Kinetics vs. thermodynamics: walking on the line for a five-fold increase in MnSi Curie temperature.

Green and digital transitions will induce tremendous demand for metals and semiconductors. This raises concerns about the availability of materials in the rather near future. Addressing this challenge requires an unprecedented effort to discover new materials that are more sustainable and also to expand their functionalities beyond conventional material limits. From this point of view, complex systems combining semiconductor and magnetic properties in a single material lay the foundations for future nanoelectronics devices. Through a combination of out-of-stable equilibrium processes, we achieved fine control over the crystallisation of non-stoichiometric MnSix (x = 0.92). The Curie temperature shows non-monotonous evolution with crystallisation. At the earliest and final stages, the Curie temperature is comparable with stoichiometric MnSi (TC = 30 K). At the intermediate stage, while the material is crystalline and remains non-stoichiometric, a remarkable fivefold increase in Curie temperature (TC = 150 K) is observed. This finding highlights the potential for controlling the metastability of materials as a promising and relatively unexplored pathway to enhance material properties, without relying on critical materials such as rare earth elements.

All-optical generation of static electric field in a single metal-semiconductor nanoantenna.

Electric field is a powerful instrument in nanoscale engineering, providing wide functionalities for control in various optical and solid-state nanodevices. The development of a single optically resonant nanostructure operating with a charge-induced electrical field is challenging, but it could be extremely useful for novel nanophotonic horizons. Here, we show a resonant metal-semiconductor nanostructure with a static electric field created at the interface between its components by charge carriers generated via femtosecond laser irradiation. We study this field experimentally, probing it by second-harmonic generation signal, which, in our system, is time-dependent and has a non-quadratic signal/excitation power dependence. The developed numerical models reveal the influence of the optically induced static electric field on the second harmonic generation signal. We also show how metal work function and silicon surface defect density for different charge carrier concentrations affect the formation of this field. We estimate the value of optically-generated static electric field in this nanoantenna to achieve ≈108V/m. These findings pave the way for the creation of nanoantenna-based optical memory, programmable logic and neuromorphic devices.

Three-Dimensional-Printed Molds from Water-Soluble Sulfate Ceramics for Biocomposite Formation through Low-Pressure Injection Molding.

Powder mixtures of MgSO4 with 5-20 mol.% Na2SO4 or K2SO4 were used as precursors for making water-soluble ceramic molds to create thermoplastic polymer/calcium phosphate composites by low pressure injection molding. To increase the strength of the ceramic molds, 5 wt.% of tetragonal ZrO2 (Y2O3-stabilized) was added to the precursor powders. A uniform distribution of ZrO2 particles was obtained. The average grain size for Na-containing ceramics ranged from 3.5 ± 0.8 µm for MgSO4/Na2SO4 = 91/9% to 4.8 ± 1.1 µm for MgSO4/Na2SO4 = 83/17%. For K-containing ceramics, the values were 3.5 ± 0.8 µm for all of the samples. The addition of ZrO2 made a significant contribution to the strength of ceramics: for the MgSO4/Na2SO4 = 83/17% sample, the compressive strength increased by 49% (up to 6.7 ± 1.3 MPa), and for the stronger MgSO4/K2SO4 = 83/17% by 39% (up to 8.4 ± 0.6 MPa). The average dissolution time of the ceramic molds in water did not exceed 25 min.

Development of Nanocarrier-Based Radionuclide and Photothermal Therapy in Combination with Chemotherapy in Melanoma Cancer Treatment.

Conventional cancer therapy methods have serious drawbacks that are related to the nonspecific action of anticancer drugs that leads to high toxicity on normal cells and increases the risk of cancer recurrence. The therapeutic effect can be significantly enhanced when various treatment modalities are implemented. Here, we demonstrate that the radio- and photothermal therapy (PTT) delivered through nanocarriers (gold nanorods, Au NRs) in combination with chemotherapy in a melanoma cancer results in complete tumor inhibition compared to the single therapy. The synthesized nanocarriers can be effectively labeled with 188Re therapeutic radionuclide with a high radiolabeling efficiency (94-98%) and radiochemical stability (>95%) that are appropriate for radionuclide therapy. Further, 188Re-Au NRs, mediating the conversion of laser radiation into heat, were intratumorally injected and PTT was applied. Upon the irradiation of a near-infrared laser, dual photothermal and radionuclide therapy was achieved. Additionally, the combination of 188Re-labeled Au NRs with paclitaxel (PTX) has significantly improved the treatment efficiency (188Re-labeled Au NRs, laser irradiation, and PTX) compared to therapy in monoregime. Thus, this local triple-combination therapy can be a step toward the clinical translation of Au NRs for use in cancer treatment.

