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Poly(N,N-diethylacrylamide) (PdEA), one of the thermoresponsive polymers, in aqueous solutions has attracted much attention because of its characteristic properties, such as coil-to-globule (CG) transition. We performed two-dimensional infrared spectroscopy and molecular dynamics (MD) simulations to understand the hydration dynamics in the vicinity of the CG transition at the molecular level via vibrational frequency fluctuations of the carbonyl stretching modes in the side chains of PdEA. Furthermore, N,N-diethylpropionamide, a repeating monomer unit of PdEA, is also investigated for comparison. From decays of the frequency–frequency time correlation functions (FFTCFs) of the carbonyl stretching modes, we consider that inhomogeneity of the hydration environments originates from various backbone configurations of PdEA. The degree of the inhomogeneity depends on temperature. Hydration water molecules near the carbonyl groups are influenced by the confinements of the polymers. The restricted reorientation of the embedded water, the local torsions of the backbone, and the rearrangement of the whole structure contribute to the slow spectral diffusion. By performing MD simulations, we calculated the FFTCFs and dynamical quantities, such as fluctuations of the dihedral angles of the backbone and the orientation of the hydration water molecules. The simulated FFTCFs match well with the experimental results, indicating that the retarded water reorientations via the excluded volume effect play an important role in the vibrational frequency fluctuations of the carbonyl stretching mode. It is also found the embedded water molecules are influenced by the local torsions of the backbone structure within the time scales of the spectral diffusion. [ABSTRACT FROM AUTHOR]

X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, and temperature-programmed reaction/desorption have been employed to investigate the reaction of CH3–CHCl–C(=O)Cl on Cu (100), with the aid of density functional theory (DFT) calculations. Experimentally, CH3–CH=C=O (methylketene) is found to be the product from the dechlorination of CH3–CHCl–C(=O)Cl on Cu(100) at 120 K. The CH3–CH=C=O generated on the surface would dimerize to form 2,4-dimethylcyclobutane-1,3-dione below 180 K. In agreement with the experimental findings, our DFT molecular dynamics simulations demonstrate that the dechlorination of CH3–CHCl–C(=O)Cl, resulting in CH3–CH=C=O and two Cl atoms, occurs readily, completing within 0.6 ps at 300 K. The simulations also indicate that the cleavage of the CH–Cl bond precedes that of the C(=O)–Cl bond. The static DFT calculations suggest that the dimerization of CH3–CH=C=O primarily occurs through the coupling of two C=C bonds, which has a lower barrier of 38.08 kJ mol−1 compared to the 69.05 kJ mol−1 barrier for C=C + C=O coupling. [ABSTRACT FROM AUTHOR]

Vibrational spectroscopy of protein structure often utilizes 13C18O-labeling of backbone carbonyls to further increase structural resolution. However, sidechains such as arginine, aspartate, and glutamate absorb within the same spectral region, complicating the analysis of isotope-labeled peaks. In this study, we report that the waiting time between pump and probe pulses in two-dimensional infrared spectroscopy can be used to suppress sidechain modes in favor of backbone amide I′ modes based on differences in vibrational lifetimes. Furthermore, differences in the lifetimes of 13C18O-amide I′ modes can aid in the assignment of secondary structure for labeled residues. Using model disordered and β-sheet peptides, it was determined that while β-sheets exhibit a longer lifetime than disordered structures, amide I′ modes in both secondary structures exhibit longer lifetimes than sidechain modes. Overall, this work demonstrates that collecting 2D IR data at delayed waiting times, based on differences in vibrational lifetime between modes, can be used to effectively suppress interfering sidechain modes and further identify secondary structures. [ABSTRACT FROM AUTHOR]

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN−) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN− binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S–C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency–frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Finally, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs. [ABSTRACT FROM AUTHOR]

The supra-molecular structure of a liquid is strongly connected to its dynamics, which in turn control macroscopic properties such as viscosity. Consequently, detailed knowledge about how this structure changes with temperature is essential to understand the thermal evolution of the dynamics ranging from the liquid to the glass. Here, we combine infrared spectroscopy (IR) measurements of the hydrogen (H) bond stretching vibration of water with molecular dynamics simulations and employ a quantitative analysis to extract the inter-molecular H-bond length in a wide temperature range of the liquid. The extracted expansivity of this H-bond differs strongly from that of the average nearest neighbor distance of oxygen atoms obtained through a common conversion of mass density. However, both properties can be connected through a simple model based on a random loose packing of spheres with a variable coordination number, which demonstrates the relevance of supra-molecular arrangement. Furthermore, the exclusion of the expansivity of the inter-molecular H-bonds reveals that the most compact molecular arrangement is formed in the range of ∼ 316 − 331 K (i.e., above the density maximum) close to the temperature of several pressure-related anomalies, which indicates a characteristic point in the supra-molecular arrangement. These results confirm our earlier approach to deduce inter-molecular H-bond lengths via IR in polyalcohols [Gabriel et al. J. Chem. Phys. 154, 024503 (2021)] quantitatively and open a new alley to investigate the role of inter-molecular expansion as a precursor of molecular fluctuations on a bond-specific level. [ABSTRACT FROM AUTHOR]

Ethane ( C 2 H 6 ) is anticipated to be the most stable compound within the carbon–hydrogen system under the 100 GPa pressure range. Nevertheless, the properties of ethane under pressure are still poorly documented. Here, we present a comprehensive study of the structural and vibrational properties of C 2 H 6 in a diamond anvil cell at pressures up to 150 GPa. To obtain detailed data, ethane single-crystal was grown in a helium pressure-transmitting medium. Utilizing single-crystal x-ray diffraction, the distortion mechanism between the tetragonal and monoclinic phases, occurring over the 3.2–5.2 GPa pressure range, is disclosed. Subsequently, no phase transition is observed up to 150 GPa. The accurately measured compression curve is compared to various computational approximations. The vibrational modes measured by Raman spectroscopy and infrared absorption are well identified, and their evolution is well reproduced by ab initio calculations. In particular, an unusual anticrossing phenomenon occurs near 40 GPa between a rocking and a stretching mode, likely attributable to intermolecular interactions through hydrogen bonding. [ABSTRACT FROM AUTHOR]

Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work, isomers of C3H4+ were produced upon electron ionization of propyne and allene molecules and interrogated via infrared spectroscopy inside He nanodroplet matrices. It was found that the spectrum of C3H4+ has at least three distinct groups of bands. The relative intensities of the bands depend on the precursor employed and its pickup pressure, which indicates the presence of at least three different isomers. Two isomers were identified as allene and propyne radical cations. The third isomer, which has several new bands in the range of 3100–3200 cm−1, may be the elusive vinylmethylene H2C=CH–CH+ radical cation. The observed bands for the allene and propyne cations are in good agreement with the results of density functional theory calculations. However, there is only moderate agreement between the new bands and the theoretically calculated vinylmethylene spectrum, which indicates more work is necessary to unambiguously assign it. [ABSTRACT FROM AUTHOR]

Small molecule inhibitors (SMIs) have been gaining attention in the field of area-selective atomic layer deposition (ALD) because they can be applied in the vapor-phase. A major challenge for SMIs is that vapor-phase application leads to a disordered inhibitor layer with lower coverage as compared to self-assembled monolayers, SAMs. A lower coverage of SMIs makes achieving high selectivity for area-selective ALD more challenging. To overcome this challenge, mechanistic understanding is required for the formation of SMI layers and the resulting precursor blocking. In this study, reflection adsorption infrared spectroscopy measurements are used to investigate the performance of aniline as an SMI. Our results show that aniline undergoes catalytic surface reactions, such as hydrogenolysis, on a Ru non-growth area at substrate temperatures above 250 °C. At these temperatures, a greatly improved selectivity is observed for area-selective TaN ALD using aniline as an inhibitor. The results suggest that catalytic surface reactions of the SMI play an important role in improving precursor blocking, likely through the formation of a more carbon-rich inhibitor layer. More prominently, catalytic surface reactions can provide a new strategy for forming inhibitor layers that are otherwise very challenging or impossible to form directly through vapor-phase application. [ABSTRACT FROM AUTHOR]

