Molecular Spectroscopy Research Articles

Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets.

Solar photoexcitation of chromophoric groups in dissolved organic matter (DOM), when coupled to photoreduction of ubiquitous Fe(III)-oxide nanoparticles, can significantly accelerate DOM degradation in near-surface terrestrial systems, but the mechanisms of these reactions remain elusive. We examined the photolysis of chromophoric soil DOM coated onto hematite nanoplatelets featuring (001) exposed facets using a combination of molecular spectroscopies and density functional theory (DFT) computations. Reactive oxygen species (ROS) probed by electron paramagnetic resonance (EPR) spectroscopy revealed that both singlet oxygen and superoxide are the predominant ROS responsible for DOM degradation. DFT calculations confirmed that Fe(II) on the hematite (001) surface, created by interfacial electron transfer from photoexcited chromophores in DOM, can reduce dioxygen molecules to superoxide radicals (•O2-) through a one-electron transfer process. 1H nuclear magnetic resonance (NMR) and electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) spectroscopies show that the association of DOM with hematite enhances the cleavage of aromatic groups during photodegradation. The findings point to a pivotal role for organic matter at the interface that guides specific ROS generation and the subsequent photodegradation process, as well as the prospect of using ROS signatures as a forensic tool to help interpret more complicated field-relevant systems.

Binding mechanism, photo-induced cleavage and computational studies of interaction cefepime drug with Human serum albumin

The binding interaction of cefepime to human serum albumin (HSA) in aqueous solution was investigated by molecular spectroscopy (UV spectra, fluorescence spectra and CD spectra), photo-cleavage and modeling studies under simulative physiological conditions. Spectrophotometric results are rationalized in terms of a static quenching process and binding constant (Kb ) and the number of binding sites (n ≈ 1) were calculated using fluorescence quenching approaches at three temperature settings. Thermodynamic data of ΔG, ΔH and ΔS at different temperatures were evaluated. The results showed that the electrostatic and hydrogen bonding interactions play a major role in the binding of cefepime to HSA. The value of 3.4 nm for the distance r between the donor (HSA) and acceptor (cefepime) was derived from the fluorescence resonance energy transfer (FRET). FTIR and CD measurements has been reaffirmed HSA–cefepime association and demonstrated reduction in α-helical content of HSA. Furthermore, the study of molecular modeling also indicated that cefepime could strongly bind to the site I (subdomain IIA) of HSA. Additionally, cefepime shows efficient photo- cleavage of HSA cleavage. Our results may provide valuable information to understand the pharmacological profile of cefepime drug delivery in blood stream. Communicated by Ramaswamy H. Sarma

Validation of a small-scale method for determination of phosphorus in meat and meat products by molecular absorption spectroscopy

The purpose of this study was to evaluate the applicability of an alternative analytical technique to the reference method for phosphorus detection in meat and meat products established by ISO 2294:1974, revised by ISO 23776:2021. When an analytical method is modified or a new one is developed and implemented, it should be validated before being accepted for routine determinations. Furthermore, it is necessary to demonstrate that the new or alternative method has good performance characteristics in comparison with the reference method. Therefore, a comparison of the performance of the alternative and the reference method should be made. In the present study, a statistical evaluation of the calibration model of the alternative method was made with data from interlaboratory studies made in five consecutive years using fifty analyses of meat and meat products. The statistical parameters evaluated over time for the calibration curve were the y-intercept and slope; correlation and linearity; analytical limits: detection and quantification; working range; and accuracy (precision and trueness). In the interlaboratory tests, the results obtained by the alternative analytical method were compared with those obtained by the reference method, and their performance in these tests was also evaluated. The results obtained by the alternative method indicated better accuracy than the reference method due to lower relative errors, more precision, and a good trueness evaluation through lower absolute values of the z-score. The study demonstrated that the phosphorus alternative method is applicable for the determination of total phosphorus in the matrix of meat and meat products.

