Transport Dynamics of Water Molecules Confined between Lipid Membranes.

Water molecules confined between biological membranes exhibit a distinctive non-Gaussian displacement distribution, far different from that of bulk water. Here, we introduce a new transport equation for water molecules in the intermembrane space, quantitatively explaining molecular dynamics simulation results. We find that the unique transport dynamics of water molecules stems from the lateral diffusion coefficient fluctuation caused by their longitudinal motion in the direction perpendicular to the membranes. We also identify an interfacial region where water possesses distinct physical properties, which is unaffected by changes in the intermembrane separation.

Dual phase-detected infrared photothermal microscopy.

Infrared photothermal microscopy (IPM) has recently gained considerable attention as a versatile analytical platform capable of providing spatially resolved molecular insights across diverse research fields. This technique has led to numerous breakthroughs in the study of compositional variations in functional materials and cellular dynamics in living cells. However, its application to investigate multiple components of temporally dynamic systems, such as living cells and operational devices, has been hampered by the limited information content of the IP signal, which only covers a narrow spectral window (< 1 cm-1). Here, we present a straightforward approach for measuring two distinct IPM images utilizing the orthogonality between the in-phase and quadrature outputs of a lock-in amplifier, called dual-phase IR photothermal (DP-IP) detection. We demonstrate the feasibility of DP-IP detection for IPM in distinguishing two different micro-sized polymer beads.

Water-Ion Interaction Determines the Mobility of Ions in Highly Concentrated Aqueous Electrolytes.

Solvation engineering plays a critical role in tailoring the performance of batteries, particularly through the use of highly concentrated electrolytes, which offer heterogeneous solvation structures of mobile ions with distinct electrochemical properties. In this study, we employed spectroscopic techniques and molecular dynamics simulations to investigate mixed-cation (Li+/K+) acetate aqueous electrolytes. Our research unravels the pivotal role of water in facilitating ion transport within a highly viscous medium. Notably, Li+ cations primarily form ion aggregates, predominantly interacting with acetate anions, while K+ cations emerge as the principal charge carriers, which is attributed to their strong interaction with water molecules. Intriguingly, even at a concentration as high as 40 m, a substantial amount of water molecules persistently engages in hydrogen bonding with one another, creating mobile regions rich in K+ ions. Our observations of a redshift of the OH stretching band of water suggest that the strength of the hydrogen bond alone cannot account for the expansion of the electrochemical stability window. These findings offer valuable insights into the cation transfer mechanism, shedding light on the contribution of water-bound cations to both the ion conductivity and the electrochemical stability window of aqueous electrolytes for rechargeable batteries. Our comprehensive molecular-level understanding of the interplay between cations and water provides a foundation for future advances in solvation engineering, leading to the development of high-performance batteries with improved energy storage and safety profiles.

Molecular dynamics simulation study of water structure and dynamics on the gold electrode surface with adsorbed 4-mercaptobenzonitrile.

Understanding water dynamics at charged interfaces is of great importance in various fields, such as catalysis, biomedical processes, and solar cell materials. In this study, we implemented molecular dynamics simulations of a system of pure water interfaced with Au electrodes, on one side of which 4-mercaptobenzonitrile (4-MBN) molecules are adsorbed. We calculated time correlation functions of various dynamic quantities, such as the hydrogen bond status of the N atom of the adsorbed 4-MBN molecules, the rotational motion of the water OH bond, hydrogen bonds between 4-MBN and water, and hydrogen bonds between water molecules in the interface region. Using the Luzar-Chandler model, we analyzed the hydrogen bond dynamics between a 4-MBN and a water molecule. The dynamic quantities we calculated can be divided into two categories: those related to the collective behavior of interfacial water molecules and the H-bond interaction between a water molecule and the CN group of 4-MBN. We found that these two categories of dynamic quantities exhibit opposite trends in response to applied potentials on the Au electrode. We anticipate that the present work will help improve our understanding of the interfacial dynamics of water in various electrolyte systems.

Efficient and Inexpensive Synthesis of 15N-Labeled 2-Azido-1,3-dimethylimidazolinium Salts Using Na15NO2 Instead of Na15NNN.

