RSC Applied Interfaces最新文献

{"title":"Modeling heterojunctions: a computational chemistry perspective","authors":"Mesfin Eshete and Giovanni Di Liberto","doi":"10.1039/D5LF00104H","DOIUrl":"https://doi.org/10.1039/D5LF00104H","url":null,"abstract":"<p >The design of heterojunction photocatalysts with enhanced photocatalytic performance is a key challenge. Computational chemistry is a valid strategy to access, with atomistic details, the nature of heterojunction-based materials. In this review, we revise and recall a series of important modeling aspects to account for in the modeling of heterojunctions, such as structural models (including lattice mismatch), band offsets, and interface polarization. Lattice mismatch is essential to be considered to avoid spurious effects. Band offsets determine the relative positioning of the band edges, which in turn indicates the way photogenerated charge carriers prefer to move. The charge polarization has an effect on efficient charge separation which instructs the unidirectional charge migration through the preferential migration path of photogenerated charge carriers. In general, we describe general concepts for designing heterojunction photocatalysts. Drawbacks and potential prospects are discussed to help the field in creating more effective photocatalysts.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 897-916"},"PeriodicalIF":0.0,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00104h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ionic rectification via electrical double layer modulation at hydrogel interfaces","authors":"Yaowen Ouyang, Zhong Lin Wang and Di Wei","doi":"10.1039/D5LF00098J","DOIUrl":"https://doi.org/10.1039/D5LF00098J","url":null,"abstract":"<p >Hydrogel-based iontronics have emerged as key enablers for sustainable energy harvesting and bio-inspired sensing, with applications spanning human–machine interfaces, brain–computer interfaces, and neuromorphic computing. Central to their operation is precise modulation of the electrical double layer (EDL) at hydrogel interfaces, which governs ionic rectification, a critical function for efficient iontronic performance. This review systematically examines EDL modulation strategies for achieving ionic rectification in hydrogel systems, classifying them into four fundamental mechanisms: (1) EDL formation on charged polymer chains in polyelectrolyte hydrogels; (2) nanopore-confined EDL enhanced by hydrogel modification; (3) EDL at hydrogel-based p–n junctions; and (4) asymmetric EDL at hydrogel/electrode interfaces. Representative studies highlighting breakthrough applications of these mechanisms are discussed, alongside an outlook on the future of EDL engineering in hydrogel-based iontronics, emphasizing both opportunities and challenges in optimizing performance.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 873-896"},"PeriodicalIF":0.0,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00098j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Vanadium pentoxide mesoporous cathodes for Li-ion batteries†","authors":"Andrea Palumbo, Ullrich Steiner, Andrea Dodero and Ilja Gunkel","doi":"10.1039/D5LF00033E","DOIUrl":"https://doi.org/10.1039/D5LF00033E","url":null,"abstract":"<p >The combination of micro- and nanoporosity is advantageous for Li-ion intercalation in battery electrodes. In this work, we synthesize porous 10 μm-sized poly(styrene-vinylpyridine) block copolymer particles <em>via</em> an emulsion-based approach. The vinylpyridine-phase was then subjected to methanol swelling to enable vanadium ions infiltration, followed by calcination to obtain mesoporous vanadium pentoxide particles. These exhibited a hierarchical porosity, and electrodes manufactured from them displayed a very high specific surface area. Two liquid electrolytes were compared to manage solid-electrolyte-interface growth, which can clog nanopores. Notably, the combination of a lithium bis(trifluoromethane)sulfonimide-containing tetraethylene glycol dimethyl ether tetraglyme electrolyte with the hierarchically porous vanadium pentoxide electrodes demonstrated a substantial enhancement in cycling performance, surpassing established industry benchmarks.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 1082-1090"},"PeriodicalIF":0.