bluuebunny/crossref_metadata_2025 huggingface dataset:
Visible‐Light‐Driven CO₂ Reduction Using Imidazole‐Based Metal–Organic Frameworks as Heterogeneous Photocatalysts.
Authors: Bhunia Asamanjoy , Jana Anupam , Saha Sinthia , Mondal Suvendu Sekhar , Kaur Navjot
Published: December 2024

The development of robust, efficient, and cost‐effective heterogeneous photocatalysts for visible light‐driven CO2 reduction continues to be a significant challenge in the quest for sustainable energy solutions. As a result, increasing attention is being directed towards the exploration of high‐performance photocatalysts capable of converting CO2 into chemical feedstocks. Imidazolate Frameworks Potsdam (IFPs) can be a promising candidate for CO2 photoreduction due to their ease of synthesis, use of low‐cost, earth‐abundant metals, and high chemical and thermal stability. Herein, we report the  synthesis of Zn(II)‐ and Co(II)‐based IFPs, specifically IFP‐1(Zn) and IFP‐5(Co), for photocatalytic CO2 reduction. Moreover, we demonstrate the enhanced photocatalytic activity of redox‐innocent Zn‐based IFP‐1 by partially substituting Zn(II) with redox‐active Co(II) in IFP‐1(Zn), resulting in the formation of a bimetallic photocatalyst, IFP‐1(Zn/Co). The  IFP‐1(Zn/Co) exhibited significantly improved CO evolution (637 μmol g−1 in 1 hour), compared to the pristine IFP‐1(Zn) (29 μmol g−1). Among all the prepared photocatalysts, IFP‐5(Co) outperformed both the systems, achieving a CO evolution of 1174 μmol g−1 within 1 hour, due to the presence of catalytic cobalt sites. In addition, through the combination of photophysical and electrochemical studies, along with DFT calculations, we have proposed a plausible mechanism for the photocatalytic CO2 reduction.
Dual Activities of Flower‐Like Gold‐Iron Oxide Nanozyme for Peroxidase‐Mimicking and Glucose Detection
Authors: Bharti Kanika , Dalal Sancharika , Tyagi Avni , K. Sadhu Kalyan
Published: December 2024

Nanozymes, constituting of inorganic nanomaterials, are the sustainable and cost‐effective alternatives of the naturally abundant enzymes. For more than a decade, nanozymes have shown astonishingly enhanced enzymatic activity as compared to its naturally occurring counterpart and emerged as a potential platform in biomedical science. The current study reports a novel flower shaped gold‐iron oxide nanocomposite prepared via a facile and green solution phase redox mediated synthesis. The precursor gold salt conversion to nanometallic Au(0) is mediated by iron metal powder, which acts both as reductant and metal source in the resultant gold nanoparticle decorated iron oxide nanocomposite. Calcination of the synthesized nanocomposites leads to morphological evolution into unique flower shape with improved homogeneity between gold and iron components along with metal surface exposure. The gold‐iron oxide nanocomposites have been utilized first time for peroxidase mimicking study and exhibit enhanced catalytic activity at 25 °C with low Michaelis‐Menten constant (Km) and higher maximum reaction velocity (Vmax) as compared to the natural enzyme Horseradish peroxidase (HRP). In addition, combined assembly of this nanozyme with natural enzyme glucose oxidase also serves a potential platform for the visible colorimetric detection and quantification of glucose with limit of detection (LOD) of 15 μM.
“On Water” Cationic Ruthenium(II) Catalysed Direct Aryl C(sp2)–H Amidation of Biorelevant Heterocyclic Scaffolds
Authors: Pipaliya Bhavin V. , Saha Nirjhar , Chakraborti Asit Kumar
Published: December 2024

Ru(II)‐Catalyzed “On Water” direct aryl C(sp2)–H amidation of 2‐arylbenzo[d]‐thiazole/oxazole with acyl azide is reported under silver‐free condition. Deuterium scrambling experiments suggested reversible C–H activation catalyzed by active cationic ruthenium species. The organic solvents such as DCE, DMF, DMSO, MeCN, dioxane, and PhMe were not conducive for the C‐H amidation except for PhCl in which case, however, inferior yield (31%) was obtained. Water plays critical roles (i) during the formation of active cationic Ru‐species, (ii) as proton scavenger during ligand‐assisted C–H activation through hydrogen bond formation as evidenced by solvent kinetic isotope effect, and (iii) in the final protodissociation step. The mechanistic proposal resembles secondary coordination sphere hydrogen bond controlled transition metal catalysis showcasing the aryl C–H amidation through outer sphere nitrene insertion. The “on water” aryl C‐H amidation protocol showed wide substrate scope with respect to the 2‐arylbenzo[d]‐thiazole/oxazole scaffold as well as the aryl moiety of the aroyl azide. While the applicability of the Ru(II)‐catalysed “on water” C‐H amidation protocol to 2‐arylbenzo[d]‐thiazole and 2‐arylbenzo[d]‐oxazole demonstrates its scope with respect to the directing group the effectiveness for sulfonamidation and phosphoramidation further broaden the synthetic scope.
An educated society is an ideas‐informed society: A proposed theoretical framework for effective ideas engagement
Authors: Brown Chris , Luzmore Ruth
Published: December 2024

