bluuebunny/crossref_metadata_2025 huggingface dataset:
Reversible Multi‐Complexation of CO2 to Alkaline Earth Metal Ion‐Pair at 400 ppm and 298 K
Authors: Oda Akira , Sawabe Kyoichi , Satsuma Atsushi
Published: September 2024

The efficient capture of low‐pressure CO2 remains a significant challenge due to the lack of established multi‐complexation of CO2 to active sites in microporous materials. In this study, we introduce a novel concept of reversible multi‐complexation of CO2 to alkaline earth metal (AEM) ion pairs, utilizing a host site in ferrierite‐type zeolite (FER). This unique site constrains two AEM ions in proximity, thereby enhancing and isotopically spreading their electrostatic potentials within the zeolite cavity. This electrostatic potential‐engineered micropore can trap up to four CO2 molecules, forming M2+−(CO2)n−M2+ (n=0–4, M=Ca, Sr, Ba) complexes, where each CO2 molecule is stabilized by interactions between terminal oxygen (Ot) in CO2 and the AEM ions. Notably, the Ba2+ pair site exhibits higher thermodynamic stability for multiple adsorptions due to the optimal binding mode of Ba2+−Ot−Ba2+. Through high‐accuracy energy calculations, we have established the relationship among structure, CO2 uptake, and operating temperature/pressure, demonstrating that the Ba2+ pair site can capture four CO2 molecules even at concentrations as low as 400 ppm and at 298 K. Three of the four molecules of CO2 trapped were removable at room temperature and under vacuum. The findings in the present study provide a new direction for developing efficient CO2 adsorbents.
Anilines Formation via Molybdenum‐Catalyzed Intermolecular Reaction of Ynones with Allylic Amines
Authors: Yu Yi‐Zhe , Su Hong‐Yi , Zhuo Chun‐Xiang
Published: September 2024

The multi‐substituted anilines are widely found in organic synthesis, medicinal chemistry and material science. The quest for robust and efficient methods to construct a diverse array of these compounds using readily accessible starting materials under simple reaction conditions is of utmost importance. Here, we report an unprecedented and efficient approach for the synthesis of 2,4‐di and 2,4,6‐trisubstituted anilines. With a simple molybdenum(VI) catalyst, a wide range of 2,4‐di and 2,4,6‐trisubstituted anilines were efficiently prepared in generally good to excellent yields from readily accessible ynones and allylic amines. The synthetic potential of this methodology was further underscored by its applications in several synthetic transformations, gram‐scale reactions, and derivatization of bioactive molecules. Preliminary mechanistic studies suggested that this aniline formation might involve a cascade of aza‐Michael addition, [1,6]‐proton shift, cyclization, dehydration, 6π‐electrocyclization, and aromatization. This novel strategy provided a robust, simple, and modular approach for the syntheses of various valuable di‐ or trisubstituted anilines, some of which were otherwise challenging to access.
Anodisches Recycling von gängigen Polymeren: Die Kombination von Eisen‐Elektrokatalyse und skalierbarer Wasserstoffentwicklungsreaktion
Authors: Hourtoule Maxime , Trienes Sven , Ackermann Lutz
Published: September 2024

Kunststoffe sind in unserem Alltag allgegenwärtig, und die Akkumulation von Kunststoffabfällen in unserer Umwelt stellt ein großes gesellschaftliches Problem dar. Daher sind Methoden für das Recycling von Kunststoffabfällen im Hinblick auf eine künftige Kreislaufwirtschaft von hohem Interesse. Insbesondere der Abbau von Polymeren nach Nutzung durch Verbraucher hin zu wertschöpfenden kleinen Molekülen stellt eine nachhaltige Strategie für eine Kohlenstoff‐Kreislaufwirtschaft dar. Trotz jüngster Fortschritte ist der chemische Polymerabbau nach wie vor weitgehend auf chemische Redox‐Reagenzien beschränkt oder durch eine geringe Energieeffizienz photochemischer Prozesse limitiert. In dieser Arbeit berichten wir über einen leistungsstarken eisenkatalysierten Abbau von Polystyrolen mit hohem Molekulargewicht durch Elektrochemie, um effizient monomere Benzoylprodukte zu liefern. Die Robustheit der Ferraelektrokatalyse wurde durch den Abbau von verschiedenen realen Nach‐Gebrauchs‐Kunststoffen, ebenfalls im Gramm‐Maßstab, bestätigt. Die kathodische Halbreaktion wurde weitgehend durch die Wasserstoffentwicklungsreaktion (HER) dargestellt. Der skalierbare elektrolytische Polymerabbau konnte ausschließlich mit Solarenergie über ein handelsübliches Solarpanel betrieben werden, was auf ein herausragendes Potenzial für eine dezentralisierte, grüne Wasserstoffwirtschaft hinweist.
An Atomic‐Scale Explanation for The High Selectivity Towards Carbon Dioxide Reduction Observed On Liquid Metal Catalysts
Authors: Ruffman Charlie , Steenbergen Krista G. , Gaston Nicola
Published: September 2024

