Transforming biobased resources, such as glucose, into value-added chemicals is a crucial step in utilizing biomass. Herein, we report on the one-pot conversion of glucose to glucaric acid, by selectively steering the oxidation of glucose from the typical production of gluconic acid toward the production of glucaric acid, using monometallic Au and Pt and bimetallic AuPt nanocatalysts supported on zirconia. While the monometallic catalysts promote the production of gluconic acid, bimetallic catalysts favor the direct formation of glucaric acid from glucose, with efficacy depending on the Au/Pt ratio, reaching up to 44% selectivity with the AuPt@ZrO catalyst. Theoretical calculations confirm the formation of alloys, as experimentally evidenced by EDX-mapping and HR-TEM imaging.

The efficacy of nucleic acid-based therapeutics is often hindered by nuclease degradation and poor cellular uptake. To address these challenges, the complexation with cationic polymers to form polyplexes has been increasingly investigated. In our previous work, we developed a platform technology composed of a mannosylated block for targeting dendritic cells (DCs) via endocytic mannose receptor (CD206), an agmatinyl block for nucleic acid condensation in diblock copolymers (M--A, M--A, and M--A), elongated with a poly-(butyl acrylate) block to promote endosomal escape in triblock copolymers (M--A--B and M--A--B). We exploited these copolymers to efficiently target DCs for cancer vaccination by delivering plasmid DNA encoding tumor-associated antigens (TAAs), using ovalbumin (pOVA) as a model antigen. However, successful T-cell activation requires an antigen presentation on DCs as major histocompatibility complex (MHC)-antigen complexes, along with immune stimulation, making vaccine adjuvants essential. In this study, we utilized mannosylated cationic copolymers to deliver cytosine-phosphate-guanosine oligodeoxynucleotides (CpG ODN) as a vaccine adjuvant and tested their effect in conjunction with pOVA to further enhance immune activation. Cationic glycopolymers efficiently condensed single-stranded DNA (ssDNA), forming stable, predominantly spherical glycoplexes with sizes ranging from 20 to 40 nm, as assessed by transmission electron microscopy (TEM) analysis. These mannosylated complexes showed high internalization by CD206-expressing cells. Confocal laser microscopy studies revealed rapid nuclear localization mediated by M--A--B triblock copolymer and slower endosomal escape for M--A diblock copolymer-based glycoplexes. Furthermore, for M--A diblock copolymer-based complexes, codelivering CpG and pOVA in the same particles induced stronger DC activation compared to coadministration of glycoplexes containing CpG and glycoplexes containing pOVA. These provide a structure-activity relationship for this class of mannosylated cationic glycopolymers for nucleic acid delivery to DCs and underscore the synergistic benefits of codelivering CpG and nucleic acid encoding TAAs for DC activation.

Methane synthesis from CO hydrogenation is a promising approach for CO recycling despite challenges such as nickel species loss and sintering. This study investigates reduced graphene aerogels (rGOA) doped with nitrogen (N-rGOA) and boron (B-rGOA) as supports for nickel-based CO methanation catalysts. Boron doping (Ni/B-rGOA) improved Ni dispersion and increased the number of active sites through structural and electronic modifications. However, it exhibited slightly lower catalytic performance than nitrogen doping (Ni/N-rGOA), which is attributed to larger Ni particles and higher surface acidity, hindering CO activation. ICP and XPS analyses revealed a higher Ni surface segregation in doped samples than in undoped Ni/rGOA. XPS also confirmed the presence of metallic Ni and Ni species, with satellite peaks at 861 eV indicative of NiO. Boron doping modified the electronic structure of the carbon support, increasing Ni electron density and catalytic activity. TEM imaging showed well-dispersed Ni nanoparticles (5.9 to 7.3 nm) with no signs of aggregation. Among the tested catalysts, Ni/N-rGOA demonstrated superior CO conversion and CH selectivity, maintaining stable performance over 60 h of continuous operation. These findings underscore the potential of nitrogen-doped graphene aerogels as robust and efficient supports for the production of CO methanation catalysts.