An IR–vacuum ultraviolet (VUV) ion-dip spectroscopy method is utilized to examine the IR spectrum of acetaldehyde oxide (CH3CHOO) in the overtone CH stretch (2νCH) spectral region. IR activation creates a depletion of the ground state population that reduces the VUV photoionization signal on the parent mass channel. IR activation of the more stable and populated syn-CH3CHOO conformer results in rapid unimolecular decay to OH + vinoxy products and makes the most significant contribution to the observed spectrum. The resultant IR–VUV ion-dip spectrum of CH3CHOO is similar to that obtained previously for syn-CH3CHOO using IR action spectroscopy with UV laser-induced fluorescence detection of OH products. The prominent IR features at 5984 and 6081 cm−1 are also observed using UV + VUV photoionization of OH products. Complementary theoretical calculations utilizing a general implementation of second-order vibrational perturbation theory provide new insights on the vibrational transitions that give rise to the experimental spectrum in the overtone CH stretch region. The introduction of physically motivated small shifts of the harmonic frequencies yields remarkably improved agreement between experiment and theory in the overtone CH stretch region. The prominent features are assigned as highly mixed states with contributions from two quanta of CH stretch and/or a combination of CH stretch with an overtone in mode 4. The generality of this approach is demonstrated by applying it to three different levels of electronic structure theory/basis sets, all of which provide spectra that are virtually indistinguishable despite showing large deviations prior to introducing the shifts to the harmonic frequencies. [ABSTRACT FROM AUTHOR]

Small anionic nickel clusters with ethanol are investigated with a combination of mass-selective infrared photodissociation spectroscopy in a molecular beam and density functional theory simulations at the BLYP/6-311g(d,p) and TPSSh/def2-TZVPP level. In this context, the O–H stretching vibration of the ethanol is analyzed to obtain information about the structural motif, the geometry of the metal core, and the spin state of the clusters. For the [Ni2(EtOH)]− and [Ni3(EtOH)]− clusters, we assign quartet states of motifs with a hydrogen bond from the ethanol to the linear nickel core. The aggregation of a further ethanol molecule, yielding the [Ni3(EtOH)2]− cluster, results in the formation of a cooperative hydrogen bond network between the nickel core and the two ethanol molecules. [ABSTRACT FROM AUTHOR]

The gas-phase rotational spectrum from 8 to 750 GHz and the high-resolution infrared (IR) spectrum of pyridazine (o-C4H4N2) have been analyzed for the ground and four lowest-energy vibrationally excited states. A combined global fit of the rotational and IR data has been obtained using a sextic, centrifugally distorted-rotor Hamiltonian with Coriolis coupling between appropriate states. Coriolis coupling has been addressed in the two lowest-energy coupled dyads (ν16, ν13 and ν24, ν9). Utilizing the Coriolis coupling between the vibrational states of each dyad and the analysis of the IR spectrum for ν16 and ν9, we have determined precise band origins for each of these fundamental states: ν16 (B1) = 361.213 292 7 (17) cm−1, ν13 (A2) = 361.284 082 4 (17) cm−1, ν24 (B2) = 618.969 096 (26) cm−1, and ν9 (A1) = 664.723 378 4 (27) cm−1. Notably, the energy separation in the ν16-ν13 Coriolis-coupled dyad is one of the smallest spectroscopically measured energy separations between vibrational states: 2122.222 (72) MHz or 0.070 789 7 (24) cm−1. Despite ν13 being IR inactive and ν24 having an impractically low-intensity IR intensity, the band origins of all four vibrational states were measured, showcasing the power of combining the data provided by millimeter-wave and high-resolution IR spectra. Additionally, the spectra of pyridazine-dx isotopologues generated for a previous semi-experimental equilibrium structure (reSE) determination allowed us to analyze the two lowest-energy vibrational states of pyridazine for all nine pyridazine-dx isotopologues. Coriolis-coupling terms have been measured for analogous vibrational states across seven isotopologues, both enabling their comparison and providing a new benchmark for computational chemistry. [ABSTRACT FROM AUTHOR]

Functionalization of perovskite nanocrystal surfaces with thiocyanate anions presents a transformative approach to enhancing stability and photoluminescence quantum yield (PLQY) through surface defect passivation. This study investigates the role of thiocyanate ligands in modifying the optoelectronic properties of CsPbBr3 nanocrystals. We employed ultrafast two-dimensional infrared spectroscopy to investigate the nature of the dynamic interaction of thiocyanate ligands with nanocrystal surfaces, providing insights into the mechanisms underlying the observed increase in PLQY and stability. Our analysis reveals that the thiocyanate ligands efficiently passivate the surface defects, thereby enhancing the PLQY and the stability of the treated nanocrystals. The spectroscopic evidence supports a model where thiocyanate binds to under-coordinated lead atoms, contributing to a stable nanocrystal surface with enhanced optoelectronic performance. This ligand-induced passivation mechanism advances our understanding of surface chemistry's role in optimizing nanomaterials for solar cell and LED applications. [ABSTRACT FROM AUTHOR]

Fluorescence-encoded infrared (FEIR) spectroscopy is a recently developed technique for solution-phase vibrational spectroscopy with detection sensitivity at the single-molecule level. While its spectroscopic information content and important criteria for its practical experimental optimization have been identified, a general understanding of the electronic and nuclear properties required for highly sensitive detection, i.e., what makes a molecule a "good FEIR chromophore," is lacking. This work explores the molecular factors that determine FEIR vibrational activity and assesses computational approaches for its prediction. We employ density functional theory (DFT) and its time-dependent version (TD-DFT) to compute vibrational and electronic transition dipole moments, their relative orientation, and the Franck–Condon factors involved in FEIR activity. We apply these methods to compute the FEIR activities of normal modes of chromophores from the coumarin family and compare these predictions with experimental FEIR cross sections. We discuss the extent to which we can use computational models to predict the FEIR activity of individual vibrations in a candidate molecule. The results discussed in this work provide the groundwork for computational strategies for choosing FEIR vibrational probes or informing the structure of designer chromophores for single-molecule spectroscopic applications. [ABSTRACT FROM AUTHOR]

β-Ga2O3 is an ultrawide bandgap semiconductor that is attracting much attention for applications in next-generation high-power, deep UV, and extreme-environment devices. Hydrogen impurities have been found to have a strong effect on the electrical properties of β-Ga2O3. This Tutorial is a survey of what has been learned about O–H centers in β-Ga2O3 from their vibrational properties. More than a dozen, O–H centers have been discovered by infrared absorption spectroscopy. Theory predicts defect structures with H trapped at split configurations of a Ga(1) vacancy that are consistent with the isotope and polarization dependence of the O–H vibrational spectra that have been measured by experiment. Furthermore, O–H centers in β-Ga2O3 have been found to evolve upon thermal annealing, giving defect reactions that modify conductivity. While much progress has been made toward understanding the microscopic properties and reactions of O–H centers in β-Ga2O3, many questions are discussed that remain unanswered. A goal of this Tutorial is to inspire future research that might solve these puzzles. [ABSTRACT FROM AUTHOR]

We describe Reflection Absorption Infrared Spectroscopy (RAIRS) and first-principles Density Functional Theory (DFT) studies of ammonia adsorption on the Cu{311} surface. Our experimental results indicate an upright chemisorbed species at low coverages, with at least one additional species accompanying this at higher coverages. Our high-coverage RAIRS data cannot be fully explained by DFT models containing only ammonia or its dissociation products, even allowing for molecular tilt and/or the formation of a bilayer. We therefore also consider urea and formamide as possible products of surface reaction with residual carbon monoxide, but these species are again not fully compatible with our observed spectra. The overlayer composition at high coverages remains mysterious. [ABSTRACT FROM AUTHOR]

Doubly resonant sum frequency generation (DR-SFG) serves as a potent characteristic technique for probing the electronic spectra and vibronic coupling of molecules on surfaces. In this study, we successfully developed a novel infrared (IR)–white light (WL) DR-SFG spectroscopy based on narrowband IR and tunable broadband WL. This novel method was employed to explore the excitation spectrum and vibronic couplings of sub-monolayer Rhodamine 6G molecules. Our findings elucidate that the xanthene skeleton vibrational modes exhibit strong coupling with the S0–S1 electronic transition. Notably, we observed not only the 0–0 transition of the S0–S1 electronic continuum but also the 0–1 transition, a first time observation in the realm of DR-SFG spectroscopy. This advanced DR-SFG spectroscopy methodology facilitates a more sensitive examination of electronic spectra and the coupling between electronic transitions and vibrational modes, heralding a significant advancement in the understanding of molecular interactions on surfaces. [ABSTRACT FROM AUTHOR]

