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Process-monitoring laboratories in the pulp and paper industry generally use a combination of wet chemical analyses and physical measurements to certify the fitness of a production pulp for a specific end-use. These laboratory tests require time and the effort of trained personnel, limiting their utility for real-time process control. Here we show that Raman probes of unrefined cellulosic pulps, well-suited to the online measurement of in-process materials, can predict the quality attributes of manufactured papers. The accuracy of prediction improves when the covariance is modelled in a reduced measurement space selected by a data-driven, feature-selection technique referred to as a Template Oriented Genetic Algorithm (TOGA). TOGA, combined with discrete wavelet transform (DWT), isolates functional-group features that correlate best with mechanical properties paper derived from refined pulp. Paper makers refine market pulps to build sheet strength using a beating process that decreases freeness as it increases fibre-fibre bonding. Methods demonstrated here predict manufactured sheet properties obtainable after any specified degree of refining from the Raman spectrum of an unrefined pulp. This analysis capacity will enable both vendors of market pulp and makers of sheet paper to specify in advance the amount of beating required to produce a desired product, thereby saving cost and conserving resources.

Rising concern about the use of non-permitted colourants, in common food items such as dals and green vegetables sold in Indian markets, have led to a demand for low-cost point-of-use chemical analysis tools. Conventional food-analysis techniques involving tedious sample preparation protocols are not suited for in-field applications. Surface Enhanced Raman Spectroscopy (SERS) is an analytical technique that is well-suited for point-of-use chemical analysis with molecular level detection capability, which can also serve as a quality assurance tool for businesses. Effective and rapid signal collection from a large-area sample within a field-setting using disposable, low-cost SERS substrates is a key challenge in implementing such a solution. Herein, we demonstrate the use of inkjet-printed thin films comprising of robust nanostructured-silver as flexible, paper-based SERS (P-SERS) swabs for the direct detection of Metanil Yellow (MY) from toor dal (yellow split pigeon peas) samples and Malachite Green (MG) from green peas and green chillies. The macroscopic uniformity of these thin-films in combination with a portable Raman spectrometer equipped with orbital raster scanning (ORS™) technology for signal collection results in an unprecedented precision (RSD ∼ 1.6%) upon characterizing samples saturated with Rhodamine-6G (R6G), a standard Raman probe. As several food-cleansing products have appeared in the marketplace, the adulterant removal efficacy of some commercially available ‘washes’ as well as products such as ‘ozoniser’, which was determined by SERS characterization of swabs before and after use, is also reported.

A graphene oxide paper (GOP) was irradiated with 500 keV proton for total fluence of 2 × 1013 cm−2 to 2 × 1015 cm−2 in a ground-based irradiation simulator. The spacing of layer, surface chemical composition, structural defects, thermal conductivity and electrical property of the GOP before and after irradiation was measured. The results indicated that the spacing of layer decreased after irradiation. The ratio of total carbon atom and total oxygen atom increased from 2.40 to 4.31 as well as the sp2 hybridized carbons obviously increased after 2 × 1015 cm−2 irradiation. The XPS analysis suggested the occurrence of reduction, and the Raman spectra indicated that the defects were produced after proton irradiation. Furthermore, the thermal conductivity of GOP decreased, and then increased smoothly as the irradiation fluences were increased, and the electrical property showed the similar trend. The change in the thermal and electrical properties for GOP could be attributed to the defects and the removal of oxygen-containing functional groups, which lead to the phonon conduct path and scattering centers changed under proton irradiation. This study could promote the application of GOP in future space expeditions.

Estazolam (EST) is a common sedative-hypnotic drug with a risk of abuse. Therefore, rapid on-site detection of EST is necessary to control the abuse of EST. In this paper, a fast, simple, and sensitive method is demonstrated for the detection of EST in both water and beverages, using surface-enhanced Raman spectroscopy (SERS) techniques. Au@Ag core-shell nanoparticles (NPs) assembled on the filter paper as a SERS substrate exhibit good applicability and practicality. At the same time, density functional theory (DFT) is used to assign the vibration mode of the EST molecules, which can be used as a guide for subsequent experiments. The lowest detectable concentration of EST in aqueous solution can be as low as 5 mg/L, and signal uniformity is excellent (RSD687 = 5.56%, RSD1000 = 4.35%). In addition, EST components artificially added to orange juice and pomegranate juice can be effectively detected by simple pretreatment with a minimum detection concentration as low as 10 mg/L. Therefore, this study found that the use of Au@Ag core-shell nanoparticles paper-based SERS substrate provides a quick and easy method for the detection of illegally added drugs in beverages.

A colorimetric paper-based enzyme-coupled antimony tin oxide nanoparticle (ATONP) nanobiosensor for selective detection of Cd2+ ions in clams and mussels is presented. Alkaline phosphatase (ALP) was immobilized on ATONPs via 16-phosphonohexadecanoic acid (16-PHA) to develop ATONP-ALP nanobiosensor. The biosensor was characterized using XPS, Raman spectroscopy, SEM, and EDX. ATONP-ALP nanobiosensor exhibited high selectivity towards detection of Cd2+ ion with a LOD 0.006 μg L−1 and linear range of detection 0.005–1 μg L−1. The developed biosensor was further integrated into a low-cost paper-based format. A visual color change was obtained for Cd2+ ion in the range 0.1–10 μg L−1. The developed biosensor was successfully demonstrated for the analysis of Cd2+ ions in clams with recoveries 101–104%. The ATONP-ALP nanobiosensor was validated using mussel tissue (BCR-668) and the conventional ICP-OES and ICP-MS techniques.