The presence of free palmitic acid modulates the effects of lutein on structural and dynamic properties of lipid membranes

Free fatty acids, like palmitic acid (PA), and xanthophyll pigments, like lutein (LUT) are the natural membrane compounds in plants. To study the effect of PA on LUT and their organization, a model membrane of 1,2-dimyristoyl-sn-glycerol-3-phosphocholine (DMPC) enriched with 2 mol% PA and 1 mol% LUT was formed. Molecular mechanisms underlying the interaction between these two compounds were examined with application of molecular spectroscopy techniques, e.g., visible spectroscopy, electron paramagnetic resonance and Fourier transform infrared. We determined the monomeric/dimeric organization of LUT in the membrane. We proved that the presence of PA in the lipid phase facilitated and stabilized the formation of LUT structures in the membrane. Lutein with PA did not form strong molecular aggregates like H- and J-structures. We presented the simplified model membrane that could be a suitable representation of the physiological process of de-esterification of PA from LUT appearing in natural biomembranes in humans.

Towards molecular understanding of surface and interface catalytic engineering in TiO2/TiOF2 nanosheets photocatalytic antibacterial under visible light irradiation

TiO2/TiOF2 Z-scheme nanosheets have been successfully synthesized for photocatalytic antibacterial. The antibacterial efficiency of TiO2/TiOF2 against E. coli and S. aureus were 99.90 % and 81.89 % at low material concentration (110 μg/mL), respectively, which are higher than those of pure TiO2, TiOF2, and Degussa P25. In situ molecular spectroscopy results demonstrate that the microstructure of the synthesized material can be reconstructed and optimized to enhance the exposure of the active sites·H2O and O2 are effectively adsorbed on the catalyst surface and activated to form OH…Ti and O…Ti surface active species. Furthermore, the dense interface formed in TiO2/TiOF2 acts as an efficient transport path for photoexcited electrons from TiO2 to TiOF2, and thus accelerates the formation of reactive oxygen species. Finally, the mechanism of bacterial inactivation is systematically discussed considering the main active substances, cell morphological changes, and activity of antioxidant enzymes.

An Automated, Highly Selective Reaction Monitoring Instrument Using Molecular Rotational Resonance Spectroscopy.

Online monitoring of chemical reactions by using analytical chemistry tools is a powerful way to maximize control over these processes. In this paper, we demonstrate the use of molecular rotational resonance, an emerging and extraordinarily selective spectroscopic technique, to perform automated reaction monitoring measurements. An interface using a six-port valve with a calibrated sample loop, coupled to a temperature controlled inlet for analyte volatilization, was developed and tested. Two reactions were chosen for initial characterization: an amine-aldehyde condensation reaction to form an imine product and an isotopic exchange reaction of a β-ketoester with keto-enol tautomerization. The spectrometer was able to provide kinetic information about the reaction and determine reaction completion. In the future, this system can be extended to detect and quantify impurities and characterize reaction selectivity, in addition to the reaction progress.

Vibrationally unusual behaviors predicted for [XeHXe]+: A computational molecular spectroscopy study

To obtain more evidence for our assertion that the ro-vibrationally averaged structure of a linear molecule is to be observed as being “bent,” we here chose a linear molecule X˜Σg+1 [XeHXe]+.Using the basis sets and calculation level checked against the gas-phase spectroscopy data for XeH+, the 3D potential energy surface (PES) of [XeHXe]+ was calculated at the valence CCSD(T)/[5ZP ANO-RCC (Xe), cc-pV5Z-DK (H)] level. Then, ro-vibrational properties were calculated over the DVR3D wavefunctions derived by the Discrete Variable Representation method.The [XeHXe]+ is a covalently bound, stable cation with 110 kcal/mol of the heat of formation, showing a large amplitude bending motion.Three unusual features are noticed and elucidated. (1) Although the [XeHXe]+ is a linear molecule with re(Xe–H) = re(H–Xe) = 1.8682 Å in D∞h symmetry and the PES is symmetric for the two Xe–H bonds, the r0 structure is unsymmetric with 〈r(Xe–H)〉0 = 1.8881 Å, 〈r(H–Xe)〉0 = 1.9028 Å, and 〈∠(Xe–H–Xe)〉0 = 166.6∘. The 〈∠(Xe–H–Xe)〉0 value of 166.6∘ again confirmed our assertion that a linear molecule is to be observed as being bent. (2) The term value ν3 (846 cm−1, antisymmetric stretching mode) is higher than the harmonic frequency ω3 (820 cm−1), which is unusual since in ordinary molecules νi <ωi (i=1,2,3) due to the anharmonicity. (3) The doubly degenerate bending mode, consisting of a perpendicular motion of the central H atom against the a axis, is anharmonic since this motion is essentially a simultaneous stretching motion of the two Xe–H bonds, which are inherently anharmonic.All these unusual features result from the situation that the (ultra)heavy Xe atoms at both ends stay almost at a standstill during the vibrations, and hence, these three features are specific and characteristic to the [(Ultra)heavy–Light–(Ultra)heavy] atoms system.In addition, from the analysis of the normal modes, the reason is clarified why only the ν1 (symmetric stretching mode) is severely affected by the matrix medium (Tsuge et al.) in the matrix infrared spectroscopy.

