bluuebunny/crossref_metadata_2025 huggingface dataset:
A Comprehensive Review on Selective Catalytic Methods for Functionalization of Adamantane Scaffolds
Authors: Kumar Marappan Pradeep , Annie Aksa S , Solanke Jayshree Nandkumar , Dandela Rambabu , Dhayalan Vasudevan
Published: May 2024

Over the decades, conventional techniques have been reported for the direct conversion of a substantial framework of adamantyl C(sp3)‐H/Br/COOH bonds to various C−C, C−N, and other C−X bonds enabled by various catalytic conditions and reagents. There are various simple and direct methods for converting adamantane tertiary and secondary C‐(Sp3)‐H/X/M bonds to quaternary/ tertiary carbon‐carbon bonds that have been reported in previous years, which include methods such as catalytic approaches, cross‐coupling reactions, C−H bond functionalization, radical reactions, organometallics, and dual catalysis, etc. The selective catalytic techniques published between 2010 and 2023 are covered in this article. These adamantane derivatives are broadly studied in various fields such as medicinal chemistry applications, drug development, supramolecular chemistry, material science, catalysts/ligands, and nanotechnologies.
A Rationally Designed Iron(II) Catalyst for C(sp3)−C(sp2) and C(sp3)−C(sp3) Suzuki–Miyaura Cross‐Coupling
Authors: Chen Donghuang , Lepori Clément , Guillot Régis , Gil Richard , Bezzenine Sophie , Hannedouche Jérôme
Published: May 2024

Despite the paramount importance of the Suzuki–Miyaura coupling (SMC) in academia and industry, and the great promise of iron to offer sustainable catalysis, iron‐catalyzed SMC involving sp3‐hybridized partners is still in its infancy. We herein report the development of a versatile, well‐defined electron‐deficient anilido‐aldimine iron(II) catalyst. This catalyst effectively performed C(sp3)−C(sp2) and C(sp3)−C(sp3) SMC of alkyl halide electrophiles and (hetero)aryl boronic ester and alkyl borane nucleophiles respectively, in the presence of a lithium amide base. These couplings operated under mild reaction conditions and displayed wide functional group compatibility including various medicinally relevant N‐, O‐ and S‐based heterocycles. They also tolerated primary, secondary and tertiary alkyl halides (Br, Cl, I), electron‐neutral, ‐rich and ‐poor boronic esters and primary and secondary alkyl boranes. Our methodology could be directly and efficiently applied to synthesize key intermediates relevant to pharmaceuticals and a potential drug candidate. For C(sp3)−C(sp2) couplings, radical probe experiments militated in favor of a carbon‐centered radical derived from the electrophile. At the same time, reactions run with a pre‐formed activated boron nucleophile coupled to competition experiments supported the involvement of neutral, rather than an anionic, (hetero)aryl boronic ester in the key transmetalation step.
Viscoelastic response of amine cured epoxy composites with imidazolium ionic liquid‐modified aramid pulp
Authors: Kerche Eduardo Fischer , da Cruz Joziel Aparecido , Ornaghi Heitor Luiz , Schrekker Henri Stephan , Amico Sandro Campos
Published: May 2024

Three ethanolic solutions containing different imidazolium ionic liquids (IL), namely 1‐butyl‐3‐methylimidazolium chloride, 1‐carboxymethyl‐3‐methylimidazolium chloride or 1,3‐dicarboxymethylimidazolium chloride), were used for the surface modification of aramid pulp (AP) (5 wt.% of IL in relation to AP mass) to improve its interfacial interaction with triethylene tetramine‐cured epoxy resin. Composites were prepared by casting with 0.4 phr of AP. Scanning electron microscopy, mechanical tests, isothermal dynamic mechanical analysis (at 1, 10 and 100 Hz), and conventional non‐isothermal analysis were performed. The IL‐modified AP (AP‐IL) presented greater defibrillation and strengthened interaction with the polymeric matrix, minimizing fiber pullout in the mechanical tests. The AP distribution in the epoxy matrix was assessed, and morphological changes were partly responsible for the improvement in the mechanical and dynamical mechanical response of the AP‐IL/epoxy composites. The AP/epoxy composite compatibilized with IL 1‐butyl‐3‐methylimidazolium chloride presented the lowest activation energy and, in turn, the strongest interaction with the epoxy matrix. Normalized DMA curves provided more detailed information on the differences between neat epoxy and the studied composites.
Boron‐Salphen Conjugate based Molecular Probe Exhibiting Fluorescence On‐Off‐On Response in Detection of Cu2+ and ATP through Displacement Approach
Authors: Bhandari Rimpi , Rai Ravisen , Kaleem Mohammed , Pratap Rajesh , Shraogi Nikita , Patnaik Satyakam , Bhattacharya Subrato , Misra Arvind
Published: May 2024

Synthesis and photophysical properties of a fluorescent probe HBD is described. Probe upon interaction with metal ions, anions and nucleoside pyrophosphates (NPPs) showed fluorescence quenching with Cu2+ due to chelation enhanced quenching effect (CHEQ). Moreover, interaction of ensemble HBD.Cu2+ with anions and NPPs showed fluorescence “turn‐On” response with ATP selectively. “On‐Off‐On” responses observed with Cu2+ and ATP is attributed to an interplay between ESIPT and TICT processes. Cyclic voltammogram of probe exhibited quasi‐reversible redox behaviour with three oxidation and two reduction potentials and the change in band gaps of probe suggested the interaction with Cu2+ and ATP. The 2 : 1 and 1 : 1 binding stoichiometry for an interaction between probe and Cu2+ (LOD, 62 nM) and ensemble, HBD.Cu2+ with ATP (LOD, 0.4 μM) respectively are realised by Job's plot and HRMS data. Cell imaging studies carried out to detect Cu2+ and ATP in HeLa cells. Also, the output emission observed with Cu2+ and ATP is utilized to construct an implication (IMP) logic gate. Test paper strips showed naked‐eye visible color responses to detect Cu2+ and ATP. In real water samples probe successfully detected copper (0.03 μM) between 5–6.5 ppb level (ICP‐MS method).
Introducing Ag Dopants into CdSe Nanoplatelets (NPLs) Leads to Effective Charge Separation for Better Photodetector Performance
Authors: Ghosh Soubhik , Medda Anusri , Patra Amitava
Published: May 2024