Paper-based analytical devices (PADs) have encountered a wealth of applications in recent years thanks to the numerous advantages of paper as a support. A silver nanoflower (AgNF) modified paper-based dual substrate for both surface-enhanced Raman spectroscopy (SERS) and ambient pressure paper spray mass spectrometry (PS-MS) was developed. AgNFs were immobilized on nylon-coated paper modified with silver and ethylenediamine. The developed substrate was characterized via scanning electron microscopy and infrared spectroscopy. The densely packed nanoscale petals of the AgNFs lead to a large number of so-called hot spots at their overlapping points, which result in an enhancement of the Raman signal. In addition, the presence of the AgNFs produces an increase in the sensitivity of the mass spectrometric analysis as compared with bare paper and nylon/Ag-coated paper. The dual substrate was evaluated for the identification and quantification of ketoprofen in aqueous standards as well as human saliva from healthy volunteers. The method enables the determination of ketoprofen with a limit of detection and limit of quantification via PS-MS of 0.023 and 0.076 mg L−1, respectively, with a relative standard deviation (RSD) of 3.4% at a concentration of 0.1 mg L−1. This dual substrate enables the simple and fast detection of ketoprofen with minimal sample preparation, providing complementary Raman and mass spectrometric information.

7 pags., 6 figs., 1 tab., Safflower red is a natural dye extracted from the petals of Carthamus tinctorius L. Its main coloring matter is carthamin. Despite its poor lightfastness, safflower was greatly appreciated in Asia for its bright red color. It was particularly important in nishiki-e multicolor Japanese woodblock printing. In the present work, safflower red was analyzed by Fourier transform (FT)-Raman and surface-enhanced Raman scattering (SERS) spectroscopies and the band assignment was carried out with the support of density functional theory calculations. Different pH values were tested in order to determine the optimal conditions for SERS analysis. Changes in the relative intensity of the Raman bands at neutral and acid pH suggest a deprotonation of the acidic groups in the molecule. From the obtained results, the adsorption geometry of the dye molecule on Ag nanoparticles was deducted. Finally, SERS was successfully applied to the detection of safflower red in a paper fiber from a Japanese woodblock print., This research was supported by CSIC (Spanish NationalResearch Council) through I-link+ Internalization Program (project i-link1148) and Ministerio de Economía, Industria y Competitividad de España (project FIS2017-84318-R)

In Lithium-air cathode, graphene containing materials have been reported as ideal cathode materials due to their large theoretical specific surface area, chemical stability, high electrical conductivity and charge capacity. In this study; three free-standing flexible graphene cathodes were produced with different thickness by vacuum filtration technique. For preparation of the graphene electrodes, graphene oxide (GO) papers were chemically reduced. Surface morphology of the produced graphene cathodes were characterized using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) was conducted to understand elemental composition of the GO paper. X-ray diffraction (XRD) technique and Raman spectroscopy were carried out to investigate the structure of the GO paper electrode. Moreover, specific surface area and porosity distribution of the GO paper was performed using Brunauer-Emmett-Teller (BET) method from N-2 adsorption and desorption isotherms and the pore size were calculated using the Barrett-Joyner-Halenda (BJH) algorithm on the desorption branch. Electrochemical performance of the freestanding graphene electrodes were assessed in ECC-Air test cell from 1.5 V to 4.5 V at a constant current density. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

The separation and chemical analysis of mixtures in an emergency situation represent major challenges, especially in remote or poverty-stricken areas. A novel method was developed for the rapid separation and detection of multiple components via paper centrifugal chromatography, which costs as little as $2.26 US. The method was realized based on the combination of portable paper centrifugal chromatography and surface-enhanced Raman scattering (SERS) detection. This coupled technique was successfully implemented for the separation and qualitative analysis of a rhodamine 6G-crystal violet mixture and a colorless aniline-pyrocatechol-benzidine mixture. A chromatographic mobile phase was collected using absorbent cotton, which was demonstrated to have no effect on the SERS results. The optimized device achieved rapid and effective separation of the colorless aniline-pyrocatechol-benzidine mixture with a high centrifugal force (0.3303π2 N). The newly developed method involving multicomponent paper centrifugal chromatography-SERS detection will be of great value for emergency-related substance separation and analysis in remote and poor areas.

We construct a multiplex surface-enhanced Raman scattering (SERS) platform based on a plasmonic paper substrate and a double-labeled probe for the detection of multiple fluorescent dyes at high sensitivity in a single-wavelength light source system. Plasmonic paper, made of silver nanodots on three-dimensional cellulose fibers, enables highly sensitive SERS biosensing based on localized surface plasmon resonance (LSPR). The proposed method enables the identification and quantification of a range of fluorescent dyes ranging from picomolar to millimolar concentrations. The use of 5' fluorescent dyes and 3' biotin-modified probes as SERS-coded probes renders possible the separation of fluorescent dyes with streptavidin-coated magnetic beads (SMBs) and the sensitive detection of multiple dyes after the reverse transcription polymerase chain reaction (RT-PCR). This experimental study reveals the multiplex detection capability of PCR-based SERS under existing PCR conditions without modifying primer and probe sequences. The combination of magnetic bead-based separation and paper SERS platform is efficient, economical, and can be used for the simultaneous detection of two or more pathogens.

Electrochemical Paper-based Analytical Devices (ePADs) are an alternative to traditional portable analytical techniques due to features such as low-cost, easy surface modification with different materials, and high sensitivity. A fast and simple method to fabricate enhanced ePADs using pencil-drawing which involves the CO2 laser treatment of the carbon surface deposited on paper is described. The electrochemical performances of the devices were evaluated using cyclic voltammetry (CV) with different redox probes and electrochemical impedance spectroscopy (EIS). The electrochemical results show that a treated surface presents a lower resistance to charge transfer and changes the approach of the probe and the overlap of its orbitals with the electrode. To investigate the effects of the laser treatment process, chemical and structural characteristics were evaluated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. These results indicated that laser treatment promoted the restoration of carbon–carbon double bonds and removed a thin layer of nanodebris present in commercial pencils, resulting in an improvement of the electrochemical kinetics. As a proof-of-concept, the Pencil-Drawing Electrode (PDE) was used for the detection and quantification of furosemide (FUR) in a sample of synthetic urine, exhibiting a limit of detection (LOD) of 2.4 × 10−7 mol L−1. The percentages of recovery of the FUR added to the samples A and B were 95% and 110%, respectively. The analysis using CO2 laser-treated PDE resulted in a fast, simple, and reliable method for this doping agent.

