Laser-induced spatially-selective tailoring of high-index dielectric metasurfaces.

Optically resonant high-index dielectric metasurfaces featuring Mie-type electric and magnetic resonances are usually fabricated by means of planar technologies, which limit the degrees of freedom in tunability and scalability of the fabricated systems. Therefore, we propose a complimentary post-processing technique based on ultrashort (≤ 10 ps) laser pulses. The process involves thermal effects: crystallization and reshaping, while the heat is localized by a high-precision positioning of the focused laser beam. Moreover, for the first time, the resonant behavior of dielectric metasurface elements is exploited to engineer a specific absorption profile, which leads to a spatially-selective heating and a customized modification. Such technique has the potential to reduce the complexity in the fabrication of non-uniform metasurface-based optical elements. Two distinct cases, a spatial pixelation of a large-scale metasurface and a height modification of metasurface elements, are explicitly demonstrated.

Rapid detection of the aspergillosis biomarker triacetylfusarinine C using interference-enhanced Raman spectroscopy.

Triacetylfusarinine C (TAFC) is a siderophore produced by certain fungal species and might serve as a highly useful biomarker for the fast diagnosis of invasive aspergillosis. Due to its renal elimination, the biomarker is found in urine samples of patients suffering from Aspergillus infections. Accordingly, non-invasive diagnosis from this easily obtainable body fluid is possible. Within our contribution, we demonstrate how Raman microspectroscopy enables a sensitive and specific detection of TAFC. We characterized the TAFC iron complex and its iron-free form using conventional and interference-enhanced Raman spectroscopy (IERS) and compared the spectra with the related compound ferrioxamine B, which is produced by bacterial species. Even though IERS only offers a moderate enhancement of the Raman signal, the employment of respective substrates allowed lowering the detection limit to reach the clinically relevant range. The achieved limit of detection using IERS was 0.5 ng of TAFC, which is already well within the clinically relevant range. By using an extraction protocol, we were able to detect 1.4 µg/mL TAFC via IERS from urine within less than 3 h including sample preparation and data analysis. We could further show that TAFC and ferrioxamine B can be clearly distinguished by means of their Raman spectra even in very low concentrations.

Raman Signal Enhancement Tunable by Gold-Covered Porous Silicon Films with Different Morphology.

The ease of fabrication, large surface area, tunable pore size and morphology as well surface modification capabilities of a porous silicon (PSi) layer make it widely used for sensoric applications. The pore size of a PSi layer can be an important parameter when used as a matrix for creating surface-enhanced Raman scattering (SERS) surfaces. Here, we evaluated the SERS activity of PSi with pores ranging in size from meso to macro, the surface of which was coated with gold nanoparticles (Au NPs). We found that different pore diameters in the PSi layers provide different morphology of the gold coating, from an almost monolayer to 50 nm distance between nanoparticles. Methylene blue (MB) and 4-mercaptopyridine (4-MPy) were used to describe the SERS activity of obtained Au/PSi surfaces. The best Raman signal enhancement was shown when the internal diameter of torus-shaped Au NPs is around 35 nm. To understand the role of plasmonic resonances in the observed SERS spectrum, we performed electromagnetic simulations of Raman scattering intensity as a function of the internal diameter. The results of these simulations are consistent with the obtained experimental data.

UV-Raman Spectroscopic Identification of Fungal Spores Important for Respiratory Diseases.

