This study delves into the effects of titanium (Ti) doping on the optical properties of vanadium dioxide (VO2), a material well known for its metal-to-insulator transition (MIT) near room temperature. By incorporating Ti into VO2\'s crystal lattice, we aim to uncover the resultant changes in its physical properties, crucial for enhancing its application in smart devices. Utilizing polarized infrared micro-spectroscopy, we examined TixV1-xO2 single crystals with varying Ti concentrations (x = 0.059, x = 0.082, and x = 0.187) across different crystal phases (the conductive rutile phase and insulating monoclinic phases M1 and M2) from the far-infrared to the visible spectral range. Our findings reveal that Ti doping significantly influences the phononic spectra, introducing absorption peaks not attributed to pure VO2 or TiO2. This is especially notable with polarization along the crystal growth axis, mainly in the x = 0.187 sample. Furthermore, we demonstrate that the electronic contribution to optical conductivity in the metallic phase exhibits strong anisotropy, higher along the c axis than the a-b plane. This anisotropy, coupled with the progressive broadening of the zone center infrared active phonon modes with increasing doping, highlights the complex interplay between structural and electronic dynamics in doped VO2. Our results underscore the potential of Ti doping in fine-tuning VO2\'s electronic and thermochromic properties, paving the way for its enhanced application in optoelectronic devices and technologies.

BACKGROUND: Inclusion bodies (IBs) are well-known subcellular structures in bacteria where protein aggregates are collected. Various methods have probed their structure, but single-cell spectroscopy remains challenging. Atomic Force Microscopy-based Infrared Spectroscopy (AFM-IR) is a novel technology with high potential for the characterisation of biomaterials such as IBs.
RESULTS: We present a detailed investigation using AFM-IR, revealing the substructure of IBs and their variation at the single-cell level, including a rigorous optimisation of data collection parameters and addressing issues such as laser power, pulse frequency, and sample drift. An analysis pipeline was developed tailored to AFM-IR image data, allowing high-throughput, label-free imaging of more than 3500 IBs in 12,000 bacterial cells. We examined IBs generated in Escherichia coli under different stress conditions. Dimensionality reduction analysis of the resulting spectra suggested distinct clustering of stress conditions, aligning with the nature and severity of the applied stresses. Correlation analyses revealed intricate relationships between the physical and morphological properties of IBs.
CONCLUSIONS: Our study highlights the power and limitations of AFM-IR, revealing structural heterogeneity within and between IBs. We show that it is possible to perform quantitative analyses of AFM-IR maps over a large collection of different samples and determine how to control for various technical artefacts.

In the present study, cellulose purified from finger millet agricultural waste is subjected to enzymatic hydrolysis, and the hydrolysate (predominantly glucose) is used as a carbon source supplement in the media for the mixotrophic growth of Chlamydomonas reinhardtii. Interestingly, a switch between excess starch production and excess lipid (triacylglycerols, TAG) production occurs by a small change in hydrolysate concentration in the media. Starch production increased 4.5-fold with respect to the photoautotrophic control, with a glucose concentration of 3 mg/mL in the media after hydrolysate addition. This culture had TAG production enhancement by 1.5-fold. However, mixotrophic cultivation with 4 mg/mL glucose concentration in the media with hydrolysate addition resulted in TAG productivity enhancement by 4.2-fold compared to control and starch amount increase of 1.3-fold. The organic carbon source (glucose) and the inorganic carbon source (citrate ions) in the hydrolysate together played a role in this delicate switching between starch and lipid pathways. Proteins, starch, and TAG molecules are analyzed in the microalgal cells grown under different conditions with FTIR spectroscopy, a rapid, high-throughput method of biomolecular estimation. High-resolution single-cell AFM studies of the cell wall structure reveal enhanced corrugations in surface morphology during mixotrophic growth with cellulose hydrolysate, illustrating an adaptive mechanism with improved mechanical stress management. Lipid droplet morphology at the single-cell level points to two distinct mechanisms of lipid accumulation: one in which the lipids are segregated as droplets, and the other in which lipid molecules are uniformly dispersed in the cytosol as unresolved, ultra-small droplets. The present study therefore analyzes both the bulk and the single-cell level changes when cellulose hydrolysate is used as a carbon source for Chlamydomonas reinhardtii mixotrophic cultivation, which serves a four-fold purpose: value from waste, fixation of atmospheric CO2, production of lipids for biodiesel, and starch for bioethanol.