Green synthesis and defect engineering of LaCoO model nanocatalysts by femtosecond pulsed laser ablation in liquid (fs-PLAL) led to the formation of two types of nanoperovskites: stoichiometric LaCoO and nonstoichiometric cobalt-rich nanoparticles. Micro-Raman analysis revealed pronounced second-order phonon scattering, suggesting a high defect density. The defect spatial distribution was evaluated by high-resolution electron microscopy, employing Fourier filtering and image reconstruction. Increasing the laser fluence increases the surface defect density due to the fast cooling of primary nanoparticles, a process intensified by the inherently ultrashort pulses. Laser-produced nanoparticles exhibited internal defects, a characteristic absent in those produced by a chemical method. Chemically derived nanoparticles, originally perfectly crystalline, formed grain/twin boundaries during calcination when their irregular shapes coalesced. Compared to a chemically synthesized reference catalyst, nanoparticles laser-synthesized at 5.8 J cm showed the highest CO conversion during PROX in excess H at 400 °C. Perovskite produced at 5.8 J cm and 5.1 J cm also showed higher CO selectivity (89% and 83%, respectively, versus 28% of the reference), as well as excellent stability at 350-400 °C.

A method to process boron nitride nanotube (BNNT) fibers with a high degree of alignment, high modulus, and good tensile strength is presented. This has been achieved by dispersing BNNTs in a polymer solution, spinning the resulting polymer/BNNT dispersion into fibers, and removing the polymer. Significant alignment is imparted to the BNNTs within the fiber during drawing and heat treatment under tension. These BNNT fibers are characterized structurally and elementally to confirm the BNNT structure. This work has resulted in a highly oriented BNNT fiber with a modulus as high as 396 GPa and a tensile strength as high as 500 MPa. These tensile values represent the current state of the art for BNNT fibers, and the alignment of BNNTs in the fiber is the highest ever achieved for nanotubes-based fibers. Significant porosity is observed from the TEM images of the BNNT fibers' cross section, indicating that further processing optimization can be expected to further increase these properties. A knot can be made in some of the resulting BNNT fibers, suggesting that some of these BNNT fibers are suitable for typical textile processing techniques. BNNT fibers, their textile preforms, and BNNT fiber containing composites will be suitable for applications requiring high thermal conductivity without electrical conductivity, high temperature oxidative resistance, and low dielectric constant, particularly in aerospace and electronics areas.

We studied the effect of Ti substitution on nickel B-sites in LaNiO to unravel the influence of Ti doping on structural stability, Ni exsolution, and methane dry reforming (DRM) properties. Ni can be substituted by Ti down to compositions of x = 0.25 without compromising both phase and structure purity. At even higher Ti doping levels, formation of the pyrochlore-type LaTiO phase occurs. Ti substitution has a significant influence on the stability under reducing conditions and the appearance of specific intermediate structures relevant for DRM operation. Full decomposition is only observed for LaNiO and the x = 0.75 sample, which yield the LaO phase relevant for DRM activity at low Ti doping levels. A common impurity phase between x = 0.75 and 0.25 is LaTiO, which acts as a Ti and La sink and hinders the formation of LaO. For higher Ti doping levels, hydrogen reduction increases the amount of LaTiO. A common denominator of all samples after hydrogen reduction is the full leaching of all nominally available Ni from the perovskite. The self-activation properties during DRM operation strongly depend on the Ti substitution level. Self-activation with either full or partial decomposition is only possible for LaNiO and x = 0.75, where intermediate lanthanum oxycarbonate formation occurs. For x = 0.50, the remaining perovskite structure is stable, but Ni exsolution nevertheless occurs, triggering DRM activity. Successive Ti doping invokes a change in the DRM mechanism from oxycarbonate-based at low Ti amounts (LaNiO and x = 0.75) to a more reactive-oxygendominated one for samples x ≤ 0.50, as indicated by X-ray photoelectron spectra. Ti doping also allows to economize the amount of Ni for DRM applications it can be lowered to a quarter of the initial amount referenced to pure LaNiO without compromising DRM activity.

The direct integration of graphene onto technologically relevant insulating substrates is crucial for next-generation electronic and optoelectronic devices. Here, we present a density functional theory (DFT) study of the structural, electronic, and adhesion properties of graphene on the α-AlO(0001) surface. A 12-layer Al-terminated slab with two middle layers fixed is shown to provide an optimal balance between computational efficiency and accuracy, reproducing key surface properties such as work functions and electronic structures. The adsorption of graphene reveals a transition from planar to corrugated geometries with an increasing supercell size. Buckling notably modifies the local electronic structure, inducing a small bandgap and charge redistribution within graphene without significant charge transfer to the substrate. Energetics, corrugation patterns, and simulated scanning tunnelling microscopy images indicate that the interaction is dominated by weak van der Waals forces and lattice-induced modulation. Additionally, a rotated (R30) graphene configuration minimizes interface strain and exhibits enhanced stability. These findings offer valuable insights into the interfacial physics of graphene on dielectric oxides, relevant for applications in electronics, optoelectronics, and sensing.