The molecular imaging of paper cross sections containing the wet-strength additive poly(amidoamine)–epichlorohydrin (PAE) was effected by Fourier transform infrared (FT-IR) spectroscopic imaging. Thin cross sections of laboratory sheet samples were prepared and transferred onto CaF2 substrates. A laboratory sheet sample without PAE acted as a reference. Principal component analysis (PCA) was applied to identify and to reveal the distribution of PAE across the section. Differences in the loading plots of the fourth and fifth principal components for the sheets with and without PAE were found in the region of the amide I, amide II, and amine bands within a variance of 0.4–0.8 %. The score images of the PCA reveal inhomogeneous distribution of PAE. Small areas of higher concentration of PAE occur across the cross section. The aim of this study was to demonstrate that FT-IR spectroscopic imaging provides spatially resolved quantitative information about the chemical composition of paper, which was successfully achieved.

Paper being the basis of different documents is often the subject of forensic examination. Growing number of bogus or in other manner fraudulently alternated documents causes necessity of identification of individual paper sheets and discrimination between sheets being the parts of analyzed questioned document. Frequently it is necessary to distinguish between paper of the same type but of a different age. Thus, it is essential to know whether the degradation process of paper influences the possibility of differentiation between paper samples. Samples of five types of office paper from different manufacturers were artificially aged in a climatic chamber under 65% relative humidity in air at 90 °C for various periods of time up to 35 days. The conditioned samples were examined by the use of infrared and Raman spectroscopy. Three cards of each paper type were chosen for the experiment. Three different spots on each paper card were measured to assure reproducibility of the experiment in both spectroscopic methods. The possibility of differentiation between aged samples was evaluated. The 2D correlation analysis based on the Noda’s method was carried out using ATR FTIR spectra as an input data for generating the correlation maps. It was found that pattern of 2D maps allow to distinguish tested paper samples, identified its components and get insight into paper degradation mechanism.

Free-standing paper-like electrochemical sensors have many advantages such as high flexibility, thickness adjustability, and large electroactive surface area, when compared to traditional metal electrodes. Generally, carbon nanomaterials, e.g., graphene and carbon nanotubes (CNTs), are main materials of paper-like sensors, and these materials are supported by different species such as metal nanoparticles, dyes, and polymers. We present the fabrication procedure of free-standing composite paper electrode including CNTs and methylene blue (MB) with a simple vacuum filtration process of a suspension including oxidized CNTs (CNTs-ox) and MB through a suitable membrane. CNTs-ox/MB paper was peeled from membrane, and this paper was electrochemically reduced to improve its electrical conductivity. Characterization of this paper-like electrode was performed by using scanning electron microscopy, scanning tunneling microscopy, electron-dispersive X-ray analysis, powder X-ray diffraction spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, four-point probe electrical conductivity, and cyclic voltammetry techniques. Amperometric response of the composite paper electrode for determination of nitrite was linearly proportional to nitrite amount in the range of 12–2500 μM, with a detection limit of 3.6 μM. The sensitivity of the free-standing CNTs/MB paper sensor was calculated as 0.40 μA μM−1 cm−2.

In this paper, the surface hydrophilicity of carbon paper was modified by use of Caro’s acid, and MnO2 electrodeposited on carbon paper (CP) or surface-modified carbon paper (SMCP) were prepared through an anodic electrochemical deposition method. The attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of CP, SMCP-30, SMCP-60, and SMCP-90 indicated that the peaks at 1054, 1214, 1722, and 3426 cm−1 correspond to the stretching vibrations of C–O, C–H, C=O, and –OH. Our study results show that with the extension period of oxidation treatment time, the corresponding content of these groups C–O, C–H, C=O, and –OH increased; then, their surface hydrophilic properties enhanced; and finally, their capacitances increased. This study results indicate that introducing these groups C–O, C–H, C=O, and –OH into the surface of electrode materials is an important strategy for improving their capacitances.

This study focused on two-dimensional fast Fourier transform (2D-FFT) as a new technique for the discrimination of kraft tapes, which is a kind of adhesive packing tape. The 2D power spectrum (2D-PS) obtained by applying 2D-FFT to an image enables us to obtain information about the spatial periodicity, even if the periodicity is invisible within the image. However, in the case of kraft tape, peaks in the 2D-PS are too unclear to determine its periodicity. We developed novel analytical image processes combined with 2D-FFT. 2D-FFT was applied to 50 randomly selected areas in a transmitted light image of kraft tape. The 2D-PSs were calculated from each area without applying a logarithmic transformation, accumulated, and processed by the removal of the area surrounding the center, and finally normalized for visualization. These processes enhanced the peaks and eliminated local variations. Through an intra-roll comparison, the 2D-PSs collected from a roll were similar in the location of the peaks and in their patterns at low frequency area. Using an inter-roll comparison, the 2D-PSs from 50 commercially available brand-name products were classified into 26 groups based on these peaks and patterns. All results demonstrate that this method, which is convenient, rapid, and non-destructive, could be a valuable tool for the identification of kraft tapes.

Failure to control the levels of emerging pollutants in water supply can affect the quality of human life, and this may be mitigated with a low-cost, real-time monitoring system. Herein, we describe a paper-based fully printed electrochemical sensor with reduced graphene nanoribbons (rGNR) capable of detecting sulfamethoxazole (SMX) and trimethoprim (TMP) antibiotics simultaneously in real water samples. The electrodes were printed on parchment paper, which is environmentally friendly and has an efficient printing capacity. Deposition of rGNRs in the matrix was confirmed with Raman spectroscopy, transmission electron microscopy (TEM), and X-ray photoemission spectroscopy (XPS). Optimized sensing performance was obtained using an electrochemical treatment of the electrodes at neutral pH. The paper-based sensor displayed a linear response from 1 μmol l−1 to 10 μmol l−1 for both antibiotics, with detection limits of 0.09 μmol l−1 and 0.04 μmol l−1 for SMX and TMP, respectively. The sensor was reproducible, with an RSD below 5%, and selective for the antibiotics including in real samples, in a demonstration of its potential for real-time monitoring of water supply systems.

