bluuebunny/crossref_metadata_2025_split huggingface dataset:
NiCo2O4/MXene Hybrid as an Efficient Bifunctional Electrocatalyst for Oxygen Evolution and Reduction Reaction
Authors: Vazhayil Ashalatha , Vazhayal Linsha , Ashok C Shyamli , Thomas Jasmine , Thomas Nygil 
Published: January 2024

AbstractFor the advancement of electrochemical energy conversion and storage technologies, bifunctional electrocatalysts are crucial for efficiently driving both the oxygen evolution (OER) and reduction reactions (ORR). Cobalt‐based spinel oxides are a class of promising bifunctional electrocatalysts. However their low electrical conductivity and stability may hinder further improvement. A novel composite material composed of NiCo2O4 nanoparticles integrated with emerging two dimensional MXene nanosheets (NiCo2O4/MXene) was developed. The successful integration of NiCo2O4 with MXene brings about a number of attractive structural features. This includes synergistic effects between NiCo2O4 and MXene, highly accessible surface areas, complete exposure of numerous active sites, and excellent electronic conductivity, all of which collectively contribute to the desirability of composite material for OER and ORR. The synthesized NiCo2O4/MXene composite showed extraordinary OER electrocatalytic activity with a lower overpotential of 360 mV at a current density of 10 mA/cm2, and a small Tafel slope of 64 mV/dec compared to NiCo2O4, MXene and NiCo2O4+MXene (physically mixed). Additionally, NiCo2O4/MXene displays an ORR limiting current density of −4 mA/cm2 and exhibited highest onset potential and half wave potential of 0.92 V and 0.72 V vs. RHE, respectively, for the ORR in alkaline media compared to NiCo2O4, MXene and NiCo2O4+MXene (physically mixed).
Chalcogen Atom Size: A Key Parameter in Modulating Carbonyl Compound Properties
Authors: Nieuwland Celine , Fonseca Guerra Célia 
Published: January 2024

AbstractExchanging oxygen in the functional group C=O (i. e., carbonyl) for the less electronegative Group 16 elements, sulfur or selenium, unexpectedly enhances the electronegativity of the C=X group in π‐conjugated molecules and reduces the molecular π HOMO–LUMO energy gap. Quantum‐chemical analyses revealed that the steric size of the chalcogen atom X is at the origin of this seemingly counterintuitive behavior. This tuning of the chemical properties of carbonyl compounds by varying the chalcogen atom size in the C=X bond can be applied in many fields of chemistry. This concept article delineates several useful applications in the fields of organocatalysis, supramolecular chemistry, and photo(electro)chemistry.
Site‐Selective Palladium‐catalyzed Oxidation of Unprotected Aminoglycosides and Sugar Phosphates
Authors: Marinus Nittert , Reintjens Niels R. M. , Haldimann Klara , Mouthaan Marc L. M. C. , Hobbie Sven N. , Witte Martin D. , Minnaard Adriaan J. 
Published: January 2024

AbstractThe site‐selective modification of complex biomolecules by transition metal‐catalysis is highly warranted, but often thwarted by the presence of Lewis basic functional groups. This study demonstrates that protonation of amines and phosphates in carbohydrates circumvents catalyst inhibition in palladium‐catalyzed site‐selective oxidation. Both aminoglycosides and sugar phosphates, compound classes that up till now largely escaped direct modification, are oxidized with good efficiency. Site‐selective oxidation of kanamycin and amikacin was used to prepare a set of 3’‐modified aminoglycoside derivatives of which two showed promising activity against antibiotic‐resistant E. coli strains.
Geometry‐Induced Oligomerization of Fluorine‐Substituted Phenylazothiazole Photoswitches
Authors: Hashim P. K. , Sahu Saugata , Takahashi Kiyonori , Thazhathethil Shakkeeb , Nakamura Takayoshi , Tamaoki Nobuyuki 
Published: January 2024

