Iridium-Based Selective Emitters for Thermophotovoltaic Applications.

The long-term operation of refractory-metal-based metamaterials is crucial for applications such as thermophotovoltaics. The metamaterials based on refractory metals like W, Mo, Ta, Nb, and Re fail primarily by oxidation. Here, the use of the noble metal Ir is proposed, which is stable to oxidation and has optical properties comparable to gold. The thermal endurance of Ir in a 3-layer-system, consisting of HfO2 /Ir/HfO2 , by performing annealing experiments up to 1240 °C in a pressure range from 2 × 10-6  mbar to 1 bar, is demonstrated. The Ir layer shows no oxidation in a vacuum and inert gas atmosphere. At temperatures above 1100 °C, the Ir layer starts to agglomerate due to the degradation of the confining HfO2 layers. An in situ X-ray diffraction experimental comparison between 1D multilayered Ir/HfO2 and W/HfO2 selective emitters annealed at 1000 °C, 2 × 10-6  mbar, over 100 h, confirms oxidation stability of Ir while W multilayers gradually disappear. The results of this work show that W-based metamaterials are not long-term stable even at 1000 °C. However, the oxidation resistance of Ir can be leveraged for refractory plasmonic metamaterials, such as selective emitters in thermophotovoltaic systems with strong suppression of long wavelength radiation.

A new species of Scolytus Geoffroy (Coleoptera, Curculionidae, Scolytinae) from Yunnan, China.

Scolytus unicornis, a new species of Scolytus Geoffroy from Yunnan, China, is described and illustrated. Three DNA barcoding sequences (COI, 28S, CAD) of this species are provided. The new species is distinguished from other Asian Scolytus species by the longitudinal wrinkles on the frons only in the area below the eyes, a large median spine situated in the middle of the ventrite 2 base, and female frons with a slightly raised blunt tubercle above the epistoma.

Quantum Control of Atom-Ion Charge Exchange via Light-Induced Conical Intersections.

Conical intersections are crossing points or lines between two or more adiabatic electronic potential energy surfaces in the multidimensional coordinate space of colliding atoms and molecules. Conical intersections and corresponding nonadiabatic coupling can greatly affect molecular dynamics and chemical properties. In this paper, we predict significant or measurable nonadiabatic effects in an ultracold atom-ion charge-exchange reaction in the presence of laser-induced conical intersections (LICIs). We investigate the fundamental physics of these LICIs on molecular reactivity under unique conditions: those of relatively low laser intensity of 108 W/cm2 and ultracold temperatures below 1 mK. We predict irregular interference effects in the charge-exchange rate coefficients between K and Ca+ as functions of the laser frequency. These irregularities occur in our system due to the presence of two LICIs. To further elucidate the role of the LICIs on the reaction dynamics, we compare these rate coefficients with those computed for a system where the CIs have been "removed". In the laser frequency window, where conical interactions are present, the difference in rate coefficients can be as large as 1 × 10-9 cm3/s.

Synopsis of the Neotropical Premnobiina (Coleoptera: Curculonidae: Scolytinae: Ipini) with descriptions of new species, new synonymy and keys to species.

One new species of Neotropical Premnobius Eichhoff is described: P. brownei Atkinson & Flechtmann from Brazil. The presence of the related genus Premnophilus Browne is confirmed from South America and six new species are described: P. bertii Atkinson & Flechtmann from Brazil, P. jordali Petrov from Peru, P. maiai Atkinson & Flechtmann from Brazil, P. pedrosai Atkinson & Flechtmann from Brazil, P. sarahsmithae Atkinson & Flechtmann from Brazil and Trinidad and Tobago, and P. wilsoni Atkinson & Flechtmann from Brazil. French Guiana, and Peru. Gnathotrupes megapunctatus Bright, 2019 is recognized as a synonym of Premnobius perezdelacruceii Petrov & Atkinson, 2018. A synopsis of previously described Premnobius species and keys to species in both genera are presented. Generic characters for the three genera of Neotropical Ipini are discussed.