Solution‐processed colloidal cadmium chalcogenide nanoplatelets (NPLs)–based photodetectors (PD) are promising materials for next‐generation optoelectronic devices due to their excellent optical properties. Here, we report on ultrafast carrier relaxation dynamics of four monolayer (4 ML) Ag‐doped CdSe (Ag: CdSe) NPLs using ultrafast transient absorption spectroscopy and their photodetectors applications. A broad dopant emission is observed at around 650 nm with a large FWHM of ~431 meV and band edge emission at 515 nm. The intragap dopant state acts as a hole acceptor, which leads to better charge separation. The ultrafast transient absorption spectroscopy study shows faster carrier recombination dynamics with a hole transfer time scale of ~10 ps in Ag‐doped CdSe NPLs. This supports the excited hole capture phenomenon at the dopant state. Ag‐doped CdSe NPLs‐based PD performed better than undoped CdSe NPLs with detectivity and responsivity values of 1.3×1010 Jones and 2.4 mA/W, respectively.
Impact of water quality and operational factors on microcystin removal by powdered activated carbon
Authors: Alexander Matthew T. , Waters Thomas E. , McNeely Morgan , Speth Thomas F. , Dugan Nicholas R.
Published: May 2024

The feasibility of using a 26‐1 fractional factorial design to screen the relative importance of six water quality and operational factors in the removal of microcystin‐LR (MC‐LR) by powdered activated carbon (PAC) was evaluated through jar testing. The factors were: PAC type, PAC dose, total organic carbon (TOC) concentration, turbidity, alum dose, and timing of PAC versus coagulant application. Follow‐up tests were performed to examine the interaction of PAC dose and TOC concentrations. All MC‐LR analyses were performed by enzyme linked immunosorbent assay (ELISA) and liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The top three effect magnitudes were the same by ELISA and LC/MS/MS:PAC dose > PAC type > PAC application time. Correlation coefficients between removals estimated by ELISA and LC/MS/MS were >0.9 (p « .05). With both methods, the effects of PAC type and dose were found to be markedly larger than the other factors. The follow‐up tests indicated a greater impact of PAC dose at higher natural organic matter concentrations. Factorial designs are not commonly used to plan drinking water jar test experiments. The results generated in this study were plausible with respect to the existing body of adsorption knowledge, thus helping to demonstrate the feasibility of the factorial approach.
Utility of serum chemokine–like factor 1 as a biomarker of severity and prognosis after severe traumatic brain injury: A prospective observational study
Authors: Wu Xiaoyu , Su Chang , Tian Da , Ye Yufei , Du Qinghua , Chen Junxia , Li Huguang , Liu Jin
Published: May 2024

Background

Chemokine‐like factor 1 (CKLF1) may be involved in the inflammatory response and secondary brain injury after severe traumatic brain injury (sTBI). We determined serum CKLF1 levels of sTBI patients to further investigate the correlation of CKLF1 levels with disease severity, functional prognosis, and 180‐day mortality of sTBI.

Methods

Serum CKLF1 levels were measured at admission in 119 sTBI patients and at entry into study in 119 healthy controls. Serum CKLF levels of 50 patients were also quantified at days 1–3, 5, and 7 after admission. Glasgow coma scale (GCS) scores and Rotterdam computerized tomography (CT) classification were utilized to assess disease severity. Extended Glasgow outcome scale (GOSE) scores were recorded to evaluate function prognosis at 180 days after sTBI. Relations of serum CKLF1 levels to 180‐day poor prognosis (GOSE scores of 1–4) and 180‐day mortality were analyzed using univariate analysis, followed by multivariate analysis. Receiver‐operating characteristic (ROC) curve was built to investigate prognostic predictive capability.

Results

Serum CKLF1 levels of sTBI patients increased at admission, peaked at day 2, and then gradually decreased; they were significantly higher during the 7 days after sTBI than in healthy controls. Differences of areas under ROC curve (areas under the curve [AUCs]) were not significant among the six time points. Multivariate analysis showed that serum CKLF1 levels were independently correlated with GCS scores, Rotterdam CT classification, and GOSE scores. Serum CKLF1 levels were significantly higher in non‐survivors than in survivors and in poor prognosis patients than in good prognosis patients. Serum CKLF1 levels independently predicted 180‐day poor prognosis and 180‐day mortality, and had high 180‐day prognosis and mortality predictive abilities, and their AUCs were similar to those of GCS scores and Rotterdam CT classification. Combination model containing serum CKLF1, GCS scores, and Rotterdam CT classification performed more efficiently than any of them alone in predicting mortality and poor prognosis. The models were visually described using nomograms, which were comparatively stable under calibration curve and were relatively of clinical benefit under decision curve.

