Diverse Applications of Two-Dimensional Correlation Spectroscopy (2D-COS).

This second of the two-part series of a comprehensive survey review provides the diverse applications of two-dimensional correlation spectroscopy (2D-COS) covering different probes, perturbations, and systems in the last two years. Infrared spectroscopy has maintained its top popularity in 2D-COS over the past two years. Fluorescence spectroscopy is the second most frequently used analytical method, which has been heavily applied to the analysis of heavy metal binding, environmental, and solution systems. Various other analytical methods including laser-induced breakdown spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, capillary electrophoresis, seismologic, and so on, have also been reported. In the last two years, concentration, composition, and pH are the main effects of perturbation used in the 2D-COS fields, as well as temperature. Environmental science is especially heavily studied using 2D-COS. This comprehensive survey review shows that 2D-COS undergoes continuous evolution and growth, marked by novel developments and successful applications across diverse scientific fields.

Novel Developments and Progress in Two-Dimensional Correlation Spectroscopy (2D-COS).

This first of the two-part series of the comprehensive survey review on the progress of the two-dimensional correlation spectroscopy (2D-COS) field during the period 2021-2022, covers books, reviews, tutorials, novel concepts and theories, and patent applications that appeared in the last two years, as well as some inappropriate use or citations of 2D-COS. The overall trend clearly shows that 2D-COS is continually growing and evolving with notable new developments. The technique is well recognized as a powerful analytical tool that provides deep insights into systems in many science fields.

Physiological and metabolic analyses reveal the proline-mediated flowering delay mechanism in Prunus persica.

Peaches are susceptible to various environmental stresses. Particularly in late spring, freezing temperatures can damage peaches and consequently, affect their productivity. Therefore, flowering delay is a prominent strategy for avoiding spring frost damage. Our previous study confirmed that treatment with 5% sodium alginate and 100 mM CaCl2 (5AG) to avoid frost damage during the blooming stage delays flowering. To reveal the flowering delay mechanism of peaches, this study systematically analyzed the modification of amino acid profiles in control and 5AG-treated peach plants at different day intervals. Our findings indicate that arginine (Arg), glutamate (Glu), and proline (Pro) levels differed between the control and 5AG-treated peach shoots throughout the phenological development of flower buds. Furthermore, two amino acids (Arg and Glu) are involved in the Pro pathway. Thus, using a computational metabolomics method, Pro biosynthesis and its characteristics, gene ontology, gene synteny, cis-regulatory elements, and gene organizations were examined to decipher the involvement of Pro metabolism in peach flowering delay. In addition, qRT-PCR analysis revealed the transcriptional regulation of Pro-related and flowering-responsive genes and their role in flowering delay. Overall, this pilot study provides new insights into the role of Pro in the flowering delay mechanisms in Prunus persica through 5AG treatment.

Effect of a Ag-rGO structure on the SERS activity of PEDOT:PSS films.

π-Conjugated organic semiconductors with tunable electronic structures are new prospective active substrate materials for surface-enhanced Raman scattering (SERS). However, observing higher SERS activity when using organic semiconductors as substrates could be difficult because there is no plasmonic effect of hot electrons. Here, we designed a Ag-reduced graphene oxide (rGO) structure, introduced it into a poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) solution, and spin-coated the solution to obtain a Ag-rGO/PEDOT:PSS (ARPP) film. Our analyses demonstrate that the introduction of this Ag-rGO structure can not only enhance the electromagnetic field effect based on plasmon resonance but also improve the interaction between the target molecule and the substrate in the ARPP film. This innovative approach not only improves the SERS activity of π-conjugated organic polymers but also provides novel ideas for the preparation of other organic semiconductor-based SERS substrates.

Investigation of selective SERS enhancement mechanism of Au nanospheres and Au nanorods based on 2T2D-SERS correlation spectroscopy.

The selective enhancement mechanism in surface-enhanced Raman scattering (SERS) is demonstrated. Two different types of single nanoparticles (Au nanosphere and Au nanorod) were used to investigate the role of the localized surface plasmon resonance (LSPR) in SERS spectra by using the two-trace two-dimensional (2T2D) correlation spectroscopy. The SERS intensities of three probe molecules, 4-mercaptobenzoic acid (4-MBA), 4-aminothiophenol (4-ATP), and 4-bromobenzenethiol (4-BBT), respectively, were enhanced but slightly different when adsorbed on Au nanospheres and Au nanorods. 2T2D correlation SERS spectra clearly showed that even with the same shape of Au nanoparticles, the main factors influencing the SERS enhancement can vary depending on the specific type of SERS tags used. Such subtle difference could not be clearly identified by the conventional spectral analysis. This result sheds light on potential applications of 2T2D correlation spectroscopy. For 4-MBA molecules, the a1 and b2 modes are mainly affected by the Au nanospheres and Au nanorods. For 4-ATP molecules, the a1 and b2 modes related to C-S stretching combined with C-C stretching band are mainly affected by Au nanorods and Au nanospheres. For 4-BBT molecules, the a1 and b2 modes of C-C (aromatic ring) stretching band are mainly affected by Au nanorods and Au nanospheres. This study offers valuable insights into the relationship between nanoparticle shape and SERS enhancement.

