Rapid Prototyping for Nanoparticle-Based Photonic Crystal Fiber Sensors.

The advent of nanotechnology has motivated a revolution in the development of miniaturized sensors. Such sensors can be used for radiation detection, temperature sensing, radio-frequency sensing, strain sensing, and more. At the nanoscale, integrating the materials of interest into sensing platforms can be a common issue. One promising platform is photonic crystal fibers, which can draw in optically sensitive nanoparticles or have its optical properties changed by specialized nanomaterials. However, testing these sensors at scale is limited by the the need for specialized equipment to integrate these photonic crystal fibers into optical fiber systems. Having a method to enable rapid prototyping of new nanoparticle-based sensors in photonic crystal fibers would open up the field to a wider range of laboratories that could not have initially studied these materials in such a way before. This manuscript discusses the improved processes for cleaving, drawing, and rapidly integrating nanoparticle-based photonic crystal fibers into optical system setups. The method proposed in this manuscript achieved the following innovations: cleaving at a quality needed for nanoparticle integration could be done more reliably (≈100% acceptable cleaving yield versus ≈50% conventionally), nanoparticles could be drawn at scale through photonic crystal fibers in a safe manner (a method to draw multiple photonic crystal fibers at scale versus one fiber at a time), and the new photonic crystal fiber mount was able to be finely adjusted when increasing the optical coupling before inserting it into an optical system (before, expensive fusion splicing was the only other method).

Octahedral Hexapalladium Pseudo-Td Pd6(µ3-CO)4(PEt3)6 with 80 Electron-Deficient Cluster Valence Electrons (CVEs) and a Comparison with Octahedral Hexapalladium Pseudo-C2v Pd6(µ3-CO)4(PMe3)7 with 82 CVEs: Computational Analysis and Resulting Implications.

The elusive octahedral hexapalladium Pd6(µ3-CO)4(PEt3)6 (1) was obtained by the reaction of Pd10(CO)12(PEt3)6 with TlCo(CO)4 in tetrahydrofuran under N2 at 55 °C. Its pseudo-Td octahedral structure, established from a CCD X-ray diffractometry study at 100 K, has the highest ideal symmetry of any of the characterized octahedral-based CO/PR3-ligated homopalladium Pdn clusters (n = 6, 7, 8, 10). Each Pd atom in 1 is coordinated to a PEt3 ligand, and each nonadjacent triangular Pd3 face is capped by a triply bridging µ3-CO ligand. The 31P{1H} NMR and IR spectra of 1 are in accordance with its solid-state molecular structure. Cluster 1 has a total of 80 cluster valence electrons (CVEs), the lowest reported for octahedral-based metal polyhedra that normally conform to the Wade-Mingos bonding rule with an 86 CVE count. Comparative density functional theory calculations involving natural population analysis are presented for trimethylphosphine analogues of the triethylphosphine (1-Me) and the previously reported octahedral hexapalladium trimethylphosphine Pd6(µ3-CO)4(PMe3)7 (2), which has pseudo-C2v symmetry with 82 total CVEs.

Complex pH-Dependent Interactions between Weak Polyelectrolyte Block Copolymer Micelles and Molecular Fluorophores.

Amphiphilic block copolymers with weak polyelectrolyte blocks can assemble stimulus-responsive nanostructures and interfaces. Applications of these materials in drug delivery, biomimetics, and sensing largely rely on the well-understood swelling of polyelectrolyte chains upon deprotonation, often induced by changes in pH or ionic strength. This deprotonation can also tune interfacial interactions between the polyelectrolyte blocks and surrounding solution, an effect which is less studied than morphological swelling of polyelectrolytes but can be just as critical for intended function. Here, we investigate whether the pH-driven morphological response of polyelectrolyte-bearing nanostructures also affects the interactions of these nanostructures with molecules in solution, using micelles of a short-chain polybutadiene-block-poly(acrylic acid) (pBd-pAA) as a model system. We introduce a Förster resonance energy transfer (FRET) approach to probe interactions between micelles and fluorescent molecular solutes as a function of solution pH. As expected, the pAA corona of these pBd-pAA micelles increases in thickness monotonically as a function of pH. However, FRET efficiency, which provides a metric of the spatial proximity of fluorescently labeled micelles and freely diffusing fluorophores, exhibits complex nonmonotonic behavior as a function of pH, indicating that the average separation of micelles and acceptor fluorophores is not strictly correlated with micelle swelling. Dialysis experiments quantify the affinity of fluorophores for micelles as a function of pH, confirming that changes in FRET are driven almost entirely by the pH-dependent affinity of the pAA block for the investigated molecular fluorophores, not simply by a shape change of the pAA corona. This study provides key insights into the interfacial interactions between weak-polyelectrolyte-bearing nanostructures and molecular solutes, of importance for the development of their stimulus-responsive applications.

