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Mikroplastika (MP) posljednjih desetak godina izaziva zabrinutost znanstvene zajednice zbog velike prisutnosti u okolišu, dok mogući štetni učinci još nisu u potpunosti poznati. MP su čvrste, polimerne čestice, s dodanim aditivima, netopljive u vodi dimenzija od 1 µm do 5 mm. Dosad je dokazana prisutnost MP-a u različitim dijelovima okoliša, poput tla, oceana, jezera, sedimenata i izoliranih područja poput Marijanske brazde. Ljudi su izloženi MP-u unosom kontaminirane hrane. Mnogobrojna istraživanja rezultirala su pronalaskom znatne količine MP-a u pitkoj vodi, flaširanim pićima, soli, morskoj hrani i sl. Zakonska ograničenja i dalje nisu na izravan način obuhvatila MP kao skupinu onečišćivala, ali se direktivom EU-a do 2024. godine želi usvojiti metodologija za kvantificiranje MP-a s ciljem uvrštavanja MP-a na popis praćenih onečišćavala. Postojeće metode analize MP-a, iako u razvoju, najčešće uključuju spektroskopske metode poput infracrvene spektroskopije s Furierovom transformacijom (FTIR) i Ramanove spektroskopije, koje mogu pružiti informaciju o veličini, broju i obliku čestice, ali i o tipu polimera. No, unatoč napretku, još uvijek ne postoje standardizirane metode za usporedbu rezultata različitih istraživanja. U ovom preglednom radu glavni je cilj pružiti pregled metoda analize i izazova s kojima se istraživači suočavaju. Kroz analizu raznih metoda, poput destruktivnih (pirolize) i nedestruktivnih (kao što su spektroskopske metode), dobiva se širi uvid u tipove polimera, broj, veličinu i oblik čestica. Međutim, nedostatak standardiziranih protokola za pripremu uzorka, analizu i obradu podataka otežava usporedbu rezultata i smanjuje pouzdanost istraživanja. Stoga je ključno propisati eksperimentalne uvjete da bi se osigurala kvaliteta istraživanja i omogućila meta-analiza te pregled prisutnosti MP-a u različitim okolišnim matricama.

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.

In this paper, we demonstrate Er3+ doped tellurite single and multi-mode microlasers in 1.5 μm–1.6 μm wavelength range fabricated via the plasma torch method. It is a simple and cost-effective method to produce microspheres with diameter ranges from 11 to 88 μm. Single mode laser output were observed with 0.98 μm and 1.48 μm pump, respectively. In addition, the quality factor of the fabricated microsphere is measured.

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.

The electrode configuration is an important element in the development of Li-ion cells. The energy density is proportional to the loading of the active material. Therefore, increasing the electrode thickness is the simplest way to achieve higher capacities. In this paper, we compare the effects of three different thicknesses of Ag-decorated Si electrode anode (HCSi) on the electrochemical performances such as the SEI layer formation, impedances, and mass capacitances. We prepared three different silicon electrode thicknesses to optimize the electrodes: 20, 40 and 60 µm and measured in situ galvanostatic electrochemical impedance spectroscopy (GEIS). Using GEIS, we studied the intercalation mechanism of Li+ ions in detail and found that despite having the same capacities (≈3500 mAh g−1), the thinnest electrode, HCSi20, allows diffusion of Li+ ions into the bulk, whereas thicker layers prevent smooth diffusion into the bulk of the silicon electrode due to increased layer resistance. The Voigt model was used to analyze the anomaly of the frequency dependence of the measured impedance, in which, the classical Randles circuit is connected in series with one or two R ‖ C parallel combinations. One R ‖ C circuit could be the result of the SEI formation, and the second R ‖ C circuit could be the contribution of Li. To increase the number of charge and discharge cycles, we improved the electrolyte by adding fluoroethylene carbonate (FEC), which reduced the capacity of the HCSi20 electrode to 50% of the initial capacity (≈3500 mAh g−1) after 60 cycles, whereas it dropped to 20% of the initial capacity after 10 cycles without the addition of FEC.

