bluuebunny/crossref_metadata_2025 huggingface dataset:
Porous biochar supported PET plastic waste MOF heterostructure as a novel, efficient and recyclable catalyst for acetaminophen degradation
Authors: Vigneshwaran Sivakumar , Kim Do-Gun , Ko Seok-Oh
Published: October 2024

Herein, the innovative hybrid photocatalyst PET-based Zn-MOF on orange peel biochar (BC)(PZM/BC) was designed and synthesized via the hydrothermal method. Electrochemical methods have been used to demonstrate the action of the PET-MOF in the PZM/BC photocatalyst as a medium for electron transfer. The latter involved the synthesis of a zinc-containing metal–organic framework (MOF) in which the linkers were derived from the depolymerization of polyethylene terephthalate (PET) originating from plastic wastes. According to research, the catalytic reactions are sped up when porous BC and linker PET are assimilated into PZM/BC photocatalyst hetero-junction. Furthermore, BC stored electrons under light and released these electrons under dark conditions. When BC was combined with PET-MOF, the electrons on the biochar activated the catalytic redox activity of acetaminophen. Additionally, it lowers the reassimilation rate due to the combined meshed nanostructures and functionality of PET-MOF and PZM/BC. UV–Vis DRS, Mott-Schottky, Photoluminescence(PL), and Electrochemical Impedance spectra(EIS) results showed that the PZM/BC exhibited efficient spatial separation and transportation of photogenerated charge carriers and exhibited superior photocatalytic ability. Electron spin resonance(ESR) analysis confirmed that ⋅OH and h+ were the predominant radical species responsible for the degradation of acetaminophen(ACT). The optimum conditions for ACT removal were observed at pH 6.07, with a PZM/BC dosage of 0.1 g L−1, and an initial ACT concentration of 50 mg L−1, highlighting the pivotal role of the PZM/BC system in ACT degradation. Furthermore, potential photocatalytic degradation pathways of ACT were inferred renders on the identified intermediates which are responsible for the degradation of refractory intermediates. Regeneration trials were carried out to assess the stability of the photocatalyst. Additionally, the degraded intermediates generated during the degradation processes were examined, providing a comprehensive elucidation of the degradation mechanism.

Graphical Abstract
Unlocking epigenetic breeding potential in tomato and potato
Authors: Zhang Pingxian , He Yuehui , Huang Sanwen
Published: October 2024

Tomato (Solanum lycopersicum) and potato (Solanum tuberosum), two integral crops within the nightshade family, are crucial sources of nutrients and serve as staple foods worldwide. Molecular genetic studies have significantly advanced our understanding of their domestication, evolution, and the establishment of key agronomic traits. Recent studies have revealed that epigenetic modifications act as “molecular switches”, crucially regulating phenotypic variations essential for traits such as fruit ripening in tomatoes and tuberization in potatoes. This review summarizes the latest findings on the regulatory mechanisms of epigenetic modifications in these crops and discusses the integration of biotechnology and epigenomics to enhance breeding strategies. By highlighting the role of epigenetic control in augmenting crop yield and adaptation, we underscores its potential to address the challenges posed by a growing global population as well as changing climate.
Interaction of lump, periodic, bright and kink soliton solutions of the (1+1)-dimensional Boussinesq equation using Hirota-bilinear approach
Authors: Shakeel Muhammad , Liu Xinge , Al-Yaari Abdullah
Published: October 2024

In this paper, we explore the characteristics of lump and interaction solutions for a (1+1) dimensional Boussinesq equation. By employing the Hirota bilinear method, we derive and analyze the exact solutions of this equation. Specifically, we achieve the lump with bright-bright soliton solution, 1-lump,2-lumps and 3-lumps with single bright soliton solution, lump with periodic, kink, and anti-kink soliton solutions. Alongside deriving these solutions, we also illustrate their dynamic properties through graphical simulations. The Boussinesq equation holds significant importance due to its applications in various domains, such as water wave modeling, coastal engineering, and the numerical simulation of water wave dynamics in harbors and shallow seas. Our research shows that the employed method is straightforward, easy to understand, and highly efficient, providing valuable insights into the equation’s nature and its practical applications.
AI-assisted prescreening of biomedical research proposals: ethical considerations and the pilot case of “la Caixa” Foundation
Authors: Carbonell Cortés Carla , Parra-Rojas César , Pérez-Lozano Albert , Arcara Francesca , Vargas-Sánchez Sarasuadi , Fernández-Montenegro Raquel , Casado-Marín David , Rondelli Bernardo , López-Verdeguer Ignasi
Published: October 2024

The “la Caixa” Foundation has been experimenting with artificial intelligence (AI)-assisted decision-making geared toward alleviating the administrative burden associated with the evaluation pipeline of its flagship funding program, piloting an algorithm to detect immature project proposals before they reach the peer review stage, and suggest their removal from the selection process to a human overseer. In this article, we explore existing uses of AI by publishers and research funding organizations to automate their selection pipelines, in addition to analyzing the conditions under which the focal case corresponds to a responsible use of AI and the extent to which these conditions are met by the current implementation, highlighting challenges and areas of improvement.
Assessing effectiveness of cleaning and disinfection of equipment and environmental surfaces in cystic fibrosis clinics using an ATP assay
Authors: Muhlebach Marianne S. , Shields Thomas , Shah Kushal K. , Ansar Maria , Virella-Lowell Isabel , Zhou Juyan J. , LiPuma John J. , Saiman Lisa
Published: October 2024

Background:

Infection control guidelines for cystic fibrosis (CF) stress cleaning of environmental surfaces and patientcare equipment in CF clinics. This multicenter study measured cleanliness of frequently touched surfaces in CF clinics using an ATP bioluminescence assay to assess the effectiveness of cleaning/disinfection and the impact of feedback.

