bluuebunny/crossref_metadata_2025 huggingface dataset:
Inhibited Passivation by Bioinspired Cell Membrane Zn Interface for Zn–Air Batteries with Extended Temperature Adaptability
Authors: Bai Yu , Deng Danni , Wang Jinxian , Wang Yuchao , Chen Yingbi , Zheng Huanran , Liu Mengjie , Zheng Xinran , Jiang Jiabi , Zheng Haitao , Yi Maozhong , Li Weijie , Fang Guozhao , Wang Dingsheng , Lei Yongpeng
Published: August 2024

Due to the slow dynamics of mass and charge transfer at Zn|electrolyte interface, the stable operation of Zn–air batteries (ZABs) is challenging, especially at low temperature. Herein, inspired by cell membrane, a hydrophilic‐hydrophobic dual modulated Zn|electrolyte interface is constructed. This amphiphilic design enables the quasi‐solid‐state (QSS) ZABs to display a long‐term cyclability of 180 h@50 mA cm−2 at 25 °C. Moreover, a record‐long time of 173 h@4 mA cm−2 at −60 °C is also achieved, which is almost threefolds of untreated QSS ZABs. Control experiments and (in situ) characterization reveal that the growth of insulating ZnO passivation layers is largely inhibited by tuned hydrophilic–hydrophobic behavior. Thus, the enhanced transfer dynamic of Zn2+ at Zn|electrolyte interface from 25 to −60 °C is attained. As an extension, the QSS Al‐air batteries (AABs) with bioinspired interface also show unprecedented discharge stability of 420 h@1 mA cm−2 at ‐40 °C, which is about two times of untreated QSS AABs. This bioinspired‐hydrophilic‐hydrophobic dual modulation strategy may provide a reference for energy transform and storage devices with broad temperature adaptability.
Iron‐Catalyzed Regioselective Borobenzylation of Vinyl Arenes
Authors: Meng Deyuan , Yun Jaesook
Published: August 2024

Herein, catalytic difunctionalization of vinyl arenes is reported using an iron salt as a catalyst without ligands. A series of substituted alkylboronic acid esters was obtained as a single regioisomer from vinyl arenes at 50 °C. This multicomponent protocol enabled the formation of C−C and C−B bonds to produce boroalkylated products in a single process. A non‐radical pathway is proposed for the reaction in contrast to the radical pathways of iron‐catalyzed hydroalkylation reactions. The organoboron compounds generated from this reaction were further utilized for diverse functional group conversions.
Giant Photodegradation Rate Enabled by Vertically Grown 1T/2H MoS2 Catalyst on Top of Silver Nanoparticles
Authors: Mouloua Driss , Rajput Nitul S , Lejeune Michael , Beruete Miguel , El Marssi Mimoun , El Khakani My Ali , Jouiad Mustapha
Published: August 2024

The exaltation of the photodegradation performance of dichalcogenide MoS2 grown on top of silver nanoparticles (Ag‐NPs) is reported on. The fabricated MoS2 nanosheets nucleate vertically from Ag‐NPs seeds, enabling the growth of both metallic and semiconductor phases 1T/2H‐MoS2. Findings reveal remarkable enhancement of the Raman scattering and an exceptional broadband optical absorption attributed to plasmonic effects induced by the presence of both metallic 1T‐MoS2 and Ag‐NPS at 2H‐MoS2 interfaces. To leverage this effect, photodegradation tests are conducted to remove methyl orange pollutant. Notably, results reveal a significant increase in photodegradation efficiency and rate constant, reaching up to 120% and 550% over pristine 2H‐MoS2, respectively. This finding underscores the role of Ag‐NPs and 1T‐MoS2 tandem to unlock the superior photodegradation properties of vertically aligned 2H‐MoS2 toward methyl orange, paving the way for the development of dichalcogenide‐based hybrid photocatalyst for wastewater treatment and environmental remediation.
Characterization of health and safety hazards of deconstruction activities
Authors: Bhattacharjee Kaushik , Chaudhary Shamita , Vishnoi Avni , Patel D. A. , Bugalia Nikhil
Published: August 2024

Background

Manual deconstruction—an alternative to mechanical demolition—is a crucial technique in the building industry that facilitates a circular economy for the built environment and achieves sustainable development goals (SDGs). However, the current body of literature lacks a thorough grasp of the OHS (occupational health and safety) hazards related to the deconstruction process. The current work closes this scholarly gap by outlining the deconstruction process as phases and sets of activities and highlighting potential health and safety hazards throughout different activities and phases.

Methods

The study uses numerous case studies and applies a descriptive case study technique to gather and analyze primary data from hundreds of photos and notes from over 40 field visits. The primary data are first used to prepare a comprehensive process map of deconstruction. Six construction safety experts and four industrial hygiene experts were then interviewed to identify and characterize health and safety hazards in images representative of the deconstruction activities.

Results

A taxonomy of OHS hazards for deconstruction was developed based on identifying 35 unique safety and 51 unique health hazards. Significant safety hazards in deconstruction activities include “struck‐by,” “trip, slip, and fall” hazards, and “lack of personal protective equipment.” Major health hazards include ergonomic concerns, respiratory diseases, and eye strain.