Favipiravir vs. Deferiprone: Tautomeric, photophysical, in vitro biological studies, and binding interactions with SARS-Cov-2-MPro/ACE2

Coronavirus disease 2019 (COVID-19) still remains the most disastrous infection continuously affecting millions of people worldwide. Herein, we performed a comparative study between the anti-influenza drug favipiravir (FAV) and the anti-thalassemia drug deferiprone (DFP) in order to examine their potential as basic scaffolds for the generation of most effective and structurally novel antivirals. To conduct the initial molecular modelling and virtual screening steps, our recently proposed single crystal X-ray diffraction (SCXRD)/HYdrogen DEssolvation (HYDE) technology platform has been used. This platform allows molecular design, interactive prioritization and virtual evaluation of newly designed molecules, simultaneously affecting two COVID-related targets, including angiotensin-converting enzyme 2 (ACE2) as a host-cellular receptor (host-based approach) and the main protease (Mpro) enzyme of the spike glycoprotein of SARS-Cov-2 (virus-based approach). Based on the molecular docking results, DFP has shown higher binding affinity (Ki HYDE values) over FAV towards both biological targets. The tautomeric, physicochemical, and biological properties of FAV and DFP have been studied both experimentally and theoretically using molecular spectroscopy (UV–VIS absorption), parallel artificial membrane permeability assay, and cell biology (PAMPA and MTT assay), as well as DFT quantum chemical calculations. According to the obtained results, the enol tautomers of both compounds are considerably more stable in different organic solvents. However, the keto tautomer of FAV was estimated to be most preferable under physiological conditions, which is in good agreement with the molecular docking studies. The isolated crystal structure of DFP is in an excellent agreement with the computation in respect of the most stable tautomer. Combined single X-ray/molecular modeling studies including HYDE analyses provided not only insights into the protein–ligand interactions within the binding site of SARS-Cov-2-ACE2 and SARS-Cov-2-Mpro, but also a valuable information regarding the most stable enol tautomeric form of DFP that contributes to its estimated higher potency against these targets.

How does theory compare to experiment for oscillator strengths in electronic spectra? Proposing range-separated hybrids with reliable accountability.

