Safety evaluation of INFAT® PLUS: Acute, genetic, teratogenic, and subchronic (90-day) toxicity studies.

INFAT®PLUS, is a sn-2 palmitate enriched fat ingredient intended for infant formula. A battery of toxicological studies was conducted in accordance with the Food Safety Toxicological Assessment GB-15193 (China), to confirm the safety of INFAT®PLUS. In the acute oral toxicity test, the LD50 of INFAT® PLUS was higher than 53.4 g /kg BW and 26.7 g/kg BW for ICR mice and SD rats, respectively. In a subchronic study, INFAT® PLUS was administered by oral gavage to SD rats with maximal daily dose of 8.90 g/kg BW for 90 days. No treatment-related clinical signs or mortalities were observed. The no-observed-adverse-effect level (NOAEL) was set at 8.90 g/kg BW. Similarly, no evidence of genotoxicity effect was noted in several in vitro and in vivo tests, including bacterial reverse mutation (Ames) test, mouse erythrocyte micronucleus test, and chromosome aberration test of mouse spermatogonia/spermatocyte. For the teratogenic evaluations, no toxicological signs were observed in both pregnant SD rat and fetuses, and the NOAEL of INFAT® PLUS was determined to be 8.90 g/kg BW. Based on the obtained results we concluded that INFAT® PLUS was found non-toxic under the experimental conditions, and the totality of the safety data supports its use for infant nutrition.

Engineering chirality at wafer scale with ordered carbon nanotube architectures.

Creating artificial matter with controllable chirality in a simple and scalable manner brings new opportunities to diverse areas. Here we show two such methods based on controlled vacuum filtration - twist stacking and mechanical rotation - for fabricating wafer-scale chiral architectures of ordered carbon nanotubes (CNTs) with tunable and large circular dichroism (CD). By controlling the stacking angle and handedness in the twist-stacking approach, we maximize the CD response and achieve a high deep-ultraviolet ellipticity of 40 ± 1 mdeg nm-1. Our theoretical simulations using the transfer matrix method reproduce the experimentally observed CD spectra and further predict that an optimized film of twist-stacked CNTs can exhibit an ellipticity as high as 150 mdeg nm-1, corresponding to a g factor of 0.22. Furthermore, the mechanical rotation method not only accelerates the fabrication of twisted structures but also produces both chiralities simultaneously in a single sample, in a single run, and in a controllable manner. The created wafer-scale objects represent an alternative type of synthetic chiral matter consisting of ordered quantum wires whose macroscopic properties are governed by nanoscopic electronic signatures and can be used to explore chiral phenomena and develop chiral photonic and optoelectronic devices.

Effects of interlayer reflection and interpixel interaction in diffractive optical neural networks.

Multilayer diffractive optical neural networks (DONNs) can perform machine learning (ML) tasks at the speed of light with low energy consumption. Decreasing the number of diffractive layers can reduce inevitable material and diffraction losses to improve system performance, and incorporating compact devices can reduce the system footprint. However, current analytical DONN models cannot accurately describe such physical systems. Here we show the ever-ignored effects of interlayer reflection and interpixel interaction on the deployment performance of DONNs through full-wave electromagnetic simulations and terahertz (THz) experiments. We demonstrate that the drop of handwritten digit classification accuracy due to reflection is negligible with conventional low-index THz polymer materials, while it can be substantial with high-index materials. We further show that one- and few-layer DONN systems can achieve high classification accuracy, but there is a trade-off between accuracy and model-system matching rate because of the fast-varying spatial distribution of optical responses in diffractive masks. Deep DONNs can break down such a trade-off because of reduced mask spatial complexity. Our results suggest that new accurate and trainable DONN models are needed to advance the development and deployment of compact DONN systems for sophisticated ML tasks.

Earth-abundant photocatalyst for H2 generation from NH3 with light-emitting diode illumination.

Catalysts based on platinum group metals have been a major focus of the chemical industry for decades. We show that plasmonic photocatalysis can transform a thermally unreactive, earth-abundant transition metal into a catalytically active site under illumination. Fe active sites in a Cu-Fe antenna-reactor complex achieve efficiencies very similar to Ru for the photocatalytic decomposition of ammonia under ultrafast pulsed illumination. When illuminated with light-emitting diodes rather than lasers, the photocatalytic efficiencies remain comparable, even when the scale of reaction increases by nearly three orders of magnitude. This result demonstrates the potential for highly efficient, electrically driven production of hydrogen from an ammonia carrier with earth-abundant transition metals.

