Search

Highlights This study aims at the assessment of damage on crystallinity of fiber reinforced thermoplastic (FRTP) composites resulting from mechanical polishing to demonstrate a novel methodology enabling comprehensive crystalline structural characterization. Investigating the crystalline structure is relevant for understanding the relationship with the mechanical properties. In a previous study, FRTPs have successfully been processed to the thickness of 5 μm or below via an innovative polishing strategy, which for the first time visualized the crystalline morphologies by polarized optical microscopy. Analyzing these sections via micro‐Raman and micro‐infrared spectroscopies facilitate the quantification of these structure. However, no study reports on the correct interpretation of FRTP data appropriately considering the damage resulting from mechanical polishing to date. Herein, we report fundamental knowledge on this aspect via detailed Raman micro‐spectroscopic investigations to demonstrate our novel strategy. Four types of FRTPs with major matrix resins (GF/PBT, CF/PA6, CF/PEEK and GF/PP) were analyzed and the damage on both polished cross‐sections, prepared by traditional process, and the thin sections was confirmed to be approx. 1%–2% crystallinity, which solidified the credibility of the obtained analytical data. Then, the newly established methodology of ‘cross‐referenceable microscopic and micro‐spectroscopic analyses for FRTPs’ was applied for comprehensive crystalline structural characterization. Cross‐sectioning and thin‐sectioning of FRTPs. Evidencing of damage on the crystallinity resulting from mechanical polishing. Equations to convert Raman spectral data into crystallinity. Strategy for considering the anisotropy of Raman measurements. Practical application of novel microscopic and micro‐spectroscopic strategies. [ABSTRACT FROM AUTHOR]

Aims This study aims to assess the potential bacterial inactivation pathway triggered by argon (Ar) cold atmospheric pressure plasma jet (CAPJ) discharge using spectroscopic and imaging techniques. Methods and results Electrical and reactive species of the Ar CAPJ discharge was characterized. The chemical composition and morphology of bacteria pre- and post-CAPJ exposure were assessed using Fourier transform infrared (FTIR), Raman micro-spectroscopy, and transmission electron microscopy (TEM). A greater than 6 log reduction of Escherichia coli and Staphylococcus aureus was achieved within 60 and 120 s of CAPJ exposure, respectively. Extremely low D- values (<20 s) were recorded for both the isolates. The alterations in the FTIR spectra and Raman micro-spectra signals of post-CAPJ exposed bacteria revealed the degree of destruction at the molecular level, such as lipid peroxidation, protein oxidation, bond breakages, etc. Further, TEM images of exposed bacteria indicated the incurred damages on cell morphology by CAPJ reactive species. Also, the inactivation process varied for both isolates, as evidenced by the correlation between the inactivation curve and FTIR spectra. It was observed that the identified gas-phase reactive species, such as Ar I, O I, OH•, NO+, OH+, NO2−, NO3−, etc. played a significant role in bacterial inactivation. Conclusions This study clearly demonstrated the effect of CAPJ exposure on bacterial cell morphology and molecular composition, illuminating potential bacterial inactivation mechanisms. [ABSTRACT FROM AUTHOR]

Main conclusion: Using Raman micro-spectroscopy on tef roots, we could monitor cell wall maturation in lines with varied genetic lodging tendency. We describe the developing cell wall composition in root endodermis and cylinder tissue. Tef [Eragrostis tef (Zucc.) Trotter] is an important staple crop in Ethiopia and Eritrea, producing gluten-free and protein-rich grains. However, this crop is not adapted to modern farming practices due to high lodging susceptibility, which prevents the application of mechanical harvest. Lodging describes the displacement of roots (root lodging) or fracture of culms (stem lodging), forcing plants to bend or fall from their vertical position, causing significant yield losses. In this study, we aimed to understand the microstructural properties of crown roots, underlining tef tolerance/susceptibility to lodging. We analyzed plants at 5 and 10 weeks after emergence and compared trellised to lodged plants. Root cross sections from different tef genotypes were characterized by scanning electron microscopy, micro-computed tomography, and Raman micro-spectroscopy. Lodging susceptible genotypes exhibited early tissue maturation, including developed aerenchyma, intensive lignification, and lignin with high levels of crosslinks. A comparison between trellised and lodged plants suggested that lodging itself does not affect the histology of root tissue. Furthermore, cell wall composition along plant maturation was typical to each of the tested genotypes independently of trellising. Our results suggest that it is possible to select lines that exhibit slow maturation of crown roots. Such lines are predicted to show reduction in lodging and facilitate mechanical harvest. [ABSTRACT FROM AUTHOR]

Prostate cancer is the most common cancer among men. An accurate diagnosis of its severity at detection plays a major role in improving their survival. Recently, machine learning models using biomarkers identified from Raman micro-spectroscopy discriminated intraductal carcinoma of the prostate (IDC-P) from cancer tissue with a ≥85  %   detection accuracy and differentiated high-grade prostatic intraepithelial neoplasia (HGPIN) from IDC-P with a ≥97.8  %   accuracy. To improve the classification performance of machine learning models identifying different types of prostate cancer tissue using a new dimensional reduction technique. A radial basis function (RBF) kernel support vector machine (SVM) model was trained on Raman spectra of prostate tissue from a 272-patient cohort (Centre hospitalier de l'Université de Montréal, CHUM) and tested on two independent cohorts of 76 patients [University Health Network (UHN)] and 135 patients (Centre hospitalier universitaire de Québec-Université Laval, CHUQc-UL). Two types of engineered features were used. Individual intensity features, i.e., Raman signal intensity measured at particular wavelengths and novel Raman spectra fitted peak features consisting of peak heights and widths. Combining engineered features improved classification performance for the three aforementioned classification tasks. The improvements for IDC-P/cancer classification for the UHN and CHUQc-UL testing sets in accuracy, sensitivity, specificity, and area under the curve (AUC) are (numbers in parenthesis are associated with the CHUQc-UL testing set): +4  %   (+8  %  ), +7  %   (+9  %  ), +2  %   (6%), +9 (+9) with respect to the current best models. Discrimination between HGPIN and IDC-P was also improved in both testing cohorts: +2.2  %   (+1.7  %  ), +4.5  %   (+3.6  %  ), +0  %   (+0  %  ), +2.3 (+0). While no global improvements were obtained for the normal versus cancer classification task [+0  %   (-2  %  ), +0  %   (-3  %  ), +2  %   (-2  %  ), +4 (+3)], the AUC was improved in both testing sets. Combining individual intensity features and novel Raman fitted peak features, improved the classification performance on two independent and multicenter testing sets in comparison to using only individual intensity features.