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00033e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573080","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DNA origami adsorption at single-crystalline TiO2 surfaces†","authors":"Xiaodan Xu, Sandra Gołębiowska, Teresa de los Arcos, Guido Grundmeier and Adrian Keller","doi":"10.1039/D5LF00109A","DOIUrl":"https://doi.org/10.1039/D5LF00109A","url":null,"abstract":"<p >The immobilization of DNA origami nanostructures on solid surfaces is an important prerequisite for their application in many biosensors. So far, DNA origami immobilization has been investigated in detail only on a few surfaces such as mica, SiO<small>₂</small>, and graphite. TiO<small>₂</small> is a conductive oxide with extensive applications in photocatalysis, energy conversion, and (bio)sensing. Despite its great importance, however, TiO<small>₂</small> has not been investigated as a substrate for DNA origami immobilization yet. Here, we systematically investigate the adsorption of 2D DNA origami triangles on single-crystalline TiO<small>₂</small> surfaces under various experimental conditions. Interestingly, the effect of the Mg<small>²⁺</small> concentration on DNA origami surface coverage is found to depend on the orientation of the TiO<small>₂</small> surface. On TiO<small>₂</small>(110) and TiO<small>₂</small>(111), 10 mM Mg<small>²⁺</small> yields a higher surface coverage than 5 mM. However, the inverse is observed for the TiO<small>₂</small>(001) surface, where the lower Mg<small>²⁺</small> concentration leads to an increase in surface coverage by up to 75%. This is explained by the interplay between Mg<small>²⁺</small> binding to the DNA phosphates and Mg<small>²⁺</small> adsorption at the TiO<small>₂</small> surfaces, which in the case of TiO<small>₂</small>(001) results in a maximum density of Mg<small>²⁺</small> salt bridges already at a low Mg<small>²⁺</small> concentration. At higher concentrations, both the surface and the DNA phosphates are getting saturated with Mg<small>²⁺</small> ions, which introduces electrostatic repulsion at the TiO<small>₂</small>–DNA interface and thus lowers the surface coverage. Our results demonstrate that DNA origami surface coverage at different TiO<small>₂</small> surfaces can be controlled by the Mg<small>²⁺</small> concentration. However, the same mechanism may also play a role in DNA origami adsorption at other single-crystalline oxide surfaces.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 931-939"},"PeriodicalIF":0.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00109a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Asymmetric nanocavity: from color-selective reflector to broadband near-infrared absorber","authors":"Kirtan P. Dixit and Don A. Gregory","doi":"10.1039/D4LF00421C","DOIUrl":"https://doi.org/10.1039/D4LF00421C","url":null,"abstract":"<p >Advances in photonics and energy systems increasingly rely on engineering material interfaces to achieve multifunctional performance. In this study, we present a scalable, lithography-free design for asymmetric Fabry–Perot nanocavities (AFPNs) that function as both narrowband visible reflectors and broadband near-infrared absorbers. By utilizing a dielectric–semiconductor–dielectric spacer with silicon as a critical material, we demonstrate tunable color reflection with just a 5 nm thickness variation and over 80% broadband absorption across the 0.8–1.3 μm range. Adding an anti-reflection coating further extends absorption efficiency to near unity while preserving color fidelity. This planar architecture reduces angular sensitivity and eliminates the need for complex nanopatterning, addressing key challenges in scalability and optical efficiency. These findings highlight a versatile platform for optical coatings in display technologies, photovoltaics, and thermal emitters, advancing the design of multifunctional nanophotonic devices.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 1059-1068"},"PeriodicalIF":0.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d4lf00421c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Amino acid interactions dependent on the polymerization of charged residues and surface properties of monolayers†","authors":"Akira Nomoto, Kentaro Shiraki and Tsukuru Minamiki","doi":"10.1039/D5LF00069F","DOIUrl":"https://doi.org/10.1039/D5LF00069F","url":null,"abstract":"<p >Charged amino acids are the key residues that regulate protein function and stability, and successive sequences of charged amino acids contribute significantly to protein assembly. Therefore, an in-depth understanding of the strengths and manners of amino acid–amino acid interactions (AAIs) caused by successive sequences of charged residues is required. In this study, we prepared self-assembled monolayers (SAMs) bearing charged alkanethiols as ligands to mimic protein surfaces with accumulated charged amino acids. Moreover, we used peptides as analytes to evaluate the AAIs based on chain length. The strengths of the AAIs of tri- and tetrapeptides varied per residue, depending on the properties of the SAMs, such as their densities and hydrophobicities, whereas those of mono- and dipeptides did not vary significantly. Remarkably, the strengths of the AAIs per residue decreased significantly with increasing peptide length, even when the strengths of the AAIs increased at the peptide scale. These results enabled us to quantify the microscopic changes in the AAIs, in addition to the overall interactions governed by the reaction field and alignment of the charged amino acids. Our analysis of AAIs shall be beneficial in protein engineering <em>via</em> genetic mutations based on charged amino acids.