Titanium dioxide (TiO2) nanoparticles, have been routinely used in cosmetic and sunscreen applications, due to their ability to absorb in the UV spectrum. Nevertheless, one of the main disadvantages has been the generation of reactive oxygen species (ROS), especially the hydroxyl radical, upon photoexcitation of titania. In this work, we investigate TiO2 nanoparticles doped with 0.6–0.7% manganese (Mn), based in the more stable rutile polymorph of titania. In particular, while the anatase crystal form has the ability to destroy almost any organic matter under UV illumination, rutile is less photoreactive, and with Mn doping its photoactivity is reduced further. In particular, we study its optical, structural and semiconducting properties via the Seebeck effect and show that the material displays p-type characteristics. This is very significant because it shifts the energy levels with respect to formation of hydroxyl free radicals. This ensures that for Mn doped p-type titania it is not energetically possible for the hole created in the valence band by photoexcitation to create an OH. free radical and this may explain its low photoreactivity. It also means that this material can act as a very effective scavenger for hydroxyl free radicals.

Large specific surface area nanostructures are desirable in a wide range of sensing applications due to their longer light-trapping path and increased absorption. Engineering of the specific nanotree structure which possesses a high branch density turned out to be challenging from the experimental point of view, and certainly not adequately explored. This paper shows how to design substrates with a silicon nanotree structure for surface-enhanced Raman spectroscopy (SERS) applications. Silicon nanotrees were synthesized by a Ag-Au nanocluster-catalyzed low-pressure chemical vapor deposition method (LPCVD). By the presented approaches, it is possible to manipulate branches’ number, length and thickness. The synthesized nanostructures are flexible after immersion in water which improves SERS performance. The amount of sputtered metal played a key role in preserving the flexibility of the nanotree structure. The obtained substrates with highly fractal nanostructure were tested on 4-mercaptophenylboronic acid (MPBA) to match the optimal SERS parameters. The silicon nanotrees fabrication, and particularly obtained SERS substrates plated with Ag and Au nanoparticles, demonstrated good features and a promising approach for further sensor development.

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.

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.

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.

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.

We report the effects of thermal oxidation on the sensing properties of porous silicon. Porous silicon substrates were prepared by electrochemical etching and thermally oxidized at different temperatures. A comparative EDS analysis shows that porous surfaces oxidized at higher temperatures have higher oxygen-to-silicon ratios. Our results indicate that the chemoresistive response due to the presence of isopropanol vapors at room temperature also increases with an increasing oxidation temperature. The presence of oxygen atoms in the PS layer could both protect the sensor from further atmospheric oxidation and increase its sensitivity.

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.

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.

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).

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.

In this paper, results on preparation of stable and uniform SERS solid substrates using macroporous silicon (pSi) with deposited silver and gold are presented. Macroporous silicon is produced by anodisation of p-type silicon in hydrofluoric acid. The as prepared pSi is then used as a template for Ag and Au depositions. The noble metals were deposited in three different ways: by immersion in silver nitrate solution, by drop-casting silver colloidal solution and by pulsed laser ablation (PLA). Substrates obtained by different deposition processes were evaluated for SERS efficiency using methylene blue (MB) and rhodamine 6G (R6G) at 514.5, 633 and 785 nm. Using 514.5 nm excitation and R6G the limits of detection (LOD) for macroporous Si samples with noble metal nanostructures obtained by immersion of pSi sample in silver nitrate solution and by applying silver colloidal solution to pSi template were 10–9 M and 10–8 M respectively. Using 633 nm laser and MB the most noticeable SERS activity gave pSi samples ablated with 30000 and 45000 laser pulses where the LODs of 10–10 M were obtained. The detection limit of 10–10 M was also reached for 4 mA cm–2-15 min pSi sample, silver ablated with 30000 pulses. Macroporous silicon proved to be a good base for the preparation of SERS substrates.

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.

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.

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.

Time dependence of the grain growth in phosphorus doped silicon thin films deposited in situ at 530 °C was investigated. The samples were annealed at 950 °C in different time intervals. The theories, which give the tn time dependent increase of grain size, cannot fit the observed data. We derived a differential equation which describes the grain growth from amorphous phase. Our experimental results and the solution of the differential equation show the effect of grain growth stagnation and even grain growth stop. The solution also comprises all the features of the result of the Monte Carlo simulation of the grain growth of pure materials.