The low‐temperature liquid metals Ga‐In and Ga‐Sn have previously showcased >95 % selectivity towards the electrochemical reduction of CO2 to formate, occuring only when the alloys are melted, not solid. Here, density functional theory molecular dynamics and metadynamics simulations reveal that CO2 does not directly adsorb to the Ga‐alloy surface, but instead is reduced indirectly by reaction with an adsorbed hydrogen. The reaction barrier is vastly more favourable when this process occurs at In or Sn sites (average: 0.26 eV), than when it occurs on Ga (average: 0.47 eV). However, there is no difference in barrier between solid and liquid surfaces. Instead, we find that Hads is mobile only on the liquid surface, travelling due to the motion of the liquid beneath. This process drives Hads to In/Sn sites, allowing low‐barrier CO2 reduction to occur only on the liquid. Therefore, the dynamic motion of liquid metal catalysts can underpin their unique reactivity. The result has far reaching implications for any protonation reaction conducted with a liquid metal catalyst.
Optimization of Rhizoclonium hieroglyphicum extract for enhanced synthesis of nickel oxide nanoparticles using response surface methodology and its potential exploration in biological application
Authors: Swathilakshmi Ammapettai Varanavasu , Geethamala Gunaseelan Vivekananth , Aldawood Saad , Kavipriya Nachimuthu , Kokilaselvi Senniappan , Chitra Pechimuthu , Selvankumar Thangaswamy , Poonkothai Mani
Published: September 2024

The study investigates the potential of Rhizoclonium hieroglyphicum as a novel source for synthesizing nickel oxide nanoparticles (RH‐NiONPs) and evaluates its biological applications. Phytochemicals in the algal extract serve as capping, reducing and stabilizing agent for nickel oxide nanoparticles. The process variables were optimized using BBD based RSM to obtain maximum RH‐NiONPs. Characterization of RH‐NiONPs using UV–Vis and FT‐IR spectroscopy reveals the plasmon resonance peak at 340 nm and the functional groups responsible for reduction and stabilization. XRD confirmed the crystalline nature while the stability and size of the RH‐NiONPs were determined by DLS and zeta potential. Toxicity assessments demonstrated the effect of RH‐NiONPs against Vigna radiata, Allium cepa and Artemia salina was low. RH‐NiONPs revealed significant zone of inhibition against the selected bacteria and fungi. The results of larvicidal activity showed that RH‐NiONPs are toxic to 4th instar larvae of Daphnis nerii. Also, RH‐NiONPs efficiently decolorized Reactive Violet 13 (92%) under sunlight irradiation and the experimental data well fits to Langmuir isotherm along with pseudo second order kinetic model. The thermodynamic studies enunciate the exothermic and non‐spontaneous photocatalytic decolorization of reactive violet 13. Thus, the current study assesses the eco‐friendly and cost‐effective nature of RH‐NiONPs along with its biological applications.
Clinical and molecular response to alpha1‐oleate treatment in patients with bladder cancer
Authors: Haq Farhan , Sabari Samudra , Háček Jaromir , Brisuda Antonín , Ambite Ines , Cavalera Michele , Esmaeili Parisa , Wan Murphy Lam Yim , Ahmadi Shahram , Babjuk Marek , Svanborg Catharina
Published: September 2024

Background

The tumoricidal complex alpha1‐oleate targets bladder cancer cells, triggering rapid, apoptosis‐like tumor cell death. Clinical effects of alpha1‐oleate were recently observed in patients with non‐muscle invasive bladder cancer (NMIBC), using a randomized, placebo‐controlled study protocol.

Aims

To investigate if there are dose‐dependent effects of alpha1‐oleate.

Materials and Methods

Here, patients with NMIBC were treated by intravesical instillation of increasing concentrations of alpha1‐oleate (1.7, 8.5, or 17 mM) and the treatment response was defined relative to a placebo group.

Results

Strong, dose‐dependent anti‐tumor effects were detected in alpha1‐oleate treated patients for a combination of molecular and clinical indicators; a complete or partial response was detected in 88% of tumors treated with 8.5 mM compared to 47% of tumors treated with 1.7 mM of alpha1‐oleate. Uptake of alpha1‐oleate by the tumor triggered rapid shedding of tumor cells into the urine and cell death by an apoptosis‐like mechanism. RNA sequencing of tissue biopsies confirmed the activation of apoptotic cell death and strong inhibition of cancer gene networks, including bladder cancer related genes. Drug‐related side effects were not recorded, except for local irritation at the site of instillation.

Discussion and Conclusions

These dose‐dependent anti‐tumor effects of alpha1‐oleate are promising and support the potential of alpha1‐oleate treatment in patients with NMIBC.
Immune‐dysregulation harnessing in myeloid neoplasms
Authors: Sharifi Mohammad Jafar , Xu Ling , Nasiri Nahid , Ashja‐Arvan Mehnoosh , Soleimanzadeh Hadis , Ganjalikhani‐Hakemi Mazdak
Published: September 2024

Myeloid malignancies arise in bone marrow microenvironments and shape these microenvironments in favor of malignant development. Immune suppression is one of the most important stages in myeloid leukemia progression. Leukemic clone expansion and immune dysregulation occur simultaneously in bone marrow microenvironments. Complex interactions emerge between normal immune system elements and leukemic clones in the bone marrow. In recent years, researchers have identified several of these pathological interactions. For instance, recent works shows that the secretion of inflammatory cytokines such as tumor necrosis factor‐α (TNF‐α), from bone marrow stromal cells contributes to immune dysregulation and the selective proliferation of JAK2V617F+ clones in myeloproliferative neoplasms. Moreover, inflammasome activation and sterile inflammation result in inflamed microenvironments and the development of myelodysplastic syndromes. Additional immune dysregulations, such as exhaustion of T and NK cells, an increase in regulatory T cells, and impairments in antigen presentation are common findings in myeloid malignancies. In this review, we discuss the role of altered bone marrow microenvironments in the induction of immune dysregulations that accompany myeloid malignancies. We also consider both current and novel therapeutic strategies to restore normal immune system function in the context of myeloid malignancies.
Potential therapeutic effects of apigenin for colorectal adenocarcinoma: A systematic review and meta‐analysis
Authors: Ahmadzadeh Koohyar , Roshdi Dizaji Shayan , Ramezani Fatemeh , Imani Farnad , Shamseddin Jebreil , Sarveazad Arash , Yousefifard Mahmoud
Published: September 2024

Purpose

Therapeutic management of colorectal cancer (CRC) does not yet yield promising long‐term results. Therefore, there is a need for further investigation of possible therapeutic options. Various experiments have studied the effects of apigenin on CRC and have shown conflicting results. This systematic review and meta‐analysis investigates the currently existing evidence on the effect of apigenin on CRC.