Two-dimensional semiconductor-transition-metal dichalcogenide (2D-STMD) based semiconductors have emerged as promising materials for future spintronic and optoelectronic applications, including photodetectors and transistors. Transferring high-quality chemical vapor deposition (CVD)-grown monolayer 2D-STMDs and their alloys to the target substrate is very challenging for fabricating efficient devices. Unfortunately, current post-transfer methods struggle to completely remove unwanted contamination residues during wet-transfer processes, which adversely affects material quality and intrinsic properties. In this work, the effect of ethanol cleaning on the qualitative and quantitative assessment of molecular adsorbates is demonstrated, based on atomic-resolution high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) image analysis supported by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and density functional theory (DFT) calculations, which showcases ultraclean material structures. We estimate the unidentified molecular adsorbates in the proximity of molybdenum (Mo) and chalcogen (S, Se) atomic sites, which are tentatively assigned as 'CHOH (EtOH)', 'HO', and 'O' related adsorbates. The attribution is based on HAADF-STEM Gaussian line shape fitting of atomic intensity columns and corresponding computed adsorption energy values after ethanol treatment of the MoSSe (MSSE) alloy. In line with experimental observations of persistent OH-containing residues on the surface, DFT simulations show that EtOH has better adsorption on both pristine and sulfur-vacancy MSSE monolayers than HO and O. Photodetector device measurements revealed a remarkable ∼90% enhancement in photocurrent values for ultraclean samples, significantly boosting the material's photoresponsivity. DFT calculations on the adsorption energy and density of electronic states were also conducted to validate our experimental findings.

We report a deposition pathway for barium titanate (BTO) onto hydrophobically coated cobalt ferrite (CFO) nanoparticles, resulting in the formation of magnetoelectric core-shell nanoparticles. Our strategy utilizes a bimetallic Ba and Ti oleate (BTOle) precursor, which hydrophobically interacts with dimethyl-dioctadecyl-ammonium bromide (DDAB)-stabilized CFO particles during an interfacial phase transfer step. Thermal post-treatment yields a crystalline structure comprising distinguishable BTO and CFO phases, with BTO adopting a distorted cubic to tetragonal crystal phase. Magnetoelectric characterization yields a millivolt voltage-range output associated with the mechanical coupling between the piezoelectric and magnetostrictive phases. This method circumvents traditional sol-gel limitations and phase transfer hurdles, offering a streamlined route for fabricating magnetoelectric nanoparticles. Our results suggest magnetoelectric particles are suitable for incorporation in wireless actuation technologies.

This study aims to develop a green, solvent-free synthesis of ZIF-93 (ZIF stands for zeolitic imidazolate framework) and to explore the formation of different phases. We report the solvent-free synthesis of a previously unreported nanoporous ZIF phase, ZIF-93_HP (HP referring to "high-pressure"), from zinc oxide using a dual high-pressure (150 MPa) and thermal (110 °C) method. The influence of key synthesis parameters, such as the amount of NHNO promotor and reaction steps, was systematically investigated to maximize the conversion of ZnO into the intermediate ZIF-93_HP, while, in parallel, preventing its further conversion into nanoporous ZIF-93 phase. The material was extensively characterized by X-ray diffraction, thermogravimetry, electron microscopy and N and CO adsorption, which revealed insights into the structure, morphology and nanoporosity of ZIF-93_HP. ZIF-93_HP, with empirical formula of Zn-(CNOH)·1.2-(NHNO)·(HO), is related to the previously reported ZIF-93 (Zn-(CNOH)). Water washing of this phase led to the transformation into ZIF-93 and a significant increase in the BET specific surface area (from 4 to 181 m/g). In addition, the presence of NH and NO ions into its structure makes ZIF-93_HP proton conductor at room temperature and moisture conditions (3.76 × 10 S/cm), a property that decreases with increasing temperature due to dehydration. The discovery of ZIF-93_HP highlights the potential of the high-pressure, solvent-free synthesis as a powerful tool for the exploration of different ZIFs and reticular materials that are inaccessible through traditional solvothermal methods. As crystallization under solvent-free conditions is often influenced by nonthermodynamic equilibrium, this approach holds a great potential for expanding the material landscape by enabling the discovery of different phases and structures with unique properties, such as the promising proton conductivity demonstrated here.