The quantitative determination of topically applied substances in the skin is severely limited and represents a challenging task. The porcine skin ex vivo was topically treated with a gel containing caffeine (CF) and propylene glycol (PG), and depth‐resolved Raman spectra were recorded with two confocal Raman microscopes. We applied a novel tailored multivariate curve resolution‐alternating least squares method to the selected spectral regions (512–604 and 778–1148 cm−1) of gel‐treated skin and quantitatively determined the concentrations of CF and PG in the stratum corneum (SC). The highest concentration of CF (181 mg/cm3) was found at the surface, while PG (384 mg/cm3) was found at 10% SC depth, indicating the formation of a reservoir at the superficial SC. The concentrations of CF and PG decreased monotonically and reached the detection limit at ≈60% and ≈80% SC depth, respectively, indicating that neither permeate the SC. [ABSTRACT FROM AUTHOR]

Information on the penetration depth, pathways, metabolization, storage of vehicles, active pharmaceutical ingredients (APIs), and functional cosmetic ingredients (FCIs) of topically applied formulations or contaminants (substances) in skin is of great importance for understanding their interaction with skin targets, treatment efficacy, and risk assessment—a challenging task in dermatology, cosmetology, and pharmacy. Non-invasive methods for the qualitative and quantitative visualization of substances in skin in vivo are favored and limited to optical imaging and spectroscopic methods such as fluorescence/reflectance confocal laser scanning microscopy (CLSM); two-photon tomography (2PT) combined with autofluorescence (2PT-AF), fluorescence lifetime imaging (2PT-FLIM), second-harmonic generation (SHG), coherent anti-Stokes Raman scattering (CARS), and reflectance confocal microscopy (2PT-RCM); three-photon tomography (3PT); confocal Raman micro-spectroscopy (CRM); surface-enhanced Raman scattering (SERS) micro-spectroscopy; stimulated Raman scattering (SRS) microscopy; and optical coherence tomography (OCT). This review summarizes the state of the art in the use of the CLSM, 2PT, 3PT, CRM, SERS, SRS, and OCT optical methods to study skin penetration in vivo non-invasively (302 references). The advantages, limitations, possibilities, and prospects of the reviewed optical methods are comprehensively discussed. The ex vivo studies discussed are potentially translatable into in vivo measurements. The requirements for the optical properties of substances to determine their penetration into skin by certain methods are highlighted. [ABSTRACT FROM AUTHOR]

Pesticide residues are chemicals frequently found in food as contaminants. Pesticides may have adverse health effects, particularly when the digestive tract is concerned, as a consequence of food ingestion. Deltamethrin is a pyrethroid pesticide widely used in various fields, such as agriculture, veterinary and in the household, so the ingestion of a small amount of this chemical may occasionally occur. To assess whether exposure to pesticide residues may have a biological effect at the intestinal level, it is primarily necessary to perform in vitro exposure experiments about cell lines models of the intestinal barrier at low concentrations of the chemical. In the present study, CaCo-2 cells were exposed to different concentrations of a Deltamethrin-based commercial pesticide, which was diluted in the cell medium. An MTT viability test indicated that the cytotoxic concentration value of the pesticide inside 1 mL of medium is between 10−6 and 10−5 mL. However, the analysis of Raman spectra found that biochemical changes occur inside cells exposed to a non-cytotoxic concentration of 10−6 mL of the pesticide inside 1 mL of the medium. Such changes involve mainly an increase in the ratio between the amount of lipid with respect to that of the protein components in the cell cytoplasm. The results obtained by Raman micro-spectroscopy were confirmed by fluorescence images obtained by using a fluorophore staining neutral lipids. Overall, the obtained results suggest that Raman micro-spectroscopy can be successfully used to monitor the cellular modifications due to exposure at low concentrations of pesticides, as those values that can be found inside food are residuals. [ABSTRACT FROM AUTHOR]

[Display omitted] • Scaffolds made of PCL, CNT, MNPs-c and phenolic compounds were tested. • The presence of nanoadditives leads to a decrease in the crystallinity of the polymer matrix. • Scaffolds obtained by porogen leaching have an interconnected porous structure. • Magnetic nanoparticles coated with silica form complexes with tannic acid in the scaffold. • Gallic acid does not complex with silica-coated magnetic nanoparticles. Scaffolds acting as an artificial matrix for cell proliferation are one of the bone tissue engineering approaches to the treatment of bone tissue defects. In the presented study, novel multicomponent scaffolds composed of a poly(ε-caprolactone) (PCL), phenolic compounds such as tannic (TA) and gallic acids (GA), and nanocomponents such as silica-coated magnetic iron oxide nanoparticles (MNPs-c) and functionalized multi-walled carbon nanotubes (CNTs) have been produced as candidates for such artificial substitutes. Well-developed interconnected porous structures were observed using scanning electron microscopy (SEM). Raman spectra showed that the highly crystalline nature of PCL was reduced by the addition of nanoadditives. In the case of scaffolds containing MNPs-c and TA, the formation of a Fe-TA complex was concluded because characteristic bands of chelation of the Fe3+ ion by phenolic catechol oxygen appeared. It was found that the necessary conditions for the crystallization of the PCL/MNPs-c/TA are for the catechol groups to be able to penetrate the porous silica shell of MNPs-c, as during experiment with MNPs-c and TA without polymer, no such complexation was observed. Moreover, the number of catechol groups, the spatial structure and molecular size of this phenolic compound are also crucial for complexation process because GA does not form complexes. Therefore, the PCL/CNTs/MNPs-c/TA scaffolds are interesting candidates to consider for their possible medical applications. [ABSTRACT FROM AUTHOR]

Water is a key element for wood performance, as water molecules interact with the wood structure and affect important material characteristics such as mechanical properties and durability. Understanding wood-water interactions is consequently essential for all applications of wood, including the design of wood materials with improved durability by chemical modification. In this work, we used Raman micro-spectroscopy in combination with a specially designed moisture chamber to map molecular groups in wood cell walls under controlled moisture conditions in the hygroscopic range. We analyzed both untreated and chemically modified (acetylated to achieve two different spatial distributions of acetyl groups within the cell wall) Norway spruce wood. By moisture conditioning the specimens successively to 5, 50, and 95% relative humidity using deuterium oxide (D2O), we localized the moisture in the cell walls as well as distinguished between hydroxyl groups accessible and inaccessible to water. The combination of Raman micro-spectroscopy with a moisturizing system with deuterium oxide allowed unprecedented mapping of wood-water interactions. The results confirm lower moisture uptake in acetylated samples, and furthermore showed that the location of moisture within the cell wall of acetylated wood is linked to the regions where acetylation is less pronounced. The study demonstrates the local effect that targeted acetylation has on moisture uptake in wood cell walls, and introduces a novel experimental set-up for simultaneously exploring sub-micron level wood chemistry and moisture in wood under hygroscopic conditions. [ABSTRACT FROM AUTHOR]

Water is a key element for wood performance, as water molecules interact with the wood structure and affect important material characteristics such as mechanical properties and durability. Understanding wood-water interactions is consequently essential for all applications of wood, including the design of wood materials with improved durability by chemical modification. In this work, we used Raman micro-spectroscopy in combination with a specially designed moisture chamber to map molecular groups in wood cell walls under controlled moisture conditions in the hygroscopic range. We analyzed both untreated and chemically modified (acetylated to achieve two different spatial distributions of acetyl groups within the cell wall) Norway spruce wood. By moisture conditioning the specimens successively to 5, 50, and 95% relative humidity using deuterium oxide (D2O), we localized the moisture in the cell walls as well as distinguished between hydroxyl groups accessible and inaccessible to water. The combination of Raman micro-spectroscopy with a moisturizing system with deuterium oxide allowed unprecedented mapping of wood-water interactions. The results confirm lower moisture uptake in acetylated samples, and furthermore showed that the location of moisture within the cell wall of acetylated wood is linked to the regions where acetylation is less pronounced. The study demonstrates the local effect that targeted acetylation has on moisture uptake in wood cell walls, and introduces a novel experimental set-up for simultaneously exploring sub-micron level wood chemistry and moisture in wood under hygroscopic conditions.

