Concept: Infrared spectroscopy
Near infrared spectroscopy (NIRS) has been successfully used for non-invasive diagnosis of diseases and abnormalities where water spectral patterns are found to play an important role. The present study investigates water absorbance patterns indicative of estrus in the female giant panda. NIR spectra of urine samples were acquired from the same animal on a daily basis over three consecutive putative estrus periods. Characteristic water absorbance patterns based on 12 specific water absorbance bands were discovered, which displayed high urine spectral variation, suggesting that hydrogen-bonded water structures increase with estrus. Regression analysis of urine spectra and spectra of estrone-3-glucuronide standard concentrations at these water bands showed high correlation with estrogen levels. Cluster analysis of urine spectra grouped together estrus samples from different years. These results open a new avenue for using water structure as a molecular mirror for fast estrus detection.
Cholesterol has been suggested to play a role in stable vesicle formation by adjusting the molecular packing of the vesicular bilayer. To explore the mechanisms involved in adjusting the bilayer structure by cholesterol, the molecular packing behavior in a mimic outer layer of cationic dialkyldimethylammonium bromide (DXDAB)/cholesterol vesicular bilayer was investigated by the Langmuir monolayer approach with infrared reflection-absorption spectroscopy (IRRAS). The results indicated that the addition of cholesterol in the DXDAB Langmuir monolayers not only restrained the desorption of the DXDAB with short hydrocarbon chains, such as ditetradecyldimethylammonium bromide or dihexadecyldimethylammonium bromide, into the aqueous phase but also induced a condensing effect on the DXDAB monolayers. At a liquid-expanded (LE) state, the ordering effect of cholesterol accompanying the condensing effect occurred in the mixed DXDAB/cholesterol monolayers due to the tendency of maximizing hydrocarbon chain contact between cholesterol and the neighboring hydrocarbon chains. However, for the mixed monolayers containing the DXDAB with long hydrocarbon chains, such as dioctadecyldimethylammonium bromide (DODAB), the disordering effect of cholesterol took place at a liquid-condensed (LC) state. This was related to the molecular structure of cholesterol and hydrocarbon chain length of DODAB. The rigid sterol ring of cholesterol hindered the portion of neighboring hydrocarbon chains from motion. However, the flexible alkyl side-chain of cholesterol along with the corresponding portion of neighboring hydrocarbon chains formed a fluidic region, counteracting the enhanced conformational order induced by the sterol ring of cholesterol. Furthermore, the long hydrocarbon chains of DODAB possessed a more pronounced motion freedom, resulting in a more disordered packing of the monolayers.
Collisions of excitation pulses in dissipative systems lead usually to their annihilation. In this paper, we report electrochemical experiments exhibiting more complex pulse interaction with collision survival and pulse splitting, phenomena that have rarely been observed experimentally and are only poorly understood theoretically. Using spatially resolved in-situ Fourier transform infrared spectroscopy (FTIR) in the attenuated total reflection configuration, we monitored reaction pulses during the electrochemical oxidation of CO on Pt thin film electrodes in a flow cell. The system forms quasi-1d pulses that align parallel to the flow and propagate perpendicular to it. The pulses split once in a while, generating a second solitary wave in the backward moving direction. Upon collision, the waves penetrate each other in a soliton-like manner. These unusual pulse dynamics could be reproduced with a 3-component reaction-diffusion-migration model with two inhibitor species, one of them exhibiting a long-range spatial coupling. The simulations shed light on existence criteria of such dissipative solitons.
Conventional arthroscopic evaluation of articular cartilage is subjective and poorly reproducible. Therefore, implementation of quantitative diagnostic techniques, such as near infrared spectroscopy (NIRS) and optical coherence tomography (OCT), is essential. Locations (n = 44) with various cartilage conditions were selected from mature equine fetlock joints (n = 5). These locations and their surroundings were measured with NIRS and OCT (n = 530). As a reference, cartilage proteoglycan (PG) and collagen contents, and collagen network organization were determined using quantitative microscopy. Additionally, lesion severity visualized in OCT images was graded with an automatic algorithm according to International Cartilage Research Society (ICRS) scoring system. Artificial neural network with variable selection was then employed to predict cartilage composition in the superficial and deep zones from NIRS data, and the performance of two models, generalized (including all samples) and condition-specific models (based on ICRS-grades), was compared. Spectral data correlated significantly (p < 0.002) with PG and collagen contents, and collagen orientation in the superficial and deep zones. The combination of NIRS and OCT provided the most reliable outcome, with condition-specific models having lower prediction errors (9.2%) compared to generalized models (10.4%). Therefore, the results highlight the potential of combining both modalities for comprehensive evaluation of cartilage during arthroscopy.
