Beating the Stoner criterion using molecular interfaces.

Only three elements are ferromagnetic at room temperature: the transition metals iron, cobalt and nickel. The Stoner criterion explains why iron is ferromagnetic but manganese, for example, is not, even though both elements have an unfilled 3d shell and are adjacent in the periodic table: according to this criterion, the product of the density of states and the exchange integral must be greater than unity for spontaneous spin ordering to emerge. Here we demonstrate that it is possible to alter the electronic states of non-ferromagnetic materials, such as diamagnetic copper and paramagnetic manganese, to overcome the Stoner criterion and make them ferromagnetic at room temperature. This effect is achieved via interfaces between metallic thin films and C60 molecular layers. The emergent ferromagnetic state exists over several layers of the metal before being quenched at large sample thicknesses by the material's bulk properties. Although the induced magnetization is easily measurable by magnetometry, low-energy muon spin spectroscopy provides insight into its distribution by studying the depolarization process of low-energy muons implanted in the sample. This technique indicates localized spin-ordered states at, and close to, the metal-molecule interface. Density functional theory simulations suggest a mechanism based on magnetic hardening of the metal atoms, owing to electron transfer. This mechanism might allow for the exploitation of molecular coupling to design magnetic metamaterials using abundant, non-toxic components such as organic semiconductors. Charge transfer at molecular interfaces may thus be used to control spin polarization or magnetization, with consequences for the design of devices for electronic, power or computing applications (see, for example, refs 6 and 7).

Developing Hollow-Channel Gold Nanoflowers as Trimodal Intracellular Nanoprobes.

Gold nanoparticles-enabled intracellular surface-enhanced Raman spectroscopy (SERS) provides a sensitive and promising technique for single cell analysis. Compared with spherical gold nanoparticles, gold nanoflowers, i.e., flower-shaped gold nanostructures, can produce a stronger SERS signal. Current exploration of gold nanoflowers for intracellular SERS has been considerably limited by the difficulties in preparation, as well as background signal and cytotoxicity arising from the surfactant capping layer. Recently, we have developed a facile and surfactant-free method for fabricating hollow-channel gold nanoflowers (HAuNFs) with great single-particle SERS activity. In this paper, we investigate the cellular uptake and cytotoxicity of our HAuNFs using a RAW 264.7 macrophage cell line, and have observed effective cellular internalization and low cytotoxicity. We have further engineered our HAuNFs into SERS-active tags, and demonstrated the functionality of the obtained tags as trimodal nanoprobes for dark-field and fluorescence microscopy imaging, together with intracellular SERS.

Unexpected magnetic properties of gas-stabilized platinum nanostructures in the tunneling regime.

Nanostructured materials often have properties widely different from bulk, imposed by quantum limits to a physical property of the material. This includes, for example, superparamagnetism and quantized conductance, but original properties such as magnetoresistance in nonmagnetic molecular structures may also emerge. In this Letter, we report on the atomic manipulation of platinum nanocontacts in order to induce magnetoresistance. Platinum is a paramagnetic 5d metal, but atomic chains of this material have been predicted to be magnetically ordered with a large anisotropy. Remarkably, we find that a gas flow stabilizes Pt atomic structures in a break junction experiment, where we observe extraordinary resistance changes over 30,000% in a temperature range up to 77 K. Simulations indicate that this behavior may stem from a previously unknown magnetically ordered, low-energy state in platinum oxide atomic chains. This is supported by measurements in Pt/PtOx superlattices revealing the presence of a ferromagnetic moment. These properties open new paths of research for atomic scale "dirty" magnetic sensors and quantum devices.

Analysis of Clinical Samples of Pancreatic Cyst's Lesions with A Multi-Analyte Bioelectronic Simot Array Benchmarked Against Ultrasensitive Chemiluminescent Immunoassay.

Pancreatic cancer, ranking as the third factor in cancer-related deaths, necessitates enhanced diagnostic measures through early detection. In response, SiMoT-Single-molecule with a large Transistor multiplexing array, achieving a Technology Readiness Level of 5, is proposed for a timely identification of pancreatic cancer precursor cysts and is benchmarked against the commercially available chemiluminescent immunoassay SIMOA (Single molecule array) SP-X System. A cohort of 39 samples, comprising 33 cyst fluids and 6 blood plasma specimens, undergoes detailed examination with both technologies. The SiMoT array targets oncoproteins MUC1 and CD55, and oncogene KRAS, while the SIMOA SP-X planar technology exclusively focuses on MUC1 and CD55. Employing Principal Component Analysis (PCA) for multivariate data processing, the SiMoT array demonstrates effective discrimination of malignant/pre-invasive high-grade or potentially malignant low-grade pancreatic cysts from benign non-mucinous cysts. Conversely, PCA analysis applied to SIMOA assay reveals less effective differentiation ability among the three cyst classes. Notably, SiMoT unique capability of concurrently analyzing protein and genetic markers with the threshold of one single molecule in 0.1 mL positions it as a comprehensive and reliable diagnostic tool. The electronic response generated by the SiMoT array facilitates direct digital data communication, suggesting potential applications in the development of field-deployable liquid biopsy.

A Single-Molecule Bioelectronic Portable Array for Early Diagnosis of Pancreatic Cancer Precursors.