Discussion

The study highlights the occupational health and safety issues faced by the deconstruction trade with a granularity rarely covered in existing literature. The assessments can be helpful for OHS practitioners to identify potential health and safety improvements across various deconstruction phases.
Chromosomal translocation resolves a diagnostic odyssey for familial Ruvalcaba syndrome
Authors: Boyd Brenna M. , Fang He , Allingham‐Hawkins Diane , Fischer Gregory J. , Peng Siwu , Puryear Lauren , Liu Yajuan J. , Hisama Fuki M.
Published: August 2024

In 1971, Ruvalcaba and colleagues reported a new syndrome in two brothers with severe intellectual disability, dysmorphic features, osseous dysplasia, and overlapping features in two intellectually disabled female maternal first cousins. No genetic cause was identified. We report on updated genomic studies and clinical follow‐up in this family, including one of the original probands and their niece, whose own lifelong diagnostic odyssey had been unresolved for over four decades. Trio exome sequencing and copy number variant analysis in an original proband revealed an unbalanced chromosome translocation with a 3.18 Mb terminal deletion of 2q37.3qter and 6.54 Mb terminal duplication of 5q35.2qter. His unaffected sister had no evidence of a chromosomal imbalance, and her affected daughter has the reciprocal terminal duplication at 2q37.3qter and terminal deletion at 5q35.2qter. We used optical genome mapping and Hi‐C analysis to further characterize the t(2;5)(q37.3;q35.2) translocation as well as RNA‐seq analysis and genome‐wide methylation profiling to elucidate the functional consequences of the genomic alterations. Candidate genes for the observed phenotypes include HDAC4, KIF1A, D2HGDH, FLT4, HNRNPH1, and NSD1.
Atomically Dispersed Vanadium‐Induced Ru‐V Dual Active Sites Enable Exceptional Performance for Acidic Water Oxidation
Authors: Qin Qing , Li Zijian , Zhao Xuhao , Zhao Hongyan , Zhai Li , Gyu Kim Min , Cho Jaephil , Jang Haeseong , Liu Shangguo , Liu Xien
Published: August 2024

Regulating the catalytic reaction pathway to essentially break the activity/stability trade‐off that limits RuO2 and thus achieves exceptional stability and activity for the acidic oxygen evolution reaction (OER) is important yet challenging. Herein, we propose a novel strategy of incorporating atomically dispersed V species, including O‐bridged V dimers and V single atoms, into RuO2 lattices to trigger direct O−O radical coupling to release O2 without the generation of *OOH intermediates. Vn−RuO2 showed high activity with a low overpotential of 227 mV at 10 mA cm−2 and outstanding stability during a 1050 h test in acidic electrolyte. Operando spectroscopic studies and theoretical calculations revealed that compared with the V single atom‐doping case, the introduction of the V dimer into RuO2 further decreases the Ru‐V atomic distance and weakens the adsorption strength of the *O intermediate to the active V site, which supports the more energetically favorable oxygen radical coupling mechanism (OCM). Furthermore, the highly asymmetric Ru−O−V local structure stabilizes the surface Ru active center by lowering the valence state and increasing the resistance against overoxidation, which result in outstanding stability. This study provides insight into ways of increasing the intrinsic catalytic activity and stability of RuO2 by atomically dispersed species modification.
Positive and negative intergroup contact: Evidence of their interactions in a child sample
Authors: Trifiletti Elena , Shamloo Soraya Elizabeth , Burro Roberto , Vicentini Giada , Raccanello Daniela
Published: August 2024

Research has demonstrated that positive intergroup contact improves intergroup relations among children. However, empirical evidence about how positive and negative intergroup contact relates to intergroup outcomes at different ages is scant. By combining theories and empirical evidence in social and developmental psychology, this study aimed to examine positive and negative intergroup contact in a sample of N = 394, 9 and 12‐year‐old Italian children (females and males). We expected to find interactive effects of positive and negative intergroup contact on outgroup trust and behavioural intentions. Furthermore, for both types of contact, we predicted that associations with intergroup outcomes (outgroup trust, behavioural intentions) would be stronger among older than younger children. Results provided support for the interactive effects of positive and negative intergroup contact (bs ≥ .08, ps ≤ .08, interaction coefficients), but not for age‐related differences. Negative intergroup contact facilitated the effects of positive intergroup contact and positive intergroup contact buffered the effects of negative intergroup contact. These findings suggest that intergroup relations in childhood can be improved by creating opportunities for positive intergroup contact in educational and social settings.
An evaluation of the role of social identity processes for enhancing health outcomes within UK‐based social prescribing initiatives designed to increase social connection and reduce loneliness: A systematic review
Authors: Staras Chase O. , Wakefield Juliet R. H. , McDermott Daragh T. , Jones Bethany A.
Published: August 2024

The UK's National Health Service has introduced Social Prescribing initiatives to tackle loneliness and ill‐health, yet it lacks a theoretical foundation and evidence base for Social Prescribing's effectiveness. Recent research applies the Social Identity Approach to Health (SIAH) to explain Social Prescribing's health benefits, emphasising how social connection unlocks health‐enhancing psychological mechanisms. This systematic review therefore aims to assess UK‐based Social Prescribing programmes designed to boost social connection and alleviate loneliness, examining programme efficacy and the role of SIAH processes in health outcomes. Following PRISMA guidelines, a narrative synthesis of articles published from May 5, 2006 (when social prescribing was first introduced in the NHS), to April 8, 2024, was conducted, and their quality assessed using CONSORT‐SPI (2018). Of these programmes, 10 employed a mixed‐methods design, 8 qualitative and 1 quantitative service evaluation, totalling 3,298 participants. Results indicate that Social Prescribing's psychological value lies in quality rather than quantity of social connections, with meaningful connections fostering shared identity, perceived support and self‐efficacy, the latter of which sustains social engagement post‐programme. The SIAH was a useful tool for mapping mixed‐methods findings onto a common theoretical framework to highlight these key proponents. Overall, this review underscores the importance of SIAH‐informed Social Prescribing interventions in enhancing social connectedness, reducing loneliness, and promoting overall health. Please refer to the Supplementary Material section to find this article's Community and Social Impact Statement.
Optimization of Extraction Conditions for Biological Attributes of Newly Developed NARC‐G1 Garlic Using Response Surface Methodology and Its GC‐MS Characterization
Authors: Ullah Sami , Fayyaz ur Rehman Muhammad
Published: August 2024