Conclusion

Serum CKLF1 levels are significantly associated with disease severity, poor 180‐day prognosis, and 180‐day mortality in sTBI patients. Hence, complement CKLF1 may serve as a potential prognostic biomarker of sTBI.
Correlation of diffusion tensor tractography with obstructive sleep apnea severity
Authors: Park Bong Soo , Lee Dong Ah , Lee Ho‐Joon , Kim Jinseung , Ko Junghae , Lee Won Hee , Yi Jiyae , Park Kang Min
Published: May 2024

Introduction

Using correlation tractography, this study aimed to find statistically significant correlations between white matter (WM) tracts in participants with obstructive sleep apnea (OSA) and OSA severity. We hypothesized that changes in certain WM tracts could be related to OSA severity.

Methods

We enrolled 40 participants with OSA who underwent diffusion tensor imaging (DTI) using a 3.0 Tesla MRI scanner. Fractional anisotropy (FA), mean diffusivity (MD), axial diffusivity (AD), radial diffusivity (RD), and quantitative anisotropy (QA)‐values were used in the connectometry analysis. The apnea‐hypopnea index (AHI) is a representative measure of the severity of OSA. Diffusion MRI connectometry that was used to derive correlational tractography revealed changes in the values of FA, MD, AD, RD, and QA when correlated with the AHI. A false‐discovery rate threshold of 0.05 was used to select tracts to conduct multiple corrections.

Results

Connectometry analysis revealed that the AHI in participants with OSA was negatively correlated with FA values in WM tracts that included the cingulum, corpus callosum, cerebellum, inferior longitudinal fasciculus, fornices, thalamic radiations, inferior fronto‐occipital fasciculus, superior and posterior corticostriatal tracts, medial lemnisci, and arcuate fasciculus. However, there were no statistically significant results in the WM tracts, in which FA values were positively correlated with the AHI. In addition, connectometry analysis did not reveal statistically significant results in WM tracts, in which MD, AD, RD, and QA values were positively or negatively correlated with the AHI.

Conclusion

Several WM tract changes were correlated with OSA severity. However, WM changes in OSA likely involve tissue edema and not neuronal changes, such as axonal loss. Connectometry analyses are valuable tools for detecting WM changes in sleep disorders.
Conformational Dynamics, Energetics, and the Divergent Evolution of Allosteric Regulation: The Case of the Yeast MAPK Family
Authors: Guarra Federica , Colombo Giorgio
Published: May 2024

Allosteric mechanisms provide finely‐tuned control over signalling proteins. Proteins of the same family may share high sequence identity and structural similarity but show distinct traits of allosteric control and evolutionary divergent regulation. Revealing the determinants of such properties may be important to understand the molecular bases of different regulatory pathways. Herein, we investigate whether and how evolutionarily‐divergent traits of allosteric regulation in homologous proteins can be decoded in terms of internal dynamics and interaction networks that support functionally oriented conformations. In this framework, we start from the comparative analysis of the dynamics and energetics of the yeast MAP Kinases (MAPKs) Fus3 and Kss1 in their native basins. Importantly, distinctive dynamic and energetic stabilization features emerge, which can be related to the two proteins’ differential ability to be phosphorylated and engage with the allosteric activator Ste5. We then expanded our study to other evolutionarily‐related MAPKs. We show that the dynamical and energetical traits defining the distinct regulatory profiles of Fus3 and Kss1 can be traced along their evolutionary tree. Overall, our approach is able to reconnect (latent) allostery with the principal elements of protein structural stabilization and dynamics, showing how allosteric regulation was encrypted in MAPKs structure well before Ste5 appearance.
The Dynamic Plasticity of P. aeruginosa CueR Copper Transcription Factor upon Cofactor and DNA Binding
Authors: Yasin Ameer , Mandato Alysia , Hofmann Lukas , Igbaria‐Jaber Yasmin , Shenberger Yulia , Gevorkyan‐Airapetov Lada , Saxena Sunil , Ruthstein Sharon
Published: May 2024

Bacteria use specialized proteins, like transcription factors, to rapidly control metal ion balance. CueR is a Gram‐negative bacterial copper regulator. The structure of E. coli CueR complexed with Cu(I) and DNA was published, since then many studies have shed light on its function. However, P. aeruginosa CueR, which shows high sequence similarity to E. coli CueR, has been less studied. Here, we applied room‐temperature electron paramagnetic resonance (EPR) measurements to explore changes in dynamics of P. aeruginosa CueR in dependency of copper concentrations and interaction with two different DNA promoter regions. We showed that P. aeruginosa CueR is less dynamic than the E. coli CueR protein and exhibits much higher sensitivity to DNA binding as compared to its E. coli CueR homolog. Moreover, a difference in dynamical behavior was observed when P. aeruginosa CueR binds to the copZ2 DNA promoter sequence compared to the mexPQ‐opmE promoter sequence. Such dynamical differences may affect the expression levels of CopZ2 and MexPQ‐OpmE proteins in P. aeruginosa. Overall, such comparative measurements of protein‐DNA complexes derived from different bacterial systems reveal insights about how structural and dynamical differences between two highly homologous proteins lead to quite different DNA sequence‐recognition and mechanistic properties.
Construction of Multi‐Enzyme Integrated Catalysts for Deracemization of Cyclic Chiral Amines
Authors: Zhou Liya , Li Chunliu , Dong Lele , Liu Yunting , He Ying , Liu Guanhua , Bai Jing , Ma Li , Jiang Yanjun
Published: May 2024

