Showing papers in "Applied Spectroscopy in 2013"
TL;DR: This review highlights recent developments in QDs in bioanalysis and bioimaging in the context of specific methods for fluorescence spectroscopy and imaging, and surveys the use of QDs across different platforms for biological fluorescence imaging.
Abstract: Semiconductor quantum dots (QDs) are brightly luminescent nanoparticles that have found numerous applications in bioanalysis and bioimaging. In this review, we highlight recent developments in these areas in the context of specific methods for fluorescence spectroscopy and imaging. Following a primer on the structure, properties, and biofunctionalization of QDs, we describe select examples of how QDs have been used in combination with steady-state or time-resolved spectroscopic techniques to develop a variety of assays, bioprobes, and biosensors that function via changes in QD photoluminescence intensity, polarization, or lifetime. Some special attention is paid to the use of Forster resonance energy transfer-type methods in bioanalysis, including those based on bioluminescence and chemiluminescence. Direct chemiluminescence, electrochemiluminescence, and charge transfer quenching are similarly discussed. We further describe the combination of QDs and flow cytometry, including traditional cellular analyses and spectrally encoded barcode-based assay technologies, before turning our attention to enhanced fluorescence techniques based on photonic crystals or plasmon coupling. Finally, we survey the use of QDs across different platforms for biological fluorescence imaging, including epifluorescence, confocal, and two-photon excitation microscopy; single particle tracking and fluorescence correlation spectroscopy; super-resolution imaging; near-field scanning optical microscopy; and fluorescence lifetime imaging microscopy. In each of the above-mentioned platforms, QDs provide the brightness needed for highly sensitive detection, the photostability needed for tracking dynamic processes, or the multiplexing capacity needed to elucidate complex systems. There is a clear synergy between advances in QD materials and spectroscopy and imaging techniques, as both must be applied in concert to achieve their full potential.
475 citations
TL;DR: This work reviews the evolution of the use of portable near-infrared spectrometers in the agro-food industry and highlights the need for a cost-effective and nondestructive quality-control analysis system.
Abstract: Industry has created the need for a cost-effective and nondestructive quality-control analysis system. This requirement has increased interest in near-infrared (NIR) spectroscopy, leading to the development and marketing of handheld devices that enable new applications that can be implemented in situ. Portable NIR spectrometers are powerful instruments offering several advantages for nondestructive, online, or in situ analysis: small size, low cost, robustness, simplicity of analysis, sample user interface, portability, and ergonomic design. Several studies of on-site NIR applications are presented: characterization of internal and external parameters of fruits and vegetables; conservation state and fat content of meat and fish; distinguishing among and quality evaluation of beverages and dairy products; protein content of cereals; evaluation of grape ripeness in vineyards; and soil analysis. Chemometrics is an essential part of NIR spectroscopy manipulation because wavelength-dependent scattering effects, instrumental noise, ambient effects, and other sources of variability may complicate the spectra. As a consequence, it is difficult to assign specific absorption bands to specific functional groups. To achieve useful and meaningful results, multivariate statistical techniques (essentially involving regression techniques coupled with spectral preprocessing) are therefore required to extract the information hidden in the spectra. This work reviews the evolution of the use of portable near-infrared spectrometers in the agro-food industry.
237 citations
TL;DR: The study has demonstrated the importance of the optimization of the SG parameters during the conversion of spectra into derivative form, specifically window size and polynomial order of the fitting curve.
Abstract: Calculating derivatives of spectral data by the Savitzky-Golay (SG) numerical algorithm is often used as a preliminary preprocessing step to resolve overlapping signals, enhance signal properties, and suppress unwanted spectral features that arise due to nonideal instrument and sample properties. Addressing these issues, a study of the simulated and measured infrared data by partial least-squares regression has been conducted. The simulated data sets were modeled by considering a range of undesired chemical and physical spectral anomalies and variations that can occur in a measured spectrum, such as baseline variations, noise, and scattering effects. The study has demonstrated the importance of the optimization of the SG parameters during the conversion of spectra into derivative form, specifically window size and polynomial order of the fitting curve. A specific optimal window size is associated with an exact component of the system being estimated, and this window size does not necessarily apply for some other component present in the system. Since the optimization procedure can be time-consuming, as a rough guideline spectral noise level can be used for assessment of window size. Moreover, it has been demonstrated that, when the extended multiplicative signal correction (EMSC) is used alongside the SG procedure, the derivative treatment of data by the SG algorithm must precede the EMSC normalization.