The present paper is a comprehensive study on the optimization of ultrasonic assisted extraction and characterization of valued components from the newly developed garlic cultivar NARC‐G1. The response surface methodology was employed to optimize the extraction time, solvent‐to‐solid ratio and extraction temperature, for optimal total phenolic contents (TPC), DPPH radical scavenging activity, α‐amylase inhibition, and α‐glucosidase inhibition. Under the optimized conditions (23 min extraction time, 60 °C temperature, and 39 : 1 solvent‐to‐solute ratio) the optimal TPC (13.76 mg GAE/g), DPPH radical scavenging activity (62.76 %), α‐amylase inhibition (71.43 %), and α‐glucosidase inhibition (79.43 %) were obtained. Significant correlations were observed between actual values and predicted values for the selected responses. Gas chromatography‐mass spectrometry (GC‐MS), revealed 26 high‐value bioactives, with diallyl disulphide being the most abundant (16.22 %), followed by 2,3‐dihydro‐3,5‐dihydroxy‐6‐methyl, 4H‐pyran‐4‐one and 5‐Hydroxymethylfurfural. Additionally, in silico investigation indicated that stigmasterol, arbutin, squalene, α‐tocopherol and linoleic acid were responsible for antihyperglycemic potential. Moreover, antimicrobial activity revealed that S. mutans (19.25±1.98 mm) and L. monocytogenes (19.34±2.04 mm) were the most sensitive, while P. aeruginosa was the least sensitive bacterial strains against the optimized NARC‐G1 garlic extract. This research effectively explains the optimal recovery of high‐valued components from NARC‐G1 and may contribute to nutra‐pharmaceutical and functional food developments.
Suaedamas A‐D: Four New Compounds from the Aerial Parts of Suaeda maritima with Inhibition of NO Production Activity
Authors: Trang Bui Thi Nha , Anh Bui Thi Mai , Mai Nguyen Thi , Cuc Nguyen Thi , Huyen Le Thi , Nga Nhu Thi Hang , Kiem Phan Van , Tai Bui Huu
Published: August 2024

Four new compounds, suaedamas A–D (1–4), and seven known ones (5–11) were isolated from the aerial parts of Suaeda maritima. Their chemical structures were evaluated by the IR, HR‐ESI‐MS, 1D‐, and 2D‐NMR, experimental and calculated ECD spectra. Compounds 1–6 inhibited nitric oxide production in LPS activated RAW 264.7 cells with IC50 values ranging from 29.3 to 85.5 μM, compared to that of the positive control compound, dexamethasone, which showed IC50 value of 13.4 μM.
New Cytotoxic Sesquiterpene Lactones from the Leaves of Tithonia Diversifolia and their Apoptosis Effect Evaluation in KB Cancer Cells
Authors: Tran Minh The , Do Thi Quynh , Phi Thi Dao , Nguyen Thi Thu Ha , Litaudon Marc , Tran Thu Huong , Nguyen Thuy Linh , Pham Van Cuong , Doan Thi Mai Huong
Published: August 2024

From the leaves of Tithonia diversifolia, nine sesquiterpenoids (1–9), including two new ones (tagitinin J (1) and tagitinin K (2)) were isolated and structurally determined. Their chemical structures were elucidated by extensive analyses of the HRESIMS and NMR spectral data, as well as comparison with the literature. All of the isolated compounds (except compounds 7–9) significantly exhibited cytotoxic activity against four human cancer cell lines (KB, HepG2, A549 and MCF7), with IC50 values ranging from 0.29–17.0 μM, which were in the same range as the positive control ellipticine or even lower. Further, the apoptosis induction effects of two new compounds 1 and 2 were also investigated and reported. While compound 2 did not induce the apoptosis in KB cells at test concentrations, compound 1 was found to possess anti‐proliferative activity through concentration‐dependently inducing cell cycle arrest at S phase, morphological changes, activation of caspase 3, and an increase in the early‐stage apoptosis of KB cells at a concentration of 7.26 μM.
The humoral immune landscape in Parkinson's disease: Unraveling antibody and B cell changes
Authors: Baridjavadi Zahra , Mahmoudi Mahmoud , Abdollahi Narges , Ebadpour Negar , mollazadeh Samaneh , Haghmorad Dariush , Esmaeili Seyed‐Alireza
Published: August 2024

Parkinson's disease (PD) is a complex neurodegenerative disorder characterized by the accumulation of α‐synuclein (α‐syn) in the brain and progressive loss of dopaminergic neurons in the substantia nigra (SN) region of the brain. Although the role of neuroinflammation and cellular immunity in PD has been extensively studied, the involvement of humoral immunity mediated by antibodies and B cells has received less attention. This article provides a comprehensive review of the current understanding of humoral immunity in PD. Here, we discuss alterations in B cells in PD, including changes in their number and phenotype. Evidence mostly indicates a decrease in the quantity of B cells in PD, accompanied by a shift in the population from naïve to memory cells. Furthermore, the existence of autoantibodies that target several antigens in PD has been investigated (i.e., anti‐α‐syn autoantibodies, anti‐glial‐derived antigen antibodies, anti‐Tau antibodies, antineuromelanin antibodies, and antibodies against the renin‐angiotensin system). Several autoantibodies are generated in PD, which may either provide protection or have harmful effects on disease progression. Furthermore, we have reviewed studies focusing on the utilization of antibodies as a potential treatment for PD, both in animal and clinical trials. This review sheds light on the intricate interplay between antibodies and the pathological processes in PD, including complement system activation.
A 13‐year‐old soccer player presenting with a Morel‐Lavallee lesion of the knee: A case report and review of literature
Authors: Williams Nicholas R. , Guzman Alvarho J. , Waldron Patrick , Vallelanes Ethan , Cheng Samantha J. , Chen James L.
Published: August 2024