We study by femtosecond infrared spectroscopy the ultrafast and persistent photoinduced phase transition of the Rb0.94Mn0.94Co0.06[Fe(CN)6]0.98∙0.2H2O material, induced at room temperature by a single laser shot. This system exhibits a charge-transfer based phase transition with a 75 K wide thermal hysteresis, centred at room temperature, from the low temperature Mn3+-N-C-Fe2+ tetragonal phase to the high temperature Mn2+-N-C-Fe3+ cubic phase. At room temperature, the photoinduced phase transition is persistent. However, the out-of-equilibrium dynamics leading to this phase is multi-scale. Femtosecond infrared spectroscopy, particularly sensitive to local reorganizations through the evolution of the frequency of the N-C vibration modes with the different characteristic electronic states, reveals that at low laser fluence and on short time scale, the photoexcitation of the Mn3+-N-C-Fe2+ phase creates small charge-transfer polarons [Mn2+-N-C-Fe3+]* within ≃ 250 fs. The local trapping of photoinduced intermetallic charge-transfer is characterized by the appearance of a polaronic infrared band, due to the surrounding Mn2+-N-C-Fe2+ species. Above a threshold fluence, when a critical fraction of small CT-polarons is reached, the macroscopic phase transition to the persistent Mn2+-N-C-Fe3+ cubic phase occurs within ≃ 100 ps. This non-linear photo-response results from elastic cooperativity, intrinsic to a switchable lattice and reminiscent of a feedback mechanism.

Plastic pollution is now ubiquitous in the environment and represents a growing threat to wildlife, who can mistake plastic for food and ingest it. Tackling this problem requires reliable, consistent methods for monitoring plastic pollution ingested by seabirds and other marine fauna, including methods for identifying different types of plastic. This study presents a robust method for the rapid, reliable chemical characterisation of ingested plastics in the 1-50 mm size range using infrared and Raman spectroscopy. We analysed 246 objects ingested by Flesh-footed Shearwaters (Ardenna carneipes) from Lord Howe Island, Australia, and compared the data yielded by each technique: 92 % of ingested objects visually identified as plastic were confirmed by spectroscopy, 98 % of those were low density polymers such as polyethylene, polypropylene, or their copolymers. Ingested plastics exhibit significant spectral evidence of biological contamination compared to other reports, which hinders identification by conventional library searching. Machine learning can be used to identify ingested plastics by their vibrational spectra with up to 93 % accuracy. Overall, we find that infrared is the more effective technique for identifying ingested plastics in this size range, and that appropriately trained machine learning models can be superior to conventional library searching methods for identifying plastics.

To analyze the effect of various drying treatments (microwave drying (MD), hot air drying (HAD), vacuum drying (VD), and vacuum freeze drying (VFD)) on taste compounds in Penaeus vannamei, relevant indicators such as free amino acids, 5\'-nucleotides, and organic acids were performed. Multidimensional infrared spectroscopy (MM-IR) results found that there were notable variations in taste properties of P. vannamei. There were 18 autocorrelation peaks in 3400-900 cm-1 were screened using second-derivative infrared spectroscopy (SD-IR) and two-dimensional correlation infrared spectroscopy (2DCOS-IR). Variations in functional groups were the major contributors to taste profiles. The TAV of glutamic acid (Glu), guanine (GMP), and inosinemonphosphate (IMP) were greater than one and had notable impacts on taste profiles. VD had the highest equivalent umami value, followed by VFD, HAD, and MD. This study may provide a theoretical guide for the production of dried P. vannamei products on an industrial scale.

The ability of oxyamines to undergo homolytic cleavage of the O-C bond, leading to the formation of stable radicals, is widely used in polymerization processes and to prevent oxidative stress in materials. We present a mid and near-infrared spectroscopy study on two model compounds, the commercial N,N-diethylhydroxyloxyamine (C4H11NO) and the non-commercial N,N-diethylacetyloxyamine (C6H13NO2) in the liquid phase. The analysis of the spectra is based on a complete exploration of the conformational space, coupled to harmonic and anharmonic calculations performed using the generalized second-order vibrational perturbation theory (GVPT2) formalism at the B3LYP-D3(BJ)/Def2-TZVP level of calculation and potential energy distribution analysis. In the most stable species out of 25, the three amine chains present an all-anti arrangement, with the carbonyl oxygen atom pointing towards the nitrogen lone pair. The simulated spectra are in overall good agreement with the experimental ones, and suitable for the assignment of the main observed bands. Furthermore, similarities and divergences between the two molecules are discussed.