146 citations
TL;DR: The most recent applications of single cell analysis by Raman spectroscopy and their biomedical implications that have enabled the noninvasive characterization of specific metabolic states of eukaryotic cells, the identification and characterization of stem cells, and the rapid identification of bacterial cells are highlighted.
Abstract: Raman spectroscopy is a powerful biochemical analysis technique that allows for the dynamic characterization and imaging of living biological cells in the absence of fluorescent stains. In this review, we summarize some of the most recent developments in the noninvasive biochemical characterization of single cells by spontaneous Raman scattering. Different instrumentation strategies utilizing confocal detection optics, multispot, and line illumination have been developed to improve the speed and sensitivity of the analysis of single cells by Raman spectroscopy. To analyze and visualize the large data sets obtained during such experiments, sophisticated multivariate statistical analysis tools are necessary to reduce the data and extract components of interest. We highlight the most recent applications of single cell analysis by Raman spectroscopy and their biomedical implications that have enabled the noninvasive characterization of specific metabolic states of eukaryotic cells, the identification and characterization of stem cells, and the rapid identification of bacterial cells. We conclude the article with a brief look into the future of this rapidly evolving research area.
125 citations
TL;DR: Spectroscopy, especially the mid-IR technique in association with Savitzky–Golay smoothing and derivatization and the least squares support vector machine (LS-SVM) algorithm, can be useful in determining SOM quantity and quality.
Abstract: Visible near-infrared (Vis-NIR) reflection spectroscopy and mid-infrared (mid-IR) reflection spectroscopy are cost- and time-effective and environmentally friendly techniques that could be alternatives to conventional soil analysis methods. Successful determination of spectrally active soil components, including soil organic matter (SOM), depends on the selection of suitable pretreatment and multivariate calibration techniques. The objective of the present review is to critically examine the suitability of Vis-NIR (350-2500 nm) and mid-IR (4000-400 cm−1) spectroscopy as a tool for SOM quantity and quality determination. Particular attention is paid to different pretreatment and calibration procedures and methods, and their ability to predict SOM content from Vis-NIR and mid-IR data is discussed. We then review the most recent research using spectroscopy in different calibration scales (local, regional, or global). Finally, accuracy and robustness, as well as uncertainty in Vis-NIR and mid-IR spectroscopy, are considered. We conclude that spectroscopy, especially the mid-IR technique in association with Savitzky-Golay smoothing and derivatization and the least squares support vector machine (LS-SVM) algorithm, can be useful in determining SOM quantity and quality. Future research conducted for the standardization of protocols and soil conditions will allow more accurate and reliable results on a global and international scale.
116 citations
TL;DR: A model for light propagation through an IR spectroscopic imaging system based on scalar wave theory is presented and the ability to perform high-definition IR imaging in the laboratory by using minimally-modified commercial instruments is demonstrated.
Abstract: The quality of images from an infrared (IR) microscope has traditionally been limited by considerations of throughput and signal-to-noise ratio (SNR). An understanding of the achievable quality as a function of instrument parameters, from first principals is needed for improved instrument design. Here, we first present a model for light propagation through an IR spectroscopic imaging system based on scalar wave theory. The model analytically describes the propagation of light along the entire beam path from the source to the detector. The effect of various optical elements and the sample in the microscope is understood in terms of the accessible spatial frequencies by using a Fourier optics approach and simulations are conducted to gain insights into spectroscopic image formation. The optimal pixel size at the sample plane is calculated and shown much smaller than that in current mid-IR microscopy systems. A commercial imaging system is modified, and experimental data are presented to demonstrate the validity of the developed model. Building on this validated theoretical foundation, an optimal sampling configuration is set up. Acquired data were of high spatial quality but, as expected, of poorer SNR. Signal processing approaches were implemented to improve the spectral SNR. The resulting data demonstrated the ability to perform high-definition IR imaging in the laboratory by using minimally-modified commercial instruments.
110 citations
TL;DR: A brief overview of both established and novel ellipsometry techniques, as well as their applications, can be found in this paper, where the basic theory of polarization, standard ellipsometrics, and Mueller ellipsometers are discussed.
