Enhancing Micro-Raman Spectroscopy: A Variable Spectral Resolution Instrument Using Zoom Lens Technology.

Raman spectroscopy is a powerful analytical technique based on the inelastic scattering of photons. Conventional macro-Raman spectrometers are suitable for mass analysis but often lack the spatial resolution required to accurately examine microscopic regions of interest. For this reason, the development of micro-Raman spectrometers has been driven forward. However, even with micro-Raman spectrometers, high resolution is required to gain better insight into materials that provide low-intensity Raman signals. Here, we show the development of a micro-Raman spectrometer with implemented zoom lens technology. We found that by replacing a second collimating mirror in the monochromator with a zoom lens, the spectral resolution could be continuously adjusted at different zoom factors, i.e., high resolution was achieved at a higher zoom factor and lower spectral resolution was achieved at a lower zoom factor. A quantitative analysis of a micro-Raman spectrometer was performed and the spectral resolution was analysed by FWHM using the Gaussian fit. Validation was also performed by comparing the results obtained with those of a high-grade laboratory Raman spectrometer. A quantitative analysis was also performed using the ANOVA method and by assessing the signal-to-noise ratio between the two systems.

Influence of One-Dimensional Photonic Crystal on Raman Signal Enhancement: A Detailed Experimental Study.

The enhancement of Raman signals using photonic crystal structures has been the subject of numerous experimental and theoretical studies, leading to a variety of issues and inconsistencies. This paper presents a comprehensive experimental investigation into the impact of alignment between the laser excitation wavelength and the specific position of the photonic band gap on signal enhancement in Raman spectroscopy. By employing one-dimensional (1D) porous silicon photonic crystals, a systematic analysis across a large number of spectra was conducted. The study focused on examining the signal enhancement of both the Raman ∼520 cm-1 silicon band, representing the constituent material of photonic crystal, and the most prominent Raman bands of crystal violet, used as a probe molecule. The probe molecules were both infiltrated into and adsorbed on top of the photonic crystal structure. The obtained experimental results for the contribution of 1D photonic crystals to Raman signal enhancement are much smaller compared to most predictions. The Raman signal of silicon and the signal from the probe molecule are enhanced ≤2.5 times when the laser excitation aligns with the edge of the photonic band gap, strictly defined as the position at the very bottom of the reflectance peak. The results have been discussed within the context of theoretical explanations.

Effects of Gamma Irradiation on Polyethylene Terephthalate and Detection of Microplastic Particles Down to 1 µm.

In response to increasing concern about the impact of plastic degradation on the environment, this study investigates the degradation of virgin and recycled polyethylene terephthalate (PET) under γ-irradiation in aqueous solutions, with particular focus on the resulting formation of microplastic particles (MP). By exposing both virgin and recycled PET samples to different doses of γ-irradiation (10, 50, and 100 kGy), a comprehensive analysis using UV-vis spectroscopy, dynamic light scattering (DLS) and micro-Raman spectroscopy is presented. The results, highlighted by micro-Raman spectroscopy, show that γ-irradiation produces micrometer-sized plastic particles, with the recycled PET having a significantly higher MP content than its original counterpart. Careful examination reveals the presence of a stabilizer in samples of recycled PET juice bottles. This study not only contributes to our understanding of the effects of γ-irradiation on PET but also highlights the need for further research into the environmental impact of such processes. The insights gained shed light on the behavior of PET under γ-irradiation and the resulting impact on microplastic pollution and make an important contribution to our understanding of the broader environmental context.

UV Irradiation of Polyethylene Terephthalate and Polypropylene and Detection of Formed Microplastic Particles Down to 1†µm.

The degradation of plastics upon UVC irradiation in aqueous solution and the formation of microplastic (MP) particles were investigated. Polypropylene (PP) and recycled and virgin polyethylene terephthalate (PET) were irradiated with a UV lamp emitting light at 254 nm. Irradiation was performed for 15 and 30 min, respectively, at an intensity of about 0.3 W cm-2 . The formation of MP was studied by Raman spectroscopy. The results showed that MP particles were formed after irradiation and that their number was significantly higher in the recycled PET than in the virgin material. The number of PP MP formed was lower compared to PET and was not significantly different after 15 and 30 min. In addition, ethanol was used as an alternative solvent to investigate how its chemical properties and interactions with UVC irradiation affect the degradation of PET and PP plastics. The use of ethanol and recycled PET resulted in a lower number of MP particles at both irradiation times. When ethanol was used after 30 min of irradiation, significantly more PP MP formed. The different chemical structures of PET and PP combined with the different solvent properties of water and ethanol contribute to the differences in their susceptibility to UVC degradation.