As an important quantity in atomic and molecular spectroscopy, oscillator strength should be mentioned. Oscillator strength is linked to the transition dipole moment and consequently to the transition probability between two states, where its magnitude is directly connected to the intensity of the peaks in ultraviolet-visible spectra. However, accurately accounting for oscillator strengths still remains one of the greatest challenges in theory and experiment. Given previous efforts in the context of investigations into oscillator strengths, the related theoretical treatments are relatively limited and have proven to be challenging. In this work, the oscillator strengths in the electronic spectra of organic compounds have thoroughly been investigated with the help of optimally tuned range-separated hybrids (OT-RSHs). In particular, variants of the OT-RSHs combined with the polarizable continuum model (PCM), OT-RSHs-PCM, as well as their screened versions accounting for the screening effects by the electron correlation through the dielectric constant, OT-SRSHs-PCM, are proposed for reliable prediction of the oscillator strengths. The role of the involved ingredients in the proposed methods, namely the underlying density functional approximations, short-range and long-range Hartree-Fock (HF) exchange, as well as the range-separation parameter, has been examined in detail. It is shown that any combination of the parameters in the proposed approximations does not render the reliable oscillator strengths, but a particular compromise among them is needed to describe the experimental data well. Perusing all the results of our developed methods, the best ones are found to be the generalized gradient approximation-based OT-RSHs-PCM, coupled with the linear response theory in the non-equilibrium solvation regime, with the correct asymptotic behavior and incorporating no (low) HF exchange contributions in the short-range part. The best proposed approximations also reveal superior performances not only with respect to their standard counterparts with the default parameters but also as compared to earlier range-separated functionals. Finally, the applicability of the best approximation is also put into broader perspective, where it is used for predicting the oscillator strengths in other sets of compounds not included in the process of developing the approximations. Hopefully, our proposed method can function as an affordable alternative to the expensive wave function-based methods for both theoretical modeling and confirming the experimental observations in the field of electronic spectroscopy.

Porous titanium scaffolds modified with Zeolitic Imidazolate Framework (ZIF-8) with enhanced osteogenic activity for the prevention of implant-associated infections.

In this study, zeolitic imidazolate framework 8 (ZIF-8) was coated on porous Ti6Al4V scaffolds, either bare or previously modified using hydroxyapatite (HA) or HA and gelatin (HAgel), via a growing single-step method in aqueous media using two contact times at 6h and 24h. The coated scaffolds termed ZIF-8@Ti, ZIF-8@HA/Ti, and ZIF-8@HAgel/Ti were characterized via scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and molecular plasma-atomic emission spectroscopy (MP-AES). In order to assess the cell proliferation rate, the cytocompatibility of the scaffolds was evaluated in primary osteoblasts (hOBs) using alamarBlue assay, while the osteoconductivity was analyzed in hOBs using a real-time approach, evaluating the expression of secreted phosphoprotein 1 (SPP1). Osteopontin, which is the protein encoded by this gene, represents the major non-collagenous bone protein that binds tightly to HA. The scaffolds were shown to be non-cytotoxic based on hOB proliferation at all time points of analysis (24h and 72h). In hOB cultures, the scaffolds induced the upregulation of SPP1 with different fold changes. Some selected scaffolds were assayed in vitro for their antibacterial potential against Staphylococcus epidermidis; the scaffolds coated with ZIF-8 crystals, regardless of the presence of HA and gelatin, strongly inhibited bacterial adhesion to the materials and reduced bacterial proliferation in the culture medium, demonstrating the suitable release of ZIF-8 in a bioactive form. These experiments suggest that the innovative scaffolds, tested herein, provide a good microenvironment for hOB adhesion, viability, and osteoconduction with effective prevention of S. epidermidis adhesion.

Silver Triangular Nanoplates as Analytical Reagents in Optical Molecular Absorption Spectroscopy: Possibilities and Prospects

Silver Triangular Nanoplates as Analytical Reagents in Optical Molecular Absorption Spectroscopy: Possibilities and Prospects

In silico and in vitro Studies Evaluating the Promising Antiureolytic Activity of Schiff’s Base 4-(3-Hydroxybenzylideneamino)phenol and Its Amine Derivative

Urea is the most widely used nitrogen fertilizer worldwide. However, ammonia volatilization, resulting from applying urea to the soil surface, causes economic and environmental losses; thus, urease inhibitors have been developed to mitigate these losses. In this work, the anti-ureolytic activity of Schiff’s base 4-(3-hydroxybenzylideneamino) phenol (3B4) and its amine-derived (3B4a) was evaluated. The most promising urease inhibitor in soil was 3B4 (55.0 ± 3.9% inhibition), with comparable results to N-(butyl) thiophosphoric triamide (p = 0.659). In the in vitro analysis (Canavalia ensiformis), the results of anti-ureolytic activity were similar, 22.6 ± 6.9% for 3B4 and 24.2 ± 9.6% for 3B4a. Biophysical interaction studies were also carried out through molecular docking studies and molecular fluorescence spectroscopy. These studies showed that both substances are preferentially competitive inhibitors, with the interaction between 3B4a and urease forming a more stable complex. In the analysis by Fourier transform infrared spectroscopy, no interaction was observed when 3B4 or 3B4a was mixed with urea (1:1) for 48 h, providing evidence of compatibility. Thus, the Schiff base 3B4 and its corresponding amine 3B4a may represent potential additives for urea fertilization aiming to assist in the urease inhibition process.