Abstract: This article provides a brief overview of both established and novel ellipsometry techniques, as well as their applications. Ellipsometry is an indirect optical technique, in that information about the physical properties of a sample is obtained through modeling analysis. Standard ellipsometry is typically used to characterize optically isotropic bulk and/or layered materials. More advanced techniques such as Mueller ellipsometry, also known as polarimetry in the literature, are necessary for the complete and accurate characterization of anisotropic and/or depolarizing samples that occur in many instances, both in research and in real-life activities. In this article, we cover three main subject areas: Basic theory of polarization, standard ellipsometry, and Mueller ellipsometry. The first section is devoted to a short, pedagogical introduction of the formalisms used to describe light polarization. The second section is devoted to standard ellipsometry. The focus is on the experimental aspects, including both pros and cons of commercially available instruments. The third section is devoted to recent advances in Mueller ellipsometry. Application examples are provided in the second and third sections to illustrate how each technique works.
98 citations
TL;DR: The superiority of the instrument and algorithm in terms of background removal and signal-to-noise ratio is demonstrated by comparison to FT-Raman, standard deviation spectra, shifted excitation Raman difference spectroscopy (SERDS), and conventional multiple-shift excitation methods.
Abstract: A novel Raman spectrometer is presented in a handheld format. The spectrometer utilizes a temperature-controlled, distributed Bragg reflector diode laser, which allows the instrument to operate in a sequentially shifted excitation mode to eliminate fluorescence backgrounds, fixed pattern noise, and room lights, while keeping the Raman data in true spectral space. The cost-efficient design of the instrument allows rapid acquisition of shifted excitation data with a shift time penalty of less than 2 s. The Raman data are extracted from the shifted excitation spectra using a novel algorithm that is typically three orders of magnitude faster than conventional shifted-excitation algorithms operating in spectral space. The superiority of the instrument and algorithm in terms of background removal and signal-to-noise ratio is demonstrated by comparison to FT-Raman, standard deviation spectra, shifted excitation Raman difference spectroscopy (SERDS), and conventional multiple-shift excitation methods.
80 citations
TL;DR: THz transmission measurements of honey mixtures with antibiotics have been performed, revealing that antibiotic residues are traceable in highly absorptive food products, such as honey, at concentrations down to 1% weight percentage, thanks to their THz fingerprints.
Abstract: Terahertz time-domain spectroscopy (THz-TDS) has been applied for the detection and discrimination of harmful chemical residues in honey Three antibiotics (sulfapyridine, sulfathiazole, and tetracycline) and two acaricides (coumaphos and amitraz) were characterized in the THz frequency regime between 05 THz and 60 THz All chemical substances present distinct absorption peaks THz transmission measurements of honey mixtures with antibiotics have been performed, revealing that antibiotic residues are traceable in highly absorptive food products, such as honey, at concentrations down to 1% weight percentage, thanks to their THz fingerprints Moreover, multiple antibiotics were identified in their mixture with honey, pointing out the potential of the technique to be used in the near future as a fast, real-time technique for detecting and discriminating multi-residues strictly related to food safety issues
60 citations
TL;DR: The initial results of a feasibility study are described to design and build a miniature, fiber optic probe incorporated into a standard hypodermic needle intended for use in optical biopsies of solid tissues to provide valuable information of disease type.
Abstract: Raman spectroscopy is a powerful tool for studying the biochemical composition of tissues and cells in the human body. We describe the initial results of a feasibility study to design and build a miniature, fiber optic probe incorporated into a standard hypodermic needle. This probe is intended for use in optical biopsies of solid tissues to provide valuable information of disease type, such as in the lymphatic system, breast, or prostate, or of such tissue types as muscle, fat, or spinal, when identifying a critical injection site. The optical design and fabrication of this probe is described, and example spectra of various ex vivo samples are shown.
60 citations
TL;DR: The use of automated continuous flow reactors is described, with real-time online Fourier transform infrared spectroscopy (FT-IR) analysis to enable rapid optimization of reaction yield using a self-optimizing feedback algorithm to provide process understanding and validation of the optimization algorithms.
Abstract: The use of automated continuous flow reactors is described, with real-time online Fourier transform infrared spectroscopy (FT-IR) analysis to enable rapid optimization of reaction yield using a self-optimizing feedback algorithm. This technique has been applied to the solvent-free methylation of 1-pentanol with dimethyl carbonate using a γ-alumina catalyst. Calibration of the FT-IR signal was performed using gas chromatography to enable quantification of yield over a wide variety of flow rates and temperatures. The use of FT-IR as a real-time analytical technique resulted in an order of magnitude reduction in the time and materials required compared to previous studies. This permitted a wide exploration of the parameter space to provide process understanding and validation of the optimization algorithms.
TL;DR: The proposed model achieved a much better prediction performance than conventional PLS and obtained the same calibration quality while decreasing the root mean square error of prediction (RMSEP) from 4.47 to 3.77%, proving the robustness of the present PLS model.