AbstractPhotoswitches are molecules that can absorb light of specific wavelengths and undergo a reversible transformation between their trans and cis isomeric forms. In phenylazo photoswitches, it is common for the less stable cis (Z) isomer to convert back to the more stable trans (E) isomer either through photochemical or thermal means. In this research, we designed new derivatives of phenylazothiazole (PAT) photoswitches, PAT‐Fn, which feature fluorine substituents on their phenyl component. These derivatives can reversibly isomerize under visible light exposure with the enrichment of E and Z isomers at photostationary state (PSS). Surprisingly, we observed an unconventional phenomenon when these PAT‐Fn (n≧2) photoswitches were in their cis isomeric state in the absence of light. Instead of the anticipated transformation from cis to trans isomer, these compounds converted to an oligomeric compound. Our detailed experimental investigation and theoretical calculations, indicated the crucial role of fluorine substituents and the distinctive geometric arrangement of the cis isomer in driving the unexpected oligomerization process originating from the cis isomeric state.
In Silico Investigation of Palladium‐Catalyzed Chemoselective Monoalkoxycarbonylation of 1,3‐diynes for Conjugated Enynes Synthesis
Authors: Ning Xiaoyu , Jing Yaru , Cheng Zuohui , Li Jingjing 
Published: January 2024

AbstractThe palladium‐catalyzed monoalkoxycarbonylation of 1,3‐diynes provides a chemoselective method for the construction of synthetically useful conjugated enynes. Here, in silico unraveling the detailed mechanism of this reaction and the origin of chemoselectivity were conducted. It is shown that the alkoxycarbonylation reaction preferably proceeds by a NH−Pd pathway, which including three substeps: hydropalladation, CO migratory insertion and methanolysis. The effectiveness of the NH−Pd catalytic system is attributed to the alkynyl‐palladium π‐back‐bonding interaction, C−H⋅⋅⋅π interaction in reactant moiety and d–pπ conjugation between the Pd center and alkenyl group. The hydropalladation step was identified as the rate‐ and chemoselectivity‐determining step, and the first alkoxycarbonylation requires a much lower energy barrier in comparison with the second alkoxycarbonylation, in line with the experimental outcomes that the monoalkoxycarbonylation product was obtained in high yield. Distortion‐interaction analysis indicates the more favorable monoalkoxycarbonylation (compared to double alkoxycarbonylation) is caused by steric effect.
Evaluation of Copper(II) Transfer between Amyloid‐beta Peptides by Relaxation‐Induced Dipolar Modulation Enhancement (RIDME)
Authors: Stehle Juliane , Hülsmann Miriam , Godt Adelheid , Drescher Malte , Azarkh Mykhailo 
Published: January 2024

AbstractIn the brains of Alzheimer's disease patients, fibrillar aggregates containing amyloid‐beta (Aβ) peptides are found, along with elevated concentrations of Cu(II) ions. The aggregation pathways of Aβ peptides can be modulated by Cu(II) ions and is determined by the formation and nature of the Cu(II)‐Aβ complex. If spin‐labeled, the Cu(II)‐Aβ complex contains two dipolar coupled paramagnetic centers, the spin label and the Cu(II) ion. Measurement of the dipolar coupling between these paramagnetic centers by relaxation‐induced dipolar modulation enhancement (RIDME) allows to monitor the complex formation and thus opens a way to follow the Cu(II) transfer between peptides if a mixture of wild‐type and spin‐labeled ones is used. We evaluate this approach for a specific Cu(II)‐Aβ complex, the aggregation‐inert Component II. The kinetics of the Cu(II) transfer can be resolved by performing RIDME in a time‐dependent manner. A temporal resolution of seconds has been achieved, with the potential to reach milliseconds, using a rapid‐freeze quench device to stop the Cu(II) transfer in solution after defined incubation times.
Azo‐Cyanamide Bridged Dinuclear Iron Complexes Exhibiting no Electronic Coupling but Moderate Magnetic Coupling between the two Iron Centers
Authors: Mao Zhong‐Dong , Fu Jin‐Hui , He Yong , Song Ying , Tan Bing‐Chang , Chen Ling‐Ting , Wu Xin‐Tao , Sheng Tian‐Lu 
Published: January 2024

