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We investigate the chemical interaction of carbon monoxide (CO) and oxygen (O2) with kink atoms on steps of platinum crystal surfaces using a specially designed Pt curved sample. We aim at describing the fundamental stages of the CO oxidation reaction, i.e., CO-covered/poisoned stage and O-covered/active stage, at the poorly known kinked Pt facets by probing CO uptake/saturation and O2 saturation, respectively. Based on the systematic analysis that the curved surface allows, and using high-resolution X-ray photoemission, a diversity of terrace and step/kink species are straightforwardly identified and accurately quantified, defining a smooth structural and chemical variation across different crystal planes. In the CO-saturated case, we observe a preferential adsorption at step edges, where the CO coverage reaches a CO molecule per step Pt atom, significantly higher than their close-packed analogous steps with straight terrace termination. For the O-saturated surface, a significantly higher O coverage is observed in kinked planes compared to the Pt(111) surface. While the strong adsorption of CO at the kinked edges points toward a higher ignition temperature of the CO oxidation at kinks as compared to terraces, the large O coverage at steps may lead to an increased reactivity of kinked surfaces during the active stage of the CO oxidation.

Liquid-phase transmission electron microscopy is a burgeoning experimental technique for monitoring nanoscale dynamics in a liquid environment, increasingly employing microfluidic reactors to control the composition of the sample solution. Current challenges comprise fast mass transport dynamics inside the central nanochannel of the liquid cell, typically flow cells, and reliable fixation of the specimen in the limited imaging area. In this work, we present a liquid cell concept – the diffusion cell – that satisfies these seemingly contradictory requirements by providing additional on-chip bypasses to allow high convective transport around the nanochannel in which diffusive transport predominates. Diffusion cell prototypes are developed using numerical mass transport models and fabricated on the basis of existing two-chip setups. Important hydrodynamic parameters, i.e., the total flow resistance, the flow velocity in the imaging area, and the time constants of mixing, are improved by 2-3 orders of magnitude compared to existing setups. The solution replacement dynamics achieved within seconds already match the mixing timescales of many ex-situ scenarios, and further improvements are possible. Diffusion cells can be easily integrated into existing liquid-phase transmission electron microscopy workflows, provide correlation of results with ex-situ experiments, and can create additional research directions addressing fast nanoscale processes.

The field of quantum technology has been rapidly expanding in the past decades, yielding numerous applications, such as quantum information, quantum communication, and quantum cybersecurity. At the core of these applications lies the quantum emitter (QE), a precisely controllable generator of either single photons or photon pairs. Semiconductor QEs, such as perovskite nanocrystals and semiconductor quantum dots, have shown much promise as emitters of pure single photons, with the potential for generating photon pairs when hybridized with plasmonic nanocavities. In this study, we have developed a system in which individual quantum emitters and their ensembles can be traced before, during, and after the interaction with an external plasmonic metasurface in a controllable way. Upon coupling the external plasmonic metasurface to the QE array, the individual QEs switch from the single-photon emission mode to the multiphoton emission mode. Remarkably, this method preserves the chemical structure and composition of the QEs, allowing them to revert to their initial state after decoupling from the plasmonic metasurface. This significantly expands the potential applications of semiconductor QEs in quantum technologies.

The characterization of thin films containing nanopores with diameters exceeding 50 nm poses significant challenges, especially when deploying sorption-based techniques. Conventional volumetric physisorption or mercury intrusion methods have limited applicability in thin films due to constraints in sample preparation and nondestructive testing. In this context, ellipsometric porosimetry represents a viable alternative, leveraging its optical sensitivity to thin films. With existing setups relying on the capillary condensation of volatile compounds such as water, applicability is typically restricted to pore dimensions <50 nm. In this study, we introduce two high-molar-mass hydrocarbon adsorptives, namely ethylbenzene and n-nonane. These adsorptives exhibit substantial potential in improving the accuracy of physisorption measurements beyond mesoporosity (i.e., >50 nm). Specifically, with n-nonane, applicability is extended up to 80 nm pores. Our measurement guidelines propose a nondestructive, expeditious (<60 min), low-pressure (<0.03 bar) approach to investigate nanoporous thin films with potential adaptability to diverse structural architectures.

Thin layers of in-plane anisotropic materials can support ultraconfined polaritons, whose wavelengths depend on the propagation direction. Such polaritons hold potential for the exploration of fundamental material properties and the development of novel nanophotonic devices. However, the real-space observation of ultraconfined in-plane anisotropic plasmon polaritons (PPs)-which exist in much broader spectral ranges than phonon polaritons-has been elusive. Here we apply terahertz nanoscopy to image in-plane anisotropic low-energy PPs in monoclinic Ag2Te platelets. The hybridization of the PPs with their mirror image-by placing the platelets above a Au layer-increases the direction-dependent relative polariton propagation length and the directional polariton confinement. This allows for verifying a linear dispersion and elliptical isofrequency contour in momentum space, revealing in-plane anisotropic acoustic terahertz PPs. Our work shows high-symmetry (elliptical) polaritons on low-symmetry (monoclinic) crystals and demonstrates the use of terahertz PPs for local measurements of anisotropic charge carrier masses and damping.

Compared to other animal movements, prospecting by adult individuals for a future breeding site is commonly overlooked. Prospecting influences the decision of where to breed and has consequences on fitness and lifetime reproductive success. By analysing movements of 31 satellite- and GPS-tracked gull and tern populations belonging to 14 species in Europe and North America, we examined the occurrence and factors explaining prospecting by actively breeding birds. Prospecting in active breeders occurred in 85.7% of studied species, across 61.3% of sampled populations. Prospecting was more common in populations with frequent inter-annual changes of breeding sites and among females. These results contradict theoretical models which predict that prospecting is expected to evolve in relatively predictable and stable environments. More long-term tracking studies are needed to identify factors affecting patterns of prospecting in different environments and understand the consequences of prospecting on fitness at the individual and population level.