15N-Labeled azides are important probes for infrared and magnetic resonance spectroscopy and imaging. They can be synthesized by reaction of primary amines with a 15N-labeled diazo-transfer reagent. We present the synthesis of 15N-labeled 2-azido-1,3-dimethylimidazolinium salts 1 as a 15N-labeled diazo-transfer reagent. Nitrosation of 1,3-dimethylimidazolinium-2-yl hydrazine (2) with Na15NO2 under acidic conditions gave 1 as a 1:1 mixture of α- and γ-15N-labeled azides, α- and γ-1, rather than γ-1 alone. The isotopomeric mixture thus obtained was then subjected to the diazo-transfer reaction with primary amines 3 to afford azides 4 as a 1:1 mixture of ß-15N-labeled azides ß-4 and unlabeled ones 4'. The efficient and inexpensive synthesis of 1 as a 1:1 mixture of α- and γ-1 using Na15NO2 instead of Na15NNN facilitates their wide use as a 15N-labeled diazo-transfer reagent for preparing 15N-labeled azides as molecular probes.

Dielectric Response and Linear Absorption Spectroscopy of Ionic Systems.

Time-dependent electric fields applied to ionic systems can induce both a dielectric and a conductive response, leading to the generation of macroscopic polarization and current, respectively. It has long been recognized that it is not possible to determine the two types of responses separately. However, this aspect is often not adequately accounted for in dielectric and absorption spectroscopies of ionic systems. To clarify this, we theoretically investigate the dielectric and conductive responses of ionic systems containing polyatomic ions based on linear response theory. We derive general expressions for the frequency-dependent dielectric functions, conductivity, and absorption coefficient, including those measured experimentally. Furthermore, we show that the dielectric and conductive responses cannot be uniquely distinguished even at the theoretical level and, therefore, cannot represent experimentally measured quantities. Instead, dielectric and absorption spectra of ionic systems should be expressed in terms of the generalized dielectric function that encompasses both dielectric and conductive responses. We propose a computational method to calculate this generalized dielectric function reliably. Model calculations on concentrated aqueous solutions of NaCl, a monatomic salt, and LiTFSI, a polyatomic salt, show that the dielectric and linear absorption spectra of the two systems based on the generalized dielectric function are significantly different from purely dielectric counterparts in the far-IR, terahertz, and lower-frequency regions. Moreover, the spectra are mainly determined by the autocorrelations of total dipole and total current, but dipole-current cross-correlation can also significantly contribute to the spectra of the LiTFSI solution. The present theoretical approach could be extended to nonlinear spectroscopy of ionic liquids and electrolyte solutions.

Monitoring the synthesis of neutral lipids in lipid droplets of living human cancer cells using two-color infrared photothermal microscopy.

There has been growing interest in the functions of lipid droplets (LDs) due to recent discoveries regarding their diverse roles. These functions encompass lipid metabolism, regulation of lipotoxicity, and signaling pathways that extend beyond their traditional role in energy storage. Consequently, there is a need to examine the molecular dynamics of LDs at the subcellular level. Two-color infrared photothermal microscopy (2C-IPM) has proven to be a valuable tool for elucidating the molecular dynamics occurring in LDs with sub-micrometer spatial resolution and molecular specificity. In this study, we employed the 2C-IPM to investigate the molecular dynamics of LDs in both fixed and living human cancer cells (U2OS cells) using the isotope labeling method. We investigated the synthesis of neutral lipids occurring in individual LDs over time after exposing the cells to excess saturated fatty acids while simultaneously comparing inherent lipid contents in LDs. We anticipate that these research findings will reveal new opportunities for studying lesser-known biological processes within LDs and other subcellular organelles.

Molecular photothermal effects, diffusion, and sample flow in time-resolved spectroscopy and microscopy.

Time-resolved pump-probe and two-dimensional spectroscopy are widely used to study ultrafast chemical and biological processes in solutions. However, the corresponding signals at long times can be contaminated by molecular photothermal effects, which are caused by the nonradiative heat dissipation of photoexcited molecules to the surroundings. Additionally, molecular diffusion affects the transient spectroscopic signals because photoexcited molecules can diffuse away from the pump and probe beam focuses. Recently, a theoretical description of molecular photothermal effects on time-resolved IR spectroscopy was reported. In this work, I consider the molecular photothermal process, molecular diffusion, and sample flow to develop a generalized theoretical description of time-resolved spectroscopy. The present work can be used to interpret time-resolved spectroscopic signals of electronic or vibrational chromophores and understand the rate and mechanisms of the conversion of high-frequency molecular electronic and vibrational energy to solvent kinetic energy in condensed phases.

The hydrogen-bonding dynamics of water to a nitrile-functionalized electrode is modulated by voltage according to ultrafast 2D IR spectroscopy.