Herein, a pH sensitive paper SERS chip was prepared by selecting m-cresol purple, a molecule with halochromic properties in the neutral pH range as a Raman reporter. The adsorbed m-cresol purple underwent a reversible change in its electronic configuration from a non-resonant species to a resonant species, which resulted in a significant Raman signal intensity variation due to the transformation of the sensing mode from SERS to surface-enhanced resonance Raman scattering (SERRS). The chips have a sensitive pH range of 6.0 to 8.0 and exhibited good performance for the detection of natural water samples with detection precision of approximately 0.03 pH units, suggesting great potential for environmental pH monitoring applications.

We present paper-based test strips for chemical sensing with surface enhanced Raman scattering as detection method. The test strips are prepared on glass fibre paper with silver nanoparticles and a spray method with an airbrush spray setup as a low cost fabrication approach. The properties of the test strips are investigated with three classical Raman analytes rhodamine 6G, 4-aminothiophenol and adenine and optimized for a good reproducibility of the intensity measurements. All test analytes can be identified at low concentrations. For adenine, a concentration series from 10−4 M to 10−8 M is measured and the calibration data can be fitted and evaluated with a Langmuir isotherm model. The optimized test strips are applied for the identification of two antibiotics enoxacin and enrofloxacin.

A simple and facile method has been demonstrated to fabricate low-cost surface enhanced Raman scattering (SERS) active microfluidic paper chips using a painting brush. This strategy solves the problem of mass production of highly reproducible SERS substrates without complicated or bulky micro- or nanofabrication instruments. Rhodamine 6G (R6G) was chosen as a probe molecule to evaluate the performance of the SERS active chip. To further demonstrate the possibility of this method's potential application in environmental monitoring, trace malachite green (MG) was successfully analyzed on this chip. The performance of our chips was desirable. The paper substrates with silver nanoparticles deposited by brush were found to be cost-efficient and highly sensitive (LOD for R6G and MG are 1 nM and 10 nM, respectively), and have good reproducibility (∼15% relative standard deviation).

In this study, a fast, low-cost, and facile spray method was proposed. This method deposits highly sensitive surface-enhanced Raman scattering (SERS) silver nanoparticles (AgNPs) on the paper-microfluidic scheme. The procedures for substrate preparation were studied including different strategies to synthesize AgNPs and the optimization of spray cycles. In addition, the morphologies of the different kinds of paper substrates were characterized by SEM and investigated by their SERS signals. The established method was found to be favorable for obtaining good sensitivity and reproducible results. The RSDs of Raman intensity of randomly analyzing 20 spots on the same paper or different filter papers depositing AgNPs are both below 15%. The SERS enhancement factor is approximately 2 x 10(7). The whole fabrication is very rapid, robust, and does not require specific instruments. Furthermore, the total cost for 1000 pieces of chip is less than $20. These advantages demonstrated the potential for growing SERS applications in the area of environmental monitoring, food safety, and bioanalysis in the future.

This study examines and quantifies the effect of cationic polyacrylamide (CPAM) dissolution kinetics and charge density on the adsorption and aggregation state of gold nanoparticles (AuNPs) on paper and the resulting Surface Enhanced Raman Scattering (SERS) performance. Dissolution kinetics of CPAM of different charge density was studied by monitoring their viscosity and hydrodynamic diameter over regular intervals of time. It was found that the degree of dissolution of CPAM greatly affected the surface coverage and aggregation of AuNPs on the CPAM pre-adsorbed paper substrate and their SERS reproducibility. CPAM of higher charge density dissolves faster and produced a more uniform aggregation and higher surface coverage of AuNPs on paper for a higher and more reproducible Raman EF. Understanding the CPAM dissolution process enables the optimization of SERS performance of the AuNPs-paper as a bio-diagnostic platform.

It is essential to evaluate the quality of Hanji record paper without damaging the record paper by previous destructive methods. The samples were Hanji record paper produced in the 1900s. Near-infrared (NIR) spectrometer was used as a non destructive method for evaluating the quality of record papers. Fourier transform (FT) spectrometer was used with 12,500 to 4,000 wavenumber range for quantitative analysis and it has high accuracy and good signal-to-noise ratio. The acidity and moisture content of Hanji record paper were measured by integrating sphere as diffuse reflectance type. The acidity (pH) of chemical factors as a quality evaluated factor of Hanji was correlated to NIR spectrum. The NIR spectrum was pretreated to obtain the coefficients of optimum correlation. Multiplicative scatter correction (MSC) and First derivative of Savitzky-Golay were used as pretreated methods. The coefficients of optimum correlation were calculated by PLSR (partial least square regression). The correlation coefficients () of acidity had 0.92 on NIR spectra without pretreatment. Also the standard error of prediction (SEP) of pH was 0.24. And then the NIR spectra with pretreatment would have better correlation coefficient (

In order to examine the surface distribution of polyacrylamide (PAM) or the in-plane distribution within a paper sheet, the latest microscopic ATR/FT-IR imaging analysis was adapted to the papers containing a PAM dry strength resin by means of the internal and external application methods. The variation of contacting situation with the ATR prism deeply affected on the microscopic ATR/FT-IR imaging of the surface of the papers. Thus, the some part of paper surface contacting with the prism was only available to examine the distribution. The imaging based on 1315 cm-1 absorbance assigned to cellulose showed the contacted area and the change of the absorbance indicated the contacting degree within the area. The imaging based on absorbance ratio of characteristic wave numbers for PAM and cellulose was useful to show the PAM distribution. Local uneven distribution of PAM was observed on the fiber surface in part for papers containing PAM made by both internal and external application methods.

Cortisol in the human hair is a clinical biomarker of long-term social-and-work-related mental stress, which is of high morbidity rate in the current modern society. This study developed a sensitive hair cortisol assay, featuring surface- enhanced Raman spectroscopy, immunoreaction, and a double-layer paper microdevice. The first layer of the paper microdevice was used to remove the hair residue in the hair extract by filtration (sample pretreatment). The second layer was used for competitive immunoreaction and detection. Standard cortisol antigen immobilized in the second layer and the free cortisol in hair extract competed to bind the spiked Raman-active cortisol monoclonal antibody solution. The hair cortisol can be quantitated by the intensity of Raman signal of monoclonal antibody bound on the paper. We found the Raman signal decreased as the cortisol concentration increases in hair samples. The relative Raman intensity measured was linearly proportional to the logarithmic value of the cortisol concentration in hair samples we measured. The detection of limit (LOD) was 1 pg/mL with the portable Raman spectrometer. The RSD of measurement was 8.38% (n=6). In addition, we used LC-MS to measure two real samples as a comparison with our method as above. The results are 0.771 and 0.153 ng/mL by LC-MS method and 0.63 and 0.247 ng/mL by the proposed method. It can be observed that the results are in same order, demonstrating the validity of the proposed method. In addition, 48 samples can be measured in a single chip. These results showed that this method is sensitive, specific, and suitable for large-scale screening of hair cortisol samples.