In situ activation of Pt(IV) to Pt(II) species is a promising strategy to control the anticancer activity and overcome the off-target toxicity linked to classic platinum chemotherapeutic agents. Herein, we present the design and synthesis of two new asymmetric Pt(IV) derivatives of cisplatin and oxaliplatin (1·TARF and 2·TARF, respectively) bearing a covalently bonded 2′,3′,4′,5′-tetraacetylriboflavin moiety (TARF). 1H and 195Pt NMR spectroscopy shows that 1·TARF and 2·TARF can be effectively activated into toxic Pt(II) species, when incubated with nicotinamide adenine dinucleotide, sodium ascorbate, and glutathione in the dark and under light irradiation. Density functional theory studies of the dark Pt(IV)-to-Pt(II) conversion of 2·TARF indicate that the process involves first hydride transfer from the donor to the flavin moiety of the complex, followed by electron transfer to the Pt(IV) center. When administered to MDA-MB-231 breast cancer cells preincubated with nontoxic amounts of ascorbate, 2·TARF displays enhanced toxicity (between 1 and 2 orders of magnitude), suggesting that the generation of oxaliplatin can selectively be triggered by redox activation. Such an effect is not observed when 2 and TARF are coadministered under the same conditions, demonstrating that covalent binding of the flavin to the Pt complex is pivotal.

Thioether polymers are fundamental for a variety of applications. Their synthesis is, however, more challenging than that of other metal-catalyzed reactions due to the reported detachment of the S atom during thermal activation. In this study, it has been demonstrated unambiguously that thermal annealing results in the thioetherification of the 4-bromo-4-mercaptobiphenyl molecule (Br-MBP) adsorbed on the surface of Au(111). Through complementary techniques, such as scanning tunneling microscopy, spectroscopy, and first-principle calculations, we have identified four reaction steps, involving sulfhydryl or bromine molecular functional groups and leading to the formation of intermolecular C–S bonds. To form the thioether polymer and to overcome the competitive formation of C–C bonds, two reaction steps, the dehalogenation, and dissociation of the S–Au bond, must occur simultaneously. We detail the electronic properties of the phenyl–sulfur bond and the polymer as a function of the ligand length. This result suggests a wider perspective of this chemical synthesis.

Even with the widespread uptake of vaccines, the SARS-CoV-2-induced COVID-19 pandemic continues to overwhelm many healthcare systems worldwide. Consequently, massive scale molecular diagnostic testing remains a key strategy to control the ongoing pandemic, and the need for instrument-free, economic and easy-to-use molecular diagnostic alternatives to PCR remains a goal of many healthcare providers, including WHO. We developed a test (Repvit) based on gold nanoparticles that can detect SARS-CoV-2 RNA directly from nasopharyngeal swab or saliva samples with a limit of detection (LOD) of 2.1 × 105 copies mL−1 by the naked eye (or 8 × 104 copies mL−1 by spectrophotometer) in less than 20 min, without the need for any instrumentation, and with a manufacturing price of <$1. We tested this technology on 1143 clinical samples from RNA extracted from nasopharyngeal swabs (n = 188), directly from saliva samples (n = 635; assayed by spectrophotometer) and nasopharyngeal swabs (n = 320) from multiple centers and obtained sensitivity values of 92.86%, 93.75% and 94.57% and specificities of 93.22%, 97.96% and 94.76%, respectively. To our knowledge, this is the first description of a colloidal nanoparticle assay that allows for rapid nucleic acid detection at clinically relevant sensitivity without the need for external instrumentation that could be used in resource-limited settings or for self-testing.

Liquid-Phase Transmission Electron Microscopy (LP-TEM) offers the opportunity to study nanoscale dynamics of phenomena related to materials and life science in a native liquid environment and in real time. Until now, the opportunity to control/induce such dynamics by changing the chemical environment in the liquid flow cell (LFC) has rarely been exploited due to an incomplete understanding of hydrodynamic properties of LP-TEM flow systems. This manuscript introduces a method for hydrodynamic characterization of LP-TEM flow systems based on monitoring transmitted intensity while flowing a strongly electron scattering contrast agent solution. Key characteristic temporal indicators of solution replacement for various channel geometries were experimentally measured. A numerical physical model of solute transport based on realistic flow channel geometries was successfully implemented and validated against experiments. The model confirmed the impact of flow channel geometry on the importance of convective and diffusive solute transport, deduced by experiment, and could further extend understanding of hydrodynamics in LP-TEM flow systems. We emphasize that our approach can be applied to hydrodynamic characterization of any customized LP-TEM flow system. We foresee the implemented predictive model driving the future design of application-specific LP-TEM flow systems and, when combined with existing chemical reaction models, to a flourishing of the planning and interpretation of experimental observations.

The food available in open-air landfills, one of the most common predictable anthropogenic food subsidies (PAFS), can have a profound impact on animal biodiversity. Understanding how and to what extent PAFS affect wildlife is crucial for a sustainable management of resources. Most large gulls behave as opportunistic foragers and constitute a good avian model to analyze the effect of PAFS reduction on animal populations. Using individual data from a yellow-legged gull population of the Basque coast (northern Iberia) collected over a 15-year period, we estimated survival and reproductive parameters and used them to parameterize an age-structured population model to explore the effects of the local landfill closure. Local survival probability declined with time as a consequence of the progressive closure of the local landfill sites. The top-ranked models included a quadratic function of time, suggesting an acceleration of mortality during the later years, especially in juveniles, while survival in adults was linear. An effect more pronounced in first year birds than in older birds. Population models predict a decrease of the population and confirmed a greater sensitivity of the population growth rate to adult survival probability. Overall, our results suggest that the reduced carrying capacity of the system resulted after landfill closures have caused a population decline which is expected to continue in the near future.

