Yeonju Park

Ultrafast carrier dynamics and radiative recombination in multiferroic BiFeO3

We report a comprehensive study of ultrafast carrier dynamics in single crystals of multiferroic BiFeO3. Using degenerate femtosecond optical pump-probe spectroscopy, we find that the photoexcited electrons relax to the conduction band minimum through electron-phonon coupling with a ∼1 ps time constant that does not significantly change across the antiferromagnetic transition. Electrons subsequently leave the conduction band and primarily decay via radiative recombination on a nanosecond timescale, as supported by photoluminescence measurements. We find that despite the coexisting ferroelectric and antiferromagnetic orders in BiFeO3, its intrinsic nature results in carrier relaxation similar to that observed in bulk semiconductors.

Two-dimensional correlation spectroscopy in polymer study

This review outlines the recent works of two-dimensional correlation spectroscopy (2DCOS) in polymer study. 2DCOS is a powerful technique applicable to the in-depth analysis of various spectral data of polymers obtained under some type of perturbation. The powerful utility of 2DCOS combined with various analytical techniques in polymer studies and noteworthy developments of 2DCOS used in this field are also highlighted.

Preparation of a Superhydrophobic and Peroxidase-like Activity Array Chip for H2O2 Sensing by Surface-Enhanced Raman Scattering

In this paper, we propose a novel and simple method for preparing a dual-biomimetic functional array possessing both superhydrophobic and peroxidase-like activity that can be used for hydrogen peroxide (H2O2) sensing. The proposed method is an integration innovation that combines the above two properties and surface-enhanced Raman scattering (SERS). We integrated a series of well-ordered arrays of Au points (d = 1 mm) onto a superhydrophobic copper (Cu)/silver (Ag) surface by replicating an arrayed molybdenum template. Instead of using photoresists and the traditional lithography method, we utilized a chemical etching method (a substitution reaction between Cu and HAuCl4) with a Cu/Ag superhydrophobic surface as the barrier layer, which has the benefit of water repellency. The as-prepared Au points were observed to possess peroxidase-like activity, allowing for catalytic oxidation of the chromogenic molecule o-phenylenediamine dihydrochloride (OPD). Oxidation was evidenced by a color change in the presence of H2O2, which allows the array chip to act as an H2O2 sensor. In this study, the water repellency of the superhydrophobic surface was used to fabricate the array chip and increase the local reactant concentration during the catalytic reaction. As a result, the catalytic reaction occurred when only 2 μL of an aqueous sample (OPD/H2O2) was placed onto the Au point, and the enzymatic product, 2,3-diaminophenazine, showed a SERS signal distinguishable from that of OPD after mixing with 2 μL of colloidal Au. Using the dual-biomimetic functional array chip, quantitative analysis of H2O2 was performed by observing the change in the SERS spectra, which showed a concentration-dependent behavior for H2O2. This method allows for the detection of H2O2 at concentrations as low as 3 pmol per 2 μL of sample, which is a considerable advantage in H2O2 analysis. The as-prepared substrate was convenient for H2O2 detection because only a small amount of sample was required in each analysis. Highly sensitive detection was realized using SERS. Therefore, this chip was shown to exhibit significant potential for applications in bioanalysis.

Salt Triggers the Simple Coacervation of an Underwater Adhesive When Cations Meet Aromatic π Electrons in Seawater

Adhesive systems in many marine organisms are postulated to form complex coacervates (liquid-liquid phase separation) through a process involving oppositely charged polyelectrolytes. Despite this ubiquitous speculation, most well-characterized mussel adhesive proteins are cationic and polyphenolic, and the pursuit of the negatively charged proteins required for bulk complex coacervation formation internally remains elusive. In this study, we provide a clue for unraveling this paradox by showing the bulky fluid/fluid separation of a single cationic recombinant mussel foot protein, rmfp-1, with no additional anionic proteins or artificial molecules, that is triggered by a strong cation-π interaction in natural seawater conditions. With the similar condition of salt concentration at seawater level (>0.7 M), the electrostatic repulsion between positively charged residues of mfp-1 is screened significantly, whereas the strong cation-π interaction remains unaffected, which leads to the macroscopic phase separation (i.e., bulky coacervate formation). The single polyelectrolyte coacervate shows interesting mechanical properties including low friction, which facilitates the secretion process of the mussel. Our findings reveal that the cation-π interaction modulated by salt is a key mechanism in the mussel adhesion process, providing new insights into the basic understanding of wet adhesion, self-assembly processes, and biological phenomena that are mediated by strong short-range attractive forces in water.