The term ‘ideas‐informed society’ describes democracies in which citizens believe in the value of staying well‐informed and up‐to‐date with current affairs. They also put these beliefs into action: critically engaging with new ideas and perspectives, delving into scientific discoveries or emerging technologies and exploring aspects of history and culture. Likewise, they stay abreast of political, economic and health‐related events, new products, new forms of media and so on. While ideas engagement can, in theory, lead to citizens becoming better informed, better able to engage in effective decision‐making and better able to understand the world around them, these benefits do not reach everybody. Likewise, in the ideas ecosystem generally, we can often see ‘dark’ ideas winning through: resulting in less optimal outcomes for both citizens and nations. While interest in the notion of the ideas‐informed society is burgeoning, we argue that, if future research is to be effectively positioned to support meaningful ideas engagement, what is now required is a theoretical frame to guide this research moving forward. We use this paper to argue for such a framework based on three principal elements: (1) whether individuals possess a prospective mindset, enabling them to value ideas engagement, as well as become more likely to commit to behaviours concomitant with ideas that have optimal and wide‐reaching outcomes; (2) the features of individuals' social networks, and how these impact on citizens' access to ideas and the nature of their ideas engagement; and (3) individuals' levels of education and the extent to which the education people receive allows them to engage with ideas critically. As well as setting out the case for our proposed framework, we conclude by proposing future research to enable us to further specify and verify this framework as well as develop instruments to test it nationally and internationally.
Adaptable Manufacturing and Biofabrication of Milliscale Organ Chips With Perfusable Vascular Beds
Authors: Byrne Charles Ethan , Martier Ashley T. , Kpeli Gideon Wills , Conrad Kevin Michael , Bralower William , Olsen Elisabet , Fortes Gabrielle , Culp Caroline C. , Wendell Max , Boone Keefer A. , Burow Matthew R. , Mondrinos Mark J.
Published: December 2024

Microphysiological systems (MPS) containing perfusable vascular beds unlock the ability to model tissue‐scale elements of vascular physiology and disease in vitro. Access to inexpensive stereolithography (SLA) 3D printers now enables benchtop fabrication of polydimethylsiloxane (PDMS) organ chips, eliminating the need for cleanroom access and microfabrication expertise, and can facilitate broader adoption of MPS approaches in preclinical research. Rapid prototyping of organ chip mold designs accelerates the processes of design, testing, and iteration, but geometric distortion and surface roughness of SLA resin prints can impede the development of standardizable manufacturing workflows. This study reports postprocessing procedures for manufacturing SLA‐printed molds that produce fully cured, flat, patently bonded, and optically clear polydimethyl siloxane (PDMS) organ chips. Injection loading tests were conducted to identify milliscale membrane‐free organ chip (MFOC) designs that allowed reproducible device loading by target end‐users, a key requirement for broad nonexpert adoption in preclinical research. The optimized milliscale MFOC design was used to develop tissue engineering protocols for (i) driving bulk tissue vasculogenesis in MFOC, and (ii) seeding the bulk tissue interfaces with a confluent endothelium to stimulate self‐assembly of perfusable anastomoses with the internal vasculature. Comparison of rocker‐ and pump‐based protocols for flow‐conditioning of anastomosed vascular beds revealed that continuous pump‐driven flow is required for reproducible barrier maturation throughout the 3D tissue bulk. Demonstrated applications include nanoparticle perfusion and engineering perfusable tumor vasculature. These easily adaptable methods for designing and fabricating vascularized microphysiological systems can accelerate their adoption in a diverse range of preclinical laboratory settings.
Enhancing Sustainability in Renewable Energy Innovation: The Role of Peer Dynamics and Firm Characteristics Amid Climate Crises
Authors: Rastegar Hiva , Sajjad Aymen , Eweje Gabriel , Kobayashi Kazunori
Published: December 2024

This study investigates peer influence on a firm's pursuit of renewable energy innovation following climate change–induced disasters. While mimetic pressures and competitive dynamics have been recognized as drivers of green innovation, the impact of external uncertainties, such as climate change–induced disasters, on these dynamics remains underexplored. This study fills this gap by revealing how firms pursue renewable energy innovation amid competitive pressures and environmental challenges. Utilizing the behavioral theory of the firm and the threat rigidity model, we analyze US firms' pursuit of renewable energy innovation following climatological disasters from 2013 to 2018 through a difference‐in‐difference‐in‐differences approach. Our findings reveal that peers' pursuit of renewable energy innovation can dampen a firm's own pursuit of renewable energy innovation postdisaster, and this effect is less pronounced among multinational enterprise subsidiaries. Theoretically, this study deepens our understanding of how climatological disasters shape competitive dynamics and innovation, challenging the view that competition invariably drives innovation. Practically, it provides insights into effective resource allocation and prioritizing collaborations for sustainability. For policy‐makers, the findings highlight the need for regulatory environments that encourage collaborative innovation and enhance resilience, directly contributing to Sustainable Development Goal 7 (affordable and clean energy) by promoting sustainable energy use.
Increased Early‐Mortality in Children With Solid Tumors During the COVID‐19 Pandemic in a Middle‐Income Country
Authors: Ramirez Oscar , Piedrahita Vivian , Bolivar Santiago , Grillo Karina , Linares Adriana , Pardo Carlos , Piña Martha , Suarez Amaranto , Portilla Carlos A. , Ardila Jesus , Lotero Viviana , Urcuqui Luz A. , Trujillo Angela , Montenegro Patricia , Bravo Luis E. , Aristizabal Paula ,   VIGICANCER Working Group
Published: December 2024

Background

Measures to control COVID‐19 transmission disrupted childhood cancer care. Data on the effects of the COVID‐19 pandemic on childhood cancer mortality are lacking. This study describes the impact of the pandemic on childhood cancer early‐mortality (≤ 24 months).

Methods

A multicenter prospective cohort was conducted in 10 Colombian cities. Children with newly diagnosed cancer registered in the Childhood Cancer Clinical Outcomes Surveillance System (VIGICANCER) were included. Our primary outcome was cumulative mortality at 3, 6, 12, and 24 months. The exposed cohort (EC = March 25, 2020–December 31, 2021) was compared with a historic cohort (HC = January 1, 2017–March 24, 2020). Covariates included sociodemographics, place of residence, health insurance type, and tumor classification.

