{"title":"Stereoselective convergent total synthesis of tonkinelins.","authors":"Rodney A Fernandes, Anupama Kumari","doi":"10.1039/d5ob01214g","DOIUrl":"https://doi.org/10.1039/d5ob01214g","url":null,"abstract":"<p><p>We report the stereoselective synthesis of (17<i>S</i>,18<i>S</i>,36<i>S</i>)-tonkinelin and its diastereomer (17<i>R</i>,18<i>R</i>,36<i>S</i>)-tonkinelin <i>via</i> a convergent strategy involving the stepwise construction of two key fragments: a chiral ester-derived phosphonium salt and a requisite aldehyde for a convergent Wittig olefination. Key transformations in the sequence include asymmetric dihydroxylation, Wittig olefination, ring-closing metathesis (RCM) and chemoselective diimide olefin reduction. The synthesized tonkinelins were fully characterized, and their spectroscopic data were found to be consistent with previously reported data.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Composite nano copper carrier combining cuproptosis and photodynamic therapy for spatiotemporal synergistic anti-tumor therapy.","authors":"Yong-Guo Hu, Fang Zhang, Li-Li Chen, Xin-Yue Xu, Pei-Jie Zhang, Yong Li, Jin-Xuan Fan, Jia-Hua Zou, Yuan-Di Zhao","doi":"10.1039/d5bm00954e","DOIUrl":"https://doi.org/10.1039/d5bm00954e","url":null,"abstract":"<p><p>Cuproptosis is a copper-dependent programmed cell death triggered by mitochondrial dysfunction, which offers significant anti-tumor potential but requires tumor-specific copper delivery to avoid systemic toxicity. Here, we developed a synergistic nanoplatform (Cu<sub>2</sub>O@SiO<sub>2</sub>-Ce6, CSC) integrating cuproptosis induction with photodynamic therapy (PDT). A cuprous oxide (Cu<sub>2</sub>O) core was encapsulated in silicon dioxide and covalently linked to the photosensitizer Ce6. After accumulating in tumor regions <i>via</i> the EPR effect, CSC releases a surge of copper ions upon encountering the acidic tumor microenvironment and lysosomes. These ions induce mitochondrial cuproptosis by aggregating lipoylated TCA cycle proteins and depleting Fe-S cluster proteins. Concurrently, laser irradiation activates Ce6 to generate cytotoxic reactive oxygen species, actively disrupting tumor membranes. The experiments showed that the nanoplatform significantly enhanced the tumor cell killing effect and reduced the toxicity to normal tissues through a dual mechanism, which provided a new strategy for overcoming the drug resistance of PDT and the precise regulation of cuproptosis.</p>","PeriodicalId":65,"journal":{"name":"Biomaterials Science","volume":" ","pages":""},"PeriodicalIF":5.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Soft MatterPub Date : 2025-09-04DOI: 10.1039/d5sm00502g
Mohammad Shojaeifard, Mattia Bacca
{"title":"Hyperelastic characterization <i>via</i> deep indentation.","authors":"Mohammad Shojaeifard, Mattia Bacca","doi":"10.1039/d5sm00502g","DOIUrl":"https://doi.org/10.1039/d5sm00502g","url":null,"abstract":"<p><p>Hyperelastic material characterization is crucial for sensing and understanding the behavior of soft materials-such as tissues, rubbers, hydrogels, and polymers-under quasi-static loading before failure. Traditional methods typically rely on uniaxial tensile tests, which require the cumbersome preparation of dumbbell-shaped samples for clamping in a uniaxial testing machine. In contrast, indentation-based methods, which are non-destructive and can be conducted <i>in situ</i> without sample preparation, remain underexplored. To characterize the hyperelastic behavior of soft materials, deep indentation is required, where the material response extends beyond linear elasticity. In this study, we perform finite element analysis to link the force (<i>F</i>) <i>vs.