Microwave-Assisted Synthesis of Pt/SnO2 for the Catalytic Reduction of 4-Nitrophenol to 4-Aminophenol.

In this study, we present a new approach for the synthesis of Pt/SnO2 catalysts using microwave radiation. Pt(IV) and Sn(IV) inorganic precursors (H2PtCl6 and SnCl4) and ammonia were used, which allowed the controlled formation of platinum particles on the anisotropic SnO2 support. The synthesized Pt/SnO2 samples are mesoporous and exhibit a reversible physisorption isotherm of type IV. The XRD patterns confirmed the presence of platinum maxima in all Pt/SnO2 samples. The Williamson-Hall diagram showed SnO2 anisotropy with crystallite sizes of ~10 nm along the c-axis (< 00l >) and ~5 nm along the a-axis (< h00 >). SEM analysis revealed anisotropic, urchin-like SnO2 particles. XPS results indicated relatively low average oxidation states of platinum, close to Pt metal. 119Sn Mössbauer spectroscopy indicated electronic interactions between Pt and SnO2 particles. The synthesized samples were used for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of excess NaBH4. The catalytic activity of the Pt/SnO2 samples for the reduction of 4-NP to 4-AP was optimized by varying the synthesis parameters and Pt loading. The optimal platinum loading for the reduction of 4-NP to 4-AP on the anisotropic SnO2 support is 5 mol% with an apparent rate constant k = 0.59 × 10-2 s-1. The Pt/SnO2 sample showed exceptional reusability and retained an efficiency of 81.4% after ten cycles.

Theoretical Analysis of the Refractometric Sensitivity of a Coated Whispering Gallery Mode Resonator for Gas Sensing Applications.

We present a theoretical analysis of the refractometric sensitivity of a spherical microresonator coated with a porous sensing layer performed for different whispering gallery modes. The effective refractive index of the modes is also calculated. The calculations are also made for a system which has an additional high-refractive index layer sandwiched between the microsphere and the porous sensing layer. The results of the calculation are discussed in regards to the applicability of the studied systems for gas sensor construction.

Ge/Al and Ge/Si3N4/Al Core/Shell Quantum Dot Lattices in Alumina: Boosting the Spectral Response by Tensile Strain.

We investigated the production conditions and optoelectrical properties of thin film material consisting of regularly ordered core/shell Ge/Al and Ge/Si3N4/Al quantum dots (QDs) in an alumina matrix. The materials were produced by self-assembled growth achieved by means of multilayer magnetron sputtering deposition. We demonstrated the successful fabrication of well-ordered 3D lattices of Ge/Al and Ge/Si3N4/Al core/shell quantum dots with a body-centred tetragonal arrangement within the Al2O3 matrix. The addition of shells to the Ge core enables a strong tuning of the optical and electrical properties of the material. An Al shell induces a bandgap shift toward smaller energies, and, in addition, it prevents Ge oxidation. The addition of a thin Si3N4 shell induces huge changes in the material spectral response, i.e., in the number of extracted excitons produced by a single photon. It increases both the absolute value and the width of the spectral response. For the best sample, we achieved an enhancement of over 250% of the produced number of excitons in the measured energy range. The observed changes are, as it seems, the consequence of the large tensile strain in Ge QDs which is induced by the Si3N4 shell addition and which is measured to be about 3% for the most strained QDs. The tensile strain causes activation of the direct bandgap of germanium, which has a very strong effect on the spectral response of the material.

Comparison of Glyphosate Detection by Surface-Enhanced Raman Spectroscopy Using Gold and Silver Nanoparticles at Different Laser Excitations.

Glyphosate is one of the most widely used pesticides in the world, but it has been shown to persist in the environment and therefore needs to be detected in food. In this work, the detection of glyphosate by surface-enhanced Raman scattering (SERS) using gold and silver nanoparticles and three different commonly used laser excitations (532, 632, and 785 nm wavelengths) of a Raman microscope complemented with a portable Raman spectrometer with 785 nm excitation is compared. The silver and gold nanosphere SERS substrates were prepared by chemical synthesis. In addition, colorimetric detection of glyphosate using cysteamine-modified gold and silver nanoparticles was also tested. The best results were obtained with Ag NPs at 532 nm excitation with a detection limit of 1 mM and with Au nanoparticles at 785 nm excitation with a detection limit of 100 µM. The SERS spectra of glyphosate with cysteamine-modified silver NPs improved the detection limits by two orders of magnitude for 532 nm excitation, i.e., up to 10 µM, and by one order of magnitude for 632 and 785 nm excitation wavelengths.