Liquid saliva-based Raman spectroscopy device with on-board machine learning detects COVID-19 infection in real-time.

With greater population density, the likelihood of viral outbreaks achieving pandemic status is increasing. However, current viral screening techniques use specific reagents, and as viruses mutate, test accuracy decreases. Here, we present the first real-time, reagent-free, portable analysis platform for viral detection in liquid saliva, using COVID-19 as a proof-of-concept. We show that vibrational molecular spectroscopy and machine learning (ML) detect biomolecular changes consistent with the presence of viral infection. Saliva samples were collected from 470 individuals, including 65 that were infected with COVID-19 (28 from hospitalized patients and 37 from a walk-in testing clinic) and 251 that had a negative polymerase chain reaction (PCR) test. A further 154 were collected from healthy volunteers. Saliva measurements were achieved in 6 minutes or less and led to machine learning models predicting COVID-19 infection with sensitivity and specificity reaching 90%, depending on volunteer symptoms and disease severity. Machine learning models were based on linear support vector machines (SVM). This platform could be deployed to manage future pandemics using the same hardware but using a tunable machine learning model that could be rapidly updated as new viral strains emerge.

A new and highly efficient CuMOF-based nanoenzyme and its application to the aptamer SERS/FL/RRS/Abs quadruple-mode analysis of ultratrace malachite green.

Malachite green (MG) is highly toxic, persistent, and carcinogenic, and its widespread use is a danger to the ecosystem and a threat to public health and food safety, making it necessary to develop new sensitive multimode molecular spectroscopy methods. In this work, a new copper-based nanomaterial (CuNM) was prepared by a high-temperature roasting using a copper metal-organic framework (CuMOF) as precursor. The as-prepared CuNM was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), and BET surface area analysis. CuNM was found to catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce the oxidation product TMBOX; however, subsequently, the MG aptamer (Apt) could be adsorbed on the CuNM surface by intermolecular interaction, which would inhibit the catalytic performance. After the addition of MG to be tested, the CuNM previously adsorbed by the Apt was transformed into its free state, thus restoring its catalytic activity. This new nanocatalytic indicator reaction could be monitored by surface-enhanced Raman scattering (SERS)/resonance Rayleigh scattering (RRS)/fluorescence (FL)/absorption (Abs) quadruple-mode methods. The SERS determination range was 0.004-0.4 nmol L-1 MG, with a limit of detection of 0.0032 nM. In this way, a rapid, stable, and sensitive method for the determination of MG residues in the environment was established.

On the role of non-additive interactions in three-body recombination.

Non-additive forces are a cornerstone of molecular spectroscopy and reaction dynamics. However, the relevance of non-additive forces in three-body recombination remains largely unexplored. In this work, we present a global study on the impact of non-additive interactions in three-body recombination: atom-atom-atom and ion-atom-atom. Our study explores these reactions in a wide range of energies, from the cold to the hyperthermal regime, finding no effect of non-additive interactions. Therefore, pair-wise interactions are enough to describe the three-body recombination dynamics adequately.