Results

The cohort included 4124 children, comprised of 1627 children in the EC and 2497 children in the HC. Hematolymphoid, central nervous system, and extracranial solid tumors represented 57%, 15%, and 28% of patients, respectively. Participants' median age was 6.7 years (IQR, 3.2–11.3), 54% were male, 7% were Afro‐descendant, and 47% had public insurance. In the EC, the 6‐month and 24‐month mortality adjusted hazard ratio (aHR) in children with solid tumors was 1.7 (95% CI, 1.1–2.7) and 1.3 (95% CI, 1.0–1.7), respectively, and in children with bone tumors 4.0 (95% CI, 1.2–13.0) and 2.1 (95% CI, 1.2–3.6), respectively. These associations persisted after accounting for metastatic disease. Six‐month mortality aHRs for retinoblastoma, bone tumors, and soft tissue sarcomas due to progressive disease were 4.3 (95% CI, 1.3–14.5), 4.0 (95% CI, 1.4–11.3), and 5.4 (95% CI, 2.2–13.5), respectively. In the EC, the adjusted odds ratio (aOR) for metastatic solid tumors vs. nonmetastatic was 1.4 (95% CI, 1.0–1.8) and in children with retinoblastoma and public insurance the 24‐month mortality aHR was 4.9 (95% CI, 1.1–21.7).

Conclusions

We observed increased early‐mortality for solid tumors, particularly bone tumors and retinoblastoma, likely attributed to more advanced‐stage presentation and loss of treatment effectiveness due to healthcare disruptions. Early‐mortality was higher in patients with public insurance, a vulnerable population that warrants attention.
One Year Duration of Immune Response Following a 3rd Booster Dose of mRNA Vaccine Against COVID‐19 in 292 Patients With Hematological Malignancies in University Hospital Ostrava, Czech Republic
Authors: Šušol Ondrej , Šušolová Barbora , Klempíř Ondřej , Navrátil Milan , Gumulec Jaromír , Kořístek Zdeněk , Ďuraš Juraj , Kaščák Michal , Mihályová Jana , Stejskal Lukáš , Jelínek Tomáš , Richterová Petra , Szeligová Lenka , Plonková Hana , Zuchnická Jana , Dluhošová Barbora , Demel Ivo , Buffa David , Hradská Katarína , Popková Tereza , Muroňová Ludmila , Lachnit Martin , Lančová Klára , Hájek Roman
Published: December 2024

Aims

To evaluate antibody response to mRNA vaccine, identify subgroups with poor response and to determine long‐term antibody durability in hematological patients.

Materials and Methods

We have vaccinated 292 patients with all hematological malignancies with a third dose of mRNA COMIRNATY vaccine with a 12‐month follow‐up period in our center in Ostrava, Czech Republic.

Results

Antibody response for the whole cohort exceeded 74% through the whole 12‐month follow‐up. Lowest seroconversion was observed in CLL cohort (20/41, 48.8%), patients who received anti‐CD20 therapy < 6 months before vaccination (8/30, 26.7%) and BTK inhibitors (3/6, 50.0%). On the contrary, patients with chronic myeloproliferative neoplasms and acute leukemia performed comparably with healthy population (33/33; 100% and 12/13; 92.3%, respectively). We have seen better results if the time interval between anti‐CD20 therapy and additional vaccine dose was longer than 6 months (5/8 patients achieved seroconversion on 4th booster dose after previous failure). Also, 36 patients received a 4th dose of vaccine as a booster with measurable increase in protective antibodies in 50% (18/36).

Conclusions

Additional doses show promise for a well‐timed revaccination even in poor responders. To our knowledge, no study comparable to our work in terms of follow‐up length, vaccine consistency or variety of hematological malignancies and/or treatment has been reported yet. Our findings shed more light on long‐term antibody response to mRNA vaccines against SARS‐CoV‐2 in patients with hematological cancer and bring important data for the evaluation of possible vaccine failure and scheduling of subsequent doses.
Natural Products in Precision Neurological Disease (Cryptococcal Meningitis): Structure‐Based Phytochemical Screening of Glycyrrhiza glabra Plant Against Cryptococcus neoformans Farnesyltransferase (FTase)
Authors: Siddiquee Noimul Hasan , Sujan Md. Shiful Islam , Dremit Tasnuva Islam , Rahat Ekramul Hasan , Barman Kripa , Karim Mahima , Nandi Chinmoy , Akter Sumi , Talukder Md. Enamul Kabir , Hosen Md. Sapan , Khaled Md. , Saha Otun
Published: December 2024

Cryptococcus neoformans causes cryptococcal meningitis, which is lethal to immune‐compromised people, especially AIDS patients. This study employed diverse in silico techniques to find the best phytochemical to block farnesyltransferase (FTase). Based on molecular docking, the top two compounds selected from a screening of 5807 phytochemical compounds from 29 medicinal plants were CID_8299 (hydroxyacetone) and CID_71346280 (1,7‐bis (4‐hydroxyphenyl)‐1,4,6‐heptatrien‐3‐one), with docking scores of −5.786 and −0.078 kcal/mol, respectively, indicating stronger binding affinities than the control CID_3365 (fluconazole), which scored −4.2 kcal/mol. The control and lead compounds bind at the common active site of protein by interacting with common amino acid residues (HIS97, GLN408, PHE93, and TRP94). Post‐docking MM‐GBSA verified docking score where CID_8299 and CID_71346280 had negative binding free energies of −19.81 and −0.27 kcal/mol, respectively. These two lead compounds were reassessed through molecular dynamics simulation (100 ns), and several post‐dynamics analyses were conducted. CID_71346280, 8299, and 3365 (control) showed average RSMD values of 3.17, 1.904, and 2.08; average root mean square fluctuation values of 1.167, 0.886, and 1.028 Å; average radius of gyration values of 5.13, 1.58, and 3.54 Å; average solvent accessible surface area values of 121.16, 3.51, and 183.81 Å2; average H‐bond values of 466.05, 470.84, and 456.84 Å, respectively. The results revealed that CID_8299 had the highest stability and consistent interaction with the target protein throughout the simulation period. According to the toxicity analysis, CID_8299, which is found in the Glycyrrhiza glabra plant, can also cross the BBB, which makes it unbeatable in treating neuro‐disease caused by C. neoformans and may potentially block FTase protein's activity inhibiting post‐translational lipidation of essential signal transduction protein.
Plant Endophytic Fungi: Powerful Catalytic Cells for Biotransformation of Chemical Structures of Biologically Active Compounds
Authors: Palupi Kartika Dyah , Oktavia Listiana , Wulansari Dewi , Fathoni Ahmad , Praptiwi Praptiwi , Rahmi Dwinna , Agusta Andria
Published: December 2024