Methods:

Eight surfaces were tested across 19 clinics (10 pediatric, 9 adult) over 5 rounds of testing. Rounds 1 and 2 served as uncleaned baseline, and Round 3 occurring after routine cleaning. Rounds 4 and 5 were performed after feedback provided to staff and measured after cleaning. Pass rates defined as <250 relative light units were the primary outcome.

Results:

Of the 750 tests performed, 72% of surfaces passed at baseline, and 79%, 83%, and 85% of surfaces passed in Rounds 3, 4, and 5, respectively. The overall pass-rate was significantly higher in adult compared to pediatric clinics (86% vs 71%; P < 0.001). In pediatric clinics, blood pressure equipment and computer keyboards in the pulmonary function lab consistently passed, but the exam room patient/visitor chairs consistently failed in all rounds. In adult clinics blood pressure equipment, keyboards in exam rooms and exam tables passed in all rounds and no surface consistently failed.

Conclusion:

We demonstrate the feasibility of an ATP bioluminescence assay to measure cleanliness of patient care equipment and surfaces in CF clinics. Pass rates improved after cleaning and feedback for certain surfaces. We found that surfaces are more challenging to keep clean in clinics taking care of younger patients.
The impact of statewide educational webinars on infection prevention and control knowledge and policy updates in acute and long-term care facilities during the COVID-19 pandemic: the Nebraska experience
Authors: Brailita Daniel M. , Soma Mounica , Martinez Rebecca , Tyner Laura , McConville Josette , Plasencia Juan Teran , Donahue Matthew , Ashraf Muhammad Salman
Published: October 2024

A Nebraska statewide webinar series was initiated during the coronavirus disease 2019 (COVID-19) pandemic for long-term care (LTC) and acute care/outpatient (AC) facilities. An impact survey was completed by 48 of 96 AC and 109 of 429 LTC facilities. The majority reported increased regulatory awareness (AC: 65%, LTC: 54%) and updated COVID-19 (AC: 61%, LTC: 69%) and general infection prevention (AC: 61%, LTC: 60%) policies.
Gravity-driven flow of liquid bridges between vertical fibres
Authors: Gabbard Chase T. , Bostwick Joshua B.
Published: October 2024

Liquid bridges are formed when a flowing liquid interacts with multiple parallel fibres, as relevant to heat and mass transfer applications that utilize flow down fibre arrays. We perform a comprehensive experimental study of flowing liquid bridges between two vertical fibres whose spacing is controlled dynamically in our experimental apparatus. The bridge patterns exhibit a regular periodic spacing typical of absolute instability for low flow rates, but become spatially inhomogeneous above a critical flow rate where the base flow is convectively unstable. The shapes of individual bridges and their associated dynamics are measured, as they depend upon the liquid properties, and fibre geometry/spacing. The bridge length scales similarly to static bridges between parallel fibres. The bridge dynamics exhibits a dependence on viscosity and scale with the impedance. A simple energy balance is used to derive a scaling relationship for the bridge velocity that captures the general trend of our experimental data. Finally, we demonstrate that these scalings similarly apply when the fibres are dynamically separated or brought together.
Making sense of chromosome polymorphisms in two leptysmine grasshoppers
Authors: Colombo Pablo C.
Published: October 2024

The touchstone of the ‘New Synthesis’ was population cytogenetics –rather than genetics – due to the abundant polymorphic inversions in the genus Drosophila. Grasshoppers were not a material of choice because of their conservative karyotypes. However, nowadays seven species of Acrididae were described for polymorphic centric fusions, five of them in South-America. Leptysma argentina and the likely biocontrol of water-hyacinth Cornops aquaticum are semiaquatic Leptysminae (Acrididae: Orthoptera), polymorphic for centric fusions, supernumerary segments and a B-chromosome. We sought to demonstrate the operation of natural selection on them, by detecting: (I) latitudinal clines; (II) regression on environmental variables; (III) deviation from null models, such as linkage equilibrium; (IV) seasonal variation; (V) comparison between age classes and (VI) selection component analyses. All of them were confirmed in L. argentina, just (I) and (II) in C. aquaticum. Furthermore, the relationship between karyotype, phenotype and recombination was confirmed in both species. Karyotype–phenotype relationship may be due to the body enlargement the fusions are associated with, along with a latitudinal transition in voltinism. Karyotype-related recombination reduction in both species may help explain all fusion clines, although there is probably more than one factor at work. No effects were noticed for a supernumerary segment in L. argentina, but it is ubiquitous and certainly non-neutral. C. aquaticum is poised for introduction in South-Africa as a biocontrol of water-hyacinths; the recent discovery of four more segment polymorphisms may imply more chromosomal markers to make sense of its genetic system.
Association of STAT1 gene with milk fat and protein yield in Holstein Friesian crossbred cattle maintained in the sub-tropical climate of India
Authors: Sharma Anika , Kaur Simarjeet , Arora Jaspreet Singh , Kashyap Neeraj
Published: October 2024