Surface Functionalisation of Dental Implants with a Composite Coating of Alendronate and Hydrolysed Collagen: DFT and EIS Studies.

The success of the osseointegration process depends on the surface characteristics and chemical composition of dental implants. Therefore, the titanium dental implant was functionalised with a composite coating of alendronate and hydrolysed collagen, which are molecules with a positive influence on the bone formation. The results of the quantum chemical calculations at the density functional theory level confirm a spontaneous formation of the composite coating on the titanium implant, ∆G*INT = -8.25 kcal mol-1. The combination of the results of X-ray photoelectron spectroscopy and quantum chemical calculations reveals the structure of the coating. The alendronate molecules dominate in the outer part, while collagen tripeptides prevail in the inner part of the coating. The electrochemical stability and resistivity of the implant modified with the composite coating in a contact with the saliva depend on the chemical nature of alendronate and collagen molecules, as well as their inter- and intramolecular interactions. The formed composite coating provides a 98% protection to the implant after the 7-day immersion in the artificial saliva. From an application point of view, the composite coating could effectively promote osseointegration and improve the implant's resistivity in contact with an aggressive environment such as saliva.

To generate a photonic nanojet outside a high refractive index microsphere illuminated by a Gaussian beam.

A non-resonant, concentrated, narrow beam of light emerging from an illuminated microlens is called a photonic nanojet (PNJ). According to currently prevailing opinion, microspheres and microcylinders are only able to generate a PNJ in their exterior when their refractive index ns (or refractive index contrast) is less than 2. In this Letter we demonstrate that a PNJ can emerge from a microsphere even when ns > 2: first by employing the laws of geometrical optics for a divergent light source; then, by using ray transfer matrix analysis, a mathematical condition for the Gaussian beam (GB) outside the high ns microsphere is derived. The PNJ outside the microsphere with ns = 2.5 is simulated using Generalized Lorenz-Mie theory (GLMT), by using a front focused GB source. The simulated difference between front and back focusing on the dependence of ns is confirmed experimentally by Raman imaging. By opening the PNJ field for high refractive index materials, we believe this work will be a nucleus for new ideas in the field and enable new PNJ applications.

Raman and Photoluminescence Spectroscopy with a Variable Spectral Resolution.

Raman and photoluminescence (PL) spectroscopy are important analytic tools in materials science that yield information on molecules' and crystals' vibrational and electronic properties. Here, we show results of a novel approach for Raman and PL spectroscopy to exploit variable spectral resolution by using zoom optics in a monochromator in the front of the detector. Our results show that the spectral intervals of interest can be recorded with different zoom factors, significantly reducing the acquisition time and changing the spectral resolution for different zoom factors. The smallest spectral intervals recorded at the maximum zoom factor yield higher spectral resolution suitable for Raman spectra. In contrast, larger spectral intervals recorded at the minimum zoom factor yield the lowest spectral resolution suitable for luminescence spectra. We have demonstrated the change in spectral resolution by zoom objective with a zoom factor of 6, but the perspective of such an approach is up to a zoom factor of 20. We have compared such an approach on the prototype Raman spectrometer with the high quality commercial one. The comparison was made on ZrO2 and TiO2 nanocrystals for Raman scattering and Al2O3 for PL emission recording. Beside demonstrating that Raman spectrometer can be used for PL and Raman spectroscopy without changing of grating, our results show that such a spectrometer could be an efficient and fast tool in searching for Raman and PL bands of unknown materials and, thereafter, spectral recording of the spectral interval of interest at an appropriate spectral resolution.

Influence of Sample Matrix on Determination of Histamine in Fish by Surface Enhanced Raman Spectroscopy Coupled with Chemometric Modelling.