Rapid Identification and Monitoring of Multiple Bacterial Infections Using Printed Nanoarrays.

Fast and accurate detection of microbial cells in clinical samples is highly valuable but remains a challenge. Here, a simple, culture-free diagnostic system is developed for direct detection of pathogenic bacteria in water, urine, and serum samples using an optical colorimetric biosensor. It consists of printed nanoarrays chemically conjugated with specific antibodies that exhibits distinct color changes after capturing target pathogens. By utilizing the internal capillarity inside an evaporating droplet, target preconcentration is achieved within a few minutes to enable rapid identification and more efficient detection of bacterial pathogens. More importantly, the scattering signals of bacteria are significantly amplified by the nanoarrays due to strong near-field localization, which supports a visualizable analysis of the growth, reproduction, and cell activity of bacteria at the single-cell level. Finally, in addition to high selectivity, this nanoarray-based biosensor is also capable of accurate quantification and continuous monitoring of bacterial load on food over a broad linear range, with a detection limit of 10 CFU mL-1 . This work provides an accessible and user-friendly tool for point-of-care testing of pathogens in many clinical and environmental applications, and possibly enables a breakthrough in early prevention and treatment.

Eco-friendly Approach for Creation of Resonant Silicon Nanoparticle Colloids.

The commercial application of Mie-resonant nanophotonic technologies currently used in various laboratory studies, from biosensing to quantum optics, appears to be challenging. Development of colloidal-based fabrication approaches is a solution to face the issue. In our research, we studied the fabrication of resonant Si nanoparticle (NP) arrays on a surface with controlled wettability. First, we use nanosecond (ns) laser ablation in water and subsequent density gradient separation to obtain colloids of resonant spherical crystalline silicon NPs with a low polydispersity index. Then, the same industrial ns laser is applied to create a wetting gradient on the steel substrate to initiate a self-assembly of the NPs deposited by drop casting. Thus, we use a single commercial ns laser for producing both the NPs and the hydrophilic wetting gradient. We apply an easily operating size separation technique and only non-toxic media. This research contributes to the large-scale fabrication of various optical devices based on resonant high-refractive index nanostructures by ecologically friendly self-assembly techniques.

Femtosecond Laser-Assisted Formation of Hybrid Nanoparticles from Bi-Layer Gold-Silicon Films for Microscale White-Light Source.

It is very natural to use silicon as a primary material for microelectronics. However, silicon application in nanophotonics is limited due to the indirect gap of its energy band structure. To improve the silicon emission properties, it can be combined with a plasmonic part. The resulting metal-dielectric (hybrid) nanostructures have shown their excellence compared to simple metallic dielectric nanostructures. Still, in many cases, the fabrication of such structures is time consuming and quite difficult. Here, for the first time, we demonstrate a single-step and lithography-free laser-induced dewetting of bi-layer nanoscale-thickness gold-silicon films supported by a glass substrate to produce hybrid nanoparticles. For obtaining hybrid nanoparticles, we study nonlinear photoluminescence by mapping their optical response and morphology by scanning electron microscopy. This method can be used for the fabrication of arrays of hybrid nanoparticles providing white-light photoluminescence with a good control of their microscopic sizes and position. The developed approach can be useful for a wide range of photonic applications including the all-optical data processing and storage where miniaturization down to micro- and nanoscale together with an efficiency increase is of high demand.

Printed Nanochain-Based Colorimetric Assay for Quantitative Virus Detection.

Fast and ultrasensitive detection of pathogens is very important for efficient monitoring and prevention of viral infections. Here, we demonstrate a label-free optical detection approach that uses a printed nanochain assay for colorimetric quantitative testing of viruses. The antibody-modified nanochains have high activity and specificity which can rapidly identify target viruses directly from biofluids in 15 min, as well as differentiate their subtypes. Arising from the resonance induced near-field enhancement, the color of nanochains changes with the binding of viruses that are easily observed by a smartphone. We achieve the detection limit of 1 PFU µL-1 through optimizing the optical response of nanochains in visible region. Besides, it allows for real-time response to virus concentrations ranging from 0 to 1.0×105  PFU mL-1 . This low-cost and portable platform is also applicable to rapid detection of other biomarkers, making it attractive for many clinical applications.