Epitopes are specific regions on an antigen’s surface that the immune system recognizes. Epitopes are usually protein regions on foreign immune-stimulating entities such as viruses and bacteria, and in some cases, endogenous proteins may act as antigens. Identifying epitopes is crucial for accelerating the development of vaccines and immunotherapies. However, mapping epitopes in pathogen proteomes is challenging using conventional methods. Screening artificial neoepitope libraries against antibodies can overcome this issue. Here, we applied conventional sequence analysis and methods inspired in natural language processing to reveal specific sequence patterns in the linear epitopes deposited in the Immune Epitope Database (www.iedb.org) that can serve as building blocks for the design of universal epitope libraries. Our results reveal that amino acid frequency in annotated linear epitopes differs from that in the human proteome. Aromatic residues are overrepresented, while the presence of cysteines is practically null in epitopes. Byte pair encoding tokenization shows high frequencies of tryptophan in tokens of 5, 6, and 7 amino acids, corroborating the findings of the conventional sequence analysis. These results can be applied to reduce the diversity of linear epitope libraries by orders of magnitude.

We argue that the formation of Yu-Shiba-Rusinov excitations in proximitized thin films is largely mediated by a type of Andreev-bound state named after de Gennes and Saint-James. This is shown by studying an experimentally motivated model and computing the overlap of the wave functions of these two subgap states. We find the overlap stays close to unity even as the system moves away from weak coupling across the parity-changing quantum phase transition. Based on this observation, we introduce a single-site model of the bound state coupled to a quantum spin. The adequacy of this description is assessed by reintroducing the coupling to the continuum as a weak perturbation and studying its scaling flow using Anderson's poor man's scaling.

Interferometry is a powerful technique used to extract valuable information about the wave function of a system. In this work, we study the response of spin carriers to the effective field textures developed in curved one-dimensional interferometric circuits subject to the joint action of Rashba and Dresselhaus spin-orbit interactions. By using a quantum network technique, we establish that the interplay between these two non-Abelian fields and the circuit’s geometry modify the geometrical characteristics of the spinors, particularly on square circuits, leading to the localisation of the electronic wave function and the suppression of the quantum conductance. We propose a topological interpretation by classifying the corresponding spin textures in terms of winding numbers.

Amyotrophic lateral sclerosis and frontotemporal dementia patients with a hexanucleotide repeat expansion in C9ORF72 (C9-HRE) accumulate poly-GR and poly-PR aggregates. The pathogenicity of these arginine-rich dipeptide repeats (R-DPRs) is thought to be driven by their propensity to bind low-complexity domains of multivalent proteins. However, the ability of R-DPRs to bind native RNA and the significance of this interaction remain unclear. Here, we used computational and experimental approaches to characterize the physicochemical properties of R-DPRs and their interaction with RNA. We find that poly-GR predominantly binds ribosomal RNA (rRNA) in cells and exhibits an interaction that is predicted to be energetically stronger than that for associated ribosomal proteins. Critically, modified rRNA “bait” oligonucleotides restore poly-GR–associated ribosomal deficits and ameliorate poly-GR toxicity in patient neurons and Drosophila models. Our work strengthens the hypothesis that ribosomal function is impaired by R-DPRs, highlights a role for direct rRNA binding in mediating ribosomal dysfunction, and presents a strategy for protecting against C9-HRE pathophysiological mechanisms.

The conformation of poly(methyl methacrylate) (PMMA)-based single-chain nanoparticles (SCNPs) and their corresponding linear precursors in the presence of deuterated linear PMMA in deuterated dimethylformamide (DMF) solutions has been studied by small-angle neutron scattering (SANS). The SANS profiles were analyzed in terms of a three-component random phase approximation (RPA) model. The RPA approach described well the scattering profiles in dilute and crowded solutions. Considering all the contributions of the RPA leads to an accurate estimation of the single chain form factor parameters and the Flory–Huggins interaction parameter between PMMA and DMF. The value of the latter in the dilute regime indicates that the precursors and the SCNPs are in good solvent conditions, while in crowding conditions, the polymer becomes less soluble.

B(C6F5)3 is a strong electrophilic catalyst that promote the ring-opening polymerization of a number of epoxides via the formation of zwitterionic growing chains. Cyclic chains frequently are the major component of the reaction, which makes this synthetic route a viable strategy for the generation of cyclic polyethers in large quantities. We present a systematic study on the bulk and quasi-bulk polymerization of glycidol with B(C6F5)3, including kinetic experiments that evidences an abrupt chain growth at high monomer conversions. Ring fusion and branching mechanisms are invoked to explain such phenomenology. Branched cyclic polyglycidols (bcPG) are the major compounds with Mn up to 8 kg/mol and Ð ∼ 2. The glass transition temperature of bcPG exhibits lower values than that of reference linear PG samples likely associated to the dominating effect of branches.

Since the discovery of the first topological material 15 years ago, the search for material realizations of novel topological phases has become the driving force of the field. While oftentimes we search for new materials, we forget that well established materials can also display very interesting topological properties. In this work, we revisit CoS${}_2$, a metallic ferromagnetic pyrite that has been extensively studied in the literature due to its magnetic properties. We study the topological features of its electronic band structure and identify Weyl nodes and nodal lines, as well as a symmetry-protected fourfold fermion close to the Fermi level. Looking at different surface cleavage planes, we observe both spin polarized Fermi arcs in the majority channel and drumhead states. These findings suggest that CoS2 is a promising platform to study topological phenomena, as well as a good candidate for spintronic applications.

Cyclic polymers present a topology that differ significantly from their linear counterparts due to their circular structure and therefore, the lack of chain ends. These simple characteristics are responsible for important unique properties (e.g. lower intrinsic and melt viscosity, lower hydrodynamic volumes, slower degradation profiles, increased blood circulation times and more selective bioaccumulation) thanks to which the cyclic polymers are today a vanguard in macromolecular chemistry. However, the preparation of cyclic polymers with high topological purity and in large quantities is challenging, therefore demanding the continuous development of synthetic methods. Advances in organic chemistry and the development of new catalytic systems has allowed the field of cyclic polymers to expand enormously in recent decades. In this review, ring closure and ring expansion polymerization strategies are described along the milestones that have characterized the evolution of cyclic (bio)polymer chemistry over the years. We also focus on very recent advances and state-of-the-art techniques for the synthesis and purification of cyclic polymers and provide an overview of properties and applications of cyclic polymers in different fields.

