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Molecular vibrations that bear information about intrinsic properties of chemical compounds are challenging to detect at submonolayer densities. Surface-enhanced infrared absorption (SEIRA) spectroscopy has been proven to be a viable approach to enhance and detect weak vibration signals. Here, we report a SEIRA sensor based on mid-infrared surface plasmon resonances supported by single-walled carbon nanotubes (SWCNTs). Due to the 1D nature of SWCNTs, their plasmon modes are highly polarized with the electromagnetic fields spatially confined to nanometer scales. Leveraging these characteristics of SWCNTs, we observe a polarization selective coupling between their surface plasmons and vibrational modes of chemical bonds introduced onto their surfaces. A maximum modulation of ∼15% to the plasmon resonance peak is obtained for a submonolayer chemical group coverage. These findings suggest that SWCNTs may potentially serve as a highly sensitive SEIRA platform for revealing intricate information about molecular compositions and bond orientations.

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A green, fast and effective multivariate method for the determination of atrazine (ATZ) was developed using conventional infrared equipment furnished with an attenuated total reflectance module (ATR-IR), providing limit of detection (LOD) and limit of quantification (LOQ) in the ranges from 1.9 to 4.6 µg/mL and from 5.6 to 14 µg/mL, respectively. Furthermore, the surface-enhanced infrared absorption (SEIRA) approach was investigated to improve the sensitivity of the measurements and detect ATZ at low concentrations, addressing the compatibility with reference methods. To this end, a substrate formed by silver selenide quantum dots stabilized with mercaptopropionic acid (Ag2Se/MPA), synthesized in aqueous medium by an one-pot synthesis, was used. The spectral data were investigated by univariate and multivariate calibrations, allowing to calculate the enhancement factor (EF) and the multivariate enhancement factor (MEF), respectively. The SEIRA strategy proved to be able to enhance the atrazine signal up to 86-fold, allowing the detection of ATZ at concentrations as low as 0.001 µg/mL.

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Scientific studies have demonstrated that conjugates of anticancer drugs with metal nanoparticles (MeNPs) lead to a more effective deactivation of tumor cells compared to free drugs. Similarly, it has been established that conjugates of antibiotics with MeNPs exhibit higher biocidal activity against bacteria than their unbound counterparts. However, limited information is available regarding conjugates formed from drugs other than anticancer and antibiotics. Therefore, our research aims to develop synthesis methods for conjugates of chlorpromazine (CPZ), a neuroleptic, with gold nanoparticles (AuNPs). CPZ-AuNP conjugates were prepared through a ligand exchange reaction conducted on the surface of quasi-spherical, negatively charged citrate-stabilized TC-AuNPs with an average size of 55 ± 5 nm. UV-vis spectroscopy was employed to determine the stability range of the conjugates under controlled conditions of pH and ionic strength. Based on electrokinetic measurements, it was observed that the zeta potential of CPZ-AuNP conjugates strongly depends on the amount of CPZ adsorbed on the TC-AuNP surface. Additionally, the conjugates exhibited an isoelectric point at pH 8.8. Surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRA) were employed to elucidate the adsorption structure of CPZ on TC-AuNPs. The interpretation of the spectra was conducted based on the Raman and FTIR spectra of CPZ, along with calculations performed using Density Functional Theory (DFT). The results indicated that CPZ primarily interacts with the TC-AuNP surface through the angularly oriented phenothiazine ring and the propylene bridge. Furthermore, it was demonstrated that the C-N-C fragment is perpendicular to the surface of the TC-AuNP with which it interacts. The findings from this analysis suggest the potential for further research on the use of these conjugates in biomedical applications.