Key Clinical Message

Morel‐Lavallee lesions are uncommon injuries and there is a lack of data to support what the most effective management is. In the case of a young athlete with a small lesion, we propose that conservative treatment with rest and close follow up is appropriate.
Emergence of acute quadriparesis in a young patient following myocardial infarction. A case report
Authors: Daneshyar Sajjad , Khazaei Mojtaba , Nazifi Mozhgan
Published: August 2024

Key Clinical Message

Cerebrovascular events are closely related to cardiac events. Chronic inflammatory diseases, such as rheumatoid arthritis (RA), increase the risk of cardiovascular and cerebrovascular stroke. The link between RA, myocardial infarction, and resulting neurological issues highlights the case's complexity, stressing the need for a comprehensive, interdisciplinary medical approach.
Severe hypokalemia mimicking classical electrocardiographic pattern of left Main coronary artery disease: A case report and a focused review of the literature
Authors: Humberto Vásquez Lozano Sergio , Orlando Porras Bueno Cristian , Fernando Ruiz Hernández Gabriel , Lucero Olarte Jurado Mabel , Rueda Maria Paula Blanco
Published: August 2024

Key Clinical Message

Several electrocardiographic alterations due to hypokalemia have been described, but the electrocardiographic presentation meeting criteria for occlusion of the left main coronary artery is very rare. We describe a case of hypokalemia simulating it.
A case of porokeratosis with a variety of morphological manifestations
Authors: Zhang Xiang , Shi Weiwei , Wang Jun , Zhang Ruzhi
Published: August 2024

Key Clinical Message

This case illustrates the clinical heterogeneity of porokeratosis (PK), with a patient presenting with both disseminated superficial actinic PK‐like facial lesions and PK of Mibelli‐like lesions on the buttocks and lower limbs. Ultraviolet exposure, infection, and immunosuppression may contribute to the manifestation of multiple clinical forms in a single patient. Close monitoring for potential malignant transformation is essential, particularly in elderly patients with long disease duration and a history of oncological conditions.
Catalytic Synthesis of Fluoroalkyl Ketones
Authors: Li Shun‐Xi , Du Hai‐Wu , Li Yu‐Long , Shu Wei
Published: August 2024

Fluoroalkyl ketones are a class of structural motifs which are ubiquitous in bioactive molecules, and serve as synthons for diverse value‐added fluorine‐containing targets. The presence of fluorine significantly alters the lipophilicity and bioactivity of alkyl ketones as well as imposes additional challenges on the synthesis of fluoroalkyl ketones. Traditional methods for the synthesis of fluoroalkyl ketones heavily rely on multiple‐step manipulations which require stoichiometric reagents and suffer from low efficiency. Thus, the development of synthesizing fluoroalkyl ketones enabled by catalytic methods is highly valuable yet challenging. This Concept summarizes the recent renaissance in developing catalytic methods for the synthesis of fluoroalkyl ketones with diverse substitution patterns from different fluorine‐containing precursors. In addition, further efforts for catalytic method development are also discussed.
In‐Situ Electrolyte for Electrosynthesis: Scalable Anodically‐Enabled One‐Pot Sequence from Aldehyde to Isoxazol(in)es
Authors: Al‐Romema Abdulaziz A. , Xia Honglin , Mayrhofer Karl J. J. , Tsogoeva Svetlana B. , Nikolaienko Pavlo
Published: August 2024

Electrochemical transformations are considered a green alternative to classical redox chemistry as it eliminates the necessity for toxic and waste producing redox reagents. Typical electrochemical reactions require the addition of a supporting electrolyte – an ionic compound to facilitate reaction medium conductivity. However, this is often accompanied by an increase in the amount of produced waste. Here, we report an “in‐situ electrolyte” concept for facile, transition‐metal‐free, additive‐free one‐pot electrochemical preparation of isoxazol(in)es, important scaffolds for biologically active natural and synthetic molecules, from the respective aldehydes. The protocol utilizes no halogenated solvents and no external oxidants, while salt side‐products provide the ionic conductivity necessary for the electrosynthesis. The electrolysis is performed in an undivided cell, using the state‐of‐the‐art electrodes for the chlor‐alkali industry dimensionally stable and scalable mixed metal oxide anode and platinized titanium cathode of high durability. The cascade transformation comprises the condensation of aldehyde to oxime followed by its anodic oxidation and subsequent intra‐ and/or intermolecular [3+2] cycloadditions with an appropriate dipolarophile. Chemical yields up to 97 %, and good Faradaic efficiency, scalability, and stability are observed for most substrates in a broad scope.
Assay for Characterizing Adsorption‐Properties of Surfaces (APS)
Authors: Siebels Bente , Moritz Manuela , Hübler Diana , Gocke Antonia , Riedner Maria , Voß Hannah , Schlüter Hartmut
Published: August 2024