Low molecular weight NGF mimetic GK-2 normalizes the parameters of glucose and lipid metabolism and exhibits a hepatoprotective effect on a prediabetes model in obese Wistar rats.

Signs of metabolic syndrome and prediabetes preceding type 2 diabetes are modelled in an experiment using a high-fat diet (HFD). The aim of this work was to study the effect of a low molecular weight systemically active nerve growth factor mimetic, compound GK-2 (hexamethylenediamide bis[N-monosuccinyl-L-glutamyl-L-lysine]), on indicators of abdominal obesity, basal blood glucose level, glucose tolerance, cholesterol and triglyceride blood levels, as well as the morphological structure of the liver in male Wistar rats fed a HFD. Rats were divided into three groups: one of them received standard food (control) and two others were fed a HFD containing 45% fat, 35% carbohydrates and 20% protein, with a total caloric value of 516 kcal/100 g, over 12 weeks. Starting from the ninth week, for the next 4 weeks, one of the HFD groups was treated orally with saline whilst the other group was treated orally with GK-2 at a dose of 5 mg/kg. GK-2 was found to reduce the basal glycaemia level and improve glucose tolerance, as well as to reduce the blood level of cholesterol by 30% and that of triglycerides by 28% in comparison with the saline-treated HFD animals. GK-2 reduced the degree of abdominal obesity to the level of the healthy animals and eliminated morphological abnormalities in the liver caused by the HFD. The results of the study determine the feasibility of further GK-2 research as a potential agent for prediabetes treatment.

RSS/TDoA-Based Source Localization in Microwave UWB Sensors Networks Using Two Anchor Nodes.

The manuscript presents an algorithm for the optimal estimation of the amplitude and propagation delay time of an ultra-wideband radio signal, in systems for the passive location of fixed targets based on the hybrid RSS/TDoA method in two-dimensional space with two base stations. The optimal estimate is based on the Bayesian strategy of maximum a posteriori probability density, taking into account a priori data on the statistical properties of the Line of Sight radio channel during Gaussian monocycle propagation. The Bayesian Cramer-Rao lower bound (BCRLB) of the delay time and the amplitude estimates for a time-discrete signal are calculated, and the resulting parameter estimate is compared with BCRLB. An algorithm has been developed for optimal estimation of distances from the radiation source to base stations, based on the results of the measurements of the amplitude and the propagation delay time of the UWB radio signal. The calculation of the statistical characteristics of the obtained estimate is carried out, and the functional dependence of the characteristics on various parameters is analyzed.

Nebulized Non-Immunogenic Staphylokinase in the Mice Acute Lung Injury Model.