AbstractTo investigate the effect of long‐distance organic ligand on electronic coupling between metallic atoms, the mononuclear and dinuclear complexes [Cp(dppe)Fe(apc)] (1), [{Cp(dppe)Fe}2(μ‐adpc)] (2), [{CpMe5(dppe)Fe}2(μ‐adpc) (3) and their oxidized complexes [Cp(dppe)Fe(apc)][PF6] (1[PF6]), [{Cp(dppe)Fe}2(μ‐adpc)][PF6] (2[PF6]2), [{CpMe5(dppe)Fe}2(μ‐adpc)][PF6]2 (3[PF6]2) (Cp=1,3‐cyclopentadiene, CpMe5=1,2,3,4,5‐pentamethylcyclopentadiene, dppe=1,2‐bis(diphenylphosphino)ethane), apc−=4‐azo(phenylcyanamido)benzene and adpc2−=4,4′‐azodi(phenylcyanamido)) were synthesized and characterized by cyclic voltammetry, UV‐vis, single‐crystal X‐ray diffraction and Mössbauer spectra. Electrochemical measurements showed no electronic coupling between the two terminal Fe units, However, the investigation results of the magnetic properties of the two‐electron oxidized complexes indicate the presence of moderate antiferromagnetic coupling across 18 Å distance.
Maternal high‐fat diet associated with LPS gestational injection induces hypothalamic inflammation and metabolic disorders in male Wistar rat offspring
Authors: Rocha‐Gomes Arthur , Escobar Teixeira Amanda , da Silva Alexandre Alves , da Silva Mariana Muniz , Santos Tatielly Roberta , Alvarenga e Castro Túlio Pereira , Lessa Mayara Rodrigues , Villela Daniel Campos , Riul Tania Regina , Leite Hércules Ribeiro 
Published: January 2024

AbstractMaternal high‐fat diet (HFD) is linked to obesity and inflammation, predisposing offspring to metabolic and nutritional disorders. Accordingly, elevated blood levels of lipopolysaccharide (LPS) are also related to inflammation and metabolic complications in the offspring. The aim of this study was to evaluate the effects of the association of maternal HFD (gestation and lactation) and the LPS injection (gestation) on metabolic, inflammatory, and redox status parameters in male adolescent offspring. Female pregnant Wistar rats received randomly a standard or an HFD during gestation and lactation. On gestation Days 8, 10, and 12, half of the females in each group were intraperitonially injected with LPS (0.1 mg.kg−1). After weaning, all offspring received a standard diet. The dams and part of the male offspring were evaluated at weaning (Postnatal Day [PND] 21; food intake and inflammatory parameters), while the rest of the male offspring were evaluated during adolescence (PND50; food intake, redox status, and inflammatory parameters). HFD dams showed during gestation a lower weight gain. After lactation, HFD and LPS+HFD dams reported higher fat mass accumulation and increased interleukin‐6 (IL‐6) blood levels. HFD and LPS+HFD offspring showed at weaning higher levels of fat mass, body weight, and body length, besides an increased in hypothalamic IL‐6 levels. Noteworthy, at PND50, the LPS+HFD offspring showed higher energy intake, fat mass, and hypothalamic IL‐6 levels, in addition to an increased sucrose preference. Therefore, LPS+HFD offspring presented a worsening in energy metabolism, which was probably due to persistent hypothalamic inflammation, and also have a predisposition for the consumption of sweet foods.
Caudate volume is prospectively associated with irritability in toddlerhood: A preliminary investigation
Authors: Dufford Alexander J. , MacNeill Leigha , Zhang Yudong , Nielsen Ashley , Smyser Christopher , Luby Joan L. , Rogers Cynthia E. , Norton Elizabeth , Wakschlag Lauren 
Published: January 2024