Analytes, from sample preparation, until entering an analytical instrument, are prone to adsorb to surfaces, driven by the chemical properties of the surface and the liquids they are dissolved in. This problem can be addressed with internal standards when a single or few known analytes are quantified that are usually not available in omics. However, minimal to no loss of analytes is the aim. Here, we present a novel assay for qualifying and quantifying interactions responsible for adsorption of molecules to surfaces (APS) by using LC–MS/MS‐based differential quantitative analysis. To reflect a broad range of chemical interactions with surfaces, a reference mixture of thousands of tryptic peptides, with known compositions was selected, representing a variety of different chemical characteristics. The assay was tested by investigating the adsorption properties of several different vials with different surface chemistries. A significant number of hydrophobic peptides adsorbed to conventional polypropylene vials. In contrast, only few peptides adsorbed to polypropylene vials, assigned as low‐protein‐binding. The highest number of peptides adsorbed to glass vials driven by electrostatic interactions. In summary, the new assay is suitable to characterize adsorption properties of different surfaces and to approximate the loss of analytes during sample preparation.
Targeted Therapy With Vemurafenib in Brazilian Children With Refractory Langerhans Cell Histiocytosis: Two Case Reports and Review of Literature
Authors: Silva Klerize Anecely de Souza , Magalhães Isis Maria Quezado Soares , Benincasa Daniela Elaine Roth , Cecconello Daiane Keller , Michalowski Mariana Bohns
Published: August 2024

Background

Langerhans cell histiocytosis (LCH) is a clonal myeloid neoplasm with inflammatory component. Refractory disease is a challenge, but vemurafenib has emerged as a therapeutic option. We will delineate the cases of two Brazilian children suffering from refractory LCH with a positive response to vemurafenib.

Cases

Both cases had a diagnosis of multisystem disease with involvement of organs at risk and had not responded to standard and second‐line treatment. After refractoriness to classic treatment regimens, the BRAF mutation was investigated and found to be positive in both patients, and target therapy with vemurafenib was sought. The first case has been using vemurafenib for about 2 years and the second case has been using it for about 3 years, having had an attempt to suspend the medication after concomitant use with maintenance therapy. However, the disease returned 4 months after stopping the medication. Fortunately, the disease returned to remission status after the medication was reintroduced.

Conclusion

These cases represent the first reported instances of off‐label vemurafenib use in Brazil for the treatment of LCH and both patients have demonstrated excellent responses to the medication. However, the long‐term side effects are unknown in children, and prospective studies are needed. In addition, there is a lack of epidemiological data on histiocytosis in Brazil and studies evaluating the budgetary impact of incorporating BRAF mutation research and the use of vemurafenib into the public health system. These reports could be a starting point.
Porous Pd‐Loaded IRMOF‐9 as Highly Efficient Recyclable Material Towards the Reduction of Nitroaromatics in Aqueous Media
Authors: Rimi  , Kumar Ravi , Uttam Bhawna
Published: August 2024

Nitroaromatic compounds (NACs) cause severe hazardous impacts on human health as well as on the environment. Therefore, there is dire need to develop a robust material to reduce the toxicity of these organic pollutants. In this regard, our group developed a series of porous MOF materials viz., Pdx@IRMOF‐9 (x=2 %, 5 % and 10 %) by loading different concentration of Pd(II) on IRMOF‐9 and explored them towards reduction of different nitroaromatic compounds. Pd10%@IRMOF‐9showed ~30 % greater efficiency for the reduction of 4‐NP as compared to Pd2%@IRMOF‐9. Pd10%@IRMOF‐9showed excellent reduction ability (>85 %) towards 4‐NP, 2‐NP, 2‐NA, 3‐NA and 2,4‐DNPH. The kinetic studies indicates that the reduction follows the pseudo‐first‐order kinetics. Moreover, the rate constant value for reduction of 3‐NA was ~9 times higher than that of 2‐NP. Based on the kinetic parameters, the t1/2 values for all the nitroaromatics have been calculated. The kinetic parameters, Km and Vmax have been calculated from double reciprocal Lineweaver‐Burk plot and found to be 65.984 μM and 116×10−6 Mmin−1 respectively. Pd10%@IRMOF‐9showed excellent recyclability towards the reduction of 4‐NP for few consecutive cycles without any remarkable loss in its activity. Thus, highly efficient, porous and robust material for the reduction of nitroaromatic compounds in aqueous media have been demonstrated.
Synthesis and Characterization of Thiol‐Ene Networks Derived from Levoglucosenone
Authors: Timilsina Mahesh Prasad , Stanfield Melissa K. , Smith Jason A. , Thickett Stuart C.
Published: August 2024

Levoglucosenone (LGO), a renewable compound obtained from cellulose biomass, has been utilized to prepare novel monomers bearing alkene functional groups. These monomer derivatives of LGO were subsequently cured via ultraviolet (UV)‐initiated radical thiol‐ene “click” chemistry with commercially available multifunctional thiols to obtain colourless, optically transparent cross‐linked thermosets. The monomers prepared in this work are unique due to utilising the internal double bond of the LGO ring during polymerization as part of the cross‐linked network. The thermal and mechanical properties along with the degradation of thermosets containing both ether and ester linkages within the LGO monomers were studied. These thermosets had tensile strengths of 1.3–3.3 MPa, glass transition temperatures between 23.2 and 27.2 °C, and good thermal stability of up to 300 °C.
Superprotonic Conductivity by Synergistic Blending of Coordination Polymers with Organic Polymers: Fabrication of Durable and Flexible Proton Exchange Membranes
Authors: Dawn Mouli Das , Roy Sambit , Garai Abhijit , Banerjee Susanta , Biradha Kumar
Published: August 2024