We present a comprehensive study of the atomic-scale electronic behavior of ZrSe, focusing on the effects of intrinsic point defects, grain boundaries, and edge configurations. Using a combination of low-temperature scanning tunnelling microscopy/spectroscopy (STM/STS) and density functional theory (DFT), we identify and characterize the spectroscopic fingerprints of various intrinsic point defects, including vacancies, antisites, and interstitials, and reveal how these features perturb the band edges or introduce in-gap states. These defect-induced features are shown to significantly influence the local electronic properties of ZrSe. Our analysis of grain boundaries identifies shear-type interfaces that shift the Fermi level without introducing deep in-gap states, thereby preserving the semiconducting character of pristine ZrSe. In contrast, the edge configuration has a pronounced effect on the electronic structure, with armchair and zigzag edges exhibiting distinctly different behaviors. While the former is characterized by a prominent peak near the valence band edge, indicating the presence of edge-localized states and a clean semiconducting character, the latter instead introduces a significant density of states at midgap and within the upper half of the bandgap. These findings offer atomic-level insights into the interplay between defects, edge chemistry, and electronic behavior in ZrSe, establishing a framework for defect- and edge-state engineering in two-dimensional semiconductors for nanoelectronics and quantum device applications.

The limited efficacy of chemotherapy induced by the hypoxic tumor microenvironment remains a major obstacle in clinical oncology. To address this, we designed and synthesized a series of aggregation-induced emission photosensitizers with donor-π-acceptor structures, exemplified by SC-3. Upon assembly with cucurbit[8]-uril (CB[8]), the nanosupramolecular photosensitizer 2SC-3/CB[8] significantly enhanced singlet oxygen (O) generation and exacerbated cellular hypoxia. When coadministered with the hypoxia-activated chemotherapeutic tirapazamine (TPZ), we found that 2SC-3/CB[8] further amplified TPZ's antitumor efficacy in MDA-MB-231 breast cancer cells. Experimental studies and density functional theory calculations confirmed that SC-3 exhibits potent photodynamic therapy activity with high mitochondrial specificity. In addition, we found that CB[8]-induced depletion of intracellular spermine further contributed to the death of the tumor cells. Together, these findings highlight the potential of combining supramolecular photosensitizers with hypoxia-activated chemotherapy as a promising and synergistic strategy for the treatment of solid tumors.

The stability of WO photoelectrodes in neutral media remains a significant challenge, particularly for those fabricated by anodic W oxidation. We report a simple, one-step hydrothermal treatment that transforms porous anodic WO into nanorods with a dispersed FeWO phase. This morphological evolution combines the advantages of high-aspect-ratio structures for improved light absorption with reduced charge recombination losses. The treatment also promotes preferential WO growth along the monoclinic (002) planeknown to favor water splitting. The modified electrodes exhibited considerable photoluminescence quenching, significantly enhanced charge separation efficiency, and higher photon-to-current conversion, resulting in a photocurrent density that was ∼1.8 times higher at 1.0 V vs RHE. Additionally, oxygen vacancy formation during operation likely contributes to charge redistribution, mitigating surface degradation in sodium sulfate and enabling rapid stabilization of the photocurrent over several hours. Electrochemical impedance spectroscopy reveals evidence of p-n heterojunction due to integration of the tungstate phase with WO, extended charge carrier lifetimes, and enhanced charge transfer. This scalable surface engineering approach offers a promising route to enhance the performance and durability of anodic WO for practical solar-driven water oxidation.

Detection of special nuclear materials (SNMs) is of vital importance in the prevention of nuclear terrorism and to secure states' national security. Neutron detection is a particularly useful tool to identify SNM, and neutron-sensitive scintillators have many promising properties, such as ease of use, good time resolution, and high detection efficiency. In this work, we develop highly stable, self-oriented, ultrafast 1D ZnO:Li (and codoped with Al, Ga, and In) nanorods (NRs) as thermal neutron-sensitive scintillators. Lithium-6 has high thermal neutron cross section for the (, α) reaction in ZnO:Li scintillators which have a vertical nano array design greatly increasing the effective surface area and scintillation efficiency. Cost-effective low-temperature (95 °C) hydrothermal growth is used to obtain highly crystalline ZnO:Li nano scintillators by combining nuclear range data and electron transport mechanisms. Among the studies using low-temperature hydrothermal synthesis and a relatively low annealing temperature (≈350 °C) along with optimized NRs (length ≈ 5-8 μm, mean diameter ≈ 700 nm) for thermal neutron detection, this study reports the shortest scintillation decay time (≈ 470 ps) so far to the best of our knowledge. This nano array scintillator combines the advantages of a low-cost growth technique with environmentally friendly and widely available materials.