Vibrational spectroscopy can detect characteristic biomolecular signatures and thus has the potential to support diagnostics. Fabry disease (FD) is a lipid disorder disease that leads to accumulations of globotriaosylceramide in different organs, including the heart, which is particularly critical for the patient's prognosis. Effective treatment options are available if initiated at early disease stages, but many patients are late- or under-diagnosed. Since Coherent anti-Stokes Raman (CARS) imaging has a high sensitivity for lipid/protein shifts, we applied CARS as a diagnostic tool to assess cardiac FD manifestation in an FD mouse model. CARS measurements combined with multivariate data analysis, including image preprocessing followed by image clustering and data-driven modeling, allowed for differentiation between FD and control groups. Indeed, CARS identified shifts of lipid/protein content between the two groups in cardiac tissue visually and by subsequent automated bioinformatic discrimination with a mean sensitivity of 90–96%. Of note, this genotype differentiation was successful at a very early time point during disease development when only kidneys are visibly affected by globotriaosylceramide depositions. Altogether, the sensitivity of CARS combined with multivariate analysis allows reliable diagnostic support of early FD organ manifestation and may thus improve diagnosis, prognosis, and possibly therapeutic monitoring of FD. [ABSTRACT FROM AUTHOR]

Leaf imaging via microscopy has provided critical insights into research on photosynthesis at multiple junctures, from the early understanding of the role of stomata, through elucidating C4 photosynthesis via Kranz anatomy and chloroplast arrangement in single cells, to detailed explorations of diffusion pathways and light utilization gradients within leaves. In recent decades, the original two-dimensional (2D) explorations have begun to be visualized in three-dimensional (3D) space, revising our understanding of structure–function relationships between internal leaf anatomy and photosynthesis. In particular, advancing new technologies and analyses are providing fresh insight into the relationship between leaf cellular components and improving the ability to model net carbon fixation, water use efficiency, and metabolite turnover rate in leaves. While ground-breaking developments in imaging tools and techniques have expanded our knowledge of leaf 3D structure via high-resolution 3D and time-series images, there is a growing need for more in vivo imaging as well as metabolite imaging. However, these advances necessitate further improvement in microscopy sciences to overcome the unique challenges a green leaf poses. In this review, we discuss the available tools, techniques, challenges, and gaps for efficient in vivo leaf 3D imaging, as well as innovations to overcome these difficulties. [ABSTRACT FROM AUTHOR]

Abstract Many Middle Stone Age sites in South Africa yielded hundreds, even thousands, of ochre pieces sometimes showing use traces. Less attention has been paid to the tools used for their processing. Here, seven tools excavated from the oldest layers (71,000 to 77,000 years ago) of Sibudu rock shelter were studied non-invasively to identify the micro-residues on them. The tools were first examined with optical microscopy to detect areas of interest. Then, Raman micro-spectroscopy was performed on the residues present, as well as on random areas of tool surfaces. These Raman signatures were compared to those obtained from the sediments and ochre samples recovered from the same layers. All tools exhibited red, orange and brown stains on their surfaces and these comprised iron oxides (haematite and maghemite) and oxyhydroxide (goethite). The other compounds detected include amorphous carbon, quartz, anatase and manganese oxides. All of these can occur within ochre, but they may alternatively be natural components of other rocks and sediments, formed secondarily by decay processes. However, the large and thick residues present on the surfaces of the artefacts imply their use for ochre processing (microscopic observations and chemical analyses of the sediments and the local rocks showed that they contain only traces of haematite). Ochre seems to have been the only material processed with these old Sibudu artefacts whereas in younger occupations, items such as bone were also processed with grindstones. The grinding tools are morphologically varied and the ochre pieces are both morphologically and chemically diverse.

Pesticide residues are chemicals frequently found in food as contaminants. Pesticides may have adverse health effects, particularly when the digestive tract is concerned, as a consequence of food ingestion. Deltamethrin is a pyrethroid pesticide widely used in various fields, such as agriculture, veterinary and in the household, so the ingestion of a small amount of this chemical may occasionally occur. To assess whether exposure to pesticide residues may have a biological effect at the intestinal level, it is primarily necessary to perform in vitro exposure experiments about cell lines models of the intestinal barrier at low concentrations of the chemical. In the present study, CaCo-2 cells were exposed to different concentrations of a Deltamethrin-based commercial pesticide, which was diluted in the cell medium. An MTT viability test indicated that the cytotoxic concentration value of the pesticide inside 1 mL of medium is between 10−6 and 10−5 mL. However, the analysis of Raman spectra found that biochemical changes occur inside cells exposed to a non-cytotoxic concentration of 10−6 mL of the pesticide inside 1 mL of the medium. Such changes involve mainly an increase in the ratio between the amount of lipid with respect to that of the protein components in the cell cytoplasm. The results obtained by Raman micro-spectroscopy were confirmed by fluorescence images obtained by using a fluorophore staining neutral lipids. Overall, the obtained results suggest that Raman micro-spectroscopy can be successfully used to monitor the cellular modifications due to exposure at low concentrations of pesticides, as those values that can be found inside food are residuals.

Blast is one of the most devastating fungal diseases of rice caused by Magnaporthe oryzae. Plant essential oil (EO) can function as antifungal agents and are regarded as a safe and acceptable method for plant disease control. However, EOs are unstable and hydrophobic, which limits its use. In the present study, we aimed for the preparation and characterization of a nanoemulsion (NE) from green tea essential oil (GTO) by ultrasonication method and determined the antifungal activity of NE on M. oryzae. The particle size and zeta potential of the NE were 86.98 nm and −15.1 mV, respectively. The chemical composition and functional groups of GTO and NE were studied by using GC–MS analysis, portable Raman spectroscopy, and FTIR coupled with chemometric analysis. GC–MS analysis showed the major components in GTO and NE were n-Hexyl cinnamaldehyde and L-α-Terpineol. Both GTO and NE showed good antioxidant activity and total phenol content. Moreover, the NE showed good antifungal activity against M. oryzae which was further confirmed by scanning electron microscopy (SEM) examination. Also, confocal Raman micro-spectroscopy (CRM) revealed the antifungal mechanism of GTO and NE on M. oryzae which proves the cell damage. To the best of our knowledge, this is the first study on the antifungal activity of GTO and NE against M. oryzae and also the use of CRM for the evaluation of the chemical changes in single fungal hyphae in a holistic approach. This study suggests that the prepared NE could be a potential candidate for use as a substitute for synthetic fungicides.