The adsorption at low surface coverage of a series of n-alkanes on various bleached kraft paper surfaces was measured by gas chromatography. Differences in surface area of the paper samples were readily measured from the gas chromatographic retention volumes. The standard free energy, the enthalpy, and the entropy of adsorption varied linearly with the number of carbon atoms in the n-alkanes. The heats of adsorption were close to the heats of liquefaction, indicating the non-specific interactions of the hydrocarbons with the bleached kraft surfaces. The London component of the surface free energy was estimated from the gas chromatographic results to be 47.9 mN/m.

Graphical abstract The article analyzes experimentally and theoretically the influence of microscope parameters on the pinhole-assisted Raman depth profiles in uniform and composite refractive media. The main objective is the reliable mapping of deep sample regions. The easiest to interpret results are found with low magnification, low aperture, and small pinholes. Here, the intensities and shapes of the Raman signals are independent of the location of the emitter relative to the sample surface. Theoretically, the results can be well described with a simple analytical equation containing the axial depth resolution of the microscope and the position of the emitter. The lower determinable object size is limited to 2–4 μm. If sub-micrometer resolution is desired, high magnification, mostly combined with high aperture, becomes necessary. The signal intensities and shapes depend now in refractive media on the position relative to the sample surface. This aspect is investigated on a number of uniform and stacked polymer layers, 2–160 μm thick, with the best available transparency. The experimental depth profiles are numerically fitted with excellent accuracy by inserting a Gaussian excitation beam of variable waist and fill fraction through the focusing lens area, and by treating the Raman emission with geometric optics as spontaneous isotropic process through the lens and the variable pinhole, respectively. The intersectional area of these two solid angles yields the leading factor in understanding confocal (pinhole-assisted) Raman depth profiles. Spearfishing is a well-known example of the effects of refraction at the boundary between two index-mismatched media. The object Greal is seen, due to refraction, as Gvir from the angle β (without knowing the depth position). The real position is obtained under the angle α. In a microscope (see inset), index mismatch deforms the image point of Greal into an image line. The pinhole substantially reduces deformations and allows the determination of the position of the point emitter G. (Cartoon designed by Sofia Anker)

Raman spectroscopy is an analytical method to identify medical samples of bacteria. Because Raman spectroscopy detects the biochemical properties of a cell, there are many factors that can influence and modify the Raman spectra of bacteria. One possible influence is a proper method for isolation of the bacteria. Medical samples in particular never occur in purified form, so a Raman-compatible isolation method is needed which does not affect the bacteria and thus the resulting spectra. In this study, we present a Raman-compatible method for isolation of bacteria from bronchoalveolar lavage (BAL) fluid using density gradient centrifugation. In addition to measuring the bacteria from a patient sample, the yield and the spectral influence of the isolation on the bacteria were investigated. Bacteria isolated from BAL fluid show additional peaks in comparison to pure culture bacteria, which can be attributed to components in the BAL sample. The isolation gradient itself has no effect on the spectra, and with a yield of 63% and 78%, the method is suitable for isolation of low concentrations of bacteria from a complex matrix. Graphical abstract Supplementary Information The online version contains supplementary material available at 10.1007/s00216-021-03488-0.

The Henry's law region of the adsorption isotherms for a series of n-alkanes on cotton cellulose and on wood fibers has been studied by gas chromatography. On wood fibers, the three thermodynamic functions at zero surface coverage were determined. A linear relationship between the standard free energy, the enthalpy and the entropy, and the number of carbon atoms was found. Attempts were made to estimate the London contribution to the surface free energy of cellulose and wood fibers from the results at infinite dilution. A method based on the increment per CH2 group in the free energy of desorption, normalized per unit area of a methylene group, is in reasonable agreement with other estimates.

8 pasg., 7 figs., 2 tabs., Alkannin is the main coloring matter of Alkanet, a natural red dye extracted from the root of Alkanna tinctoria L. Shikonin, the optical isomer of alkannin, is extracted from Lithospermum erythrorhizon. As both red dyes are only slightly soluble in water, the application of ordinary Raman spectroscopy is limited. Thus, Surface-enhanced Raman spectroscopy (SERS) can be successfully applied to the study of the red dyes solutions. Solid alkannin and shikonin were characterized by ordinary Raman spectroscopy. Density Functional Theory (DFT) methods were used to calculate the Raman spectrum of the dyes and to assign the experimental Raman bands to their vibrational normal modes. Different pH conditions were tested in order to determine the optimal conditions for the SERS detection of alkannin and shikonin. Based on the previous results, a perpendicular orientation of the red dyes on the Ag substrate was deducted. Finally, shikonin was identify by SERS spectroscopy in a dyed paper sample from an 8th century handscroll from Japan., This research was supported by CSIC (Spanish National Research Council) through I-link + Internalization Program (project i-link1148) and Ministerio de Economía, Industria y Competitivi- dad de España (project FIS2017-84318-R

Biofluids, such as blood plasma or serum, are currently being evaluated for cancer detection using vibrational spectroscopy. These fluids contain information of key biomolecules, such as proteins, lipids, carbohydrates and nucleic acids, that comprise spectrochemical patterns to differentiate samples. Raman is a water-free and practically non-destructive vibrational spectroscopy technique, capable of recording spectrochemical fingerprints of biofluids with minimum or no sample preparation. Herein, we compare the performance of these two common biofluids (blood plasma and serum) together with ascitic fluid, towards ovarian cancer detection using Raman microspectroscopy. Samples from thirty-eight patients were analysed (n = 18 ovarian cancer patients, n = 20 benign controls) through different spectral pre-processing and discriminant analysis techniques. Ascitic fluid provided the best class separation in both unsupervised and supervised discrimination approaches, where classification accuracies, sensitivities and specificities above 80% were obtained, in comparison to 60–73% with plasma or serum. Ascitic fluid appears to be rich in collagen information responsible for distinguishing ovarian cancer samples, where collagen-signalling bands at 1004 cm−1 (phenylalanine), 1334 cm−1 (CH3CH2 wagging vibration), 1448 cm−1 (CH2 deformation) and 1657 cm−1 (Amide I) exhibited high statistical significance for class differentiation (P Graphical abstract

