The Effect of Femtosecond Laser Irradiation and Plasmon Field on the Degree of Conversion of a UDMA-TEGDMA Copolymer Nanocomposite Doped with Gold Nanorods.

In this work, the effects of femtosecond laser irradiation and doping with plasmonic gold nanorods on the degree of conversion (DC) of a urethane dimethacrylate (UDMA)-triethylene glycol dimethacrylate (TEGDMA) nanocomposite were investigated. The UDMA-TEGDMA photopolymer was prepared in a 3:1 weight ratio and doped with dodecanethiol- (DDT) capped gold nanorods of 25 × 75 or 25 × 85 nm nominal diameter and length. It was found that the presence of the gold nanorods alone (without direct plasmonic excitation) can increase the DC of the photopolymer by 6-15%. This increase was found to be similar to what could be achieved with a control heat treatment of 30 min at 180 °C. It was also shown that femtosecond laser impulses (795 nm, 5 mJ pulse energy, 50 fs pulse length, 2.83 Jcm-2 fluence), applied after the photopolymerization under a standard dental curing lamp, can cause a 2-7% increase in the DC of undoped samples, even after thermal pre-treatment. The best DC values (12-15% increase) were obtained with combined nanorod doping and subsequent laser irradiation close to the plasmon resonance peak of the nanorods (760-800 nm), which proves that the excited plasmon field can directly facilitate double bond breakage (without thermoplasmonic effects due to the short pulse length) and increase the crosslink density independently from the initial photopolymerization process.

Corporate social responsibility in agribusiness: climate-related empirical findings from Hungary.

The corporate sector is one of the most important contributors to the global emissions of carbon dioxide and other greenhouse gases. According to a representative public opinion survey 34% of Hungarian citizens believe that corporations are responsible for climate change. The business sector is motivated to take an active role in the mitigation and adaptation of climate change. As a result, the last few decades saw a marked increase in corporate measures aiming at the reduction in greenhouse gas emissions, as well as other initiatives to tackle climate-related problems which result in numerous social issues. The aim of this paper is to assess whether Corporate Social Responsibility (CSR) can be applied as a tool in agribusiness fostering steps towards the implementation of the climate-oriented and sustainable agriculture in Hungary. The research makes an effort to explore the role and opportunities of the Hungarian agricultural sector in adapting to climate change, it also examines the extent of the mitigation and adaptation activities appearing in the CSR portfolio of the companies and what specific measures are taken to realize them. The results of the evaluation show that climate-oriented CSR activities of the companies are relatively undeveloped, but businesses are working to reduce the impact of climate change on the usage of exercising adaptation strategies. There are several actions that can help to reduce vulnerability to the consequences of climate change in the agriculture sector. The results can support not only companies but other decision-makers decisions in climate-oriented CSR activities in agribusiness.

Superradiant diamond color center arrays coupled to concave plasmonic nanoresonators.

Superradiantly enhanced emission of SiV diamond color centers was achieved via numerically optimized concave plasmonic nanoresonators. Advantages of different numbers of SiV color centers, diamond-silver (bare) and diamond-silver-diamond (coated) core-shell nanoresonator types, spherical and ellipsoidal geometries were compared. Indistinguishable superradiance is reached via four color centers, which is accompanied by line-width narrowing except in a coated ellipsoidal nanoresonator that outperforms its bare counterpart in superradiance. Seeding of both spherical and bare ellipsoidal nano-resonators with six color centers results in larger fluorescence enhancement and better overridden superradiance thresholds simultaneously. Both phenomena are the best optimized in a six color centers seeded ellipsoidal bare nanoresonator according to the pronounced bad-cavity characteristics.

Plasmonic structure integrated single-photon detector configurations to improve absorptance and polarization contrast.