Analysis and optimization of optical frequency comb spectra of magnesium fluoride microbottle resonator

&lt;sec&gt;Optical frequency comb has shown great potential applications in many areas including molecular spectroscopy, RF photonics, millimeter wave generation, frequency metrology, atomic clock, and dense/ultra-dense wavelength division multiplexed high speed optical communications. Optical frequency comb in the microresonator supporting whispering-gallery mode has attracted widespread interest because of its advantages such as flexible repetition rate, wide bandwidth, and compact size. The exceptionally long photon lifetime and small modal volume enhance light-matter interaction, which enables us to realize intracavity nonlinear frequency conversions with low pump threshold. With the advantages of small size, low power consumption, wide spectral coverage and adjustable dispersion, the magnesium fluoride microresonator optical frequency comb has potential applications in optical communication and mid-infrared spectroscopy.&lt;/sec&gt;&lt;sec&gt;In this work, the spectral characteristics of the optical frequency comb generated by a magnesium fluoride whispering-gallery mode microbottle resonator platform are investigated. In order to optimize the spectral distribution of the optical frequency comb of the magnesium fluoride microbottle resonator, the second-order dispersion and higher-order dispersion of the bottle resonator structure under different curvatures and axial modes are solved iteratively by the finite element method, and the spectral evolutions of the optical frequency comb under different axial mode excitations are simulated by solving the nonlinear Schrödinger equation through the split-step Fourier method. The results show that near-zero anomalous dispersion tuning can be achieved in a wide bandwidth range by exciting low-order axial mode at an optimal radius of curvature, while the high-order axial mode will lead the microbottle resonator to present the weak normal dispersion. The weaker anomalous dispersion in the lower-order axial mode broadens the bandwidth of the optical comb, demonstrating that the third-order dispersion and the negative fourth-order dispersion can broaden the Kerr soliton optical comb; the weak normal dispersion in the higher-order axial mode suppresses the generation of the Kerr optical comb, and the Raman optical comb dominates. The selective excitation of Kerr soliton combs and Raman combs can be achieved by modulating the axial mode of the microbottle resonator under suitable pumping conditions. The present work provides guidance for designing the dispersion in magnesium fluoride microresonator and the experimental tuning of broadband Kerr soliton optical combs and Raman optical combs.&lt;/sec&gt;

Accurate Determination of Blackbody Radiation Shifts in a Strontium Molecular Lattice Clock.

Molecular lattice clocks enable the search for new physics, such as fifth forces or temporal variations of fundamental constants, in a manner complementary to atomic clocks. Blackbody radiation (BBR) is a major contributor to the systematic error budget of conventional atomic clocks and is notoriously difficult to characterize and control. Here, we combine infrared Stark-shift spectroscopy in a molecular lattice clock and modern quantum chemistry methods to characterize the polarizabilities of the Sr_{2} molecule from dc to infrared. Using this description, we determine the static and dynamic blackbody radiation shifts for all possible vibrational clock transitions to the 10^{-16} level. This constitutes an important step toward millihertz-level molecular spectroscopy in Sr_{2} and provides a framework for evaluating BBR shifts in other homonuclear molecules.

(Invited) Transistor-Injected Quantum-Cascade Devices: Novel Sources for Mid-Wave Infrared Emission