Multi‐enzyme cascade catalysis has become an important technique for chemical reactions used in manufacturing and scientific study. In this research, we designed a four‐enzyme integrated catalyst and used it to catalyse the deracemization reaction of cyclic chiral amines, where monoamine oxidase (MAO) catalyses the enantioselective oxidation of 1‐methyl‐1,2,3,4‐tetrahydroisoquinoline (MTQ), imine reductase (IRED) catalyses the stereo selective reduction of 1‐methyl‐3,4‐dihydroisoquinoline (MDQ), formate dehydrogenase (FDH) is used for the cyclic regeneration of cofactors, and catalase (CAT) is used for decomposition of oxidative reactions. The four enzymes were immobilized via polydopamine (PDA)‐encapsulated dendritic organosilica nanoparticles (DONs) as carriers, resulting in the amphiphilic core‐shell catalysts. The hydrophilic PDA shell ensures the dispersion of the catalyst in water, and the hydrophobic DON core creates a microenvironment with the spatial confinement effect of the organic substrate and the preconcentration effect to enhance the stability of the enzymes and the catalytic efficiency. The core‐shell structure improves the stability and reusability of the catalyst and rationally arranges the position of different enzymes according to the reaction sequence to improve the cascade catalytic performance and cofactor recovery efficiency.
The PIGTAIL paradigm for a fast and safe transfemoral transcatheter aortic valve replacement
Authors: Gennari Marco , Biroli Matteo , Severgnini Gaia , Olivares Paolo , Ferrari Cristina , Giacari Carlo Maria , Agrifoglio Marco , De Marco Federico , Taramasso Maurizio
Published: May 2024

Transfemoral transcatheter aortic valve replacement is the preferred primary access route whenever possible. Despite advancements in expertise and delivery system profiles, complications associated with the primary femoral access still significantly affect procedural morbidity and outcomes. The current standard for accurate main access planning involves proper preprocedural evaluation guided by computed tomography. Several baseline clinical and anatomical features serve as predictors for the risk of vascular injury occurring during or after transcatheter aortic valve replacement. In this paper, we aimed at reviewing the most up‐to‐date knowledge of the topic for a safe transfemoral access approach according to a paradigm we have called “PIGTAIL.”
One‐Pot Catalytic Approaches: Building a New Toolbox for Macromolecular Design
Authors: Yang Fan , Guillaume Lucie , Gauvin Régis M. , Thomas Christophe M.
Published: May 2024

One‐pot processes have emerged as a powerful strategy in (macro)molecular synthesis: integrating a multicatalytic process maximizes efficiency, reduces waste, improves profitability, and provides versatile tools for designing of more sustainable processes without compromising selectivity and activity. This review article provides a critical overview of the application of one‐pot transformations in polymerization, with the goal of synthesizing polymers with tailored structures and functions for a wide range of applications. Recent advances in one‐pot polymerization techniques are highlighted, including examples from controlled polymerization methods such as atom transfer radical polymerization, reversible addition‐fragmentation chain transfer polymerization, and ring‐opening polymerization, among others. Special emphasis is placed on the design and optimization of reaction conditions, catalyst systems, and monomer combinations to achieve precise control over polymer structure and functionality.
CoPS/Co4S3 Heterojunction with Highly Exposed Active Sites and Dual‐site Synergy for Effective Hydrogen Evolution Reactions
Authors: Song Kai , Yang Dian , Zhou Chenjing , Li Qingao , Zhang Lili , Gong Junjie , Zhong Wenwu , Shen Shijie , Chen Shichang
Published: May 2024

Cobalt phosphosulphide (CoPS) has recently been recognized as a potentially effective electrocatalyst for the hydrogen evolution reaction (HER). However, there have been no research on the design of CoPS‐based heterojunctions to boost their HER performance. Herein, CoPS/Co4S3 heterojunction was prepared by phosphating treatment based on defect‐rich flower‐like Co1‐xS precursors. The high specific surface area of nanopetals, together with the heterojunction structure with inhomogeneous strain, exposes more active sites in the catalyst. The electronic structure of the catalyst is reconfigured as a result of the interfacial interactions, which promote the catalyst‘s ability to adsorb hydrogen and conduct electricity. The synergistic effect of the Co and S dual‐site further enhance the catalytic activity. The catalyst has overpotentials of 61 and 70 mV to attain a current density of 10 mA cm−2 in acidic and alkaline media, respectively, which renders it competitive with previously reported analogous catalysts. This work proposes an effective technique for constructing transition metal phosphosulfide heterojunctions, as well as the development of an efficient HER electrocatalyst.
Photochemical Radical Cascade 6‐endo Cyclization of Dienes with α‐Carbonyl Bromides for the Synthesis of Six‐Membered Benzo‐Fused Lactams
Authors: Sui Jia‐Li , Guo Yang , Xiong Bi‐Quan , Tang Ke‐Wen , Huang Peng‐Fei , Liu Yu , Li Jin‐Heng
Published: May 2024

Comprehensive Summary

A novel visible‐light‐induced radical cascade 6‐endo cyclization of dienes (N‐(2‐vinylphenyl)acryl amides) is developed utilizing α‐carbonyl bromides as alkyl reagents. This approach affords an efficient way for synthesizing six‐membered benzo‐fused lactam derivatives with chemo‐ and regio‐selectivity and good functional group tolerance. Primary, secondary, and tertiary bromides are well‐compatible with this cascade cyclization reaction.
Photocatalytic [3+2] Cycloaddition of Alkyl/aryl Iodides and Internal Alkynes by Merging Halogen and Hydrogen Atom Transfer
Authors: Gu Zhenyu , Jia Rong , Zeng Tianqing , Zheng Hanliang , Zhu Gangguo
Published: May 2024