Purpose: The purpose of this work is to develop a new approach for high spatial resolution dosimetry based on Raman micro‐spectroscopy scanning of radiochromic film (RCF). The goal is to generate dose calibration curves over an extended dose range from 0 to 50 Gy and with improved sensitivity to low (<2 Gy) doses, in addition to evaluating the uncertainties in dose estimation associated with the calibration curves. Methods: Samples of RCF (EBT3) were irradiated at a broad dose range of 0.03–50 Gy using an Elekta Synergy clinical linear accelerator. Raman spectra were acquired with a custom‐built Raman micro‐spectroscopy setup involving a 500 mW, multimode 785 nm laser focused to a lateral spot diameter of 30 µm on the RCF. The depth of focus of 34 µm enabled the concurrent collection of Raman spectra from the RCF active layer and the polyester laminate. The preprocessed Raman spectra were normalized to the intensity of the 1614 cm−1 Raman peak from the polyester laminate that was unaltered by radiation. The mean intensities and the corresponding standard deviation of the active layer Raman peaks at 696, 1445, and 2060 cm−1 were determined for the 150 × 100 µm2 scan area per dose value. This was used to generate three calibration curves that enabled the conversion of the measured Raman intensity to dose values. The experimental, fitting, and total dose uncertainty was determined across the entire dose range for the dosimetry system of Raman micro‐spectroscopy and RCF. Results: In contrast to previous work that investigated the Raman response of RCFs using different methods, high resolution in the dose response of the RCF, even down to 0.03 Gy, was obtained in this study. The dynamic range of the calibration curves based on all three Raman peaks in the RCF extended up to 50 Gy with no saturation. At a spatial resolution of 30 × 30 µm2, the total uncertainty in estimating dose in the 0.5–50 Gy dose range was [6–9]% for all three Raman calibration curves. This consisted of the experimental uncertainty of [5–8]%, and the fitting uncertainty of [2.5–4.5]%. The main contribution to the experimental uncertainty was determined to be from the scan area inhomogeneity which can be readily reduced in future experiments. The fitting uncertainty could be reduced by performing Raman measurements on RCF samples at further intermediate dose values in the high and low dose range. Conclusions: The high spatial resolution experimental dosimetry technique based on Raman micro‐spectroscopy and RCF presented here, could become potentially useful for applications in microdosimetry to produce meaningful dose estimates in cellular targets, as well as for applications based on small field dosimetry that involve high dose gradients. [ABSTRACT FROM AUTHOR]

Turbidity in beer will continue to be a major topic as many origins of haze have already been discovered, but it is not always possible to identify its immediate cause. In addition to beer foam, one of the most important visual quality characteristics of filtered beers is gloss fineness. Consequently, in the case of an undesirable haze, it is first necessary to identify the haze particles and how to remove them. The topic is covered in two sections. This review labelled Part 1 and a second review labelled Part 2. Part 1 addresses turbidity in general, the causes and origins of turbidity and the different analytical methods for turbidity identification and removal. Part 2 focuses on Raman spectroscopy and provides a general overview of the physical basics, the areas of application, possible gaps and the challenge for its use for identifying turbidity in beer and beverages. [ABSTRACT FROM AUTHOR]

Beer turbidity Part 1 focused on beer turbidity, it origins and problems. Beer Turbidity Part 2 focuses on Raman spectroscopy (RS), especially on TI-RMS (Turbidity Identification - Raman Micro-Spectroscopy). The review provides a general overview of the physical basics, the areas of application, possible gaps, and the challenge for the use of Raman spectroscopy in beer and beverage analysis. Analysis of turbidity in beer is often limited to optical, microscopic and enzymatic analyses. This review explores in detail turbidity identification using Raman micro-spectroscopy as a way to identify beer turbidity particles and the possibility of establishing it as a future robust analysis method for beer. [ABSTRACT FROM AUTHOR]

Nowadays, despite significant advances in the field of biomaterials for tissue engineering applications, novel bone substituents still need refinement so they can be successfully implemented into the medical treatment of bone fractures. Generally, a scaffold made of synthetic polymer blended with nanofillers was proven to be a very promising biomaterial for tissue engineering, however the choice of components for the said scaffold remains questionable. The objects of the presented study were novel composites consisting of poly("-caprolactone) (PCL) and two types of graphene materials: graphene oxide (GO) and partially reduced graphene oxide (rGO). The technique of choice, that was used to characterize the obtained composites, was Raman micro-spectroscopy. It revealed that the composite PCL/GO differs substantially from the PCL/rGO composite. The incorporation of the GO particles into the polymer influenced the structure organisation of the polymeric matrix more significantly than rGO. The crystallinity parameters confirmed that the level of crystallinity is generally higher in the PCL/GO membrane in comparison to PCL/rGO (and even in raw PCL) that leads to the conclusion that the GO acts as a nucleation agent enhancing the crystallization of PCL. Interestingly, the characteristics of the studied nanofillers, for example: the level of the organisation (D/G ratio) and the in-plane size of the nano-crystallites (La) almost do not differ. However, they have an ability to influence polymeric matrix differently. [ABSTRACT FROM AUTHOR]

• High-producer cell-screening platform, based on label-free laser-based techniques. • Laser-induced forward transfer (LIFT). • Surface-enhanced Raman spectroscopy (SERS). • Combination of Raman micro-spectroscopy, SERS and LIFT in a single platform. • Fully automated system for cell line development for biopharmaceuticals manufacturing. Mammalian cells have become the predominant expression system for the production of biopharmaceuticals due to their capabilities in posttranslational modifications. In recent years, the efficacy of these production processes has increased significantly through technical improvements. However, the state of the art in the development of producer cell lines includes many manual steps and is as such very time and cost consuming. In this study we developed a process combination of Raman micro-spectroscopy, laser-induced forward transfer (LIFT) and surface-enhanced Raman spectroscopy (SERS) as an automated machine system for the identification, separation and characterization of single cell-clones for biopharmaceutical production. Raman spectra showed clear differences between individual antibody-producing and non-producing chinese hamster ovary (CHO) cells after their stable transfection with a plasmid coding for an immunoglobulin G (IgG) antibody. Spectra of producing CHO cells exhibited Raman signals characteristic for human IgG. Individual producing CHO cells were successfully separated and transferred into a multiwell plate via LIFT. Besides, changes in concentration of human IgG in solution were detected via SERS. SERS spectra showed the same peak patterns but differed in their peak intensity. Overall, our results show that identification of individual antibody-producing CHO cells via Raman micro-spectroscopy, cell separation via LIFT and determination of changes in concentrations of overexpressed protein via SERS are suitable and versatile tools for assembling a fully automated system for biopharmaceuticals manufacturing. [ABSTRACT FROM AUTHOR]