Histamine fish poisoning is a foodborne illness caused by the consumption of fish products with high histamine content. Although intoxication mechanisms and control strategies are well known, it remains by far the most common cause of seafood-related health problems. Since conventional methods for histamine testing are difficult to implement in high-throughput quality control laboratories, simple and rapid methods for histamine testing are needed to ensure the safety of seafood products in global trade. In this work, the previously developed SERS method for the determination of histamine was tested to determine the influence of matrix effect on the performance of the method and to investigate the ability of different chemometric tools to overcome matrix effect issues. Experiments were performed on bluefin tuna (Thunnus thynnus) and bonito (Sarda sarda) samples exposed to varying levels of microbial activity. Spectral analysis confirmed the significant effect of sample matrix, related to different fish species, as well as the extent of microbial activity on the predictive ability of PLSR models with R2 of best model ranging from 0.722-0.945. Models obtained by ANN processing of factors derived by PCA from the raw spectra of the samples showed excellent prediction of histamine, regardless of fish species and extent of microbial activity (R2 of validation > 0.99).

Nanostructured Silicon as Potential Anode Material for Li-Ion Batteries.

Commercial micrometer silicon (Si) powder was investigated as a potential anode material for lithium ion (Li-ion) batteries. The characterization of this powder showed the mean particle size of approx.75.2 nm, BET surface area of 10.6 m2/g and average pore size of 0.56 nm. Its band gap was estimated to 1.35 eV as determined using UV-Vis diffuse reflectance spectra. In order to increase the surface area and porosity which is important for Li-ion batteries, the starting Si powder was ball-milled and threatened by metal-assisted chemical etching. The mechanochemical treatment resulted in decrease of the particle size from 75 nm to 29 nm, an increase of the BET surface area and average pore size to 16.7 m2/g and 1.26 nm, respectively, and broadening of the X-ray powder diffraction (XRD) lines. The XRD patterns of silver metal-assisted chemical etching (MACE) sample showed strong and narrow diffraction lines typical for powder silicon and low-intensity diffraction lines typical for silver. The metal-assisted chemical etching of starting Si material resulted in a decrease of surface area to 7.3 m2/g and an increase of the average pore size to 3.44 nm. These three materials were used as the anode material in lithium-ion cells, and their electrochemical properties were investigated by cyclic voltammetry and galvanostatic charge-discharge cycles. The enhanced electrochemical performance of the sample prepared by MACE is attributed to increase in pore size, which are large enough for easy lithiation. These are the positive aspects of the application of MACE in the development of an anode material for Li-ion batteries.

Features and advantages of flexible silicon nanowires for SERS applications.

The paper reports on the features and advantages of horizontally oriented flexible silicon nanowires (SiNWs) substrates for surface-enhanced Raman spectroscopy (SERS) applications. The novel SERS substrates are described in detail considering three main aspects. First, the key synthesis parameters for the flexible nanostructure SERS substrates were optimized. It is shown that fabrication temperature and metal-plating duration significantly influence the flexibility of the SiNWs and, consequently, determine the SERS enhancement. Second, it is demonstrated how the immersion in a liquid followed by drying results in the formation of SiNWs bundles influencing the surface morphology. The morphology changes were described by fractal dimension and lacunar analyses and correlated with the duration of Ag plating and SERS measurements. SERS examination showed the optimal intensity values for SiNWs thickness values of 60-100 nm. That is, when the flexibility of the self-assembly SiNWs allowed hot spots occurrence. Finally, the test with 4-mercaptophenylboronic acid showed excellent SERS performance of the flexible, horizontally oriented SiNWs in comparison with several other commercially available substrates.

Near-Infrared Surface-Enhanced Raman Scattering on Silver-Coated Porous Silicon Photonic Crystals.

Surface-enhanced Raman scattering (SERS) with near-infrared (NIR) excitation offers a safe way for the detection and study of fragile biomolecules. In this work, we present the possibility of using silver-coated porous silicon photonic crystals as SERS substrates for near-infrared (1064 nm) excitation. Due to the deep penetration of NIR light inside silicon, the fabrication of photonic crystals was necessary to quench the band gap photoluminescence of silicon crystal, which acts as mechanical support for the porous layer. Optimal parameters of the immersion plating process that gave maximum enhancement were found and the activity of SERS substrates was tested using rhodamine 6G and crystal violet dye molecules, yielding significant SERS enhancement for off-resonant conditions. To our knowledge, this is the first time that the 1064 nm NIR laser excitation is used for obtaining the SERS effect on porous silicon as a substrate.

Sensing Properties of Oxidized Nanostructured Silicon Surface on Vaporized Molecules.