Spontaneous Light Emission Assisted by Mie Resonances in Diamond Nanoparticles.

Spontaneous light emission is known to be affected by the local density of states and enhanced when coupled to a resonant cavity. Here, we report on an experimental study of silicon-vacancy (SiV) color center fluorescence and spontaneous Raman scattering from subwavelength diamond particles supporting low-order Mie resonances in the visible range. For the first time to our knowledge, we have measured the size dependences of the SiV fluorescence emission rate and the Raman scattering intensity from individual diamond particles in the range from 200 to 450 nm. The obtained dependences reveal a sequence of peaks, which we explicitly associate with specific multipole resonances. The results are in agreement with our theoretical analysis and highlight the potential of intrinsic optical resonances for developing nanodiamond-based lasers and single-photon sources.

Femtomolar Biodetection by a Compact Core-Shell 3D Chiral Metamaterial.

Advanced sensing tools, detecting extremely low concentrations of circulating biomarkers, can open unexplored routes toward early diagnostics and diseases progression monitoring. Here, we demonstrate the sensing capabilities of a chip-based metamaterial, combining 3D chiral geometry with a functional core-shell nanoarchitecture. The chiral metamaterial provides a circular polarization-dependent optical response, allowing analysis in a complex environment without significant background interferences. The functional nanoarchitecture, based on the conformal coating with a polymer shell, modifies the chiral metamaterial near- and far-field optical response because of the energy transfer between dielectric shell polarization charges and plasmonic core free electrons, leading to efficient interaction with biomolecules. The system sensitivity slope is 27 nm/pM, in the detection of TAR DNA-binding protein 43, clinically relevant for neurodegenerative diseases. Measurements were performed in spiked solution and in human serum with concentrations from 1 pM down to 10 fM, which is a range not accessible with common immunological assays, opening new perspectives for next-generation biomedical systems.

Real-Time Temperature Monitoring of Photoinduced Cargo Release inside Living Cells Using Hybrid Capsules Decorated with Gold Nanoparticles and Fluorescent Nanodiamonds.

Real-time temperature monitoring within biological objects is a key fundamental issue for understanding the heating process and performing remote-controlled release of bioactive compounds upon laser irradiation. The lack of accurate thermal control significantly limits the translation of optical laser techniques into nanomedicine. Here, we design and develop hybrid (complex) carriers based on multilayered capsules combined with nanodiamonds (NV centers) as nanothermometers and gold nanoparticles (Au NPs) as nanoheaters to estimate an effective laser-induced temperature rise required for capsule rupture and further release of cargo molecules outside and inside cancerous (B16-F10) cells. We integrate both elements (NV centers and Au NPs) in the capsule structure using two strategies: (i) loading inside the capsule's cavity (CORE) and incorporating them inside the capsule's wall (WALL). Theoretically and experimentally, we show the highest and lowest heat release from capsule samples (CORE or WALL) under laser irradiation depending on the Au NP arrangement within the capsule. Applying NV centers, we measure the local temperature of capsule rupture inside and outside the cells, which is determined to be 128 ± 1.12 °C. Finally, the developed hybrid containers can be used to perform the photoinduced release of cargo molecules with simultaneous real-time temperature monitoring inside the cells.

Luminescent Erbium-Doped Silicon Thin Films for Advanced Anti-Counterfeit Labels.

The never-ending struggle against counterfeit demands the constant development of security labels and their fabrication methods. This study demonstrates a novel type of security label based on downconversion photoluminescence from erbium-doped silicon. For fabrication of these labels, a femtosecond laser is applied to selectively irradiate a double-layered Er/Si thin film, which is accomplished by Er incorporation into a silicon matrix and silicon-layer crystallization. The study of laser-induced heating demonstrates that it creates optically active erbium centers in silicon, providing stable and enhanced photoluminescence at 1530 nm. Such a technique is utilized to create two types of anti-counterfeiting labels. The first type is realized by the single-step direct laser writing of luminescent areas and detected by optical microscopy as holes in the film forming the desired image. The second type, with a higher degree of security, is realized by adding other fabrication steps, including the chemical etching of the Er layer and laser writing of additional non-luminescent holes over an initially recorded image. During laser excitation at 525 nm of luminescent holes of the labels, a photoluminescent picture repeating desired data can be seen. The proposed labels are easily scalable and perspective for labeling of goods, securities, and luxury items.