Creation of an efficient and cost‐effective proton exchange membrane (PEM) has emerged as a propitious solution to address the challenges of renewable energy development. Coordination polymers (CPs) have garnered significant interest due to their multifunctional applications and moldability, along with long‐range order. To leverage the potential of CPs in fuel cells, it is essential to integrate microcrystalline CPs into organic polymers to prepare membranes and avoid grain boundary issues. In this study, we designed and synthesized CPs containing imidazole and sulfonate moieties via gel‐to‐crystal transformation. The integration of CPs into the PVDF‐PVP matrix resulted in superprotonic conductivity in the order of 10−2 S cm−1 at room temperature (30 °C) and 98 % RH. The proton conductivity achieved with CP‐integrated composite membrane was 4.69×10−2 S cm−1 at 80 °C and 98 % RH, the highest among all CP/MOF‐integrated PVDF‐PVP membranes under hydrous conditions. The excellent compatibility of CPs with PVDF‐PVP produced highly flexible membranes with superior mechanical, chemical, and thermal stability. About 25 times higher proton conductivity value was achieved with membrane, compared to intrinsic CPs, at RT and 98 % RH. Thus, we present a cost‐effective CP‐integrated mixed‐matrix membrane with superprotonic conductivity and long‐term durability for cutting‐edge fuel cell development.
Selective C‐Methylenation of N‐Unsubstituted Indoles Using CO2 Under NaBH4/I2 System
Authors: Guo Zhiqiang , Wu Jinglong , Wei Xuehong , Xi Chanjuan
Published: August 2024

The selective C‐methylenation of N‐unsubstituted indoles using CO2 as the C1 source to access diindolylmethane (DIM) and its derivatives is described. This reaction provides a novel method for four‐electron reductive functionalization of CO2 with N‐unsubstituted indoles via formation of C−CH2−C bonds, and a new access to molecular structures.
Mutation pressure mediates a pattern of substitution rates with latitude and climate in carnivores
Authors: Zhao Chao , Liu Guangshuai , Yang Xiufeng , Wang Xibao , Zhou Shengyang , Liu Zhao , Liu Kangning , Zhang Honghai
Published: August 2024

The evolutionary patterns of the mitochondrial genome are influenced by both adaptive and nonadaptive forces, with their contributions varying among taxa. There appears to be a correlation linking mutagenesis and latitude, which could be due to differences in metabolic rates. These discrepancies in metabolic rates exhibit a positive connection with mutation pressure. On this basis, we hypothesise that nonadaptive forces play a role in the differences in mutation rates observed along latitudinal gradients. In this study, we selected widely distributed carnivores as representatives of mammals to test our hypothesis. We examined the correlations between the dN/dS ratio (ω), as well as the substitution rates (dS and dN), of 13 PCGs in the mtDNA of 122 carnivores, and the latitude and climatic factors. We found that taxa distributed in higher latitudes tend to have higher substitution rates, but not ω values indicating selective pressure. Notably, dN shows a strong positive correlation with dS, although dS is primarily influenced by mutation pressure, while dN is also influenced by effective population size (Ne). Phylogenetic generalised least squares (PGLS) regression analyses showed that both substitution rates were correlated with climatic factors representing the temperature, precipitation and variability of climate. Based on our findings, we propose that the mutations are primarily influenced by nonadaptive forces (mutation pressure). This forms the fundamental premise for natural selection and speciation. Moreover, the correlation between substitution rates and latitudinal distribution and climate, which are outcomes of nonadaptive factors, can aid in comprehending the global distribution of species diversity.
Internal transcribed spacer as effective molecular marker for the detection of natural hybridization between the bivalves Pinna nobilis and Pinna rudis
Authors: Catanese Gaetano , Vázquez‐Luis Maite , Giacobbe Salvatore , García‐March José Rafael , Zotou Maria , Patricia Prado , Papadakis Orestis , Tena‐Medialdea José , Katsanevakis Stelios , Grau Amalia
Published: August 2024

The Pinna nobilis, a Mediterranean mollusc, has suffered population declines due to a massive mortality event associated with various factors including the parasite Haplosporidium pinnae. Some populations show resilience, possibly due to local environmental conditions. In this study, a molecular multiplex PCR method was developed using species‐specific primers targeting Internal Transcribed Spacer (ITS) regions of P. nobilis and P. rudis, allowing accurate species identification and hybrid detection. Samples from Mediterranean areas were analysed, including putative hybrids and individuals from five other bivalve species. DNA was isolated, ITS regions were amplified and sequenced, and phylogenetic analyses confirmed species differentiation and primer specificity. The multiplex‐PCR successfully identified P. nobilis, P. rudis, and their hybrids based on distinct amplicon patterns. This study highlights the value of molecular tools in species conservation, especially for monitoring and managing hybridization, supporting effective biodiversity conservation strategies.
Synthesis and Anticancer Properties of Heterobimetallic Fe(II)/Pd(II) Complexes Bearing Different Butadienyl Fragments
Authors: Bortolamiol Enrica , Dalla Pozza Maria , Demitri Nicola , Rizzolio Flavio , Visentin Fabiano , Gasser Gilles , Scattolin Thomas
Published: August 2024

In this work, we describe the synthesis of heterobimetallic Fe(II)/Pd(II) complexes bearing different halides and halide‐substituted butadienyl ligands. The synthetic approach involves the preparation of suitable Pd(II)‐butadienyl precursors containing a thioquinoline moiety, followed by the substitution of this relatively labile ligand with dppf (dppf=1,1′‐bis(diphenylphosphino)ferrocene). With the exception of complexes containing at least one iodine atom, all compounds were synthesized in high yields and purity, and thoroughly characterized using spectroscopic and diffractometric methods. The investigation of the antiproliferative activity of the synthesized organometallic complexes against ovarian and breast cancer cell lines revealed that all compounds exhibit noteworthy cytotoxicity, with IC50 values in the micromolar range and generally comparable to those of cisplatin. Interestingly, significant differences of cytotoxicity among the analysed compounds were observed in the case of MRC‐5 normal cells. Of particular interest is the dichloride derivative 3 a, which is essentially inactive towards non‐cancerous cells (IC50>100 μM), thus demonstrating promising in vitro selectivity that we believe warrants further investigation in the future.
An Electrochemical Sensor Based on 3D Graphene‐Cyclodextrin Nanohybrid for Enhanced Sensitivity Detection of Nitroaromatic Compounds
Authors: Di Ziao , Zhang Yu , Ding Zuhang , Huang Jiayu , Mao Lujia , Wei Hongjun , Zhao Jin
Published: August 2024