Methods

Medline, Embase, Scopus, and Web of Science databases were searched for articles related to apigenin and its effect on CRC in the preclinical setting. Cell viability, growth inhibition, apoptosis, and cell cycle arrest for in‐vitro, and body weight, tumor size, and mortality in in‐vivo studies were extracted as outcomes.

Results

Thirty‐nine articles investigating colorectal adenocarcinoma were included in this meta‐analysis. Thirty‐seven of these studies had data for in vitro experiments, with eight studies having data for in vivo experiments. Six articles had both in vitro and in vivo assessments. Our analysis showed apigenin reduces cell viability and induces growth inhibition, apoptosis, and cell cycle arrest in in vitro studies. The few in vivo studies indicate that apigenin decreases tumor size while showing no effects on the body weight of animal colorectal adenocarcinoma models.

Conclusion

Our results demonstrated that apigenin, through reducing cell viability, inducing growth inhibition, apoptosis, and cell cycle arrest, and also by decreasing the tumor size, can be considered as a possible adjuvant agent in the management of colorectal adenocarcinoma. However, further in vivo studies are needed before any efforts to translate the current evidence into clinical studies.
Radiomic prediction for durable response to high‐dose methotrexate‐based chemotherapy in primary central nervous system lymphoma
Authors: Li Haoyi , Xiong Mingming , Li Ming , Sun Caixia , Zheng Dao , Yuan Leilei , Chen Qian , Lin Song , Liu Zhenyu , Ren Xiaohui
Published: September 2024

Background

The rarity of primary central nervous system lymphoma (PCNSL) and treatment heterogeneity contributes to a lack of prognostic models for evaluating posttreatment remission. This study aimed to develop and validate radiomic‐based models to predict the durable response (DR) to high‐dose methotrexate (HD‐MTX)‐based chemotherapy in PCNSL patients.

Methods

A total of 159 patients pathologically diagnosed with PCNSL between 2011 and 2021 across two institutions were enrolled. According to the NCCN guidelines, the DR was defined as the remission lasting ≥1 year after receiving HD‐MTX‐based chemotherapy. For each patient, a total of 1218 radiomic features were extracted from prebiopsy T1 contrast‐enhanced MR images. Multiple machine‐learning algorithms were utilized for feature selection and classification to build a radiomic signature. The radiomic‐clinical integrated models were developed using the random forest method. Model performance was externally validated to verify its clinical utility.

Results

A total of 105 PCNSL patients were enrolled after excluding 54 cases with ineligibility. The training and validation cohorts comprised 76 and 29 individuals, respectively. Among them, 65 patients achieved DR. The radiomic signature, consisting of 8 selected features, demonstrated strong predictive performance, with area under the curves of 0.994 in training cohort and 0.913 in validation cohort. This signature was independently associated with the DR in both cohorts. Both the radiomic signature and integrated models significantly outperformed the clinical models in two cohorts. Decision curve analysis underscored the clinical utility of the established models.

Conclusions

This radiomic signature and integrated models have the potential to accurately predict the DR to HD‐MTX‐based chemotherapy in PCNSL patients, providing valuable therapeutic insights.
Clinical relevance and druggability of sole reciprocal kinase fusions: A large‐scale study
Authors: Feng Jiao , Ma Tonghui , Wang Chunyang , Wang Baoming , Liu Qian , Liu Zhengchuang , Tao Houquan , Ye Zaiyuan
Published: September 2024

Background

Building on our prior work that RNA alternative splicing modulates the druggability of kinase fusions, this study probes the clinical significance of sole reciprocal fusions. These rare genomic arrangements, despite lacking kinase domains at the DNA level, demonstrated potential RNA‐level druggability in sporadic cases from our prior research.

Methods

Utilizing the large‐scale multicenter approach, we performed RNA sequencing and clinical follow‐up to evaluate a broad spectrum of kinase fusions, including ALK, ROS1, RET, BRAF, NTRK, MET, NRG1, and EGFR, in 1943 patients.

Results

Our findings revealed 51 instances (2.57%) of sole reciprocal fusions, predominantly in lung (57%), colorectal (14%), and glioma (10%) cancers. Comparative analysis with an MSKCC cohort confirmed the prevalence in diverse cancer types and identified unique fusion partners and chromosomal locales. Cross‐validation through RNA‐NGS and FISH authenticated the existence of functional kinase domains in subsets including ALK, ROS1, RET, and BRAF, which correlated with positive clinical responses to targeted kinase inhibitors (KIs). Conversely, fusions involving EGFR, NRG1, and NTRK1/2/3 generated nonfunctional transcripts, suggesting the need for alternative therapeutic interventions.