Fungal endophytes are recognized as an essential source of bioactive compounds. Besides producing a wide variety of compounds, fungal endophytes can also facilitate a biotransformation process. In this process, endophytes act as an enzyme source to catalyze chemical reactions and modify the structures of bioactive compounds. Biotransformation offers advantages over chemical synthesis, for instance, the allowance of eco‐friendly reactions and regioselective as well as stereoselective synthesis that is often difficult to achieve using chemical synthesis. This review focuses on the utilization of endophytic fungi in the biotransformation process of bioactive compounds to improve their pharmacological, pharmacokinetic, or toxicological parameters. We also discuss the future perspectives and obstacles of using the endophytic fungi‐based biotransformation process.
Gentiopicroside: An Updated Review of Its Pharmacological Activities and Mechanisms
Authors: Ding Yin , Gou Xiaoling , Wu Xinyue , Tao Yiwen , Wang Yaqian , Wang Yue , Liu Jingye , Zhou Xianhua , Kuang Tingting , Fan Gang
Published: December 2024

Gentiopicroside (GPS) is a bioactive iridoid glycoside isolated from Gentianaceae plants. In recent years, GPS has received increasing attention due to its multiple pharmacological activities. This review encapsulates the botanical origin, pharmacological activity, toxicity, and underlying mechanisms of GPS in the treatment of various diseases. The results have proved that GPS possesses a wide spectrum of pharmacological properties, including hepatoprotective, anti‐arthritic, analgesic, antidiabetic, anticancer, and neuropsychopharmacological activities. Specifically, GPS can alleviate liver injury caused by alcohol, d‐galactosamine, or lipopolysaccharide by reducing liver function impairment, improving hepatic lipid disorders, and inhibiting oxidative stress and inflammation. GPS also has good antitumor activity by inducing apoptosis and inhibiting the proliferation of cancer cells. Additionally, GPS can improve diabetes by maintaining glucose homeostasis, reducing lipid disorders, improving insulin resistance, inhibiting lipogenesis, and alleviating oxidative stress and inflammation. As for the toxicity of GPS, studies have shown that GPS has low toxicity. Collectively, given its promising pharmacological activity, GPS holds potential as a drug candidate for the treatment of liver disease, arthritis, diabetes, and cancer. In the future, more research is still needed to uncover its long‐term toxicity, oral bioavailability, and molecular mechanisms for treating these diseases.
ADME, Toxicity, Molecular Docking, Molecular Dynamics, Glucokinase activation, DPP‐IV, α‐amylase, and α‐glucosidase Inhibition Assays of Mangiferin and Friedelin for Antidiabetic Potential
Authors: Suryawanshi Ravikiran Maheshrao , Shimpi Rupali Bhalchandra , Muralidharan V. , Nemade Lalita Shashikant , Gurugubelli Simhachalam , Baig Shahajan , Vikhe Sunayana Rahul , Dhawale Sachin A. , Mortuza Mohammad Rakib , Sweilam Sherouk Hussein , Siddiqui Falak A. , Khan Sharuk L. , Tutone Marco , Ahmad Irfan , Begh Md. Zamshed Alam
Published: December 2024

Today the alarming situation of diabetes seeks innovative antidiabetic medications, especially those derived from natural sources, as natural substances are safer than manufactured pharmaceuticals. Therefore, this study investigated the inhibitory properties of mangiferin and friedelin against glucokinase (GK), dipeptidyl peptidase‐IV (DPP‐IV), α‐amylase, and α‐glucosidase using computational methods, in vitro enzyme assays, and in‐depth ADMET analysis. The study utilized a computer‐aided drug design approach to assess the potential therapeutic properties of mangiferin and friedelin as Type 2 diabetes mellitus (T2DM) therapeutic agents. Molecular docking studies’ outcomes encouraged the evaluation of both compounds in in vitro enzymatic assays. The docking study results were validated with the help of molecular dynamics simulation. Mangiferin and friedelin showed that they activated GK 20% and 5% more than the basal activity of the enzyme, respectively. In the DPP‐IV enzyme assay, mangiferin and friedelin demonstrated IC50 values (74.93 ± 0.71 and 110.64 ± 0.21 µg/mL, respectively) comparable with the reference compound sitagliptin. Moreover, mangiferin and friedelin showed IC50 comparable to acarbose against α‐amylase (9.72 ± 0.15, 11.84 ± 0.06, and 10.19 ± 0.05 mg/mL, respectively). In the α‐glucosidase enzyme assay, mangiferin, friedelin, and acarbose displayed 11.72 ± 0.10, 14.34 ± 0.02, and 9.14 ± 0.06 mg/mL of IC50 values, respectively. The compounds showed promising in silico ADMET and drug‐likeness properties, with potential binding affinities with all enzymes. In vitro enzymatic assays showed mangiferin and friedelin activated GK 20% and 5% more than basal activity, with IC50 values comparable to acarbose.
Combining Water‐Soluble Porphyrin and Phthalocyanine Photosensitizers With Doxorubicin Improves the Efficacy of Chemo‐Photodynamic Therapy Against DMBA‐Induced Breast Carcinoma
Authors: Mokhtar Aya , Mohamed Tarek , Eigza Ahmed O. , El‐Khouly Mohamed E.
Published: December 2024