The α-hydroxyethyl radical (CH3·CHOH, 2A) is a key intermediate in ethanol biochemistry, combustion, atmospheric chemistry, radiation chemistry, and astrochemistry. Experimental data on the vibrational spectrum of this radical are crucially important for reliable detection and understanding of the chemical dynamics of this species. This study represents the first detailed experimental report on the infrared absorption bands of the α-hydroxyethyl radical complemented by ab initio computations. The radical was generated in solid para-H2 and Xe matrices via the reactions of hydrogen atoms with matrix-isolated ethanol molecules and radiolysis of isolated ethanol molecules with x rays. The absorption bands with maxima at 3654.6, 3052.1, 1425.7, 1247.9, 1195.6 (1177.4), and 1048.4 cm−1, observed in para-H2 matrices appearing upon the H· atom reaction, were attributed to the OHstr, α-CHstr, CCstr, COstr + CCObend, COstr, and CCstr + CCObend vibrational modes of the CH3·CHOH radical, respectively. The absorption bands with the positions slightly red-shifted from those observed in para-H2 were detected in both the irradiated and post-irradiation annealed Xe matrices containing C2H5OH. The results of the experiments with the isotopically substituted ethanol molecules (CH3CD2OH and CD3CD2OH) and the quantum-chemical computations at the UCCSD(T)/L2a_3 level support the assignment. The photolysis with ultraviolet light (240–300 nm) results in the decay of the α-hydroxyethyl radical, yielding acetaldehyde and its isomer, vinyl alcohol. A comparison of the experimental and theoretical results suggests that the radical adopts the thermodynamically more stable anti-conformation in both matrices. [ABSTRACT FROM AUTHOR]

Fluorescence-encoded infrared (FEIR) spectroscopy is an emerging technique for performing vibrational spectroscopy in solution with detection sensitivity down to single molecules. FEIR experiments use ultrashort pulses to excite a fluorescent molecule's vibrational and electronic transitions in a sequential, time-resolved manner, and are therefore sensitive to intervening vibrational dynamics on the ground state, vibronic coupling, and the relative orientation of vibrational and electronic transition dipole moments. This series of papers presents a theoretical treatment of FEIR spectroscopy that describes these phenomena and examines their manifestation in experimental data. This first paper develops a nonlinear response function description of Fourier-transform FEIR experiments for a two-level electronic system coupled to multiple vibrations, which is then applied to interpret experimental measurements in the second paper [L. Whaley-Mayda et al., J. Chem. Phys. 159, 194202 (2023)]. Vibrational coherence between pairs of modes produce oscillatory features that interfere with the vibrations' population response in a manner dependent on the relative signs of their respective Franck–Condon wavefunction overlaps, leading to time-dependent distortions in FEIR spectra. The orientational response of population and coherence contributions are analyzed and the ability of polarization-dependent experiments to extract relative transition dipole angles is discussed. Overall, this work presents a framework for understanding the full spectroscopic information content of FEIR measurements to aid data interpretation and inform optimal experimental design. [ABSTRACT FROM AUTHOR]

Developing fluorescence-encoded infrared (FEIR) vibrational spectroscopy for single-molecule applications requires a detailed understanding of how the molecular response and external experimental parameters manifest in the detected signals. In Paper I [L. Whaley-Mayda, A. Guha, and A. Tokmakoff, J. Chem. Phys. 159, 194201 (2023)] we introduced a nonlinear response function theory to describe vibrational dynamics, vibronic coupling, and transition dipole orientation in FEIR experiments with ultrashort pulses. In this second paper, we apply the theory to investigate the role of intermode vibrational coherence, the orientation of vibrational and electronic transition dipoles, and the effects of finite pulse durations in experimental measurements. We focus on measurements at early encoding delays—where signal sizes are largest and therefore of most value for single-molecule experiments, but where many of these phenomena are most pronounced and can complicate the appearance of data. We compare experiments on coumarin dyes with finite-pulse response function simulations to explain the time-dependent behavior of FEIR spectra. The role of the orientational response is explored by analyzing polarization-dependent experiments and their ability to resolve relative dipole angles in the molecular frame. This work serves to demonstrate the molecular information content of FEIR experiments, and develop insight and guidelines for their interpretation. [ABSTRACT FROM AUTHOR]

Phenylpropiolic acid (C6H5C≡CCOOH, PPA) isolated in nitrogen and xenon cryogenic matrices was studied by infrared spectroscopy. The experimental studies were complemented by a series of quantum chemical calculations carried out at the density functional theory (B3LYP) and MP2 levels of theory (with different basis sets). The calculations predicted the existence of two planar PPA conformers, differing in the arrangement of the carboxylic group. The higher-energy trans-PPA conformer has a negligible population in the gas phase at room temperature and was prepared in situ in the N2 cryomatrix through vibrationally-induced rotamerization of the lower-energy cis-PPA conformer, achieved using selective narrowband infrared excitation of the OH stretching coordinate of the latter species. Broadband UV (λ > 235 nm) irradiation of matrix-isolated cis-PPA was also undertaken, leading to the observation of cis-PPA → trans-PPA isomerization. No other UV-induced photoreactions were observed. The in situ generated trans-PPA conformer was found to decay back to cis-PPA in the dark by tunneling, and its lifetimes under different experimental conditions were determined. The assignment of the infrared spectra of both conformers is presented, considerably extending the vibrational information available on this molecule. [ABSTRACT FROM AUTHOR]

We present an IR-PD study of tantalum cluster adsorbate complexes [Tan(N2)m]+, abbreviated (n,m), n = 5–8. We utilize infrared spectroscopy of isolated and size selected clusters as prepared and characterized by a cryogenic tandem ion trap setup, and we augment our experiments with quantum chemical simulations at the level of density functional theory. The cluster adsorbate complexes (n,m) reveal vibrational bands above 2000 cm−1, which indicate end-on coordinated μ1-N2 oscillators, and bands below 2000 cm−1, which indicate side-on μ2-κN:κN,N coordinated ones. We observe a general increase in spectral complexity and an inhomogeneous broadening, mainly towards the red, at certain points of N2 loading m, which originates from an increasingly higher amount of double and triple N2 coordination at Ta sites, eventually at all of them. Other than the small tantalum clusters Tan+, n = 2–4, the IR-PD spectra of the initial N2 adsorbate species (n,1), n = 5–8, provide strong evidence for a lack of spontaneous N2 cleavage. Spontaneous N2 cleavage by Tan+, n = 5–8, seems suppressed. Therefore, the ability of a small Ta cluster to cleave dinitrogen disappears with one more tantalum core atom. The study of stepwise N2 adsorption on size selected Tan+, n = 5–8 clusters revealed adsorption limits m(max) of [Tan(N2)m]+ that are independent of cluster size within this size range. Cryo-adsorption kinetics at 26 K allowed for kinetic fits to consecutive N2 adsorption steps, and the fits revealed significant N2 desorption rates upon higher N2 loads, and the cluster adsorbate complexes eventually reached equilibrium. Some enhanced N2 desorption rates point towards likely adsorbate shell reorganization, and there is also some evidence for the coexistence of isomeric cluster adsorbate complexes. [ABSTRACT FROM AUTHOR]