This study presents an electrochemical sensor for sensitive detection of nitroaromatic compounds using a three‐dimensional (3D) porous graphene with polyoxypropylene supported reduced graphene oxide (PEA‐RGO) and embedded β‐cyclodextrins (β‐CD). First, PEA‐RGO was synthesized by the condensation reaction between graphene oxide (GO) and amino‐terminated polyoxypropylene (PEA), followed by hydrazine hydrate reduction. Then, β‐CD was embedded into the porous of the above 3D graphene to obtain PEA‐RGO/β‐CD nanohybrid. Various characterization techniques, such as microscopy imaging, infrared spectrometry, thermal analysis and electrochemical measurements, were employed to confirm the successful synthesis and unique 3D architecture structure of PEA‐RGO/β‐CD. Afterwards, the glassy carbon electrode (GCE) was modified by PEA‐RGO/β‐CD, and its electrochemical detection performances were investigated for detecting nitroaromatic compounds, including nitrobenzene (NB), 2‐nitroaniline (2‐NA), 2‐chloronitrobenzene (2‐NCB), and 2‐nitrophenol (2‐NP). The results of electrochemical measurements exhibited relative higher sensitivities (1.88 μA/μM/cm2 for NB, 2.13 μA/μM/cm2 for 2‐NA, 2.35 μA/μM/cm2 for 2‐NP, 0.83 μA/μM/cm2 for 2‐NCB, respectively) and lower limits of detection (LOD) (39.4 nM for NB, 44.6 nM for 2‐NA, 75.6 nM for 2‐NP, 69.6 nM for 2‐NCB, respectively). Additionally, the proposed sensor was also applied in detection in real samples with recovery range of 88.13%–109.52 %. The enhanced detecting performances can be attributed to the synergistic effect of the high conductivity from RGO, recognition capabilities from β‐CD, and excellent properties from 3D structure. The present work would provide a robust tool for environmental monitoring and the detection of nitroaromatic pollutants.
Predicting the Gas Storage Capacity in Shale Formations Using the Extreme Gradient Boosting Decision Trees Method
Authors: Wang Jiaheng , Li Nong , Huo Xiangyu , Yang Mingli , Zhang Li
Published: August 2024

Accurate shale gas reserves estimation is essential for development. Existing machine learning (ML) models for predicting gas isothermal adsorption are limited by small datasets and lack verified generalization. We constructed an “original dataset” containing 2112 data points from 11 measurements on samples from 8 formations in 3 countries to develop ML‐based prediction models. Similar to previous ML models, total organic matter, pressure, and temperature are characterized as the three most significant features using the mean impurity method. In contrast to previous ML models, the study reveals that these three features are inadequate to be used to make reasonable predictions for the datasets from the measurements different from those used to train the models. Instead, the extreme gradient boosting decision trees (XGBoost) model with two more features (specific surface area and moisture) exhibits good robustness, generalization, and precision in the prediction of gas isothermal adsorption. Overall, An XGBoost model with optimal input features is developed in this work, which exhibits both good performance in gas adsorption prediction and good potential for the estimation of gas storage in shale gas development.
Mantle dynamics of the stagnating slab: A case study of Shandong Peninsula and adjacent areas
Authors: Ba Kailun , Xue Haimeng , Liu Lin , Huang Jianping , Qu Junhao
Published: August 2024

The Shandong Peninsula is located in the eastern part of the North China Craton (NCC). Influenced by the collision between the North and South China blocks and the subduction of the Pacific Plate, the tectonic evolution process is highly complex. Previous studies have proposed that the thick cratonic root beneath the eastern NCC has been destructed. To better understand the relationship between the craton reactivation and the deep subduction, more constraints on the topography variations of the mantle transition zone (MTZ) discontinuities are required. In this study, we stacked 9073 P‐to‐S receiver functions calculated from 129 broadband seismic stations to image the depth variations of the MTZ discontinuities beneath the Shandong Peninsula and its adjacent area. To decrease the influence of velocity anomaly above the MTZ discontinuities, we converted the apparent depths into corrected depth using regional and global 3D velocity models. The apparent depth of the 410‐km discontinuity exhibits a depression of approximately 6 km, which normalizes after velocity correction. This implies the existence of the low‐velocity anomaly in the upper mantle, possibly caused by slab dehydration and water infiltration into the upper mantle. The significant depression of the 660‐km discontinuity indicated the presence of the cold Pacific slab stagnating at the base of the MTZ. The gradual westward depression of the 660‐km discontinuity by 50 km could provide evidence for the sinking of the western margin of the flat‐lying subducting Pacific slab in the MTZ beneath the Shandong Peninsula.
Magnetostratigraphy and rock magnetic studies on the Cretaceous‐Paleogene transition strata along the Um Sohryngkew River, Therriaghat, Meghalaya, India
Authors: Nag Debarati , Sangode Satish J. , Singh Sarvendra P. , Uddandam Prem R. , Choudhuri Adrita , Phartiyal Binita , Prasad Vandana
Published: August 2024