Fungal spores are one of several environmental factors responsible for causing respiratory diseases like asthma, chronic obstructive pulmonary disease (COPD), and aspergillosis. These spores also are able to trigger exacerbations during chronic forms of disease. Different fungal spores may contain different allergens and mycotoxins, therefore the health hazards are varying between the species. Thus, it is highly important quickly to identify the composition of fungal spores in the air. In this study, UV-Raman spectroscopy with an excitation wavelength of 244 nm was applied to investigate eight different fungal species implicated in respiratory diseases worldwide. Here, we demonstrate that darkly colored spores can be directly examined, and UV-Raman spectroscopy provides the information sufficient for classifying fungal spores. Classification models on the genus, species, and strain levels were built using a combination of principal component analysis and linear discriminant analysis followed by evaluation with leave-one-batch-out-cross-validation. At the genus level an accuracy of 97.5% was achieved, whereas on the species level four different Aspergillus species were classified with 100% accuracy. Finally, classifying three strains of Aspergillus fumigatus an accuracy of 89.4% was reached. These results demonstrate that UV-Raman spectroscopy in combination with innovative chemometrics allows for fast identification of fungal spores and can be a potential alternative to currently used time-consuming cultivation.

Detection of Pseudomonas aeruginosa Metabolite Pyocyanin in Water and Saliva by Employing the SERS Technique.

Pyocyanin (PYO) is a metabolite specific for Pseudomonas aeruginosa. In the case of immunocompromised patients, it is currently considered a biomarker for life-threating Pseudomonas infections. In the frame of this study it is shown, that PYO can be detected in aqueous solution by employing surface-enhanced Raman spectroscopy (SERS) combined with a microfluidic platform. The achieved limit of detection is 0.5 µM. This is ~2 orders of magnitude below the concentration of PYO found in clinical samples. Furthermore, as proof of principle, the SERS detection of PYO in the saliva of three volunteers was also investigated. This body fluid can be collected in a non-invasive manner and is highly chemically complex, making the detection of the target molecule challenging. Nevertheless, PYO was successfully detected in two saliva samples down to 10 µM and in one sample at a concentration of 25 µM. This indicates that the molecules present in saliva do not inhibit the efficient adsorption of PYO on the surface of the employed SERS active substrates.

5-aminolevulinic-acid-based fluorescence spectroscopy and conventional colposcopy for in vivo detection of cervical pre-malignancy.

BACKGROUND: Sensitized fluorescence diagnostics are based on selective accumulation of photosensitizer in the tissue where carcinogenesis has started. The present study compared topical 5-aminolevulinic acid (5-ALA)-based fluorescence spectroscopy (FS) in vivo with conventional colposcopy for cervical intraepithelial neoplasia (CIN) detection. METHODS: We enrolled 48 patients who were referred for colposcopy because of high-grade changes in cervical cytology. Every inspected cervix was divided in to quadrants, and there were 174 quadrants included in the study. Each patient had a cytological smear, colposcopy, FS and histopathological analysis. For FS, 3% 5-ALA cream was used topically and after an average 135 min incubation, fluorescence spectra were recorded from the cervix in vivo. FS and colposcopy results were correlated with histopathology. RESULTS: All spectra were evaluated by a ratio of the protoporphyrin IX fluorescence intensity at 634 nm and autofluorescence intensity at 510 nm. For proper grouping of low-risk and high-risk cases, a threshold of 3.87 was calculated. Data per quadrant showed that FS had higher sensitivity than colposcopy (71.7% vs 67.4%) but specificity was greater for colposcopy (86.6% vs 75.6%). Combination of the methods showed higher sensitivity (88.0% vs 67.4%) but reduced specificity (88.0% and 69.5%), but it had the highest number of correctly identified high-risk changes and the highest (79.3%) accuracy. Data for each patient showed FS sensitivity of 91.2%, which was greater than for colposcopy (88.2%). Higher overdiagnosis resulted in decreased specificity for fluorescence methodology-71.4% versus 78.6% for colposcopy. In both cases, accuracy was 85.4% and effectiveness was >80%, which means that both methods can be used to determine high-risk cervical intraepithelial neoplasia. The diagnostic sensitivity of 97.1% for this complementary diagnosis indicates that it could be the best choice for detection of high-risk changes. CONCLUSIONS: 5-ALA-based FS is an objective method, requiring short-term administration for appropriate fluorescence measurements. FS is a promising diagnostic tool with similar accuracy as colposcopy but with the potential advantage of providing objective results.