The selective and rapid detection of FKBP12 is crucial due to its involvement in immunosuppression, neurodegenerative and oncological diseases, and some fundamental cellular processes. A low-cost point-of-care test (POCT) based on a simple setup, combined with plasmonic sensor chips for ultrasensitive detection of FKBP12, is developed. The sensing principle exploits pollen-based natural nanostructures covered by gold nanofilms and functionalized with synthetic GPS-SH1 receptors. The experimental results demonstrated ultrahigh performance due to the hybrid plasmonic phenomena, with a detection limit of 0.17 aM for FKBP12. This label-free optical-chemical sensor is based on portable and simple equipment, operates in 10 min, requires a small volume of the sample, and only requires a dilution step to perform the measurement on real samples. The high selectivity of the developed sensor chip for FKBP12 is demonstrated, and its applicability in complex matrices such as serum and plasma is validated. Furthermore, two surface functionalization strategies with different receptor-to-spacer ratios, 1:6 and 1:3, are investigated, identifying the optimal ratio to achieve better binding sensitivity. This work highlights the potential of plasmonic nanostructured pollen-based chips functionalized with GPS-SH1 receptors for the detection of FKBP12 at the single-molecule level, paving the way for advances in diagnostics and therapeutic monitoring via low-cost POCT with cheaper and disposable chips.

Gas-material interactions are crucial in various industrial processes, including microchip fabrication, fuel production, and exhaust gas treatment. Covalent organic frameworks (COFs) are a class of porous, crystalline nanomaterials composed of organic building blocks linked by strong covalent bonds. Their highly tunable surface properties make them promising candidates for gas adsorption. In this study, we explored how the presence of methyl groups influences the gas adsorption properties of volatile organic compounds, i.e., probes, in stable, imine-linked COFs. Enthalpy measurements revealed that MeTFB-BD, a methylated COF, exhibited weaker interactions with toluene (-41.3 kJ/mol) and heptane (-45.6 kJ/mol) compared to its nonmethylated derivative TFB-BD (-50.5 kJ/mol and -54.0 kJ/mol, respectively). Partition coefficient () data also indicated that TFB-BD has stronger interactions with a broader set of specific probes than MeTFB-BD, likely due to a higher imine bond accessibility. Both COFs also showed strong interactions with polar alcohol probes, which can be attributed to their high polarizability. Analysis of MeTFB-PA, a COF with a lower methyl to carbon ratio, led to further reduction in the COF-probe interaction strength. All three COFs demonstrated moderate adsorption capacities, though TFB-BD showed the highest uptake for toluene (0.1 μmol/m) and heptane (∼0.07 μmol/m), due to its stronger interactions and smaller pore size. Additionally, selectivity analysis revealed that TFB-BD exhibited the strongest affinity for a broad range of probes. Overall, this study highlights the potential of COFs as tunable and promising materials for targeted gas sensing, gas separation, and related applications.

Magnetic nanoparticles with zero magnetic remanence, which can be noninvasively switched to a high magnetization state, represent a promising route for biomedical applications. Here, we report on nanoparticles consisting of ferrimagnetic FeO half-ellipsoids in a shell of SiO whose magnetization can be noninvasively set to an antiparallel-coupled (zero stray field) or ferromagnetically coupled state (maximum stray field). The hybrid particle is enclosed by a diamagnetic SiO coating protecting it against the environment and allowing functionalization for specific drug targeting. Through micromagnetic simulations, we demonstrate the feasibility to noninvasively tune the magnetic remanence of these synthetic ellipsoidal magnetic particles from zero for the antiferromagnetic-coupled state to a maximum magnetization for the ferromagnetic-coupled state. This control renders the particles remarkable for in vivo biomedical applications requiring magnetomechanical or magnetothermal activation.