Non-covalent bonds are fundamental for designing self-assembled organic structures with potentially high responsiveness to mechanical, light, and thermal stimuli. The weak intermolecular interaction allows triggering charge-transport, energy-conversion, enzymatic, and catalytic activity, to name a few. Here, we discuss the synergistic action that multiple highly-directional and purely electrostatic bonds have in assembling one molecular specie, namely 4,7-dibromobenzo[c]-1,2,5-thiadiazole (2Br-BTD), in two different patterns on the Au(111) surface. We find, using scanning tunneling microscopy (STM) and density functional theory (DFT), that multiple secondary-interactions strengthen the electrostatic attraction between the pnicogen and chalcogen atoms forming [S–N]2 heterocycles, the building block of the two networks. Among these interactions, there are halogen–halogen bonds that form characteristic supra-molecular synthons of 3, 4, or 6 molecules. However, not all these nodal structures contribute to the cohesion of the system. In such cases, other secondary bonds involving hydrogen or nitrogen compensate for the eventual deficiency.

Helicity preserving nanostructures and metasurfaces have been recently proposed as suitable candidates to enhance spectroscopic features of chiral molecules. With this in mind, we highlight that losses in the constituent nonmagnetic materials dramatically affect the possibility of constructing structures which conserve helicity. We first present a general procedure that permits the evaluation of the normalized helicity expectation value, hLiN, i.e. the observable that allows for the identification of helicity preserving scatterers. We then apply this procedure to the case of a chiral sphere, which in an orientation averaged picture can capture the optical response of chiral inorganic nanostructures, obtaining a widely applicable analytical expression of Image hLiN. Finally, we numerically show that optical losses impose an upper bound to the helicity expectation value on nonmagnetic core–shells and chiral spheres.

[Background and Aims] Cholangiocarcinoma (CCA) includes a heterogeneous group of biliary cancers with a dismal prognosis. We investigated if lipid metabolism is disrupted in CCA and its role in tumor proliferation., [Approach and Results] The in vitro and in vivo tumorigenic capacity of five human CCA cell lines was analyzed. Proteome, lipid content, and metabolic fluxes were evaluated in CCA cells and compared with normal human cholangiocytes (NHC). The Akt1/NOTCH1 intracellular cytoplasmic domain (Nicd1)-driven CCA mouse model was also evaluated. The proteome of CCA cells was enriched in pathways involved in lipid and lipoprotein metabolism. The EGI1 CCA cell line presented the highest tumorigenic capacity. Metabolic studies in high (EGI1) versus low (HUCCT1) proliferative CCA cells in vitro showed that both EGI1 and HUCCT1 incorporated more fatty acids (FA) than NHC, leading to increased triglyceride storage, also observed in Akt1/Nicd1-driven CCA mouse model. The highly proliferative EGI1 CCA cells showed greater uptake of very-low-density and HDLs than NHC and HUCCT1 CCA cells and increased cholesteryl ester content. The FA oxidation (FAO) and related proteome enrichment were specifically up-regulated in EGI1, and consequently, pharmacological blockade of FAO induced more pronounced inhibition of their tumorigenic capacity compared with HUCCT1. The expression of acyl-CoA dehydrogenase ACADM, the first enzyme involved in FAO, was increased in human CCA tissues and correlated with the proliferation marker PCNA., [Conclusions] Highly proliferative human CCA cells rely on lipid and lipoprotein uptake to fuel FA catabolism, suggesting that inhibition of FAO and/or lipid uptake could represent a therapeutic strategy for this CCA subclass.

The computational study of DNA and its interaction with ligands is a highly relevant area of research, with significant consequences for developing new therapeutic strategies. However, the computational description of such large and complex systems requires considering interactions of different types simultaneously in a balanced way, such as non-covalent weak interactions (namely hydrogen bonds and stacking), metal–ligand interactions, polarisation and charge transfer effects. All these considerations imply a real challenge for computational chemistry. The possibility of studying large biological systems using quantum methods for the entire system requires significant computational resources, with improvements in parallelisation and optimisation of theoretical strategies. Computational methods, such as Linear-Scaling Density Functional Theory (LS-DFT) and DLPNO-CCSD(T), may allow performing ab initio quantum mechanics calculations, including the electronic structure for large biological systems, in a reasonable computing time. In this work, we study the interaction of small molecules and cations with DNA (both duplex DNA and G-quadruplexes), comparing different computational methods: a LS-DFT method at the LMKLL/DZDP level of theory, semi-empirical methods (PM6-DH2 and PM7), mixed QM/MM, and DLPNO-CCSD(T). Our goal is to demonstrate the adequacy of LS-DFT to treat the different types of interactions present in DNA-dependent systems. We show that LMKLL/DZDP using SIESTA can yield very accurate geometries and energetics in all the different systems considered in this work: duplex DNA (dDNA), phenanthroline intercalating dDNA, G-quadruplexes, and metal-G-tetrads considering alkaline metals of different sizes. As far as we know, this is the first time that full G-quadruplex geometry optimisations have been carried out using a DFT method thanks to its linear-scaling capabilities. Moreover, we show that LS-DFT provides high-quality structures, and some semi-empirical Hami

Understanding the structural and magnetic properties in layered hybrid organic-inorganic metal halide perovskites (HOIPs) is key for their design and integration in spin-electronic devices. Here, a systematic study is conducted on ten compounds to understand the effect of the transition metal (Cu2+, Mn2+, Co2+), organic spacer (alkyl- and aryl-ammonium), and perovskite phase (Ruddlesden-Popper and Dion-Jacobson) on the properties of these materials. Temperature-dependent Raman measurements show that the crystals’ structural phase transitions are triggered by the motional freedom of the organic cations as well as by the flexibility of the inorganic metal-halide lattice. In the case of Cu2+ HOIPs, an increase of the in-plane anisotropy and a reduction of the octahedra interlayer distance is found to change the behavior of the HOIP from that of a 2D ferromagnet to that of a quasi-3D antiferromagnet. Mn2+ HOIPs show inherent antiferromagnetic octahedra intralayer interactions and a phenomenologically rich magnetism, presenting spin-canting, spin-flop transitions, and metamagnetism controlled by the crystal anisotropy. Co2+ crystals with non-linked tetrahedra show a dominant paramagnetic behavior irrespective of the organic spacer and the perovskite phase. This study demonstrates that the chemical flexibility of HOIPs can be exploited to develop novel layered magnetic materials with tailored magnetic properties.