Accurate and sensitive determination of human immunoglobulin G (HIgG) level is critical for diagnosis and treatment of various diseases, including rheumatoid arthritis, humoral immunodeficiencies, and infectious disease. In this study, versatile tri-signal probes were developed by preparing CdS@SiO2 nanorods that integrate photoluminescence (PL), multi-phonon resonant Raman scattering (MRRS) and infrared absorption (IRA) properties. Through the coating of multiple CdS nanoparticles as cores within SiO2 shells, the PL and MRRS properties of CdS were improved, resulting in a significantly lowered limit of detection (LOD), with the lowest LOD of 12.37 ag mL-1. Integration with the distinctive IRA property of SiO2 shells widened the detection range towards higher concentrations, establishing a final linear range of 50 ag mL-1 to 10 μg mL-1. The remarkable consistency among the three signals highlighted the robust internal verification capability for accurate detection. This approach enhances flexibility in selecting detection methodologies to suit diverse scenarios, facilitating HIgG detection. The tri-signal nanoprobes also exhibited excellent detection selectivity, specificity and repeatability. This study presents a fresh idea for developing high-performance detection strategies.

Two-dimensional (2D) hybrid organic/inorganic perovskites are an emerging materials class for optoelectronic and spintronic applications due to strong excitonic absorption and emission, large spin-orbit coupling, and Rashba spin-splitting effects. For many of the envisioned applications, tuning the majority charge carrier (electron or hole) concentration is desirable, but electronic doping of metal-halide perovskites has proven to be challenging. Here, we demonstrate electron injection into the lower-energy branch of the Rashba-split conduction band of 2D phenethylammonium lead iodide by means of n-type molecular doping at room temperature. The molecular dopant, benzyl viologen (BV), is shown to compensate adventitious p-type impurities and can lead to a tunable Fermi level above the conduction band minimum and increased conductivity in intrinsic samples. The doping-induced carrier concentration is monitored by the observation of free-carrier absorption and intraband optical transitions in the infrared spectral range. These optical measurements allow for an estimation of the Rashba splitting energy ER ≈38 ± 4 meV. Photoinduced quantum beating measurements demonstrate that the excess electron density reduces the electron spin g-factor by ca. 6%. This work demonstrates controllable carrier concentrations in hybrid organic/inorganic perovskites and yields potential for room temperature spin control through the Rashba effect.

OBJECTIVE: To assess the impact of various organic and inorganic acids on the roughness, demineralization, and collagen secondary structures of human dentin and to compare these effects with those of traditional agents, specifically phosphoric acid (PA) and ethylenediaminetetraacetic acid (EDTA).
METHODS: Coronal dentin discs (n = 10) were examined by optical profilometry (roughness) and ATR-FTIR before and after conditioning with 32 % PA, 3 % nitric acid (NA), 20 % citric acid (CA), 20 % phytic acid (IP6) or 17 % EDTA. Spectra data were processed to quantify dentin demineralization (DM%) and percentage area of amide I curve-fitted components of β-turns, 310-helix, α-helix, random coils, β-sheets, and collagen maturation index. Statistical analysis was performed by one-way ANOVA or Kruskal-Wallis for DM% and roughness parameters, and paired t-test/Wilcoxon test for amide I components at significance level set at α = 0.05.
RESULTS: All treatments resulted in increased roughness parameters, with the most significant changes occurring primarily with PA, while EDTA exhibited the least changes. DM% was NA>PA>IP6>CA>EDTA in a descending order. Regarding amide I components, NA demonstrated a significant reduction in β-turns, 310-helices, and α-helices and it increased β-sheets and random coils. PA resulted in reduction in β-turns and α-helices while it increased β-sheets. CA and EDTA did not cause significant changes. The collagen maturation index significantly increased only after IP6 treatment.
CONCLUSIONS: The effect on dentin roughness parameters, demineralization, and collagen secondary structures varied based on the type of dentin surface treatment.
CONCLUSIONS: Understanding the impact of acids on the intrinsic properties of dentin is clinically essential for gaining insights into how these effects influence adhesion to dentin, the long-term stability of resin-based restorations, and the success of remineralization therapies.