Self-Healable Adhesive Hydrogel with a Preserved Underwater Adhesive Ability Based on Histidine-Zinc Coordination and a Bioengineered Hybrid Mussel Protein.

Mussels are marine organisms that are capable of constructing an underwater adhesion between their bodies and rigid structures. It is well known that mussels achieve underwater adhesion through the presence of mussel adhesive proteins (MAPs) that contain high levels of 3,4-dihydroxyphenylalanine (DOPA). Although the extraordinary underwater adhesive properties of mussels are attributed to DOPA, its capacity to play a dual role in surface adhesion and internal cohesion is inherently limited. However, mussels employ a combination of chemical moieties, not just DOPA, along with anatomical components, such as plaque and byssus, in underwater adhesion. This also involves junction proteins that connect the plaque and byssus. In this study, a novel hybrid MAP was bioengineered via the fusion of the plaque protein (foot protein type 1) and the histidine-rich domain of the junction protein (foot protein type 4). To achieve direct adhesion underwater, the adhesive should maintain surface adhesion without disintegrating. Notably, the histidine-Zn-coordinated hybrid MAP hydrogel maintained a high surface adhesion ability even after cross-linking because of the preservation of its unoxidized and non-cross-linked DOPA moieties. The formulated adhesive hydrogel system based on the bioengineered hybrid MAP exhibited self-healing properties, owing to the reversible metal coordination bonds. The developed adhesive hydrogel exhibits outstanding levels of bulk adhesion in underwater environments, highlighting its potential as an effective adhesive biomaterial. Therefore, the introduction of histidine-rich domains into MAPs may be applied in various studies to formulate mussel-inspired adhesives with self-healing properties and to fully utilize the adhesive ability of DOPA.

Investigation of Minerals Extracted during Seawater Desalination Using Two-Dimensional Correlation Spectroscopy.

In this study, mineral components extracted during the desalination process were concentrated and dried, and then identified using energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), infrared (IR), and Raman spectroscopy. For detailed identification, two-dimensional correlation spectroscopy (2D-COS) was also applied to the XRD patterns, IR spectra, and Raman spectra of the minerals obtained from each desalination step. The EDS results confirm the presence of seawater minerals rich in Na+ ions in the first and second extracts, Ca2+ ions are present only in these stages, and Mg2+ ions are abundant in the third and final extracts. The presence of NaCl and MgSO4 minerals in the first to third and final extracts, respectively, was confirmed using XRD patterns. From the IR and Raman spectra, we found that the degree of hydration of SO42--related extracts decreased as seawater underwent desalination. Furthermore, 2D-COS provides information about the changes in the extracts obtained from the first to final stage. Heterospectral XRD and Raman 2D-COS provides clear assignments for Raman spectra. The use of 2D-COS helps to understand the characteristics of seawater extracts during the desalination process, and provides a better understanding of chemical and structural adaptations within the extract. As a result, this method contributes to an improved understanding of the desalination process and final products.

Reactive oxygen species-responsive clicked assembly of gold nanoparticles to enhance photothermal therapy.

To enhance the efficacy of photothermal therapy (PTT) at tumor sites, we designed a reactive oxygen species (ROS)-responsive gold nanoparticle (AuNP)-based nanosystem in which azide-decorated AuNPs (N3@AuNPs) and diselenide-coated alkyne-decorated AuNPs (Se/Ak@AuNPs) were separately prepared for selective clicking into nanoclusters when exposed to ROS. Se/Ak@AuNPs were dual-functionalized with alkyne moieties and diselenide linkers embedded in a long chain of polyethylene glycol (PEG) to enable the alkyne moieties of Se/Ak@AuNPs to be inaccessible to the azide moieties of N3@AuNPs owing to steric hindrance. At tumor sites where the ROS level is elevated due to the increased metabolic activity, cellular receptor signaling, mitochondrial dysfunction, and oncogene activity, the diselenide linkers were cleaved, leading to the liberation of the long PEG chains tethered to AuNPs, and the alkyne moieties could be recognized by the surrounding azide moieties to generate a click reaction. The clicked AuNPs formed clustered nanoparticles with increased size. Upon 808 nm laser irradiation, these large clusters of AuNPs significantly enhanced the photothermal conversion efficiency compared with that of isolated AuNPs. In vitro studies revealed that the AuNP clusters exhibited a noticeably higher apoptosis rate than AuNPs. Therefore, ROS-responsive clicked AuNP clusters can be a potential tool for PTT enhancement in cancer treatment.