Hierarchical self-assembly of structural elements gives rise to superstructures often with outstanding properties when compared to individual elements, as first observed in nature. While folding of individual synthetic chains leads to discrete single-chain nanoparticles (SCNPs) of significant interest for a number of applications, its full potential utility through integration into well-defined superstructures is recently being recognized. Remarkably, SCNPs in good solvent resemble randomly branched polymers with ideal connectivity in a theta-solvent or percolating clusters with screened excluded-volume interactions. Herein we consider the integration of SCNPs into star, comb and bottlebrush topologies and investigate the dimensions of the resulting superstructures under different conditions (good solvent, ideal conformations, 1D- and 2D-confinement in nanopores and nanoslits, anchored to flat surfaces). A detailed comparison of the equilibrium conformational properties of star, comb and bottlebrush polymers composed of elastic SCNPs to those of equivalent topologies based on linear chains is provided. This analysis reveals the effect of hierarchical topology on superstructure dimensions in several relevant environments, as well as how the structural parameters of the SCNPs influence the location of the comb-to-bottlebrush transition as a function of grafting density. The degree of intra-chain cross-linking arises as an additional parameter for controlling the local and global dimensions of stars, combs and bottlebrushes of SCNPs.

Atomically thin van der Waals magnetic crystals are characterized by tunable magnetic properties related to their low dimensionality. While electrostatic gating has been used to tailor their magnetic response, chemical approaches like intercalation remain largely unexplored. Here, we demonstrate the manipulation of the magnetism in the van der Waals antiferromagnet NiPS3 through the intercalation of different organic cations, inserted using an engineered two-step process. First, the electrochemical intercalation of tetrabutylammonium cations (TBA+) results in a ferrimagnetic hybrid compound displaying a transition temperature of 78 K, and characterized by a hysteretic behavior with finite remanence and coercivity. Then, TBA+ cations are replaced by cobaltocenium via an ion-exchange process, yielding a ferrimagnetic phase with higher transition temperature (98 K) and higher remanent magnetization. Importantly, we demonstrate that the intercalation and cation exchange processes can be carried out in bulk crystals and few-layer flakes, opening the way to the integration of intercalated magnetic materials in devices.

Strain is an effective strategy to modulate the optoelectronic properties of 2D materials, but it has been almost unexplored in layered hybrid organic–inorganic metal halide perovskites (HOIPs) due to their complex band structure and mechanical properties. Here, we investigate the temperature-dependent microphotoluminescence (PL) of 2D (C6H5CH2CH2NH3)2Cs3Pb4Br13 HOIP subject to biaxial strain induced by a SiO2 ring platform on which flakes are placed by viscoelastic stamping. At 80 K, we found that a strain of <1% can change the PL emission from a single peak (unstrained) to three well-resolved peaks. Supported by micro-Raman spectroscopy, we show that the thermomechanically generated strain modulates the bandgap due to changes in the octahedral tilting and lattice expansion. Mechanical simulations demonstrate the coexistence of tensile and compressive strain along the flake. The observed PL peaks add an interesting feature to the rich phenomenology of photoluminescence in 2D HOIPs, which can be exploited in tailored sensing and optoelectronic devices.

Single-chain nanoparticles (SCNPs) result from the folding of isolated polymer chains via intramolecular interactions. Currently, there is no theory able to rationalize the astonishing conformational behaviour of SCNPs under severe crowding conditions (e.g., highly concentrated solutions, all-polymer nanocomposites) and, specifically, the significant size reduction observed in highly crowded solutions of covalent-bonded SCNPs and all-polymer nanocomposites containing SCNPs. Herein, we propose a valuable method to estimate the size of SCNPs under crowding. The method – which is based on combining MD simulations results with scaling concepts – is also useful for ring polymers and nanostructured Janus-shaped SCNPs.

The exfoliation of layered magnetic materials generates atomically thin flakes characterized by an ultrahigh surface sensitivity, which makes their magnetic properties tunable via external stimuli, such as electrostatic gating and proximity effects. Another powerful approach to engineer magnetic materials is molecular functionalization, generating hybrid interfaces with tailored magnetic interactions, called spinterfaces. However, spinterface effects have not yet been explored on layered magnetic materials. Here, the emergence of spinterface effects is demonstrated at the interface between flakes of the prototypical layered magnetic metal Fe3GeTe2 and thin films of Co-phthalocyanine. Magnetotransport measurements show that the molecular layer induces a magnetic exchange bias in Fe3GeTe2, indicating that the unpaired spins in Co-phthalocyanine develop antiferromagnetic ordering and pin the magnetization reversal of Fe3GeTe2 via magnetic proximity. The effect is strongest for a Fe3GeTe2 thickness of 20 nm, for which the exchange bias field reaches −840 Oe at 10 K and is measurable up to ≈110 K. This value compares very favorably with previous exchange bias fields reported for Fe3GeTe2 in all-inorganic van der Waals heterostructures, demonstrating the potential of molecular functionalization to tailor the magnetism of van der Waals layered materials.

Chiral materials are an ideal playground for exploring the relation between symmetry, relativistic effects and electronic transport. For instance, chiral organic molecules have been intensively studied to electrically generate spin-polarized currents in the last decade, but their poor electronic conductivity limits their potential for applications. Conversely, chiral inorganic materials such as tellurium have excellent electrical conductivity, but their potential for enabling the electrical control of spin polarization in devices remains unclear. Here, we demonstrate the all-electrical generation, manipulation and detection of spin polarization in chiral single-crystalline tellurium nanowires. By recording a large (up to 7%) and chirality-dependent unidirectional magnetoresistance, we show that the orientation of the electrically generated spin polarization is determined by the nanowire handedness and uniquely follows the current direction, while its magnitude can be manipulated by an electrostatic gate. Our results pave the way for the development of magnet-free chirality-based spintronic devices.