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This study focuses on the adsorption process of L-cysteine (Cys), a sulfur-containing amino acid, onto monolayers of gold nanoparticles (AuNPs) prepared through distinct protocols on mica substrates. Two types of AuNPs were prepared using two different methods: the first employed a physical approach, which combined the Inert Gas Condensation (IGC) technique with the magnetron sputtering method, while the second utilized a chemical method involving the reduction of tetrachloroauric acid with trisodium citrate (TC). The characterization of AuNPs was performed using transmission electron microscopy (TEM) and atomic force microscopy (AFM), of up to 5 ± 1.3 nm for bare AuNPs obtained through vacuum techniques, and up to 12 ± 5 nm for negatively charged, citrate-stabilized TCAuNPs(-). The application of spectroscopic techniques based on the surface-enhanced effects allows for describing the adsorption process in both micro- and nanoscale systems: Cys/bare AuNPs and Cys/ TCAuNPs(-). The commonly used surface-enhanced Raman spectroscopy (SERS) technique provided insights into adsorption behaviours at the microscale level. In the case of TCAuNPs(-), an interaction involving the lone electron pair of sulfur (S) atom and metal surface, while on the bare AuNPs, S is adsorbed on the surface, but the cleavage of the SH group is not discernible. Nanoscale analysis was complemented using AFM combined with the surface-enhanced infrared absorption spectroscopy (AFM-SEIRA) technique. AFM-SEIRA map indicated the formation of hot spot which were predominantly located between aggregated TCAuNPs(-) and on specific NPs surfaces (area between NPs and gold-coated tip). Results from the SERS and AFM-SEIRA techniques were in good agreement, underscoring the comprehensive understanding achieved through the chosen experimental approach regarding the Cys interactions with layers of AuNPs.

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Surface-enhanced infrared absorption spectroscopy (SEIRA) has emerged as a powerful technique for ultrasensitive chemical-specific analysis. SEIRA can be realized by employing metasurfaces that can enhance light-matter interactions in the spectral bands of molecular vibrations. Increasing sample complexity emphasizes the need for metasurfaces that can operate simultaneously at different spectral bands, both accessing rich spectral information over a broad band, and resolving subtle differences in the absorption fingerprints through narrow-band resonances. Here, a novel concept of resonance-gradient metasurfaces is introduced, where the required spectral selectivity is achieved via local high-quality-factor (high-Q) resonances, while the continuous coverage of a broad band is enabled by the gradual adjustment of the unit-cell dimensions along the planar structure. The highly tailorable design of the gradient metasurfaces provides flexibility for shaping the spectral sampling density to match the relevant bands of target analytes while keeping a compact device footprint. The versatility of the gradient metasurfaces is demonstrated through several sensing scenarios, including polymer mixture deconvolution, detecting a multistep bioassay, and identification of the onset of vibrational strong coupling regime. The proposed gradient-resonance platform significantly contributes to the rapidly evolving landscape of nonlocal metasurfaces, enabling applications in molecular detection and analysis of fundamental light-matter interaction phenomena.

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Polycyclic aromatic hydrocarbons (PAHs) constitute a class of universally prevalent carcinogenic environmental contaminants. It is increasingly recognized, however, that PAHs derivatized with oxygen, sulfur, or nitrogen functional groups are frequently more dangerous than their unfunctionalized counterparts. This much larger family of chemicals─polycyclic aromatic compounds─PACs─is far less well characterized than PAHs. Using surface-enhanced Raman and IR Absorption spectroscopies (SERS + SEIRA) combined on a single substrate, along with density functional theoretical (DFT) calculations, we show that direct chemical detection and identification of PACs at sub-parts-per-billion concentration can be achieved. Focusing our studies on 9,10-anthraquinone, 5,12-tetracenequinone, 9-nitroanthracene, and 1-nitropyrene as model PAC contaminants, detection is made possible by incorporating a hydroxy-functionalized self-assembled monolayer that facilitates hydrogen bonding between analytes and the SERS + SEIRA substrate. 5,12-Tetracenequinone was detected at 0.3 ppb, and the limit of detection was determined to be 0.1 ppb using SEIRA alone. This approach is straightforwardly extendable to other families of analytes and will ultimately facilitate fieldable chemical detection of these dangerous yet largely overlooked environmental contaminants.