Acute lung injury (ALI) as a model of acute respiratory distress syndrome is characterized by inflammation, complex coagulation, and hematologic abnormalities which result in the formation of fibrin-platelet microthrombi in the pulmonary vessels with the rapid development of progressive respiratory dysfunction. We hypothesize that a nebulized fibrinolytic agent, non-immunogenic staphylokinase (nSta), may be useful for ALI therapy. First, the effect of the nebulized nSta (0.2 mg/kg, 1.0 mg/kg, or 2.0 mg/kg) on the coagulogram parameters was studied in healthy rats. ALI was induced in mice by nebulized administration of lipopolysaccharide (LPS) at a dose of 10 mg/kg. nSta (0.2 mg/kg, 0.4 mg/kg or 0.6 mg/kg) was nebulized 30 min, 24 h, and 48 h after LPS administration. The level of pro-inflammatory cytokines was determined in the blood on the 8th day after LPS and nSta administration. The assessment of lung damage was based on their weighing and microscopic analysis. Fibrin/fibrinogen deposition in the lungs was determined by immunohistochemistry. After nSta nebulization in healthy rats, the fibrinogen blood level as well as activated partial thromboplastin time and prothrombin time did not change. In the nebulized ALI model, the mice showed an increase in lung weight due to their edema and rising fibrin deposition. An imbalance of proinflammatory cytokines was also found. Forty percent of mice with ALI without nSta nebulization had died. Nebulized nSta at a dose of 0.2 mg/kg reduced the severity of ALI: a decrease in interstitial edema and inflammatory infiltration was noted. At a dose of 0.4 mg/kg of nebulized nSta, the animals showed no peribronchial edema and the bronchi had an open clear lumen. At a dose of 0.6 mg/kg of nebulized nSta, the manifestations of ALI were completely eliminated. A significant dose-dependent reduction of the fibrin-positive areas in the lungs of mice with ALI was established. Nebulized nSta had a normalizing effect on the proinflammatory cytokines in blood- interleukin (IL)-1α, IL-17A, IL-6, and granulocyte-macrophage colony-stimulating factor (GM-CSF). These data showed the effectiveness of nebulized nSta and the perspectives of its clinical usage in COVID-19 patients with acute respiratory distress syndrome (ARDS).

The intrinsic electrochemical behavior of layered Cu2WSe4nanoparticles.

Nanoplates of Cu2WSe4(∼50 nm) were synthesized via a hot-injection method by one-pot selenation of WCl6and Cu(acac)2. This synthetic route provided another perspective towards the intrinsic electrochemical properties of Cu2MSe4(M = Mo or W), where their nanoparticles were previously synthesized via a metathesis route. Cations-dependent cathodic events and surface activation anodic events were identified by cyclic voltammetry in acetonitrile.

MnSn2and MnSn2-TiO2nanostructured anode materials for lithium-ion batteries.

The high theoretical lithium storage capacity of Sn makes it an enticing anode material for Li-ion batteries (LIBs); however, its large volumetric expansion during Li-Sn alloying must be addressed. Combining Sn with metals that are electrochemically inactive to lithium leads to intermetallics that can alleviate volumetric expansion issues and still enable high capacity. Here, we present the cycling behavior of a nanostructured MnSn2intermetallic used in LIBs. Nanostructured MnSn2is synthesized by reducing Sn and Mn salts using a hot injection method. The resulting MnSn2is characterized by x-ray diffraction and transmission electron microscopy and then is investigated as an anode for LIBs. The MnSn2electrode delivers a stable capacity of 514 mAh g-1after 100 cycles at a C/10 current rate with a Coulombic efficiency >99%. Unlike other Sn-intermetallic anodes, an activation overpotential peak near 0.9 V versus Li is present from the second lithiation and in subsequent cycles. We hypothesize that this effect is likely due to electrolyte reactions with segregated Mn from MnSn2. To prevent these undesirable Mn reactions with the electrolyte, a 5 nm TiO2protection layer is applied onto the MnSn2electrode surface via atomic layer deposition. The TiO2-coated MnSn2electrodes do not exhibit the activation overpotential peak. The protection layer also increases the capacity to 612 mAh g-1after 100 cycles at a C/10 current rate with a Coulombic efficiency >99%. This higher capacity is achieved by suppressing the parasitic reaction of Mn with the electrolyte, as is supported by x-ray photoelectron spectroscopy analysis.

Atmospheric Processing of Iron-Bearing Mineral Dust Aerosol and Its Effect on Growth of a Marine Diatom, Cyclotella meneghiniana.