Molecular-Orbital Delocalization Enhances Charge Transfer in π-Conjugated Organic Semiconductors.

π-Conjugated organic semiconductors are promising materials for surface-enhanced Raman scattering (SERS)-active substrates based on the tunability of electronic structures and molecular orbitals. Herein, we investigate the effect of the temperature-mediated resonance-structure transitions of poly(3,4-ethylenedioxythiophene) (PEDOT) in poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT : PSS) films on the interactions between substrate and probe molecules, thereby affecting the SERS activity. Absorption spectroscopy and density functional theory calculations show that this effect occurs mainly due to delocalization of the electron distribution in molecular orbitals, effectively promoting the charge transfer between the semiconductor and probe molecules. In this work, we investigate for the first time the effect of electron delocalization in molecular orbitals on SERS activity, which will provide new design ideas for the development of highly sensitive SERS substrates.

Highly selective and quantitative in situ monitoring of cell surface proteins by SERS immunoassay system.

Due to their pivotal roles in many biological functions, cell surface proteins (CSPs) are often used for cancer prognosis, as evidenced by a number of studies that have reported significant changes in the expression levels of specific surface proteins depending on the stage of tumorigenesis and selection/variety of reprogrammed cells during cell fate conversion. Current CSP detection strategies suffer from poor selectivity and lack the ability for in situ analysis but maintain the spatial information between cells. Here, we have fabricated nanoprobes for surface-enhanced Raman scattering (SERS) immunoassays by conjugating a specific antibody onto silica-coated gold nanoparticles incorporating an individual Raman reporter (Au-tag@SiO2-Ab NPs) for highly sensitive and selective in situ detection in different types of cells. When multiple HEK293 cell lines stably expressing different levels of the CSP, ACE2, were investigated by the SERS immunoassay, we demonstrated that the level of ACE2 expression in each cell line could be statistically distinguished from that in the other cell lines, indicating the quantitative feature of this biosensing system. When detecting living cells without cell lysis or fixation, as well as fixed cells, the levels of the epithelial CSPs, EpCAM (epithelial cell adhesion molecule) and E-cadherin, were successfully determined using our Au-tag@SiO2-Ab NPs and SERS immunoassay system in a highly selective and quantitative manner without significant cytotoxicity. Hence, our work provides technical insight into the development of a biosensing platform for a variety of biomedical applications, such as cancer metastasis prognosis and the in situ monitoring of stem cell reprogramming and differentiation.

Interface Design of 3D Flower-like Ag@ZnSe Composites: SERS and Photocatalytic Performance.

In this work, we cosputtered Ag and ZnSe on a polystyrene template to form a three-dimensional (3D) Ag@ZnSe (x) structure. The 3D surface morphology and material composition that provided abundant "hot spots" were controlled by adjusting the sputtering power of the ZnSe, which was confirmed by finite-difference time-domain (FDTD) simulation. The introduction of ZnSe into the noble metal Ag also introduced a charge-transfer (CT) effect into the system, and the CT path was proven with the two-dimensional correlation spectroscopy (2D-COS)-surface-enhanced Raman scattering (SERS) technique. In addition, the substrate exhibited excellent catalytic activity due to the CT effect. The catalyzed degradation of malachite green (MG) was due to the CT effect in the system, and the catalytic process was successfully monitored by in situ SERS. Most importantly, the catalytic degradation by Ag@ZnSe (x) with different parameters was proportional to the degree of CT (ρCT). The SERS and catalytic mechanisms were analyzed in depth with the 2D-COS-SERS technique, which was also useful in verifying the CT process. The catalytic sites for MG were successfully monitored with the 2D-COS-SERS technique. This study provides a reference for studies of the synergistic effects of the electromagnetic mechanism and CT, as well as a new perspective on photocatalysis with dye molecules and monitoring of the catalytic processes.

One Carbon Ring Expansion of Bipyrrole to Bipyridine Enables Access to a π-Extended, Non-innocent, Corrole-like Ligand.