AbstractIrritability refers to the dispositional tendency to respond with anger and frustration to environmental challenges or limits, with both mood and behavioral elements. The dimensional spectrum of irritability is an RDoC‐informed transdiagnostic marker of psychopathology risk, specifically for the common and modifiable internalizing and externalizing disorders. Despite substantial interest in this robust developmentally based transdiagnostic indicator of psychopathology risk, its early brain markers are understudied. Here, we leveraged high‐quality, longitudinal behavioral phenotyping of irritability within an imaging substudy (n = 31) of toddlers, from the When to Worry (W2W) study. We examined prospective associations between volume in three subcortical regions implicated in irritability (the caudate, putamen, and amygdala) around the infants’ first birthday (Baseline) and the dimensional spectrum of observed irritability using the Disruptive Behavior Diagnostic Observation Schedule (DB‐DOS) around toddlers’ second birthday (Follow‐up). Both left (q = .04, FDR corrected) and right caudate volumes (q = .04, FDR corrected) at Baseline were negatively associated with observed irritability at Follow‐up. We did not find support for associations between putamen and amygdala volumes at Baseline and observed irritability at Follow‐up. These findings identify early prospective neuroanatomical correlates of toddler irritability and provide preliminary support for the caudate being one important brain region for further investigation regarding the early neural correlates of irritability.
Optimizing detectability of the endangered fan mussel using eDNA and ddPCR
Authors: Marques Virginie , Loot Géraldine , Blanchet Simon , Miaud Claude , Planes Serge , Peyran Claire , Arnal Véronique , Calvet Coralie , Pioch Sylvain , Manel Stéphanie 
Published: January 2024

AbstractSpatial and temporal monitoring of species threatened with extinction is of critical importance for conservation and ecosystem management. In the Mediterranean coast, the fan mussel (Pinna nobilis) is listed as critically endangered after suffering from a mass mortality event since 2016, leading to 100% mortality in most marine populations. Conventional monitoring for this macroinvertebrate is done using scuba, which is challenging in dense meadows or with low visibility. Here we developed an environmental DNA assay targeting the fan mussel and assessed the influence of several environmental parameters on the species detectability in situ. We developed and tested an eDNA molecular marker and collected 48 water samples in two sites at the Thau lagoon (France) with distinct fan mussel density, depths and during two seasons (summer and autumn). Our marker can amplify fan mussel DNA but lacks specificity since it also amplifies a conspecific species (Pinna rudis). We successfully amplified fan mussel DNA from in situ samples with 46 positive samples (out of 48) using ddPCR, although the DNA concentrations measured were low over almost all samples. Deeper sampling depth slightly increased DNA concentrations, but no seasonal effect was found. We highlight a putative spawning event on a single summer day with much higher DNA concentration compared to all other samples. We present an eDNA molecular assay able to detect the endangered fan mussel and provide guidelines to optimize the sampling protocol to maximize detectability. Effective and non‐invasive monitoring tools for endangered species are promising to monitor remaining populations and have the potential of ecological restoration or habitat recolonization following a mass mortality event.
Trust and monetary policy
Authors: De Grauwe Paul , Ji Yuemei 
Published: January 2024

AbstractWe analyze how trust affects the transmission of negative demand and supply shocks using a behavioral macroeconomic model. We define trust to have two dimensions: trust in the central bank's inflation target and trust in the central bank's capacity to stabilize the business cycle. We find, first, that when large negative shocks occur, the subsequent trajectories taken by output gap and inflation typically coalesce around a good and a bad trajectory. Second, these good and bad trajectories are correlated with movements in trust. In the bad trajectories, trust collapses, and in the good trajectories, it is not affected. This feature is stronger when a negative supply shock occurs than in the case of a negative demand shock. Third, initial conditions, in particular the initial state of inflation and output expectations, matter. Unfavorable initial expectations drive the economy into a bad trajectory, and favorable initial expectations produce good trajectories. Fourth, we analyze the sensitivity of our results with respect to the size of the shocks. Fifth, we derive implications of our results for our capacity of making forecasts about the effects of large demand and supply shocks.
The effects of social pensions on nutrition‐related health outcomes of the poor: Quasi‐experimental evidence from Peru
Authors: Bernal Noelia , Olivera Javier , Suhrcke Marc 
Published: January 2024

AbstractThis paper exploits the discontinuity around a welfare index of eligibility to assess the impact of Peru's social pension program Pension 65 on nutrition‐related health outcomes among elderly poor individuals. Overall, we find evidence of how a relatively inexpensive program can produce improvements in anemia and nutrition‐related mortality risk markers. The effects appear to be driven by plausible underlying mechanisms, including via improved nutritional quality as well as greater food expenditures and healthcare utilization. These positive effects are only modestly countered by tentative signs of an increased obesity risk among women in the short term (<2 years), but not beyond this term. As the program evolves further, policymakers need to confront the challenge of continuing to ensure the health benefits in terms of reducing nutritional deficits while avoiding potential undesirable side effects in terms of over‐nutrition in Peru. The findings may serve to highlight the wider benefits of similar pension policies for the poor also in other middle income countries, well beyond the immediate economic welfare effects that the policies have primarily been designed for.
Banking uncertainty and corporate financial constraints
Authors: Huynh Japan 
Published: January 2024