Surface Reaction of LiCoO2/Li System under High-Voltage Conditions by X-Ray Spectroscopy and Two-Dimensional Correlation Spectroscopy (2D-COS)

We studied the surface reactions of a LiCoO2/Li cell under high-voltage conditions using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and two-dimensional correlation spectroscopy (2D-COS). 2D XPS correlation spectra show that Li2CO3 is formed first by decomposition of the organic solvents, and then polycarbonate, which is formed by polymerization of the electrolytes, is produced on the cathode surface of the LiCoO2/Li system under high-voltage conditions. XAS measurements also confirm that the solid electrolyte interface (SEI) layer is formed on the LiCoO2 electrode by decomposition of the organic solvents. The thickness of the SEI layer is less than 100 Å.

Understanding the structural differences between spherical and rod-shaped human insulin nanoparticles produced by supercritical fluids precipitation.

In this study, the thermal denaturation mechanism and secondary structures of two types of human insulin nanoparticles produced by a process of solution-enhanced dispersion by supercritical fluids using dimethyl sulfoxide (DMSO) and ethanol (EtOH) solutions of insulin are investigated using spectroscopic approaches and molecular dynamics calculations. First, the temperature-dependent IR spectra of spherical and rod-shaped insulin nanoparticles prepared from DMSO and EtOH solution, respectively, are analyzed using principal component analysis (PCA) and 2D correlation spectroscopy to obtain a deeper understanding of the molecular structures and thermal behavior of the two insulin particle shapes. All-atom molecular dynamics (AAMD) calculations are performed to investigate the influence of the solvent molecules on the production of the insulin nanoparticles and to elucidate the geometric differences between the two types of nanoparticles. The results of the PCA, the 2D correlation spectroscopic analysis, and the AAMD calculations clearly reveal that the thermal denaturation mechanisms and the degrees of hydrogen bonding in the spherical and rod-shaped insulin nanoparticles are different. The polarity of the solvent might not alter the structure or function of the insulin produced, but the solvent polarity does influence the synthesis of different shapes of insulin nanoparticles.

Formation mechanism of α-lactalabumin/oleic acid complex characterized by 2D correlation analysis ☆

Partially unfolded α-lactalbumin (ALA) forms a complex with oleic acid (OA) that exhibits cytotoxic activity. In this study, for the first time, the pH-induced formation mechanism for ALA/OA complexes with two different molar ratios was investigated at the molecular level. For a deeper understanding of the formation mechanism of the two different ALA/OA complexes with decreasing pH, principal component analysis (PCA) and two-dimensional (2D) correlation spectroscopy were used to examine the pH-dependent IR spectra of ALA/OA complexes. By tracking the secondary structural variations in the ALA/OA complexes with decreasing pH, we successfully elucidated the formation mechanism of the ALA/OA complexes at the molecular level. The results showed that the secondary structures of theses complexes exhibited the greatest change between pH4 and pH3.5 and that the components that mainly contributed to the pH-induced transition from the N-state to the A-state were dissimilar in the two different ALA/OA complexes.

High-yield clicking and dissociation of doxorubicin nanoclusters exhibiting differential cellular uptakes and imaging.