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its NiII complex were synthesized from a diaza-triphenylene precursor, which was obtained from a double one-carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid-catalyzed condensation with pyrrole, subsequent reaction with pentafluorobenzaldehyde afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted NiII insertion with Ni(OAc)2 ⋅ 4H2 O resulted an ESR active, NiII bipyricorrole radical complex, which was converted to a stable cationic NiII complex upon treatment with [(Et3 O)+ (SbCl6 )- ]. Both complexes were characterized by 1 H and 13 C NMR, UV/Vis spectroscopy and single crystal X-ray diffraction analysis. The NiII bipyricorrole radical complex is converted to a cationic NiII complex by single-electron reduction using cobaltocene. Both the cationic NiII complex and the radical NiII complex exhibited ligand-centered redox behavior, whereas the NiII remains in the +2 oxidation state.

Continuing progress in the field of two-dimensional correlation spectroscopy (2D-COS): Part III. Versatile applications.

In this review, the comprehensive summary of two-dimensional correlation spectroscopy (2D-COS) for the last two years is covered. The remarkable applications of 2D-COS in diverse fields using many types of probes and perturbations for the last two years are highlighted. IR spectroscopy is still the most popular probe in 2D-COS during the last two years. Applications in fluorescence and Raman spectroscopy are also very popularly used. In the external perturbations applied in 2D-COS, variations in concentration, pH, and relative compositions are dramatically increased during the last two years. Temperature is still the most used effect, but it is slightly decreased compared to two years ago. 2D-COS has been applied to diverse systems, such as environments, natural products, polymers, food, proteins and peptides, solutions, mixtures, nano materials, pharmaceuticals, and others. Especially, biological and environmental applications have significantly emerged. This survey review paper shows that 2D-COS is an actively evolving and expanding field.

Continuing progress in the field of two-dimensional correlation spectroscopy (2D-COS), part II. Recent noteworthy developments.

This comprehensive survey review compiles noteworthy developments and new concepts of two-dimensional correlation spectroscopy (2D-COS) for the last two years. It covers review articles, books, proceedings, and numerous research papers published on 2D-COS, as well as patent and publication trends. 2D-COS continues to evolve and grow with new significant developments and versatile applications in diverse scientific fields. The healthy, vigorous, and diverse progress of 2D-COS studies in many fields strongly confirms that it is well accepted as a powerful analytical technique to provide an in-depth understanding of systems of interest.

Probe-Free Identification of RNA Virus Variants with Point Mutations by Surface-Enhanced Raman Spectroscopy.

As observed in the COVID-19 pandemic, RNA viruses continue to rapidly evolve through mutations. In the absence of effective therapeutics, early detection of new severely pathogenic viruses and quarantine of infected people are critical for reducing the spread of the viral infections. However, conventional detection methods require a substantial amount of time to develop probes specific to new viruses, thereby impeding immediate response to the emergence of viral pathogens. In this study, we identified multiple types of viruses by obtaining the spectral fingerprint of their surface proteins with probe-free surface-enhanced Raman scattering (SERS). In addition, the SERS-based method can remarkably distinguish influenza virus variants with several surface protein point mutations from their parental strain. Principal component analysis (PCA) of the SERS spectra systematically captured the key Raman bands to distinguish the variants. Our results show that the combination of SERS and PCA can be a promising tool for rapid detection of newly emerging mutant viruses without a virus-specific probe.

Electrospun Nanofibrils Surface-Decorated with Photo-Cross-Linked Hyaluronic Acid for Cell-Directed Assembly.

Hyaluronic acid (HA) was chemically immobilized on the surface of electrospun nanofibrils to form a cell/NF complex. Poly(caprolactone) (PCL) was electrospun into nanofibrous mats that were subsequently aminolyzed into nanofibrils. The aminolyzed nanofibrils were surface-decorated with methacrylated HA via Michael type addtion and by photo-cross-linking. Fourier transform infrared spectroscopy revealed the presence of HA on the surface of the nanofibrils. The thermogravimetric and colorimetric analyses indicate that the degree of HA immobilization could be varied by varying the photo-cross-linking duration. Thus, on increasing the photo-cross-linking duration, the swelling ratios increased gradually, and the surface charge of the decorated nanofibrils decreased. NIH3T3 cells and surface-decorated nanofibrils spontaneously assembled into the cell/NF complex. A higher degree of surface-immobilized HA enhanced cell viability and proliferation compared to nanofibrils without surface-immobilized HA. Thus, we envision that HA-immobilized nanofibrils can be employed as a tissue-engineering matrix to control cell proliferation and differentiation.