Role of Dietary Inclusion of Phytobiotics and Mineral Adsorbent Combination on Dairy Cows' Milk Production, Nutrient Digestibility, Nitrogen Utilization, and Biochemical Parameters.

Our research purpose was to study the effect of the inclusion of a combination of phytobiotics in the form of dry Fucus vesiculosus grits (FG) and a mineral adsorbent from the heat-treated mineral shungite (TMS) on milk productivity, nutrient digestibility, and biochemical parameters of the Suksun dairy cows. A total of 80 dry-hardy cows of the Suksun breed were divided into four groups (20 heads each), balanced primarily by breed, age, body weight, body condition score, and indicators of milk yield for the previous lactation. The selected cows were with an average live body weight of 512.0 ± 1.28 kg, BCS 3.0-3.5, and parities of 6250 kg milk. The control group (CON) were fed the basic ration only; the second (TMS), third (FG), and fourth (TMS + FG) groups were fed the basic ration provided by 50 g of the mineral adsorbent from heat-treated shungite, 100 g of Fucus grits (Fucus vesiculosus), 50 g of the mineral adsorbent from heat-treated shungite, and 100 g of dry grits from Fucus vesiculosus, respectively. The total protein content in milk was significantly higher in the group receiving Fucus vesiculosus by 0.05% and the group receiving a combination of mineral adsorbent and Fucus vesiculosus by 0.03%. The percentage of milk fat content recorded the highest significant value in (TMS) group when compared to the control and represented (4.37 vs. 3.95). The group of cows that received (TMS + FG) revealed a significant difference in the digestibility of both ether extract and crude fiber when compared to the control group and represented (54.74 vs. 51.71 and 60.68 vs. 55.15%), respectively. The cows supplemented with a mineral adsorbent or a combination of mineral adsorbent and Fucus vesiculosus revealed a significant difference in the digestibility of ether extract and crude fiber in the group receiving TMS + FG by 3.0% (p < 0.05) and 5.5% (p < 0.05), respectively. The intake of nitrogen with the diet increased in (FG) and (TMS + FG) groups by 11.3 g (p < 0.05) and 13.4 g (p < 0.05) of nitrogen. There was an increase (p < 0.05) in the concentration of rumen ammonia in the control group compared to the other groups. The glucose content of those cows that received FG and TMS + FG combination increased (p < 0.05) by 0.76 mmol/L and 0.90 mmol/l in relation to the control group. The globulin, albumin/globulin ratio, and the level of triglycerides revealed a significant difference between the different experimental groups. In brief, the inclusion of a combination of phytobiotics in the form of dry Fucus vesiculosus grits and a mineral adsorbent from the heat-treated mineral shungite in Suksun dairy cows' diets improved milk composition, digestibility of nutrients, utilization of nitrogen, and did not cause deleterious effects on blood biochemical indicators.

First Results of the Implementation of the Doppler Backscattering Diagnostic for the Investigation of the Transition to H-Mode in the Spherical Tokamak Globus-M2.

This paper presents the first results of a study of the LH transition on the new spherical Globus-M2 tokamak using the Doppler backscattering (DBS) diagnostic. New data characterizing the H-mode of discharges with higher values of the plasma parameters, such as magnetic field Bt up to 0.9 T and plasma current Ip up to 450 kA, were collected and analyzed. An upgraded neutral beam injection (NBI) system was used to initiate the LH transition. DBS allows the measurement of the poloidal rotation velocity and the turbulence amplitude of the plasma. The multi-frequency DBS system installed on Globus-M2 can simultaneously collect data in different areas spanning from the separatrix to the plasma core. This allowed for the radial profiles of the rotation velocity and electric field to be calculated before and after the LH transition. In addition, the values and temporal evolution of the velocity shear were obtained. The associated turbulence suppression after the transition to the H-mode was investigated using DBS.

Crosstalk between G-Quadruplexes and Dnmt3a-Mediated Methylation of the c-MYC Oncogene Promoter.