Signal transducers and activators of transcription (STAT) genes are involved in signal mediation of various hormones and cytokines. STAT1 located on chromosome number 2 is involved in mammary gland development and is associated with milk composition traits in bovines. This study aimed to find any relationship and impact of STAT1/BspHI gene with milk fat and protein yields in a herd of Holstein Friesian (HF) crossbred cattle of sub-tropical climate of Northern India. Milk composition data of 535 adult HF crossbred cows for a period of 12 years was collected from the records maintained at Livestock Farm, Guru Angad Dev Veterinary and Animal Sciences University. First lactation data of 222 animals was chosen for further analysis. After data correction for non-genetic factors (season of calving, period of calving, interaction effect of season and period of calving and age at first calving) these animals were categorised into two groups based on corrected high and low milk fat and protein yields. Forty animals were then selected for blood collection and further laboratory analysis. Amplified using PCR-RFLP technique, the 314 bp STAT1 gene was digested using BspHI restriction enzyme. C-T polymorphism at nucleotide position 201 and 260 of the STAT1 amplicon was observed. At 201, for genotype AA and Aa, the genotypic frequencies were 0.80 and 0.20%. At 260, for genotype BB and Bb, the genotypic frequencies were 0.25 and 0.75%. Least square analysis showed a significant association of all genotypes with milk fat and protein yields. Hence, STAT1 can be used as a potential candidate gene to aid in better animal selection in breeding programmes.
Increased intra-individual variability among individuals with ADHD: first evidence from numerosity judgment and verbal and quantitative reasoning
Authors: Barneron Meir , Saka Noa , Shlepack Shaul , Khattab Aseel , Pollak Yehuda
Published: October 2024

Background

This article presents the results of two studies investigating increased intra-individual variability (IIV) in the performance of individuals with attention deficit hyperactivity disorder (ADHD), in two cognitive domains: numerosity judgments and quantitative and verbal reasoning.

Methods

Study 1, a pre-registered experiment, involved approximately 200 participants (42.66% female; mean age: 36.86; standard deviation of age: 10.70) making numerical judgments at two time-points. ADHD-symptom severity was assessed on a continuous scale. In Study 2, we collected the data of approximately 3000 examinees who had taken a high-stakes admissions test for higher education (assessing quantitative and verbal reasoning). The sample comprised only people formally diagnosed with ADHD. The control group consisted of approximately 200 000 examinees, none of whom presented with ADHD.

Results

The results of Study 1 revealed a positive correlation between IIV (distance between judgments at the two time-points) and ADHD symptom severity. The results of Study 2 demonstrated that IIV (distance between the scores on two test chapters assessing the same type of reasoning) was greater among examinees diagnosed with ADHD. In both studies, the findings persisted even after controlling for performance level.

Conclusions

The results indicate that individuals with ADHD, v. those without, exhibit less consistent numerosity judgments and greater fluctuation in performance on verbal and quantitative reasoning. The measurement of the same psychological constructs appears to be less precise among individuals with ADHD compared to those without. We discuss the theoretical contributions and practical implications of our results for two fields: judgment and decision-making, and assessment.
Apples, tomatoes, and health: comparison of structural characteristics of the L1 and L2 mental lexicons
Authors: Agustín-Llach María Pilar , Palapanidi Kiriakí
Published: October 2024

The present study delves into the structure and lexical organization of L1 and L2 mental lexicons. Indirect access to the mental lexicon is provided by semantic fluency tasks, which inform researchers about how the words are organized in the mental lexicon and retrieved when necessary. Here, two groups of participants were asked to retrieve as many words of the categoryfruits and vegetablesas possible in two minutes. The first group is made up of native speakers of Spanish who responded in Spanish L1, whereas the second group is made up of native speakers of Greek who are learning Spanish foreign language (SFL) who responded first in Spanish FL and later in Greek L1. The three sets of responses were scrutinized and compared for similarities and differences. Results point to a retrieval mechanism based on L1-mediated access for SFL learners and slightly different structures of the mental lexicon. Even in very advanced learners, lexical organization and word retrieval in the FL resembles L1 organization.
Large Ensemble Exploration of Global Energy Transitions Under National Emissions Pledges
Authors: Wessel Jacob , Iyer Gokul , Wild Thomas , Ou Yang , McJeon Haewon , Lamontagne Jonathan
Published: October 2024

