In this study, we proposed and tested different procedures for the preparation of Au/Si cantilevers for Tip-enhanced Raman spectroscopy (TERS). The preparation of Au/Si TERS sensors was based on three methods: chemical (electroless) deposition, thermal evaporation of Au on the tip of commercially available cantilevers in a vacuum, and electrochemical etching of Au microwires. We fabricated and tested four types of TERS probes, and then used these probes for TERS measurements using graphene oxide (GO) as the target analyte. The probe tips were characterized using scanning electron microscopy (SEM). This article presents a comparative analysis of the fabrication methods, quality of the obtained probe tips, and enhancement factors (EFs) for the four types of TERS cantilevers (probes) produced by chemical deposition, sputtering, and electrochemical methods.

Possibility to produce the biogrease using rapeseed oil as a base oil, beeswax as a thickener and its modification with functional anti-wear and antioxidant additives and carbon nanoparticles of graphene oxide and thermally expanded graphite nanoparticles were evaluated. Tribological tests were performed using a four-ball tribo-tester and the rheological characterization using a cone-plate Brookfield rheometer. The rheological parameters were correlated with the physico-chemical properties of the greases. The resulting variation of the rheological parameters with the temperature exhibits non-Newtonian behavior. Although the increasing proportion of beeswax worsens the tribological properties of investigated grease, the functional additives and nanoparticles significantly improve the thermal properties of the lubricant, yield stress, viscosity and tribological properties reducing the wear rate.

The most common neurological disorders, i.e., Parkinson's disease (PD) and Alzheimer's disease (AD), are characterized by degeneration of cognitive functions due to the loss of neurons in the central nervous system. The aggregation of amyloid proteins is an important pathological feature of neurological disorders.The aggregation process involves a series of complex structural transitions from monomeric to the formation of fibrils. Despite its potential importance in understanding the pathobiology of PD and AD diseases, the details of the aggregation process are still unclear. Nanoparticles (NPs) absorbed by the human circulatory system can interact with amyloid proteins in the human brain and cause PD. In this work, we report the study of the interaction between TiO2 nanoparticles (TiO2-NPs) and ZnO nanoparticles (ZnO-NPs) on the aggregation kinetics of β-amyloid fragment 1-40 (βA) and α-synuclein protein using surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS). The characterizations of ZnO-NPs and TiO2-NPs were evaluated by X-ray diffraction (XRD) spectrum, atomic force microscopy (AFM), and UV-Vis spectroscopy. The interaction of nanoparticles with amyloid proteins was investigated by SERS. Our study showed that exposure of amyloid protein molecules to TiO2-NPs and ZnO-NPs after incubation at 37 °C caused morphological changes and stimulated aggregation and fibrillation. In addition, significant differences in the intensity and location of active Raman frequencies in the amide I domain were found. The principal component analysis (PCA) results show that the effect of NPs after incubation at 4 °C does not cause changes in βA structure.

The process of nanoparticles entering the cells of living organisms is an important step in understanding the influence of nanoparticles on biological processes. The interaction of nanoparticles with the cell membrane is the first step in the penetration of nanoparticles into cells; however, the penetration mechanism is not yet fully understood. This work reported the study of the interaction between TiO2 nanoparticles (TiO2-NPs) and Chinese hamster ovary (CHO) cells using an in vitro model. The characterization of crystalline phases of TiO2 NPs was evaluated by transmission electron microscopy (TEM), X-ray diffraction (XRD) spectrum, and atomic force microscopy (AFM). Interaction of these TiO2 nanoparticles (TiO2- NPs) with the CHO cell membrane was investigated using atomic force microscopy (AFM) and Raman spectroscopy. The XRD analysis result showed that the structure of the TiO2 particles was in the rutile phase with a crystallite size of 60 nm, while the AFM result showed that the particle size distribution had two peaks with 12.1 nm and 60.5 nm. The TEM analysis confirmed the rutile phase of TiO2 powder. Our study showed that exposure of CHO cells to TiO2-NPs caused morphological changes in the cell membranes and influenced the viability of cells. The TiO2-NPs impacted the cell membrane surface; images obtained by AFM revealed an ‘ultra structure‘ with increased roughness and pits on the surface of the membrane. The depth of the pits varied in the range of 40–80 nm. The maximal depth of the pits after the treatment with TiO2-NPs was 100% higher than the control values. It is assumed that these pits were caveolae participating in the endocytosis of TiO2-NPs. The research results suggest that the higher maximal depth of the pits after the exposure of TiO2-NPs was determined by the interaction of these TiO2-NPs with the cell’s plasma membrane. Moreover, some of pits may have been due to plasma membrane damage (hole) caused by the interaction of TiO2-NPs with membrane constituents. The analysis of AFM images demonstrated that the membrane roughness was increased with exposure time of the cells to TiO2-NPs dose. The average roughness after the treatment for 60 min with TiO2-NPs increased from 40 nm to 78 nm. The investigation of the membrane by Raman spectroscopy enabled us to conclude that TiO2-NPs interacted with cell proteins, modified their conformation, and potentially influenced the structural damage of the plasma membrane.