Conclusion

This inaugural multicenter study introduces a novel algorithm for detecting and treating sole reciprocal fusions in advanced cancers, expanding the patient population potentially amenable to KIs.
Recent Advances of Light/Hypoxia‐Responsive Azobenzene in Nanomedicine Design
Authors: Zhao Yu , Huang Qingqing , Liu Yang
Published: September 2024

Azobenzene (Azo) and its derivatives are versatile stimuli‐responsive molecules. Their reversible photoisomerization and susceptibility to reduction‐mediated cleavage make them valuable for various biomedical applications. Upon exposure to the UV light, Azo units undergo a thermodynamically stable trans‐to‐cis transition, which can be reversed by heating in the dark or irradiation with visible light. Additionally, the N=N bonds in azobenzenes can be cleaved under hypoxic conditions by azoreductase, making azobenzenes useful as hypoxia‐responsive linkers. The integration of azobenzenes into nanomedicines holds promise for enhancing therapeutic efficacy, particularly in tumor targeting and controllable drug release. In this Concept paper, recent advances in the design and applications of azobenzene‐based nanomedicines are updated, and future development opportunities are also summarized.
Impact of commissural alignment on the hemodynamic performance of supra‐annular self‐expandable transcatheter aortic valves
Authors: Amat‐Santos Ignacio J. , Gómez‐Herrero Javier , Pinon Pablo , Nombela‐Franco Luis , Moreno Raúl , Munoz‐García Antonio J. , Redondo Alfredo , Gómez‐Menchero Antonio , Gómez‐Salvador Itziar , San Román J. Alberto
Published: September 2024

Background

Hemodynamic impact of commissural alignment (CA) with self‐expandable transcatheter aortic valves (TAVR) has not been investigated yet.

Aims

To determine hemodynamic impact of CA with self‐expandable TAVR.

Methods

Multicentric ambispective study comparing patients who underwent self‐expandable TAVR in seven centers with the Evolut Pro/Pro+ (EP) (Medtronic) and Acurate neo2 (AN2) (Boston Scientific) with and without CA strategies. The degree of commissural misalignment (CMA) was assessed by computed tomography/angiography and 1‐year transvalvular gradients/regurgitation evaluated by echocardiography. A matched comparison according to annular dimensions/eccentricity, prosthesis size/type, and baseline left ventricular function and gradients was performed.

Results

A total of 557 patients, mean age 80.7 ± 6.6 years, 61.4% men, and STS score of 4.3 ± 3.1% were analyzed. A CA technique was attempted in 215 patients (38.6%), including 113 patients with AN2 and 102 patients with EP. None/mild CMA was found in 158 (73.5% vs. 43.6% if no CA attempted, p < 0.001) with no differences between devices (AN2:75.2%; EP:71.6%, p = 0.545). Patients with moderate/severe CMA had a greater aortic peak gradient (22.3 ± 8.7 vs. 19.7 ± 8.5, p = 0.001), significantly greater progression of both peak (p = 0.002) and mean gradients (p = 0.001) after matching, and higher rate of central aortic regurgitation (1.2% vs. 0.4%, p = 0.005) at 1‐year, but not a greater proportion of patients with mean gradient ≥ 10 mmHg.

Conclusions

The use of CA strategies significantly reduced the rate of CMA for the self‐expandable TAVR devices ACN2 and EP which was associated to lower transvalvular gradients and intra‐prosthetic regurgitation progression at 1‐year although no criteria of structural deterioration were met at this follow up. Clinicaltrials.org: NCT05097183.
Nickel‐Catalyzed Asymmetric Michael Addition of Acyl‐Imidazoles to Acrolein or β‐Ester Enones
Authors: Shi Qian , Sun Jiani , Wu Jiangbo , Lu Xuehe , Wu Xiaoyu
Published: September 2024

An enantioselective Michael addition of α‐substituted acyl‐imidazoles to acrolein catalyzed by a nickel‐bisoxazoline complex has been developed. The use of strong Lewis acid TMSOTf as an additive to activate the Michael acceptors proved to be vital to the success of this process. This process tolerates a wide range of acyl‐imidazoles, and a series of conjugate adducts are obtained in high yields and good enantioselectivities. Besides acrolein, β‐ester ennones are also applicable in this process affording the corresponding conjugate adducts in high yields with good diastereoselectivities and enantioselectivites in most cases. The potential utility of the reaction system is confirmed through 2 mmol‐scale reaction and derivatization experiments.
Superactivity of Bimetallic CuFeO2 Submicron Particles towards Selective Proteolysis, Depending on their Surface Hydroxyls
Authors: Guo Mingxiu , Wang Yaru , Xu Xiaolong
Published: September 2024

Nano bimetallic oxides as nanoproteases have the great advantages in the heterogeneous hydrolysis of proteins. Here, we report that bimetallic delafossite CuFeO2 submicron particles (CuFeO2 SMPs) display a high protease activity towards selective cleavage of peptide bond involving hydrophobic residue at 25 °C. CuFeO2 SMPs have excellent regeneration performance with high structural stability. The strong Lewis acidity of Fe3+ and the strong nucleophilicity of Cu+ bound hydroxyl groups are both necessary for the high protease activity of CuFeO2 SMPs. Low‐valent metal ion has a great advantage in that low‐valent Cu+ bound hydroxyl has strong nucleophilicity, resulting in promotion of protein hydrolysis via high‐efficient bimetallic catalysis. This study provides evidence that the protease activity of CuFeO2 SMPs depends on metal ion‐bound hydroxyls on their surface. Our findings highlight that the valence of metal ions in artificial protease and their surface hydroxyls are two important factors that determine their catalytic efficiency.
Photochemical Decarboxylative Radical Alkylation/Cyclization Reaction to Fused Nitrogen Heterocycles by LiI/PPh3 Catalysis
Authors: Sui Jia‐Li , Liu Xin‐Qian , Li Shun‐Dan , Huang Peng‐Fei , Liu Yu , Li Jin‐Heng
Published: September 2024