Comprehensive Summary

A visible light photocatalytic [3+2] cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein. By merging halogen atom transfer (XAT) and hydrogen atom transfer (HAT), alkyl/aryl iodides serve as a formal diradical precursor and add across C‐C triple bonds to deliver a number of functionalized cyclopentanes in moderate to high yields with exceptional regio‐ and diastereoselectivity. A reductive radical‐polar crossover mechanism, involving the cascade XAT, radical addition, 1,5‐HAT, polar effect‐promoted 5‐endo annulation, single electron transfer (SET) reduction, and protonation, may account for this unprecedented dehalogenative [3+2] cycloaddition. This work not only expands the repertoire of the traditional RATC methodology, but also provides a robust platform for the expedient assembly of cyclopentanes, a valuable structural motif in the realms of medicinal chemistry and material sciences.
Harnessing the Synergy of ZIF‐67 Derived Nanohybrid‐Based Immunosensing for sensitive Detection of Helicobacter pylori
Authors: Saxena Kirti , Bhattacharyya Puja , Deshwal Akanksha , Shrivastava Neeraj , Jain Utkarsh , Malhotra Bansi Dhar , Chakrabarti Sandip , Tripathi Ravi Mani
Published: May 2024

Detection of Helicobacter pylori (H. pylori) infection, a significant risk factor for chronic gastritis, peptic ulcers, and gastric adenocarcinoma, poses a formidable challenge due to the lack of sensitive and selective sensing platforms. Herein, we report the synthesis of a zeolitic imidazolate framework‐67 (ZIF‐67) derived Co/Co3O4/C (CoNH) porous nanostructure, optimized for the electrochemical immunosensing of H. pylori‐specific antigen VacA. By calcining ZIF‐67 at elevated temperatures, we obtained CoNH with enhanced electroactivity and conductivity, crucial for signal enhancement. The synthesized CoNH was thoroughly characterized using SEM, TEM, XPS, Raman, and FT‐IR techniques. Further signal amplification was achieved by introducing gold nanoparticles (AuNPs) onto CoNH‐modified screen‐printed carbon electrodes. Systematic investigation at each modification stage led to an optimized immunosensing platform with high sensitivity and selectivity for VacA detection. The developed immunosensor demonstrated the capability to detect low concentrations of VacA (0.1 ng/ml) within a wide linear range (0.1–50 ng/ml) with long‐term stability. This highly sensitive and selective biosensor holds promise for early‐stage diagnosis of H. pylori infection and gastric cancer.
An investigation of the Excitation Wavelength‐Dependent Dynamic Changes in the Mechanism of Detection of Picric Acid using Pyrene‐Based Donor‐Acceptor Systems
Authors: Sreelaya V. , Rohman Shahnaz S. , Parameswaran Pattiyil , Chakkumkumarath Lakshmi
Published: May 2024

Picric acid (PA) is an important industrial feedstock and hence the release of industrial effluents without proper remediation results in its buildup in soil and water bodies. The adverse effects of PA accumulation in living beings necessitate the development of efficient methods for its detection and quantification. Herein, we describe pyrene‐based fluorescent sensors for PA, where pyrene is appended with electron‐withdrawing groups, malononitrile, and 2‐(3‐cyano‐4,5,5‐trimethylfuran‐2(5H)‐ylidene) malononitrile (DCDHF). These molecules displayed the typical emission of pyrene monomers, as well as a broad red‐shifted emission resulting from an intramolecular charge transfer (ICT) in the excited state. Both the emissions displayed a turn‐off response to PA with high selectivity and sensitivity and the lowest limit of detection was estimated as 27 nM. To prove the feasibility of on‐site detection, test paper strips were prepared, which could detect PA up to 4.58 picograms. Using a combination of experimental and theoretical studies the mechanism of the detection was identified as primary/secondary inner filter effect, oxidative photoinduced electron transfer, or a combination of both depending on the excitation wavelength. Interestingly, the contribution of each of these mechanisms to the total quenching process varied with a change in the excitation wavelength.
Atomic Insight into the Enzymatic Selectivity of Acetyltransferase for Endogenous Polyamines
Authors: Guo Baolin , Xue Qian , Zhang Zhiyang , Zhai Jihang , Wang Chaojie , Zhao Yuan , Zhang Jie
Published: May 2024

The N1−Spermidine/spermine acetyltransferase (SSAT) serves as the rate‐limiting enzyme in the polyamine metabolism pathway, specifically catalyzing the acetylation of spermidine, spermine, and other specific polyamines. The source of its enzymatic selectivity remains elusive. Here, we used quantum mechanics and molecular mechanics simulations combined with various technologies to explore the enzymatic mechanism of SSAT for endogenous polyamines from an atomic perspective. The static binding and chemical transformation were considered. The binding affinity was identified to be dependent on protonated state of polyamine. The order of the binding affinity for Spm, Spd, and Put is consistent with the experimental results, which is also verified by the dynamic separation of polyamine and SSAT. Hydrogen bond interactions and salt bridges contribute most, and the common hot residues were identified. In addition, the transfer of acetyl and proton between polyamine and AcCoA was discovered to follow a concert mechanism, and thermodynamic properties are responsible for the catalytic efficiency of SSAT. This work may be helpful for development of polyamine derivatives based on catalysis to regulate polyamine metabolism.
Buckybowl Molecular Tweezers for Recognition of Fullerenes
Authors: Oshchepkov Alexander S.
Published: May 2024