A fluid-guided printing strategy for patterning high refractive index photonic microarrays.

High refractive index (HRI, n > 1.8) photonic structures offer strong light confinement and refractive efficiencies, cover the entire visible spectrum and can be tuned by designing geometric arrayed features. However, its practical applications are still hindered by the applicability and material limitation of lithography-based micro/nano fabrication approaches. Herein, we demonstrate a fluid-guided printing process for preparing HRI selenium microarrays. The microstructured flexible template is replicated from the diced silicon wafer without any lithography-based methods. When heated above the glass transition temperature, the flow characteristics of selenium endows the structure downsizing and orientation patterning between the target substrate and the template. Near 10 times narrowing selenium microarrays (1.9 µm width) are patterned from the non-lithography template (18 µm width). HRI selenium microarrays offer high refractive efficiencies and strong optical confinement abilities, which achieve angle-dependent structurally coloration and polarization. Meanwhile, the color difference can be recognized under the one degree distinction of the angle between incident and refracted light. This printing platform will facilitate HRI optical metasurfaces in a variety of applications, ranging from photonic sensor, polarization modulation to light manipulation.

Light-Emitting Nanophotonic Designs Enabled by Ultrafast Laser Processing of Halide Perovskites.

Nanophotonics based on resonant nanostructures and metasurfaces made of halide perovskites have become a prospective direction for efficient light manipulation at the subwavelength scale in advanced photonic designs. One of the main challenges in this field is the lack of large-scale low-cost technique for subwavelength perovskite structures fabrication preserving highly efficient luminescence. Here, unique properties of halide perovskites addressed to their extremely low thermal conductivity (lower than that of silica glass) and high defect tolerance to apply projection femtosecond laser lithography for nanofabrication with precise spatial control in all three dimensions preserving the material luminescence efficiency are employed. Namely, with CH3 NH3 PbI3 perovskite highly ordered nanoholes and nanostripes of width as small as 250 nm, metasurfaces with periods less than 400 nm, and nanowire lasers as thin as 500 nm, corresponding to the state-of-the-art in multistage expensive lithographical methods are created. Remarkable performance of the developed approach allows to demonstrate a number of advanced optical applications, including morphology-controlled photoluminescence yield, structural coloring, optical- information encryption, and lasing.

Identification and Preclinical Evaluation of the Bicyclic Pyrimidine γ-Secretase Modulator BMS-932481.

A triazine hit identified from a screen of the BMS compound collection was optimized for potency, in vivo activity, and off-target profile to produce the bicyclic pyrimidine γ-secretase modulator BMS-932481. The compound showed robust reductions of Aß1-42 and Aß1-40 in the plasma, brain, and cerebrospinal fluid of mice and rats. Consistent with the γ-secretase modulator mechanism, increases in Aß1-37 and Aß1-38 were observed, with no change in the total amount of Aß1-x produced. No Notch-based toxicity was observed, and the overall preclinical profile of BMS-932481 supported its further evaluation in human clinical trials.

The conformation of bovine serum albumin adsorbed to the surface of single all-dielectric nanoparticles following light-induced heating.

Interaction between nanoparticles and biomolecules leads to the formation of biocompatible or bioadverse complexes. Despite the rapid development of nanotechnologies for biology and medicine, relatively little is known about the structure of such complexes. Here, we report on the changes in conformation of a blood protein (bovine serum albumin) adsorbed on the surface of single all-dielectric nanoparticles (silicon and germanium) following light-induced heating to 640 K. This protein is considerably more resistant to heat when adsorbed on the nanoparticle than when in solution or in the solid state. Intriguingly, with germanium nanoparticles this heat resistance is more pronounced than with silicon. These observations will facilitate biocompatible usage of all-dielectric nanoparticles.

Resonant Nonplasmonic Nanoparticles for Efficient Temperature-Feedback Optical Heating.