The methylation of cytosines at CpG sites in DNA, carried out de novo by DNA methyltransferase Dnmt3a, is a basic epigenetic modification involved in gene regulation and genome stability. Aberrant CpG methylation in gene promoters leads to oncogenesis. In oncogene promoters, CpG sites often colocalize with guanine-rich sequences capable of folding into G-quadruplexes (G4s). Our in vitro study aimed to investigate how parallel G4s formed by a sequence derived from the c-MYC oncogene promoter region affect the activity of the Dnmt3a catalytic domain (Dnmt3a-CD). For this purpose, we designed synthetic oligonucleotide constructs: a c-MYC G4-forming oligonucleotide and linear double-stranded DNA containing an embedded stable extrahelical c-MYC G4. The topology and thermal stability of G4 structures in these DNA models were analyzed using physicochemical techniques. We showed that Dnmt3a-CD specifically binds to an oligonucleotide containing c-MYC G4, resulting in inhibition of its methylation activity. c-MYC G4 formation in a double-stranded context significantly reduces Dnmt3a-CD-induced methylation of a CpG site located in close proximity to the quadruplex structure; this effect depends on the distance between the non-canonical structure and the specific CpG site. One would expect DNA hypomethylation near the G4 structure, while regions distant from this non-canonical form would maintain a regular pattern of high methylation levels. We hypothesize that the G4 structure sequesters the Dnmt3a-CD and impedes its proper binding to B-DNA, resulting in hypomethylation and activation of c-MYC transcription.

Quantum chemical modeling of the thermodynamics of the formation of Au(III), Pd(II), and Pt(II) chloride complexes.

Quantitative prediction of physical properties of liquids and equilibrium constants is important for many applications. Computational methods based on either explicit or implicit solvent models can be used to approximate thermodynamics of complexation. A practical method for calculating the stability constant of d8 chlorocomplexes (PdCl42-, PtCl42-, AuCl4-) in aqueous solution has been developed by using DFT and DLPNO-CCSD with the SMD solvation model and 100 unique explicit water molecules. Stability constants have been calculated by using methods, such as DFT/PBE0-D3, DLPNO-CCSD, DLPNO-CCSD-DK, and DLPNO-CCSD(T), and basis sets, such as def2-TZVPD, def2-TZVPP, ma-def2-TZVP, ma-DKH-def2-TZVP, SARC-TZVP, and SARC-TZVPP. Calculations using DFT/PBE0-D3/def2-TZVPD and DLPNO-CCSD-DK/ma-DKH-Def2-TZVP/SARC-DKH-TZVP with SMD solvation with explicit waters are found to have errors of 2-3 log units relative to experimental data. The best results are obtained by using 8 explicit waters for d8 aqua complexes, 14 explicit waters for d8 chlorocomplexes, and 4 explicit waters for chloride ion.

Impact of ligand deformation on the P,T-violation effects in the YbOH molecule.

Ytterbium monohydroxide is a promising molecule in the search for new physics. It is well known that levels of opposite parity, separated by energy split, the so-called l-doublets, define the experimental electric field strength required for molecule polarization. In addition, in our previous paper [Phys. Rev. A 105, L050801 (2022)], we have shown that the value of l-doubling directly influences the sensitivity of linear triatomic molecules toward the P,T-odd effects. In our work [J. Chem. Phys. 155, 164301 (2021)], we have calculated the value of l-doubling for YbOH molecules with the approximation of fixed O-H bond length. Taking the importance of this property into account, in the present study, we consider the additional degree of freedom corresponding to ligand (OH) deformation.

Are mirror-symmetric objects of special importance for 3D shape perception? A reply to Sawada and Pizlo (2022).

Yu, Todd, and Petrov (2021) and Yu, Petrov, and Todd (2021) investigated failures of shape constancy that occur when objects are viewed stereoscopically at different distances. Although this result has been reported previously with simple objects such as pyramids or cylinders, we examined more complex objects with bilateral symmetry to test the claim by Li, Sawada, Shi, Kwon, and Pizlo (2011) that the perception of those objects is veridical. Sawada and Pizlo (2022) offer several criticisms of our experiments, but they seem to suggest that the concept of shape is defined by what is computable by their model. If stimuli are used that cannot be discriminated by their model, they are dismissed as degenerate, and tasks that cannot be performed by their model are assumed to be based on something other than shape. This allows them to disregard empirical evidence that is inconsistent with their model. We argue, in contrast, that all reliable aspects of shape perception are deserving of explanation. We also argue that there are many different attributes of shape and many different sources of information about shape that may be relevant in different contexts. It is unlikely that all of them can be explained by a single model.