Comprehensive Summary

A visible‐light‐induced decarboxylative radical cascade cyclization reaction between N‐(2‐cyanoaryl)‐acrylamides and alkyl N‐(acyloxy)phthalimide (NHPI esters) for the construction of phenanthridine derivatives has been developed. This approach utilizes lithium iodide (LiI) and triphenylphosphine (PPh3) as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor‐acceptor (EDA) complex. A series of primary, secondary, and tertiary alkyl‐substituted phenanthridines are prepared in up to 82% yield without transition‐metal catalysts, chemical oxidants, or metal‐/organic dye‐based photocatalysts.
Boosting Photogenerated Electrons Transfer from FeVO4 to Peroxymonosulfate via Cu Doping for Stable Degradation of Organic Contaminants
Authors: Zhong Zhou , Liu Xiang‐Ji , Ma Li , Zhan Zi‐Jian , Yuan Yu‐Xin , Zhang Heng‐Jian , Cai Feng‐Ying , Hou Yi‐Dong , Lü Jian , Cao Rong
Published: September 2024

Comprehensive Summary

Electron transfer is an important way to activate persulfate. Currently, the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself, which can lead to selective activation of persulfate or oxidation of the catalyst, respectively, and thus become a bottleneck restricting its application. In this work, Cu−doped FeVO4 (Cu−FVO) was prepared, and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate (PMS) activation. The optimized Cu−FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light. This system manifested a broad applicability to various organic contaminants even with complex matrix. Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO. Furthermore, Cu doping led to the establishment of an electron transfer channel from Cu−FVO to PMS, through which photogenerated electrons achieved an efficient PMS activation. Meanwhile, holes were consumed by organic contaminants to avoid the oxidation of catalyst. These collectively enhanced the photocatalytic activity and stability of Cu−FVO, which also maintained high catalytic activity even after 20 cycling degradation reactions.
Divergent Assembly of Functionalized Pyrazolo[1,5‐a]pyridine Derivatives via [3+2] Cyclization of N‐Aminopyridinium Salts with Various Unsaturated Hydrocarbons
Authors: Liu Xiang , Ma Shaohong , Yan Shi , Shi Xiaotian , Li Shuting , Ma Yanlong , Cao Hua
Published: September 2024

Comprehensive Summary

Two reaction modes for metal‐free [3 + 2] cyclization of N‐aminopyridinium derivatives with β‐alkoxyvinyl trifluoromethylketones have been described through selective C—O or C—O/C—C bond cleavage. This strategy can also be extended to the [3 + 2] cyclization of N‐aminopyridinium derivatives with enaminones and bromoalkynes. A broad range of N‐aminopyridinium, N‐aminoquinolinium, and N‐aminoisoquinolinium salts are well tolerated, enabling the divergent synthesis of trifluoroacylated, non‐substituted, acylated, and brominated pyrazolo[1,5‐a]pyridine derivatives (62 examples).
Catalytic Asymmetric [4+2] Cyclization of Hydroxyphenyl Indolinone with Azlactone to Construct Spirooxindole δ‐Lactone
Authors: Wang Xuerui , Ren Weiwu
Published: September 2024

Comprehensive Summary

An efficient asymmetric [4+2] cyclization of hydroxyphenyl indolinone with azlactone for the synthesis of spirooxindole δ‐lactone has been developed, which realized the first asymmetric reaction of hydroxyphenyl indolinone. A series of intricate structures with congested vicinal quaternary chiral centers were provided in good yields with excellent enantioselectivities via the in situ generated o‐QM from hydroxyphenyl indolinone.
Meeting the Industrial Challenges of CO2 Photocatalytic Reduction: Moving From Molybdenum Disulfides to Oxysulfides Based Materials?
Authors: Roth Sébastien , Bonduelle‐Skrzypczak Audrey , Legens Christèle , Raybaud Pascal
Published: September 2024

Reducing CO2 emissions is one of the greatest challenges of the century. Among the means employed to tackle CO2 emissions, the photocatalytic conversion of CO2 is an appealing way to valorize CO2 since it uses the sun energy, which is abundant. However, nowadays, the best photocatalytic systems still report too low efficiencies, and use expensive materials, so they cannot be readily industrialized for use at large scale. In this report, we first highlight general industrial and process challenges (including operating conditions). Then, focusing on MoS2/TiO2 heterojunction systems, we analyze advantages and limitations of such systems and open perspectives on Mo oxysulfides supported on TiO2 discussing their potential to reach higher efficiency for CO2 photoconversion.
Exploring the Photocatalytic Cleavage Pathway of the β‐5 Linkage Lignin Model Compound on Carbon Nitride
Authors: Liu Junhong , Ralphs Kathryn , Murnaghan Christopher W. J. , Skillen Nathan , Sheldrake Gary N. , McCarron Philip , Robertson Peter K. J.
Published: September 2024

As a globally abundant source of biomass, lignocellulosic biomass has been the centre of attention as a potential resource for green energy generation and value‐added chemical production. A key component of lignocellulosic biomass, lignin, which is comprised of aromatic monomers, is a potential feedstock for value added chemical production. The cleavage processes of the linkages between monomers to obtain high value products, however, requires significant investigation as it is a complex, non‐facile process. This study focuses on the photocatalytic valorization of a β‐5 lignin model compound, a key linkage in the lignin structure. It was found that greater yields of aromatic products were obtained from the photocatalytic conversion of β‐5 lignin model compound using carbon nitride (CN) when compared to Evonik P25 titanium dioxide (TiO2). Products of the β‐5 model compound photocatalytic conversion were determined and C−C bond cleavage was observed. It was also determined that the solvent participated in the reactions with the introduction of a cyano group to one of the products. Radical quenching experiments revealed that superoxide radicals participated in the CN photocatalytic conversion. These results reveal for the first time the products and possible mechanism of the photocatalytic transformation of β‐5 model compounds using CN photocatalysis.
Neuro‐fuzzy‐based cluster formation scheme for energy‐efficient data routing in IOT‐enabled WSN
Authors: Sundaram Paulraj Sakthi Shunmuga , Kannabiran Vijayan
Published: September 2024