This study demonstrates the efficacy of Raman micro‐spectroscopy of oral cytological samples for differentiating dysplastic, potentially malignant lesions from those of normal, healthy donors. Cells were collected using brush biopsy from healthy donors (n = 20) and patients attending a Dysplasia Clinic (n = 20). Donors were sampled at four different sites (buccal mucosa, tongue, alveolus, gingiva), to ensure matched normal sites for all lesions, while patient samples were taken from clinically evident, histologically verified dysplastic lesions. Spectra were acquired from the nucleus and cytoplasm of individual cells of all samples and subjected to partial least squares‐discriminant analysis. Discriminative sensitivities of 94% and 86% and specificity of 85% were achieved for the cytoplasm and nucleus, respectively, largely based on lipidic contributions of dysplastic cells. Alveolar/gingival samples were differentiated from tongue/buccal samples, indicating that anatomical site is potentially a confounding factor, while age, gender, smoking and alcohol consumption were confirmed not to be. [ABSTRACT FROM AUTHOR]

Ostrich eggshell and gastropod shell beads provide important evidence for understanding how past peoples decorated and cultured their bodies and may also be used as proxy evidence for interpreting the nature and extent of past social networks. This study focuses on the ostrich eggshell and gastropod shell bead assemblages from the terminal Pleistocene (~ 13.5 to 11.6 ka) and mid-Holocene (~ 7.3 to 6.7 ka) occupations from Grassridge Rockshelter, South Africa. We present results from a multi-method approach to understanding bead manufacture and use that combines a technological analysis of the bead assemblages with Raman spectroscopy. Raman spectroscopy analyses were conducted on surface residues identified on the beads, ochre pieces, a grooved stone, and sediment samples, and provide further insight into past behaviours and taphonomy, as well as modern contaminants. Results indicate that ostrich eggshell beads were manufactured at Grassridge during both occupations, and that bead size changed through time. Use-wear and residue analyses demonstrate the complex taphonomy associated with bead studies from archaeological contexts, and the need for further taphonomic research. These analyses also suggest that some ostrich eggshell and Nassarius beads were potentially worn against ochred surfaces, such as skin or hide, as evidenced by the amount and location of the ochreous residues identified on the beads. [ABSTRACT FROM AUTHOR]

The increasing international interest in contemporary architecture has drawn attention to the numerous listed buildings made of reinforced concrete in Europe, and especially in France. The main source of deterioration of this cultural heritage is the corrosion of rebars through carbonation or chloride contamination, but also often by a combination of both. The present study explored this combined corrosion mechanism in reinforced concretes, and investigated Electrochemical Chloride Extraction (ECE) as a technique to stop or decrease corrosion. The analytical approach was based on physico-chemistry, electrochemical measurements, Raman spectroscopy and SEM examinations. The results evidenced the aggressiveness of the combined carbonation and chloride-induced corrosion, and demonstrated the efficiency of the ECE treatment in terms of chloride extraction and reduction of corrosion rate. It appears that ECE treatment only reduces corrosion activity by increasing pH to a value of 10. Nevertheless, the long term durability of the treatment is questionable as the return to a sound concrete passivity is not obtained. • High corrosion rate show the aggressiveness of combined contamination (Cl−, CO 2). • Electrochemical chloride treatment is provisionally efficient. • Long term durability of ECE is questionable (pH increase is insufficient). [ABSTRACT FROM AUTHOR]

The objective of this study was to determine the molecular and biochemical changes in dental pulp stem cells (DPSCs) due to consecutive low-dose ionizing radiation exposures using label-free Raman micro-spectroscopy (RMS). Ionizing radiation produces biological damage leading to health effects of varying severity. The effects and subsequent health implications caused by exposure to low-dose radiation, such as diagnostic exposure, remain ambiguous. We identified Raman biomarkers characteristic to low-dose cone beam computed tomography (CBCT) irradiation of the DPSCs. The biomarkers were monitored inside the cells using the relative intensity distribution of the 785 and 1734 cm−1 bands. The control cells presented a higher relative intensity of the nucleic acid specific Raman bands, whereas the irradiated cells revealed an increased intensity of the lipid-induced bands. The results obtained in this study demonstrate the capability of RMS for the detection of cell response to diagnostic radiation dose levels. This may indicate the potential of the technique for future applications such as monitoring the radiation responses in pediatric patients suffering repeated radiological exposures. [ABSTRACT FROM AUTHOR]

Polyhydroxyalkanoates (PHAs), polyphosphate (poly-P) and polysulfide or elemental sulfur (poly-S) are the key functionally relevant polymers involved in the recently reported Denitrifying Sulfur conversion-associated Enhanced Biological Phosphorus Removal (DS-EBPR) process. However, little is known about the structural dynamics and storage states of these polymers. In particular, investigating the poly-S generated in this process is quite a superior challenge. This study was thus aimed at simultaneously qualitative-quantitative investigating poly-S and associated poly-P and PHAs through the integrated chemical analysis and Raman micro-spectroscopy coupled with multiple microscopic methods (i.e. optical microscopy, confocal laser scanning microscopy, and differential interference contrast microscopy). The chemical analytical results displayed a stable DS-EBPR phenotype in terms of sulfur conversion, P release/uptake and the dynamics of relevant polymers. The multiple microscopic images and Raman spectrum profiles further clearly demonstrated the existence of the polymers and their dynamic changes under alternating anaerobic-anoxic conditions, consistent with the chemical analytical results. In particular, Raman analysis for the first time unraveled the co-existence of S0/S n 2− species stored either intracellularly or extracellularly; and the dynamic conversions between S0/S n 2− and other sulfur species suggest that there might be a universal pool of bioavailable sulfur. The results reveal the mechanisms underlying the structural dynamics and changes in storage states of the relevant polymers that are functionally relevant to the carbon/phosphorus/sulfur-cycles during different metabolic phases. These mechanisms would otherwise not be obtained only using a traditional chemical analysis-based approach. Image 1 • Relevant polymers (e.g. PHA, poly-P and poly-S) play key roles in DS-EBPR. • Polymers were semi-quantitatively identified by Raman spectra and microscopes. • The dynamics of polymers analyzed by Raman/microscopes matches chemical analysis. • Mixed S0/S n 2− species in bacteria were stored either intra- or extracellularly. [ABSTRACT FROM AUTHOR]