It is desirable to extend the surface-enhanced Raman scattering (SERS) from the conventionally used visible range into the infrared region, because the fluorescence background is lower in the long-wavelength regime. To do this, it is important to have a SERS substrate suitable for infrared operation. In this work, we report the near infrared SERS operation based on the substrates employing star-shaped gold/silver nanoparticles and hyperbolic metamaterial (HMM) structure. We first fabricate the SERS substrate in which nanoparticles are separated from a silver film by a thin dielectric layer. Performance of the SERS substrate is investigated with a 1064-nm excitation source. Compared with similar silver film-based substrates employing respectively gold and silver spherical nanoparticles, it is found that, Raman intensity scattered by the substrate with star-shaped nanoparticles is 7.4 times stronger than that with gold nanoparticles, and 3.4 times stronger than that with silver nanoparticles. Following this, we fabricate the SERS substrate where the star-shaped nanoparticles are deposited over a HMM structure. The HMM structure comprises three pairs of germanium-silver multilayers. Further experimental result shows that, with the star-shaped nanoparticles, the HMM-based substrate yields 30% higher Raman intensity for near infrared SERS operation than the silver film-based substrate does.
Cystic echinococcosis (CE)/hydatid cyst is one of the most important helminthic diseases in the world. The treatment of hydatid cyst ranges from surgical intervention to chemotherapy, although the efficacy of chemotherapy is still unclear. Postoperative complication which results from the spillage of cysts during surgical operation is one of the most important concerns in surgical treatment of hydatid cyst. The aim of the current study was to solidify the hydatid cyst fluid (HCF) with an injectable and thermosensitive chitosan (CS)/carboxymethyl cellulose (CMC)/β-glycerol phosphate (BGP) hydrogel for effective control of spillage during the aspiration of hydatid cysts. Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), water uptake, rheological analysis, and Alamar Blue cytotoxicity assay were employed to characterize the hydrogel. A five level with three times replication at the central point using a central composite design (CCD), which is a response surface methodology (RSM), was used to optimize the experimental conditions. Assessment of the produced hydrogel showed that the intermolecular interactions of amino groups of chitosan and hydrogen groups of CMC were correctively established and appreciable swelling with a good strength was obtained. Hydrogels morphology had a porous structure. Rheological analysis showed that CS/CMC/BGP blends had a phase transition (32-35 °C) of sol-gel close to the body temperature. Alamar Blue cytotoxicity assay showed that CS (1.75%)/CMC (1.4%)/BGP (2.9%) had IC50 values of 0.598, 0.235 and 0.138 (µg/µL) for 24, 48 and 72 h, which indicated that the produced polymer solution had no significant cytotoxic effect for human fibroblast cell line. In vitro injection of the polymer solution of CS/CMC/BGP with CS/CMC ratio of 1.75/1.4 was done on HCF (1 mL polymer solution to 3 mL of HCF) at 37 °C with a final concentration of 2.9% for BGP resulting in solidification of HCF in less than 45 min.
The present study investigates brain-to-brain coupling, defined as inter-subject correlations in the hemodynamic response, during natural verbal communication. We used functional near-infrared spectroscopy (fNIRS) to record brain activity of 3 speakers telling stories and 15 listeners comprehending audio recordings of these stories. Listeners' brain activity was significantly correlated with speakers' with a delay. This between-brain correlation disappeared when verbal communication failed. We further compared the fNIRS and functional Magnetic Resonance Imaging (fMRI) recordings of listeners comprehending the same story and found a significant relationship between the fNIRS oxygenated-hemoglobin concentration changes and the fMRI BOLD in brain areas associated with speech comprehension. This correlation between fNIRS and fMRI was only present when data from the same story were compared between the two modalities and vanished when data from different stories were compared; this cross-modality consistency further highlights the reliability of the spatiotemporal brain activation pattern as a measure of story comprehension. Our findings suggest that fNIRS can be used for investigating brain-to-brain coupling during verbal communication in natural settings.