A Dual Catalyst Strategy for Controlling Aluminum Nanocrystal Growth.

The synthesis of Al nanocrystals (Al NCs) is a rapidly expanding field, but there are few strategies for size and morphology control. Here we introduce a dual catalyst approach for the synthesis of Al NCs to control both NC size and shape. By using one catalyst that nucleates growth more rapidly than a second catalyst whose ligands affect NC morphology during growth, one can obtain both size and shape control of the resulting Al NCs. The combination of the two catalysts (1) titanium isopropoxide (TIP), for rapid nucleation, and (2) Tebbe's reagent, for specific facet-promoting growth, yields {100}-faceted Al NCs with tunable diameters between 35 and 65 nm. This dual-catalyst strategy could dramatically expand the possible outcomes for Al NC growth, opening the door to new controlled morphologies and a deeper understanding of earth-abundant plasmonic nanocrystal synthesis.

Pyrroloquinoline quinone ameliorates diabetic cardiomyopathy by inhibiting the pyroptosis signaling pathway in C57BL/6 mice and AC16 cells.

PURPOSE: Diabetic cardiomyopathy (DCM), a common complication of diabetes mellitus and is characterized by myocardial hypertrophy and myocardial fibrosis. Pyrroloquinoline quinone (PQQ), a natural nutrient, exerts strong protection against various myocardial diseases. Pyroptosis, a type of inflammation-related programmed cell death, is vital to the development of DCM. However, the protective effects of PQQ against DCM and the associated mechanisms are not clear. This study aimed to investigate whether PQQ protected against DCM and to determine the underlying molecular mechanism. METHODS: Diabetes was induced in mice by intraperitoneal injection of streptozotocin, after which the mice were administered PQQ orally (10, 20, or 40 mg/kg body weight/day) for 12 weeks. AC16 human myocardial cells were divided into the following groups and treated accordingly: control (5.5 mmol/L glucose), high glucose (35 mmol/L glucose), and HG + PQQ groups (1 and 10 nmol/L PQQ). Cells were treated for 24 h. RESULTS: PQQ reduced myocardial hypertrophy and the area of myocardial fibrosis, which was accompanied by an increase in antioxidant function and a decrease in inflammatory cytokine levels. Moreover, myocardial hypertrophy-(ANP and BNP), myocardial fibrosis-(collagen I and TGF-ß1), and pyroptosis-related protein levels decreased in the PQQ treatment groups. Furthermore, PQQ abolished mitochondrial dysfunction and the activation of NF-κB/IκB, and decreased NLRP3 inflammation-mediated pyroptosis in AC16 cells under high-glucose conditions. CONCLUSION: PQQ improved DCM in diabetic mice by inhibiting NF-κB/NLRP3 inflammasome-mediated cell pyroptosis. Long-term dietary supplementation with PQQ may be greatly beneficial for the treatment of DCM. Diagram of the underlying mechanism of the effects of PQQ on DCM. PQQ inhibits ROS generation and NF-κB activation, which stimulates activation of the NLRP3 inflammasome and regulates the expression of caspase-1, IL-1ß, and IL-18. The up-regulated inflammatory cytokines trigger myocardial hypertrophy and cardiac fibrosis and promote the pathological process of DCM.

Hot carrier multiplication in plasmonic photocatalysis.

Light-induced hot carriers derived from the surface plasmons of metal nanostructures have been shown to be highly promising agents for photocatalysis. While both nonthermal and thermalized hot carriers can potentially contribute to this process, their specific role in any given chemical reaction has generally not been identified. Here, we report the observation that the H2-D2 exchange reaction photocatalyzed by Cu nanoparticles is driven primarily by thermalized hot carriers. The external quantum yield shows an intriguing S-shaped intensity dependence and exceeds 100% for high light intensities, suggesting that hot carrier multiplication plays a role. A simplified model for the quantum yield of thermalized hot carriers reproduces the observed kinetic features of the reaction, validating our hypothesis of a thermalized hot carrier mechanism. A quantum mechanical study reveals that vibrational excitations of the surface Cu-H bond is the likely activation mechanism, further supporting the effectiveness of low-energy thermalized hot carriers in photocatalyzing this reaction.

UV-Resonant Al Nanocrystals: Synthesis, Silica Coating, and Broadband Photothermal Response.