Breast cancer ranks as the second most widespread form of cancer globally. Currently, combination therapy is being actively employed in clinical practice to augment the efficiency of anticancer treatment. Hence, the objective of this study was to assess the therapeutic efficacy of a combination of femtosecond laser‐based photodynamic therapy (PDT) utilizing two distinct photosensitizers (PSs), zinc phthalocyanine tetrasulfonate (ZnPcS4) and α,β,χ,δ porphyrin‐Tetrakis (1‐methylpyridinium‐4‐yl) p‐Toluenesulfonate porphyrin (TMPyP) in conjunction with doxorubicin chemotherapeutic agent, on mammary carcinomas experimentally induced in female mice using 7,12‐dimethylbenz[a] anthracene (DMBA). Our results showed the efficiency of the combined therapy for promoting tissue apoptosis and necrosis as evidenced by histopathological observations and the noticeable reduction of Bcl‐2 and Ki‐67 expression. Moreover, there was a reduction in serum levels of the carcinoma antigen CA15‐3 and transforming growth factor beta (TGF‐β). Co‐treatment of doxorubicin with ZnPcS4‐PDT or TMPyP‐PDT or a combination of both resulted in a decrease in the expression of epidermal growth factor receptor (EGFR) and its downstream oncogenes NRAS, NF‐κB, mTERT, and c‐Myc, and an increase in the expression of the caspase‐3 apoptotic gene. These results validate the therapeutic potential of combining doxorubicin with PDT, highlighting the potential of this co‐treatment strategy as a promising alternative for enhancing existing anticancer approaches.
Phytochemistry, Antibacterial and Antioxidant Activities of Grewia lasiocarpa E. Mey. Ex Harv. Fungal Endophytes: A Computational and Experimental Validation Study
Authors: Akwu Nneka Augustina , Naidoo Yougasphree , Singh Moganavelli , Lin Johnson , Aribisala Jamiu Olaseni , Sabiu Saheed , Lekhooa Makhotso , Aremu Adeyemi Oladapo
Published: December 2024

The genus Grewia are well‐known for their medicinal properties and are widely used in traditional remedies due to their rich phytochemical composition and potential health benefits. This study isolated and characterized five endophytic fungi from Grewia lasiocarpa E. Mey. Ex Harv. and evaluated their in vitro antibacterial and antioxidant activities. Five [Aspergillus fumigatus (MK243397.1), A. fumigatus (MK243451.1), Penicillium raistrickii (MK243492.1), P. spinulosum (MK243479.1), Meyerozyma guilliermondii (MK243634.1)] of the 22 isolated endophytic fungi had inhibitory activity (62.5–1000 µg/mL) against methicillin‐resistant Staphylococcus aureus (MRSA). The antioxidant activities were 66.5% and 98.4% for 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) and ferric ion reducing antioxidant power (FRAP), respectively. In silico evaluation of the phytochemicals of the extract (containing majorly n‐hexadecanoic acid) was performed against penicillin‐binding protein 2a (PBP2a) implicated in the broad clinical resistance of MRSA to conventional beta‐lactams. Molecular docking and molecular dynamic simulation analyses revealed that the phytosterol constituents of the extract, especially dehydroergosterol (−46.28 kcal/mol), had good stability (4.35 Å) and compactness (35.08 Å) with PBP2a relative to the unbound PBP2a and amoxicillin‐PBP2a complex during the 100 ns simulation period, reinforcing them as putative leads that may be developed as viable alternatives to beta‐lactams against infections caused by MRSA. However, the prediction that dehydroergosterol lacks oral bioavailability with poor water solubility suggests that it could benefit from structural optimization for improved druggability. Hence, isolating and derivatizing dehydroergosterol for subsequent evaluation against PBP2a in vitro and in vivo is highly recommended.
Design, Synthesis, and Anti‐Infective Effect Against Candida Albicans of a New Urolithin Derivative
Authors: Zhu Chenyan , Tang Long , Zhou Feng , Tang Yingmao , Hu Qiulin , Wang Chenchen , Feng Xiaoqing , Zhuang Ziheng
Published: December 2024

Deep mucosal and organ infections caused by the infestation of Candida albicans in immunocompromised patients represent a significant cause of mortality in hospitalized patients. The rise in fungal resistance is a consequence of the overuse of antibiotics. Therefore, innovative immunostimulants must be developed to combat pathogenic fungal infections. We used urolithin A (UA), an intestinal metabolite rich in the naturally occurring polyphenolic antioxidants ellagic acid (EA) or ellagitannin (ET), as a lead compound for structural modification. Through liquid screening of 17 synthesized compounds, we discovered compound 1e effectively inhibited C. albicans biofilm formation, thereby reducing its virulence. Furthermore, it protects animals from severe infections by enhancing tolerance to infection by intestinal pathogens and reducing oxidative stress. Moreover, our findings indicate that compound 1e exerts its effects through the p38 mitogen‐activated protein kinase (MAPK) innate immune pathway, which is evolutionarily conserved. These observations not only enhance our comprehension of immune mechanisms but also provide a crucial foundation for the development of immune activators with the potential to resist pathogenic bacterial infections.
Palumoids A and B, Two New Dimeric Phenylpropanoids With Anti‐gouty Activity From Erythropalum scandens Blume
Authors: Wei Xia , Dou Bo‐Qiang , Zhang Cai‐Neng , Su Xun , Ouyang Wan‐Qiong , Shi Zhimian , Yang Ying‐Zhu , Wang De‐Bao , Gao De‐Feng , Su Jun‐Cheng
Published: December 2024