Blueberries (Vaccinium sp.) are consumed all around the globe, however, their endophytic community has not been thoroughly researched, specifically their fruit endophytes. We aimed to isolate and analyze easily cultivable blueberry fruit endophytes to help in future research, concerning probiotic microorganisms. Twelve strains were isolated in this pilot study, genetically homologous with Staphylococcus hominis, Staphylococcus cohnii, Salmonella enterica, Leuconostoc mesenteroides, and [Candida] santamariae. To determine the molecular composition of these isolates we used label-free surface-enhanced Raman spectroscopy (SERS). To our knowledge, this is the first time that SERS spectra for L. mesenteroides and C. santamariae are presented, as well as the first report of Candida yeast, isolated specifically from blueberry fruits. Our findings suggest that the differences in tested yeast and bacteria SERS spectra and subsequent differentiation are facilitated by minor shifts in spectral peak positions as well as their intensities. Moreover, we used principal component and discriminant function analyses to differentiate chemotypes within our isolate group, proving the sensitivity of the technique and its usefulness to recognize different strains in plant-associated microbe samples, which will aid to streamline future studies in biofertilizers and biocontrol agents.

Food traceability is a major issue in the industry. We investigated whether bilberries (Vaccinium myrtillus L.) from 4 different locations within the Baltic-Nordic region could be effectively differentiated using surface-enhanced Raman scattering (SERS) based spectral data and chemometric analyses. Furthermore, we aimed to determine if nucleobase (adenine and cytosine) methylation could be responsible for any observed variation. Our experi-ment was successful in that both principal component (PCA) and discriminant function analyses (DFA) showed differentiation between bilberry DNA from all 4 geographical regions. Density functional theory (DFT) based simulations allowed us to analyze whether DNA's spectral data dissimilarities may be due to nucleobase methylation. Although results were inconclusive on this, our investigation provides valuable data on simulated versus experimental DNA and DNA component spectra. Further research will be directed towards understanding what other epigenetic changes could be responsible for the observed DNA variation as well as determining the optimal parameters for using DFT simulations in upcoming projects.

The detection of molecular traces in the environment is a technical problem that is critical in pollutant control procedures at all stages of spacecraft assembly, in space flight, as well as in other technological processes such as food production, medical diagnostics, environmental control, warfare. However, in the aerospace industry, it is necessary to detect molecular traces of contaminants with extreme sensitivity, as even concentrations as low as part-per-billion (ppb) can be critical during long missions. The high sensitivity of the Volatile Organic Compounds (VOCs) detection within the air can be a challenge because of the poor affinity of VOC’s to the metal surface of the sensor substrate. In this work, we present a surface‐enhanced Raman scattering (SERS) spectroscopy technique as a highly sensitive and selective molecular sensor for gas trace detection not sensitive to molecules adsorbtion on sensing element. The developed hybrid SERS platform for molecular trace detection is supported by the hybrid nanoplasmonic porous silicon membrane in conjunction with micropump to achieve the trace level detection of VOCs in the environment. The combination of silicon membrane, made by electrochemical etching of the microchannels in the silicon chip, with chemical deposition of the silver nanoparticles inside the channels, produce a porous Ag nanoparticles membrane with a high density of plasmonic nanostructures (“hot spots”). The micropump integrated with the SERS sensor, pump the air with VOC’s molecules through the plasmonic membrane “hot spots” to increase the probability of interaction of VOC’s molecules with SERS substrate and to increase the enhancement factor. The sensor chip structure was designed, gas flow in the sensor was simulated, and the sensor was fabricated using 3D printing. The limit of detection of hydrazine with concentration level 10–12 M from solution and the vapor phase 0.1 ppm was demonstrated. The anisole vapors with concentration 0.5 ppb spectra in the air were recorded. Our results demonstrate that plasmonic membrane can be used as a high enhancement factor SERS sensor for many pollutants molecules detection with the nanomolar sensitivity and can be applied in the design of sensors for space applications, environment control, biomedical diagnostic.