The field of plasmonics has largely been inspired by the properties of Au and Ag nanoparticles, leading to applications in sensing, photocatalysis, nanomedicine, and solar water treatment. Recently the quest for new plasmonic materials has focused on earth-abundant elements, where aluminum is a sustainable, low-cost potential alternative. Here we report the chemical synthesis of sub-50 nm diameter Al nanocrystals with a plasmon-resonant absorption in the UV region of the spectrum. We observe a transition from a UV-resonant response, that is, a colorless solution, to a broadband absorptive response, that is, a completely black solution, as the nanocrystal concentration is increased. The strong absorptive interband transition in Al provides the dominant mechanism responsible for this effect. We developed a robust method to functionalize Al nanocrystals with silica to increase their stability in H2O from hours to weeks enabling us to observe efficient broadband photothermal heating with these nanoparticles.

Plasmon Energy Transfer in Hybrid Nanoantennas.

Plasmonic metal nanoparticles exhibit large dipole moments upon photoexcitation and have the potential to induce electronic transitions in nearby materials, but fast internal relaxation has to date limited the spatial range and efficiency of plasmonic mediated processes. In this work, we use photo-electrochemistry to synthesize hybrid nanoantennas comprised of plasmonic nanoparticles with photoconductive polymer coatings. We demonstrate that the formation of the conductive polymer is selective to the nanoparticles and that polymerization is enhanced by photoexcitation. In situ spectroscopy and simulations support a mechanism in which up to 50% efficiency of nonradiative energy transfer is achieved. These hybrid nanoantennas combine the unmatched light-harvesting properties of a plasmonic antenna with the similarly unmatched device processability of a polymer shell.

Attenuation of the Na/K­ATPase/Src/ROS amplification signaling pathway by astaxanthin ameliorates myocardial cell oxidative stress injury.

The 3S, 3'S­ASTaxanthin (3S, 3'S­AST) isomer has strong antioxidant activity; however, its protective roles and potential mechanisms against oxidative stress damage in cardiomyocytes have not been investigated. Na+/K+­ATPase (NKA)/Src signal activation has an important role in increasing reactive oxygen species (ROS) production. The aim of the present study was to investigate the protective effects and mechanism of 3S, 3'S­AST on hydrogen peroxide (H2O2)­induced oxidative stress injury in H9c2 myocardial cells. The protective effects of 3S, 3'S­AST on H2O2­induced H9c2 cell injury was observed by measuring lactate dehydrogenase and creatine kinase myocardial band content, cell viability and nuclear morphology. The antioxidant effect was investigated by analyzing ROS accumulation and malondialdehyde, glutathione (GSH) peroxidase, GSH and glutathione reductase activity levels. The protein expression levels of Bax, Bcl­2, caspase­3 and cleaved caspase­3 were analyzed using western blotting to determine cardiomyocyte apoptosis. Western blot analysis of the phosphorylation levels of Src and Erk1/2 were also performed to elucidate the molecular mechanism involved. The results showed that 3S, 3'S­AST reduced the release of LDH and promoted cell viability, and attenuated ROS accumulation and cell apoptosis induced by H2O2. Furthermore, 3S, 3'S­AST also restored apoptosis­related Bax and Bcl­2 protein expression levels in H2O2­treated H9c2 cells. The phosphorylation levels of Src and Erk1/2 were significantly higher in the H2O2 treatment group, whereas 3S, 3'S­AST pretreatment significantly decreased the levels of phosphorylated (p)­Src and p­ERK1/2. The results provided evidence that 3S, 3'S­AST exhibited a cardioprotective effect against oxidative stress injury by attenuating NKA/Src/Erk1/2­modulated ROS amplification.

Aluminum Nanocrystals Grow into Distinct Branched Aluminum Nanowire Morphologies.

Plasmonic nanowires (NWs) have generated great interest in their applications in nanophotonics and nanotechnology. Here we report the synthesis of Al nanocrystals (NCs) with controlled morphologies that range from nanospheres to branched NW and NW bundles. This is accomplished by catalyzing the pyrolysis of triisobutyl aluminum (TIBA) with Tebbe's reagent, a titanium(III) catalyst with two cyclopentadienyl ligands. The ratio of TIBA to Tebbe's reagent is critical in determining the morphology of the resulting Al NC. The branched Al NWs grow in their ⟨100⟩ directions and are formed by oriented attachment of isotropic Al NCs on their {100} facets. Branched NWs are strongly absorptive from the UV to the mid-IR, with longitudinal dipolar, higher-order, and transverse plasmons, all contributing to their broadband response. This rapid Al NW synthesis enables the expanded use of Al for plasmonic and nanophotonic applications in the ultraviolet, visible, and infrared regions of the spectrum.