Configurations capable of maximizing both the absorption component of system detection efficiency and the achievable polarization contrast were determined for 1550 nm polarized light illumination of different plasmonic structure integrated superconducting nanowire single-photon detectors (SNSPDs) consisting of p = 264 nm and P = 792 nm periodic niobium nitride (NbN) patterns on silica substrate. Global effective NbN absorptance maxima appear in case of p/s-polarized light illumination in S/P-orientation (γ = 90°/0° azimuthal angle) and the highest polarization contrast is attained in S-orientation of all devices. Common nanophotonical origin of absorptance enhancement is collective resonance on nanocavity gratings with different profiles, which is promoted by coupling between localized modes in quarter-wavelength metal-insulator-metal nanocavities and laterally synchronized Brewster-Zenneck-type surface waves in integrated SNSPDs possessing a three-quarter-wavelength-scaled periodicity. The spectral sensitivity and dispersion characteristics reveal that device design specific optimal configurations exist.

Detection and isolation of cell-derived microparticles are compromised by protein complexes resulting from shared biophysical parameters.

Numerous diseases, recently reported to associate with elevated microvesicle/microparticle (MP) counts, have also long been known to be characterized by accelerated immune complex (IC) formation. The goal of this study was to investigate the potential overlap between parameters of protein complexes (eg, ICs or avidin-biotin complexes) and MPs, which might perturb detection and/or isolation of MPs. In this work, after comprehensive characterization of MPs by electron microscopy, atomic force microscopy, dynamic light-scattering analysis, and flow cytometry, for the first time, we drive attention to the fact that protein complexes, especially insoluble ICs, overlap in biophysical properties (size, light scattering, and sedimentation) with MPs. This, in turn, affects MP quantification by flow cytometry and purification by differential centrifugation, especially in diseases in which IC formation is common, including not only autoimmune diseases, but also hematologic disorders, infections, and cancer. These data may necessitate reevaluation of certain published data on patient-derived MPs and contribute to correct the clinical laboratory assessment of the presence and biologic functions of MPs in health and disease.

Metamaterial properties of Babinet complementary complex structures.

Single and multiple layers of sub-wavelength periodic Babinet complementary patterns composed of rounded nano-object miniarrays were investigated. In case of illumination with linearly and circularly polarized light the azimuthal orientation and handedness (in)dependence of (cross-polarized) copolarized transmitted signal components was proven for all types of patterns. Considerable (weak) asymmetric transmission was demonstrated in extended bands exclusively for both types of copolarized (cross-polarized) signals transmitted through single layer of convex miniarrays. Three-dimensional structures constructed with convex-concave-convex complex pattern-layers resulted in a negative index at the visible region boundary both for linearly and circularly polarized light illuminations. This is because dipolar modes on the convex nano-objects are synchronized with co-existent reversal dipoles on the concave nano-objects via interlayer coupling. Although during linearly polarized light illumination, the interlayer interaction decouples the localized and propagating modes excitable on the concave pattern in the 90° azimuthal orientation, the synchronization via tilted-rotating nanoring dipoles is almost perfect in the 0° azimuthal orientation. For circularly polarized light illumination, both the dispersion maps and the negative index phenomena synthesize the characteristics of the two orthogonal linearly polarized light illuminations. Important aspect is the appearance of a small/intermediate (large) time-averaged amplitude magnetic dipole due to the tilted (twisted) electric dipole on the concave nanoring, which less/more quickly turns (continuously rotates) with large/intermediate (small) out-of-plane tilting, when illumination is realized with linearly polarized light in the 90°/0° azimuthal orientation (with circularly polarized light). The location of the negative index can be predicted based on the copolarized transmittance signals computed for circularly polarized light illumination by using the linear base representation of Jones transmission matrix elements.

Enhancing Diamond Color Center Fluorescence via Optimized Configurations of Plasmonic Core-Shell Nanoresonator Dimers.

Numerical optimization of silica-metal core-shell nanoresonator dimer geometries was realized to maximize the fluorescence of the NV and SiV diamond color centers. The configurations combine the advantages stemming from the elongation and reduced metal volume of hollow spheroids and the wide tunability and good antenna efficiency due to hybridization of composite modes on the core-shell dimers. The optimized coupled dimers sustain plasmonic modes that maximize the fluorescence by ensuring the simultaneous enhancement of excitation and emission. Asymmetry is advantageous in terms of good enhancement with a compromised corrected quantum efficiency. The directional fluorescence can be significantly increased in the optimized asymmetrically coupled dimer configurations.