Dislipidemia is a risk factor for cognitive impairment. We studied the association between interindividual variability of plasma lipids and white matter (WM) microstructure, using diffusion tensor imaging (DTI) in 273 healthy adults. Special focus was placed on 7 regions of interest (ROI) which are structural components of cognitive neurocircuitry. We also investigated the effect of plasma lipids on cerebrospinal fluid (CSF) neurofilament light chain (NfL), an axonal degeneration marker. Low density lipoprotein (LDL) and triglyceride (TG) levels showed a negative association with axial diffusivity (AxD) in multiple regions. High density lipoproteins (HDL) showed a positive correlation. The association was independent of Apolipoprotein E (APOE) genotype, blood pressure or use of statins. LDL moderated the relation between NfL and AxD in the body of the corpus callosum (p = 0.041), right cingulum gyrus (p = 0.041), right fornix/stria terminalis (p = 0.025) and right superior longitudinal fasciculus (p = 0.020) and TG in the right inferior longitudinal fasciculus (p = 0.004) and left fornix/stria terminalis (p = 0.001). We conclude that plasma lipids are associated to WM microstructural changes and axonal degeneration and might represent a risk factor in the transition from healthy aging to disease.

The epidemic spread of many viral infections is mediated by the environmental conditions and influenced by the ambient humidity. Single virus particles have been mainly visualized by atomic force microscopy (AFM) in liquid conditions, where the effect of the relative humidity on virus topography and surface cannot be systematically assessed. In this work, we employed multi-frequency AFM, simultaneously with standard topography imaging, to study the nanoscale wetting of individual Tobacco Mosaic virions (TMV) from ambient relative humidity to water condensation (RH > 100%). We recorded amplitude and phase vs. distance curves (APD curves) on top of single virions at various RH and converted them into force vs. distance curves. The high sensitivity of multifrequency AFM to visualize condensed water and sub-micrometer droplets, filling gaps between individual TMV particles at RH > 100%, is demonstrated. Dynamic force spectroscopy allows detecting a thin water layer of thickness ⁓1 nm, adsorbed on the outer surface of single TMV particles at RH < 60%.

We provide an exhaustive characterization of structural properties and nuclear dynamics in tungstic acid (WO3·H2O). To this end, we employ neutron and X-ray diffraction (ND and XRD) combined with inelastic neutron scattering (INS) and neutron Compton scattering (NCS) experiments, and we corroborate the analysis with extensive ab initio modeling. The first step in our analysis is the elucidation of the crystal structure based on the refinement of low-temperature powder ND data, extending the knowledge gained from XRD analysis of a mineral specimen of tungstite. These results are confronted with low-temperature INS experiments and zero-temperature phonon calculations. The analysis reveals an inconsistency in the definition of the structure of confined water with respect to crystallographic data, also showing a concomitant failure of the phonon calculations due to a strongly anharmonic confining potential. Extending the computational route toward ab initio MD (AIMD) simulations allows us to probe different structural configurations and provides an improved description of the vibrational dynamics as compared to high-resolution INS experiments, nevertheless, requiring the use of effective classical temperatures. The analysis of both INS and the NCS data reveals a remarkable similarity to the nuclear dynamics earlier reported for water confined in single-wall carbon nanotubes (SWNT), which has been qualitatively described as a new phase of ice. Our analysis reveals a strong two-dimensional hydrogen-bonding network, similar to the shell model for water in SWNT. The reported NCS data show narrowing of the hydrogen momentum distribution with respect to the reference ab initio calculations, indicating a great deal of conformational freedom due to spatial delocalization of protons in the ground state of the system, a clear signature of the quantum character of the nuclei.

The folding of certain proteins (e.g., enzymes) into perfectly defined 3D conformations via multi-orthogonal interactions is critical to their function. Concerning synthetic polymers chains, the “folding” of individual polymer chains at high dilution via intra-chain interactions leads to so-called single-chain nanoparticles (SCNPs). This review article describes the advances carried out in recent years in the folding of single polymer chains into discrete SCNPs via multi-orthogonal interactions using different reactive chemical species where intra-chain bonding only occurs between groups of the same species. First, we summarize results from computer simulations of multi-orthogonally folded SCNPs. Next, we comprehensively review multi-orthogonally folded SCNPs synthesized via either non-covalent bonds or covalent interactions. Finally, we conclude by summarizing recent research about multi-orthogonally folded SCNPs prepared through both reversible (dynamic) and permanent bonds.

Atlantic horse mackerel (Trachurus trachurus) fillets were coated by gallic acid and chitosan solutions, including chitosan nanoparticles, and fish quality and shelf life were assessed during chilled storage for 13 days. All chitosan-containing coatings decreased microorganisms’ growth in more than 2 log cycles up to late storage stages; however, those with chitosan nanoparticles resulted to be more effective, probably due to a greater contact surface with fish muscle. Furthermore, the lowest total volatile basic nitrogen (TVB-N) values, as well as pH values below 7, were found for horse mackerel fillets coated by those solutions with chitosan nanoparticles. Additionally, horse mackerel fillets coated by solutions with chitosan nanoparticles also showed the lowest thiobarbituric acid reactive substances (TBARS) values, maybe owing to a more sustained release of gallic acid. In this regard, it is worth noting that, although gallic acid solution showed no antimicrobial activity, this prevented lipid oxidation and, therefore, preserved color and texture during the chilling storage.