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Viroporins are small ion channels in membranes of enveloped viruses that play key roles during viral life cycles. To use viroporins as drug targets against viral infection requires in-depth mechanistic understanding and, with that, methods that enable investigations under in situ conditions. Here, we apply surface-enhanced infrared absorption (SEIRA) spectroscopy to Influenza A M2 reconstituted within a solid-supported membrane, to shed light on the mechanics of its viroporin function. M2 is a paradigm of pH-activated proton channels and controls the proton flux into the viral interior during viral infection. We use SEIRA to track the large-scale reorientation of M2's transmembrane α-helices in situ during pH-activated channel opening. We quantify this event as a helical tilt from 26° to 40° by correlating the experimental results with solid-state nuclear magnetic resonance-informed computational spectroscopy. This mechanical motion is impeded upon addition of the inhibitor rimantadine, giving a direct spectroscopic marker to test antiviral activity. The presented approach provides a spectroscopic tool to quantify large-scale structural changes and to track the function and inhibition of the growing number of viroporins from pathogenic viruses in future studies.

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Surface plasmon polaritons in graphene can enhance the performance of mid-infrared spectroscopy, which is key for the study of both the composition and the conformation of organic molecules via their vibrational resonances. In this paper, a plasmonic biosensor using a graphene-based van der Waals heterostructure on a piezoelectric substrate is theoretically demonstrated, where far-field light is coupled to surface plasmon-phonon polaritons (SPPPs) through a surface acoustic wave (SAW). The SAW creates an electrically-controlled virtual diffraction grating, suppressing the need for patterning the 2D materials, that limits the polariton lifetime, and enabling differential measurement schemes, which increase the signal-to-noise ratio and allow a quick commutation between reference and sample signals. A transfer matrix method has been used for simulating the SPPPs propagating in the system, which are electrically tuned to interact with the vibrational resonances of the analytes. Furthermore, the analysis of the sensor response with a coupled oscillators model has proven its capability of fingerprinting ultrathin biolayers, even when the interaction is too weak to induce a Fano interference pattern, with a sensitivity down to the monolayer limit, as tested with a protein bilayer or a peptide monolayer. The proposed device paves the way for the development of advanced SAW-assisted lab-on-chip systems combining the existing SAW-mediated physical sensing and microfluidic functionalities with the chemical fingerprinting capability of this novel SAW-driven plasmonic approach.

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BACKGROUND: Extracellular Vesicles (EVs) are sub-micrometer lipid-bound particles released by most cell types. They are considered a promising source of cancer biomarkers for liquid biopsy and personalized medicine due to their specific molecular cargo, which provides biochemical information on the state of parent cells. Despite this potential, EVs translation process in the diagnostic practice is still at its birth, and the development of novel medical devices for their detection and characterization is highly required. RESULTS: In this study, we demonstrate mid-infrared plasmonic nanoantenna arrays designed to detect, in the liquid and dry phase, the specific vibrational absorption signal of EVs simultaneously with the unspecific refractive index sensing signal. For this purpose, EVs are immobilized on the gold nanoantenna surface by immunocapture, allowing us to select specific EV sub-populations and get rid of contaminants. A wet sample-handling technique relying on hydrophobicity contrast enables effortless reflectance measurements with a Fourier-transform infrared (FTIR) spectro-microscope in the wavelength range between 10 and 3 µm. In a proof-of-principle experiment carried out on EVs released from human colorectal adenocarcinoma (CRC) cells, the protein absorption bands (amide-I and amide-II between 5.9 and 6.4 µm) increase sharply within minutes when the EV solution is introduced in the fluidic chamber, indicating sensitivity to the EV proteins. A refractive index sensing curve is simultaneously provided by our sensor in the form of the redshift of a sharp spectral edge at wavelengths around 5 µm, where no vibrational absorption of organic molecules takes place: this permits to extract of the dynamics of EV capture by antibodies from the overall molecular layer deposition dynamics, which is typically measured by commercial surface plasmon resonance sensors. Additionally, the described metasurface is exploited to compare the spectral response of EVs derived from cancer cells with increasing invasiveness and metastatic potential, suggesting that the average secondary structure content in EVs can be correlated with cell malignancy. CONCLUSIONS: Thanks to the high protein sensitivity and the possibility to work with small sample volumes-two key features for ultrasensitive detection of extracellular vesicles- our lab-on-chip can positively impact the development of novel laboratory medicine methods for the molecular characterization of EVs.