Global climate goals require a transition to a deeply decarbonized energy system. Meeting the objectives of the Paris Agreement through countries' nationally determined contributions and long‐term strategies represents a complex problem with consequences across multiple systems shrouded by deep uncertainty. Robust, large‐ensemble methods and analyses mapping a wide range of possible future states of the world are needed to help policymakers design effective strategies to meet emissions reduction goals. This study contributes a scenario discovery analysis applied to a large ensemble of 5,760 model realizations generated using the Global Change Analysis Model. Eleven energy‐related uncertainties are systematically varied, representing national mitigation pledges, institutional factors, and techno‐economic parameters, among others. The resulting ensemble maps how uncertainties impact common energy system metrics used to characterize national and global pathways toward deep decarbonization. Results show globally consistent but regionally variable energy transitions as measured by multiple metrics, including electricity costs and stranded assets. Larger economies and developing regions experience more severe economic outcomes across a broad sampling of uncertainty. The scale of CO2 removal globally determines how much the energy system can continue to emit, but the relative role of different CO2 removal options in meeting decarbonization goals varies across regions. Previous studies characterizing uncertainty have typically focused on a few scenarios, and other large‐ensemble work has not (to our knowledge) combined this framework with national emissions pledges or institutional factors. Our results underscore the value of large‐ensemble scenario discovery for decision support as countries begin to design strategies to meet their goals.
Multiday Soil Moisture Persistence and Atmospheric Predictability Resulting From Sahelian Mesoscale Convective Systems
Authors: Taylor C. M. , Klein C. , Harris B. L.
Published: October 2024

Skill in predicting where damaging convective storms will occur is limited, particularly in the tropics. In principle, near‐surface soil moisture (SM) patterns from previous storms provide an important source of skill at the mesoscale, yet these structures are often short‐lived (hours to days), due to both soil drying processes and the impact of new storms. Here, we use satellite observations over the Sahel to examine how the strong, locally negative, SM‐precipitation feedback there impacts rainfall patterns over subsequent days. The memory of an initial storm pattern decays rapidly over the first 3–4 days, but a weak signature is still detected in surface observations 10–20 days later. The wet soil suppresses rainfall over the storm track for the first 2–8 days, depending on aridity regime. Whilst the negative SM feedback initially enhances mesoscale rainfall predictability, the transient nature of SM likely limits forecast skill on sub‐seasonal time scales.
Multifractal Analysis for Evaluating the Representation of Clouds in Global Kilometer‐Scale Models
Authors: Freischem Lilli J. , Weiss Philipp , Christensen Hannah M. , Stier Philip
Published: October 2024

Clouds are one of the largest sources of uncertainty in climate predictions. Global km‐scale models need to simulate clouds and precipitation accurately to predict future climates. To isolate issues in their representation of clouds, models need to be thoroughly evaluated with observations. Here, we introduce multifractal analysis as a method for evaluating km‐scale simulations. We apply it to outgoing longwave radiation fields to investigate structural differences between observed and simulated anvil clouds. We compute fractal parameters which compactly characterize the scaling behavior of clouds and can be compared across simulations and observations. We use this method to evaluate the nextGEMS ICON simulations via comparison with observations from the geostationary satellite GOES‐16. We find that multifractal scaling exponents in the ICON model are significantly lower than in observations. We conclude that too much variability is contained in the small scales leading to less organized convection and smaller, isolated anvils.
Impacts of the Thermocline Feedback Uncertainty on El Niño Simulations in the Tropical Pacific
Authors: Li Tiaoye , Tao Lingjiang , Zhang Rong‐Hua
Published: October 2024

As a key dynamic element of the Bjerknes feedback mechanism, the thermocline effect (TE) is critically important to El Niño modeling. In this study, the potential influence of TE‐related parametric uncertainties on El Niño is investigated using the conditional nonlinear optimal parametric perturbation (CNOP) method based on an intermediate coupled model (ICM). The optimal perturbation of the TE‐related parameter (OTEP), which substantially affects El Niño simulations, is estimated through the CNOP approach. Results reveal that the El Niño simulation is highly sensitive to the TE uncertainty in the eastern equatorial Pacific, with OTEP‐induced simulation errors demonstrating an El Niño‐like growth trend. On one hand, as indicated by the simulated El Niño intensity, the uncertainty in the TE in the eastern region can easily affect the strength of the Bjerknes feedback‐related thermocline effect and atmospheric circulation. On the other hand, the enhanced TE is highly favored to accelerate the growth of the SST error due to the air–sea interaction, thus severely affecting the El Niño simulations. Therefore, adequately representing the TE in the equatorial eastern Pacific is emphasized for effectively improving El Niño simulations.
Hepatocyte-specific NR5A2 deficiency induces pyroptosis and exacerbates non-alcoholic steatohepatitis by downregulating ALDH1B1 expression
Authors: Zhao Rong , Guo Zizhen , Lu Kaikai , Chen Qian , Riaz Farooq , Zhou Yimeng , Yang Luyun , Cheng Xiaona , Wu Litao , Cheng Kexin , Feng Lina , Liu Sitong , Wu Xiaodan , Zheng Minghua , Yin Chunyan , Li Dongmin
Published: October 2024