Porous silicon has been intensely studied for the past several decades and its applications were found in photovoltaics, biomedicine, and sensors. An important aspect for sensing devices is their long⁻term stability. One of the more prominent changes that occur with porous silicon as it is exposed to atmosphere is oxidation. In this work we study the influence of oxidation on the sensing properties of porous silicon. Porous silicon layers were prepared by electrochemical etching and oxidized in a tube furnace. We observed that electrical resistance of oxidized samples rises in response to the increasing ambient concentration of organic vapours and ammonia gas. Furthermore, we note the sensitivity is dependent on the oxygen treatment of the porous layer. This indicates that porous silicon has a potential use in sensing of organic vapours and ammonia gas when covered with an oxide layer.

Preparation and characterization of polycarbonate/multiwalled carbon nanotube nanocomposites.

A polymer nanocomposite was produced by ultrasonic-assisted dispersion of multiwalled carbon nanotubes (MWCNTs) in a polycarbonate matrix using p-xylene and dichloromethane as the solvents. The filler loading was varied from 1 to 3 wt % in order to examine the effect of MWCNTs on the structure and properties of the composites. The nanocomposites were characterized by DSC, DTA, TGA, UV-vis, FTIR and Raman spectroscopy to evaluate the changes induced by the filler in the polymer matrix. UV-vis, FTIR and Raman spectroscopy measurements confirmed the presence of the dispersed phase in the composite films, while TGA and DSC analysis of the nanocomposites revealed enhanced thermal stability and decreased crystallinity, respectively, as compared to the neat polymer. The proposed composites can find application in a number of everyday products where polycarbonate is the base polymer.

Determination of histamine in fish by Surface Enhanced Raman Spectroscopy using silver colloid SERS substrates.

This study was focused on development of a rapid and sensitive method for histamine determination in fish based on Surface Enhanced Raman Spectroscopy (SERS) using simple and widely available silver colloid SERS substrate. Extraction of histamine with 0.4M perchloric acid and purification with 1-butanol significantly shortened sample preparation (30min) and provided clear SERS spectra with characteristic Raman bands of histamine. Principal component analysis effectively distinguished SERS spectra of fish samples with different histamine content. Partial least square (PLS) regression models confirmed reliability of detection and spectral analysis of histamine with SERS. In histamine concentration range 0-200mgkg-1, significant in legislative and fish quality control aspects, PLS regression model based on spectral range 1139.9-1643.7cm-1 showed linear trend with R2pred=0.962, RPD=7.250. Presented protocol for histamine extraction and purification followed by SERS analysis coupled with chemometric approach, enabled development of rapid and inexpensive method for histamine determination in fish.

Porous Silicon Covered with Silver Nanoparticles as Surface-Enhanced Raman Scattering (SERS) Substrate for Ultra-Low Concentration Detection.

Microporous and macro-mesoporous silicon templates for surface-enhanced Raman scattering (SERS) substrates were produced by anodization of low doped p-type silicon wafers. By immersion plating in AgNO3, the templates were covered with silver metallic film consisting of different silver nanostructures. Scanning electron microscopy (SEM) micrographs of these SERS substrates showed diverse morphology with significant difference in an average size and size distribution of silver nanoparticles. Ultraviolet-visible-near-infrared (UV-Vis-NIR) reflection spectroscopy showed plasmonic absorption at 398 and 469 nm, which is in accordance with the SEM findings. The activity of the SERS substrates was tested using rhodamine 6G (R6G) dye molecules and 514.5 nm laser excitation. Contrary to the microporous silicon template, the SERS substrate prepared from macro-mesoporous silicon template showed significantly broader size distribution of irregular silver nanoparticles as well as localized surface plasmon resonance closer to excitation laser wavelength. Such silver morphology has high SERS sensitivity that enables ultralow concentration detection of R6G dye molecules up to 10(-15) M. To our knowledge, this is the lowest concentration detected of R6G dye molecules on porous silicon-based SERS substrates, which might even indicate possible single molecule detection.

Tailoring of the free spectral range and geometrical cavity dispersion of a microsphere by a coating layer.

The modal dispersion of a whispering gallery mode (WGM) resonator is a very important parameter for use in all nonlinear optics applications. In order to tailor the WGM modal dispersion of a microsphere, we have coated a silica microsphere with a high-refractive-index coating in order to study its effect on the WGM modal dispersion. We used Er(3+) ions as a probe for a modal dispersion assessment. We found that, by varying the coating thickness, the geometrical cavity dispersion can be used to shift overall modal dispersion in a very wide range in both the normal and anomalous dispersion regime.