We report the hydrogen-bonding dynamics of water to a nitrile-functionalized and plasmonic electrode surface as a function of applied voltage. The surface-enhanced two-dimensional infrared spectra exhibit hydrogen-bonded and non-hydrogen-bonded nitrile features in similar proportions, plus cross peaks between the two. Isotopic dilution experiments show that the cross peaks arise predominantly from chemical exchange between hydrogen-bonded and non-hydrogen-bonded nitriles. The chemical exchange rate depends upon voltage, with the hydrogen bond of the water to the nitriles breaking 2 to 3 times slower (>63 vs. 25 ps) under a positive as compared to a negative potential. Spectral diffusion created by hydrogen-bond fluctuations occurs on a ~1 ps timescale and is moderately potential-dependent. Timescales from molecular dynamics simulations agree qualitatively with the experiment and show that a negative voltage causes a small net displacement of water away from the surface. These results show that the voltage applied to an electrode can alter the timescales of solvent motion at its interface, which has implications for electrochemically driven reactions.

Long-term cargo tracking reveals intricate trafficking through active cytoskeletal networks in the crowded cellular environment.

A eukaryotic cell is a microscopic world within which efficient material transport is essential. Yet, how a cell manages to deliver cellular cargos efficiently in a crowded environment remains poorly understood. Here, we used interferometric scattering microscopy to track unlabeled cargos in directional motion in a massively parallel fashion. Our label-free, cargo-tracing method revealed not only the dynamics of cargo transportation but also the fine architecture of the actively used cytoskeletal highways and the long-term evolution of the associated traffic at sub-diffraction resolution. Cargos frequently run into a blocked road or experience a traffic jam. Still, they have effective strategies to circumvent those problems: opting for an alternative mode of transport and moving together in tandem or migrating collectively. All taken together, a cell is an incredibly complex and busy space where the principle and practice of transportation intriguingly parallel those of our macroscopic world.

Construction of N-Rich Aminal-Linked Porous Organic Polymers for Outstanding Precombustion CO2 Capture and H2 Purification: A Combined Experimental and Theoretical Study.

A large number of scientific investigations are needed for developing a sustainable solid sorbent material for precombustion CO2 capture in the integrated gasification combined cycle (IGCC) that is accountable for the industrial coproduction of hydrogen and electricity. Keeping in mind the industrially relevant conditions (high pressure, high temperature, and humidity) as well as good CO2/H2 selectivity, we explored a series of sorbent materials. An all-rounder player in this game is the porous organic polymers (POPs) that are thermally and chemically stable, easily scalable, and precisely tunable. In the present investigation, we successfully synthesized two nitrogen-rich POPs by extended Schiff-base condensation reactions. Among these two porous polymers, TBAL-POP-2 exhibits high CO2 uptake capacity at 30 bar pressure (57.2, 18.7, and 15.9 mmol g-1 at 273, 298, and 313 K temperatures, respectively). CO2/H2 selectivities of TBAL-POP-1 and 2 at 25 °C are 434.35 and 477.93, respectively. On the other hand, at 313 K the CO2/H2 selectivities of TBAL-POP-1 and 2 are 296.92 and 421.58, respectively. Another important feature to win the race in the search of good sorbents is CO2 capture capacity at room temperature, which is very high for TBAL-POP-2 (15.61 mmol g-1 at 298 K for 30 to 1 bar pressure swing). High BET surface area and good mesopore volume along with a large nitrogen content in the framework make TBAL-POP-2 an excellent sorbent material for precombustion CO2 capture and H2 purification.

Revisiting Ultrafast Dynamics in Carbonate-Based Electrolytes for Li-Ion Batteries: Clarifying 2D-IR Cross-Peak Interpretation.

Understanding chemical exchange in carbonate-based electrolytes employed in Li-ion batteries (LIBs) is crucial for elucidating ion transport mechanisms. Ultrafast two-dimensional (2D) IR spectroscopy has been widely used to investigate the solvation structure and dynamics of Li-ions in organic carbonate-based electrolytes. However, the interpretation of cross-peaks observed in picosecond carbonyl stretch 2D-IR spectra has remained contentious. These cross-peaks could arise from various phenomena, including vibrational couplings between neighboring carbonyl groups in the first solvation shell around Li-ions, vibrational excitation transfers between carbonyl groups in distinct solvation environments, and local heating effects. Therefore, it is imperative to resolve the interpretation of 2D-IR cross-peaks to avoid misinterpretations regarding ultrafast dynamics found in LIB carbonate-based electrolytes. In this study, we have taken a comprehensive investigation of carbonate-based electrolytes utilizing 2D-IR spectroscopy and molecular dynamics (MD) simulations. Through meticulous analyses and interpretations, we have identified that the cross-peaks observed in the picosecond 2D-IR spectra of LIB electrolytes predominantly arise from intermolecular vibrational excitation transfer processes between the carbonyl groups of Li-bound and free carbonate molecules. We further discuss the limitations of employing a picosecond 2D-IR spectroscopic technique to study chemical exchange and intermolecular vibrational excitation transfer processes, particularly when the effects of the molecular photothermal process cannot be ignored. Our findings shed light on the dynamics of LIB electrolytes and resolve the controversy related to 2D-IR cross-peaks. By discerning the origin of these features, we could provide valuable insights for the design and optimization of next-generation Li-ion batteries.