Crater formation and deuterium production in laser irradiation of polymers with implanted nano-antennas.

Recent validation experiments on laser irradiation of polymer foils with and without implanted golden nanoparticles are discussed. First we analyze characteristics of craters, formed in the target after its interaction with the laser beam. Preliminary experimental results show significant production of deuterons when both the energy of laser pulse and concentration of nanoparticles are high enough. We consider the deuteron production via the nuclear transmutation reactions p+C→d+X where protons are accelerated by the Coulomb field generated in the target plasma. We argue that maximal proton energy can be above threshold values for these reactions and the deuteron yield may noticeably increase due to presence of nanoparticles.

Single-photon detectors based on ultranarrow superconducting nanowires.

We report efficient single-photon detection (η = 20% at 1550 nm wavelength) with ultranarrow (20 and 30 nm wide) superconducting nanowires, which were shown to be more robust to constrictions and more responsive to 1550 nm wavelength photons than standard superconducting nanowire single-photon detectors, based on 90 nm wide nanowires. We also improved our understanding of the physics of superconducting nanowire avalanche photodetectors, which we used to increase the signal-to-noise ratio of ultranarrow-nanowire detectors by a factor of 4, thus relaxing the requirements on the read-out circuitry and making the devices suitable for a broader range of applications.

Plasmonically Enhanced Superradiance of Broken-Symmetry Diamond Color Center Arrays Inside Core-Shell Nanoresonators.

Superradiance was demonstrated in broken-symmetry arrays of SiV diamond color centers embedded into concave plasmonic nanoresonators. The coupled configurations, including the diamond-silver (bare) and diamond-silver-diamond (coated) nanoresonators' geometry parameters as well as the emitters' azimuthal orientation and distance from the metal, were numerically optimized. An objective function consisting of the total fluorescence enhancement multiplied by the corrected emission quantum efficiency was used to design nanoresonators that promote superradiance. A larger total fluorescence enhancement was achieved via a larger number of emitters in both geometries, in coated spherical and in bare ellipsoidal nanoresonators. The superradiance performance was better in the case of a smaller number of emitters in bare spherical and coated ellipsoidal nanoresonators and in the case of a larger number of emitters in coated spherical and bare ellipsoidal nanoresonators. Ellipsoidal geometry is advantageous independent of composition and seeding. The configurations optimal for non-cooperative fluorescence enhancement and superradiance are coincidental. A radiative rate enhancement proportional to the number of emitters was found in wide spectral regions; therefore, superradiance implies N-fold enhancements coexist at excitation and emission. In ellipsoidal nanoresonators, the better superradiance achieved via a smaller quality-factor is accompanied by larger frequency pulling.

Numerical method to optimize the polar-azimuthal orientation of infrared superconducting-nanowire single-photon detectors.

A finite-element method for calculating the illumination-dependence of absorption in three-dimensional nanostructures is presented based on the radio frequency module of the Comsol Multiphysics software package (Comsol AB). This method is capable of numerically determining the optical response and near-field distribution of subwavelength periodic structures as a function of illumination orientations specified by polar angle, φ, and azimuthal angle, γ. The method was applied to determine the illumination-angle-dependent absorptance in cavity-based superconducting-nanowire single-photon detector (SNSPD) designs. Niobium-nitride stripes based on dimensions of conventional SNSPDs and integrated with ~ quarter-wavelength hydrogen-silsesquioxane-filled nano-optical cavity and covered by a thin gold film acting as a reflector were illuminated from below by p-polarized light in this study. The numerical results were compared to results from complementary transfer-matrix-method calculations on composite layers made of analogous film-stacks. This comparison helped to uncover the optical phenomena contributing to the appearance of extrema in the optical response. This paper presents an approach to optimizing the absorptance of different sensing and detecting devices via simultaneous numerical optimization of the polar and azimuthal illumination angles.

Active Individual Nanoresonators Optimized for Lasing and Spasing Operation.