Raman spectroscopy is a fast and sensitive technique able to identify molecular changes in biological specimens. Herein, we report on three cases where Raman microspectroscopy was used to distinguish normal vs. oesophageal adenocarcinoma (OAC) (case 1) and Barrett’s oesophagus vs. OAC (cases 2 and 3) in a non-destructive and highly accurate fashion. Normal and OAC tissues were discriminated using principal component analysis plus linear discriminant analysis (PCA-LDA) with 97% accuracy (94% sensitivity and 100% specificity) (case 1); Barrett’s oesophagus vs. OAC tissues were discriminated with accuracies ranging from 98 to 100% (97–100% sensitivity and 100% specificity). Spectral markers responsible for class differentiation were obtained through the difference-between-mean spectrum for each group and the PCA loadings, where C–O–C skeletal mode in β-glucose (900 cm−1), lipids (967 cm−1), phosphodioxy (1296 cm−1), deoxyribose (1456 cm−1) and collagen (1445, 1665 cm−1) were associated with normal and OAC tissue differences. Phenylalanine (1003 cm−1), proline/collagen (1066, 1445 cm−1), phospholipids (1130 cm−1), CH2 angular deformation (1295 cm−1), disaccharides (1462 cm−1) and proteins (amide I, 1672/5 cm−1) were associated with Barrett’s oesophagus and OAC tissue differences. These findings show the potential of using Raman microspectroscopy imaging for fast and accurate diagnoses of oesophageal pathologies and establishing subtle molecular changes predisposing to adenocarcinoma in a clinical setting. Graphical abstract Graphical abstract demonstrating how oesophageal tissue is processed through Raman mapping analysis in order to detect spectral differences between stages of oesophageal transformation to adenocarcinoma Electronic supplementary material The online version of this article (10.1007/s00216-020-02637-1) contains supplementary material, which is available to authorized users.

The electrochemical behavior of cefotaxime (CTX+) was investigated at the polarized macro- and micro-interface between two immiscible electrolyte solutions (ITIES) by cyclic voltammetry and alternating current voltammetry. Miniaturization was achieved with fused silica microcapillary tubing entrapped in a polymeric casing. Scanning electron microscopy (SEM) was employed for the fabricated LLI support characterization. Voltammetric investigation of CTX+ at macro- and μ-ITIES allowed the determination of many physicochemical parameters, such as formal Galvani potential of the ion transfer reaction ($${\Delta }_{org}^{aq}{\varPhi}^{\prime }$$ Δ org aq Φ ′ ), diffusion coefficients (D), formal free Gibbs energy of the ion transfer reaction (∆G′aq → org), and water-1,2-dichloroethane partition coefficient ($${\log}{P}_{water/ DCE}^{CTX+}$$ log P w a t e r / D C E C T X + ). Additionally, based on the results obtained the analytical parameters including voltammetric sensitivity, limits of detection and the limits of quantification (in micromolar range) were calculated. The applicability of the developed procedures was verified in spiked still mineral and tap water samples. Graphical abstract

The exploitation of fibre based Raman probes has been challenged by often complicated fabrication procedures and difficulties in reproducibility. Here, we have demonstrated a simple and cost-effective approach for sensing pH through an optical fibre, by employing a wax patterned filter paper-based substrate for surface enhanced Raman spectroscopy (SERS). Through this method, high reproducibility between fibres was achieved. In addition to sensing pH, it was possible to extract fluid samples containing P. aeruginosa for further analysis. This dual purpose fibre is bronchoscope deployable, and is able to gather information about both the host and pathogen, which may lead to an improved treatment plan in future in vivo applications.

Fourier transform infrared (FTIR) spectroscopic imaging of colon biopsy tissues in transmission combined with machine learning for the classification of different stages of colon malignancy was carried out in this study. Two different approaches, an optical and a computational one, were applied for the elimination of the scattering background during the measurements and compared with the results of the machine learning model without correction for the scattering. Several different data processing pathways were implemented in order to obtain a high accuracy of the prediction model. This study demonstrates, for the first time, that C–H stretching and amide I bands are of little to no significance in the classification of the colon malignancy, based on the Gini importance values by random forest (RF). The best prediction outcome is found when supervised RF classification was carried out in the fingerprint region of the spectral data between 1500 and 1000 cm−1 (excluding the contribution of amide I and II bands). An overall prediction accuracy higher than 90% is achieved through the RF. The results also show that dysplastic and hyperplastic tissues are well distinguished. This leads to the insight that the important differences between hyperplastic and dysplastic colon tissues lie within the fingerprint region of FTIR spectra. In this study, computational correction performed better than optical correction, but the findings show that the disease states of colon biopsies can be distinguished effectively without elimination of Mie scattering effect. Graphical abstract Electronic supplementary material The online version of this article (10.1007/s00216-019-02069-6) contains supplementary material, which is available to authorized users.

Zn/F co-doped SnO2 nanoparticles with a mean diameter of less than 15 nm and a narrow size distribution were synthesized by a one-step laser pyrolysis technique using a reactive mixture containing tetramethyltin (SnMe4) and diethylzinc (ZnEt2) vapors, diluted Ar, O2 and SF6. Their structural, morphological, optical and electrical properties are reported in this work. The X-ray diffraction (XRD) analysis shows that the nanoparticles possess a tetragonal SnO2 crystalline structure. The main diffraction patterns of stannous fluoride (SnF2) were also identified and a reduction in intensity with increasing Zn percentage was evidenced. For the elemental composition estimation, energy dispersion X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) measurements were performed. In general, both analyses showed that the Zn percentage increases with increasing ZnEt2 flow, accompanied at the same time by a decrease in the amount of F in the nanopowders when the same SF6 flow was employed. The Raman spectra of the nanoparticles show the influence of both Zn and F content and crystallite size. The fluorine presence is due to the catalytic partial decomposition of the SF6 laser energy transfer agent. In direct correlation with the increase in the Zn doping level, the bandgap of co-doped nanoparticles shifts to lower energy (from 3.55 to 2.88 eV for the highest Zn dopant concentration).