Highlights • Raman spectroscopy on nuclear and membrane regions of single human neuroblastoma cells. • Measurements are performed after irradiation by clinically relevant X-ray doses. • The acquired spectra are analyzed by PCA and interval-PCA methods. • The most relevant effects are evidenced in the spectra from the cell nucleus region. • Potential markers of an apoptotic process could be singled out for some X- ray doses. Abstract Raman micro-spectroscopy was performed in vitro on nuclear and membrane regions of single SH-SY5Y human neuroblastoma cells after irradiation by graded X-ray doses (2, 4, 6, 8 Gy). The acquired spectra were analyzed by principal component analysis (PCA) and interval-PCA (i-PCA) methods. Biochemical changes occurring in the different regions of single cells as a consequence of the radiation exposure were observed in cells fixed immediately after the irradiation. The most relevant effects arose from the analysis of the spectra from the cell nucleus region. The observed changes were discussed in terms of the modifications in the cell cycle, resulting in an increase in the DNA-related signal, a protein rearrangement and changes in lipid and carbohydrates profiles within the nucleus. Potential markers of an apoptotic process in cell population irradiated with 6 and 8-Gy X-ray doses could have been singled out. No significant effects were found in spectra from cells fixed 24 h after the irradiation, thus suggesting the occurrence of repairing processes of the X-ray induced damage. [ABSTRACT FROM AUTHOR]

[Display omitted] • A rare wood ash glass tessera from Malbork Madonna was studied in detail. • It was found to be original mediaeval, from the area north of Alps, coloured by Co. • Opacification was achieved by Ca-phosphate grains, a Mediterranean technology. • Two phases detected in tessera for the first time: leucite and pseudowollastonite. • Pseudowollastonite indicates production temperature above ca. 1125 °C. While the natron and plant ash glass tesserae may be found on places of importance across the former Roman and Byzantine empires, wood ash glass tesserae are scarce. This is the first time a wood ash glass tessera is studied in detail. It was part of a magnificent 8-metres tall statue of Madonna in Malbork, Poland, created at the end of the 14th century and destroyed at the end of World War Two. It was found to be coloured by cobalt with possible impact of copper, and opacified by Ca-phosphate. Processes previously described in sodium-rich glasses were observed also in the studied potassium-rich wood ash glass tessera, such as diffusion of the respective alkali metal into the Ca-phosphate grains. The elemental composition of the tessera indicates that it is original – mediaeval, from the area north of Alps. Two phases were identified for the first time, to authors' best knowledge, in any glass tessera – leucite (tetragonal KAlSi 2 O 6) and pseudowollastonite (monoclinic CaSiO 3). As pseudowollastonite is a high-temperature phase, it may serve as an indicator of production temperature, which was further supported by the study of polymerisation index of model glasses. This study contributes to the knowledge of old technologies and showed that the know-how for opacification was imported from the Mediterranean, while the raw materials employed for the base glass preparation were from the area north of Alps. [ABSTRACT FROM AUTHOR]

Over decades, synthetic dyes have become increasingly dominated by azo dyes posing a significant environmental risk due to their toxicity. Microalgae-based systems may offer an alternative for treatment of azo dye effluents to conventional physical-chemical methods. Here, microalgae were tested to decolorize industrial azo dye wastewater (ADW). Chlorella sorokiniana showed the highest decolorization efficiency in a preliminary screening test. Subsequently, the optimization of the experimental design resulted in 70% decolorization in a photobioreactor. Tolerance of this strain was evidenced using multiple approaches (growth and chlorophyll content assays, scanning electron microscopy (SEM), and antioxidant level measurements). Raman microspectroscopy was employed for the quantification of ADW-specific compounds accumulated by the microalgal biomass. Finally, RNA-seq revealed the transcriptome profile of C. sorokiniana exposed to ADW for 72 h. Activated DNA repair and primary metabolism provided sufficient energy for microalgal growth to overcome the adverse toxic conditions. Furthermore, several transporter genes, oxidoreductases-, and glycosyltransferases-encoding genes were upregulated to effectively sequestrate and detoxify the ADW. This work demonstrates the potential utilization of C. sorokiniana as a tolerant strain for industrial wastewater treatment, emphasizing the regulation of its molecular mechanisms to cope with unfavorable growth conditions. [Display omitted] • Microalgae-based system achieves up to 70% decolorization of azo dye wastewater. • Transcriptome profile of C. sorokiniana reveals several genes for azo dye tolerance. • Bioaccumulation is the main mechanism for azo dye removal by microalgae. • Microalgae treatment reduces effluent water toxicity and pollutant concentrations. • Integrated approach offers a novel platform for microalgae-based technologies. [ABSTRACT FROM AUTHOR]

Previous works showed that spatially resolved Raman spectra of cytoplasm and nucleus region of single cells exposed to X-rays evidence different features. The present work aims to introduce a new approach to profit from these differences to deeper investigate X-ray irradiation effects on single SH-SY5Y human neuroblastoma cells. For this aim, Raman micro-spectroscopy was performed in vitro on single cells after irradiation by graded X-ray doses (2, 4, 6, 8 Gy). Spectra from nucleus and cytoplasm regions were selectively acquired. The examination by interval Principal Component Analysis (i-PCA) of the difference spectra obtained by subtracting each cytoplasm-related spectrum from the corresponding one detected at the nucleus enabled us to reveal the subtle modifications of Raman features specific of different spatial cell regions. They were discussed in terms of effects induced by X-ray irradiation on DNA/RNA, lipids, and proteins. The proposed approach enabled us to evidence some features not outlined in previous investigations.

Pacific Ocean trawl samples, stomach contents of laboratory-raised fish as well as fish from the subtropical gyres were analyzed by Raman micro-spectroscopy (RMS) to identify polymer residues and any detectable persistent organic pollutants (POP). The goal was to access specific molecular information at the individual particle level in order to identify polymer debris in the natural environment. The identification process was aided by a laboratory generated automated fluorescence removal algorithm. Pacific Ocean trawl samples of plastic debris associated with fish collection sites were analyzed to determine the types of polymers commonly present. Subsequently, stomach contents of fish from these locations were analyzed for ingested polymer debris. Extraction of polymer debris from fish stomach using KOH versus ultrapure water were evaluated to determine the optimal method of extraction. Pulsed ultrasonic extraction in ultrapure water was determined to be the method of choice for extraction with minimal chemical intrusion. The Pacific Ocean trawl samples yielded primarily polyethylene (PE) and polypropylene (PP) particles >1 mm, PE being the most prevalent type. Additional microplastic residues (1 mm - 10 μm) extracted by filtration, included a polystyrene (PS) particle in addition to PE and PP. Flame retardant, deca-BDE was tentatively identified on some of the PP trawl particles. Polymer residues were also extracted from the stomachs of Atlantic and Pacific Ocean fish. Two types of polymer related debris were identified in the Atlantic Ocean fish: (1) polymer fragments and (2) fragments with combined polymer and fatty acid signatures. In terms of polymer fragments, only PE and PP were detected in the fish stomachs from both locations. A variety of particles were extracted from oceanic fish as potential plastic pieces based on optical examination. However, subsequent RMS examination identified them as various non-plastic fragments, highlighting the importance of chemical analysis in distinguishing between polymer and non-polymer residues. [ABSTRACT FROM AUTHOR]