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Surface-enhanced infrared absorption (SEIRA) spectroscopy has been developed for the nondestructive analysis of trace molecules. Herein, we found that ethylene glycol (EG) decorated TiO2 nanosheet exhibits a selective SEIRA effect for molecules with nucleophilic groups, such as -NH2 and -OH. The SEIRA effect was attributed to the chemical mechanism originating from the interactions between the surface EG and the analytes. The enhancement factor was negatively correlated with the electrophilicity index of the analytes (p = 0.004), and the noncovalent bond dominates the interactions between the analytes and EG. The charge distribution analysis revealed that the -CH2 groups of EG exposed on the TiO2 surface are positively charged, attracting the electron-rich groups of the analyte. This attraction concentrates the analyte, redistributes its charge, defines its molecular dipole moment, and thereby enhances the SEIRA effect. The insights gained from this study shed light on developing new SEIRA substrates and emphasized the critical role of surface ligands in SEIRA applications.

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In this paper, silver nanoparticles (AgNPs) were prepared as enhanced substrates for the detection of glutathione in dairy products by polyol reduction of silver nitrate. The infrared spectra were collected and analyzed by surface-enhanced infrared absorption spectroscopy (SEIRA) method of transmission mode using a cell of calcium fluoride window sheet immobilization solution for the study. The disappearance of the thiol (-SH) absorption peak in the infrared spectrum, and the shift of its characteristic absorption peak when glutathione was bound to AgNPs solvate indicated the Ag-S bond interaction and the aggregation of AgNPS. AgNPs accumulate to form "hot spots", resulting in enhanced electromagnetic fields and thus enhanced infrared signals of glutathione. The intensity of the characteristic absorption peak at 1,654 cm-1 (carbonyl C=O bond stretching) was used for the quantitative analysis of glutathione. After optimizing the conditions, glutathione content in pretreated pure milk and pure ewe's milk was determined using AgNPs in combination with SEIRA. Good linearity was obtained in the range of 0.02-0.12 mg/mL with correlation coefficients (R 2) of 0.9879 and 0.9833, respectively, and LOD of 0.02 mg/mL with average spiked recoveries of 101.3 and 92.5%, respectively. The results show that the method can be used for accurate determination of glutathione content in common dairy products.

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Metasurfaces can enable the confinement of electromagnetic fields on huge surfaces and zones, and they can thus be applied to biochemical sensing by using surface-enhanced Raman scattering (SERS) and surface-enhanced infrared absorption (SEIRA). Indeed, these metasurfaces have been examined for SERS and SEIRA sensing thanks to the presence of a wide density of hotspots and confined optical modes within their structures. Moreover, some metasurfaces allow an accurate enhancement of the excitation and emission processes for the SERS effect by supporting resonances at frequencies of these processes. Finally, the metasurfaces allow the enhancement of the absorption capacity of the solar light and the generation of a great number of catalytic active sites in order to more quickly produce the surface reactions. Here, we outline the latest advances in metasurfaces for SERS and SEIRA sensors as well as photocatalysis.