The many facets of shape.

Shape is an interesting property of objects because it is used in ordinary discourse in ways that seem to have little connection to how it is typically defined in mathematics. The present article describes how the concept of shape can be grounded within Euclidean and non-Euclidean geometry and also to human perception. It considers the formal methods that have been proposed for measuring the differences among shapes and how the performance of those methods compares with shape difference thresholds of human observers. It discusses how different types of shape change can be perceptually categorized. It also evaluates the specific data structures that have been used to represent shape in models of both human and machine vision, and it reviews the psychophysical evidence about the extent to which those models are consistent with human perception. Based on this review of the literature, we argue that shape is not one thing but rather a collection of many object attributes, some of which are more perceptually salient than others. Because the relative importance of these attributes can be context dependent, there is no obvious single definition of shape that is universally applicable in all situations.

Rovibrational structure of the ytterbium monohydroxide molecule and the P,T-violation searches.

The spectrum of triatomic molecules with close rovibrational opposite parity levels is sensitive to the P,T-odd effects. This makes them a convenient platform for the experimental search of a new physics. Among the promising candidates, one may distinguish YbOH as a non-radioactive compound with a heavy atom. The energy gap between levels of opposite parity, l-doubling, is of great interest as it determines the electric field strength required for the full polarization of the molecule. Likewise, the influence of the bending and stretching modes on the sensitivities to the P,T-violation requires a thorough investigation since the measurement would be performed on the excited vibrational states. This motivates us to obtain the rovibrational nuclear wavefunctions, taking into account the anharmonicity of the potential. As a result, we get the values of Eeff and Es for the lowest excited vibrational state and determine the l-doubling.

Bilateral Symmetry Has No Effect on Stereoscopic Shape Judgments.

A single experiment is reported that measured the apparent stereoscopic shapes of symmetric and asymmetric objects at different viewing distances. The symmetric stimuli were specifically designed to satisfy the minimal conditions for computing veridical shape from symmetry. That is to say, they depicted complex, bilaterally symmetric, plane-faced polyhedra whose symmetry planes were oriented at an angle of 45° relative to the line of sight. The asymmetric stimuli were distorted versions of the symmetric ones in which the 3D position of each vertex was randomly displaced. Prior theoretical analyses have shown that it is mathematically possible to compute the 3D shapes of symmetric stimuli under these conditions, but those algorithms are useless for asymmetric objects. The results revealed that the apparent shapes of both types of objects were expanded or compressed in depth as a function of viewing distance, in exactly the same way as has been reported in many other studies, and that the presence or absence of symmetry had no detectable effect on performance.

Failures of stereoscopic shape constancy over changes of viewing distance and size for bilaterally symmetric polyhedra.

Two shape matching experiments examined the effects of viewing distance and object size on observers' judgments of 3D metric shape under binocular viewing. Unlike previous studies on this topic, the stimuli were specifically designed to satisfy the minimal conditions for computing veridical shape from symmetry. Concretely, the stimuli were complex, mirror-symmetric polyhedra whose symmetry planes were oriented at an angle of 45o relative to the line of sight in a shape-matching task. Although it is mathematically possible to accurately compute the 3D shapes of these stimuli using relatively simple algorithms, the results indicated that human observers are unable to do so. Indeed, the apparent shapes of the objects were systematically expanded or compressed in depth as a function of viewing distance, in exactly the same way as has been reported for simpler stimuli that do not satisfy the minimal conditions for an accurate computational analysis. For objects presented at near distances, we also obtained statistically significant effects of object size on observers' shape judgments.

A new genus and two new species of Tarsonemidae (Acari: Heterostigmata) associated with bark beetles (Coleoptera: Curculionidae: Scolytinae) from Peru.