Internet of things–enabled wireless sensor networks face challenges like inflexibility, poor scalability, suboptimal cluster head selection, and energy inefficiencies. This is due to the faster data transmission rates between cluster nodes during data packet routing. This creates unnecessary energy consumption burdens for those actively transmitting nodes. Conceptually, an effective cluster formation phase supports better data routing mechanisms, while sustaining the energy efficiency of individual nodes. This paper proposes a Neuro‐Fuzzy based Cluster Formation (NFCF) scheme to facilitate adaptive and energy‐efficient cluster topologies. NFCF utilizes fuzzy logic and neural networks to identify optimal super nodes for flexible cluster formations. This approach enables configurable cluster sizes along with inclusion/exclusion criteria for member nodes based on energy thresholds. Parameters evaluated for node selection include the degree of super node, expected energy per cluster, energy variance, and residual energy. Nodes not meeting the thresholds are excluded. The neural network updates fuzzy rules to guide optimal clustering decisions based on anticipated energy dynamics under different conditions. The performance of the proposed NFCF scheme is evaluated based on objective function changes related to data transmission, individual node energy variation, energy variance before and after transmissions, and averaged end‐to‐end delay across transmission cycles. Results are compared against genetic fuzzy clustering, fuzzy energy‐aware clustering, fuzzy‐based distributed clustering, fuzzy logic‐based multi‐hop clustering, and fuzzy weighted k‐means clustering.
A thiourea‐bridged 99mTc(CO)3‐dipicolylamine‐2‐nitroimidazole complex for targeting tumor hypoxia: Utilizing metabolizable thiourea‐bridge to improve pharmacokinetics
Authors: Mittal Sweety , Kumar Chandan , Jha Laxmi , Mallia Madhava B.
Published: September 2024

The 2‐nitroimidazole based 99mTc‐radiopharmaceuticals are widely explored for imaging tumor hypoxia. Radiopharmaceuticals for targeting hypoxia are often lipophilic and therefore, show significant uptake in liver and other vital organs. In this context, lipophilic radiopharmaceuticals with design features enabling faster clearance from liver may be more desirable. A dipicolylamine‐NCS bifunctional chelator that could generate a thiourea‐bridge up on conjugation to primary amine bearing molecule was used to synthesize a 2‐nitroimidazole‐dipicolyl amine ligand for radiolabeling with 99mTc(CO)3 core. Corresponding Re(CO)3‐analogue was prepared to establish the structure of 2‐nitroimidazole‐99mTc(CO)3 complex prepared in trace level. The 2‐nitroimidazole‐99mTc(CO)3 complex showed a hypoxic to normoxic ratio of ~2.5 in CHO cells at 3 h. In vivo, the complex showed accumulation and retention in tumor with high tumor to blood and tumor to muscle ratio. The study demonstrated the utility of metabolizable thiourea‐bridge in 2‐nitroimidazole‐99mTc(CO)3 complex in inducing faster clearance of the radiotracer from liver. The dipicolylamine‐NCS bifunctional chelator reported herein can also be used for radiolabeling other class of target specific molecules with 99mTc(CO)3 core.
Thinning followed by slash burning enhances growth and reduces vulnerability to drought for Pinus nigra
Authors: Vilà‐Vilardell Lena , Valor Teresa , Hood‐Nowotny Rebecca , Schott Katharina , Piqué Míriam , Casals Pere
Published: September 2024

Increasingly frequent severe drought events are pushing Mediterranean forests to unprecedented responses. Lack of management leads to dense forests that are highly susceptible to drought stress, potentially resulting in extensive dieback and increased vulnerability to other disturbances. Forest treatments like thinning and slash burning reduce competition for resources and have the potential to enhance tree growth and vigor and minimize tree vulnerability to drought. Here, we used tree rings to study the growth and physiological response of black pine (Pinus nigra) to drought in northeastern Spain under different treatments, including two thinning intensities (light and heavy, with 10% and 40% basal area reduction, respectively) followed by two understory treatments (clearing alone and in combination with slash burning), resulting in a research design of four treatments plus an untreated control with three replicates. Specifically, we studied basal area increment (BAI), resilience indices, and intrinsic water use efficiency (iWUE) using carbon and oxygen isotope composition (δ13C and δ18O in tree‐ring cellulose) before and after treatments. Our results showed that BAI and resistance to drought increased in the heavy‐thin (burned and unburned) and light‐thin burned units. Resilience increased in the burned units regardless of the thinning intensity, while recovery was not affected by treatment. Slash burning additionally increased BAI in the light‐thin and resistance and resilience in the heavy‐thin units compared with clearing alone. The stable isotope analysis revealed a minor effect of treatments on δ13C and δ18O. No change in iWUE among treatments was presumably linked to a proportional increase in both net CO2 assimilation and stomatal conductance, which particularly increased in the heavy‐thin (burned and unburned) and light‐thin burned units, indicating that these trees were the least affected by drought. This study shows that management approaches aimed at reducing wildfire hazard can also increase the vigor of dominant trees under drought stress. By reducing competition both from the overstory and the understory, thinning followed by clearing alone or in combination with slash burning promotes tree growth and vigor and increases its resistance and resilience to drought.
Construction of high‐loading WO3‐x sub‐nanometer clusters via orderly‐anchored top–down strategy boost acidic hydrogen evolution
Authors: Wu Di , Du Haoyang , Liu Ziyi , Bagliu G. A. , Lai Jianping , Wang Lei
Published: September 2024