</i> indentation depth (<i>D</i>) curve with the hyperelastic behavior of a soft incompressible material, using a one-term Ogden model for simplicity. We identify three indentation regimes based on the ratio between indentation depth and the radius (<i>R</i>) of the spherical-tipped cylindrical indenter: (1) the Hertzian regime (<i>D</i> ≪ <i>R</i>) with <i>F</i> = <i>ER</i><sup>0.5</sup><i>D</i><sup>1.5</sup>16/9 (<i>E</i> is elastic modulus), (2) the parabolic regime (<i>D</i> ≫ <i>R</i>) with <i>F</i> = <i>ED</i><sup>2</sup><i>β</i>, where the indenter radius becomes irrelevant, and (3) an intermediate regime (<i>D</i> ~ <i>R</i>) bridging the two extremes. We find that the Ogden strain-stiffening coefficient (<i>α</i>) increases the parabolic indentation coefficient (<i>β</i>), allowing for the estimation of <i>α</i> from <i>β</i>. Furthermore, we observe that Coulomb friction increases <i>β</i>, potentially masking the effect of strain-stiffening for small <i>α</i>. However, for <i>α</i> > 3, friction has a negligible effect. Finally, our results show good agreement with experimental data: the two power-law regimes are observed in Ecoflex 10, 30, Mold Star 16, and porcine skin. The extrapolation of α and <i>E</i> from deep indentation and uniaxial tension deviates by at most 20% in these materials. These findings unravel a universal parabolic force-depth scaling in deep hyperelastic indentation and demonstrate that deep indentation offers a reliable and practical alternative to tensile testing for <i>in situ</i> extraction of hyperelastic properties in soft materials.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144990955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Soft MatterPub Date : 2025-09-04DOI: 10.1039/d5sm00521c
Pierre Rognon, François Guillard
{"title":"Drag forces in granular materials.","authors":"Pierre Rognon, François Guillard","doi":"10.1039/d5sm00521c","DOIUrl":"https://doi.org/10.1039/d5sm00521c","url":null,"abstract":"<p><p>Objects moving through granular materials experience a drag force. In the past two decades, many studies have revealed its non-trivial properties, including dependencies on the velocity of the object and the pressure around it. This tutorial review introduces some of these properties and their associated scaling laws. It highlights how they relate to the non-Newtonian behaviour of granular matter, and how they compare to drag forces in Newtonian fluids and other soft materials.</p>","PeriodicalId":103,"journal":{"name":"Soft Matter","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144990964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-09-04DOI: 10.1039/D5RA04467G
Rabab Azizi and Stefan Seeger
{"title":"Gas phase water-initiated droplet-assisted growth and shaping (DAGS) synthesis of poly(ethyl cyanoacrylate) (PECA) nanostructures","authors":"Rabab Azizi and Stefan Seeger","doi":"10.1039/D5RA04467G","DOIUrl":"https://doi.org/10.1039/D5RA04467G","url":null,"abstract":"<p >The DAGS bottom-up method employs water nanodroplets as ‘templates’ for the fabrication of diverse 1D polymeric nanostructures. Herein, we successfully applied this approach in the gas phase to obtain poly(ethyl cyanoacrylate) nanofibres (PECA-NF) with a diameter ranging from 137 to 721 nm. Their 1D growth was unveiled using energy-dispersive X-ray spectroscopy (EDX).</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 38","pages":" 31763-31766"},"PeriodicalIF":4.6,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra04467g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144934490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-09-04DOI: 10.1039/D5RA05303J
Qasim Shakir Kahdim, Zohra Benzarti, Mohanad H. Mousa, Maher Hassan Rasheed, Najmeddine Abdelmoula and Ali Khalfallah
{"title":"Enhancing the multifunctional properties of polycaprolactone/chitosan films with zirconium dioxide nanoparticles for biomedical and flexible optoelectronic applications","authors":"Qasim Shakir Kahdim, Zohra Benzarti, Mohanad H. Mousa, Maher Hassan Rasheed, Najmeddine Abdelmoula and Ali Khalfallah","doi":"10.1039/D5RA05303J","DOIUrl":"https://doi.org/10.1039/D5RA05303J","url":null,"abstract":"<p >This study addresses the growing need for sustainable and multifunctional materials by developing novel polycaprolactone (PCL)/chitosan (CS)/zirconium dioxide (ZrO<small><sub>2</sub></small>) nanocomposite films. While PCL and CS offer biocompatibility and biodegradability, their combined use presents limitations for advanced applications requiring specific functional features. The incorporation of ZrO<small><sub>2</sub></small> nanoparticles aims to overcome these limitations and create materials with enhanced mechanical, electrical, optical, and antibacterial properties. The nanocomposites were synthesized <em>via</em> a simple casting method, and their properties were comprehensively characterized. Results show that the addition of