The applications of Raman microspectroscopy have been extended in recent years into the field of clinical medicine, and specifically in cancer research, as a non-invasive diagnostic method in vivo and ex vivo, and the field of pharmaceutical development as a label-free predictive technique for new drug mechanisms of action in vitro. To further illustrate its potential for such applications, it is important to establish its capability to fingerprint drug mechanisms of action and different cellular reactions. In this study, cytotoxicity assays were employed to establish the toxicity profiles for 48 and 72 hours exposure of lung cancer cell lines, A549 and Calu- 1, after exposure to Actinomycin D (ACT) and Raman micro-spectroscopy was used to track its mechanism of action at subcellular level and subsequent cellular responses. Multivariate data analysis was used to elucidate the spectroscopic signatures associated with ACT chemical binding and cellular resistances. Results show that the ACT uptake and mechanism of action are similar in the 2 cell lines, while A549 cells exhibits spectral signatures of resistance to apoptosis related to its higher chemoresistance to the anticancer drug ACT. The observations are discussed in comparison to previous studies of the similar anthracyclic chemotherapeutic agent Doxorubicin. A, Preprocessed Raman spectrum of ACT stock solution dissolved in sterile water and mean spectrum with SD of (B) nucleolus, (C) nucleus and (D) cytoplasm of A549 cell lines after 48 hours exposure to the corresponding IC50. [ABSTRACT FROM AUTHOR]

The applications of Raman microspectroscopy have been extended in recent years into the field of clinical medicine, and specifically in cancer research, as a non‐invasive diagnostic method in vivo and ex vivo, and the field of pharmaceutical development as a label‐free predictive technique for new drug mechanisms of action in vitro. To further illustrate its potential for such applications, it is important to establish its capability to fingerprint drug mechanisms of action and different cellular reactions. In this study, cytotoxicity assays were employed to establish the toxicity profiles for 48 and 72 hours exposure of lung cancer cell lines, A549 and Calu‐1, after exposure to Actinomycin D (ACT) and Raman micro‐spectroscopy was used to track its mechanism of action at subcellular level and subsequent cellular responses. Multivariate data analysis was used to elucidate the spectroscopic signatures associated with ACT chemical binding and cellular resistances. Results show that the ACT uptake and mechanism of action are similar in the 2 cell lines, while A549 cells exhibits spectral signatures of resistance to apoptosis related to its higher chemoresistance to the anticancer drug ACT. The observations are discussed in comparison to previous studies of the similar anthracyclic chemotherapeutic agent Doxorubicin. A, Preprocessed Raman spectrum of ACT stock solution dissolved in sterile water and mean spectrum with SD of (B) nucleolus, (C) nucleus and (D) cytoplasm of A549 cell lines after 48 hours exposure to the corresponding IC50. [ABSTRACT FROM AUTHOR]

Abstract: Raman micro‐spectroscopy is a non‐invasive analytical tool, whose potential in cellular analysis and monitoring drug mechanisms of action has already been demonstrated, and which can potentially be used in pre‐clinical and clinical applications for the prediction of chemotherapeutic efficacy. To further investigate such potential clinical application, it is important to demonstrate its capability to differentiate drug mechanisms of action and cellular resistances. Using the example of Doxorubicin (DOX), in this study, it was used to probe the cellular uptake, signatures of chemical binding and subsequent cellular responses, of the chemotherapeutic drug in two lung cancer cell lines, A549 and Calu‐1. Multivariate statistical analysis was used to elucidate the spectroscopic signatures associated with DOX uptake and subcellular interaction. Biomarkers related to DNA damage and repair, and mechanisms leading to apoptosis were also measured and correlated to Raman spectral profiles. Results confirm the potential of Raman spectroscopic profiling to elucidate both drug kinetics and pharmacodynamics and differentiate cellular drug resistance associated with different subcellular accumulation rates and subsequent cellular response to DNA damage, pointing towards a better understanding of drug resistance for personalised targeted treatment. [ABSTRACT FROM AUTHOR]

Silicon nitride (Si 3 N 4 ) ceramics possesses surface chemistry that accelerates bone repair, as previously established by in vitro experiments using both osteosarcoma and mesenchymal cells. The release of silicic acid and nitrogen compounds from the surface Si 3 N 4 enhanced in vitro cellular activity. The results of this study demonstrate for the first time that the osseointegration behavior previously observed is operative with a peculiar chemistry within the human milieu. Si and N elements stimulated progenitor cell differentiation and osteoblastic activity, which ultimately resulted in accelerated bone ingrowth. At the molecular scale, insight into the effect of silicon and nitrogen ions released from the Si 3 N 4 surface was obtained through combined histomorphometric analyses, Raman, Fourier-transform-infrared, and X-ray photoelectron spectroscopies. Identical analyses conducted on a polyetheretherketone (PEEK) spinal explant showed no chemical changes and a lower propensity for osteogenic activity. Silicon and nitrogen are key elements in stimulating cells to generate bony apatite with crystallographic imperfections, leading to enhanced bioactivity of Si 3 N 4 biomedical devices. Statement of Significance This research studies osseointegration processes comparing results from explanted PEEK and Si 3 N 4 spinal spacers. Data show that the formation of hydroxyapatite on silicon nitride bio-ceramic surfaces happens with a peculiar mechanism inside the human body. Silicon and nitrogen were incorporated inside the bony tissue structure allowing the developing of off-stoichiometric bony apatite and stimulating progenitor cell differentiation/osteoblastic activity. Silicon and nitrogen ions released from the Si 3 N 4 surface were detected through combined histologic analyses, Raman microspectroscopy, Fourier-transform-infrared, and X-ray photoelectron spectroscopies. [ABSTRACT FROM AUTHOR]

Despite the many advances intended to enhance the response to treatment, the survival rate of patients with ovarian cancer has only marginally improved in the past few decades. One major cause for this, is the lack of diagnostics for platinum-resistant disease. The goal of this study was to determine whether Raman micro-spectroscopy in conjunction with multivariate statistical analysis could discriminate between chemically fixed cisplatin-resistant (A2780cp) and cisplatin-sensitive (A2780s) human ovarian carcinoma cells. Raman spectra collected from individual cells were pre-processed and subsequently analyzed with Principal Component Analysis - Linear Discriminant Analysis (PCA-LDA). Statistically significant differences ( P < 0.0001) were observed between the Raman spectra of A2780s and A2780cp cells. A diagnostic accuracy of 82% was obtained using the PCA-LDA classifier model for the discrimination between the A2780s and A2780cp cells. The loading plot analysis suggests that relative increases in proteins and glutathione in the cisplatin-resistant cells compared to the cisplatin-sensitive cells [ABSTRACT FROM AUTHOR]