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 976-983"},"PeriodicalIF":0.0,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00069f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Functionalization of siliceous materials, part 4: immobilization of fluorinated dyes for optical chemical sensor applications","authors":"Saskia Czihal, Frank Bauer, Marko Bertmer, Axel Kahnt, Sergej Naumov, Matthias Lau and Dirk Enke","doi":"10.1039/D5LF00060B","DOIUrl":"https://doi.org/10.1039/D5LF00060B","url":null,"abstract":"<p >Porous glass (PG) particles are ideal supports in developing optical gas sensors as they combine fast mass transfer in macropores with large specific surface areas which are predestined for the deposition of indicator molecules. The well-established PG material is chemically stable and can be post-synthetically functionalized for introducing specific surface properties. Thus, surface functionalization with 3-mercaptopropyltrimethoxysilane (MPTMS) or 3-aminopropyl-triethoxysilane (APTES) provides the basis for the covalent coupling of the indicator molecule platinum(<small>II</small>)-5,10,15,20-<em>meso</em>-tetrakis-(2,3,4,5,6-pentafluorophenyl)-porphyrin (PtTFPP) to the sensor matrix, reducing the risk of migration, aggregation, and leaching of the fluorescent dye. Nucleophilic substitution of a fluorine atom of the pentafluorophenyl PtTFPP groups by amino (APTES) and thiol (MPTMS) groups enables a covalent linkage of the oxygen indicator PtTFPP to the PG surface. The spectroscopic detection of the PtTFPP-silica bonding by solid-state <small>¹³</small>C CP MAS NMR spectroscopy has turned out to be rather difficult due to very low indicator amounts. As an inexpensive alternative for PtTFPP, hexafluorobenzene C<small>₆</small>F<small>₆</small> was used successfully for the spectroscopic proof of covalent bonds between fluorophenyl groups of an indicator dye and amino- or mercapto-silane cross-linker molecules. The PtTFPP/MPTMS- and the PtTFPP/APTES-modified PG sensor particles showed no leaching in organic solvents and have been applied for oxygen sensing up to oxygen pressures of 400 mbar <em>p</em><small>_{O<small>₂</small>}</small>. The PG sensor particles show non-linear Stern–Volmer calibration plots and it has been found that the covalent bonding of PtTFPP <em>via</em> APTES linkage onto silica surfaces is better suited for various sensor applications.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 995-1007"},"PeriodicalIF":0.0,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00060b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DNA-guided interparticle energy transfer between rare earth doped nanoparticles†","authors":"Mingrui Guo, Vivienne Tam, Fiorenzo Vetrone and Marta Cerruti","doi":"10.1039/D5LF00083A","DOIUrl":"https://doi.org/10.1039/D5LF00083A","url":null,"abstract":"<p >Rare earth doped nanoparticles (RENPs) emit upconverted radiation in the ultraviolet (UV), visible (vis), and higher energy near-infrared (NIR) range, and downshifted, lower NIR energy. Most RENP-based optical sensors depend on energy transfer between the RENP and another entity that emits UV/vis light upon detection of the target of interest. However, attenuation of the emitted UV/vis light by biological tissue components prevents <em>in vivo</em> sensing in deep tissue regions. To avoid this, we propose a sensor that works entirely in the NIR range, composed of two RENPs. The sensor is based on core@shell RENPs comprising Tm<small>³⁺</small> (energy donor) and Nd<small>³⁺</small> (energy absorber) ions doped in a LiYF<small>₄</small> host matrix, functionalized with complementary DNA strands. Hybridization of the DNA strands reduces interparticle distance allowing interparticle energy transfer (IPET) to occur, as shown by a decrease in intensity of the NIR emission from the Tm<small>³⁺</small> doped RENPs observed only in the presence of DNA-functionalized Nd<small>³⁺</small> doped RENPs. While previous works showed IPET occurring between RENPs held in close proximity by hydrophobic interactions between surface molecules, this work shows that responsive linkers (in our case, DNA) can be used to enable IPET. This result lays the foundation for an RENP-based NIR-excited and NIR-emitting optical sensor for deep tissue sensing.