ZrO<small><sub>2</sub></small> significantly improves the mechanical, electrical, optical, and antibacterial characteristics of the PCL-CS copolymer. Specifically, a 2 wt% ZrO<small><sub>2</sub></small> concentration yielded an optimal balance of mechanical strength, stiffness, ductility, and toughness, with a 63% increase in ultimate tensile strength and a 93% increase in toughness compared to neat PCL-CS. The electrical conductivity was significantly enhanced with increasing ZrO<small><sub>2</sub></small> content and temperature, and the dielectric properties were improved, positioning ZrO<small><sub>2</sub></small> as a mid-range dielectric filler. Optical analysis revealed that ZrO<small><sub>2</sub></small> content tunes the absorbance, energy gap, and refractive index, making these films suitable for optical applications. Furthermore, the nanocomposites exhibited remarkable antibacterial activity against both Gram-positive <em>Staphylococcus aureus</em> and Gram-negative <em>Escherichia coli</em>, with inhibition zones increasing with ZrO<small><sub>2</sub></small> concentration, demonstrating the synergistic effect between chitosan and ZrO<small><sub>2</sub></small>. These findings highlight the potential of PCL-CS/ZrO<small><sub>2</sub></small> nanocomposite films as versatile and sustainable alternatives for a wide range of applications, including biomedical devices, flexible optoelectronics, and smart packaging.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 38","pages":" 31788-31805"},"PeriodicalIF":4.6,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra05303j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144934491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
RSC AdvancesPub Date : 2025-09-04DOI: 10.1039/D5RA05894E
Orkhan Gulahmadov, Lala Gahramanli, Mustafa Muradov, Nahida Musayeva, Stefano Bellucci, Nadia Todorova and Christos Trapalis
{"title":"Porous polysiloxane MWCNT nanocomposites for high-performance and scalable triboelectric nanogenerators","authors":"Orkhan Gulahmadov, Lala Gahramanli, Mustafa Muradov, Nahida Musayeva, Stefano Bellucci, Nadia Todorova and Christos Trapalis","doi":"10.1039/D5RA05894E","DOIUrl":"https://doi.org/10.1039/D5RA05894E","url":null,"abstract":"<p >In this study, porous polysiloxane (PS)/multi-walled carbon nanotube (MWCNT) nanocomposite films were developed as high-performance triboelectric layers for flexible triboelectric nanogenerators (TENGs). TENGs convert mechanical motion into electricity and offer a promising solution for self-powered electronic systems. The nanocomposites were fabricated using a doctor blading method, and porosity was introduced <em>via</em> a simple, scalable salt-leaching technique. Sieved salt particles of varying sizes produced films with fine, medium, and large pores. Raman spectroscopy confirmed uniform MWCNT dispersion and strong interfacial interaction within the PS matrix. SEM analysis verified controlled pore morphology. Dielectric measurements showed reduced permittivity with increasing pore size due to air void incorporation. Triboelectric performance improved significantly with porosity; the medium porosity sample exhibited the best output with an open-circuit voltage of 65 V, short-circuit current of 6.9 μA, and a power density of 280.6 mW m<small><sup>−2</sup></small>. This enhancement is attributed to the optimized combination of surface roughness, contact area, and dielectric behavior, promoting efficient charge generation and transfer. These results highlight the potential of microstructural engineering in porous nanocomposites for next-generation energy harvesting applications.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 38","pages":" 31917-31930"},"PeriodicalIF":4.6,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d5ra05894e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144934496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Atomically dispersed Ru in ZIF-67 as a high-performance HER catalyst: <i>in situ</i> structural evolution and deactivation mechanism elucidation.","authors":"Zhe Liu, Rui Jin, Gui Zhao, Qinshan Tang, Tianrui Kang, Maolin Wang, Jia Liu, Xiaoxiao Huang, Bingrong Guo, Xi Liu, Siwei Li","doi":"10.1039/d5mh01223f","DOIUrl":"https://doi.org/10.1039/d5mh01223f","url":null,"abstract":"<p><p>Despite the prevalence