IR-Spectroscopic Study of Complex Formation of Nitrogen Oxides (NO, N2O) with Cationic Forms of Zeolites and the Reactivity of Adsorbed Species in CO and CH4 Oxidation

The formation of complexes and disproportionation of nitrogen oxides (NO, N2O) on cationic forms of LTA, FAU, and MOR zeolites was investigated by diffuse-reflectance IR spectroscopy. N2O is adsorbed on the samples under study in the molecular form and the frequencies of the first overtone of the stretching vibrations ν10–2 and the combination bands of the stretching vibrations with other vibrational modes for N2O complexes with cationic sites in zeolites (ν30–1 + ν10–1, ν10–1 + δ0–2) are more significantly influenced by the nature of the zeolite. The presence of several IR bands in the region of 2400–2600 cm−1 (the ν10–1 + δ0–2 transitions) for different zeolite types was explained by the availability of different localization sites for cations in these zeolites. The frequencies in this region also depend on the nature of the cation (its charge and radius). The data can be explained by the specific geometry of the N2O complex formed, presumably two-point adsorption of N2O on a cation and a neighboring oxygen atom of the framework. Adsorption of CO or CH4 on the samples with preliminarily adsorbed N2O at 20–180 °C does not result in any oxidation of these molecules. NO+ and N2O3 species formed by disproportionation of NO are capable of oxidizing CO and CH4 molecules to CO2, whereas NOx is reduced simultaneously to N2 or N2O. The peculiarities in the behavior of cationic forms of different zeolites with respect to adsorbed nitrogen oxides determined by different density and localization of cations have been established.

RELICS: ICL Analysis of the z = 0.566 Merging Cluster WHL J013719.8–08284

We present a pilot study of the intracluster light (ICL) in massive clusters using imaging of the z = 0.566 cluster of galaxies WHL J013719.8–08284 observed by the RELICS project with the Hubble Space Telescope. We measure the ICL fraction in four optical ACS/WFC filters (F435W, F475W, F606W, and F814W) and five infrared WFC3/IR bands (F105W, F110W, F125W, F140W, and F160W). The ICL maps are calculated using the free-of-a-priori-assumptions algorithm CICLE, and the cluster membership is estimated from photometric properties. We find optical ICL fractions that range between ∼6% and 19%, in nice agreement with the values found in previous works for merging clusters. We also observe an ICL fraction excess between 3800 Å and 4800 Å, previously identified as a signature of merging clusters at 0.18 < z < 0.55. This excess suggests the presence of an enhanced population of young/low-metallicity stars in the ICL. All indicators thus point to WHL J013719.8–08284 as a disturbed cluster with a significant amount of recently injected stars, bluer than the average stars hosted by the cluster members and likely stripped out from infalling galaxies during the current merging event. Infrared ICL fractions are ∼50% higher than optical ones, which could be signatures of an older and/or higher-metallicity ICL population that can be associated with the buildup of the brightest cluster galaxy, passive evolution of previously injected young stars, or preprocessing in infalling groups. Finally, investigating the photometry of the cluster members, we tentatively conclude that WHL J013719.8–08284 fulfills the expected conditions for a fossil system progenitor.

Nitrogen as a Probe Molecule for the IR Studies of the Heterogeneity of OH Groups in Zeolites

One of the methods of IR studies of the heterogeneity of Si–OH–Al groups in zeolites is the investigation of the frequency shift of the band of free OH bands restored upon the adsorption of ammonia and subsequent desorption at increasing temperatures. We extended this method by following the shift of the band of the OH group interacting by hydrogen bonding with nitrogen. The advantage of nitrogen, compared with CO, which has been commonly used as a probe molecule in studies on hydrogen bonding, is that for nitrogen the frequency shift is smaller than for CO and therefore there is no overlapping of shifted OH band with the bands of ammonium ions. For zeolites NaHY, HMFI, and HBEA, the frequency shift of IR bands of both free and hydrogen-bonded Si–OH–Al with the increase of ammonia desorption temperature evidences the heterogeneity of these hydroxyls. On the other hand, in zeolite HFAU of Si/Al = 31, Si–OH–Al were found to be homogeneous. Heterogeneity of OH groups may be explained both by the presence of Si–OH–Al of various number of Al near the bridge and of Si–OH–Al of various geometry.