Exploring a simple, rapid, and scalable synthesis method for the synthesis of high loading nonprecious metal sub‐nanometer clusters (SNCs) electrocatalysts is one of the most promising endeavors today. Herein, an orderly‐anchored top–down strategy is proposed for fabricating a new type of high loading WO3‐x SNCs on O‐functional group‐modified Ketjen black (WO3‐x‐C(O)) to balance the high loading (49.29 wt.%) and sub‐nanometer size. By optimizing the vacancy number, WO2.71‐C(O) has extremely large electrochemically active surface area (402 m2 g−1) and high turnover frequency value of 1.722 s−1 at −50 mV (vs. reversible hydrogen electrode). The overpotential of WO2.71‐C(O) reaches 22 mV at a current density of 10 mA cm−2, which is significantly better than the commercial Pt/C level (32 mV), achieving a breakthrough in the hydrogen evolution reaction (HER) catalytic activity of nonprecious metals in acidic environment. Theoretical calculations and in situ characterization show that this material allows for the enrichment of reactants (H*) and the optimization of intermediate adsorption, which leads to the enhancement of acidic HER catalytic activity.
RHDV2 outbreak reduces survival and juvenile recruitment, causing European rabbit population collapse
Authors: Letty Jérôme , Besnard Aurélien , Chatelain Nicolas , Choquet Rémi , Holé Gilles , Léonard Yves , Vannesson Régis , Marchandeau Stéphane
Published: September 2024

Infectious diseases can cause considerable mortality in vertebrate populations, especially when a new pathogen emerges. Quantifying the impact of diseases on wild populations and dissecting the underlying mechanisms requires longitudinal individual monitoring combining demographic and epidemiologic data. Such longitudinal population studies are rare. Rabbit hemorrhagic disease (RHD) is one of the main causes of the decline in European wild rabbit (Oryctolagus cuniculus) populations. A new genotype of RHD virus (RHDV), called RHDV2 or GI.2, emerged in 2010, posing a new threat to previously weakened populations, particularly as this virus can infect individuals already immune to classical RHDV strains. Taking advantage of intensive monitoring from 2009 to 2014 by physical captures and microchip detections of a semi‐captive population of rabbits, we finely assessed the demographic impact of an initial RHDV2 outbreak that occurred in the population and identified the most affected demographic parameters. A multi‐event modeling analysis revealed decreased survival in both juveniles and adults in 2011 and 2012, suggesting an RHDV2 outbreak for two consecutive years. The short‐term survival benefit of vaccination against classical RHDV strains only during these years, and the recovery of carcasses with RHDV2 detection, supported this hypothesis. Variations in population vaccination coverage also explain the difference in adult survival between the two years of the outbreak. And the transient protective effect of vaccination could explain the prolonged duration of the outbreak. A brief episode of myxomatosis in 2011 seems to have had only a limited impact on the population. During outbreak years, in individuals not recently vaccinated, monthly juvenile survival crashed (0.55), and annual adult survival was three times lower than in normal years (0.21 vs. 0.69). The combination of successive juvenile and adult survival estimates for unvaccinated rabbits during the outbreak years resulted in a very low recruitment rate in the breeding population. Finally, RHDV2 outbreaks appear to have caused mortalities comparable to those caused by older classical RHDV strains and may have a strong demographic impact on wild populations of European rabbit. This work highlights the importance of long‐term observational and experimental studies to better understand the impact of epidemics on animal populations.
Efficacy and safety of angiotensin receptor–neprilysin inhibition in heart failure patients with end‐stage kidney disease on maintenance dialysis: A systematic review and meta‐analysis
Authors: Nguyen Dung Viet , Le Thanh Ngoc , Truong Binh Quang , Nguyen Hoai Thi Thu
Published: September 2024

Aims

Angiotensin receptor–neprilysin inhibitor (ARNI) has played an increasingly important role in the management of heart failure (HF). However, the evidence on the benefits of ARNI in HF patients with end‐stage kidney disease (ESKD) undergoing dialysis is limited. This study aimed to investigate the efficacy and safety of ARNI in patients with concomitant HF and ESKD on maintenance dialysis.

Methods and results

We systematically searched the MEDLINE, Embase, Web of Science, Cochrane, and ClinicalTrials.gov databases for studies reporting outcomes after ARNI treatment in HF patients with ESKD on dialysis. All meta‐analyses were performed using the random effects model. Twenty‐six studies comprising 2494 patients with concomitant HF and ESKD undergoing dialysis were included. Our synthesis showed a significant improvement in left ventricular ejection fraction (LVEF) between before and after ARNI treatment (mean change: 8.05%; 95% confidence interval [CI] 5.57–10.54). Compared to the conventional group, the ARNI group showed a greater improvement in LVEF (mean difference: 4.03%; 95% CI 2.90–5.16). This effect was more pronounced in patients with HF with reduced ejection fraction (pinteraction < 0.0001). Patients treated with ARNI had a lower risk of all‐cause mortality (risk ratio [RR] 0.64; 95% CI 0.45–0.92; p = 0.01) but had a similar rate of HF hospitalization (RR 0.71; 95% CI 0.43–1.18; p = 0.19). ARNI treatment showed benefits in the improvement of left ventricular end‐systolic diameter, left ventricular mass index, left atrial diameter, and E/e′ ratio (p < 0.05), while it did not significantly increase the risk of severe hyperkalaemia (p = 0.33) or symptomatic hypotension (p = 0.53).