Abstract: A nonlinearized multivariate dominant factor-based partial least-squares (PLS) model was applied to coal elemental concentration measurement. For C concentration determination in bituminous coal, the intensities of multiple characteristic lines of the main elements in coal were applied to construct a comprehensive dominant factor that would provide main concentration results. A secondary PLS thereafter applied would further correct the model results by using the entire spectral information. In the dominant factor extraction, nonlinear transformation of line intensities (based on physical mechanisms) was embedded in the linear PLS to describe nonlinear self-absorption and inter-element interference more effectively and accurately. According to the empirical expression of self-absorption and Taylor expansion, nonlinear transformations of atomic and ionic line intensities of C were utilized to model self-absorption. Then, the line intensities of other elements, O and N, were taken into account for inter-element interference, considering the possible recombination of C with O and N particles. The specialty of coal analysis by using laser-induced breakdown spectroscopy (LIBS) was also discussed and considered in the multivariate dominant factor construction. The proposed model achieved a much better prediction performance than conventional PLS. Compared with our previous, already improved dominant factor-based PLS model, the present PLS model obtained the same calibration quality while decreasing the root mean square error of prediction (RMSEP) from 4.47 to 3.77%. Furthermore, with the leave-one-out cross-validation and L-curve methods, which avoid the overfitting issue in determining the number of principal components instead of minimum RMSEP criteria, the present PLS model also showed better performance for different splits of calibration and prediction samples, proving the robustness of the present PLS model.
TL;DR: A method based on laser-induced breakdown spectroscopy (LIBS) and neural networks (NNs) has been developed and applied to the identification, quality control, traceability, and adulteration detection of extra virgin olive oils.
Abstract: The adulteration and traceability of olive oils are serious problems in the olive oil industry. In this work, a method based on laser-induced breakdown spectroscopy (LIBS) and neural networks (NNs) has been developed and applied to the identification, quality control, traceability, and adulteration detection of extra virgin olive oils. Instant identification of the samples is achieved using a spectral library, which was obtained by analysis of representative samples using a single laser pulse and treatment by NNs. The samples used in this study belong to four countries. The study also included different regions of each country. The results obtained allow the identification of the oils tested with a certainty of more than 95%. Single-shot measurements were enough for clear identification of the samples. The method can be developed for automatic real-time, fast, reliable, and robust measurements, and the system can be packed into portable form for non-specialist users.
TL;DR: The mathematical description of the optical physics underlying light-spherical sample interaction within an instrument is provided and the developed analytical expressions are used to predict recorded data from spheres using Fourier transform infrared (FT-IR) spectroscopic imaging.
Abstract: An infrared spectrum recorded from a microscopic sample depends on spectral properties of the constituent material as well as on morphology. Many samples or domains within heterogeneous materials can be idealized as spheres, in which both scattering and absorption from the three-dimensional shape affect the recorded spectrum. Spectra recorded from such objects may be altered to such an extent that they bear little resemblance to spectra recorded from the bulk material; there are no methods, however, to reconcile the two from first principles. Here we provide the mathematical description of the optical physics underlying light-spherical sample interaction within an instrument. We use the developed analytical expressions to predict recorded data from spheres using Fourier transform infrared (FT-IR) spectroscopic imaging. Recorded spectra are shown to depend strongly on the size of the sphere as well as the optical arrangement of the instrument. Next, we present theory and experiments demonstrating the recovery of the complex refractive index of the material using data recorded from a sphere. The effects of the sample morphology on the measured spectra can be removed, and using the imaginary part of the index, the shape-independent IR absorption spectrum of the material is recovered.
TL;DR: An analytical methodology is proposed based on constant ratio and absorbance correction methods to quantify sodium carbonate, Na2CO3 (1450 cm−1), and sodium bicarbonate,NaHCO3, in solid mixtures using Fourier transform infrared (FT-IR) spectroscopy.
Abstract: An analytical methodology is proposed based on constant ratio and absorbance correction methods to quantify sodium carbonate, Na₂CO₃ (1450 cm⁻¹), and sodium bicarbonate, NaHCO₃ (1000 cm⁻¹, 1923 cm⁻¹), in solid mixtures using Fourier transform infrared (FT-IR) spectroscopy. Potassium ferricyanide, K₃Fe(CN)₆ (2117cm⁻¹), was used as an internal standard to get characteristic parameters. NaHCO₃ was quantified using the constant ratio method. Spectral interference of NaHCO₃ in Na₂CO₃ (1450 cm⁻¹) was corrected using the absorbance correction method. The corrected absorbance was successfully applied to quantify Na₂CO₃ (1450 cm⁻¹) in the mixture using the constant ratio method. The results obtained for simulated samples were satisfactory (relative standard deviation less than 7%) for all samples.