Dual irradiation-triggered anticancer therapeutics composed of polydopamine-coated gold nanoparticles.

The therapeutic efficacy of nanoparticles depends on their ability to release encapsulated photosensitizers. Here, surface-engineered metallic gold nanoparticles (AuNP) were irradiated with dual near-infrared (NIR) light to enhance the release of photosensitizer. Dopamine hydrochloride was surface-polymerized to polydopamine (PDA) layers on AuNP, and chlorin-e6 (Ce6) was chemically tethered to primary amines of PDA. The resulting Ce6-conjugated AuNP were characterized by Raman and X-ray photoelectron spectroscopy and visualized by electron microscopy and light scattering. The generation of reactive oxygen species was increased following dual NIR irradiation at 650 nm and 808 nm, which was attributed to the increased liberation of Ce6. In vitro, dual NIR irradiation significantly enhanced the anticancer effect of Ce6-incorporating AuNP by increasing the population of apoptotic cells. In vivo, tumor xenografted animals exhibited much better tumor suppression when subjected to dual NIR irradiation. Thus, we propose the use of Ce6-incorporating AuNP coupled to dual NIR irradiation for future anticancer treatment of solid tumors.

Continuing progress in the field of two-dimensional correlation spectroscopy (2D-COS), part I. Yesterday and today.

This comprehensive survey review, as the first of three parts, compiles past developments and early concepts of two-dimensional correlation spectroscopy (2D-COS) and subsequent evolution, as well as its early applications in various fields for the last 35 years. It covers past review articles, books, proceedings, and numerous research papers published on 2D-COS. 2D-COS continues to evolve and grow with new significant developments and versatile applications in diverse scientific fields. The healthy, vigorous, and diverse progress of 2D-COS studies in many fields confirms that it is well accepted as a powerful analytical technique to provide the in-depth understanding of systems of interest.

Grain Growth Behavior and Electrical Properties of 0.96(K0.46-xNa0.54-x)Nb0.95Sb0.05O3-0.04Bi0.5(Na0.82K0.18)0.5ZrO3 Ceramics.

This study investigated the causes of microstructural changes and the resultant electrical properties according to the sintering temperature of 0.96(K0.46-xNa0.54-x)Nb0.95Sb0.05O3-0.04Bi0.5(Na0.82K0.18)0.5ZrO3 lead-free ceramics by analyzing the correlation between vacancy concentrations and 2D nucleation. When sintered for 4 h, no grain growth occurred for the x = 0.000 composition over a wide temperature range, demonstrating that the existence of initial vacancies is essential for grain growth. As x increased, that is, as the vacancy concentration increased, the critical driving force (ΔGC) for 2D nucleation decreased, and abnormal grain growth was promoted. The number and size of these abnormal grains increased as the sintering temperature increased, but at sintering temperatures above 1100 °C, they decreased again owing to a large drop in ΔGC. The x = 0.005 specimen sintered at 1085 °C exhibited excellent piezoelectric properties of d33 = 498 pC/N and kp = 0.45 due to the large number of large abnormal grains with an 83% tetragonal phase fraction. The x = 0.000 specimen sintered at 1130 °C with suppressed grain growth exhibited good energy storage properties because of its very high relative density and small grain size of 300 to 400 nm.

Fluorescence-Shadowing Nanoparticle Clusters for Real-Time Monitoring of Tumor Progression.

Monitoring tumor progression is important for elucidating appropriate therapeutic strategies in response to anticancer therapeutics. To fluorescently monitor the in vivo levels of tumor-specific enzymes, we prepared matrix metalloprotease (MMP)-responsive gold nanoparticle (AuNP) clusters to sense tumor microenvironments. Specifically, AuNPs and quantum dots (QDs) were surface-engineered with two poly(ethylene glycol) [PEG] shells and cyclooctyne moieties, respectively, for the copper-free click reaction. Upon "peeling off" of the secondary shell from the double-PEGylated AuNPs under MMP-rich conditions, shielded azide moieties of the AuNPs were displayed toward the QD, and those two particles were clicked into nanoparticle clusters. This consequently resulted in a dramatic size increase and fluorescence quenching of QDs via fluorescence energy transfer (FRET) due to the molecular proximity of the particles. We observed that FRET efficiency was modulated via changes in MMP levels and exposure time. Cancer cell numbers exhibited a strong correlation with FRET efficiency, and in vivo studies that employed solid tumor models accordingly showed that FRET efficiency was dependent on the tumor size. Thus, we envision that this platform can be tailored and optimized for tumor monitoring based on MMP levels in solid tumors.