We propose a novel photothermal approach based on resonant dielectric nanoparticles, which possess imaginary part of permittivity significantly smaller as compared to metal ones. We show both experimentally and theoretically that a spherical silicon nanoparticle with a magnetic quadrupolar Mie resonance converts light to heat up to 4 times more effectively than similar spherical gold nanoparticle at the same heating conditions. We observe photoinduced temperature raise up to 900 K with the silicon nanoparticle on a glass substrate at moderate intensities (<2 mW/µm2) and typical laser wavelength (633 nm). The advantage of using crystalline silicon is the simplicity of local temperature control by means of Raman spectroscopy working in a broad range of temperatures, that is, up to the melting point of silicon (1690 K) with submicrometer spatial resolution. Our CMOS-compatible heater-thermometer nanoplatform paves the way to novel nonplasmonic photothermal applications, extending the temperature range and simplifying the thermoimaging procedure.

Efficient Second-Harmonic Generation in Nanocrystalline Silicon Nanoparticles.

Recent trends to employ high-index dielectric particles in nanophotonics are motivated by their reduced dissipative losses and large resonant enhancement of nonlinear effects at the nanoscale. Because silicon is a centrosymmetric material, the studies of nonlinear optical properties of silicon nanoparticles have been targeting primarily the third-harmonic generation effects. Here we demonstrate, both experimentally and theoretically, that resonantly excited nanocrystalline silicon nanoparticles fabricated by an optimized laser printing technique can exhibit strong second-harmonic generation (SHG) effects. We attribute an unexpectedly high yield of the nonlinear conversion to a nanocrystalline structure of nanoparticles supporting the Mie resonances. The demonstrated efficient SHG at green light from a single silicon nanoparticle is 2 orders of magnitude higher than that from unstructured silicon films. This efficiency is significantly higher than that of many plasmonic nanostructures and small silicon nanoparticles in the visible range, and it can be useful for a design of nonlinear nanoantennas and silicon-based integrated light sources.

Robust Translation of γ-Secretase Modulator Pharmacology across Preclinical Species and Human Subjects.

The amyloid-ß peptide (Aß)-in particular, the 42-amino acid form, Aß1-42-is thought to play a key role in the pathogenesis of Alzheimer's disease (AD). Thus, several therapeutic modalities aiming to inhibit Aß synthesis or increase the clearance of Aß have entered clinical trials, including γ-secretase inhibitors, anti-Aß antibodies, and amyloid-ß precursor protein cleaving enzyme inhibitors. A unique class of small molecules, γ-secretase modulators (GSMs), selectively reduce Aß1-42 production, and may also decrease Aß1-40 while simultaneously increasing one or more shorter Aß peptides, such as Aß1-38 and Aß1-37. GSMs are particularly attractive because they do not alter the total amount of Aß peptides produced by γ-secretase activity; they spare the processing of other γ-secretase substrates, such as Notch; and they do not cause accumulation of the potentially toxic processing intermediate, ß-C-terminal fragment. This report describes the translation of pharmacological activity across species for two novel GSMs, (S)-7-(4-fluorophenyl)-N2-(3-methoxy-4-(3-methyl-1H-1,2,4-triazol-1-yl)phenyl)-N4-methyl-6,7-dihydro-5H-cyclopenta[d]pyrimidine-2,4-diamine (BMS-932481) and (S,Z)-17-(4-chloro-2-fluorophenyl)-34-(3-methyl-1H-1,2,4-triazol-1-yl)-16,17-dihydro-15H-4-oxa-2,9-diaza-1(2,4)-cyclopenta[d]pyrimidina-3(1,3)-benzenacyclononaphan-6-ene (BMS-986133). These GSMs are highly potent in vitro, exhibit dose- and time-dependent activity in vivo, and have consistent levels of pharmacological effect across rats, dogs, monkeys, and human subjects. In rats, the two GSMs exhibit similar pharmacokinetics/pharmacodynamics between the brain and cerebrospinal fluid. In all species, GSM treatment decreased Aß1-42 and Aß1-40 levels while increasing Aß1-38 and Aß1-37 by a corresponding amount. Thus, the GSM mechanism and central activity translate across preclinical species and humans, thereby validating this therapeutic modality for potential utility in AD.