8% decrease in the hydrogen evolution rate. Consequently, the cycling stability of a fibrous-ZrO2-based Zn/Zn symmetric cell (3000h at 1mAhcm-2 and 5mAcm-2) is approximately ten times greater than that of the conventional variant. Furthermore, a fibrous-ZrO2-based Zn-I2 full cell exhibits a notably high energy density (271.4Whkg-1) as well as a long lifespan (≈5000 cycles) at an ultrahigh current density (4Ag-1).

Recent Progress on Cobalt‐Based Heterogeneous Catalysts for Hydrogen Production from Ammonia Borane

AbstractAmmonia borane (NH3BH3, AB) is a quintessential exemplar of chemical hydrogen storage materials and has been widely used in hydrogen evolution. Although expensive metal catalysts (such as Rh, Ru, Pt, Ag, etc.) exhibit high activity in the hydrolysis of ammonia borane, inexpensive metals are more economical. Cobalt (Co), in particular, is not only relatively inexpensive and readily available, but also possesses high activity and selectivity. Compared to other catalysts, cobalt‐based catalysts have better durability and can maintain catalytic activity for a longer period of time, making them favored by researchers. These catalysts demonstrate excellent stability, hydrogen evolution rate, and turn over frequency. This article summarized previous progress in low price metal cobalt‐based catalysts for hydrogen precipitation from ammonia borane, focusing on cobalt‐based catalysts supported on various supports, especially those supported on carbon materials, metal oxides, MOFs, and nickel foams. The characteristics of high‐performance catalytic systems are analyzed in detail. The development prospects of Co catalysts for hydrogen production from ammonia borane were also discussed. In summary, this review compiles various supported and other types of cobalt based catalysts in recent years, and also identifies the existing problems with these catalysts, providing a reference for developers to study these catalysts. It is believed that through careful regulation of the electronic and spatial structures of Co based catalysts, well‐designed Co based non precious metal catalysts will play a significant role in the decomposition of ammonia borane.

Boosting Photocatalytic Hydrogen Evolution by a Light Coupling and Charge Carrier Confinement Strategy

AbstractHigh‐performance photocatalysis requires efficient light absorption and low charge carrier recombination rates. Herein, a light coupling and charge carrier confinement strategy is demonstrated to simultaneously enhance the light absorption efficiency and suppress the charge carrier recombination for high‐performance photocatalysis. The strategy is achieved by the delicate incorporation of catalysts into a dual‐core‐shell structure (e.g., CdS@SiO2@NaYF4:Yb/Tm), in which CdS (catalyst), SiO2, and NaYF4:Yb/Tm serve as shell, outer core, and inner core, respectively. Interestingly, the absorbed light can be confined within the CdS layer through multiple reflections between the CdS and SiO2 interfaces, achieving light confinement. This confinement endows a longer light residence time, enhanced light reabsorption and reutilization efficacy, and a higher concentration of photogenerated charge carriers per unit of time. Moreover, the insulating SiO2 can confine the photogenerated charge carriers within CdS layer, thus shortening their diffusion length for reduced recombination rates. Notably, when employed as the photocatalyst, this dual‐core‐shell structure showed a superb photocatalytic hydrogen evolution rate up to 74.67 mmol g−1 h−1, which is 11 times higher than that of pristine CdS. This work provides a new strategy for the design and synthesis of high‐performance photocatalysts.

How the Structure of Signaling Regulation Evolves: Insights from an Evolutionary Model.

To remain responsive to environmental changes, signaling pathways attenuate their activity with negative feedback loops (NFLs), where proteins produced upon stimulation downregulate the response. NFLs function both upstream of signaling to reduce input and downstream to reduce output. Unlike upstream NFLs, downstream NFLs directly regulate gene expression without the involvement of intermediate proteins. Thus, we hypothesized that downstream NFLs evolve under more stringent selection than upstream NFLs. Indeed, genes encoding downstream NFLs exhibit a slower evolutionary rate than upstream genes. Such differences in selective pressures could result in the robust evolution of downstream NFLs while making the evolution of upstream NFLs more sensitive to changes in signaling proteins and stimuli. Here, we test these assumptions within the context of immune signaling. Our minimal model of immune signaling predicts robust evolution of downstream NFLs to changes in model parameters. This is consistent with their critical role in regulating signaling and the conservative rate of evolution. Furthermore, we show that the number of signaling steps needed to activate a downstream NFL is influenced by the cost of signaling. Our model predicts that upstream NFLs are more likely to evolve under a shorter half-life of signaling proteins, absence of host-pathogen co-evolution, and a high infection rate. Although it has been proposed that NFLs evolve to reduce the cost of signaling, we show that a high cost does not necessarily predict the evolution of upstream NFLs. The insights from our model have broad implications for understanding the evolution of regulatory mechanisms across signaling pathways.

Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

Photocatalytic hydrogen (H2) evolution using covalent organic frameworks (COFs) is an attractive and promising avenue for exploration, but one of its big challenges is low photo-induced charge separation. In this study, we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency, achieved through atomic modulation (O, S, and Se) of the COF monomer. Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment, thereby affecting charge separation efficiency and photostability, which in turn affects the rates of photocatalytic H2 evolution. As a result, the newly developed TMT-BO-COF, which contains highly electronegative O atoms, exhibits the lowest exciton binding energy, the highest efficiency in charge separation and transportation, and the longest lifetime of the active charges. This leads to an impressive average H2 production rate of 23.7 mmol g−1 h−1, which is 2.5 and 24.5 times higher than that of TMT-BS-COF (containing S atoms) and TMT-BSe-COF (containing Se atoms), respectively. A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations. Our findings provide new insights into the design of highly photoactive organic framework materials for H2 evolution and beyond.

Interfacial coordination bonds accelerate charge separation for unprecedented hydrogen evolution over S-scheme heterojunction

Inspired by natural photosynthesis, fabricating high-performance S-scheme heterojunction is regarded as a successful tactic to address energy and environmental issues. Herein, NH2-MIL-125(Ti)/Zn0.5Cd0.5S/NiS (NMT/ZCS/NiS) S-scheme heterojunction with interfacial coordination bonds is successfully synthesized through in-situ solvothermal strategy. Notably, the optimal NMT/ZCS/NiS S-scheme heterojunction exhibits comparable photocatalytic H2 evolution (PHE) rate of about 14876.7 μmol h−1 g−1 with apparent quantum yield of 24.2% at 420 nm, which is significantly higher than that of recently reported MOFs-based photocatalysts. The interfacial coordination bonds (Zn–N, Cd–N, and Ni–N bonds) accelerate the separation and transfer of photogenerated charges, and the NiS as cocatalyst can provide more catalytically active sites, which synergistically improve the photocatalytic performance. Moreover, theoretical calculation results display that the construction of NMT/ZCS/NiS S-scheme heterojunction also optimize the binding energy of active site-adsorbed hydrogen atoms to enable fast adsorption and desorption. Photoassisted Kelvin probe force microscopy, in-situ irradiation X-ray photoelectron spectroscopy, femtosecond transient absorption spectroscopy, and theoretical calculations provide sufficient evidence of the S-scheme charge migration mechanism. This work offers unique viewpoints for simultaneously accelerating the charge dynamics and optimizing the binding strength between the active sites and hydrogen adsorbates over S-scheme heterojunction.