Buckybowl tweezers are a relatively young research area closely associated with the development of non‐planar polycyclic aromatic systems and supramolecular chemistry. Since the appearance of the first prototypes in the early 2000s, the tweezers have undergone evolutionary changes. Nowadays they are able to effectively interact with fullerenes and the results opened up prospects for development in the field of sensing, nonlinear optics, and molecular switchers. In the present study, examples of corannulene‐based and other buckybowl tweezers for the recognition of C60 and C70 fullerenes were summarized and analyzed. The main structural components of the tweezers were also reviewed in detail and their role in the formation of complexes with fullerenes was evaluated. The revealed structural patterns should trigger the development of novel recognition systems and materials with a wide range of applications.
Design, Synthesis, and Photochemical Properties of Gene‐directed Caged RyR Probes for Photopharmacological Studies
Authors: Yokoyama Aika , Aoki Hanami , Funayama Mizuki , Shinozaki Ryo , Yoshida Hiroto , Suzuki Akinobu Z. , Furuta Toshiaki
Published: May 2024

Ryanodine receptor (RyR) is a crucial intracellular Ca2+ channel involved in various physiological processes associated with several diseases. This paper presents the synthesis and evaluation of novel photoactivatable caged compounds for the RyR. We used (6‐bromo‐7‐hydroxycoumarn‐4‐yl)methyl (Bhc) as the photolabile protecting group to develop caged versions of 4‐CmC, a broad‐spectrum RyR agonist, and FLA365, an antagonist. The synthesized compounds, Bhcmoc‐4‐CmC and Bhcmoc‐FLA365, exhibited photoreactivity that enabled spatiotemporal control over the RyR activity. Bhcmoc‐4‐CmC presents a quantum yield of 25 % and a photolysis efficiency of 1,075 M−1 cm−1 under 405 nm light, triggering Ca2+ release from the endoplasmic reticulum. Conversely, Bhcmoc‐FLA365 presents a reduced quantum yield of 0.61 %, which can be attributed to the quenching effects of its tertiary amine structure. We also applied gene‐directed caging, synthesizing β‐galactosidase (β‐Gal) activatable Gal‐Bhcmoc‐4‐CmC and Gal‐Bhcmoc‐FLA365, and porcine liver esterase (PLE)‐activatable CM‐Bhcmoc‐FLA365, to target these probes to the specific cell types. These caged compounds contribute significantly to photopharmacology, providing tools for the precise analysis and manipulation of the RyR functions. Future research objectives involve further optimization and analysis of the photochemical mechanisms of these caged compounds to enhance their applications in biological and medical research.
Surface Plasmon Resonance‐Mediated Photocatalytic H2 Generation
Authors: Zhang Xiaohan , Wang Cong , Zhang Menglong , Luo Dongxiang , Ye Siyu , Weng Bo
Published: May 2024

The limited yield of H2 production has posed a significant challenge in contemporary research. To address this issue, researchers have turned to the application of surface plasmon resonance (SPR) materials in photocatalytic H2 generation. SPR, arising from collective electron oscillations, enhances light absorption and facilitates efficient separation and transfer of electron‐hole pairs in semiconductor systems, thereby boosting photocatalytic H2 production efficiency. However, existing reviews predominantly focus on SPR noble metals, neglecting non‐noble metals and SPR semiconductors. In this review, we begin by elucidating five different SPR mechanisms, covering hot electron injection, electric field enhancement, light scattering, plasmon‐induced resonant energy transfer, and photo‐thermionic effect, by which SPR enhances photocatalytic activity. Subsequently, a comprehensive overview follows, detailing the application of SPR materials‐metals, non‐noble metals, and SPR semiconductors‐in photocatalytic H2 production. Additionally, a personal perspective is offered on developing highly efficient SPR‐based photocatalysis systems for solar‐to‐H2 conversion in the future. This review aims to guide the development of next‐gen SPR‐based materials for advancing solar‐to‐fuel conversion.
Bimetallic MOFs‐Derived NiFe2O4/Fe2O3 Enabled Dendrite‐free Lithium Metal Anodes with Ultra‐High Area Capacity Based on An Intermittent Lithium Deposition Model
Authors: Wang Mengting , Wei Tao , Lu Jiahao , Guo Xingtong , Sun Cheng , Zhou Yanyan , Su Chao , Chen Shanliang , Wang Qian , Yang Ruizhi
Published: May 2024

In practical operating conditions, the lithium deposition behavior is often influenced by multiple coupled factors and there is also a lack of comprehensive and long‐term validation for dendrite suppression strategies. Our group previously proposed an intermittent lithiophilic model for high‐performance three‐dimensional (3D) composite lithium metal anode (LMA), however, the electrodeposition behavior was not discussed. To verify this model, this paper presents a modified 3D carbon cloth (CC) backbone by incorporating NiFe2O4/Fe2O3 (NFFO) nanoparticles derived from bimetallic NiFe‐MOFs. Enhanced Li adsorption capacity and lithiophilic modulation were achieved by bimetallic MOFs‐derivatives which prompted faster and more homogeneous Li deposition. The intermittent model was further verified in conjunction with the density functional theory (DFT) calculations and electrodeposition behaviors. As a result, the obtained Li‐CC@NFFO||Li‐CC@NFFO symmetric batteries exhibit prolonged lifespan and low hysteresis voltage even under ultra‐high current and capacity conditions (5 mA cm−2, 10 mAh cm−2), what's more, the full battery coupled with a high mass loading (9 mg cm−2) of LiFePO4 cathode can be cycled at a high rate of 5 C, the capacity retention is up to 95.2 % before 700 cycles. This work is of great significance to understand the evolution of lithium dendrites on the 3D intermittent lithiophilic frameworks.
A 2.72 μs row conversion time 11‐bit column‐parallel single‐slope analog to digital converter with differential‐clocks‐assisted time to digital converter interpolation for complementary metal oxide semiconductors image sensor
Authors: Duan Hao , Nie Kaiming , Xu Jiangtao
Published: May 2024