Towards Raman spectroscopy of urine as screening tool.

For the screening purposes urine is an especially attractive biofluid, since it offers easy and noninvasive sample collection and provides a snapshot of the whole metabolic status of the organism, which may change under different pathological conditions. Raman spectroscopy (RS) has the potential to monitor these changes and utilize them for disease diagnostics. The current study utilizes mouse models aiming to compare the feasibility of the urine based RS combined with chemometrics for diagnosing kidney diseases directly influencing urine composition and respiratory tract diseases having no direct connection to urine formation. The diagnostic models for included diseases were built using principal component analysis with linear discriminant analysis and validated with a leave-one-mouse-out cross-validation approach. Considering kidney disorders, the accuracy of 100% was obtained in discrimination between sick and healthy mice, as well as between two different kidney diseases. For asthma and invasive pulmonary aspergillosis achieved accuracies were noticeably lower, being, respectively, 77.27% and 78.57%. In conclusion, our results suggest that RS of urine samples not only provides a solution for a rapid, sensitive and noninvasive diagnosis of kidney disorders, but also holds some promises for the screening of nonurinary tract diseases.

Rapid detection of the bacterial biomarker pyocyanin in artificial sputum using a SERS-active silicon nanowire matrix covered by bimetallic noble metal nanoparticles.

Early stage detection of Pseudomonas infections is life-saving, especially in the case of patients with cystic fibrosis. Pyocyanin (PYO) is a specific metabolite of the Pseudomonas aeruginosa bacteria, and detection of it directly in the sputum can significantly reduce the diagnosis time of the infection. In the present study, aiming to achieve this goal, a simple and cost-effective surface-enhanced Raman spectroscopy (SERS) detection platform was proposed. For this, a silicon nanowire (SiNW) matrix, produced by metal-assisted chemical etching of silicon substrates was variously modified by noble metal (silver and gold) nanoparticles (NPs) and tested for the detection of the metabolite PYO in the complex matrix of artificial sputum. We found the SERS substrate with Ag NPs on the bottom of SiNWs and deposited bimetallic Ag/Au NPs on the top of them the best suited for the sensitive detection of PYO. The investigated plasmonic substrate showed good point-to-point and batch-to-batch signal reproducibility and allowed for the detection of PYO in artificial sputum down to 6.25 µM, which is the required sensitivity for clinical applications.

3D Cinema and Headache: The First Evidential Relation and Analysis of Involved Factors.

BACKGROUND: A possible link between 3D movies and headache (HA) has never been a target of specific and systematic investigations. The aim of this study was to investigate the relationship between 3D cinema and HA and to evaluate possible risk factors of developing HA during or after watching a 3D movie. METHODS: This was a prospective, non-randomized, observational study. Six thousand specifically designed questionnaires were distributed to consecutive cinema visitors. Relative HA risks for 2D- vs. 3D-movie visitors and the effects of background variables were analyzed. RESULTS: The questionnaire was filled and returned by 1293 persons. The mean age of responders was 33.0 ± 11.3 years. Individuals who viewed 3D movies reported HA during or after the movie 1.61 times more often than 2D-movie viewers (11.1% in 3D vs. 7.2% in 2D movies, p = 0.017). The risk was higher in women: 2.65 times for 2D (p = 0.019) and 1.85 times for 3D movies (p = 0.06), and decreased with age by 4.6% with each year for 2D (p = 0.0035) and by 3.2% for 3D movies (p = 0.0098). Among 3D-movie visitors, those with previous HAs were 4.17 times more prone to get a cinema-induced HA (p = 0.02). The risk was the highest for persons with migraine (OR = 3.37, p = 0.001). CONCLUSION: For the first time, it was evidentially shown that 3D movies can provoke HA. Persons at risk are mostly younger women and/or migraineurs. Based on our results, for those belonging to the aforementioned risk groups, it can be mainly recommended to choose passive 3D technology and to view movies from the farthest possible distance.