Nonalcoholic steatohepatitis (NASH) is a prevalent chronic disease, yet its exact mechanisms and effective treatments remain elusive. Nuclear receptor subfamily 5 group A member 2 (NR5A2), a transcription factor closely associated with cholesterol metabolism in the liver, has been hindered from comprehensive investigation due to the lethality of NR5A2 loss in cell lines and animal models. To elucidate the role of NR5A2 in NASH, we generated hepatocyte-specific knockout mice for Nr5a2 (Nr5a2HKO) and examined their liver morphology across different age groups under a regular diet. Furthermore, we established cell lines expressing haploid levels of NR5A2 and subsequently reintroduced various isoforms of NR5A2. In the liver of Nr5a2HKO mice, inflammation and fibrosis spontaneously emerged from an early age, independent of lipid accumulation. Pyroptosis occurred in NR5A2-deficient cell lines, and different isoforms of NR5A2 reversed this form of cell death. Our findings unveiled that inhibition of NR5A2 triggers pyroptosis, a proinflammatory mode of cell death primarily mediated by the activation of the NF-κB pathway induced by reactive oxygen species (ROS). As a transcriptionally regulated molecule of NR5A2, aldehyde dehydrogenase 1 family member B1 (ALDH1B1) participates in pyroptosis through modulation of ROS level. In conclusion, the diverse isoforms of NR5A2 exert hepatoprotective effects against NASH by maintaining a finely tuned balance of ROS, which is contingent upon the activity of ALDH1B1.
VASH2 enhances KIF3C-mediated EGFR-endosomal recycling to promote aggression and chemoresistance of lung squamous cell carcinoma by increasing tubulin detyrosination
Authors: Wang Jing , Liu Pengpeng , Zhang Rui , Xing Biyuan , Chen Guidong , Han Lei , Yu Jinpu
Published: October 2024

Lung squamous cell carcinoma (LUSC) is associated with high mortality and has few therapeutic options. Chemotherapy remains the main treatment for LUSC patients, but multi-drug resistance has become the dominant challenge in the failure of chemotherapy in various cancers. Therefore, the effective therapeutic strategy for LUSC patients is an urgent unmet need. Here, we found vasohibin-2 (VASH2) was a prognostic biomarker for LUSC patients, and VASH2 promoted the malignant biological behaviors of LUSC cells and chemoresistance by increasing the detyrosination of α-tubulin. The high level of detyrosinated-tubulin was negatively associated with patient prognosis. Blocking the tubulin carboxypeptidase (TCP) activity of VASH2 inhibited the xenograft tumor growth and improved the treatment efficacy of paclitaxel in vivo. Results revealed that VASH2-induced increase in tubulin detyrosination boosted the binding of kinesin family member 3C (KIF3C) to microtubules and enhanced KIF3C-dependent endosomal recycling of EGFR, leading to the prolonged activation of PI3K/Akt/mTOR signaling. This study demonstrated that VASH2 was not only a prognostic biomarker but also a promising therapeutic target in LUSC, which offers a novel insight that combination of chemotherapy and EpoY, a TCP inhibitor, may be a promising treatment strategy for LUSC patients.
The origin and maintenance of supergenes contributing to ecological adaptation in Atlantic herring
Authors: Jamsandekar Minal , Ferreira Mafalda S. , Pettersson Mats E. , Farrell Edward D. , Davis Brian W. , Andersson Leif
Published: October 2024

Chromosomal inversions are associated with local adaptation in many species. However, questions regarding how they are formed, maintained and impact various other evolutionary processes remain elusive. Here, using a large genomic dataset of long-read and short-read sequencing, we ask these questions in one of the most abundant vertebrates on Earth, the Atlantic herring. This species has four megabase-sized inversions associated with ecological adaptation that correlate with water temperature. The S and N inversion alleles at these four loci dominate in the southern and northern parts, respectively, of the species distribution in the North Atlantic Ocean. By determining breakpoint coordinates of the four inversions and the structural variations surrounding them, we hypothesize that these inversions are formed by ectopic recombination between duplicated sequences immediately outside of the inversions. We show that these are old inversions (>1 MY), albeit formed after the split between the Atlantic herring and its sister species, the Pacific herring. There is evidence for extensive gene flux between inversion alleles at all four loci. The large Ne of herring combined with the common occurrence of opposite homozygotes across the species distribution has allowed effective purifying selection to prevent the accumulation of genetic load and repeats within the inversions.
Efficient and stable inverted perovskite solar cells enabled by homogenized PCBM with enhanced electron transport
Authors: Gong Cheng , Li Haiyun , Xu Zhiyuan , Li Yuheng , Wang Huaxin , Zhuang Qixin , Wang Awen , Li Zhijun , Guo Zhihao , Zhang Cong , Wang Baiqian , Li Xiong , Zang Zhigang
Published: October 2024

Fullerene derivatives are extensively employed in inverted perovskite solar cells due to their excellent electron extraction capabilities. However, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) agglomerates easily in solution and exhibits a relatively low ionization barrier, increasing charge recombination losses and charge accumulation in the interface. Here, tetramethylthiuram disulfide (TMDS) is introduced into the PCBM solution to induce the formation of reducing sulfur radicals through UV light irradiation, allowing for n doping of the PCBM material. The resulting modified PCBM layer exhibits enhanced conductivity and electron mobility, significantly suppressing charge recombination. As a result, the resulting devices incorporating TMDS achieve a champion efficiency of 26.10% (certified 25.39%) and 24.06% at a larger area (1.0 cm2) with negligible hysteresis. More importantly, the optimized devices retain 95% and 90% of their initial efficiency after 1090 h under damp heat testing (85 °C and 85% relative humidity) and after 1271 h under maximum power point-tracking conditions, respectively.
Sensory experience steers representational drift in mouse visual cortex
Authors: Bauer Joel , Lewin Uwe , Herbert Elizabeth , Gjorgjieva Julijana , Schoonover Carl E. , Fink Andrew J. P. , Rose Tobias , Bonhoeffer Tobias , Hübener Mark
Published: October 2024