We present an IR-PD study of tantalum cluster adsorbate complexes [Tan(N2)m]+, abbreviated (n,m), n = 5–8. We utilize infrared spectroscopy of isolated and size selected clusters as prepared and characterized by a cryogenic tandem ion trap setup, and we augment our experiments with quantum chemical simulations at the level of density functional theory. The cluster adsorbate complexes (n,m) reveal vibrational bands above 2000 cm−1, which indicate end-on coordinated μ1-N2 oscillators, and bands below 2000 cm−1, which indicate side-on μ2-κN:κN,N coordinated ones. We observe a general increase in spectral complexity and an inhomogeneous broadening, mainly towards the red, at certain points of N2 loading m, which originates from an increasingly higher amount of double and triple N2 coordination at Ta sites, eventually at all of them. Other than the small tantalum clusters Tan+, n = 2–4, the IR-PD spectra of the initial N2 adsorbate species (n,1), n = 5–8, provide strong evidence for a lack of spontaneous N2 cleavage. Spontaneous N2 cleavage by Tan+, n = 5–8, seems suppressed. Therefore, the ability of a small Ta cluster to cleave dinitrogen disappears with one more tantalum core atom. The study of stepwise N2 adsorption on size selected Tan+, n = 5–8 clusters revealed adsorption limits m(max) of [Tan(N2)m]+ that are independent of cluster size within this size range. Cryo-adsorption kinetics at 26 K allowed for kinetic fits to consecutive N2 adsorption steps, and the fits revealed significant N2 desorption rates upon higher N2 loads, and the cluster adsorbate complexes eventually reached equilibrium. Some enhanced N2 desorption rates point towards likely adsorbate shell reorganization, and there is also some evidence for the coexistence of isomeric cluster adsorbate complexes. [ABSTRACT FROM AUTHOR]

The structure and dynamics of water on solid surfaces critically affect the chemistry of materials in ambient and aqueous environments. Here, we investigate the hydrogen bonding network of water adsorbed on the majority (101) surface of anatase TiO2, a widely used photocatalyst, using polarization- and azimuth-resolved infrared spectroscopy combined with neural network potential molecular dynamics simulations. Our results show that one monolayer of water saturates the undercoordinated titanium (Ti5c) sites, forming one-dimensional chains of molecule hydrogen bonded to surface undercoordinated bridging oxygen (O2c) atoms. As the coverage increases, water adsorption on O2c sites leads to significant restructuring of the water monolayer and the formation of a two-dimensional hydrogen bond network characterized by tightly bound pairs of water molecules on adjacent Ti5c and O2c sites. This structural motif likely persists at ambient conditions, influencing the reactions occurring there. The results reported here provide critical details of the structure of the water–anatase (101) interface that were previously hypothesized but unconfirmed experimentally. [ABSTRACT FROM AUTHOR]

Cellulose diacetate (CDA) and triacetate (CTA) were derived from Egyptian cotton to fabricate reverse osmosis (RO) membranes. The Pphase inversion method was utilized for the production of CDA-based membranes. Comprehensive characterization of these membranes involved structural, morphologial, and hydrophilic property analyses through techniques such as nuclear magnetic resonance (NMR), infrared spectroscopy, thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle measurements. NMR spectra indicated a degree of substitution of 2.9 for CTA and 2 for CDA. The resulting RO membrane demonstrated a water flux of 6.1 L/[m.sup.2]*h and a salt rejection of 90.3%. Annealing led to an enhanced top layer with reduced defects and macrovoids in the support layer. Moreover, grafting the RO membranes with 15 wt% of 2-acrylamidopropane-2-methyl sulphonic acid improved salt rejection to 96.2% and water flux to 8.7 L/[m.sup.2]*h. These findings underscore the significant performance enhancements achieved through both annealing and grafting processes in RO membranes. KEYWORDS cellulose triacetate acetate, cotton, desalination, phase inversion, sustainable, 1 | INTRODUCTION The issue of water scarcity has reached a critical level in Egypt, where per capita water availability is diminishing. (1) Additionally, the undervaluation of Egyptian cotton compounds [...]

In this paper, a series of novel trans-1, 4-polyisoprene/isotactic polybutene (TPI/iPB) in-reactor blends were synthesized by isoprene and butene sequential two-stage polymerization technology with spherical Ti[Cl.sub.4]/Mg[Cl.sub.2] type Ziegler-Natta catalyst. The components, structures, and properties of the asobtained TPI/iPB reactor blends were characterized by gel permeation chromatography, Fourier transform Infrared spectroscopy, and differential scanning calorimetry. The active trans-1, 4-polyisoprene (TPI) particles obtained in the initial isoprene polymerization by the Z-N catalyst can be acted as microreactors to initiate butene polymerization subsequently. The TPI/iPB reactor blends with varied components were in situ synthesized within the reactor. The preparative-temperature rising elution fractionation (p-TREF) technique was used to fractionate the TPI/iPB reactor blends based on the elution temperature ranged from -40[degrees]C to 90[degrees]C. The weight distribution and microstructure of each fraction were investigated. The reactor blends are composed of crystallizable high trans-1, 4-uint polyisoprene obtained from the first-stage isoprene polymerization, high isotactic polybutene obtained from the secondstage butene polymerization and TPI-b-iPB block copolymer with different sequence structure obtained from the initial time of the second stage. This work is expected to propose the possible polymerizations of a-olefins and conjugated dienes by using heterogeneous Ziegler-Natta catalyst and provide a kind of novel rubber/plastic reactor blend materials. Highlights * The first synthesis of the trans-1,4-polyisoprene/isotactic polybutene reactor blends. * p-TREF technique was used to analyze the composition of TPI/iPB reactor blends. * Detailed structure characterization of the fractions including GPC and NMR * TPI-b-iPB block copolymer can be obtained through the sequential polymerization. * Rubber/plastic reactor blend materials were fabricated by the Z-N catalyst. KEYWORDS 4-polyisoprene, in-reactor blends, polybutene, temperature rising elution fractionation, trans-1, Ziegler-Natta catalyst, 1 | INTRODUCTION The discovery of Ziegler-Natta catalysts has been one of the greatest developments in the synthesis of stereospecific polymers in both academy and modern industry. (1-4) The first [...]

In order to better understand the hydrolysis and pyrolysis process of polylactic acid (PLA), we carried out in-situ experiments by observing the decomposition process of PLA at high temperature (up to 285[degrees]C) in both aqueous and anhydrous environments through fused silica capillary reactor (FSCR) combined with Raman spectroscopy analysis. By analyzing the strength change of characteristic peaks of PLA with increasing temperature, it was found that the initial melting temperature of PLA, in both the hydrolysis and pyrolysis processes, is around 170[degrees]C. Based on infrared spectroscopy analysis, it was found that the products of PLA pyrolysis are C[O.sub.2], C[H.sub.3]CH=C=O, and C[H.sub.3]CHO, indicating that the pyrolysis process of PLA results from a free radical reaction. By comparing the Raman peak area ratios at different peak positions at different temperatures, it was found that the hydrolysis process of PLA mainly involves breaking the COC and CCO bonds of PLA, producing lactic acid, ethanol, C[O.sub.2], and [H.sub.2]O. The hydrolysis reaction rate of PLA increases with the increase of temperature and exhibits a slow-fast-slow S-shaped trend. The kinetic process of hydrolysis of PLA was well described using the Logistic model. The activation energy for the hydrolysis (Q) of PLA is 18.1 kcal*[mol.sup.-1] in the temperature range of 250-285[degrees]C. The results of this study provide important insights and crucial parameters for the production and application of PLA. KEYWORDS activation energy, fused silica capillary reactor, hydrolysis, polylactic acid, pyrolysis, Raman spectrum Highlights * Determined the melting temperature of PLA by in-situ experiments. * For the hydrolysis process of PLA, the reaction rate and activation energy were quantified by fitting experimental data. * Gained valuable insights into the hydrolysis and pyrolysis mechanisms of PLA., 1 | INTRODUCTION With growing concern for sustainable development, there has been an increased focus on biodegradable polymers as alternatives to synthetic plastics. Polylactic acid (PLA), typically derived from agricultural [...]