This paper presents an innovative readout scheme that utilizes a pair of differential‐clocks‐assisted time‐to‐digital converter (DCA‐TDC) in CMOS image sensors (CISs). The DCA‐TDC utilizes only half the number of ordinary TDC delay chain units by employing a binary‐weighted search algorithm to determine the most significant bit (MSB) for fine quantization of a single‐slope analog‐to‐digital converter (SS ADC). Additionally, the layout area and dynamic power introduced by the improved DCA‐TDC delay chain are halved compared to an ordinary TDC delay chain. The proposed SS ADC is designed and simulated using the 0.11 
m standard CMOS proces, achieving an 11‐bit ADC with a column‐level power consumption of 65.4 
W, and a row conversion time of 2.72 
s, within a design environment featuring an analog voltage of 3.3 V, a digital voltage of 1.5 V, a clock frequency of 62.5 MHz, and a temporal resolution of 500 ps. Furthermore, this design achieves an effective number of bits (ENOB) of 10.71 and a figure of merit (FoM) of 110.5 fJ/step. By interpolating a DCA‐TDC, the quantization speed is enhanced compared to traditional SS ADCs, presenting an effective solution for high‐frame‐rate CIS implementations.
High voltage gain minimum‐phase isolated DC‐DC converter with improved transformer utilization
Authors: Obulapathi Balapanuru , Lokhande Makarand M. , Aware M. V.
Published: May 2024

The standard structure of an isolated SEPIC (iSEPIC) does not have a minimum‐phase nature, which signifies no additional support for the output capacitor during ON‐time conditions. Consequently, it has high voltage stress, right half plane (RHP) zeros presence, DC component in the transformer core, and less transformer utilization. This paper presents a modification in a iSEPIC converter having higher voltage gain over a conventional iSEPIC converter. This work analyzes a modified iSEPIC structure by providing additional support to the output capacitor during ON‐time conditions. As a result, the nonminimum‐phase nature will be transformed into the minimum‐phase nature. Consequently, all the mentioned demerits of the standard iSEPIC structure are eliminated The derived discrete‐time modeling analyzes the RHP zeros dependence on the load variation. This modification also leads to improvement in dynamic performance to accommodate the load variation. Finally, a 60 W modified iSEPIC prototype is developed to validate the proposed analysis.
Energy efficient data dissemination in wireless sensor network enabled IoT using domain‐adaptive message passing graph neural network
Authors: Shiny G. Susan , Ram R. Saravana , J Rajeshkumar , Muthalakshmi M.
Published: May 2024

In the past few years, restricted wireless sensor networks (WSNs) enabled the Internet of Things (IoT) have attracted significant attention and expansion to enhance service delivery and resource efficiency. Dissemination is a service offered by WSN that uses radio transmission and over‐the‐air programming for updating the deployed sensor nodes through online. The centralized data dissemination methods are replaced by the distributed approaches because they affect the drawbacks of a single point of failure, no scalability, and insecurity. Therefore, an Energy Efficient Protocol for Data Dissemination in Wireless Sensor network‐enabled IoT using Domain‐Adaptive Message Passing Graph Neural Network (EEP‐WSN‐IoT‐DMPGNN) is proposed in this paper. The nodes are formed as clusters utilizing the Deep Fuzzy Curriculum Clustering (DFCC) technique that rewards nodes belonging to a given cluster. By using the Crayfish Optimization Algorithm (COA), the Cluster Head (CH) selection optimally chose the ideal CH and satisfies the multiple objective functions, such as energy, delay, traffic density, and distance. Afterward, domain‐adaptive Message Passing Graph Neural Network (DMPGNN) based routing protocol is developed, the input given to the routing protocol includes a sink, action history, future node, and maximum‐distance node, which attains enhanced data transfer in the chosen path. The proposed technique attains a lower no. of dead nodes, lower energy consumption, and higher Network Lifetime while analyzed with existing techniques, such as routing technique depending on deep learning for effectual data transmission in 5G WSN communication (DL‐RPDT‐WSN), Reinforcement‐Learning base energy effectual optimized routing protocol in WSN (RL‐EERP‐WSN), and Energy‐efficient intellectual routing method for IoT‐enabled WSN (EIR‐IoT‐WSN), respectively.
A review of carbon and phosphorus ratios in fresh water ecosystems dominated by phytoplankton: Effects of climate and geography
Authors: Ayub Gohar , Su Jinzhu , Su Yuping , Zheng Luwei , Zhou Yuanyuan , Rehman Sami ur , Zahir Muhammad
Published: May 2024

In freshwater systems, carbon, nitrogen, and phosphorus are essential macroelements. Changing ecological communities as a result of anthropogenic activity and climate change has become a global issue. C:P has been demonstrated to be a trustworthy and sensitive assay for detecting and monitoring single or multiple species in a wide range of samples. We look at how C:P can be utilized to manage and reduce eutrophication and harmful algal blooms (HABs) in freshwater environments in this review work. Recent research show how C:P has been shown to be a useful strategy for gathering complete data in freshwater ecosystem studies. The total number of papers in ScienceDirect from 2000 to 2023 with the terms “carbon and phosphorus ratios, fresh water ecosystems, and phytoplankton” in the title, abstract, or keywords was acquired for this review. Based on the number of published research demonstrating an increased understanding of the basic scientific concepts behind the carbon and phosphorus ratio, the overall temporal trend in publications on the ratio showed a steady growth. Compared to eutrophic Lake Victoria, which had a C:P of 149, mesotrophic Lakes Malawi and Kivu had a ratio of 263. Applying the carbon‐to‐phosphorus ratio to lake and reservoir eutrophication assessment is feasible, and the increasing C:P ratio serves as a prime indicator for the initiation of lake and reservoir reoligotrophication. Our findings establish the framework for future study into the relationship between organic nutrients and eutrophication, as well as the ecological ramifications of these relationships in freshwater systems. Furthermore, our prediction was that increases in C:P would change the structure of phytoplankton communities.
Development of a maintenance scheduling method for power generators considering large penetration of variable renewable energy sources and system inertia
Authors: Segawa Shuhei , Ogimoto Kazuhiko , Azuma Hitoshi , Isonaga Akira , Fukutome Suguru
Published: May 2024