Representational drift—the gradual continuous change of neuronal representations—has been observed across many brain areas. It is unclear whether drift is caused by synaptic plasticity elicited by sensory experience, or by the intrinsic volatility of synapses. Here, using chronic two-photon calcium imaging in primary visual cortex of female mice, we find that the preferred stimulus orientation of individual neurons slowly drifts over the course of weeks. By using cylinder lens goggles to limit visual experience to a narrow range of orientations, we show that the direction of drift, but not its magnitude, is biased by the statistics of visual input. A network model suggests that drift of preferred orientation largely results from synaptic volatility, which under normal visual conditions is counteracted by experience-driven Hebbian mechanisms, stabilizing preferred orientation. Under deprivation conditions these Hebbian mechanisms enable adaptation. Thus, Hebbian synaptic plasticity steers drift to match the statistics of the environment.
Socio-demographic and genetic risk factors for drug adherence and persistence across 5 common medication classes
Authors: Cordioli Mattia , Corbetta Andrea , Kariis Hanna Maria , Jukarainen Sakari , Vartiainen Pekka , Kiiskinen Tuomo , Ferro Matteo ,   FinnGen, Perola Markus , Ripatti Samuli , Ganna Andrea ,   Estonian Biobank Research Team, Metspalu Andres , Milani Lili , Esko Tõnu , Mägi Reedik , Nelis Mari , Hudjashov Georgi , Perola Markus , Niemi Mikko , Ripatti Samuli , Lehto Kelli , Milani Lili , Ganna Andrea
Published: October 2024

Low drug adherence is a major obstacle to the benefits of pharmacotherapies and it is therefore important to identify factors associated with discontinuing or being poorly adherent to a prescribed treatment regimen. Using high-quality nationwide health registry data and genome-wide genotyping, we evaluate the impact of socio-demographic and genetic risk factors on adherence and persistence for 5 common medication classes that require long-term, regular therapy (N = 1,814,591 individuals from Finnish nationwide registries, 217,005 with genetic data from Finland and Estonia). Need for social assistance and immigration status show a notable negative effect on persistence and adherence across the examined medications (odd ratios between 0.48 and 0.82 for persistence and between 1.1% to 4.3% decrease in adherence) while demographic and health factors show comparably modest or inconsistent effects. A genome-wide scan does not identify genetic variants associated with the two phenotypes, while some pharmacogenes (i.e. CYP2C9 and SLCO1B1) are modestly associated with persistence, but not with adherence. We observe significant genetic correlations between medication adherence and participation in research studies. Overall, our findings suggest that socio-economically disadvantaged groups would benefit from targeted interventions to improve the dispensing and uptake of pharmacological treatments.
Training caretakers to clean community wells is a highly cost-effective way to reduce exposure to coliform bacteria
Authors: Habib Md. Ahasan , Cocciolo Serena , Raihan Md. Mir Abu , Bhattacharya Prosun , Tompsett Anna
Published: October 2024

Existing strategies for improving global access to safe drinking water have met only limited success. We consider an unglamorous and often neglected dimension of drinking water infrastructure provision: cleaning. We randomly assigned caretakers of community wells to participate in a training workshop about how to clean wells. Thirteen to seventeen months later, wells with caretakers assigned to receive training have negligible rates of contamination with Escherichia coli (13 months: 2%; 17 months: 4%), while control wells have substantial rates of E. coli contamination (13 months: 14%; 17 months: 19%). Rates of contamination with any coliform bacteria are almost halved (13 months: control 55%, treated 30%; 17 months: control 77%, treated 46%). We estimate the cost of preventing exposure to coliform bacteria in drinking water to be US$0.89 per person and that, if scaled up, each US$2376 spent on the intervention could avoid the death of a child.
Hemozoin induces malaria via activation of DNA damage, p38 MAPK and neurodegenerative pathways in a human iPSC-derived neuronal model of cerebral malaria
Authors: Pranty Abida Islam , Szepanowski Leon-Phillip , Wruck Wasco , Karikari Akua Afriyie , Adjaye James
Published: October 2024

Malaria caused by Plasmodium falciparum infection results in severe complications including cerebral malaria (CM), in which approximately 30% of patients end up with neurological sequelae. Sparse in vitro cell culture-based experimental models which recapitulate the molecular basis of CM in humans has impeded progress in our understanding of its etiology. This study employed healthy human induced pluripotent stem cells (iPSCs)-derived neuronal cultures stimulated with hemozoin (HMZ) - the malarial toxin as a model for CM. Secretome, qRT-PCR, Metascape, and KEGG pathway analyses were conducted to assess elevated proteins, genes, and pathways. Neuronal cultures treated with HMZ showed enhanced secretion of interferon-gamma (IFN-γ), interleukin (IL)1-beta (IL-1β), IL-8 and IL-16. Enrichment analysis revealed malaria, positive regulation of cytokine production and positive regulation of mitogen-activated protein kinase (MAPK) cascade which confirm inflammatory response to HMZ exposure. KEGG assessment revealed up-regulation of malaria, MAPK and neurodegenerative diseases-associated pathways which corroborates findings from previous studies. Additionally, HMZ induced DNA damage in neurons. This study has unveiled that exposure of neuronal cultures to HMZ, activates molecules and pathways similar to those observed in CM and neurodegenerative diseases. Furthermore, our model is an alternative to rodent experimental models of CM.
Photocatalytic generation of alkyl carbanions from aryl alkenes
Authors: Czyz Milena L. , Horngren Tyra H. , Kondopoulos Andrew J. , Franov Liam J. , Forni José A. , Pham Le Nhan , Coote Michelle L. , Polyzos Anastasios
Published: October 2024