TL;DR: In comparison to other analysis algorithms and functions, this new approach for background subtraction, peak analysis, and fitting returned vastly improved quantitative results, even for “hidden” details in the spectra, in particular, for nonanalytical line profiles.
Abstract: An integrated concept for post-acquisition spectrum analysis was developed for in-line (real-time) and off-line applications that preserves absolute spectral quantification; after the initializing parameter setup, only minimal user intervention is required. This spectral evaluation suite is composed of a sequence of tasks specifically addressing cosmic ray removal, background subtraction, and peak analysis and fitting, together with the treatment of two-dimensional charge-coupled device array data. One may use any of the individual steps on their own, or may exclude steps from the chain if so desired. For the background treatment, the canonical rolling-circle filter (RCF) algorithm was adopted, but it was coupled with a Savitzky–Golay filtering step on the locus-array generated from a single RCF pass. This novel only-two-parameter procedure vastly improves on the RCF's deficiency to overestimate the baseline level in spectra with broad peak features. The peak analysis routine developed here is an only-two...
TL;DR: The possibility that the change of relative content of NADH determined by native FL spectroscopy may be used as a “fingerprint” or criterion for monitoring the spoilage status of muscle foods is presented.
Abstract: The native fluorescence (FL) spectra of muscle foods (meat) stored at 4 °C (refrigerated) and 25 °C (at room temperature) were measured with the selected excitation wavelength of 340 nm as a function of storage time to detect the meat spoilage status. The contributions of the principal biochemical components to the FL spectra were extracted using Multivariate Curve Resolution with Alternating Least-Squares (MCR-ALS). The change of the reduced nicotinamide adenine dinucleotide (NADH) content was found from the measured FL spectra and the MCR-ALS analysis, which reflects the microbial spoilage of muscle foods involved in the metabolic processes. This study presents the possibility that the change of relative content of NADH determined by native FL spectroscopy may be used as a "fingerprint" or criterion for monitoring the spoilage status of muscle foods.
TL;DR: This paper describes the new picture of the evanescent wave that emerged from the reexamination of the foundations of ATR spectroscopy and believes it is virtually universally held by workers in the field.
Abstract: This is an unusual paper in that it does not address a particular research topic or present a novel experimental method or a new theoretical result. This paper addresses our basic understanding of the nature of the evanescent wave, the wave that is the basis of the entire field of Attenuated Total Reflection (ATR) spectroscopy. I recently had the opportunity to reexamine the foundations of ATR spectroscopy and was surprised to have had to change my own mental picture of the evanescent wave that I have built over the last 25 years. Over the years I have had numerous discussions with a large number of workers in the field as well as with my former mentor, and one of the originators and the principal developer of ATR spectroscopy, the late N.J. Harrick. Everything brought up in all these discussions was perfectly consistent with my old mental picture of the evanescent wave. Thus, I believe that the picture of the evanescent wave that I had is virtually universally held by workers in the field. This paper describes the new picture of the evanescent wave that emerged from said reexamination process.
TL;DR: The measured uranium line width demonstrates that LIBS acquired with moderately high spectral resolution can be utilized for isotope shift measurements in air at atmospheric pressure with single to tens of parts per million (ppm) level detection limits, as long as an appropriate transition is chosen for analysis.
Abstract: Laser-induced breakdown spectroscopy (LIBS) has been evaluated for the determination of uranium in real-world samples such as uraninite. NIST Standard Reference Materials were used to evaluate the spectral interferences on detection of uranium. The study addresses the detection limit of LIBS for several uranium lines and their relationship to non-uranium lines, with emphasis on spectral interferences. The data are discussed in the context of optimizing the choice of emission lines for both qualitative and quantitative analyses from a complex spectrum of uranium in the presence of other elements. Temporally resolved spectral emission intensities, line width, and line shifts were characterized to demonstrate the parameter influence on these measurements. The measured uranium line width demonstrates that LIBS acquired with moderately high spectral resolution (e.g., by a 1.25 m spectrometer with a 2400 grooves/mm grating) can be utilized for isotope shift measurements in air at atmospheric pressure with single to tens of parts per million (ppm) level detection limits, as long as an appropriate transition is chosen for analysis.