Conclusion

This meta‐analysis provided insights into the benefits of ARNI in HF patients with ESKD undergoing dialysis by improving left ventricular function, reversing left ventricular remodelling, and reducing the risk of all‐cause mortality, without increasing the risk of HF hospitalizations, severe hyperkalaemia, and symptomatic hypotension.
Switching Spin‐States: Spin Crossover vs. Coordination‐Induced Spin‐State Switching
Authors: Hörner Gerald , Weber Birgit
Published: September 2024

Switchable molecular materials have continued to attract the interest of chemists and physicists for decades. A prominent example are spin crossover complexes, where numerous textbooks, review articles, and special issues are available. A highly interesting alternative is the coordination‐induced spin‐state switching. In this concept, we will compare the two spin‐state switching mechanisms and discuss common aspects and differences. Additionally, a short overview of coordination‐induced spin state switching will be given.
Ramp Depositional Model in an Intracratonic Basin: The Cambrian Sedimentary Successions in Yanshan Area, North China
Authors: Kang Shilong , Shao Longyi , Banerjee Santanu , Wang Shuai , Frank Tracy
Published: September 2024

The mechanisms for the deposition of the Cambrian carbonate sedimentary successions remain controversial. The carbonate‐dominated successions (Stage 3 to Stage 10) are well developed in the North China Craton and they are commonly thought to represent a platform setting because of the flat top. In this study, we propose a new scenarioi, that the Cambrian successions in North China are more likely a carbonate ramp rather than a platform. Detailed sedimentological investigation for the Cambrian rocks in the Yanshan area (Stage 4 to Stage 10) reveals a total of 21 lithofacies which can be grouped into 7 facies associations, including sabkha and mixed tidal flat, shoal, carbonate tidal flat, tidal flat on shoal, protected lagoon, mid‐ramp and outer ramp to shelf basin. Sequence stratigraphy analysis of the Cambrian in the Yanshan area reveals nine third‐order depositional sequences, which shows an overall second‐order transgression. A number of sedimentary characteristics, including the gentle depositional slope, abundant open marine deposits, scattered shoals and microbial mounds, absence of slump or gravity flow sediment, domination of subtidal facies cycles and widespread deposits that formed below the storm wave‐base, indicate that the Cambrian sediments in the Yanshan area were deposited in an intracratonic carbonate ramp depositional system. This intracratonic carbonate ramp includes inner ramp, mid‐ramp, outer ramp and shelf basin facies belts, with the inner ramp exhibiting sub‐facies corresponding to tidal flat, protected lagoon and shoal sub‐facies. Sequence stratigraphy analysis indicates that relative sea‐level changes, corresponding to these nine third‐order sequences, show synchronous with the global sea‐level change across the studied sections. This consistency implies that eustatic sea‐level changes could have been a major factor for the sequence stacking patterns in the Yanshan Area.
Compressed cerebro‐cerebellar functional gradients in children and adolescents with attention‐deficit/hyperactivity disorder
Authors: Cao Qingquan , Wang Pan , Zhang Ziqian , Castellanos F. Xavier , Biswal Bharat B.
Published: September 2024

Both cortical and cerebellar developmental differences have been implicated in attention‐deficit/hyperactivity disorder (ADHD). Recently accumulating neuroimaging studies have highlighted hierarchies as a fundamental principle of brain organization, suggesting the importance of assessing hierarchy abnormalities in ADHD. A novel gradient‐based resting‐state functional connectivity analysis was applied to investigate the cerebro‐cerebellar disturbed hierarchy in children and adolescents with ADHD. We found that the interaction of functional gradient between diagnosis and age was concentrated in default mode network (DMN) and visual network (VN). At the same time, we also found that the opposite gradient changes of DMN and VN caused the compression of the cortical main gradient in ADHD patients, implicating the co‐occurrence of both low‐ (visual processing) and high‐order (self‐related thought) cognitive dysfunction manifesting in abnormal cerebro‐cerebellar organizational hierarchy in ADHD. Our study provides a neurobiological framework to better understand the co‐occurrence and interaction of both low‐level and high‐level functional abnormalities in the cortex and cerebellum in ADHD.
Neuropsychiatric symptoms: Risk factor or disease marker? A study of structural imaging biomarkers of Alzheimer's disease and incident cognitive decline
Authors: Guan Dylan X. , Rehman Tanaeem , Nathan Santhosh , Durrani Romella , Potvin Olivier , Duchesne Simon , Pike G. Bruce , Smith Eric E. , Ismail Zahinoor
Published: September 2024

Neuropsychiatric symptoms (NPS) are risk factors for Alzheimer's disease (AD) but can also manifest secondary to AD pathology. Mild behavioral impairment (MBI) refers to later‐life emergent and persistent NPS that may mark early‐stage AD. To distinguish MBI from NPS that are transient or which represent psychiatric conditions (non‐MBI NPS), we investigated the effect of applying MBI criteria on NPS associations with AD structural imaging biomarkers and incident cognitive decline. Data for participants (n = 1273) with normal cognition (NC) or mild cognitive impairment (MCI) in the National Alzheimer's Coordinating Center Uniform Data Set were analyzed. NPS status (MBI, non‐MBI NPS) was derived from the Neuropsychiatric Inventory Questionnaire and psychiatric history. Normalized measures of bilateral hippocampal (HPC) and entorhinal cortex (EC) volume, and AD meta‐region of interest (ROI) mean cortical thickness were acquired from T1‐weighted magnetic resonance imaging scans. Multivariable linear and Cox regressions examined NPS associations with imaging biomarkers and incident cognitive decline, respectively. MBI was associated with lower volume and cortical thickness in all ROIs in both NC and MCI, except for EC volume in NC. Non‐MBI NPS were only associated with lower HPC volume in NC. Although both of the NPS groups showed higher hazards for MCI/dementia than No NPS, MBI participants showed more rapid decline. Although both types of NPS were linked to HPC atrophy, only NPS that emerged and persisted in later‐life, consistent with MBI criteria, were related to AD neurodegenerative patterns beyond the HPC. Moreover, MBI predicted faster progression to dementia than non‐MBI NPS.