Organometallic reagents are routinely used as fundamental building blocks in organic chemistry to rapidly diversify molecular fragments via carbanion intermediates. However, the catalytic generation of carbanion equivalents, particularly from sp3-hybridized alkyl scaffolds, remains an underdeveloped goal in chemical synthesis. Here we disclose an approach for the generation of alkyl carbanions via single-electron reduction of aryl alkenes, enabled by multi-photon photoredox catalysis. We demonstrate that photocatalytically induced alkyl carbanions engage in intermolecular C–C bond-forming reactions with carbonyl electrophiles. Central to this method is the controlled formation of an alkene distonic radical anion intermediate that undergoes nucleophilic addition, followed by a kinetically favoured reductive polar crossover to produce a second carbanion available for further diversification. The versatility of this protocol was illustrated by the development of four distinct intermolecular C–C bond-forming reactions with aromatic alkenes (hydroalkoxylation, hydroamidation, aminoalkylation and carboxyaminoalkylation) to generate a range of valuable and complex scaffolds.
Follicle-intrinsic and spatially distinct molecular programs drive follicle rupture and luteinization during ex vivo mammalian ovulation
Authors: Zaniker Emily J. , Zhang Jiyang , Russo Daniela , Huang Ruixu , Suritis Kristine , Drake Riley S. , Barlow-Smith Esther , Shalek Alex K. , Woodruff Teresa K. , Xiao Shuo , Goods Brittany A. , Duncan Francesca E.
Published: October 2024

During ovulation, the apical wall of the preovulatory follicle breaks down to facilitate gamete release. In parallel, the residual follicle wall differentiates into a progesterone-producing corpus luteum. Disruption of ovulation, whether through contraceptive intervention or infertility, has implications for women’s health. In this study, we harness the power of an ex vivo ovulation model and machine-learning guided microdissection to identify differences between the ruptured and unruptured sides of the follicle wall. We demonstrate that the unruptured side exhibits clear markers of luteinization after ovulation while the ruptured side exhibits cell death signals. RNA-sequencing of individual follicle sides reveals 2099 differentially expressed genes (DEGs) between follicle sides without ovulation induction, and 1673 DEGs 12 h after induction of ovulation. Our model validates molecular patterns consistent with known ovulation biology even though this process occurs in the absence of the ovarian stroma, vasculature, and immune cells. We further identify previously unappreciated pathways including amino acid transport and Jag-Notch signaling on the ruptured side and glycolysis, metal ion processing, and IL-11 signaling on the unruptured side of the follicle. This study yields key insights into follicle-inherent, spatially-defined pathways that underlie follicle rupture, which may further understanding of ovulation physiology and advance women’s health.
Witnessing their mother’s acute and prolonged stress affects executive functioning in children
Authors: Lashani Eileen , Larsen Isabella G. , Kanske Philipp , Rosendahl Jenny , Blasberg Jost U. , Engert Veronika
Published: October 2024

Stress can detrimentally affect physical and mental health, especially during childhood. During this critical period, parental bonds can foster resilience or amplify stress. This study explored whether mothers’ everyday stress can act as a source of childhood stress, affecting children’s executive functioning. 76 healthy mother-child dyads participated, with mothers assigned to a stress-inducing or stress-free condition. Children observed their mothers and were subsequently tested for cognitive flexibility and working memory. Subjective stress, heart rate, and cortisol were measured repeatedly in mothers and children, alongside everyday stress perceptions. Linear mixed models showed that children’s acute stress response was associated with impaired cognitive flexibility. Maternal stress, both acute and past-month, was a better predictor of children’s cognitive performance than children’s own stress. Quadratic relationships indicated the highest error rates at very low and high maternal stress. We found no evidence that children’s working memory was impaired by their own or their mothers’ stress. Although expected covariations of acute or prolonged stress between mothers and children were not observed, an interaction between maternal past-month stress and acute stress condition provided insights into adaptive mechanisms in children. These findings underscore the significant impact of maternal stress on children’s executive functioning, illustrating how parental experiences shape children’s everyday outcomes.
Introduction: What Is a Metal Complex?
Authors: Tanase T.
Published: October 2024

This chapter provides a brief introduction to this textbook by explaining what a ‘metal complex’ is from a historical point of view. A metal complex is a neutral or ionic compound in which metal ions or metal atoms (M) are surrounded by ligands (L) such as organic molecules or inorganic ions, and can be divided into two historical categories: coordination compounds and organometallic compounds. The former contain M ← L coordination bonds and have been widely studied since Werner’s coordination theory in 1893, and the latter generally involve M–L covalent bonds with C donor atoms and have been developed and applied to organocatalytic reactions since the discovery of ferrocene in the 1950s. These two groups can be understood in the same way by considering the hard and soft acid and base (HSAB) principle: the former contain highly ionic coordination bonds formed by combinations of HA and HB, whereas the latter contain more covalent bonds formed by combinations of SA and SB. In addition to a number of HSAB combinations, transition metal complexes have been found to possess various properties based on d- and f-electrons and have continued to evolve, creating new interdisciplinary areas as their science deepens and their applications expand.
Structure of Metal Complexes
Authors: Tanase T.
Published: October 2024