Iron (Fe) is a growth-limiting micronutrient for phytoplankton in major areas of oceans and deposited wind-blown desert dust is a primary Fe source to these regions. Simulated atmospheric processing of four mineral dust proxies and two natural dust samples followed by subsequent growth studies of the marine planktic diatom Cyclotella meneghiniana in artificial sea-water (ASW) demonstrated higher growth response to ilmenite (FeTiO3) and hematite (α-Fe2O3) mixed with TiO2 than hematite alone. The processed dust treatment enhanced diatom growth owing to dissolved Fe (DFe) content. The fresh dust-treated cultures demonstrated growth enhancements without adding such dissolved Fe. These significant growth enhancements and dissolved Fe measurements indicated that diatoms acquire Fe from solid particles. When diatoms were physically separated from mineral dust particles, the growth responses become smaller. The post-mineralogy analysis of mineral dust proxies added to ASW showed a diatom-induced increased formation of goethite, where the amount of goethite formed correlated with observed enhanced growth. The current work suggests that ocean primary productivity may not only depend on dissolved Fe but also on suspended solid Fe particles and their mineralogy. Further, the diatom C. meneghiniana benefits more from mineral dust particles in direct contact with cells than from physically impeded particles, suggesting the possibility for alternate Fe-acquisition mechanism/s.

Charge-Separated and Lewis Paired Metal-Organic Framework for Anion Exchange and CO2 Chemical Fixation.

Charge-separated metal-organic frameworks (MOFs) are a unique class of MOFs that can possess added properties originating from the exposed ionic species. A new charge-separated MOF, namely, UNM-6 synthesized from a tetrahedral borate ligand and Co2+ cation is reported herein. UNM-6 crystalizes into the highly symmetric P43n space group with fourfold interpenetration, despite the stoichiometric imbalance between the B and Co atoms, which also leads to loosely bound NO3 - anions within the crystal structure. These NO3 - ions can be quantitatively exchanged with various other anions, leading to Lewis acid (Co2+ ) and Lewis base (anions) pairs within the pores and potentially cooperative catalytic activities. For example, UNM-6-Br, the MOF after anion exchange with Br- anions, displays high catalytic activity and stability in reactions of CO2 chemical fixation into cyclic carbonates.

An Elaborated Signal Model for Simultaneous Range and Vector Velocity Estimation in FMCW Radar.

A rigorous mathematical description of the signal reflected from a moving object for radar monitoring tasks using linear frequency modulated continuous wave (LFMCW) microwave radars is proposed. The mathematical model is based on the quasi-relativistic vector transformation of coordinates and Lorentz time. The spatio-temporal structure of the echo signal was obtained taking into account the transverse component of the radar target speed, which made it possible to expand the boundaries of the range of measuring the range and speed of vehicles using LFMCW radars. An algorithm for the simultaneous estimation of the range, radial and transverse components of the velocity vector of an object from the observation data of the time series during one frame of the probing signal is proposed. For an automobile 77 GHz microwave LFMCW radar, a computer experiment was carried out to measure the range and velocity vector of a radar target using the developed mathematical model of the echo signal and an algorithm for estimating the motion parameters. The boundaries of the range for measuring the range and speed of the target are determined. The results of the performed computer experiment are in good agreement with the results of theoretical analysis.

Method for Remote Determination of Object Coordinates in Space Based on Exact Analytical Solution of Hyperbolic Equations.

Accurate remote determination of the object coordinates in 3D space is one of the main questions in many applications. In one of the most popular methods, such determination of the location of an object uses the measurement by receiving an electromagnetic signal transmitted by several spatially distributed base stations (BS). The main problem is that it is necessary to reduce errors and computation time. To overcome these difficulties, an analytical method for determining the position of an object based on the analysis of time difference of arrival (TDoA) of signals from the transmitter of the object to the receivers of the BS is proposed. One of the main advantages of this method is that it is possible to eliminate the ambiguity in determining the coordinates of the object in space and to increase the accuracy of determining the coordinates when the TDoA measurement between base stations fluctuates. Applications for autonomous automotive vehicles and spacebased positioning systems are analyzed. The results obtained show that the proposed algorithm has an accuracy of determining coordinates several times higher than the method of linearization of hyperbolic equations and is less sensitive to TDoA fluctuations at base stations.

On computing spectral densities from classical, semiclassical, and quantum simulations.