In this study, an investigation of the wild bilberries ( Vaccinium myrtillus L.) of the different Baltic–Nordic regions using surface-enhanced Raman spectroscopy (SERS) combined with principal component analysis (PCA) is presented. The bilberries were collected in Lithuania, Latvia, Finland and Norway. The set of the SERS spectra of the berry extracts (pH ~ 4) were recorded on the silver nanoparticles based SERS substrates. The SERS spectra of the extracts were acquired using 532 nm laser as an excitation source. The morphology of the SERS substrates was evaluated by scanning electron microscopy (SEM) and the presence of the silver nanoparticles was confirmed by the energy-dispersive X-ray spectroscopy (EDX). The enhancement factor (EF) of the silver SERS substrates was found to be 10 5 . It has been shown that a strong fluorescence background, associated with the phenolic compounds found in bilberries, can be subtracted due to the fluorescence-quenching properties of the silver nanoparticles. Therefore, an application of the SERS technique allowed to observe the characteristic peaks of the bilberries and the PCA tool enabled to evaluate the spectral variation across the entire SERS data set. The results presented in this paper show that the SERS technique coupled with PCA chemometric analysis might serve as a complementary method that allows to identify the country of origin of the bilberries based on the spectral differences.

Due to the harmful effects of chemical fertilizers and pesticides, the need for an eco-friendly solution to improve soil fertility has become a necessity, thus microbial biofertilizer research is on the rise. Plant endophytic bacteria inhabiting internal tissues represent a novel niche for research into new biofertilizer strains. However, the number of species and strains that need to be differentiated and identified to facilitate faster screening in future plant-bacteria interaction studies, is enormous. Surface enhanced Raman spectroscopy (SERS) may provide a platform for bacterial discrimination and identification, which, compared with the traditional methods, is relatively rapid, uncomplicated and ensures high specificity. In this study, we attempted to differentiate 18 bacterial isolates from two oaks via morphological, physiological, biochemical tests and SERS spectra analysis. Previous 16S rRNA gene fragment sequencing showed that three isolates belong to Paenibacillus, 3—to Pantoea and 12—to Pseudomonas genera. Additional tests were not able to further sort these bacteria into strain-specific groups. However, the obtained label-free SERS bacterial spectra along with the high-accuracy principal component (PCA) and discriminant function analyses (DFA) demonstrated the possibility to differentiate these bacteria into variant strains. Furthermore, we collected information about the biochemical characteristics of selected isolates. The results of this study suggest a promising application of SERS in combination with PCA/DFA as a rapid, non-expensive and sensitive method for the detection and identification of plant-associated bacteria.

Detecting the traces of molecules in the surrounding environment are the technical challenges associated with contaminant control during space apparatus assembly stages, space research, food production, medicine, environmental control, military, etc. However, the detection of the traces of the molecules of contaminants in the environment is a challenge because the number of target molecules can be as low as part-per-billion (ppb) in the air. Moreover, the Organic Volatile Compounds in the air may have very low adsorption to the sensing element. This work presents a novel Surface Enhanced Raman spectroscopy (SERS) platform for molecular sensors based on the hybrid nanoplasmonic silicon membrane integrated with gas micropump. The proposed solution of the problem is to increase the probability of interaction of analyzes with SERS substrate plasmonic structures by the pumping gas or liquid with contaminants through the silicon membrane decorated with silicon flower like nanostructures ("hot spots"). The main objective of theoretical computational design of the sensor is to determine the optimal conditions for trace molecules flow through and interaction with SERS substrate ("hot spots") to increase the Raman scattering. The computer simulation of gas flow with the purpose to optimize the sensor chip structure was made using SolidWorks software. The sensor chip structure was designed, simulated and manufactured using 3D printing. The measured results show that the proposed sensing platform is of high sensitivity. The SERS spectra of the anizole vapors (4,6 x 10(-9) M) and crystal violet solution (10 x 10(-9) M) were recorded using Raman spectrometer (NTEGRA Spectra, NT-MDT Inc.) equipped with 532 nm laser. It was found that the developed SERS platform allows to achieve the nanomolar sensitivity in gas detection and reliably identify the type of analyze based on SERS spectral fingerprint.