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 1069-1081"},"PeriodicalIF":0.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00083a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of synergy on selective low-temperature dehydrogenation of propane to propylene over a defect-induced copper titanium catalyst†","authors":"Himanshu Raghav, Tuhin Suvra Khan, A. V. Sri Jyotsna, Piyush Gupta, Shailendra Tripathi and Bipul Sarkar","doi":"10.1039/D5LF00031A","DOIUrl":"https://doi.org/10.1039/D5LF00031A","url":null,"abstract":"<p >The TiO<small>₂</small>-supported Cu catalyst exhibits high activity in the dehydrogenation of propane at low temperatures, enabling the selective production of propylene over a prolonged period. The defect-induced Cu–TiO<small>₂</small> catalyst provided a propylene yield of 10.4% with high selectivity (∼91.9%) even at 375 °C. Surface analysis shows that the defects on the TiO<small>₂</small> surface are extrinsic and arise from doping with Cu entities. This enhanced metal–support synergy between Cu and TiO<small>₂</small> passivates C–C bond breaking, which indirectly reduces methane formation. To understand the effect of different Cu planes on the adsorption of propane molecules for their activation and conversion, the DFT-optimized geometry and reaction coordinates were investigated. The DFT study revealed that the Cu–TiO<small>₂</small> surface enhances C–H activation at lower temperatures while maintaining an encouraging propylene yield. Furthermore, the kinetic study suggests that adsorption is the rate-limiting step besides the surface reaction, and the activation energy for the propane dehydrogenation reaction is 50.04 kJ mol<small>⁻¹</small>.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 984-994"},"PeriodicalIF":0.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00031a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"One-pot synthesis of necklace-like MOF@CNTs: a universal strategy for enhancing molecular separation performance in mixed-matrix membranes†","authors":"Xuemeng Jia, Zhenting Song, Qiaomei Li, Jiacheng Huang, Xiaowen Zhai, Lei Tian, Jinlou Li, Zhihua Qiao, Yuhui Luo and Dongen Zhang","doi":"10.1039/D5LF00016E","DOIUrl":"https://doi.org/10.1039/D5LF00016E","url":null,"abstract":"<p >Metal–organic frameworks (MOFs) are usually employed as fillers within a polymer matrix to fabricate mixed matrix membranes (MMMs). However, the aggregation of MOFs, particularly at the nanoscale, frequently leads to defects at the filler–polymer interface, making it difficult to form continuous molecular transport channels. Here, a series of necklace-like MOF@carbon nanotubes (CNTs) were synthesized using a straightforward one-pot technique. Specifically, CNTs as a “lead wire” with substantial aspect ratios were first used to induce the self-assembly growth of MOFs as “beads” along the CNTs' longitudinal axis, for the preparation of necklace-like MOF@CNTs. Subsequently, necklace-like MOF@CNTs MMMs were obtained by interfacial polymerization or solvent evaporation. MOF@CNTs have good dispersibility in the polymer matrix and the MOFs within the necklace are in close contact and effectively link the MOF window to create micrometer-scale continuous molecular transport channels that can improve the separation performance of MMMs. For ZIF-90/PA mixed matrix nanofiltration membranes, the water permeability of M-ZIF-90@CNTs (27.15 L m<small>⁻²</small> h<small>⁻¹</small> bar<small>⁻¹</small>) is greater than that of M-0 (8.11 L m<small>⁻²</small> h<small>⁻¹</small> bar<small>⁻¹</small>). Furthermore, the dye rejection efficiency has been increased from 96.60% of M-0 to 99.55% of M-ZIF-90@CNTs and the rejection of NaCl remains relatively low across all nanofiltration membranes, at less than 10%, which has significant advantages in the field of dye/salt separation. For ZIF-90/PSf mixed matrix gas separation membranes, MPSf-ZIF-90@CNTs also exhibit remarkable CO<small>₂</small>/N<small>₂</small> separation selectivity. Importantly, the proposed strategy for preparing necklace-like MOF@CNTs is universally applicable, and can be easily extended to other MOFs, such as ZIF-8, MOF-801, UiO-66, and UiO-66-NH<small>₂</small>, representing a universal strategy for constructing necklace-like MOF@CNTs structures.</p>","PeriodicalId":101138,"journal":{"name":"RSC Applied Interfaces","volume":" 4","pages":" 1041-1050"},"PeriodicalIF":0.0,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/lf/d5lf00016e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144573076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}