AbstractThis article investigates an essential channel through which uncertainty may harm the economy—firms' financing constraints. Unlike prior literature focusing on the aspect of aggregate economic policy uncertainty, we look into the dimension of disaggregate uncertainty in the banking system. Examining financial data of commercial banks and listed companies in Vietnam during 2008–2022, we document that banking uncertainty positively impacts corporate financial constraints. Moreover, we explore how firm‐specific and macroeconomic factors interact with the relationship between uncertainty and financing constraints. Our analysis indicates that this link is more pronounced for non‐state‐owned firms, firms with more intangible assets, and firms listed on the Hanoi stock exchange. Meanwhile, macro shocks, such as the financial crisis and the COVID‐19 pandemic can strengthen the effect of banking uncertainty on financing constraints. Finally, we examine the mechanisms through which banking uncertainty causes an increase in firms' financial constraints. We document that banking uncertainty exacerbates financial constraints by raising the cost of external financing, not by lowering firm performance.
Unusual case of maternal megacolon diagnosed by MRI during the antenatal period
Authors: Singh Madhulika , Singh Meenakshi Manoj Kumar , Dubey Sushmita , Rai Ashok Kumar , Rai Aakansha 
Published: January 2024

SynopsisPrimigravida at 14 weeks' gestation with expeditiously growing abdominal distension was revealed to be megacolon on MRI (suspicious case of adult Hirschsprung disease).
Risk and protective factors for substance use and media addictive behaviors in adolescents during the COVID‐19 pandemic
Authors: Shoshani Anat , Kor Ariel , Farbstein‐Yavin Shaked , Gvion Yari 
Published: January 2024

AbstractObjectiveThis study examined the long‐term effects of the COVID‐19 pandemic on adolescents' substance use, digital media use, and symptoms of internet, gaming, and social media addiction.MethodA nationally representative longitudinal cohort of 1665 Israeli teens and preteens, aged 9–16, completed questionnaires assessing substance use prevalence, daily screen time, symptoms of media addiction, and potential risk and protective factors. Data were collected before the pandemic (October 2019), after the second wave lockdown (November 2020), and after the fifth wave (April 2022) in Israel.ResultsThe analysis documented significant increases in substance use, daily screen time, and social media addiction indices over time. Gratitude, life satisfaction, positive emotions, future orientation, grit, and secure attachment emerged as significant protective factors. Sensation‐seeking, negative emotions, and mental health symptoms were identified as risk factors.ConclusionsThese findings highlight the importance of educational and public mental health services in addressing the pandemic's long‐term impact on the mental health and addictive behaviors of adolescents. They also emphasize the significance of enhancing protective factors and reducing risk factors to effectively mitigate substance and digital media abuse among adolescents.
Effect of femtosecond laser process parameters on the thermal denaturation degree of skin tissue
Authors: Huang Jun , Jia Mengshi , Xia Shengnan , Chen Yuxin , Xu Tongyu , Wu Jinjin , Li Xiaopeng , Wang Kehong , Rui Yunfeng 
Published: January 2024

AbstractThe influence of femtosecond laser parameters on the degree of thermal denaturation was studied experimentally. The relationship between the degree of thermal denaturation and the characteristic parameters of skin microstructure and the secondary structure of skin tissue proteins in characterizing the degree of thermal damage was analyzed. The results showed the interaction of laser power, laser power, and scanning speed had a significant effect on the degree of thermal denaturation; greater degrees of thermal denaturation were associated with larger second‐order moments of the texture angle of the skin microtissue and smaller entropy values and contrast, indicating a greater degree of thermal damage; and higher peak temperature, the lower peak intensity of Raman spectra, decrease in the percentage area of α‐helix fitted curves and increase in the percentage area of β‐sheet and β‐turn fitted curves indicate that the protein is denatured to a large extent that means thermal damage is large.