Morphology-Dependent Reactivity of a Plasmonic Photocatalyst.

The shape of a plasmonic nanoparticle strongly controls its light-matter interaction, which in turn affects how specific morphologies may be used in applications such as sensing, photodetection, and active pixel displays. Here, we show that particle shape also controls plasmonic photocatalytic activity. Three different Al nanocrystal morphologies, octopods, nanocubes, and nanocrystals, all with very similar plasmon resonance frequencies, were used as photocatalysts for the H2 dissociation reaction. We observe widely varying reaction rates for the three different morphologies. Octopods show a 10 times higher reaction rate than nanocrystals and a 5 times higher rate than nanocubes, with lower apparent activation energies than either nanocubes or nanocrystals by 45% and 49%, respectively. A theoretical model of hot electron direct transfer from photoexcited Al nanoparticles to H2 molecules is consistent with this observed morphological dependence. This research strongly suggests that nanoparticle geometry, in addition to plasmon resonance energy, is a critical factor in plasmonic photocatalyst design.

Site-Selective Nanoreactor Deposition on Photocatalytic Al Nanocubes.

Photoactivation of catalytic materials through plasmon-coupled energy transfer has created new possibilities for expanding the scope of light-driven heterogeneous catalysis. Here we present a nanoengineered plasmonic photocatalyst consisting of catalytic Pd islands preferentially grown on vertices of Al nanocubes. The regioselective Pd deposition on Al nanocubes does not rely on complex surface ligands, in contrast to site-specific transition-metal deposition on gold nanoparticles. We show that the strong local field enhancement on the sharp nanocube vertices provides a mechanism for efficient coupling of the plasmonic Al antenna to adjacent Pd nanoparticles. A substantial increase in photocatalytic H2 dissociation on Pd-bound Al nanocubes relative to pristine Al nanocubes can be observed, incentivizing further engineering of heterometallic antenna-reactor photocatalysts. Controlled growth of catalytic materials on plasmonic hot spots can result in more efficient use of the localized surface plasmon energy for photocatalysis, while minimizing the amount and cost of precious transition-metal catalysts.

Aluminum Nanocubes Have Sharp Corners.

Of the many plasmonic nanoparticle geometries that have been synthesized, nanocubes have been of particular interest for creating nanocavities, facilitating plasmon coupling, and enhancing phenomena dependent upon local electromagnetic fields. Here we report the straightforward colloidal synthesis of single-crystalline {100} terminated Al nanocubes by decomposing AlH3 with Tebbe's reagent in tetrahydrofuran. The size and shape of the Al nanocubes is controlled by the reaction time and the ratio of AlH3 to Tebbe's reagent, which, together with reaction temperature, establish kinetic control over Al nanocube growth. Al nanocubes possess strong localized field enhancements at their sharp corners and resonances highly amenable to coupling with metallic substrates. Their native oxide surface renders them extremely air stable. Chemically synthesized Al nanocubes provide an earth-abundant alternative to noble metal nanocubes for plasmonics and nanophotonics applications.

Photocatalytic Hydrogenation of Graphene Using Pd Nanocones.

Plasmonic photocatalytic processes typically use the interaction of light with metallic nanoparticles to drive chemical reactions on their surfaces. Here we show that a plasmonic photocatalyst can also induce a reaction on an adjacent material. A combination of spontaneous H2 dissociation and plasmon-induced H desorption from tilted palladium (Pd) nanocones yields reactive H atoms which, in the direct vicinity of a graphene monolayer, results in its local hydrogenation. The conversion of pristine to hydrogenated graphene, a semiconductor, is detectable by visible local fluorescence of the hydrogenated regions of the graphene sheet, as well as by Raman spectroscopic analysis. These results may lead to new approaches for local, light-driven functionalization of graphene and other 2D materials and for precision patterning of functional devices.

Optical-Force-Dominated Directional Reshaping of Au Nanodisks in Al-Au Heterodimers.

The optical reshaping of metallic nanostructures typically requires intense laser pulses to first approach or achieve melting, followed by surface-tension-dominated reshaping, transforming the original nanostructures into more spherical morphologies. Here, we report the directional optical reshaping of the Au nanodisk of an Al-Au heterodimer in the illuminated junction of an atomic force microscope (AFM). Both the heightening and the repositioning of the Au nanodisk component are induced, reducing the gap between the two nanodisks. There are three contributors to this process: the photothermal softening of the Au lattice, the optical force applied to the Au nanodisk by the Al nanodisk, and the optical force from the nearby AFM tip. The asymmetric reshaping of the heterodimer is observable structurally, through electron microscopic imaging, and through changes in the heterodimer optical response. This optical-force-directed shape manipulation may have potential applications in nanofabrication, optically induced nanomanufacturing, sensing, and quality control.