Time Reversal Symmetry (TRS) broken topological phases provide gapless surface states protected by topology, regardless of additional internal symmetries, spin or valley degrees of freedom. Despite the numerous demonstrations of 2D topological phases, few examples of 3D topological systems with TRS breaking exist. In this article, we devise a general strategy to design 3D Chern insulating (3D CI) cubic photonic crystals in a weakly TRS broken environment with orientable and arbitrarily large Chern vectors. The designs display topologically protected chiral and unidirectional surface states with disjoint equifrequency loops. The resulting crystals present the following characteristics: First, by increasing the Chern number, multiple surface states channels can be supported. Second, the Chern vector can be oriented along any direction simply changing the magnetization axis, opening up larger 3D CI/3D CI interfacing possibilities as compared to 2D. Third, by lowering the TRS breaking requirements, the system is ideal for realistic photonic applications where the magnetic response is weak.

Diethylammonium nitrate, [N0 0 2 2][NO3], and its perdeuterated analogue, [ND D 2 2] [NO3], were structurally characterized and studied by infrared, Raman, and inelastic neutron scattering (INS) spectroscopy. Using these experimental data along with state-of-the-art computational materials modeling, we report unambiguous spectroscopic signatures of hydrogen-bonding interactions between the two counterions. An exhaustive assignment of the spectral features observed with each technique has been provided, and a number of distinct modes related to NH···O dynamics have been identified. We put a particular emphasis on a detailed interpretation of the high-resolution, broadband INS experiments. In particular, the INS data highlight the importance of conformational degrees of freedom within the alkyl chains, a ubiquitous feature of ionic liquid (IL) systems. These findings also enable an in-depth physicochemical understanding of protonic IL systems, a first and necessary step to the tailoring of hydrogen-bonding networks in this important class of materials.

The condensed phases of the carbon-based nanobowl corannulene are herein investigated in the temperature range 200–573 K, combining differential scanning calorimetry, synchrotron X-ray diffraction, and quasielastic neutron-scattering. For the first time, we identify the presence of a well-defined thermal event at 382 K, a figure well below a melting point of 540 K. Contrary to naïve expectation, detailed analysis of the neutron-scattering data below and above this pre-melting transition signals the emergence of correlated stochastic dynamics within both thermodynamically stable solid phases of the material. We find that these are progressively responsible for the suppression of molecular and supramolecular order over mesoscopic length scales, and are associated with the formation of high-symmetry rotor-like states exhibiting localized stochastic motions. Upon cooling from the melt, we have also discovered a robust hysteresis associated with the existence of hitherto-unknown metastable liquid (deep-supercooled) and disordered-solid phases. This behaviour is markedly different from that observed in the quintessential Buckminsterfullerene C60 or other chemically substituted fullerene adducts studied to date at this level of detail. These results evince new and yet-to-tapped opportunities for the use of the stable and metastable phases of carbon-based nanobowls in novel applications exploiting the emergence of dynamical disorder at the nanoscale.

This work provides an up-to-date overview of recent developments in neutron spectroscopic techniques and associated computational tools to interrogate the structural properties and dynamical behavior of complex and disordered materials, with a focus on those of a soft and polymeric nature. These have and continue to pave the way for new scientific opportunities simply thought unthinkable not so long ago, and have particularly benefited from advances in high-resolution, broadband techniques spanning energy transfers from the meV to the eV. Topical areas include the identification and robust assignment of low-energy modes underpinning functionality in soft solids and supramolecular frameworks, or the quantification in the laboratory of hitherto unexplored nuclear quantum effects dictating thermodynamic properties. In addition to novel classes of materials, we also discuss recent discoveries around water and its phase diagram, which continue to surprise us. All throughout, emphasis is placed on linking these ongoing and exciting experimental and computational developments to specific scientific questions in the context of the discovery of new materials for sustainable technologies.

The colloidal stability of metal nanoparticles is tremendously dependent on the thermal behavior of polymer brushes. Neat polyethylene glycol (PEG) presents an unconventional upper critical solution temperature in ethanol, where phase segregation and crystallization coexist. This thermal behavior translated to a PEG brush has serious consequences on the colloidal stability in ethanol of gold nanoparticles (AuNPs) modified with PEG brushes upon cooling. We observed that AuNPs (13 nm diameter) stabilized with conventional linear PEG brushes (Mn = 6 and 11 kg mol−1) in ethanol suffer from reversible phase separation upon a temperature drop over the course of a few hours. However, the use of a polymer brush with cyclic topology as a stabilizer prevents sedimentation, ensuring the colloidal stability in ethanol at −25 °C for, at least, four months. We postulate that temperature-driven collapse of chain brushes promotes the interpenetration of linear chains, causing progressive AuNP sedimentation, a process that is unfavorable for cyclic polymer brushes whose topology prevents chain interpenetration. This study reinforces the notion about the importance of polymer topology on the colloidal stability of AuNPs.

The vibrational dynamics of pure and methylammonium-doped formamidinium lead iodide perovskites (FAPbI3) has been investigated by high-resolution neutron spectroscopy. For the first time, we provide an exhaustive and accurate analysis of the cation vibrations and underlying local structure around the organic moiety in these materials using first-principles electronic-structure calculations validated by the neutron data. Inelastic neutron scattering experiments on FAPbI3 provide direct evidence of the formation of a low-temperature orientational glass, unveiling the physicochemical origin of phase metastability in the tetragonal structure. Further analysis of these data provides a suitable starting point to explore and understand the stabilization of the perovskite framework via doping with small amounts of organic cations. In particular, we find that the hydrogen-bonding interactions around the formamidinium cations are strengthened as a result of cage deformation. This synergistic effect across perovskite cages is accompanied by a concomitant weakening of the methylammonium interactions with the surrounding framework.

Essential tremor (ET) is a highly prevalent neurological disorder characterized by action-induced tremors involving the hand, voice, head, and/or face. Importantly, hand tremor is present in nearly all forms of ET, resulting in impaired fine motor skills and diminished quality of life. To advance early diagnostic approaches for ET, automated handwriting tasks and magnetic resonance imaging (MRI) offer an opportunity to develop early essential clinical biomarkers. In this study, we present a novel approach for the early clinical diagnosis and monitoring of ET based on integrating handwriting and neuroimaging analysis. We demonstrate how the analysis of fine motor skills, as measured by an automated Archimedes’ spiral task, is correlated with neuroimaging biomarkers for ET. Together, we present a novel modeling approach that can serve as a complementary and promising support tool for the clinical diagnosis of ET and a large range of tremors.