Biopolymer blend nanocomposite films composed of polyvinyl alcohol (PVA) and chitosan (CS) with varying quantities of hydroxyapatite (HA) nanoparticles were developed using a green solution casting method. The formation of blend nanocomposite was confirmed by Fourier-transform infrared spectroscopy (FTIR), ultraviolet-visible (UV) spectrometer, field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Mechanical parameters such as tensile strength, percentage elongation at break, hardness, dielectric constant, and temperature-dependent alternating current (AC) conductivity were analyzed. The bonding between the nanoparticles and PVA/CS blend was verified by the shift in distinctive peaks of blend in the nanocomposites to a higher wavenumber in the FTIR spectra. The UV spectra demonstrated the difference in absorbance and transmittance of the PVA/CS blend with the reinforcement of HA nanofillers. The bandgaps of the nanocomposites marginally decreased with an increase in nanoparticle loading. The SEM and XRD patterns revealed the ordered arrangement of the blend matrix due to the presence of nanoparticles. The assessment of thermal characteristics obtained from DSC and TGA demonstrated a clear increase in phase transition temperature and thermal stability of nanocomposites. The electrical conductivity measurement indicated a rise in dielectric constant and AC conductivity of blend nanocomposites with the addition of nanoparticles. The temperature-dependent AC conductivity showed a reduction in activation energy as temperature and nanoparticle loading increased. The tensile strength and surface hardness of the PVA/CS blend nanocomposite increased with the dosage of HA content in the blend matrix. Highlights * A series of polyvinyl alcohol (PVA)/chitosan (CS)/hydroxyapatite (HA) nanocomposites were prepared by the green method * Enhanced optical property, thermal stability, and glass transition temperature * Possess excellent dielectric constant and alternating current conductivity * The inclusion of HA increased the mechanical strength of the PVA/CS blend * A potential blend nanocomposite for flexible optoelectronic and charge storage devices. KEYWORDS AC conductivity, chitosan, crystallinity, dielectric constant, hydroxyapatite, polyvinyl alcohol, tensile strength, thermal properties, 1 | INTRODUCTION In recent years, many additional breakthroughs have been achieved to reduce environmental threats and crises. The development of economically and environmentally friendly polymers and their enhanced production [...]

Composites of carbon-graphene nanoplatelets (GNP) epoxy with nylon-66 interleaving were fabricated and investigated to understand the impact of [gamma]-irradiation on their dielectrics and relative humidity (RH) sensitivity by capacitance and water absorption measurements. The moisture sensitivity was investigated by measuring memory effect (hysteresis) and response time of the capacitance. Composites were [gamma]-irradiated at doses of 1000 and 3000 kGy and studied by the same set of measurements. X-ray diffraction analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy were used to understand the impact of [gamma]-irradiation on the morphology and surface roughness of the composites. Results of these measurements suggest that 3000-kGy dose [gamma]-irradiation produces good chain scission and cross-linking, resulting in reduced water absorption and a 360% increase in capacitance values. The sensitivity of capacitance for 3000-kGy [gamma]-irradiated composite was found to be highest at 40 pF/%RH, and hysteresis was 1.8% RH and not observed in non-irradiated composites. Based on these observations, it seems that 3000-kGy [gamma]-irradiated composite could be a potential candidate for moisture content diagnostics during condition monitoring of the carbon-epoxy structures in several industrial applications and needs to be further investigated. Highlights * Composites of carbon-GNP epoxy with nylon-66 interleaving were [gamma]-irradiated. * 3000-kGy dose [gamma]-irradiated composites exhibit 360% increase in capacitance. * Sensitivity and hysteresis were higher than those of 1000-kGy and non-irradiated samples. * Good chain scission and cross-linking resulted in reduced water absorption. KEYWORDS dielectrics, nylon-carbon-GNP epoxy composites, RH sensitivity, [gamma]-irradiation, 1 | INTRODUCTION Carbon-epoxy composites are widely used in structural applications due to superior mechanical properties, resistance to corrosion, and ease of manufacture compared to metals. In many structural applications [...]

We wrap up our discussion of the mid-infrared (mid-IR) spectra of inorganic compounds by looking at the spectra of silicates, nitrates, and phosphates. We see that silicates have complex surface [...]

β-Ga2O3 has attracted much recent attention as a promising ultrawide bandgap semiconductor. Hydrogen can affect the conductivity of β-Ga2O3 through the introduction of shallow donors and the passivation of deep acceptors. The introduction of H or D into β-Ga2O3 by annealing in an H2 or D2 ambient at elevated temperature produces different classes of O–H or O–D centers. This work is a study of the interaction of D with V Ga 1 and V Ga 2 deep acceptors as well as other impurities and native defects in Ga2O3 by infrared spectroscopy and the complementary theory. (We focus primarily on the deuterium isotope of hydrogen because the vibrational modes of O–D centers can be detected with a higher signal-to-noise ratio than those of O–H.) O–D centers in β-Ga2O3 evolve upon annealing in an inert ambient and are transformed from one type of O–D center into another. These reactions affect the compensation of unintentional shallow donors by deep acceptors that are passivated by D. Defects involving additional impurities in β-Ga2O3 compete with V Ga deep acceptors for D and modify the deuterium-related reactions that occur. The defect reactions that occur when D is introduced by annealing in a D2 ambient appear to be simpler than those observed for other introduction methods and provide a foundation for understanding the D-related reactions that can occur in more complicated situations. [ABSTRACT FROM AUTHOR]

BACKGROUND: Buffalo milk, constituting 15% of global production, has higher fatty acids content than Holstein milk. Fourier‐transform mid‐infrared (FT‐MIR) spectroscopy is widely used for dairy analysis, but its application to buffalo milk, with larger fat globules, remains understudied. The ultimate goal of this study is to develop machine learning models based on FT‐MIR spectroscopy for predicting fatty acids in buffalo milk and to assess the accuracy of commercial milk analyzers. This research provides a convenient, fast, and environmentally friendly method for detecting the fatty acid composition in buffalo milk. RESULTS: We employed six machine learning algorithms to establish a detection model for 34 fatty acids in buffalo milk. The predictive models demonstrated robust capabilities for high‐content fatty acids [C14:0, C15:0, C16:0, C17:0, C18:0, C18:1, saturated fatty acid (SFA), monounsaturated fatty acid (MUFA)], with errors within a 15% range. Traditional FT6000 detection methods exhibited limitations in measuring SFAs and polyunsaturated fatty acids (PUFA). Implementing a mean difference correction of 0.21 for MUFAs and applying regression equations (SFA × 1.0639 + 0.0705; PUFA × 0.5472 + 0.0047) significantly improved measurement accuracy. CONCLUSION: This study successfully developed a predictive model for fatty acids in Mediterranean buffalo milk based on FT‐MIR spectroscopy. Additionally, a correction was applied to the existing measurement device, FT6000, enabling more accurate measurements of fatty acids in buffalo milk. The findings have practical implications for the food industry, offering a faster and more reliable approach to assess and monitor fatty acid composition in buffalo milk, potentially influencing product development and quality control processes. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

We report the synthesis and characterization of new palladium(II) β-ketoesterate complexes [Pd(CH3COCHCO2R)2] with alkyl substituents R = tBu, iPr, Et. These compounds can have potential use in focused electron beam induced deposition (FEBID), which is a direct write method for the growth of structures at the nanoscale. However, it is still a major challenge to obtain deposits with a high metal content, and new precursor molecules are needed to overcome this. Single crystal X-ray diffraction, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density-functional theory calculations were used to confirm the compounds' composition and structure. Using thermal analysis and sublimation experiments, we investigate their thermal stability and volatility. These studies show that the palladium complexes sublimate over the range 348–353 K under 10−2 mbar pressure. The electron-induced decomposition of the complex molecules in the gas phase and their thin layers on silicon substrates were analysed using electron impact mass spectrometry (EI MS) and microscopy studies (SEM/EDX). They confirm that the precursor electron-induced fragmentation depends on the molecular structure. The obtained results reveal that [Pd(CH3COCHCO2tBu)2] with cis-positioned tert-butyl groups may be a promising FEBID precursor, and we carried out preliminary deposition experiments using this compound. [ABSTRACT FROM AUTHOR]