of zeolitic imidazolate framework (ZIF-67)-derived catalysts for the hydrogen evolution reaction (HER), the catalytic potential of pristine ZIF-67 remains obscured by its inherent inertness. In this work, we address this gap by developing an annealing-free strategy to implant atomically dispersed noble metals (Ru, Rh, and Pd) into the intact ZIF-67 framework. Remarkably, Ru single-atom modification reduces the HER overpotential of ZIF-67/CC by 252 mV at 10 mA cm<sup>-2</sup> (from 331 mV to 79 mV) and slashes the Tafel slope by 70%, representing the most significant activation of pristine ZIF-67 reported for the HER. <i>Operando</i> studies combined with theoretical calculations uncover an electrochemical reconstruction pathway: during operation, the ZIF-67 skeleton collapses into Co(OH)<sub>2</sub>, while Ru atoms aggregate into nanoparticles, causing phase segregation. This transformation excessively strengthens hydrogen adsorption, ultimately degrading performance. Our work establishes single-atom engineering as an effective approach to unlock the latent activity of pristine MOFs while revealing their reconstruction behavior under cathodic conditions.</p>","PeriodicalId":87,"journal":{"name":"Materials Horizons","volume":" ","pages":""},"PeriodicalIF":10.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144990981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NanoscalePub Date : 2025-09-04DOI: 10.1039/d5nr02474a
Z E Heywood, B L Monaghan, J B Mallinson, S A Brown
{"title":"Reservoir computing with networks of nanoscale memristors: optimisation of memristor responses for maximal computational performance.","authors":"Z E Heywood, B L Monaghan, J B Mallinson, S A Brown","doi":"10.1039/d5nr02474a","DOIUrl":"https://doi.org/10.1039/d5nr02474a","url":null,"abstract":"<p><p>Self-assembled networks of memristive elements have been shown to be effective in several types of computation, including reservoir computing. Here we use realistic simulations to explore the maximal performance that is possible in several standard computational tasks. Specifically, we investigate the extent to which tuning the parameters that control the properties of the individual memristors improves computational performance of the networks, and show that for some computational tasks a significant improvement (a factor of two) is possible with respect to previous results. We also discuss the effects of noise and compare with hypothetical devices in which outputs can be measured from all nodes of the network, and show that performance of realistic devices with a finite number of electrodes is not dramatically lower.</p>","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":" ","pages":""},"PeriodicalIF":5.1,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Construction of dansylated (fluorescent) amino acid motifs <i>via</i> C(sp<sup>3</sup>)-H arylation.","authors":"Debabrata Bhattacharya, Yashika Aggarwal, Subhankar Bodak, Sampurna Pal, Indranil Banerjee, Srinivasarao Arulananda Babu","doi":"10.1039/d5ob01017a","DOIUrl":"https://doi.org/10.1039/d5ob01017a","url":null,"abstract":"<p><p>We describe the construction of a library of novel dansylated (fluorescent) phenylalanine-type unnatural amino acid scaffolds using a Pd(II)-catalyzed C(sp<sup>3</sup>)-H arylation method. A literature survey revealed that, in general, the dansyl moiety is introduced at the N-terminus of amino acids. Various dansylated amino acids and peptides have been used as fluorophores or probes and are known to show promising biological activities. Our strategy involved the introduction of dansylated anilines into the backbone of amino acids <i>via</i> a Pd(II)-catalyzed 8-aminoquinoline directing group-aided β-C(sp<sup>3</sup>)-H arylation strategy. We have assembled novel racemic/enantioenriched dansylated α-amino acid scaffolds using norvaline, phenylalanine, leucine, norleucine, and non-α-amino acid derivatives. A preliminary study was conducted to show the application of representative dansylated phenylalanine-type molecules for detecting metal cations. We conducted screening of a library of 58 small molecules (10 μM), and identified compounds 18a-(L) and 20b-(D) as potent inhibitors of IAV infection in the human lung alveolar cell line A549.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}