The chemistry of transition metal complexes, which exhibit a wide variety of chemical and physical properties, is the result of combinations of the various electronic states of metal centres containing d- and f-electrons and the diversity of ligand systems and structures including inorganic, organic and bio-related compounds. In order to understand the structure of transition metal complexes, this chapter first introduces basic concepts of the electronic and physical properties of metal ions and shows representative mono-, bi- and multidentate ligands. The geometric structures of metal complexes are then systematically explained by following the coordination number of mononuclear complexes, and some di-, tri- and multinuclear metal complexes with and without metal–metal bonds are discussed. The isomerism observed in metal complexes and the resulting isomers, structural isomers and stereoisomers, is also explained focusing on the latter, which are divided into configurational and conformational isomers. Finally, the nomenclature of metal complexes is briefly discussed.
Electronic Structure of Metal Complexes
Authors: Tanase T.
Published: October 2024

This chapter describes crystal field theory and ligand field theory, which are the most fundamental concepts for understanding the electronic structures of transition metal complexes. Both of these theories are essential for a systematic understanding of the correlation between the structure and electronic state of transition metal complexes, and are the basis for learning about the magnetism and electronic absorption spectra of metal complexes. In crystal field theory, all ligands are treated as point charges (or electric dipole moments), and their electrostatic interaction with a d-electron in the metal centre is calculated using a perturbation method, leading to the crystal field splitting of the d orbitals. In ligand field theory, the interactions of σ- and π-orbitals of the ligands with the valence orbitals of the metal are estimated with LCAO molecular orbital techniques. In both cases, symmetry techniques based on group theory are used. The angular overlapping model is described briefly, as a semi-quantitative orbital quantum technique for estimating the splitting energies of the d orbitals from σ- and π-donor ligands. Although it is not widely used at present, treatment using the valence bond method is also outlined and its relationship to crystal field theory and ligand field theory is explained.
Magnetism of Metal Complexes
Authors: Kajiwara T.
Published: October 2024

One of the important features of transition metal complexes is that they often have open-shell electronic configurations and are paramagnetic, due to the spin and/or orbital angular momentum of the metal ions. The magnetic properties of transition metals are discussed in this chapter. The Zeeman effect in magnetic fields is first described, then magnetisation and molar susceptibility (χM) are formulated and Curie law is introduced. The Van Vleck formula derived here is the most important equation to formulate the temperature dependence of χM based on the zero- to second-order Zeeman coefficients. Then, two cases where the magnetic susceptibility does not follow the Curie law are discussed, namely the presence of magnetic anisotropy and the presence of magnetic interactions between metal ions. In both cases, the nature and magnitude of each can be estimated by precise analysis of the χMvs. T plots, and their mechanism will also be discussed. The last two sections will introduce the spin crossover phenomena and complex-based magnets, such as single molecule magnets. Research on molecular magnets has been very active in recent years, and it will be useful to learn ideas about the aforementioned magnetic anisotropy and magnetic interactions in order to understand molecular magnetism.
Electron Transfer Reactions of Metal Complexes
Authors: Inomata T.
Published: October 2024

Reactions in which a metal complex donates or receives electrons to or from another compound or an electrode are called oxidation and reduction reactions, respectively, or redox reactions together. In terms of electrons, oxidation and reduction reactions are electron transfer reactions between a metal complex and another compound or an electrode. In this chapter, the basics of electrochemistry are briefly introduced before the electron transfer reactions of metal complexes are described. Metal elements, especially transition metal elements, have multiple oxidation states, and therefore, metal complexes exhibit a variety of redox and electron transfer reactions. As for electron transfer reactions between metal complexes, a reaction in which electrons are transferred from one complex to another without any changes in the coordination sphere of the metal complexes is called an outer-sphere electron transfer mechanism. On the other hand, an inner-sphere electron transfer mechanism is one in which electrons are transferred with substitution of ligands in the coordination sphere, usually through a bridging ligand. This chapter discusses the mechanisms of the outer- and inner-sphere electron transfer mechanisms, Marcus theory, and mixed-valence complexes, which are closely related to electron transfer reactions.
Theoretical Chemistry of Metal Complexes
Authors: Kitagawa Y.
Published: October 2024

Theoretical chemistry, including molecular orbital theory and quantum chemical calculations, give us a deep understanding of the electronic structures and mechanisms derived from the chemical and physical properties of metal complexes. This chapter explains the basic concept of molecular orbital theory and some methods of quantum chemical calculations, such as Hartree–Fock theory and density functional theory (DFT) method. To start, the idea of how molecular orbitals are generated from atomic orbitals is described, and then how they are calculated is explained. Population analysis based on the molecular orbitals is also introduced. In addition, the meaning of some important technical terminology, such as basis functions, various functionals in DFT and broken-symmetry (BS) calculations, is described with concrete examples. Metal–metal and metal–ligand interactions are learned using the simple LCAO molecular orbital method, and the d–d ligand field splitting energy is actually calculated using a DFT method. The treatment of the open-shell systems with localised spins is also explained, especially for metal complexes.