Borosilicate glasses possess excellent melting properties and high stability against chemical attack by aqueous solutions, enabling this glass family to be used in various fields. In this article, we design a novel glass network in order to achieve a chemically robust glass with a low melting temperature. Therefore, the substitution effect of Na2O by MgO, Al2O3, Li2O, and K2O on the chemical durability and melting properties of sodium aluminosilicate glass (i.e., 80SiO2‒5Al2O3‒15Na2O [mol%]) was examined using a standard hydrolytic resistance test and viscosity measurement. Interestingly, we found that the partial replacement of Na2O by Al2O3, Li2O, and K2O (i.e., 80SiO2‒5Al2O3‒15Na2O → 80SiO2‒6.5Al2O3‒9Li2O‒2.25Na2O‒2.25K2O) makes the glass network with chemical durability and melting properties comparable to those of the commercial borosilicate network, resulting in a low HCl consumption of 0.04 mL/g and working temperature of 1238°C (i.e., temperature at viscosity 104 dPa s). The structural characterizations indicate that the high chemical stability of this glass composition originates from the abundance of SiO4 tetrahedrons with three and four bridging oxygen in the glass network as well as the increase in cationic field strength of mixed alkali ions. These excellent melting properties and superior chemical durability of glass imply the possibility of using the mixed alkali metal oxides aluminosilicate glass together with the commercial borosilicate glass in the markets for numerous practical applications. [ABSTRACT FROM AUTHOR]

A cationic copper‐stabilized coppoborylene was prepared and structurally characterized via infrared photodissociation spectroscopy and density functional theory calculations. This structure exemplifies a new class of borylenes stabilized by three‐center‐two‐electron metal‐boron‐metal covalent bonding interaction, displaying exceptional σ‐acidity and unparalleled π‐donor capability for CO activation that outperforms all of the known transition metal cations and is comparable or even superior to the documented base‐trapped borylenes. Its neutral form represents a monovalent boron compound with a strongly reactive amphoteric boron center built on transition‐metal‐boron bonds, which inspires the design and synthesis of new members of the borylene family. [ABSTRACT FROM AUTHOR]

This paper presents the synthesis of ZnS through solvothermal method using hydrozincite (Zn5(CO3)2(OH)6) as a precursor. Zinc sulfide (ZnS) was synthesized at four different temperatures: 80 °C, 100 °C, 140 °C, and 180 °C. All photocatalysts that were synthesized underwent characterization by X‐ray diffraction, scanning electron microscopy, infrared spectroscopy, thermogravimetric analysis, N2 adsorption‐desorption isotherms, diffuse reflectance spectroscopy, and X‐ray photoelectron analysis. The performance of H2 using photocatalysis was evaluated by utilizing methanol as a sacrificial agent. At 80 °C solvothermal temperature, the ZnS exhibited maximum photoactivity, leading to an H2 generation rate of 154.8 μmolh−1. The high photo‐activity of ZnS synthesized at 80 °C was mainly influenced by the crystallite size, which has an essential influence on the specific surface area. The photocatalytic efficiency of the most active material decreased by approximately 17 % over four reaction cycles due to the photo corrosion effect, with ZnSO3 being the primary by‐product formed after the reaction. [ABSTRACT FROM AUTHOR]

In this study, we prepared Ni‐Zn‐Cu Fe2O4 ferrite/ethylene propylene diene monomer (EPDM) rubber nanocomposites with enhanced mechanical and electrical properties. First, Ni‐Zn‐Cu Fe2O4 ferrite nanoparticles were synthesized with a tailored composition of NiZn(0.3)Cu(0.2)Fe2O4(2). Subsequently, these nanoparticles were incorporated into the EPDM rubber matrix through a two‐roll mixing mill. Scanning electron microscopy and x‐rays diffraction techniques were used to explore their morphology and structure. Fourier‐transform infrared spectroscopy was used to identify metal‐oxygen bonds in the nanoparticles and their incorporation in the nanocomposites. Similarly, curing properties, including optimum cure time, scorch time, and torque profiles, were evaluated using a moving die rheometer. While, mechanical properties of these composites, such as tensile strength and Young's modulus, were determined with a universal testing machine. Tensile strength improved from 0.11 MPa to 0.22 MPa (100% increase), whereas, the Young's modulus increased from 0.03 MPa to 0.052 MPa (86% increase). Additionally, we investigated the dielectric properties of these nanocomposites, encompassing permittivity, resistivity, and dielectric constant, using a dielectric properties analyzer. Our findings revealed a significant reduction in dielectric resistivity of nanocomposites (from 33.2 GΩ to 23.38 GΩ) upon the introduction of Ni‐Zn‐Cu Fe2O4 ferrite nanoparticles, indicating the formation of a continuous nanofiller network within the EPDM matrix. Interestingly, as the nanofiller loading increased, both dielectric permittivity and dielectric constant exhibited a gradual rise. The permittivity value increased from 2.31 to 2.39 (Fm−1), while the dielectric constant increased from 0.0091 to 0.0179. Highlights: Synthesized Ni‐Zn‐Cu Fe2O4; tuned composition NiZn(0.3)Cu(0.2)Fe2O4(2).Integrated ferrite into EPDM; optimized mixing for enhanced properties.Employed SEM, XRD, and FTIR; revealed morphology, structure, and bonding.Evaluated curing using MDR; unveiled optimal time and torque profiles.Explored dielectric properties; demonstrated reduced resistivity, heightened permittivity. [ABSTRACT FROM AUTHOR]

Hydrogen bonding is pivotal in chemical and biological systems, yet detecting it in condensed matter, especially polymers, remains challenging. We propose a straightforward method using an aggregation‐induced emission luminogen (AIEgen) probe, demonstrated in a specially designed hydrogen‐bonded polymer with UPy groups. Unlike conventional covalent bonding, our approach involves mixing the AIEgen probe with polymers, inducing a significant change in fluorescence intensity due to the exceptional AIE characteristics. Validation involved comparative analyses with traditional methods, including dynamic mechanical analysis and infrared spectroscopy, across various temperatures. Our AIEgen‐based approach offers a more intuitive assessment of hydrogen bonding dynamics than the complexity of infrared spectroscopy. Importantly, hydrogen‐bonding transition temperatures determined by our AIEgen‐based method are only 6–8 degrees higher than those from dynamic mechanical analyses, confirming accuracy under faster, simpler conditions. This innovative technique not only opens a new avenue for investigating hydrogen bonding dynamics within confined polymer chains but also enhances the precision of transition temperature determination in solid‐state materials. Our study highlights the vital role of hydrogen bonding in functional materials, promising exciting possibilities for further advancements in this field. [ABSTRACT FROM AUTHOR]

Molecular catalysts represent an exceptional class of materials in the realm of electrochemical carbon dioxide reduction (CO2RR), offering distinct advantages owing to their adaptable structure, which enables precise control of electronic configurations and outstanding performance in CO2RR. This study introduces an innovative approach to heterogeneous electrochemical CO2RR in an aqueous environment, utilizing a newly synthesized N4‐macrocyclic cobalt complex generated through a dimerization coupling reaction. By incorporating the quaterpyridine moiety, this cobalt complex exhibits the capability to catalyze CO2RR at low overpotentials and reaches near‐unity CO production across a wide potential range, as verified by the online mass spectrometry and in situ attenuated total reflectance‐Fourier transform infrared spectroscopy. Comprehensive computational models demonstrate the superiority of utilizing quarterpyridine moiety in mediating CO2 conversion compared to the counterpart. This work not only propels the field of electrochemical CO2RR but also underscores the promising potential of cobalt complexes featuring quaterpyridine moieties in advancing sustainable CO2 conversion technologies within aqueous environments. [ABSTRACT FROM AUTHOR]

The quest for high‐performance energetic materials for defense and aerospace has intensified, focusing on balancing energy output and safety. This study presents the synthesis of 3D energetic metal‐organic frameworks (EMOFs) [Na3(DNT)(H2O)]n (Na‐MOF), [K2(DNT)2(H2O)]n (K‐MOF), and [Cs2(DNT)]n (Cs‐MOF) using 1,2,4‐dinitrimino triazole (DNT) through a hydrothermal process. The synthesized EMOFs are characterized using infrared spectroscopy, powder X‐ray diffraction, scanning electron microscopy (SEM), elemental analysis, and thermogravimetric analysis and differential scanning calorimetry, and structures confirmed via single‐crystal X‐ray diffraction, revealing 3D frameworks with crystal densities of 2.15, 2.16, and 2.86 g cm−3, respectively. Among them, Na‐MOF exhibits excellent detonation performance (VOD = 8900 m s−1, DP = 26.21 GPa), high thermal stability (Td = 369 °C), and insensitivity to impact and friction (IS = 40 J, FS = 360 N). K‐MOF displays balanced energetic and mechanical properties, while Cs‐MOF, though moderate in energetic performance, shows significant potential in pyrotechnic applications, producing a bright red flame. Intermolecular interactions are analyzed through Hirshfeld surface, 2D fingerprint, and SEM analyses, enhancing the understanding of particle size and morphology. Na‐MOF also demonstrates high iodine encapsulation capacity, positioning it as a potential replacement for traditional materials like RDX and heat‐resistant explosives such as HNS, with comparability to PYX. [ABSTRACT FROM AUTHOR]