Plasmonic nanoresonators consisting of a gold nanorod and a spherical silica core and gold shell, both coated with a gain layer, were optimized to maximize the stimulated emission in the near-field (NF-c-type) and the outcoupling into the far-field (FF-c-type) and to enter into the spasing operation region (NF-c*-type). It was shown that in the case of a moderate dye concentration, the nanorod has more advantages: smaller lasing threshold and larger slope efficiency and larger achieved intensities in the near-field in addition to FF-c-type systems' smaller gain and outflow threshold, earlier dip-to-peak switching in the spectrum and slightly larger far-field outcoupling efficiency. However, the near-field (far-field) bandwidth is smaller for NF-c-type (FF-c-type) core-shell nanoresonators. In the case of a larger dye concentration (NF-c*-type), although the slope efficiency and near-field intensity remain larger for the nanorod, the core-shell nanoresonator is more advantageous, considering the smaller lasing, outflow, absorption and extinction cross-section thresholds and near-field bandwidth as well as the significantly larger internal and external quantum efficiencies. It was also shown that the strong-coupling of time-competing plasmonic modes accompanies the transition from lasing to spasing occurring, when the extinction cross-section crosses zero. As a result of the most efficient enhancement in the forward direction, the most uniform far-field distribution was achieved.

Few-cycle localized plasmon oscillations.

The generation of few-cycle laser pulses proved to be a key enabling technology in strong-field physics and ultrafast science. The question naturally arises whether one can induce few-cycle localized plasmon oscillations in optical near-fields. Here, we perform a comparative study of different plasmonic nanoresonators illuminated by few-cycle pulses. We analyze the number of cycles (NOC) of the plasmonic field, the near-field enhancement (NFE) as well as the figure of merit NFE/NOC. The pulse length dependence of these quantities is also investigated. Throughout the inspected pulse-length interval silica-gold and silica-silver core-shell monomers have the potential to preserve the NOC of the incoming pulse, silver bow-ties result in the highest NFE, whereas gold core-shell dimers have the highest NFE/NOC. Based on the analysis, silver bow-ties, gold core-shell and silver nanorod dimers proved to be the most suitable for few-cycle near-field amplification.

Mapping Fluorescence Enhancement of Plasmonic Nanorod Coupled Dye Molecules.

Plasmonically enhanced fluorescence is a widely studied and applied phenomenon, however, only a comparative theoretical and experimental analysis of coupled fluorophores and plasmonic nanoresonators makes it possible to uncover how this phenomenon can be controlled. A numerical optimization method was applied to design configurations that are capable of resulting in an enhancement of excitation and emission, moreover, of both phenomena simultaneously in coupled Cy5 dye molecule and gold nanorod systems. Parametric sensitivity studies revealed how the fluorescence enhancement depends on the molecule's location, distance and orientation. Coupled systems designed for simultaneous improvement exhibited the highest (intermediate directional) total fluorescence enhancement, which is accompanied by intermediate sensitivity to the molecule's parameters, except the location and orientation sensitivity at the excitation wavelength. Gold nanorods with a geometry corresponding to the predicted optimal configurations were synthesized, and DNA strands were used to control the Cy5 dye molecule distance from the nanorod surface via hybridization of the Cy5-labelled oligonucleotide. State-of-the-art dSTORM microscopy was used to accomplish a proof-of-concept experimental demonstration of the theoretically predicted (directional) total fluorescence enhancement. The measured fluorescence enhancement was in good agreement with theoretical predictions, thus providing a complete kit to design and prepare coupled nanosystems exhibiting plasmonically enhanced fluorescence.

Niosomes decorated with dual ligands targeting brain endothelial transporters increase cargo penetration across the blood-brain barrier.