A new genus and species, Unguitarsonemus paradoxus n. gen., n. sp. and a new species, Pseudotarsonemoides peruviensis n. sp. (Acari: Trombidiformes: Tarsonemidae), are described based on phoretic females collected on bark beetles Phloeotribus pilula and Ph. biguttatus, respectively, from Peru. A key to species of the genus Pseudotarsonemoides is provided.

TD-DFT assessment of UV-vis spectra palladium and platinum complexes with thiols and disulfides.

Time-dependent density functional theory (TD-DFT) and spectrophotometric methods were used for speciation analysis in systems disulfides (cystine, cystamine, homocystine, 3,3-dithiodipropionic acid) - [PdCl4]2- or [PtCl4]2-. We use the M06-2X and CAM-B3LYP density functionals with Def2-SVP basis set to reproduce the experimental UV-vis spectra; the polarized continuum solvation model (PCM) was fitted to take into account solvation effects of the medium (water). Used methods have shown the good agrees with the experiment - theoretical values of transition energies differ from real parameters within ±0.15 eV for functional CAM-B3LYP. Binuclear disulfide complexes of Pd(II) with cystine and cystamine have form S,N-coordination sites, instead of S,S-conformation. It was shown that Pd(II) thiolate complexes formed by cleavage of the disulfide bond exist as [PdCl3L] and [Pd2S2L2]. Pt(II)-disulfide systems have confirmed the presence of [Pt2Cl6(R-SS-R)] and [PtCl4(S-R)] complex species. The DFT/CAM-B3LYP/Def2-SVP/SMD level can be recommended for theoretical estimations of absorption spectra of complexes of palladium or platinum and sulfur-containing ligands.

Influence of Alumina Addition on the Optical Properties and the Thermal Stability of Titania Thin Films and Inverse Opals Produced by Atomic Layer Deposition.

TiO2 thin films deposited by atomic layer deposition (ALD) at low temperatures (<100 °C) are, in general, amorphous and exhibit a smaller refractive index in comparison to their crystalline counterparts. Nonetheless, low-temperature ALD is needed when the substrates or templates are based on polymeric materials, as the deposition has to be performed below their glass transition or melting temperatures. This is the case for photonic crystals generated via ALD infiltration of self-assembled polystyrene templates. When heated up, crystal phase transformations take place in the thin films or photonic structures, and the accompanying volume reduction as well as the burn-out of residual impurities can lead to mechanical instability. The introduction of cation doping (e.g., Al or Nb) in bulk TiO2 parts is known to alter phase transitions and to stabilize crystalline phases. In this work, we have developed low-temperature ALD super-cycles to introduce Al2O3 into TiO2 thin films and photonic crystals. The aluminum oxide content was adjusted by varying the TiO2:Al2O3 internal loop ratio within the ALD super-cycle. Both thin films and inverse opal photonic crystal structures were subjected to thermal treatments ranging from 200 to 1200 °C and were characterized by in- and ex-situ X-ray diffraction, spectroscopic ellipsometry, and spectroscopic reflectance measurements. The results show that the introduction of alumina affects the crystallization and phase transition temperatures of titania as well as the optical properties of the inverse opal photonic crystals (iPhC). The thermal stability of the titania iPhCs was increased by the alumina introduction, maintaining their photonic bandgap even after heat treatment at 900 °C and outperforming the pure titania, with the best results being achieved with the super-cycles corresponding to an estimated alumina content of 26 wt.%.

Tailoring Disorder and Quality of Photonic Glass Templates for Structural Coloration by Particle Charge Interactions.