The Influence of the Ceramic Nanoparticles on the Thermoplastic Polymers Matrix: Their Structural, Optical, and Conductive Properties

This paper prepared composites under the free membranes form that are based on thermoplastic polymers of the type of polyurethane (TPU) and polyolefin (TPO), which are blended in the weight ratio of 2:1, and ceramic nanoparticles (CNs) such as BaSrTiO3 and SrTiO3. The structural, optical, and conductive properties of these new composite materials are reported. The X-ray diffraction studies highlight a cubic crystalline structure of these CNs. The main variations in the vibrational properties of the TPU:TPO blend induced by CNs consist of the following: (i) the increase in the intensity of the Raman line of 1616 cm−1; (ii) the down-shift of the IR band from 800 to 791 cm−1; (iii) the change of the ratio between the absorbance of IR bands localized in the spectral range 950–1200 cm−1; and (iv) the decrease in the absorbance of the IR band from 1221 cm−1. All these variations were correlated with a preferential adsorption of thermoplastic polymers on the CNs surface. A photoluminescence (PL) quenching process of thermoplastic polymers is demonstrated to occur in the presence of CNs. The anisotropic PL measurements have highlighted a change in the angle of the binding of the TPU:TPO blend, which varies from 23.7° to ≈49.3° and ≈53.4°, when the concentration of BaSrTiO3 and SrTiO3 CNs, respectively, is changed from 0 to 25 wt. %. Using dielectric spectroscopy, two mechanisms are invoked to take place in the case of the composites based on TPU:TPO blends and CNs, i.e., one regarding the type of the electrical conduction and another specifying the dielectric–dipolar relaxation processes.

Molecular Details on Multiple Cofactor Containing Redox Metalloproteins Revealed by Infrared and Resonance Raman Spectroscopies

Vibrational spectroscopy and in particular, resonance Raman (RR) spectroscopy, can provide molecular details on metalloproteins containing multiple cofactors, which are often challenging for other spectroscopies. Due to distinct spectroscopic fingerprints, RR spectroscopy has a unique capacity to monitor simultaneously and independently different metal cofactors that can have particular roles in metalloproteins. These include e.g., (i) different types of hemes, for instance hemes c, a and a3 in caa3-type oxygen reductases, (ii) distinct spin populations, such as electron transfer (ET) low-spin (LS) and catalytic high-spin (HS) hemes in nitrite reductases, (iii) different types of Fe-S clusters, such as 3Fe-4S and 4Fe-4S centers in di-cluster ferredoxins, and (iv) bi-metallic center and ET Fe-S clusters in hydrogenases. IR spectroscopy can provide unmatched molecular details on specific enzymes like hydrogenases that possess catalytic centers coordinated by CO and CN− ligands, which exhibit spectrally well separated IR bands. This article reviews the work on metalloproteins for which vibrational spectroscopy has ensured advances in understanding structural and mechanistic properties, including multiple heme-containing proteins, such as nitrite reductases that house a notable total of 28 hemes in a functional unit, respiratory chain complexes, and hydrogenases that carry out the most fundamental functions in cells.

Applications of the Advanced Radiative Transfer Modeling System (ARMS) to Characterize the Performance of Fengyun–4A/AGRI

This study applies the Advanced Radiative Transfer Modeling System (ARMS), which was developed to accelerate the uses of Fengyun satellite data in weather, climate, and environmental applications in China, to characterize the biases of seven infrared (IR) bands of the Advanced Geosynchronous Radiation Imager (AGRI) onboard the Chinese geostationary meteorological satellite, Fengyun–4A. The AGRI data are quality controlled to eliminate the observations affected by clouds and contaminated by stray lights during the mid–night from 1600 to 1800 UTC during spring and autumn. The mean biases, computed from AGRI IR observations and ARMS simulations from the National Center for Environmental Prediction (NCEP) Final analysis data (FNL) as input, are within −0.7–1.1 K (0.12–0.75 K) for all seven IR bands over the oceans (land) under clear–sky conditions. The biases show seasonal variation in spatial distributions at bands 11–13, as well as a strong dependence on scene temperatures at bands 8–14 and on satellite zenith angles at absorption bands 9, 10, and 14. The discrepancies between biases estimated using FNL and the European Center for Medium–Range Weather Forecasts Reanalysis–5 (ERA5) are also discussed. The biases from water vapor absorption bands 9 and 10, estimated using ERA5 over ocean, are smaller than those from FNL. Such discrepancies arise from the fact that the FNL data are colder (wetter) than the ERA5 in the middle troposphere (upper–troposphere).