Disorder was induced in pristine highly oriented pyrolytic graphite (HOPG) by irradiation with H+ ions with energies of 0.4 MeV and 1 MeV, and doses of 1014 ions/cm2 and 1016 ions/cm2. Raman spectroscopy was used as the main technique to characterize different samples and gain new insights on the splitting of the D band into two components (D1 and D2), trying to correlate this feature of the vibrational spectrum with the impinging energy and dose. An increased ID2/IG ratio in comparison with ID1/IG was observed in the irradiated samples. This behavior indicates that the impinging energy mainly affects the D1 component, while the D2 component is strongly dominated by the dose. We expect a larger contribution of defects (originating from the rupture of C-C sp2 symmetry through the formation of C-H sp3 bonds) to the D2 component than to the D1 component. SQUID measurements of the irradiated samples showed an enhancement in the normalized remanence, as well as an increment in coercivity compared to pristine HOPG, consistent with H+-induced point-like defects as well as C-H bonds. AFM scanning after Raman and SQUID characterization showed a distribution of surface defects, which were ascribed to the burst of hydrogen blisters formed as a consequence of the irradiation process. The results presented in this work contribute to the current trend in nanotechnology in areas devoted to the control of properties by defect engineering in carbon-based materials. Fil: Venosta, Lisandro Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina Fil: Bajales Luna, Noelia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina Fil: Suarez, Sergio Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina Fil: Bercoff, Paula Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina

This study investigated a novel agricultural low-cost bio-waste biochar derived from wood apple fruit shell waste via the pyrolysis method, which is modified by ball milling and utilized to remove toxic phenol and chlorophenols (4-CPh and 2,4-DCPh) from contaminated aqueous media. The ball-milled wood apple fruit shell waste biochar (WAS-BC) sorbent was systematically analyzed by BET, CHN, and FTIR as well as particle size, SEM–EDS, XPS and TGA studies. The sorption equilibrium and kinetic studies exhibit that the sorption capacity was greater than 75% within the first 45 min of agitation at pH 6.0. The uptake capacity of 2,4-DCPh onto WAS-BC was greater than those of 4-CPh and phenol. Equilibrium results were consistent with the Langmuir isotherm model, while the kinetic data were best represented by the Elovich and pseudo-second-order model. The maximum uptake of phenol, 4-CPh, and 2,4-DCPh was 102.71, 172.24, and 226.55 mg/g, respectively, at 30 ± 1 °C. Thus, this study demonstrates that WAS-BC is an efficient, low-cost sorbent that can be used for the elimination of phenol and chlorophenol compounds from polluted wastewater.

An extensive round robin experiment between small-angle X-ray scattering laboratories has delivered a global uncertainty estimate for the measurands of a nanoparticle dispersion. Irrespective of the instrument pedigree, the distribution mean, width and volume fraction could be determined with an accuracy of 1, 10 and 10%, respectively., This paper presents the first worldwide inter-laboratory comparison of small-angle X-ray scattering (SAXS) for nanoparticle sizing. The measurands in this comparison are the mean particle radius, the width of the size distribution and the particle concentration. The investigated sample consists of dispersed silver nanoparticles, surrounded by a stabilizing polymeric shell of poly(acrylic acid). The silver cores dominate the X-ray scattering pattern, leading to the determination of their radius size distribution using (i) the generalized indirect Fourier transformation method, (ii) classical model fitting using SASfit and (iii) a Monte Carlo fitting approach using McSAS. The application of these three methods to the collected data sets from the various laboratories produces consistent mean number- and volume-weighted core radii of R n = 2.76 (6) nm and R v = 3.20 (4) nm, respectively. The corresponding widths of the lognormal radius distribution of the particles were σn = 0.65 (1) nm and σv = 0.71 (1) nm. The particle concentration determined using this method was 3.0 (4) g l−1 or 4.2 (7) × 10−6 mol l−1. These results are affected slightly by the choice of data evaluation procedure, but not by the instruments: the participating laboratories at synchrotron SAXS beamlines, commercial and in-house-designed instruments were all able to provide highly consistent data. This demonstrates that SAXS is a suitable method for revealing particle size distributions in the sub-20 nm region (at minimum), out of reach for most other analytical methods.

This paper presents a parallel plate-type field emission device of potassium hydroxide-doped electrochemically reduced graphene oxide (GO) manufactured using highly oriented pyrolytic graphite through electrochemical exfoliation. The material properties of the GO were tested through Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The optimal electron emission characteristics of the device were as follows: turn-on field = 2.03 V/ $\mu \text{m}$ , field emission current $= \,\, 16.4~\mu \text{A}$ , and field emission enhancement factor = 8377. At an emission peak wavelength of 563.7 nm, the optimal device had a light flux of 4.21 lumens and an illumination of 140.3 lux. These properties can be utilized in various optoelectronic devices, such as nanoelectronics devices, sensors, electrochemical systems, and energy storage devices.

Argon gas windows are shown to be effective for soft X-ray absorption spectroscopy in the low-energy region below 200 eV under atmospheric conditions., The soft X-ray region below 200 eV is important for investigating chemical and biological phenomena since it covers K-edges of Li and B and L-edges of Si, P, S and Cl. Helium gas is generally used as the soft X-ray transmission window for soft X-ray absorption spectroscopy (XAS) under atmospheric conditions. However, the helium gas window cannot be applied to XAS in the low-energy region since transmitted soft X-rays mostly consist of high-order X-rays due to the low transmission of first-order X-rays. In this study, the argon gas window is proposed as a new soft X-ray transmission window in the low-energy region. High-order X-rays are removed by the absorption of the Ar L-edge (240 eV), and first-order X-rays become the major contribution of transmitted soft X-rays in the low-energy region. Under atmospheric argon conditions, the double-excitation Rydberg series of helium gas (60 eV), Si L-edge XAS of an Si3N4 membrane (100 eV) and S L-edge XAS of di­methyl sulfoxide gas (170 eV) are successfully measured, indicating that the argon gas window is effective for soft X-ray transmission in the low-energy region from 60 eV to 240 eV.