Conventional methods to schedule power generators maintenance aim to secure enough supply reserve margin to the power system when its power generators have to go under maintenance. However, the use of such methods in scenarios of large penetration of VRE, might be problematic. This is because in such scenarios conventional scheduling methods might inadvertently concentrate maintenance operations when residual demand is particularly low, creating situations in which there is insufficient supply‐demand balancing capability and inertia to operate the power system properly. In this study, we present the development of a new method to schedule generator maintenance that ensure inertia and balancing capability constraints, and show its effectiveness.
Lanthanoid Semiquinonate/Tropolonate Complexes: Redox Chemistry and Luminescence
Authors: Dunstan Maja A. , Suryadevara Nithin , Cameron Lee , Gable Robert W. , Massi Massimiliano , Boskovic Colette
Published: May 2024

Heteroleptic lanthanoid (Ln = Eu, Gd, Tb, Dy, Ho and Yb) complexes featuring hydro‐tris(1‐pyrazolyl)borate (Tp−) ligands combined with the bidentate O‐donor ligands tropolonate (trop−) or 3,5‐di‐tertbutylseminquinonate (dbsq⋅−) have been synthesized and investigated. Despite the similarity of the bidentate O‐donor trop− and dbsq⋅− ligands, and the lanthanoid coordination geometries, the complexes [LnTp2dbsq] (Ln‐dbsq) and [LnTp2trop] (Ln‐trop) exhibit markedly different redox and photophysical properties. The electrochemistry of Ln‐dbsq is dominated by processes associated with the readily redox‐active dbsq⋅− moiety. In contrast, the relative redox inactivity of Ln‐trop allows for the observation of the Eu(III) to Eu(II) reduction process. Photophysical measurements reveal no sensitized emission for the Ln‐dbsq family, while the trop− antenna ligand is able to sensitize emission in the visible range for Eu(III) and Ho(III), and in the near‐infrared for Ho(III) and Yb(III).
Transition‐Metal‐Catalyzed Reactions Involving Trifluoro Diazo Compounds and Their Surrogates
Authors: Wang Yeming , Zhang Chaoqun , Li Shizhe , Liu Lihui , Feng Xiaodong , Liu Zhaohong
Published: May 2024

Fluorinated organic compounds represent an important and growing family of active ingredients in various fields, including material science, pharmaceutical chemistry and biological science. Developing efficient synthetic methods toward fluorinated organic compounds have attracted much attention. In recent years, transition‐metal catalyzed reaction of trifluoro diazo compounds were a powerful and convenient approach to afford trifluoromethyl‐ and difluoromethyl‐substituted compounds of value. In this review, the recent progress on transition‐metal‐catalyzed reactions involving trifluoro diazo compounds and their surrogates via trifluoromethylated transition‐metal carbene complex is described in the sequence of 2,2,2‐trifluorodiazoethane as carbene precursor, ethyl 3‐trifluoro‐2‐diazo‐propionate as carbene precursor, trifluoroethylamine hydrochloride or amines as the CF3CHN2 surrogate as well as trifluoro aldehydes/ketones N‐sulfonylhydrazones as the trifluoro diazo compounds surrogate.
Amidation of β‐Keto Sulfonyl Fluorides via C−C Bond Cleavage
Authors: Liang Hui , Liu Qian , Zhao Xueyan , He Tianyu , Luo Jinyue , Huang Shenlin
Published: May 2024

A simple protocol for amide bond construction using β‐keto sulfonyl fluorides (BKSFs) as the acyl surrogates has been achieved. The reaction of BKSFs with a range of amines could be performed in presence of N‐bromosuccinimide (NBS), affording various amides with diverse functionalities. Preliminary mechanistic studies revealed that the dibromo‐substituted sulfonyl fluorides could be the key intermediate in this amidation process.
Investigating the kinetics of small alcohol oxidation reactions using platinum supported on a doped niobium suboxide support
Authors: Black‐Araujo Keenan , Nguyen Katherine , Esfahani Reza Alipour Moghadam , Easton E. Bradley
Published: May 2024

Platinum nanoparticles deposited on a silicon‐doped niobium suboxide support provided the catalyst known as Pt/NbOS. This was compared to the commercial Pt/C electrocatalyst in the ethanol and methanol oxidation reactions for use in direct alcohol fuel cells. Cyclic voltammetry and electrochemical impedance spectroscopy demonstrate that the employment of the metal oxide support provides higher peak oxidation currents and smaller charge transfer resistances during alcohol oxidation. Carbon monoxide (CO) stripping experiments showed enhanced removal of CO by Pt/NbOS compared to Pt/C. Pt/NbOS shows its smallest apparent activation energies of 13.3 and 11.9 J mol‐1, for methanol and ethanol oxidation respectively, which are 38% and 27% lower than those of Pt/C at the same potentials. This increased activity of Pt/NbOS is attributed to the strong metal‐support interactions between the active Pt nanoparticles and the NbOS support which demonstrate its utility in replacing Pt/C in methanol and ethanol fuel cells.