Low *CO coverage on the active sites is a major hurdle in the tandem electrocatalysis, resulting in unsatisfied C2H4 production efficiencies. In this work, we developed a synergetic‐tandem strategy to construct a copper‐based composite catalyst for the electroreduction of CO2 to C2H4, which was constructed via the template‐directed polymerization of ultrathin Cu(II) porphyrin organic framework incorporating atomically isolated Cu(II) porphyrin and Cu(II) bipyridine sites on a carbon nanotube (CNT) scaffold, and then Cu2O nanoparticles were uniformly dispersed on the CNT scaffold. The presence of dual active sites within the Cu(II) porphyrin organic framework create a synergetic effect, leading to an increase in local *CO availability to enhance the C−C coupling step implemented on the adjacent Cu2O nanoparticles for further C2H4 production. Accordingly, the resultant catalyst affords an exceptional CO2‐to‐C2H4 Faradaic efficiency (FEC2H4) of 71.0 % at −1.1 V vs reversible hydrogen electrode (RHE), making it one of the most effective copper‐based tandem catalysts reported to date. The superior performance of the catalyst is further confirmed through operando infrared spectroscopy and theoretic calculations. [ABSTRACT FROM AUTHOR]

Membrane wetting caused by substances in the feed solution with low surface tension has posed serious issues for membrane distillation (MD). Omniphobic membranes could be helpful when dealing with this problem because they strongly repel liquids with a wide range of surface tensions. We fabricated electrospun omniphobic membranes containing PVDF‐TEOS‐PFDTMS, PVDF‐HFP‐TMOS‐PFDTMS, and PVDF‐HFP‐TEOS‐PFDTMS. All electrospun membranes have shown contact angles >90°, but the electrospun membrane containing PVDF‐HFP‐TEOS‐PFDTMS has shown super repellence with a contact angle >150° and maintains stable salt rejection and water flux in direct contact MD processes in the presence of sodium dodecyl sulfate surfactant (up to 0.3 mM). Furthermore, the morphology and crystallinity of the electrospun membranes were studied by scanning electron microscopy and Fourier‐transform infrared spectroscopy, and the percentage composition of elements was analyzed by x‐ray photoelectron spectroscopy. liquid entry pressure, mechanical strength, and the porosity of the electrospun omniphobic membranes were also studied. [ABSTRACT FROM AUTHOR]

Neat high-temperature vulcanized silicone rubber (HTV SR) showed bad hydrophobicity due to the existence of a large number of inorganic reinforcing fillers on its surface, which affected its security application in outdoor insulation systems. In this work, hydrophobic silane chains were grafted onto the surface of inorganic particles on the skin layer of HTV SR by a one-step coupling modification to improve its hydrophobicity. The effects of coupling agent types and coupling reaction conditions on the hydrophobicity of HTV SR were investigated. It was determined that the perfluorooctane trichlorosilicon with a large number of low surface energy fluorine atoms was the preferred coupling agent. The contact angle of HTV SR was increased by 15.70% when the optimal coupling reaction conditions were determined to be a reaction temperature of 60°C, a reaction time of 4 h, and an amount of coupling agent of 0.5%. The study found that both etching reaction and grafting reaction occurred during the whole coupling modification process, which led to the disappearance or decrease of a lot of holes on the HTV SR surface. After the fluorination coupling reaction, the surface of HTV SR became smooth and dense that led to the decrease of water absorption. The result of Fourier-transform infrared spectroscopy analysis showed the formation of C-F bond in HTV SR after fluorination modification, and the energetic dispersive spectroscopy analysis showed that the fluorine content on the surface of the fluorinated HTV SR increased significantly. Moreover, the stability analysis showed that the fluorinated HTV SR still had a good thermal stability and mechanical property stability. [ABSTRACT FROM AUTHOR]

This work deals with the influence of different heat treatment temperatures (140, 150, 160, 170, 180, 190, 200, and 210 °C) on changes in sapwood and red heartwood of European beech (Fagus sylvatica L.). According to the results of wet chemistry methods, HPLC (high-performance liquid chromatography), FTIR (Fourier transform infrared spectroscopy), SEC (size exclusion chromatography), the wood constituents in sapwood and red heartwood behaved similarly to heat treatment, but the individual proportions were different. The loss of hemicelluloses and the increase in extractives with increasing temperature were more pronounced in sapwood. The amount of cellulose in sapwood and red heartwood showed similar behaviour with increasing temperature. Thermal treatment causes changes in cellulose crystallinity, and the formation of aromatic structures, mainly in beech sapwood. However, the increase in the lignin content of red heartwood was significantly lower than that of sapwood due to its auto condensation, and formation of pseudo-lignin. Among the carbohydrates, the most significant changes were observed in xylose content, which was almost twice as high in red heartwood as in sapwood. Other carbohydrates (glucose, mannose, galactose, and arabinose) reached similar values in sapwood and red heartwood. [ABSTRACT FROM AUTHOR]

This study aims to investigate the potential of integrating natural biochar (BC) derived from eggshell waste into flexible polyurethane (FPU) foam to enhance its mechanical and acoustic performance. The study explores the impact of incorporating BC at various weight ratios (0.1, 0.3, 0.5, and 0.7 wt. %) on the properties of the FPU foam. Additionally, the effects of modifying the BC with (3-aminopropyl)trimethoxysilane (APTMS) at different ratios (10, 20, and 30 wt. %) and the influence of diverse particle sizes of BC on the thermal, mechanical, and acoustic characteristics of the FPU composite are investigated. The functional groups, morphology, and elemental composition of the developed FPU composites are analyzed using Fourier-transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (FESEM), and energy-dispersive X-ray (EDX) techniques. Characteristics such as density, gel fraction, and porosity were also assessed. The results reveal that the density of FPU foam increased by 4.32% and 7.83% while the porosity decreased to 50.22% and 47.05% with the addition of 0.1 wt. % of unmodified BC and modified BC with 20 wt. % APTMS, respectively, compared to unfilled FPU. Additionally, the gel fraction of the FPU matrix increases by 1.91% and 3.55% with the inclusion of 0.1 wt. % unmodified BC and modified BC with 20 wt. % APTMS, respectively. Furthermore, TGA analysis revealed that all FPU composites demonstrate improved thermal stability compared to unfilled FPU, reaching a peak value of 312.17°C for the FPU sample incorporating BC modified with 20 wt. % APTMS. Compression strength increased with 0.1 wt. % untreated BC but decreased at higher concentrations. Modifying BC with 20% APTMS resulted in an 8.23% increase in compressive strength compared to unfilled FPU. Acoustic analysis showed that the addition of BC improved absorption, and modified BC enhanced absorption characteristics of FPU, reaching Class D with a 20 mm thickness. BC modified with APTMS further improved acoustic properties compared to the unfilled FPU sample (Class E), with 20% modification showing the best results. These composites present promising materials for sound absorption applications and address environmental issues related to eggshell waste. [ABSTRACT FROM AUTHOR]