Metal oxide (MOX) sensors are increasingly gaining attention in analytical applications. Their fundamental operation principle is based on conversion reactions of selected molecular species at their semiconducting surface. However, the exact turnover of analyte gas in relation to the concentration has not been investigated in detail to date. In the present study, two optical sensing techniques—luminescence quenching for molecular oxygen and infrared spectroscopy for carbon dioxide and methane—have been coupled for characterizing the behavior of an example semiconducting MOX methane gas sensor integrated into a recently developed low-volume gas cell. Thereby, oxygen consumption during MOX operation as well as the generation of carbon dioxide from the methane conversion reaction could be quantitatively monitored. The latter was analyzed via a direct mid-infrared gas sensor system based on substrate-integrated hollow waveguide (iHWG) technology combined with a portable Fourier transform infrared spectrometer, which has been able to not only detect the amount of generated carbon dioxide but also the consumption of methane during MOX operation. Hence, a method based entirely on direct optical detection schemes was developed for characterizing the actual signal generating processes—here for the detection of methane—via MOX sensing devices via near real-time online analysis., publishedVersion

Lamellae of 1.5 µm thickness, prepared from well-crystallised monazite–(Ce) and zircon samples using the focused-ion-beam technique, were subjected to triple irradiation with 1 MeV Au+ ions (15.6% of the respective total fluence), 4 MeV Au2+ ions (21.9%) and 10 MeV Au3+ ions (62.5%). Total irradiation fluences were varied in the range 4.5 × 1012 – 1.2 × 1014 ions/cm2. The highest fluence resulted in amorphisation of both minerals; all other irradiations (i.e. up to 4.5 × 1013 ions/cm2) resulted in moderate to severe damage. Lamellae were subjected to Raman and laser-induced photoluminescence analysis, in order to provide a means of quantifying irradiation effects using these two micro-spectroscopy techniques. Based on extensive Monte Carlo calculations and subsequent defect-density estimates, irradiation-induced spectroscopic changes are compared with those of naturally self-irradiated samples. The finding that ion irradiation of monazite–(Ce) may cause severe damage or even amorphisation, is in apparent contrast to the general observation that naturally self-irradiated monazite–(Ce) does not become metamict (i.e. irradiation-amorphised), in spite of high self-irradiation doses. This is predominantly assigned to the continuous low-temperature damage annealing undergone by this mineral; other possible causes are discussed. According to cautious estimates, monazite–(Ce) samples of Mesoproterozoic to Cretaceous ages have stored only about 1% of the total damage experienced. In contrast, damage in ion-irradiated and naturally self-irradiated zircon is on the same order; reasons for the observed slight differences are discussed. We may assess that in zircon, alpha decays create significantly less than 103 Frenkel-type defect pairs per event, which is much lower than previous estimates. Amorphisation occurs at defect densities of about 0.10 dpa (displacements per lattice atom). Electronic supplementary material The online version of this article (10.1007/s00269-018-0975-9) contains supplementary material, which is available to authorized users.

A multi-temperature structural study of Mg2Si and Mg2Sn was carried out from 100 to 700 K using synchrotron X-ray powder diffraction. The temperature dependence of the lattice parameters can be expressed as a = 6.3272 (4) + 6.5 (2) × 10−5 T + 4.0 (3) × 10−8 T 2 Å and a = 6.7323 (7) + 8.5 (4) × 10−5 T + 3.8 (5) × 10−8 T 2 Å for Mg2Si and Mg2Sn, respectively. The atomic displacement parameters (ADPs) are reported and analysed using a Debye model for the averaged U iso giving Debye temperatures of 425 (2) K for Mg2Si and 243 (2) K for Mg2Sn. The ADPs are considerably smaller for Mg2Si than for Mg2Sn reflecting the weaker chemical bonding in the Mg2Sn structure. Following the heating, an annealing effect is observed on the lattice parameters and peak widths in both structures, presumably due to changes in the crystal defects, but the lattice thermal expansion is almost unchanged by the annealing. This work provides accurate structural parameters which are of importance for studies of Mg2Si, Mg2Sn and their solid solutions.

We provide the first in situ and real-time study of the effect of milling frequency on the course of a mechanochemical organic reaction conducted using a vibratory shaker (mixer) ball mill. The use of in situ Raman spectroscopy for real-time monitoring of the mechanochemical synthesis of a 2,3-diphenylquinoxaline derivative revealed a pronounced dependence of chemical reactivity on small variations in milling frequency. In particular, in situ measurements revealed the establishment of two different regimes of reaction kinetics at different frequencies, providing tentative insight into processes of mechanical activation in organic mechanochemical synthesis.

The variation and structural properties of interconnected and freestanding 3D graphene grown in atmospheric (AP) and low pressure (LP) conditions with varying precursor concentrations (7–14%) is reported for the first time. LP grown 3D graphene at low precursor concentration (7 vol%) shows turbostratic signature whereas AP grown 3D graphene indicates a double layer signature in the same condition. The 2D band peaks splitting evaluation through Lorentzian fitting shows the distinct variations in the number of layers grown for each precursor concentrations. Extensive Raman analysis of the grown samples revealed the existence of disordered plane stacking of graphene layers, which decreases as the precursor concentration increases. In contrast, AP grown 3D graphene shows no disordered layers for any precursor concentration. The increase in a number of layers (2 to 5) of 3D graphene grown in both AP and LP conditions co-influenced by precursor concentrations is validated by TEM. Interestingly, it was discovered that both 3D graphene grown in different conditions exhibit sp 2 ring carbon material. Thus, control over growth kinetics by varying the precursor concentration in different chamber pressures allows for total manipulation of the number of layers of 3D graphene deposited on the template nickel catalyst.