The successive self-nucleation and annealing (SSA) thermal fractionation technique has been applied for the first time to thermoplastic polyurethanes (TPUs). The changes in structure and morphology before and after SSA fractionation were monitored by Differential Scanning Calorimetry (DSC), in situ real-time Small and Wide-angle X-ray scattering synchrotron experiments (SAXS/WAXS) and Atomic Force Microscopy (AFM). SSA applies a series of successive cooling and heating runs to a self-nucleated sample that promotes the creation of a series of thermal fractions in the TPUs with a specific lamellar thicknesses and melting point distribution thanks to the multi-block structure of TPUs. The SSA fractionated samples experienced a general increase in lamellar thickness that has been revealed by both AFM and SAXS and a distribution of lamellar thickness estimated by DSC and AFM. The average lamellar thickness of SSA fractionated samples has been estimated by SAXS, AFM, and DSC. The values obtained are in quantitative agreement (within the errors involved in the techniques) when considering that phase segregation in the TPU samples has been promoted by crystallization. The refined crystalline structure obtained after SSA produced a number of clear WAXS reflections, as compared to the unfractionated materials, facilitating the determination of the TPUs crystallinity degree by WAXS.

Over the past decades, polymer mechanochemistry has focused on the development and application of advanced force application methods to better understand the mechanochemical response of mechanophores. In this regard, techniques such as ultrasonication and single-molecule force spectroscopy (SMFS) are used to activate and detect up to thousands of chemical events within a polymer single chain, allowing the researchers to probe the mechanochemical reactivity of these stress-responsive motifs. Here, the most recent contributions of the single-molecule force spectroscopy technique to this field are presented, putting emphasis on the fundamental parameters of the technique for triggering specific force responses and on the description of force–extension curves measured for single- and multi-mechanophore polymers. Moreover, new contributions of microscopy-based techniques in the field of polymer mechanochemistry, as well as the potential application of single-chain nanoparticles as mechanoresponsive materials, are highlighted.

Biofouling is a major issue in the field of nanomedicine and consists of the spontaneous and unwanted adsorption of biomolecules on engineered surfaces. In a biological context and referring to nanoparticles (NPs) acting as nanomedicines, the adsorption of biomolecules found in blood (mostly proteins) is known as protein corona. On the one hand, the protein corona, as it covers the NPs' surface, can be considered the biological identity of engineered NPs, because the corona is what cells will "see" instead of the underlying NPs. As such, the protein corona will influence the fate, integrity, and performance of NPs in vivo. On the other hand, the physicochemical properties of the engineered NPs, such as their size, shape, charge, or hydrophobicity, will influence the identity of the proteins attracted to their surface. In this context, the design of coatings for NPs and surfaces that avoid biofouling is an active field of research. The gold standard in the field is the use of polyethylene glycol (PEG) molecules, although zwitterions have also proved to be efficient in preventing protein adhesion and fluorinated molecules are emerging as coatings with interesting properties. Hence, in this review, we will focus on recent examples of anti-biofouling coatings in three main areas, that is, PEGylated, zwitterionic, and fluorinated coatings.

In this manuscript we analyze the emergence of protected multiphoton states in scattering problems with cylindrical symmetry. In order to do that, we first provide a formal definition of the concept of postselected symmetry-protection. We show that the notion of symmetry-protection is not limited to one- or two-photon states, on the contrary, it can be formally extended to the multiphoton case. In addition, we prove for the case of cylindrical symmetry that all possible multiphoton protected states are constructed from a small set of one- and two-photon states. Finally, we point out possible applications that symmetry-protected states may have in quantum communications, concretely, in the construction of decoherence-free subspaces.

In recent decades, self-confinement effects arising from the folding of individual synthetic polymer chains to single-chain nanoparticles (SCNPs) have been exploited for the construction of efficient enzyme-mimetic catalysts, improved drug delivery nanosystems and innovative sensing nanomaterials, among other uses. Remarkably, the imperfect folding of a unimolecular synthetic chain to a functional soft nano-object resembles – to some extent – the folding of a protein to its native, functional state. However, the huge possibilities that can be deployed by determining how external confinement modulates the structure, dynamics and properties of SCNPs have not been totally appreciated yet. In this article, after considering the opportunites that internal confinement in SCNPs offers for catalysis; encapsulation, transport and delivery of therapeutic cargos; and sensing, targeting and bioimaging applications, as well as other diverse advanced applications, we try to provide a unifying vision of what is the expected effect of external confinement – as imposed under different geometrical constraints as well as in solution, in the melt state, on surfaces and in membranes – on the size, shape and, hence, potential functionality/foreseen applications of SCNPs. We anticipate a plethora of opportunities that open up arising from external confinement of SCNPs: from innovative purification techniques and improved all-polymer nanocomposites, to smart responsive surfaces and new topological nanostructures.

We report the formation of five novel multifunctional coordination polymers based on 1H-indazole-4-carboxylic acid (HL). To the best of our knowledge, these complexes are the first examples of coordination compounds constructed with this interesting ligand. These materials were synthesized by solvothermal routes, possess different 2D-structures and show interesting magnetic properties due to the copper compound showing an unusual spin-canted effect while the anisotropic cobalt material behaves as a field-induced single molecule magnet. MTT assays performed on human embryonic kidney (HEK293) and mouse skin melanoma (B16-F10) cell lines indicated that the Cd-based compound was the only one exhibiting dose-dependent toxicity on B16-F10 cells, most likely due to the release of toxic Cd(ii). Cadmium and zinc polymers exhibit interesting luminescence properties. The fact that zinc polymers did not exhibit inherent toxicity against both cancer and non-cancerous cells make this new family an excellent candidate for further investigation in the field of luminescent materials with biomedical applications. This journal is