A cohort of 47 patients is screened for pancreatic cancer precursors with a portable 96-well bioelectronic sensing-array for single-molecule assay in cysts fluid and blood plasma, deployable at point-of-care (POC). Pancreatic cancer precursors are mucinous cysts diagnosed with a sensitivity of at most 80% by state-of-the-art cytopathological molecular analyses (e.g., KRASmut DNA). Adding the simultaneous assay of proteins related to malignant transformation (e.g., MUC1 and CD55) is deemed essential to enhance diagnostic accuracy. The bioelectronic array proposed here, based on single-molecule-with-a-large-transistor (SiMoT) technology, can assay both nucleic acids and proteins at the single-molecule limit-of-identification (LOI) (1% of false-positives and false-negatives). It comprises an enzyme-linked immunosorbent assay (ELISA)-like 8 × 12-array organic-electronics disposable cartridge with an electrolyte-gated organic transistor sensor array, and a reusable reader, integrating a custom Si-IC chip, operating via software installed on a USB-connected smart device. The cartridge is complemented by a 3D-printed sensing gate cover plate. KRASmut , MUC1, and CD55 biomarkers either in plasma or cysts-fluid from 5 to 6 patients at a time, are multiplexed at single-molecule LOI in 1.5 h. The pancreatic cancer precursors are classified via a machine-learning analysis resulting in at least 96% diagnostic-sensitivity and 100% diagnostic-specificity. This preliminary study opens the way to POC liquid-biopsy-based early diagnosis of pancreatic-cancer precursors in plasma.

Optical conversion of pure spin currents in hybrid molecular devices.

Carbon-based molecules offer unparalleled potential for THz and optical devices controlled by pure spin currents: a low-dissipation flow of electronic spins with no net charge displacement. However, the research so far has been focused on the electrical conversion of the spin imbalance, where molecular materials are used to mimic their crystalline counterparts. Here, we use spin currents to access the molecular dynamics and optical properties of a fullerene layer. The spin mixing conductance across Py/C60 interfaces is increased by 10% (5 × 1018 m-2) under optical irradiation. Measurements show up to a 30% higher light absorbance and a factor of 2 larger photoemission during spin pumping. We also observe a 0.15 THz slowdown and a narrowing of the vibrational peaks. The effects are attributed to changes in the non-radiative damping and energy transfer. This opens new research paths in hybrid magneto-molecular optoelectronics, and the optical detection of spin physics in these materials.Carbon-based molecules could prove useful in terahertz and optical devices controlled by pure spin currents. Here, conversely, the authors use spin currents to probe molecular dynamics and enhance the optical response of a fullerene layer, enabling hybrid magneto-molecular optoelectronic devices.

Synthetic ferrimagnet nanowires with very low critical current density for coupled domain wall motion.

Domain walls in ferromagnetic nanowires are potential building-blocks of future technologies such as racetrack memories, in which data encoded in the domain walls are transported using spin-polarised currents. However, the development of energy-efficient devices has been hampered by the high current densities needed to initiate domain wall motion. We show here that a remarkable reduction in the critical current density can be achieved for in-plane magnetised coupled domain walls in CoFe/Ru/CoFe synthetic ferrimagnet tracks. The antiferromagnetic exchange coupling between the layers leads to simple Néel wall structures, imaged using photoemission electron and Lorentz transmission electron microscopy, with a width of only ~100 nm. The measured critical current density to set these walls in motion, detected using magnetotransport measurements, is 1.0 × 1011 Am-2, almost an order of magnitude lower than in a ferromagnetically coupled control sample. Theoretical modelling indicates that this is due to nonadiabatic driving of anisotropically coupled walls, a mechanism that can be used to design efficient domain-wall devices.

One-step fabrication of hollow-channel gold nanoflowers with excellent catalytic performance and large single-particle SERS activity.

Hollow metallic nanostructures have shown potential in various applications including catalysis, drug delivery and phototherapy, owing to their large surface areas, reduced net density, and unique optical properties. In this study, novel hollow gold nanoflowers (HAuNFs) consisting of an open hollow channel in the center and multiple branches/tips on the outer surface are fabricated for the first time, via a facile one-step synthesis using an auto-degradable nanofiber as a bifunctional template. The one-dimensional (1D) nanofiber acts as both a threading template as well as a promoter of the anisotropic growth of the gold crystal, the combination of which leads to the formation of HAuNFs with a hollow channel and nanospikes. The synergy of favorable structural/surface features, including sharp edges, open cavity and high-index facets, provides our HAuNFs with excellent catalytic performance (activity and cycling stability) coupled with large single-particle SERS activity (including ∼30 times of activity in ethanol electro-oxidation and ∼40 times of single-particle SERS intensity, benchmarked against similar-sized solid gold nanospheres with smooth surfaces, as well as retaining 86.7% of the initial catalytic activity after 500 cycles in ethanol electro-oxidation). This innovative synthesis gives a nanostructure of the geometry distinct from the template and is extendable to fabricating other systems for example, hollow-channel silver nanoflowers (HAgNFs). It thus provides an insight into the design of hollow nanostructures via template methods, and offers a versatile synthetic strategy for diverse metal nanomaterials suited for a broad range of applications.