The evaluation of the cyto- and bio-compatibility is a critical step in the development of graphene oxide (GO) as a new promising material for in vivo biomedical applications. In this study, we report the impact of GO, with and without the addition of bovine serum albumin and anticancer drug- doxorubicin (DOX) on cancer (mouse hepatoma MH-22A) cells viability and the estimation of the intracellular distribution of GO inside the cells in vitro. The viability tests were performed using a colony formation assay. The intracellular distribution of GO was estimated using Raman spectroscopy and imaging. It was found that the functionalized GO with doxorubicin strengthens Doxorubicin, as anticancer drug effect. Therefore, it was revealed that a statistically significant result - the viability of MH-22A cells was approx. 20% lower than using DOX separately (from 57% to 79%, respectively). The results of viability tests correlate with results of atomic force microscopy and Raman spectroscopy and imaging findings.

In this work, the different procedures for the fabrication of Ag probes for tip-enhanced Raman spectroscopy (TERS) in a top illumination/detection setup are proposed and tested. We focus on technologically simple methods allowing Si tips coated with plasmonic silver nanostructures and bulk metal Ag tips with good shape reproducibility to be produced for atomic force microscopy (AFM) feedback setup. The preparation of Ag TERS probes was based on chemical deposition and vacuum sputtering of Ag on the tips of commercially available Si cantilevers. A straightforward technique for the fabrication of bulk metal Ag probes by the electrochemical etching of Ag microwires was also proposed. Chemically coated, sputtered, and electrochemically etched TERS tips were characterized by scanning electron microscopy (SEM). The produced tips were tested for TERS measurements using graphene oxide (GO) as the target analyte in a top illumination setup. A comparative analysis of enhancement factors (EF) for the different types of tips (probes) is presented in this work.

The authors describe a Surface enhanced Raman spectroscopy (SERS)-based method for the detection of gaseous toluene at different temperature regimes using 3D ruffled silver SERS substrates and a commercially available handheld Raman system equipped with a 785 nm laser. The 3D silver SERS substrates were synthesized via electroless deposition of silver on the ruffled sandpaper and HF-etched silicon wafers. The morphological characterization of the silver SERS substrates was carried out by atomic force microscopy and scanning electron microscopy. UV-Vis spectroscopy absorption spectra of the silver nanostructures showed plasmonic peaks at 522 nm and 731 nm. Toluene vapors were collected with a syringe at ambient temperature and at 100 °C, while SERS detection was always performed at room temperature. Toluene detection was based on the measurement of the Raman bands at 787 cm−1 and 1003 cm−1 (in the fingerprint region). The method allow gaseous toluene to be detected at its vapor concentrations of 522 ppm (mg/L), 261 ppm (mg/L) and 26 ppm (mg/L).

The field enhancement in a gap-mode tip-enhanced Raman spectroscopy (TERS) setup with hemispherical nano-protrusions on the substrate is studied numerically and is found to display a resonant behavior as a function of the protrusion radius.

In this work surface enhanced Raman spectroscopy (SERS) has been used for the investigation of the self assembled layers of lipid molecules (SALLMs) deposited on the nanostructured Au and Ag surfaces. The SALLMs were prepared from one part of 1,2-dioleoyl-sn-glycero-3-phospho-L-serine (DOPS) and four parts of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) lipids. The synthesis of Au and Ag SERS substrates was based on the direct gold and silver ions reduction onto HF etched silicon wafers. Au SERS substrates were not suitable for the formation of SALLMs because of the inappropriate contact angle of surface. It was found that the formation of the SALLM does not take place on Au SERS substrate. However, it has been shown that the modification of Au SERS substrate with 1-dodecanothiol layer allows building the SALLM on its surface. In the case of Ag SERS substrate, the SALLM was deposited directly on its surface. The SERS spectra of the SALLMs were recorded in the C-H stretching (2800-3000 cm(-1)) and the fingerprint (<1.800 cm(-1)) regions. It has been demonstrated that the SERS spectra of the SALLM recorded on Au substrate differs from that one recorded on Ag SERS substrate. These spectral differences were found to be determined by the different interaction mechanisms of the lipid molecules with nanostructured surfaces. (C) 2017 Elsevier B.V. All rights reserved.