Quantum Cascade Lasers (QCLs) [1] are important sources for coherent mid-wave infrared (MWIR) light that find widespread use in applications such as molecular spectroscopy, free-space optical communications, and defense countermeasures. These applications demand tunability of emission wavelength and high output powers. The conventional QCL is a two-terminal n-i-n device in which an externally applied bias establishes the necessary electric field in the cascade region for proper alignment of the quantum states, defines the emission wavelength, and also determines the current through the cascade structure. Because QCLs are 2-terminal devices, changing bias directly changes both wavefunction overlap and energy separation. The spectral location and magnitude of the gain peak thus has a strong dependence on applied voltage, impacting the capability to modulate. To overcome these limitations, the transistor-injected quantum-cascade laser (TI-QCL) has been proposed [2]. The TI-QCL is a three-terminal device in which the cascade region is placed within a heterojunction bipolar transistor. In forward-active mode the current injection is controlled by a forward-biased emitter-base junction, and the reverse bias on the base-collector junction is used to control the electric field for alignment of the quantum states. This novel structure enables the decoupling of emission wavelength and output power. This extra control positions the TI-QCL to impact a wide range of applications such as spectroscopy with its wide tunability, and free-space communication with its capability to separately modulate power and frequency.Previously, transistor characteristics and near-infrared (NIR) band-to-band base emission was demonstrated in a GaAs design [3, 4] before moving to an InP-based design [5]. We will review the progress made to push the TI-QCL concept towards full functionality, focusing on InP-based epitaxial designs. A self-consistent Schrodinger-Poisson solver and non-equilibrium Green’s function method is used to aid in the active-region design of the structure, which is optimized for a peak emission wavelength of 8.27 μm as shown in Figure 1 [6]. A wide wavelength tunability from approximately 7.8 μm to 8.8 μm is projected based on computational analysis. The InP-based structure is grown using molecular beam epitaxy by IntelliEpi; a cross-section of the material is depicted in Figure 2. It contains an active-region composed of 30 repeated periods of In0.41Ga0.59As/In0.36Al0.64As strain-balanced superlattice. The devices are fabricated using standard III-V processing. An image of a fabricated TI-QCL bar consisting of a sloped, 20 μm wide emitter mesa and evaporated SiO2 as the passivation layer is depicted in Figure 3. The fabricated devices are diced and cleaved into 2 to 4 mm x 500 μm die and mounted onto In-plated copper mounts followed by wire bonding. The devices are electrically characterized at room temperature, 77 K, and 18 K. Under cryogenic temperatures, the common-base characteristics exhibit negative differential resistance (NDR) in collector current at all emitter injection currents as shown in Figure 4, which signifies tunneling transport through the quantum cascade superlattice region. The base current also exhibits corresponding NDR behavior and switching in the band-to-band NIR light (1.57 m) output from the In0.53Ga0.47As base is experimentally observed when biased in a region where transport through the cascade region is rejected due to quantum state misalignment.

Terahertz molecular water laser using quantum cascade laser pumping

Molecular lasers pumped by quantum cascade laser (QCL) open new possibilities for THz generation and its numerous applications, in particular, for high resolution molecular spectroscopy. In this article, a THz water laser pumped by a mid-infrared QCL was demonstrated using the broad tunability of the pump laser. Twenty D2O laser lines were measured under a continuous wave pumping regime, in a spectral range expending from 63 to 177 cm−1 (1.9–5.3 THz), and with an output power ranging from tens to hundreds of μW. This letter contains a description of the experimental setup used to produce the THz laser radiation and a comparison of the measured output power with a molecular gain factor used to sort out the most favorable laser lines. In addition to the measured laser transitions, a complete list of laser frequencies together with their corresponding molecular gain is given in the supplementary material, for both H2O and D2O isotopologues excited in their bending and stretching vibrational states.

Hydrated Eutectic Electrolyte Induced Bilayer Interphase for High-Performance Aqueous Zn-Ion Batteries with 100°C Wide-Temperature Range.

The practical implementation of aqueous zinc-ion batteries (AZIBs) encounters challenges such as dendrite growth, parasitic reactions, and severe decay in battery performance under harsh environments. Here, a novel hydrated eutectic electrolyte (HEE) composed of Zn(ClO4 )2 ·6H2 O, ethylene glycol (EG), and InCl3 solution is introduced to effectively extend the lifespan of AZIBs over a wide temperature range from -50 to 50°C. Molecular dynamics simulations and spectroscopy analysis demonstrate that the H2 O molecules are confined within the liquid eutectic network through dual-interaction, involving coordination with Zn2+ and hydrogen bonding with EG, thus weakening the activity of free water and extending the electrochemical window. Importantly, cryo-transmission electron microscopy and spectroscopy techniques reveal that HEE in situ forms a zincophobic/zincophilic bilayer interphase by the dissociation-reduction of eutectic molecules. Specifically, the zincophilic interphase reduces the energy barrier for Zn nucleation, promoting uniform Zn deposition, while the zincophobic interphase prevents active water from contacting the Zn surface, thus inhibiting the side reactions. Furthermore, the relationships between the structural evolution of the liquid eutectic network and interfacial chemistry at electrode/electrolyte interphase are further discussed in this work. The scalability of this design strategy can bring benefits to AZIBs operating over a wide temperature range.