Nanoparticles targeting transporters of the blood-brain barrier (BBB) are promising candidates to increase the brain penetration of biopharmacons. Solute carriers (SLC) are expressed at high levels in brain endothelial cells and show a specific pattern at the BBB. The aim of our study was to test glutathione and ligands of SLC transporters as single or dual BBB targeting molecules for nanovesicles. High mRNA expression levels for hexose and neutral amino acid transporting SLCs were found in isolated rat brain microvessels and our rat primary cell based co-culture BBB model. Niosomes were derivatized with glutathione and SLC ligands glucopyranose and alanine. Serum albumin complexed with Evans blue (67 kDa), which has a very low BBB penetration, was selected as a cargo. The presence of targeting ligands on niosomes, especially dual labeling, increased the uptake of the cargo molecule in cultured brain endothelial cells. This cellular uptake was temperature dependent and could be decreased with a metabolic inhibitor and endocytosis blockers filipin and cytochalasin D. Making the negative surface charge of brain endothelial cells more positive with a cationic lipid or digesting the glycocalyx with neuraminidase elevated the uptake of the cargo after treatment with targeted nanocarriers. Treatment with niosomes increased plasma membrane fluidity, suggesting the fusion of nanovesicles with endothelial cell membranes. Targeting ligands elevated the permeability of the cargo across the BBB in the culture model and in mice, and dual-ligand decoration of niosomes was more effective than single ligand labeling. Our data indicate that dual labeling with ligands of multiple SLC transporters can potentially be exploited for BBB targeting of nanoparticles.

Improved emission of SiV diamond color centers embedded into concave plasmonic core-shell nanoresonators.

Configuration of three different concave silver core-shell nanoresonators was numerically optimized to enhance the excitation and emission of embedded silicon vacancy (SiV) diamond color centers simultaneously. Conditional optimization was performed to ensure ~20-30-40 and 50% apparent quantum efficiency (cQE) of SiV color centers. The enhancement spectra, as well as the near-field and charge distribution were inspected to uncover the underlying nanophotonical phenomena. The conditionally optimized coupled systems were qualified by the product of the radiative rate enhancements at the excitation and emission, which is nominated as P x factor. The optimized spherical core-shell nanoresonator containing a centralized emitter is capable of enhancing the emission considerably via bonding dipolar resonance. The P x factor is 529-fold with 49.7% cQE at the emission. Decentralization of the emitter leads to appearance of higher order nonradiative multipolar modes. Transversal and longitudinal dipolar resonance of the optimized ellipsoidal core-shell resonator was tuned to the excitation and emission, which results in 6.2∙105 P x factor with 50.6% cQE at the emission. Rod-shaped concave core-shell nanoresonators exploit similar transversal and longitudinal dipolar resonance, moreover they enhance the fluorescence more significantly due to their antenna-like geometry. P x factor indicating 8.34∙105 enhancement is achievable while the cQE is 50.3% at the emission.

Improvement of infrared single-photon detectors absorptance by integrated plasmonic structures.

Plasmonic structures open novel avenues in photodetector development. Optimized illumination configurations are reported to improve p-polarized light absorptance in superconducting-nanowire single-photon detectors (SNSPDs) comprising short- and long-periodic niobium-nitride (NbN) stripe-patterns. In OC-SNSPDs consisting of ~quarter-wavelength dielectric layer closed by a gold reflector the highest absorptance is attainable at perpendicular incidence onto NbN patterns in P-orientation due to E-field concentration at the bottom of nano-cavities. In NCAI-SNSPDs integrated with nano-cavity-arrays consisting of vertical and horizontal gold segments off-axis illumination in S-orientation results in polar-angle-independent perfect absorptance via collective resonances in short-periodic design, while in long-periodic NCAI-SNSPDs grating-coupled surface waves promote EM-field transportation to the NbN stripes and result in local absorptance maxima. In NCDAI-SNSPDs integrated with nano-cavity-deflector-array consisting of longer vertical gold segments large absorptance maxima appear in 3p-periodic designs due to E-field enhancement via grating-coupled surface waves synchronized with the NbN stripes in S-orientation, which enable to compensate fill-factor-related retrogression.

Effect of pH on stability and plasmonic properties of cysteine-functionalized silver nanoparticle dispersion.