In recent years, there has been remarkable progress in the reduction and functionalization of graphene oxide (GO) using nanoparticles and high-energy optical photons. Most of these reactions are carried out in solutions, whereas the local modification of GO on solid substrates still remains a challenge. In this work, we demonstrate the local reduction of GO and its further destruction, leading to the synthesis of polyaromatic hydrocarbons (PAHs) stimulated by localized surface plasmons (LSPs). The reduction of GO and the synthesis of PAHs have been carried out on a substrate designed for surface-enhanced Raman spectroscopy (SERS). We found that LSPs initiate the destruction of water molecules entrapped in the nanogaps between silver nanoparticles after the deposition of GO from the aqueous suspension. It was demonstrated that OH radicals, as a result of water decomposition, initiate the reduction of GO, leading to the synthesis of PAHs. The reactions have been observed in real time by using SERS. The measurement of current-voltage (I-V) characteristics through conductive atomic force microscopy (AFM), recorded in an LSP-stimulated area, have shown the increased electrical conductivity (more than ten times) compared with the conductivity of GO. The synthesis of new compounds in the LSP-stimulated area has been confirmed by the appearance of new peaks in the Raman spectra and nonlinear I-V characteristics typical for PAHs. We show that the used method allows the local modification of electrical properties of GO and controlled nanopattering of organic compounds on the surface.

The Raman scattering phenomenon known for more than 80 years, during the last decades is gaining more and more attention in analytical applications and can provide chemical finger prints of cells, tissues or biofluids. In contrast to established analytical techniques, Raman spectroscopy provides label-free, non-destructive, chemically selective and spatially resolved analysis. The high chemical specificity, simple sample preparation procedure and the ability to use advanced optical technologies in the visible or near-infrared spectral range have recently led to an increase in medical diagnostic applications of Raman spectroscopy. The basic idea of the application of Raman spectroscopy in medicine is the hypotesis that deseases effect the molecular structure of cells and can be detected and quantified by Raman spectroscopy. Based on advanced technical development, Raman spectroscopy can be implemented into diverse setups ranging from confocal microscopes for acquisition of threedimensional spectral information up to hand-held fiber devices for direct use in clinical diagnostics. Furthermore, recent progress in the field of multivariate data analysis allows for processing such complex spectral data into scientific information for fundamental research as well as for patients to obtain objective data for diagnosis [1]. The new strategies have been developed to overcome the weak signal problems of Raman spectroscopy by application of non-linear optics and localized nanoplasmonic effects to enhance the Raman signals to increase the acquisition speed and accuracy of diagnosis. Application of nanotechnology solutions in Raman spectroscopy and microscopy, like SERS and TERS, open a new directions in Nanomedicine, based on a single molecule science [2]. Physiological investigations of tissues and cells

Nanoparticles (NP) are broadly exploited in biomedical sciences in order to develop various methods of targeted drug delivery, novel biosensors and new therapeutic pathways.However, relatively little is known in the negotiation of NPs with complex biological environments.NP interaction with cell membranes can damage the cell membrane and cause toxicity; therefore, examining interactions between NPs and cell membranes is crucial to understanding NP toxicity mechanisms and the development of safe and nontoxic NP-based commercial and therapeutic applications.To gain a physical understanding of NP-membrane interactions, we used a simplified system built of well-defined synthetic lipid bilayers and NP.The interaction of nanoparticles (NPs) with supported lipid bilayers (SLB) can lead to structural modification of the SLB and affect the structure and dynamic of lipids.In this work TiO 2 and ZnO nanoparticles were chosen because of wide applications and usage in industry of papers, inks, medicines, food products, cosmetics, toothpastes and skin care products and among others.Therefore, a better understanding of the interactions between NP and lipid membrane may help to better clarify the potential risk of NPs.The interaction between ZnO and TiO 2 NPs and lipid membranes was studied by using scanning supercritical angle fluorescence microscopy.The biological response to elucidated changes in lipid membrane structure/characteristics under ZnO or TiO 2 NP influence was tested by fluorescence correlation spectroscopy.It was found the significant reduction of lipids diffusion mobility, which can be explained as a result of lipid-ZnO aggregates binding, depending on ZnO concentration.The TiO 2 has a little effect on lipids diffusion mobility.