Molecular structure of fac-[Mo(CO)3(DMSO)3]

The title compound, tricarbonyltris(dimethyl sulfoxide)molybdenum, [Mo(C2H6OS)3(CO)3] or fac-[Mo(CO)3(DMSO)3], crystallizes in the triclinic space group P\overline{1} with two molecules in the unit cell. The geometry around the central molybdenum is slightly distorted octahedral and the facial isomer is found exclusively. The packing within the crystal is stabilized by three-dimensional non-classical intermolecular hydrogen-bonding contacts between individual methyl substituents of dimethyl sulfoxide and the oxygen atoms of either another dimethyl sulfoxide or a carbonyl ligand on adjacent complex molecules. The observed bond lengths in the carbonyl ligands and between carbonyl carbon atoms and molybdenum are correlated to the observed FT–IR bands for the carbonyl stretches and compared to respective metrical parameters of related complexes.

Balancing Heterogeneous Image Quality for Improved Cross-Spectral Face Recognition

Matching infrared (IR) facial probes against a gallery of visible light faces remains a challenge, especially when combined with cross-distance due to deteriorated quality of the IR data. In this paper, we study the scenario where visible light faces are acquired at a short standoff, while IR faces are long-range data. To address the issue of quality imbalance between the heterogeneous imagery, we propose to compensate it by upgrading the lower-quality IR faces. Specifically, this is realized through cascaded face enhancement that combines an existing denoising algorithm (BM3D) with a new deep-learning-based deblurring model we propose (named SVDFace). Different IR bands, short-wave infrared (SWIR) and near-infrared (NIR), as well as different standoffs, are involved in the experiments. Results show that, in all cases, our proposed approach for quality balancing yields improved recognition performance, which is especially effective when involving SWIR images at a longer standoff. Our approach outperforms another easy and straightforward downgrading approach. The cascaded face enhancement structure is also shown to be beneficial and necessary. Finally, inspired by the singular value decomposition (SVD) theory, the proposed deblurring model of SVDFace is succinct, efficient and interpretable in structure. It is proven to be advantageous over traditional deblurring algorithms as well as state-of-the-art deep-learning-based deblurring algorithms.

Multispectral camouflage for infrared, visible, lasers and microwave with radiative cooling

Interminable surveillance and reconnaissance through various sophisticated multispectral detectors present threats to military equipment and manpower. However, a combination of detectors operating in different wavelength bands (from hundreds of nanometers to centimeters) and based on different principles raises challenges to the conventional single-band camouflage devices. In this paper, multispectral camouflage is demonstrated for the visible, mid-infrared (MIR, 3–5 and 8–14 μm), lasers (1.55 and 10.6 μm) and microwave (8–12 GHz) bands with simultaneous efficient radiative cooling in the non-atmospheric window (5–8 μm). The device for multispectral camouflage consists of a ZnS/Ge multilayer for wavelength selective emission and a Cu-ITO-Cu metasurface for microwave absorption. In comparison with conventional broadband low emittance material (Cr), the IR camouflage performance of this device manifests 8.4/5.9 °C reduction of inner/surface temperature, and 53.4/13.0% IR signal decrease in mid/long wavelength IR bands, at 2500 W ∙ m−2 input power density. Furthermore, we reveal that the natural convection in the atmosphere can be enhanced by radiation in the non-atmospheric window, which increases the total cooling power from 136 W ∙ m−2 to 252 W ∙ m−2 at 150 °C surface temperature. This work may introduce the opportunities for multispectral manipulation, infrared signal processing, thermal management, and energy-efficient applications.