The origin of elemental chromium for the archaeological weapons from the pits of Qin terracotta warriors in China has been highly controversial. Although previous studies have highlighted that the chromium on the surface of weapon originated from the contamination of surrounding lacquer, the exact origin of chromium in the lacquer remains unclear. In this work, the measurement by inductively coupled plasma-mass spectrometer (ICP-MS) firstly confirmed that the elemental chromium was indeed contained in the archaeological Qin original lacquer. Nevertheless, the amount of elemental chromium in the Qin lacquer was as low as 0.0759 μg/mg, disclosing that it was impossible to artificially add extra refined chromium-containing substance to the lacquer in the preparation of the terracotta warriors. The soil from the archaeological site of Qin lacquer was found to have a chromium amount of 0.0660 μg/mg by ICP-MS. After the hygrothermal and soil-buried aging cycles for the lab-prepared lacquer, the surface and depth elemental analyses by time of flight-secondary ion mass spectrometer (TOF–SIMS) showed a gradient distribution of elemental chromium from the surface to interior of aged lacquer, indicating the migration and enrichment behavior of elemental chromium from the burial soil towards the lacquer. To explore the migration mechanism of elemental chromium, fluorescence imaging technique was employed in combination with Fourier transform infrared spectrometry (FT-IR) and X-ray photoelectron spectroscopy (XPS) characterizations. The results revealed that catechol-containing fragments were formed during hygrothermal and soil-buried aging of lacquer and consequently coordinated with chromium ions, inducing the migration of elemental chromium towards the lacquer. [ABSTRACT FROM AUTHOR]

Introduction: The human immunodeficiency virus (HIV) remains a significant global health concern, with a reported high infection rate of 38.4 million cases globally; an estimated 2 million new infections and approximately 700,000 HIV/ AIDS-related deaths were reported in 2021. Despite the advent of anti-retroviral therapy (ART), HIV/AIDS persists as a chronic disease. To combat this, several studies focus on developing inhibitors targeting various stages of the HIV infection cycle, including HIV-1 protease. This study aims to synthesize and characterize novel glyco diphenylphosphino metal complexes with potential HIV inhibitory properties. Method: A series of new gold(I) thiolate derivatives and three bimetallic complexes, incorporating amino phosphines and thiocarbohydrate as auxiliary ligands, were synthesized using procedures described by Jiang, et al. (2009) and Coetzee et al. (2007). Structural elucidation and purity assessment of the synthesized compounds (1-11) were conducted using micro-analysis, NMR, and infrared spectrometry. Results and Discussion: Using molecular modeling techniques, three of the metal complexes were identified as potential HIV protease inhibitors, exhibiting strong binding affinity interactions with binding pocket residues. These inhibitors demonstrated an ability to inhibit the flexibility of the flap regions of the HIV protease, similar to the known HIV protease inhibitor, darunavir. This study sheds light on the promising avenues for the development of novel therapeutic agents against HIV/AIDS. [ABSTRACT FROM AUTHOR]

Evaluating the biodegradability and biocompatibility of hydrogels is essential for identifying materials suitable for biomedical applications. This study describes the fabrication of hydrogels utilizing physiological‐soluble chitosan (N‐succinyl chitosan, NSC) crosslinked with dialdehyde guar gum (Oxidized Galactomannan, OxGM) via the Schiff‐base reaction. Hydrogels with varying volumetric ratios of NSC/OxGM, resulting in distinct NH2/CHO functional group ratios and crosslinking degrees, underwent comprehensive characterization using Fourier‐transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), swelling, and scanning electron microscopy (SEM). Gelation time (tgel) is assessed by rheological analysis (tgel = G′ > G″), where tgel increased with higher crosslinking density, reaching a maximum value of ≈80 s. Biodegradation analysis in phosphate‐buffered saline (PBS) with lysozyme (13 mg L−1) revealed that the crosslinking degree significantly influenced degradation, with lower crosslinking associated with an elevated degradation profile. Moreover, cell viability assays with fibroblastic cells demonstrated minimal cytotoxicity, but an increase in free aldehyde groups correlated with decreased cell viability. For the 75C25C hydrogel, the compressive test yielded a Young's modulus value of 67.2 kPa (±8.5). These results imply that the hydrogels developed exhibit favorable biodegradability and biocompatibility, making them promising candidates for diverse biomedical applications. [ABSTRACT FROM AUTHOR]

Drought is one of the main factors contributing to tree mortality worldwide and drought events are set to become more frequent and intense in the face of a changing climate. Quantifying water stress of forests is crucial in predicting and understanding their vulnerability to drought‐induced mortality. Here, we explore the use of high‐resolution spectroscopy in predicting water stress indicators of two native Australian tree species, Callitris rhomboidea and Eucalyptus viminalis. Specific spectral features and indices derived from leaf‐level spectroscopy were assessed as potential proxies to predict leaf water potential (Ψleaf), equivalent water thickness (EWT) and fuel moisture content (FMC) in a dedicated laboratory experiment. New spectral indices were identified that enabled very high confidence linear prediction of Ψleaf for both species (R2 > 0.85) with predictive capacity increasing when accounting for a breakpoint in the relationships using segmented regression (E. viminalis, R2 > 0.89; C. rhomboidea, R2 > 0.87). EWT and FMC were also linearly predicted to a high accuracy (E. viminalis, R2 > 0.90; C. rhomboidea, R2 > 0.80). This study highlights the potential of spectroscopy as a tool for predicting measures of plant water noninvasively, enabling broader applications for monitoring and managing plant water stress. [ABSTRACT FROM AUTHOR]

The Philippines is primarily an agricultural country in which most Filipinos depend on the health of the soil for livelihood. Plastic pollution adversely affects agriculture by degrading soil quality, fertility, and crop growth. However, the prevalence of plastic particles such as mesoplastics (>5 mm to 25 mm) and microplastics (<5 mm) in agricultural soils in the Philippines remains poorly understood. This study investigated the prevalence of mesoplastics and microplastics in agricultural soils in Iligan City, Philippines. We collected soil samples from the six sampling stations in high-elevation and low-elevation sites. Mesoplastics and microplastics were examined through manual sorting, categorized based on color, shape, and size, and identified using Fourier-transform infrared spectroscopy (FTIR). Mesoplastics were found to be more prevalent, averaging 2.22 items/kg compared to microplastics 0.83 items/kg. Mesoplastics were mainly white-colored (42%), mostly fragmented (55%), 5–10 mm in size (55%), and were predominantly polypropylene (85%). Microplastics were mainly transparent (40%), composed of fragments and film shapes(46%), and 3–4 mm (93%) in size. Polyethylene was the abundant microplastic polymer type (47%). It was observed that the low-elevation sites had a higher abundance of plastic particles, stressing the need to address local factors in tackling plastic pollution. [ABSTRACT FROM AUTHOR]

Palm leaf manuscripts, which are crucial carriers of historical, religious, scientific, and artistic information in East and Southeast Asia, specifically encapsulate significant aspects of Buddhist culture and thus require comprehensive research and preservation efforts. The base material of palm leaf manuscripts is processed palm leaves, which are hygroscopic and profoundly affected by environmental humidity. Currently, there is a research gap regarding the impact of traditional processing crafts and natural aging on the hygroscopicity of palm leaf manuscripts. Utilizing dynamic water vapor sorption (DVS), the hygroscopic properties of palm leaves from various years were assessed before and after traditional processing in Yunnan Province, China. The results show that traditional processing slightly increases the equilibrium moisture content (EMC) in environments with 0 to 60% relative humidity (RH), but significantly lowers EMC in high humidity environments, with reductions up to 19.01%. Additionally, hysteresis doubled post-processing, indicating enhanced stability under fluctuating humidity conditions. Sorption models suggest that traditional processing increases the number of adsorption sites while reducing physical adsorption or capillary condensation. FT-IR (Fourier-transform infrared spectroscopy) analysis indicates that the relative contents of cellulose and hemicellulose were reduced by 39.90% and 3.97%, respectively. Degradation occurring in both the crystalline and amorphous regions of cellulose. After natural aging, the hygroscopicity of processed palm leaves improved across the entire humidity range of 0 to 95%, and there was a slight increase in hysteresis. This is due to the increase in both adsorption sites and physical adsorption capabilities. FT-IR results also indicate that the relative contents of cellulose and hemicellulose were decreased by 57.52% and 19.83% after nature aging, respectively. These findings confirm that traditional processing improves the writability and humidity resilience of the leaves, while natural aging enhances their overall hygroscopic properties. This research contributes to our understanding of how humidity damages palm leaf manuscripts. aids in determining optimal RH ranges for storage, and assesses the effectiveness of consolidation treatments in their long–term preservation. [ABSTRACT FROM AUTHOR]