The Caldeira-Leggett model provides a compact characterization of a thermal environment in terms of a spectral density function, which has led to a variety of numerically exact quantum methods for reduced density matrix propagation. Since spectral densities are often computed from classical molecular dynamics simulations, we investigate in this paper whether quantum effects should be accounted for in the calculations. Therefore, we reformulate the recently developed Fourier method for spectral density calculations from semiclassical simulations which approximately allow for quantum effects. We propose two possible protocols based on either correlation functions or expectation values. These protocols are tested on a generic Calderra-Leggett model for the linearized semiclassical initial-value representation (LSC-IVR), the thawed Gaussian wave packet dynamics (TGWD), and hybrid schemes combining the two with the more accurate Herman-Kluk formula. Surprisingly, spectral densities from the LSC-IVR method, which treats the dynamics completely classically, are found to be extremely accurate, even in the quantum regime, where this method does not give a correct description of the correlation functions and expectation values. In contrast, the TGWD method turns out as too inaccurate for spectral density calculations, and the hybrid schemes perform well only if the system is close to the classical regime. This implies that, if the bath has a Caldeira-Leggett form, spectral densities are insensitive to quantum effects and any effort to approximately account for them rather leads to errors. Hence, in this case, spectral densities can be computed from classical simulations and used in a reduced quantum simulation as well.

Thermal stability of volume Bragg gratings in chloride photo-thermo-refractive glass after femtosecond laser bleaching.

We demonstrate that the Joule heating of the volume Bragg grating recorded in chloride photo-thermo-refractive glass can be suppressed by bleaching the silver nanoparticles with intense ultrashort laser pulses. Measurement of the bleached grating angular selectivity showed that, at the signal wavelength at 972 nm, the spectral drift is 0.5 nm at the CW laser diode beam intensity as high as 145 W/cm2. Thus, the bleaching of silver nanoparticles results in the improved thermal stability of transmission gratings, allowing one to employ them to control the powerful CW laser radiation.

Simulating vibronic spectra via Matsubara-like dynamics: Coping with the sign problem.

Measuring vibronic spectra probes dynamical processes in molecular systems. When interpreted via suitable theoretical tools, the experimental data provides comprehensive information about the system in question. For complex many-body problems, such an approach usually requires the formulation of proper classical-like approximations, which is particularly challenging if multiple electronic states are involved. In this work, we express the imaginary-time shifted time correlation function and, thus, the vibronic spectrum in terms of the so-called Matsubara dynamics, which combines quantum statistics and classical-like dynamics. By applying the Matsubara approximation in the adiabatic limit, we derive a formal generalization of the existing Matsubara dynamics formalism to multiple potential energy surfaces (PESs), which, however, does not feature all the defining properties of its single-PES counterpart though suffering equally from the sign problem. The mathematical analysis for two shifted harmonic oscillators suggests a new modified method to practically simulate the standard correlation function via Matsubara-like dynamics. Importantly, this modified method samples the thermal Wigner function without suffering from the sign problem and yields an accurate approximation to the vibronic absorption spectrum, not only for the harmonic system but also for the anharmonic one.

Quasi-classical approaches to vibronic spectra revisited.

The framework to approach quasi-classical dynamics in the electronic ground state is well established and is based on the Kubo-transformed time correlation function (TCF), being the most classical-like quantum TCF. Here we discuss whether the choice of the Kubo-transformed TCF as a starting point for simulating vibronic spectra is as unambiguous as it is for vibrational ones. Employing imaginary-time path integral techniques in combination with the interaction representation allowed us to formulate a method for simulating vibronic spectra in the adiabatic regime that takes nuclear quantum effects and dynamics on multiple potential energy surfaces into account. Further, a generalized quantum TCF is proposed that contains many well-established TCFs, including the Kubo one, as particular cases. Importantly, it also provides a framework to construct new quantum TCFs. Applying the developed methodology to the generalized TCF leads to a plethora of simulation protocols, which are based on the well-known TCFs as well as on new ones. Their performance is investigated on 1D anharmonic model systems at finite temperatures. It is shown that the protocols based on the new TCFs may lead to superior results with respect to those based on the common ones. The strategies to find the optimal approach are discussed.

In situ infrared spectroscopy during La2O3 ALD using La( i PrCp)3 and H2O.