TL;DR: It is demonstrated that a LIBS system with a resolving power of approximately 20 000 is adequate for analyzing complex mixtures of actinide elements within the same sample.
Abstract: In this paper, we report for the first time the identification and assignments
of complex atomic emission spectra of mixed actinide oxides using laser-induced
plasma spectroscopy or laser-induced breakdown spectroscopy (LIBS) Preliminary
results of LIBS measurements on samples of uranium dioxide
(UO2)/plutonium dioxide (PuO2) and
UO2/PuO2/americium dioxide (AmO2)/neptunium
dioxide (NpO2) simulated fuel pellets (or mixed actinide oxide samples)
are reported and discussed We have identified and assigned >800 atomic emission
lines for a UO2/PuO2/AmO2/NpO2 fuel
pellet thus far The identification and assignments of spectral emission lines for
U, Pu, and Am are consistent with wavelength data from the literature However, only
a few emission lines have been assigned with a high degree of confidence for Np
compared with atomic emission data from the literature We also indicate where
atomic emission lines for Cm would most likely appear in the spectral regions shown
Finally, we demonstrate that a LIBS system with a resolving power of approximately
20 000 is adequate for analyzing complex mixtures of actinide elements within the
same sample
TL;DR: Raman spectroscopy is a highly interesting method for quality control in the production of photovoltaic (PV) modules and is unsuitable for the non-destructive determination of the degree of cross-linking of the EVA encapsulated within a PV module.
Abstract: Vibrational spectroscopy was found to be a suitable method for the determination of the degree of cross-linking of ethylene vinyl acetate (EVA) polymers. Spectral changes in the Raman spectra of EVA with increasing lamination time (which equals increasing degree of cross-linking) were mainly detected in the CH vibrational regions, namely, in the relative intensities of the characteristic CH3 and CH2 bands. These spectral regions were chosen for a chemometric evaluation where a calibration was performed with the Raman spectra of reference EVA samples and the results obtained from corresponding thermal analysis (differential scanning calorimetry) and Soxhlet extraction data. These datasets were subsequently used to non-destructively determine the progress of cross-linking in EVA foils, embedded in various mini-modules by Raman microscopy. Thus, we could show that Raman spectroscopy is a highly interesting method for quality control in the production of photovoltaic (PV) modules. However, this approach is valid only for a given grade of EVA, meaning a demand for a new calibration when changing the supplier or the type of EVA used. In addition, the applicability of infrared spectroscopy for the determination of the degree of cross-linking was tested. A good correlation of the decrease in intensity of the characteristic cross-linker infrared bands with increasing progress of the cross-linking was found, as determined by reference methods. However, this analytical method requires taking samples of the EVA foils and is, thus, unsuitable for the non-destructive determination of the degree of cross-linking of the EVA encapsulated within a PV module.
TL;DR: In this review, efforts to utilize SERS for label-free protein detection and identification is summarized after a short introduction of proteins and the technique.
Abstract: The detection and identification of biologically important molecules has critical importance in several fields such as medicine, biotechnology, and pharmacology. Surface-enhanced Raman scattering (SERS) is a powerful emerging vibrational spectroscopic technique that allows not only for the characterization, but also for the identification and detection of biomacromolecules in a very short time. In this review, efforts to utilize SERS for label-free protein detection and identification is summarized after a short introduction of proteins and the technique.
TL;DR: In this discussion, noble metals are regarded as reservoirs of photons exhibiting the functions of photon confinement and field enhancement at metallic nanostructures, including metamaterials and the extension to the ultraviolet and terahertz regions.
Abstract: The science of surface plasmon polaritons, known as “plasmonics,” is reviewed from the viewpoint of applied spectroscopy. In this discussion, noble metals are regarded as reservoirs of photons exhibiting the functions of photon confinement and field enhancement at metallic nanostructures. The functions of surface plasmons are described in detail with an historical overview, and the applications of plasmonics to a variety of industry and sciences are shown. The slow light effect of surface plasmons is also discussed for nanoimaging capability of the near-field optical microscopy and tip-enhanced Raman microscopy. The future issues of plasmonics are also shown, including metamaterials and the extension to the ultraviolet and terahertz regions.
TL;DR: It is concluded that complete spectrum LIBS is superior to UV Spectrum LIBS for predicting soil C for intact soil cores without pretreatment and LASSO and MRCE approaches provide improved calibration prediction accuracy over PLS2 but require additional testing with increased soil and target analyte diversity.