Dual-feedback mid-infrared cavity-enhanced absorption spectroscopy for H2CO detection using a radio-frequency electrically-modulated interband cascade laser.

A mid-infrared cavity-enhanced sensor system was demonstrated for the detection of formaldehyde (H2CO) using a continuous-wave (cw) interband cascade laser (ICL) centered at 3599 nm. A compact Fabry-Perot (F-P) cavity with a physical size of 38 × 52 × 76 mm3 was developed consisting of two concave mirrors with a radius of curvature of 80 mm and a reflectivity of 99.8% at 3.6 µm. Different from the widely reported electro-optical (EO) external modulation based Pound-Drever-Hall (PDH) locking technique, a radio-frequency electrical internal modulation based PDH technique was used for locking the laser mode to the cavity mode. A dual-feedback control on the laser current and on the piezo transducer (PZT) displacement was utilized for further stabilizing mode locking. A 20 m effective optical path length was achieved with a cavity length of 2 cm and a finesse of 1572. The effectiveness and sensitivity of the sensor system were demonstrated by targeting an absorption line at 2778.5 cm-1 for H2CO measurements. A linear relation between the cavity transmitted signal amplitude and the H2CO concentration was obtained within the range of 0-5 ppm. A 1σ detection limit of 25 parts-per-billion (ppb) was achieved with an averaging time of 1 s based on Allan-Werle variance analysis. The reported dual-feedback RF modulation based PDH technique led to a method for gas detection using a similar experimental setup and measurement scheme.

Aluminum Nanorods.

Al nanocrystals can be synthesized by high-temperature decomposition of triisobutyl aluminum, creating a mixture of nanoparticle geometries with a significant fraction (∼15%) being single-crystalline Al nanorods. The Al nanorods are elongated along their ⟨110⟩ direction, and generally exhibit hexagonal cross sections consisting of two adjacent {111} facets separated by {100} facets on opposite sides. Dark-field scattering spectroscopy of individual Al nanorods reveals that rods of varying aspect ratios all possess transverse quadrupolar and octupolar modes in the visible (2-3 eV) and ultraviolet (3-5 eV) regimes. Theoretical modeling indicates that the longitudinal resonances of these nanorods span the near- and mid-infrared regions of the spectrum. This work introduces a new class of anisotropic metal nanocrystals composed of single-crystalline Al, opening the door to highly modifiable plasmonic nanorods from Earth-abundant metals.

Repetitively Mode-Locked Cavity-Enhanced Absorption Spectroscopy (RML-CEAS) for Near-Infrared Gas Sensing.

A Pound-Drever-Hall (PDH)-based mode-locked cavity-enhanced sensor system was developed using a distributed feedback diode laser centered at 1.53 µm as the laser source. Laser temperature scanning, bias control of the piezoelectric ceramic transducer (PZT) and proportional-integral-derivative (PID) feedback control of diode laser current were used to repetitively lock the laser modes to the cavity modes. A gas absorption spectrum was obtained by using a series of absorption data from the discrete mode-locked points. The 15 cm-long Fabry-Perot cavity was sealed using an enclosure with an inlet and outlet for gas pumping and a PZT for cavity length tuning. The performance of the sensor system was evaluated by conducting water vapor measurements. A linear relationship was observed between the measured absorption signal amplitude and the H2O concentration. A minimum detectable absorption coefficient of 1.5 × 10-8 cm-1 was achieved with an averaging time of 700 s. This technique can also be used for the detection of other trace gas species by targeting the corresponding gas absorption line.

Compact photoacoustic module for methane detection incorporating interband cascade light emitting device.

A photoacoustic module (PAM) for methane detection was developed by combining a novel 3.2 µm interband cascade light emitting device (ICLED) with a compact differential photoacoustic cell. The ICLED with a 22-stage interband cascade active core emitted a collimated power of ~700 µW. A concave Al-coat reflector was positioned adjacent to the photoacoustic cell to enhance the gas absorption length. Assembly of the ICLED and reflector with the photoacoustic cell resulted in a robust and portable PAM without any moving parts. The PAM performance was evaluated in terms of operating pressure, sensitivity and linearity. A 1σ detection limit of 3.6 ppmv was achieved with a 1-s integration time.