Erythropalum scandens Blume is widely utilized as both a functional vegetable and herbal medicine in southern China, however, its bioactive components have yet to be fully identified. In this study, two new phenylpropanoid dimers palumoids A (1) and B (2) with distinct coupling manners were identified from the plant. Biologically, these phenylpropanoids showed superior inhibition of interleukin‐1β release in monosodium urate‐stimulated THP‐1 cells compared to the positive drug colchicine. Notably, compound 2, featuring a pyran ring linkage between the two phenylpropanoid monomers, exhibited stronger activity than 1. Further mechanistic studies revealed that compound 2 acts as an NLRP3 inflammasome inhibitor by specifically blocking the activation of NLRP3, interfering with the assembly of the NLRP3 inflammasome complex.
d‐Galactose‐Esterification of a Fungal Polyketide Catalyzed by a Carnitine Acyltransferase Domain
Authors: Nagasawa Kyle K. , Yost Karl M. , Sun Zuodong , Tang Yi
Published: December 2024

While sugar‐containing natural products are commonly biosynthesized via glycosyltranferases using sugar‐UDP as the electrophile, nature has evolved alternative strategies of glyco‐modification to expand the diversity of natural products. Hydroxyl groups on sugars can serve as nucleophiles in the release of polyketide products from polyketide synthases. Herein, we demonstrate a highly reducing polyketide synthase (HRPKS) from the biocontrol fungus Trichoderma afroharzianum T22, which is terminated with a carnitine acyltransferase (cAT) domain, catalyzes the biosynthesis of a d‐galactose esterified polyketide named as trichogalactin. Structure‐guided enzymatic assays showed that the sugar nucleophile in the esterification reaction catalyzed by cAT is α‐d‐galactose‐1‐phosphate (Gal‐1‐P) instead of free d‐galactose. The released product, trichogalactin phosphate, is subsequently dephosphorylated by a host alkaline phosphatase to complete the biosynthesis of trichogalactin. The cAT domain is highly specific for Gal‐1‐P and does not accept α‐d‐glucose‐1‐phosphate or α‐d‐mannose‐1‐phosphate. Our study expands the inventory of natural products from an agriculturally important fungus and demonstrates the potential of mining cAT‐containing HRPKSs to discover new glyco‐esterified natural products.
Flow Cytometric Analysis for Evaluating Protein Synthesis Efficiency in Giant Unilamellar Vesicles with Charged Lipids
Authors: Tsuji Gakushi
Published: December 2024

Quantitative investigation of the relationship between endosomal translation reactions and phospholipid membrane composition is crucial for enhancing protein translation efficiency in artificial cells. In this study, we quantitatively compared the translation reactions within liposomes containing negatively and positively charged lipids using green fluorescent protein fluorescence as an indicator to investigate whether lipid membrane charge affects translation reaction efficiency in artificial cells. Thus, translation efficiency reduced in liposomes containing both negatively and positively charged lipids. Interestingly, flow cytometry analysis revealed that the percentage of liposomes undergoing translational reactions was reduced by the charged phospholipids. This translation reaction inhibition was alleviated by adding equal amounts of negatively and positively charged lipids, indicating that phospholipid membrane charges affected translation reaction efficiency. The relationship between membrane composition and translation reaction efficiency identified in this study is significant for the constructing complex artificial cells, particularly concerning membrane composition design
Advanced Synthesis of Spherical Nucleic Acids: A Limit‐Pursuing Game with Broad Implications
Authors: Ye Meiyun , Li Yulin , Deng Zhaoxiang
Published: December 2024

Spherical nucleic acids (SNAs) consist of DNA strands arranged radially and packed densely on the surface of nanoparticles. Due to their unique properties, which are not found in naturally occurring linear or circular DNA, SNAs have gained widespread attention in fields such as sensing, nanomedicine, and colloidal assembly. The rapidly evolving applications of SNAs have driven a modernization of their syntheses to meet different needs. Recently, several advanced approaches have emerged, enabling ultrafast, quantitative, and low‐cost SNA synthesis with maximal DNA grafting through “counterintuitive” processes like freezing and dehydration. This concept paper discusses these critical developments from a synthetic perspective, focusing on their underlying mechanisms and broad implications, with a goal of inspiring future research in related fields.
Cost estimation model for isolation and segregation of non‐genetically modified corn and soybeans at country grain elevators
Authors: Pizarro Mateus , Mosher Gretchen A. , Ofosu Stephen A. , Hurburgh Charles R. , Bowers Erin L.
Published: December 2024

Background and Objective

Corn and soybean meal are important ingredients for livestock and poultry feed. Feed producers who wish to produce non‐genetically modified (non‐GM) feed must segregate ingredients, especially corn and soybeans, throughout the supply chain. All supply chain participants must apply segregation practices to minimize the allowable presence of GM material, termed adventitious presence (AP), in non‐GM product loads. All these actions and processes raise concerns about production costs. The approach of this study was to model the feed supply chain segregation costs at country grain elevators, focusing on non‐GM corn and soybeans. To estimate the costs of successfully reaching four specified tolerance levels (0.9%, 1.5%, 3.0%, and 5.0%), 24 scenarios were constructed and evaluated using the Monte Carlo simulation method. Input variables were drawn from previous literature findings on segregation within the grain elevator environment and the costs of segregation actions. These variables included costs for new or dedicated equipment construction, testing costs, segregation method, facility capacity, and cleaning approaches. Scenarios were categorized by segregation method and facility capacity.