Abstract: Laser-induced breakdown spectroscopy (LIBS) provides a potential method for rapid, in situ soil C measurement In previous research on the application of LIBS to intact soil cores, we hypothesized that ultraviolet (UV) spectrum LIBS (200-300 nm) might not provide sufficient elemental information to reliably discriminate between soil organic C (SOC) and inorganic C (IC) In this study, using a custom complete spectrum (245-925 nm) core-scanning LIBS instrument, we analyzed 60 intact soil cores from six wheat fields Predictive multi-response partial least squares (PLS2) models using full and reduced spectrum LIBS were compared for directly determining soil total C (TC), IC, and SOC Two regression shrinkage and variable selection approaches, the least absolute shrinkage and selection operator (LASSO) and sparse multivariate regression with covariance estimation (MRCE), were tested for soil C predictions and the identification of wavelengths important for soil C prediction Using complete spectrum LIBS for PLS2 modeling reduced the calibration standard error of prediction (SEP) 15 and 19% for TC and IC, respectively, compared to UV spectrum LIBS The LASSO and MRCE approaches provided significantly improved calibration accuracy and reduced SEP 32-55% over UV spectrum PLS2 models We conclude that (1) complete spectrum LIBS is superior to UV spectrum LIBS for predicting soil C for intact soil cores without pretreatment; (2) LASSO and MRCE approaches provide improved calibration prediction accuracy over PLS2 but require additional testing with increased soil and target analyte diversity; and (3) measurement errors associated with analyzing intact cores (eg, sample density and surface roughness) require further study and quantification
TL;DR: The detection limit of gas-phase LIBS analysis has been improved by controlling the pressure and laser pulse width and it was demonstrated that the enhancement of IHg/INO arose by decreasing the pressure to a few kilopascals, and the IHG/INO of the picosecond breakdown was always much higher than that of the nanosecond breakage at low buffer gas pressure.
Abstract: Laser-induced breakdown spectroscopy (LIBS) technology is an appealing technique compared with many other types of elemental analysis because of the fast response, high sensitivity, real-time, and noncontact features. One of the challenging targets of LIBS is the enhancement of the detection limit. In this study, the detection limit of gas-phase LIBS analysis has been improved by controlling the pressure and laser pulse width. In order to verify this method, low-pressure gas plasma was induced using nanosecond and picosecond lasers. The method was applied to the detection of Hg. The emission intensity ratio of the Hg atom to NO (IHg/INO) was analyzed to evaluate the LIBS detection limit because the NO emission (interference signal) was formed during the plasma generation and cooling process of N2 and O2 in the air. It was demonstrated that the enhancement of IHg/INO arose by decreasing the pressure to a few kilopascals, and the IHg/INO of the picosecond breakdown was always much higher than that of the nanosecond breakdown at low buffer gas pressure. Enhancement of IHg/INO increased more than 10 times at 700 Pa using picosecond laser with 35 ps pulse width. The detection limit was enhanced to 0.03 ppm (parts per million). We also saw that the spectra from the center and edge parts of plasma showed different features. Comparing the central spectra with the edge spectra, IHg/INO of the edge spectra was higher than that of the central spectra using the picosecond laser breakdown process.
TL;DR: Simulation and LIBS experimental results proved that the proposed method of the initial value estimation can effectively resolve the overlapped peaks in LIBS data processing.
Abstract: Spectral peak overlapping is a basic problem in analytical data processing of laser-induced breakdown spectroscopy (LIBS). Curve fitting is the typical method of resolving overlapped peaks. For preventing ambiguous fitting, appropriate initial values must be known. The aim of this work was to present a method that could be used to determine appropriate initial values of the curve-fitting method by using fractional differential theory. According to the variation of characteristic points of Lorentzian peaks at different fractional differential orders, parameter estimators were obtained that were used to calculate the initial values of the curve-fitting method. As it is a widely used optimization method, the Levenberg-Marquardt method was used in curve fitting. Simulation and LIBS experimental results proved that the proposed method of the initial value estimation can effectively resolve the overlapped peaks in LIBS data processing.
TL;DR: The nondestructive identification of both inorganic and organic compounds without the need for chemical or mechanical sample preparation is an advantage of the Raman spectroscopic analytical technique when applied in situ using miniaturized equipment for the geosciences.