Molecular Mechanism of Selective Al2O3 Atomic Layer Deposition on Self-Assembled Monolayers.

Area-selective atomic layer deposition (AS-ALD) of insulating metallic oxide layers could be a useful nanopatterning technique for making increasingly complex semiconductor circuits. Although the alkanethiol self-assembled monolayer (SAM) has been considered promising as an ALD inhibitor, the low inhibition efficiency of the SAM during ALD processes makes its wide application difficult. We investigated the deposition mechanism of Al2O3 on alkanethiol-SAMs using temperature-dependent vibrational sum-frequency-generation spectroscopy. We found that the thermally induced formation of gauche defects in the SAMs is the main causative factor deteriorating the inhibition efficiency. Here, we demonstrate that a discontinuously temperature-controlled ALD technique involving self-healing and dissipation of thermally induced stress on the structure of SAM substantially enhances the SAM's inhibition efficiency and enables us to achieve 60 ALD cycles (6.6 nm). We anticipate that the present experimental results on the ALD mechanism on the SAM surface and the proposed ALD method will provide clues to improve the efficiency of AS-ALD, a promising nanoscale patterning and manufacturing technique.

Axial profiling of interferometric scattering enables an accurate determination of nanoparticle size.

Interferometric scattering (iSCAT) microscopy has undergone significant development in recent years. It is a promising technique for imaging and tracking nanoscopic label-free objects with nanometer localization precision. The current iSCAT-based photometry technique allows quantitative estimation for the size of a nanoparticle by measuring iSCAT contrast and has been successfully applied to nano-objects smaller than the Rayleigh scattering limit. Here we provide an alternative method that overcomes such size limitations. We take into account the axial variation of iSCAT contrast and utilize a vectorial point spread function model to uncover the position of a scattering dipole and, consequently, the size of the scatterer, which is not limited to the Rayleigh limit. We found that our technique accurately measures the size of spherical dielectric nanoparticles in a purely optical and non-contact way. We also tested fluorescent nanodiamonds (fND) and obtained a reasonable estimate for the size of fND particles. Together with fluorescence measurement from fND, we observed a correlation between the fluorescent signal and the size of fND. Our results showed that the axial pattern of iSCAT contrast provides sufficient information for the size of spherical particles. Our method enables us to measure the size of nanoparticles from tens of nanometers and beyond the Rayleigh limit with nanometer precision, making a versatile all-optical nanometric technique.

Two-color infrared photothermal microscopy.

Infrared photothermal microscopy is an infrared (IR) imaging technique that enables non-invasive, non-destructive, and label-free investigations at the sub-micrometer scale. It has been applied in various research areas targeting pharmaceutical and photovoltaic materials as well as biomolecules in living systems. Despite its potency in observing biomolecules in living organisms, its practical application for cytological research has been restricted by the deficiency of molecular information from the IR photothermal signal, due to the narrow spectral width of a quantum cascade laser that is one of the most preferred IR excitation light sources for current IR photothermal imaging (IPI) techniques. Here, we address this issue by bringing modulation-frequency multiplexing into IR photothermal microscopy for developing a two-color IR photothermal microscopy technique. We demonstrate that the two-color IPI technique can be used to obtain the IR microscopic images of two discrete IR absorption bands and to distinguish two different chemical species in live cells with a sub-micrometer spatial resolution. We anticipate that the more general multi-color IPI technique and its use for metabolic studies of live cells could be realized by extending the present modulation-frequency multiplexing method.

Discriminating Congested Vibrational Peaks of Condensed Organic Materials with Time- and Frequency-Resolved Coherent Anti-Stokes Raman Scattering Spectroscopy.