The assessment of nuclear structural changes is considered a potential biomarker of metastatic cancer. However, accurately measuring nuclear elasticity remains challenging. Traditionally, nuclear elasticity has been measured by indenting the cell membrane with a bead-attached atomic force microscopy (AFM) probe or aspirating isolated nuclei with a micropipette tip. However, indentation using a bead-attached probe is influenced by the cell membrane and cytoskeleton, while measurements of isolated nuclei do not reflect their intact state. In this study, we employed Nanoendoscopy-AFM, a technique in which a nanoneedle probe is inserted into a living cell to directly measure nuclear elasticity and map its distribution. Our findings show that nuclear elasticity increases under serum depletion but decreases when serum-depleted cells are treated with TGF-β, which induces epithelial-mesenchymal transition (EMT). Furthermore, we found that changes in nuclear elasticity correlate positively with trimethylation levels of histone H4 at lysine 20, rather than with nuclear lamins expression levels. These findings suggest that alterations in chromatin structure underlie changes in nuclear elasticity during the progression of cancer.

The widespread use of nitroimidazole antibiotics such as ronidazole (RON) in human and veterinary medicine raises concerns about environmental persistence and antimicrobial resistance. Sensitive detection of trace RON in water is therefore essential. Here, we report for the first time, nickel telluride nanoparticles (NiTe NPs) as an electrochemical sensor specifically designed for RON detection. NiTe, a transition metal chalcogenide with high conductivity and electrocatalytic activity, was synthesized via a simple hydrothermal method and characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. When drop-cast on a glassy carbon electrode, the NiTe NPs significantly enhanced electron transfer and promoted efficient electrochemical reduction of RON. The sensor achieved a detection limit of 1.5 nM, a wide linear range of 0.01-270 μM, and a sensitivity of 0.489 μA μM cm. It also displayed excellent selectivity against common interferents and maintained stability and reproducibility during extended testing. Application to spiked tap and river water confirmed accurate recovery. This work highlights NiTe as an underutilized telluride-based material and establishes its novel application in the environmental monitoring of antibiotic contaminants, addressing a critical gap in electrochemical sensing research.

Amine-based adsorbents are considered extremely promising candidates for their efficacy in CO capture. In this study, we explore the enhancement of CO adsorption capacity through the development of a hierarchically porous material containing a mesoporous silica coating on halloysite nanotubes (HNTs), a naturally occurring clay material. The generation of a mesoporous MCM-41 skin on HNTs increases the surface area from about 60 to 400 m/g while maintaining structural integrity. This significant increase in the surface area helps enhance amine loading. The synthesis of the MCM-41/HNT (MHNT) composite particles was achieved via an aerosol-assisted method, allowing rapid coating formation of a spindle-shaped skin on the HNT external surface and leading to a hierarchical porosity that supports both large pores in the HNT lumen and small pores in the MCM-41 coating. Poly-(ethylenimine) (PEI)-loaded MHNT adsorbents exhibit superior CO adsorption capacities compared to adsorbents of PEI loaded into pristine HNT, with a 27% increase in the adsorption capacity. This work underscores the effectiveness of mesoporous skin in increasing amine adsorption efficiency on clay-based adsorbents, providing a pathway for the development of high-capacity, durable materials in carbon capture technologies.

A family of exchange-coupled core-shell (CS) nanoparticles composed of an antiferromagnetic (AFM) core (CoFeO) and a ferrimagnetic (FiM) shell (CoFeO) was investigated to unravel the role played by the dimension of the two components on the magnetic properties of the system. The series comprises three samples with different core diameters (2, 5, and 16 nm) and fixed shell thickness of ∼2 nm. Although a strong core and shell magnetic coupling occurs in all the samples, the final properties of the hybrid nanosystems are greatly influenced by the size of the two counterparts. Indeed, while the larger sample can be described as a classic > exchange-bias, where and denote the ordering temperature of the FiM and AFM phases, respectively, on reducing the size, the blocking transition of the FiM shell decreases to values well below the of the AFM. In the first case, the FiM-AFM exchange-bias effect is determined by the magnetic ordering of the AFM core; in the other cases, it is due to the reduction of the thermal-driven magnetic fluctuations of the ordered FiM shell. On the other hand, the AFM properties of the core regions also are extremely sensitive to the particle size reduction, showing, for the smallest sample, the effect of the coupling between the two phases to appear at temperature well below displayed by the bulk system, indicating the potential presence of a blocking transition in the AFM core for small particles. These findings highlight the significant influence of the size of the AFM and FiM components on the hybrid system's ultimate properties. This result is potentially relevant for defining the working conditions of nanodevices exploiting exchange-bias phenomena, which have been recently proposed in the literature for application in several technological fields, ranging from rare-earth free magnets, spintronics, optoelectronics, and magnetic-refrigeration.