Infrared spectra of surface species have been obtained during atomic layer deposition using tris(isopropylcyclopentadienyl)lanthanum, La(iPrCp)3, and water as precursors at 160 °C and 350 °C. Gas-phase spectra of La(iPrCp)3are obtained for comparison. At low temperature, ligand exchange is seen to occur, and carbonate formation is found. With extended purging, the organic ligands are found to be stable on the surface, and carbonates are not formed. These observations indicate that carbonate formation is occurring during exposure to the precursors. At high temperature, the La precursor is observed to decompose leaving an opaque deposit containing relatively little hydrogen.

A time-correlation function approach to nuclear dynamical effects in X-ray spectroscopy.

Modern X-ray spectroscopy has proven itself as a robust tool for probing the electronic structure of atoms in complex environments. Despite working on energy scales that are much larger than those corresponding to nuclear motions, taking nuclear dynamics and the associated nuclear correlations into account may be of importance for X-ray spectroscopy. Recently, we have developed an efficient protocol to account for nuclear dynamics in X-ray absorption and resonant inelastic X-ray scattering spectra [Karsten et al., J. Phys. Chem. Lett. 8, 992 (2017)], based on ground state molecular dynamics accompanied with state-of-the-art calculations of electronic excitation energies and transition dipoles. Here, we present an alternative derivation of the formalism and elaborate on the developed simulation protocol using gas phase and bulk water as examples. The specific spectroscopic features stemming from the nuclear motions are analyzed and traced down to the dynamics of electronic energy gaps and transition dipole correlation functions. The observed tendencies are explained on the basis of a simple harmonic model, and the involved approximations are discussed. The method represents a step forward over the conventional approaches that treat the system in full complexity and provides a reasonable starting point for further improvements.

Isolation and Structural Characterization of a Mackay 55-Metal-Atom Two-Shell Icosahedron of Pseudo-Ih Symmetry, Pd55L12(µ3-CO)20 (L = PR3, R = Isopropyl): Comparative Analysis with Interior Two-Shell Icosahedral Geometries in Capped Three-Shell Pd145, Pt-Centered Four-Shell Pd-Pt M165, and Four-Shell Au133 Nanoclusters.

We present the first successful isolation and crystallographic characterization of a Mackay 55-metal-atom two-shell icosahedron, Pd55L12(µ3-CO)20 (L = PPr(i)3) (1). Its two-shell icosahedron of pseudo-Ih symmetry (without isopropyl substituents) enables a structural/bonding comparison with interior 55-metal-atom two-shell icosahedral geometries observed within the multi-shell capped 145-metal-atom three-shell Pd145(CO)72(PEt3)30 and 165-metal-atom four-shell Pt-centered (µ12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x ≈ 7) nanoclusters, and within the recently reported four-shell Au133(SC6H4-p-Bu(t))52 nanocluster. DFT calculations carried out on a Pd55(CO)20(PH3)12 model analogue, with triisopropyl phosphine substituents replaced by H atoms, revealed a positive +0.84 e charge for the entire Pd55 core, with a highly positive second-shell Pd42 surface of +1.93 e.

Vibrational spectroscopy via the Caldeira-Leggett model with anharmonic system potentials.

The Caldeira-Leggett (CL) model, which describes a system bi-linearly coupled to a harmonic bath, has enjoyed popularity in condensed phase spectroscopy owing to its utmost simplicity. However, the applicability of the model to cases with anharmonic system potentials, as it is required for the description of realistic systems in solution, is questionable due to the presence of the invertibility problem [F. Gottwald et al., J. Phys. Chem. Lett. 6, 2722 (2015)] unless the system itself resembles the CL model form. This might well be the case at surfaces or in the solid regime, which we here confirm for a particular example of an iodine molecule in the atomic argon environment under high pressure. For this purpose we extend the recently proposed Fourier method for parameterizing linear generalized Langevin dynamics [F. Gottwald et al., J. Chem. Phys. 142, 244110 (2015)] to the non-linear case based on the CL model and perform an extensive error analysis. In order to judge on the applicability of this model in advance, we give practical empirical criteria and discuss the effect of the potential renormalization term. The obtained results provide evidence that the CL model can be used for describing a potentially broad class of systems.