Gold nanoparticles (AuNPs) and quantum dots (Qdots) were clicked into doxorubicin nanoclusters that showed enzyme-dependent dissociation behaviors for differential cellular uptakes and imaging. The AuNPs were co-functionalized with doxorubicin (DOX) and azide-terminated polymer (DOX/azide@AuNP), while an enzyme-cleavable peptide and alkyne-terminated polymer were sequentially conjugated on Qdot surface (Alkyne-MMP@Qdot). Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and fluorescence imaging detected the azide and alkyne groups on DOX/azide@AuNP and Alkyne-MMP@Qdot, respectively, and the click-reactivity was also confirmed. In the presence of the catalyst, two nanoparticles were clicked to doxorubicin nanoclusters, which increased the volume of the particles ca. 343-fold within 30min. Upon matrix metalloproteinase-2 (MMP-2) digestion, the nanoclusters were clearly dissociated into smaller particles, and the fluorescence of the quenched Qdot was also recovered, which suggests that the nanoclusters respond to MMP-2 concentrations and can thus be employed for cancer imaging. Confocal microscopy and an elemental analysis of the cancer cells revealed that the cellular uptakes of doxorubicin nanoclusters significantly increased at higher MMP-2 concentrations, and doxorubicin could also be cleaved for anti-cancer effects. In vivo and in vitro cytotoxicity assay accordingly showed that the cytotoxicity of doxorubicin nanoclusters against cancer cells increased in MMP-2-rich environments such as tumor site. Thus, these nanoclusters containing DOX/azide@AuNP and Alkyne-MMP@Qdot are expected to be multifunctional carriers for targeted anti-cancer treatments and imaging.

Quantitative Determination of Iron Ions Based on a Resonance Raman (RR) Probe-Phenanthroline

In this paper, we demonstrate a new promising resonance Raman (RR)-based method for the determination of Fe3+ concentrations in aqueous solutions. Iron ions were quantified at a low concentration range by employing hydroxylamine hydrochloride as the reductant, and phenanthroline as the complexing agent, thereby reducing Fe3+ to Fe2+. The addition of Fe3+ to the detection reagent resulted in a rapid color change from colorless to orange-red, together with an obvious new RR band appearing at 1459 cm-1. Herein, the RR intensity of the phenanthroline-Fe2+ complex strengthened with increasing Fe3+ concentration, which was identified from the variation of the Raman spectra. Therefore, we successfully detected Fe3+ at lower concentrations using the proposed method, illustrating its great potential for the detection of Fe3+ with abundant RR fingerprint information. More importantly, the proposed method exhibited a wide liner range from 0.05 to 10 μg/mL.

Identification of native charge-transfer status of p-aminothiolphenol adsorbed on noble metallic substrates by surface-enhanced infrared absorption (SEIRA) spectroscopy

p-Aminothiophenol (PATP) is a preferred molecule in research on surface-enhanced Raman scattering (SERS) because of its unique characteristics of high spectral activity, easily induced charge-transfer (CT), and sensitivity to molecular structural changes. However, some aspects are still unclear, such as the initial steady state of PATP on noble metallic substrates without strong additional excitation with incident and/or induced electromagnetic radiation. Information about the initial steady state, especially the intrinsic CT state, is of great importance to elucidate the dynamic processes of CT and/or molecular structural changes under additional excitation. To investigate the native state of an adsorbed molecule, a suitable probe method that does not disrupt the native state of the whole system, including both molecules and substrates, is required. SERS is not applied in this context because of its use of high-energy visible and near-infrared light. Herein, a low-energy probe method, surface-enhanced infrared-absorption (SEIRA) spectroscopy, is employed as a suitable method for studying the native adsorption state of PATP on silver nanoisland films. The molecular structure and adsorption state were investigated. The intrinsic CT state received particular attention by analyzing the CT-related vibration of B2 modes. Using Fourier transform infrared (FTIR), transmission SEIRA and reflection SEIRA spectroscopy, we explained why the relative intensities of some bands were different under different conditions. A quasi-standing orientation of PATP adsorbed on the substrates was also confirmed. More importantly, we demonstrated that there is no perceptible CT between PATP and silver nanoisland films; in contrast, CT generally occurs in a disruptive manner in SERS. Density functional theory (DFT) calculations and the selection rules for infrared (IR) transmission and reflection-absorption spectroscopy were used to analyze the spectra throughout the paper. SEIRA proved to be an effective technique to explore the native adsorption state of molecules without the excessive external disturbance induced by excitation. The results are very important in providing insight into molecules in surface-interface chemistry, enhanced spectroscopy and photoelectronics.