Tilted stems of softwoods form compression wood (CW) and opposite wood (OW) on their lower and upper sides, respectively. More is known about the most severe form of CW, severe CW (SCW), but mild CWs (MCWs) also occur widely. Two grades of MCWs, MCW1 and MCW2, as well as SCW and OW were identified in the stems of radiata pine ( Pinus radiata ) that had been slightly tilted. The four wood types were identified by the distribution of lignin in the tracheid walls determined by fluorescence microscopy. A solution of the fluorescent dye acridine orange (AO) (0.02% at pH 6 or 7) was shown to metachromatically stain the tracheid walls and can also be used to determine lignin distribution. The lignified walls fluoresced orange to yellow depending on the lignin concentration. Microscopically well-characterized discs (0.5 mm diameter) of the wood types were used to determine lignin concentrations and lignin monomer compositions using the acetyl bromide method and thioacidolysis, respectively. Lignin concentration and the proportion of p- hydroxyphenyl units (H-units) relative to guaiacyl (G-units) increased with CW severity, with <1% H-units in OW and up to 14% in SCW. Lignin H-units can be used as a marker for CW and CW severity. Similar discs were also examined by Raman and FTIR micro-spectroscopies coupled with principal component analysis (PCA) to determine if these techniques can be used to differentiate the four different wood types. Both techniques were able to do this, particularly Raman micro-spectroscopy. [ABSTRACT FROM AUTHOR]

Biomarkers detection at an ultra-low concentration in biofluids (blood, serum, saliva, etc.) is a key point for the early diagnosis success and the development of personalized therapies. However, it remains a challenge due to limiting factors like (i) the complexity of analyzed media, and (ii) the aspecificity detection and the poor sensitivity of the conventional methods. In addition, several applications require the integration of the primary sensors with other devices (microfluidic devices, capillaries, flasks, vials, etc.) where transducing the signal might be difficult, reducing performances and applicability. In the present work, we demonstrate a new class of optical biosensor we have developed integrating an optical waveguide (OWG) with specific plasmonic surfaces. Exploiting the plasmonic resonance, the devices give consistent results in surface enhanced Raman spectroscopy (SERS) for continuous and label-free detection of biological compounds. The OWG allows driving optical signals in the proximity of SERS surfaces (detection area) overcoming spatial constraints, in order to reach places previously optically inaccessible. A rutile prism couples the remote laser source to the OWG, while a Raman spectrometer collects the SERS far field scattering. The present biosensors were implemented by a simple fabrication process, which includes photolithography and nanofabrication. By using such devices, it was possible to detect cell metabolites like Phenylalanine (Phe), Adenosine 5-triphosphate sodium hydrate (ATP), Sodium Lactate, Human Interleukin 6 (IL6), and relate them to possible metabolic pathway variation.

Analyzing the cells in various body fluids can greatly deepen the understanding of the mechanisms governing the cellular physiology. Due to the variability of physiological and metabolic states, it is important to be able to perform such studies on individual cells. Therefore, we developed an optofluidic system in which we precisely manipulated and monitored individual cells of Escherichia coli. We tested optical micromanipulation in a microfluidic chamber chip by transferring individual bacteria into the chambers. We then subjected the cells in the chambers to antibiotic cefotaxime and we observed the changes by using time-lapse microscopy. Separately, we used laser tweezers Raman spectroscopy (LTRS) in a different micro-chamber chip to manipulate and analyze individual cefotaxime-treated E. coli cells. Additionally, we performed conventional Raman micro-spectroscopic measurements of E. coli cells in a micro-chamber. We found observable changes in the cellular morphology (cell elongation) and in Raman spectra, which were consistent with other recently published observations. The principal component analysis (PCA) of Raman data distinguished between the cefotaxime treated cells and control. We tested the capabilities of the optofluidic system and found it to be a reliable and versatile solution for this class of microbiological experiments.

Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major- and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data (~ 600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite (≥ 0.3 apfu F) with 0.2–2.7 wt.% SrO, 0–4.5 wt.% LREE 2 O 3 , 0–0.8 wt.% Na 2 O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO 4 ) 2 − and (VO 4 ) 3 − anions, substituting for (PO 4 ) 3 − , tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO 2 , 1.5 wt.% SO 3 and 660 ppm V). Although (CO 3 ) 2 − groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (δCe, δEu) and hydrothermal overprint (δY) form a fairly tight cluster of values (0.8–1.3, 0.8–1.1 and 0.6–0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb) cn ≤ 25, or a negative Ce anomaly]. The only significant exception is Sr(± REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonatites. Their crystallization conditions and source fluid appear to be very different from the more common Sr-REE-depleted variety. Based on the new evidence presented in this work, trace-element partitioning between apatite and carbonatitic magmas, phosphate solubility in these magmas, and compositional variation of apatite-group minerals from spatially associated carbonatitic rocks are critically re-evaluated. [ABSTRACT FROM AUTHOR]

Every step of microplastic analysis (collection, extraction and characterization) is time-consuming, representing an obstacle to the implementation of large scale monitoring. This study proposes a semi-automated Raman micro-spectroscopy method coupled to static image analysis that allows the screening of a large quantity of microplastic in a time-effective way with minimal machine operator intervention. The method was validated using 103 particles collected at the sea surface spiked with 7 standard plastics: morphological and chemical characterization of particles was performed in < 3 h. The method was then applied to a larger environmental sample ( n = 962 particles). The identification rate was 75% and significantly decreased as a function of particle size. Microplastics represented 71% of the identified particles and significant size differences were observed: polystyrene was mainly found in the 2–5 mm range (59%), polyethylene in the 1–2 mm range (40%) and polypropylene in the 0.335–1 mm range (42%). [ABSTRACT FROM AUTHOR]

Common materials used as orthopedic implants are titanium and its alloys. To improve its compatibility with the environment of a living organism titanium implant surfaces are covered with bioactive layers of MWCNT. During the insertion into a living organism such material is exposed to direct contact with the patient's blood, which includes proteins – eg. albumin. The adsorption of albumin may constitute one of the early stages of implant surface modification serving cell adhesion. An analysis of this phenomenon in terms of the kinetics of deposition of protein on the surface of the implant confirms its biocompatibility in vivo . The proposed working model of the adsorption of albumin allows for choosing the best of time for the protein to form a stable connection with the surface of the titanium implant. Traditional methods of materials engineering and chemistry allow for the obtaining of information about the presence of a protein on the surface (UV–Vis, the wettability). The application of 2D correlation analysis, in turn, gains insight into the dynamics of the changes associated with the deposition of protein (the formation of a uniform layer, the change in conformation). This analysis has allowed for the selection of an optimal time of protein adsorption to the surface of the implant. Better compatibility with the body of the implant provides its modification by introducing layers that accelerate the material–tissue interactions. Such a composition is a layer of carbon nanotubes (MWCNTs) deposited on titanium by the electrophoretic (EPD) method. Using Raman spectroscopy and analyzing the spectra with the 2D correlation method it is possible to gain insight into the molecular structure of this layer. Our studies indicate that albumin in contact with the surface of titanium has obtained stable conformation after 30 min (confirmed by: UV–Vis, Raman). Shifts of the CH 2 , CH 3 stretching bands position as well as an analysis of the amide I band confirms this conformation. The dynamics of these changes are noticed as correlation peaks observed on 2D maps. [ABSTRACT FROM AUTHOR]