Findings

According to the model, the grain elevator was expected to spend an additional $0.03 to $0.04 per bushel to handle and segregate non‐GM soybeans as compared with GM soybeans and an additional $0.07 to $0.08 per bushel to successfully segregate non‐GM corn.

Conclusion

Grain elevators are expected to spend an additional $0.03 to $0.04 per bushel to successfully handle and segregate non‐GM soybeans as compared with GM soybeans. Costs to successfully handle and segregate non‐GM corn were an additional $0.07 to $0.08 per bushel.

Significance and Novelty

The study provides cost estimates for segregating non‐GM corn and soybeans in a grain elevator. When non‐GM corn and soybeans are used as part of feed ingredients, feed costs will increase.
CORM‐Mediated Pd‐Catalyzed Coupling Reactions: Ketone Synthesis and CO‐Releasing Mechanisms
Authors: Guo Meng , Yang Hongyu , Wang Jiawei , Jian Yajun , Zhang Weiqiang , Gao Ziwei
Published: December 2024

Palladium‐catalyzed carbonylative C─C coupling reactions provide an efficient route to synthesize natural products and pharmaceuticals through three‐component condensation processes. However, the use of gaseous carbon monoxide (CO) – a colorless, odorless, and toxic gas – has hindered its broad adoption as a C1 source. Addressing this, the development of versatile CO‐releasing molecules (CORMs) and user‐friendly, nongaseous palladium‐catalyzed carbonylation techniques have emerged as a crucial research area. This review outlines recent advancements in the application of CORMs to palladium‐catalyzed carbonylative C─C coupling reactions, with a focus on CO generation mechanisms and carbonyl utilization efficiency. CORMs are classified into three categories: single carbon monoxide releasing molecules (s‐CORMs), multiple carbon monoxide releasing molecules (m‐CORMs), and binary metal carbonyl compounds (BMCCs). By offering a comprehensive overview of the current research landscape and providing practical guidelines for CORM selection, this review aims to assist researchers in developing effective carbonylative strategies.
Synergistic Effects in a Nitrogen‐Coordinated Zinc Single‐Atom Catalyst for Efficient CO2 Cycloaddition
Authors: Chand Hushan , Allasia Nicolò , Cipriano Luis A. , Liberto Giovanni Di , Kwon Ik Seon , Zhang Min , Pacchioni Gianfranco , Krishnan Venkata , Vilé Gianvito
Published: December 2024

The valorization of CO2 into organic carbonates through its cycloaddition to epoxides has garnered significant attention in catalysis. However, the reaction is often hindered by low selectivity, and a key challenge is the development of catalysts capable of effectively activating both CO2 and epoxides simultaneously. In this study, we prepared and characterized a catalyst comprising isolated zinc single atoms dispersed on carbon nitride for the selective CO2 conversion to cyclic carbonates. The monoatomic nature and homogeneous distribution of the zinc species were confirmed utilizing advanced characterization methods, including X‐ray absorption spectroscopy and aberration‐corrected scanning transmission electron microscopy. The catalyst activity and recyclability were validated through catalytic tests with epichlorohydrin as a model epoxydic compound, and the study scope was subsequently extended to include a wide range of functionalized epoxides. Density functional theory calculations were performed to elucidate the reaction mechanism, revealing that both CO2 and epichlorohydrin interact with the same zinc atom in the cycloaddition process, highlighting the key role of zinc single atoms in promoting the reaction. Overall, the present study provides new insights into the design and optimization of heterogeneous catalysts for CO2 cycloadditions, paving the way for more effective strategies in CO2 valorization and conversion for producing valuable fine chemicals.
Catalytic Conversion of CO2 to Methane Using Nickel‐Functionalized Mesoporous SBA‐1 with 3D Cage‐Type Porous Structure
Authors: Ismaili Arsh , Sathish C. I. , Kumar Ayush , Li Zhixuan , Joseph Stalin , Vinu Ajayan
Published: December 2024

Developing efficient heterogeneous catalysts for activating CO2 is of considerable interest for achieving carbon neutrality. Therefore, many researchers have devoted a lot of effort to design and develop various porous materials‐based catalysts for CO2 conversion. Catalysts with high activity and stability for CO2 conversion are crucial for easy commercialization, but it remains a significant challenge to develop these catalysts. Herein, we report the fabrication of Ni‐functionalized mesoporous silica with 3D mesoporous structure, cage‐type pores, and different Ni contents for achieving enhanced CO2 methanation and stability. The highly ordered mesoporous structure of SBA‐1 offers a high surface area (1315 m2 g−1) that helps to anchor a significant amount of nickel nanoparticles. Insight into the structure of the catalyst and fine‐tuning of metal‐support interaction were in‐depth, characterized by the combination of X‐ray diffraction, electron imaging, and spectroscopic tools. The prepared Ni‐functionalized SBA‐1 materials exhibit an ordered mesoporous structure and the specific surface area decreases with increasing the concentration of the Ni on the porous channels of SBA‐1. The optimized Ni‐functionalized SBA‐1 yielded 80.1% conversion with a CH4 selectivity of 96.9% at a gas hourly space velocity (GHSV) of 21,000 mLgcat−1h−1 under the optimized reaction conditions. Temperature‐programmed surface reaction (TPSR) studies suggest a mechanism involving CO2 dissociation into CO. The Ni‐loaded SBA‐1 catalyst demonstrated remarkable stability over five consecutive 24 h cycles, indicating its promising potential for practical application in sustainable energy production and greenhouse gas mitigation.
Chromite–Zeolite Catalysts for Syngas Conversion to Hydrocarbons: Insights into Oxide–Zeolite Interactions
Authors: Kull Tobias , Dahlhues Johannes , Wilmsen Andrea , Lohmann Heiko , Zeidler‐Fandrich Barbara , Apfel Ulf‐Peter
Published: December 2024