Time-resolved Fourier transform infrared (FTIR) spectroscopy is a powerful tool to elucidate label-free the reaction mechanisms of proteins. After assignment of the absorption bands to individual groups of the protein, the order of events during the reaction mechanism can be monitored and rate constants can be obtained. Additionally, structural information is encoded into infrared spectra and can be decoded by combining the experimental data with biomolecular simulations. We have determined recently the infrared vibrations of GTP and guanosine diphosphate (GDP) bound to Gαi1, a ubiquitous GTPase. These vibrations are highly sensitive for the environment of the phosphate groups and thereby for the binding mode the GTPase adopts to enable fast hydrolysis of GTP. In this study we calculated these infrared vibrations from biomolecular simulations to transfer the spectral information into a computational model that provides structural information far beyond crystal structure resolution. Conformational ensembles were generated using 15 snapshots of several 100 ns molecular-mechanics/molecular-dynamics (MM-MD) simulations, followed by quantum-mechanics/molecular-mechanics (QM/MM) minimization and normal mode analysis. In comparison with other approaches, no time-consuming QM/MM-MD simulation was necessary. We carefully benchmarked the simulation systems by deletion of single hydrogen bonds between the GTPase and GTP through several Gαi1 point mutants. The missing hydrogen bonds lead to blue-shifts of the corresponding absorption bands. These band shifts for α-GTP (Gαi1-T48A), γ-GTP (Gαi1-R178S), and for both β-GTP/γ-GTP (Gαi1-K46A, Gαi1-D200E) were found in agreement in the experimental and the theoretical spectra. We applied our approach to open questions regarding Gαi1: we show that the GDP state of Gαi1 carries a Mg(2+), which is not found in x-ray structures. Further, the catalytic role of K46, a central residue of the P-loop, and the protonation state of the GTP are elucidated.
We investigated microplastics in the digestive tracts of 64 Japanese anchovy (Engraulis japonicus) sampled in Tokyo Bay. Plastic was detected in 49 out of 64 fish (77%), with 2.3 pieces on average and up to 15 pieces per individual. All of the plastics were identified by Fourier transform infrared spectroscopy. Most were polyethylene (52.0%) or polypropylene (43.3%). Most of the plastics were fragments (86.0%), but 7.3% were beads, some of which were microbeads, similar to those found in facial cleansers. Eighty percent of the plastics ranged in size from 150 μm to 1000 μm, smaller than the reported size range of floating microplastics on the sea surface, possibly because the subsurface foraging behavior of the anchovy reflected the different size distribution of plastics between surface waters and subsurface waters. Engraulis spp. are important food for many humans and other organisms around the world. Our observations further confirm that microplastics have infiltrated the marine ecosystem, and that humans may be exposed to them. Because microplastics retain hazardous chemicals, increase in fish chemical exposure by the ingested plastics is of concern. Such exposure should be studied and compared with that in the natural diet.
The mid-infrared (mid-IR) is a strategically important band for numerous applications ranging from night vision to biochemical sensing. Here we theoretically analyzed and experimentally realized a Huygens metasurface platform capable of fulfilling a diverse cross-section of optical functions in the mid-IR. The meta-optical elements were constructed using high-index chalcogenide films deposited on fluoride substrates: the choices of wide-band transparent materials allow the design to be scaled across a broad infrared spectrum. Capitalizing on a two-component Huygens' meta-atom design, the meta-optical devices feature an ultra-thin profile (λ0/8 in thickness) and measured optical efficiencies up to 75% in transmissive mode for linearly polarized light, representing major improvements over state-of-the-art. We have also demonstrated mid-IR transmissive meta-lenses with diffraction-limited focusing and imaging performance. The projected size, weight and power advantages, coupled with the manufacturing scalability leveraging standard microfabrication technologies, make the Huygens meta-optical devices promising for next-generation mid-IR system applications.