A combination of magnetic polarity and rock magnetic analysis on the well‐documented section of the Um Sohryngkew River (USR) in the south Shillong Plateau, NE India, produced a sharp reversal marking the C29r‐C29n geomagnetic polarity transition at approximately 65.688 Ma. The rock magnetic studies indicate ferrimagnetic dominant mineralogy with abundance of SSD grains, with an anomalous peak in susceptibility coinciding with Ir‐rich limonitic layer. The magnetic reversal occurs precisely 61 m above the Ir‐rich distinct in situ limonitic layer, indicating that the C29r‐C29n geomagnetic reversal post‐dates the widely accepted Ir‐anomaly based K‐Pg boundary by approximately 355 Ka. Furthermore, the rock magnetic studies indicate its frequency dependence coinciding with the Ir‐rich limonitic layer suggesting a possible dust/aerosol source, while akaganéite is reported from the interval approximately 1 m below peak susceptibility, indicating signature of Deccan volcanism. This study infers the completeness of the USR section with a high rate of sedimentation of approximately 17 cm/ka among the marine K‐Pg boundary sections in the world.
All‐body concept and quantified limits of cooperativity and related effects in homodromic cyclic water clusters from a molecular‐wide and electron density‐based approach
Authors: Cukrowski Ignacy , Zaaiman Stéfan , Hussain Shahnawaz , de Lange Jurgens H.
Published: August 2024

We strongly advocate distinguishing cooperativity from cooperativity‐induced effects. From the MOWeD‐based approach, the origin of all‐body cooperativity is synonymous with physics‐ and quantum‐based processes of electron (e) delocalization throughout water clusters. To this effect, over 10 atom‐pairs contribute to the total e‐density at a BCP(H,O) between water molecules in a tetramer. Intermolecular all‐body e‐delocalization, that is, cooperativity, is an energy‐minimizing process that fully explains non‐additive increase in stability of a water molecule in clusters with an increase in their size. A non‐linear change in cooperativity and cooperativity‐induced effects, such as (i) structural (e.g., a change in d(O,O)) or topological intra‐ and intermolecular properties in water clusters (e.g., electron density or potential energy density at bond critical points) is theoretically reproduced by the proposed expression. It predicted the limiting value of delocalized electrons by a H2O molecule in homodromic cyclic clusters to be 1.58e. O‐atoms provide the vast majority of electrons that “travel throughout a cluster predominantly on a privileged exchange quantum density highway” (⋅⋅⋅O–H⋅⋅⋅O–H⋅⋅⋅O–H⋅⋅⋅) using Bader's classical bond paths as density bridges linking water molecules. There are, however, additional electron exchange channels that are not seen on molecular graphs as bond paths. A 3D visual representation of the “privileged” and “additional” exchange channels as well as detailed intra‐ and inter‐molecular patterns of e‐sharing and (de)localizing is presented. The energy stabilizing contribution made by three O‐atoms of neighboring water molecules was found to be large (−597 kcal/mol in cyclic hexamer) and 5 times more significant than that of a classical O–H⋅⋅⋅O intermolecular H‐bond.
Impact of oxytosis on the cross‐talk of mTORC with mitochondrial proteins in drug‐resistant cancer stem cells
Authors: Pandrangi Santhi L. , Chittineedi Prasanthi , Manthari Ram K. , Suhruth Balaji
Published: August 2024

By delivering the environmental inputs to transport nutrients and growth factors, Mechanistic Target of Rapamycin (mTOR) plays a significant role in the growth and metabolism of eukaryotic cells through the regulation of numerous elementary cellular processes such as autophagy, protein synthesis, via translation of mitochondrial protein transcription factor A mitochondrial, mitochondrial ribosomal proteins, and mitochondrial respiratory complexes I &V that are encoded in the nucleus with the help of translation initiation factor 4E–BP. These mitochondrial proteins are involved in cell signaling to regulate proper cell growth, proliferation, and death which are essential for tumor growth and proliferation. This suggests that tumor cells are dependent on mTORC1 for various metabolic pathways. However, this crucial regulator is activated and regulated by calcium homeostasis. Mounting evidence suggests the role of calcium ions in regulating mitochondrial enzymes and proteins. Hence, disrupting calcium homeostasis leads to calcium‐dependent cell death called “Oxytosis” through hampering the expression of various mitochondrial proteins. “Oxytosis” is a novel non‐apoptotic cell death characterized by glutamate cytotoxicity and ferritin degradation. The present review focuses on the crosstalk between mTORC1 and mitochondrial proteins in the cancer pathophysiology and the impact of calcium ions on disrupting mTORC1 leading to the induction of “Oxytosis.”
Anatomical biliary reconstruction as an ultimum refugium for selective cases—History and current state of knowledge
Authors: Sevcik Jan , Massaro Maria Stefania , Palek Richard , Moulisova Vladimira , Liska Vaclav
Published: August 2024

Reconstruction of extrahepatic bile ducts is a staple procedure of HPB surgery. The current standard for most cases is a nonanatomical bilioenteric reconstruction, a satisfactory option for the majority of patients. However, it cannot be used for a small number of selective cases (short bowel syndrome, severe abdominal adhesions), where an anatomical reconstruction with or without an interponate can be used. This review summarizes current knowledge about tissue and material usage for experimental and clinical anatomical bile duct reconstruction in the last 100 years. A Pubmed database was searched for published articles about anatomical extrahepatic bile duct reconstruction in experimental and clinical settings ranging from 1920 to 2022. To date, the truly optimal interponate material has not yet been found. However, evidence reveals important properties of such material, most importantly its biodegradability and neovascularization in the recipient's body. The role of internal bile duct stenting for anatomical reconstruction seems important for the outcome. Anatomical reconstruction of extrahepatic bile ducts is an uncommon but usable technique in unique cases when a nonanatomical reconstruction cannot be done. The optimal properties of interponate material for anatomical bile duct reconstruction have been more clarified, although further research is required.