To obtain high-quality homogeneous photonic glass-based structural color films over large areas, it is essential to precisely control the degree of disorder of the spherical particles used and reduce the crack density within the films as much as possible. To tailor the disorder and quality of photonic glasses, a heteroaggregation-based process was developed by employing two oppositely charged equal-sized polystyrene (PS) particle types. The influence of the particle size ratio on the extent of heteroaggregation in the suspension mixes is investigated and correlated with both the morphology and the resultant optical properties of the films. The results show that the oppositely charged particle size ratio within the mix greatly influences the assembled structure in the films, affecting their roughness, crack density, and the coffee-ring formation. To better differentiate the morphology of the films, scanning electron microscopy images of the microstructures were classified by a supervised training of a deep convolutional neural network model to find distinctions that are inaccessible by conventional image analysis methods. Selected compositions were then infiltrated with TiO2 via atomic layer deposition, and after removal of the PS spheres, surface-templated inverse photonic glasses were obtained. Different color impressions and optical properties were obtained depending on the heteroaggregation level and thus the quality of the resultant films. The best results regarding the stability of the films and suppression of coffee-ring formation are obtained with a 35 wt % positively charged over negatively charged particle mix, which yielded enhanced structural coloration associated with improved film quality, tailored by the heteroaggregation fabrication process.

Structural degradation of tungsten sandwiched in hafnia layers determined by in-situ XRD up to 1520 °C.

The high-temperature stability of thermal emitters is one of the critical properties of thermophotovoltaic (TPV) systems to obtain high radiative power and conversion efficiencies. W and HfO2 are ideal due to their high melting points and low vapor pressures. At high temperatures and given vacuum conditions, W is prone to oxidation resulting in instantaneous sublimation of volatile W oxides. Herein, we present a detailed in-situ XRD analysis of the morphological changes of a 3-layer-system: HfO2/W/HfO2 layers, in a high-temperature environment, up to 1520 °C. These samples were annealed between 300 °C and 1520 °C for 6 h, 20 h, and 40 h at a vacuum pressure below 3 × 10-6 mbar using an in-situ high-temperature X-ray diffractometer, which allows investigation of crucial alterations in HfO2 and W layers. HfO2 exhibits polymorphic behavior, phase transformations and anisotropy of thermal expansion leads to formation of voids above 800 °C. These voids serve as transport channels for the residual O2 present in the annealing chamber to access W, react with it and form volatile tungsten oxides. An activation energy of 1.2 eV is calculated. This study clarifies the limits for the operation of W-HfO2 spectrally selective emitters for TPV in high-temperature applications.

Interaction of Rare-Earth Metals and Some Perfluorinated ß-Diketones.

In this work, we demonstrate the fundamental relationships between stability constants and periodic, acid-base, and structural parameters for complexes of some 1,3-diketones. The four analogues of hexafluoroacetylacetone-2-thenoyltrifluoroacetone, 2-furoyltrifluoroacetone, benzoyltrifluoroacetone, and 2-naphthyltrifluoroacetone-have been studied as chelating ligands for 16 rare-earth metals (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in aqueous solutions. Systems have been investigated spectrophotometrically using a multiwave nonlinear least-squares regression algorithm for data processing. Conditional stability constants were obtained for a wide pH region (2.0-5.4) at constant ionic strength (I = 0.5 M, NaCl). To receive the apparent ("true") equilibrium parameters, acid-base and keto-enol characteristics of the studied ligands have been described and revised for specific conditions. Dissociation constants were obtained in citrate-phosphate buffer media and protonation parameters were received in concentrated hydrochloric acid by the Cox-Yates method. The apparent formation constants for monocomplex species were obtained as thermodynamic invariants (depend only on the temperature) for each ligand and lie from 4.2 to 12.7 logarithmic units. Although the studied ligands have similar values of pKa, the stabilities of their complexes vary considerably. Systematic analysis of 64 apparent stability constants demonstrates that the force of interaction between the metals and nonsymmetric ß-diketones increases as 2-furoyltrifluoroacetone < 2-thenoyltrifluoroacetone < benzoyltrifluoroacetone < 2-naphthyltrifluoroacetone. The studied ligands display varying degrees of the correlation between the periodic parameters and formation constants. Naphthyltrifluoroacetone and its complexes with heavy lanthanides exhibit a clear trend in properties with increasing ionic potential. In general, the received set of data can be described from purely electrostatic grounds within the framework of the periodic law. Spectral, keto-enol, acid-base, and complexing properties were reproduced using density functional theory modeling and explain some of the regularities discovered.