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The translocon-unassisted folding process of transmembrane domains of the microbial rhodopsins sensory rhodopsin I (HsSRI) and II (HsSRII), channelrhodopsin II (CrChR2), and bacteriorhodopsin (HsBR) during cell-free expression has been investigated by Surface-Enhanced Infrared Absorption Spectroscopy (SEIRAS). Up to now, only a limited number of rhodopsins have been expressed and folded into the functional holoprotein in cell free expression systems, while other microbial rhodopsins fail to properly bind the chromophore all-trans retinal as indicated by the missing visible absorption. SEIRAS experiments suggest that all investigated rhodopsins lead to the production of polypeptides, which are co-translationally inserted into a solid-supported lipid bilayer during the first hour after the in-vitro expression is initiated. Secondary structure analysis of the IR spectra revealed that the polypeptides form a comparable amount of α-helical structure during the initial phase of insertion into the lipid bilayer. As the process progressed (>1 h), only HsBR exhibited a further increase and association of α-helices to form a compact tertiary structure, while the helical contents of the other rhodopsins stagnated. This result suggests that the molecular reason for the unsuccessful cell-free expression of the two sensory rhodopsins and of CrChR2 is not due to the translation process, but rather to the folding process during the post-translational period. Taking our previous observation into account that HsBR fails to form a tertiary structure in the absence of its retinal, we infer that the chromophore retinal is an integral component of the compaction of the polypeptide into its tertiary structure and the formation of a fully functional protein.

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We apply surface-enhanced infrared absorption (SEIRA) spectroscopy to monitor the denaturation process of a surface-bound protein A monolayer. Our proposed platform relies on a plasmonic metasurface comprising different spatial subregions ("pixels") that are engineered to exhibit different resonances covering the infrared region of the electromagnetic spectrum that is matched to the vibrational modes of the Amide groups. Specifically, we are able to determine changes in the Amide I and Amide II vibration coupled modes, by comparing the SEIRA reflectance spectra pertaining to the native state and a denatured state induced by a pH variation. In particular, we observe some evident red-shifts in the principal Amide I mode and the Amide II vibration coupled modes (attributable to the breaking of hydrogen bonds), which result in insurmountable barriers for refolding. Thanks to the strong field localization, and consequent enhancement of the light-matter interactions, our proposed sensing platform can operate with extremely small amounts of an analyte, with an estimated detection limit of about 3 femtomoles of molecules.

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The application of surface enhanced infrared absorption (SEIRA) is severely restricted in many fields due to the SEIRA substrates are constructed mainly from expensive noble metals. Therefore, the development of new SEIRA substrates other than the noble metallic ones is very valuable. Here we introduced a new semiconductor SEIRA substrate, the indium tin oxide (ITO) nanoparticles (NPs), to study the SEIRA property. The results demonstrate that the ITO NPs show the SEIRA property and the enhancement is dependent to the doping ratio of the heteroatoms of tin. The ITO NPs with the 5% atomic doping ratio show the highest SEIRA enhancement factor (EF), which is about 24. The limit of detection (LOD) of the 1,1'-dicarboxyferrocene (dcFc) molecule was as low as 10-5 mol/L. The present study proves that the tin-doped indium oxide can be used as a new and inexpensive semiconductor SEIRA substrate. It also proves that the doped semiconductor NPs have strong potentials for being used as emerging SEIRA substrates.

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In the present work, we report the adsorption of the methylene blue (MB) dye from an aqueous solution employing resin immobilized gold nanocomposites (R-AuNCs) assisted surface-enhanced infrared absorption (SEIRA) spectroscopy. The appropriate adsorption isotherm models, including the Langmuir, Freundlich, and Temkin are tested to reveal the interactive behavior between the adsorbent (R-AuNCs) and adsorbed (MB). Interestingly, Fourier transform infrared spectroscopy (FTIR) in combination with R-AuNC materials could be another approach through which the analysis of adsorption-desorption of MB on the surface of nanocomposite adsorbents is possible in a more precise way with high sensitivity and adsorptivity. In addition, a 10-fold enhancement of the signal intensity of MB dye was obtained due to the electrostatic interaction and H-bonding interaction between COO- groups of adsorbent and the positively charged active sites of the dye molecules. The value of % removal efficiency and % adsorption obtained in the present method was 77.64% and 186.61%, respectively. Desorption of MB from adsorbent surface was also carried out using 0.1 M cetylpyridinium chloride as cationic surfactant; resulting process shows for 'n' number of cyclic process. The maximum desorption capacity for MB found in the present investigation was 44.38 mg/g, The advantages of current method are its simplicity, sensitivity, rapidity, ease to fabrication and excellent adsorption efficiencies to remove MB dye from aqueous solution.