Abstract: The nondestructive identification of both inorganic and organic compounds without the need for chemical or mechanical sample preparation is an advantage of the Raman spectroscopic analytical technique when applied in situ using miniaturized equipment for the geosciences. This is critically assessed here for several real life geoscientific scenarios in which several groups of minerals were analyzed with emphasis on evaporites, carbonates, and selected types of dark minerals and weak Raman scatterers. The role of individual analytical instrumental parameters such as focal plane precision, exposure time, and ambient light conditions that can affect the acquisition and interpretation of spectroscopic data from these specimens in field conditions was also evaluated.
TL;DR: A graphene oxide (GO) fluorescence resonance energy transfer (FRET)-based aptasensor for rapid, sensitive, and selective detection of VEGF in homogeneous solution and the application of this nanosensor for human serum sample analysis is demonstrated.
Abstract: Oncoprotein vascular endothelial growth factor (VEGF) is one of the most critical growth factors that regulates tumor growth and division. The vascular endothelial growth factor (VEGF) is also an important biomarker for different diseases and clinical disorders. Herein, we propose a graphene oxide (GO) fluorescence resonance energy transfer (FRET)-based aptasensor for rapid, sensitive, and selective detection of VEGF in homogeneous solution. The fluorescent dye-labeled anti-VEGF aptamer is adsorbed on the surface of GO via π-π interaction between the flat planar GO sheets and the ring structures in the nucleobases, which results in the fluorescence quenching of the dye due to the highly effective FRET from the dye to GO. Upon recognition and binding with the target VEGF, it specifically forms a VEGF/aptamer complex and then release from the GO surface, leading to the restoration of fluorescence signal of the dye. This GO-based sensing platform exhibits high sensitivity and specificity toward VEGF versus other proteins, with the detection limits corresponding to 2.5×10−10 M. The sensitivity of this new type of aptamer-based assay is at least one order of magnitude higher than that of conventional homogeneous optical assays. Moreover, the application of this nanosensor for human serum sample analysis is also demonstrated. The GO/aptamer-based assay approach holds great promise as a general platform for detection of a variety of target molecules.
TL;DR: The combined use of laser-induced breakdown spectroscopy with optical coherence tomography (LIBS/OCT), aiming at a realistic depth-resolved elemental analysis of multilayer stratigraphies in paintings, significantly enhances the quality and accuracy of stratigraphic analysis.
Abstract: A detailed feasibility study on the combined use of laser-induced breakdown spectroscopy with optical coherence tomography (LIBS/OCT), aiming at a realistic depth-resolved elemental analysis of multilayer stratigraphies in paintings, is presented. Merging a high spectral resolution LIBS system with a high spatial resolution spectral OCT instrument significantly enhances the quality and accuracy of stratigraphic analysis. First, OCT mapping is employed prior to LIBS analysis in order to assist the selection of specific areas of interest on the painting surface to be examined in detail. Then, intertwined with LIBS, the OCT instrument is used as a precise profilometer for the online determination of the depth of the ablation crater formed by individual laser pulses during LIBS depth-profile analysis. This approach is novel and enables (i) the precise in-depth scaling of elemental concentration profiles, and (ii) the recognition of layer boundaries by estimating the corresponding differences in material ablation rate. Additionally, the latter is supported, within the transparency of the object, by analysis of the OCT cross-sectional views. The potential of this method is illustrated by presenting results on the detailed analysis of the structure of an historic painting on canvas performed to aid planned restoration of the artwork.
TL;DR: It was found that c-AgNPs are effective SERS substrates to monitor molecular changes in theBiofilm during the biofilm formation and are suitable for in situ monitoring.
Abstract: A biofilm is a complex biochemical structure composed of microorganisms and extracellular polymeric substances used by microorganisms to adhere to each other and to surfaces. The monitoring of molecular changes during biofilm formation in situ can provide valuable insights in medicine, microbiology, and industrial processes. In this study, we investigated the characterization of biofilm produced by two model bacteria by using surface-enhanced Raman scattering (SERS) with the use of core silver (AgNPs)-shell chitosan nanoparticles (c-AgNPs), which are prepared by coating citrate-reduced AgNPs with a thin layer of chitosan averaging 10 nm. The chitosan thin film acts as porous layer and prevents the excess interactions of biological media secreted by bacteria. The two model bacteria, Escherichia coli and Staphylococcus cohnii, gram positive and gram negative, respectively, were chosen for the study. The SERS spectra were acquired directly from the growth culture by simply placing c-AgNPs substrate on the biofilm formed during the growth of the bacteria for in situ monitoring. It was found that c-AgNPs are effective SERS substrates to monitor molecular changes in the biofilm during the biofilm formation.