A key challenge in modern society is developing the sustainable processes for producing vital chemicals, such as hydrocarbons, from renewable raw materials. The OX‐ZEO process, which uses bifunctional catalysts to convert syngas into hydrocarbons, offers a potential alternative to the nonsustainable cracking process. Combining oxide materials with zeolites enables the direct synthesis of various hydrocarbon products with high selectivity. However, challenges remain, particularly regarding carbon monoxide (CO) conversion and unwanted carbon dioxide (CO2) generation. This study explores the impact of bimetallic chromites combined with H‐MOR zeolite on the reaction outcome. Comparative experiments using only the oxide versus the bifunctional catalyst revealed a clear link between the methanol synthesis activity of the oxide and the overall activity in the OX‐ZEO process. Furthermore, catalytic tests with monometallic oxides paired with H‐MOR highlighted the role of the oxide's crystal structure in syngas conversion. These findings offer insights into the oxide–zeolite interactions, enabling the development of improved catalyst combinations that enhance the CO conversion, reduce CO2 formation, and maintain high product selectivity.
A Palladium Tetraiodide Supported Catalyst for the Oxidative Carbonylation of β‐Amino Alcohols to 2‐Oxazolidinones
Authors: Ziccarelli Ida , Mancuso Raffaella , Novello Mariangela , De Salvo Alex , Calabrese Carla , Valentino Laura , Pettignano Alberto , Gruttadauria Michelangelo , Giacalone Francesco , Gabriele Bartolo
Published: December 2024

A novel PdI42−‐supported catalyst, based on imidazolium‐functionalized polyhedral oligomeric silsesquioxanes (POSS) functionalized with imidazolium arms grafted on amorphous silica, is prepared through a straightforward synthetic procedure allowing to accede to high local concentration spots of palladium sites surrounding the POSS core. The hybrid material was fully characterized by thermogravimetric analysis coupled with differential scanning calorimetry (TGA–DSC), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and X‐ray photoelectron spectroscopy (XPS). This material was successfully used as heterogeneous catalyst for the oxidative carbonylation of β‐amino alcohols to 2‐oxazolidinones as well as 2‐aminopyridin‐3‐ol to oxazolo[4,5‐b]pyridin‐2(3H)‐one under relatively mild conditions (100 °C for 3 h under 40 atm of a 4:1 mixture CO–air) in DME as the solvent and with aerobic oxygen as the simplest external oxidant, with the formation of water as benign coproduct. The catalyst could be successfully recycled up to four times, before beginning to undergo partial deactivation due to palladium reduction, as evidenced by XPS and TEM. ICP–OES analysis of some representative products evidenced a low metal contamination (palladium content <1 ppm), making our approach interesting for applications in the life science field, where a high degree of purity is required.
Three‐Component Synthesis of β‐Ketosulfonamides via Visible‐Light‐Mediated Generation of Sulfamoyl Radicals
Authors: Hofman Kamil , Friedrich Marius , Manolikakes Georg
Published: December 2024

In this study, we report a photoredox‐catalyzed, visible‐light‐mediated three‐component synthesis of β‐ketosulfonamides from silyl enol ethers, N‐aminopyridinium salts, and the sulfur dioxide (SO2) surrogate DABSO (1,4‐diazabicyclo[2.2.2]octane·bis (sulfur dioxide) adduct). Eosin Y is used as readily available and cost‐efficient organic photoredox catalyst. This method is based on the photochemical generation of sulfamoyl radicals as key intermediates from N‐aminopyridinium salts as nitrogen radical precursors and DABSO as an easy‐to‐handle, solid SO2 source. Trapping of the in situ‐generated sulfamoyl radicals with silyl enol ethers affords pharmaceutically relevant β‐ketosulfonamides in 63%–91% yields.
Impact of Double‐π‐Bridge on Bis(Triarylamine)‐Based Organic Mixed‐Valence System: A Case Study of Diaza[1.1](4,4”)ortho‐Terphenylophane Radical Cation
Authors: Yoshida Koshi , Takasaki Fumiya , Uebe Masashi , Seki Shu , Ito Akihiro
Published: December 2024

A bis(triarylamine) (BTA) radical cation, bridged by two o‐terphenylene moieties, was prepared and characterized to explore the impact of the double‐π‐bridge on the intramolecular charge/spin transfer process in the 2‐site organic mixed‐valence (MV) compound. Spectroscopic analyses on optically and thermally assisted intervalence charge‐transfer (IVCT) processes revealed that the doubly π‐bridging enhanced the charge delocalization between two nitrogen redox‐active centers, whereas the electronic coupling was not so strengthened, in comparison with the singly π‐bridging reference compound.
Water Microdroplets Promote Spontaneous Oxidation of Amino Acid‐ and Peptide‐related Thiols to Disulfide Bonds
Authors: Zhang Hong , Wang Yanjie , Yang Jiamin , Ju Yun , He Jing , Niu Yuqing , Liu Yaqi , Hou Wenhao , Qiao Lina , Jiang Jie
Published: December 2024

Disulfide bonds (S−S) play a critical role in modern biochemistry, organic synthesis and prebiotic chemistry. Traditional methods for synthesizing disulfide bonds often rely on oxygen, alkali, and metal catalysts. Herein, thiol groups involved in amino acids and peptides were spontaneously converted into symmetrical and unsymmetrical disulfide bonds within water microdroplets, without the need for catalysts or oxygen, and under room temperature. Water microdroplets displayed improved selectivity for disulfide bond formation, with minimal production of other oxidative species. Mechanistic investigations revealed that hydroxyl radicals (⋅OH) present on the water microdroplet surface facilitated the oxidation process. Thiols were firstly oxidized to thiyl radicals (RS⋅), which subsequently coupled to form disulfide bonds. This study highlights the potential of microdroplet chemistry as an efficient and mild approach for constructing disulfide bonds.