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Infrared (IR) spectroscopy is a unique and powerful method in the identification, characterization, and classification of chemical and biological molecules. However, the low absorbance of biological molecules has arisen as a major bottleneck and inhibits the application of IR in practical applications. To overcome this limitation, in the last four decades, surface-enhanced IR absorption (SEIRA) spectroscopy has been proposed and has become the focus of interest in various applications. In this study, for the first time, we proposed the employment of 3D anisotropic gold nanorod arrays (GNAs) as a highly active SEIRA platform in bacterial detection. For this, GNA platforms were fabricated through an oblique angle deposition (OAD) approach by using a physical vapor deposition (PVD) system. OAD of gold at proper deposition angle (10°) created closely-packed and columnar gold nanorod structures onto the glass slides in a well-controlled manner. GNA platform was tested as a SEIRA system in three different species of bacteria (Escherichia coli, Staphylococcus aureus, and Bacillus subtilis) by collecting IR spectra of each bacteria from different parts of GNA. The employment of GNA provided robust IR spectra with high reproducibility and signal-to-noise ratio. For the comparison, IR spectra of each bacteria were collected from aluminum foil and a smooth gold surface (SGS). No or very low IR spectra were observed in comparison to the GNA platform for these substrates. Unsupervised (PCA, HCA) and supervised (SIMCA, LDA, and SVM classification) machine learning analysis of bacteria spectra obtained from GNA substrate indicated that all bacteria samples can be detected and identified without using a label-containing biosensor, in a fast and simple manner.

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Nanofluidic devices have offered us fascinating analytical platforms for chemical and bioanalysis by exploiting unique properties of liquids and molecules confined in nanospaces. The increasing interests in nanofluidic analytical devices have triggered the development of new robust and sensitive detection techniques, especially label-free ones. IR absorption spectroscopy is one of the most powerful biochemical analysis methods for identification and quantitative measurement of chemical species in the label-free and non-invasive fashion. However, the low sensitivity and the difficulties in fabrication of IR-compatible nanofluidic devices are major obstacles that restrict the applications of IR spectroscopy in nanofluidics. Here, we realized the bonding of CaF2 and SiO2 at room temperature and demonstrated an IR-compatible nanofluidic device that allowed the IR spectroscopy in a wide range of mid-IR regime. We also performed the integration of metal-insulator-metal perfect absorber metamaterials into nanofluidic devices for plasmon-enhanced infrared absorption spectroscopy with ultrahigh sensitivity. This study also shows a proof-of-concept of the multi-band absorber by combining different types of nanostructures. The results indicate the potential of implementing metamaterials in tracking several characteristic molecular vibrational modes simultaneously, making it possible to identify molecular species in mixture or complex biological entities.

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The work presents a comprehensive vibrational analysis of the process of adsorption of threonine (Thr) onto an Fe surface with deposited Cu nanoparticles (NPs) (of about 4-5 nm in size) in a corrosive environment. The application of surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRA) provides the opportunity for detailed description of adsorption geometry of amino acid onto a metal surface. The combination of conventional infrared spectroscopy (IR) with atomic force microscopy (AFM) resulted in a nano-SEIRA technique which made it possible to provide a precise description of adsorbate binding to the metal surface. The studies presented confirmed that there is a very good correlation between the spectra recorded by the SERS, SEIRA, and nano-SEIRA techniques. Threonine significantly influenced the process of corrosion of the investigated surface due to the existing strong interaction between the protonated amine and carboxylate groups and the CuNPs deposited onto the Fe surface. In addition, the application of two polarization modulations (s and p) in nano-SEIRA allows subtle changes to be observed in the molecule geometry upon adsorption, with the carboxylate group of Thr being almost horizontally oriented onto the metal surface; whereas the amine group that contains nitrogen is oriented perpendicular to this surface.