Citrate-stabilized spherical silver nanoparticles (Ag NPs) with d=8.25±1.25 nm diameter were prepared and functionalized with L-cysteine (Cys) in aqueous dispersion. The nanosilver-cysteine interactions have been investigated by Raman and (1)H NMR spectroscopy. The effect of pH on stability of biofunctionalized Ag NPs was investigated. The cysteine-capped nanosilver dispersions remain stable at higher pH (pH>7), while the degree of aggregation increased as the pH decreased. Below pH ~7, the characteristic surface plasmon band of bare silver nanoparticles was back-shifted from λ(measured)(bareAgNP)=391 nm to λ(measured)(1)=387-391 nm, while the presence of a new band at λ(measured)(2)=550-600 nm was also observed depending on pH. Finite element method (FEM) was applied to numerically compute the absorption spectra of aqueous dispersions containing bare and cysteine-functionalized Ag NPs at different pH. Both the dynamic light scattering (DLS) measurements, Zeta potential values and the transmission electron microscopic (TEM) images confirmed our supposition. Namely, electrostatic interaction arose between the deprotonated carboxylate (COO(-)) and protonated amino groups (NH(3)(+)) of the amino acid resulting in cross-linking network of the Ag NPs between pH ~3 and 7. If the pH is measurable lower than ~3, parallel with the protonation of citrate and L-cysteine molecules the connection of the particles via l-cysteine is partly decomposed resulting in decrease of second plasmon band intensity.

Protection of the blood-brain barrier by pentosan against amyloid-ß-induced toxicity.

Endothelial cells of brain capillaries forming the blood-brain barrier play an important role in the pathogenesis and therapy of Alzheimer's disease. Amyloid-ß (Aß) peptides are key pathological elements in the development of the disease. A blood-brain barrier model, based on primary rat brain endothelial cells was used in which the barrier properties were induced by glial cells. The effects of amyloid peptides have been tested on cell viability and barrier functions. Aß showed toxic effects on primary rat brain endothelial cells measured by MTT dye conversion and the lactate dehydrogenase release. Morphologically cytoplasmic vacuolization, disruption of the structure of cytoplasmic organelles and tight junctions could be observed in brain endothelial cells. Treatment with Aß1-42 decreased the electrical resistance, and increased the permeability of brain endothelial cell monolayers for both fluorescein and albumin. Serum amyloid P component which stabilizes Aß fibrils in cortical amyloid plaques and cerebrovascular amyloid deposits significantly potentiated the barrier-weakening effect of Aß1-42. Sulfated polysaccharide pentosan could decrease the toxic effects of Aß peptides in brain endothelial cells. It could also significantly protect the barrier integrity of monolayers from damaging actions of peptides. Pentosan modified the size, and significantly decreased the number of amyloid aggregates demonstrated by atomic force microscopy. The present data further support the toxic effects of amyloid peptides on brain endothelial cells, and can contribute to the development of molecules protecting the blood-brain barrier in Alzheimer's disease.

Controlled in situ preparation of A beta(1-42) oligomers from the isopeptide "iso-A beta(1-42)", physicochemical and biological characterization.

Beta-amyloid (A beta) peptides play a crucial role in the pathology of the neurodegeneration in Alzheimer's disease (AD). Biological experiments (both in vitro and animal model studies of AD) require synthetic A beta peptides of standard quality, aggregation grade, neurotoxicity and water solubility. The synthesis of A beta peptides has been difficult, owing to their hydrophobic character, poor solubility and high tendency for aggregation. Recently an isopeptide precursor (iso-A beta(1-42)) was synthesized by Fmoc-chemistry and transformed at neutral pH to A beta(1-42) by O-->N acyl migration in a short period of time. We prepared the same precursor peptide using Boc-chemistry and studied the transformation to A beta(1-42) by acyl migration. The peptide conformation and aggregation processes were studied by several methods (circular dichroism, atomic force and transmission electron microscopy, dynamic light scattering). The biological activity of the synthetic A beta(1-42) was measured by ex vivo (long-term potentiation studies in rat hippocampal slices) and in vivo experiments (spatial learning of rats). It was proven that O-->N acyl migration of the precursor isopeptide results in a water soluble oligomeric mixture of neurotoxic A beta(1-42). These oligomers are formed in situ just before the biological experiments and their aggregation grade could be standardized.