The spectral congestion of highly overlapping vibrational peaks of molecules in condensed phases is a persistent challenge in conventional linear vibrational spectroscopy, making it difficult to accurately determine the spectroscopic parameters. This study demonstrates the utility of time- and frequency-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy with a time-delayed picosecond probe pulse in resolving congested C-H stretching vibrational peaks of condensed organic matters. The results show that the overlapping vibrational peaks of polymeric films and oily liquids, which are not easily distinguishable in spontaneous Raman spectroscopy, can be separated in the time-resolved CARS (tr-CARS) spectra. To understand the physical basis of the enhanced spectral resolution, we examine the time series of CARS spectra obtained by varying the delay time between the pump and probe pulses. The global fit analysis indicates that the effective suppression of faster Raman free-induction-decay components and instantaneous nonresonant background signals contributes to improved spectral resolution. Additionally, the present study reveals that the CARS spectra at a sufficient probe delay time are highly sensitive to the incident and detection polarizations, further improving vibrational peak distinguishability through polarization-controlled tr-CARS.

Micro-Raman spectroscopic analysis of liquid-liquid phase separation.

Liquid-liquid phase separation (LLPS) plays a significant role in various biological processes, including the formation of membraneless organelles and pathological protein aggregation. Although many studies have found various factors that modulate the LLPS process or the liquid-to-solid phase transition (LSPT) using microscopy or fluorescence-based methods, the molecular mechanistic details underlying LLPS and protein aggregation within liquid droplets remain uncharacterized. Therefore, structural information on proteins inside liquid droplets is required to understand the mechanistic link to amyloid formation. In the present study, we monitored droplet formation related to protein fibrillation using micro-Raman spectroscopy in combination with differential interference contrast (DIC) microscopy to study the conformational change in proteins and the hydrogen-bonding (H-bonding) structure of water during LLPS. Interestingly, we found that the O-D stretching band for water (HOD in H2O) inside the droplets exhibited a distinct Raman spectrum from that of the bulk water, suggesting that the time-dependent change in the hydration environment in the protein droplets during the process of LLPS can be studied. These results demonstrate that the superior spatial resolution of micro-Raman spectroscopy offers significant advantages in investigating the molecular mechanisms of LLPS and following LSPT processes.

Thermoresponse of Odd-Even Effect in n-Alkanethiolate Self-Assembled Monolayers on Gold Substrates.

This study examines thermoresponse of odd-even effect in self-assembled monolayers (SAMs) of n-alkanethiolates (SCn , n=3-18) formed on template-stripped gold (AuTS ) using macro- and microscopic analytical techniques, contact angle goniometry (CAG) and vibrational sum frequency generation (VSFG) spectroscopy, respectively. Both CAG and VSFG analyses showed that the odd-even effect in liquid-like SAMs (n=3-9) disappeared upon heating at 50-70 °C, indicating that the heating led to increased structural disorder regardless of odd and even carbon numbers. In contrast, the opposite thermoresponse was observed for odd and even SCn molecules in wax- and solid-like SAMs (n=10-18). Namely, temperature-dependent orientational change of terminal CH3 relative to the surface normal was opposite for the odd and even molecules, thereby leading to mitigated odd-even effect. Our work offers important insights into thermoresponse of supramolecular structure in condensed organic matter.

Molecular Photothermal Effects on Time-Resolved IR Spectroscopy: Solute-Solvent Intermolecular Energy Transfer.

Time-resolved IR pump-probe (IR-PP) and two-dimensional IR (2D-IR) spectroscopy are valuable tools for studying ultrafast chemical and biological processes in solutions. However, the corresponding signals at long times are obscured by the molecular photothermal effects resulting from the heat dissipation of vibrationally photoexcited molecules to the surroundings. Recently, a phenomenology model was used to describe molecular photothermal effects on IR-PP signals and the diagonal and cross-peaks of 2D-IR spectra at long pump-probe delay times. Here, we consider the thermal diffusion equation with a time-dependent heat source term to describe the solute-solvent energy transfer process. An approximate solution to the nonhomogeneous differential equation shows that the molecular photothermal effect is determined by the mean intermolecular distance between IR-absorbing molecules. We show that the time profile of heat dissipation from a vibrationally excited molecule to the surroundings, which provides information about the mechanisms involved in the solute-solvent intermolecular energy transfer process in solutions, can be directly measured by analyzing the molecular photothermal IR-PP and 2D-IR signals. We anticipate that the present work can be used to interpret local heating-induced time-resolved IR spectroscopic signals and understand the rate of and the mechanisms involved in the conversion from high-frequency molecular vibrational energy to solvent kinetic energy in condensed phases.