Publications by Year: 2024

2024
Mahdouani M, Bourguiga R, Gardelis S. A Theoretical Study of the Electron–Surface Optical Phonon Interaction in Monolayer Transition Metal Dichalcogenides Deposited on SiC and hexagonal BN Dielectric Substrates in the Vicinity of the Points K+(K−) of the Brillouin Zone. Materials [Internet]. 2024;17. WebsiteAbstract
We theoretically investigated the electron–surface optical phonon interaction across the long-range Fröhlich coupling in monolayer transition metal dichalcogenides, such as WS2, WSe2, MoS2, and MoSe2 monolayers, on SiC and hexagonal BN dielectric substrates. We employed the effective Hamiltonian in the K+(K−) valley of the hexagonal Brillouin zone to assess the electronic energy shifts induced by the interaction between electronic states and surface polar optical phonons. Our results indicate that the interaction between electrons and surface optical phonons depends upon the polar nature of the substrate. We have also calculated the polaronic oscillator strength, as well as the polaronic scattering rate of the lower polaron state in monolayer WS2, WSe2, MoS2, and MoSe2 on SiC and hexagonal BN dielectric substrates. As a result, we have theoretically proved the following: firstly, the enhancement of the polaronic scattering rate with temperature, and secondly, the notable influence of the careful selection of surrounding dielectrics on both the polaronic oscillator strength and the polaronic scattering rate. Thus, optimal dielectrics would be those exhibiting both elevated optical phonon energy and a high static dielectric constant.
Geka G, Kanioura A, Kochylas I, Likodimos V, Gardelis S, Dimitriou A, Papanikolaou N, Economou A, Kakabakos S, Petrou P. Comparison of Survivin Determination by Surface-Enhanced Fluorescence and Raman Spectroscopy on Nanostructured Silver Substrates. Biosensors [Internet]. 2024;14. WebsiteAbstract
Survivin belongs to a family of proteins that promote cellular proliferation and inhibit cellular apoptosis. Its overexpression in various cancer types has led to its recognition as an important marker for cancer diagnosis and treatment. In this work, we compare two approaches for the immunochemical detection of survivin through surface-enhanced fluorescence or Raman spectroscopy using surfaces with nanowires decorated with silver nanoparticles in the form of dendrites or aggregates as immunoassays substrates. In both substrates, a two-step non-competitive immunoassay was developed using a pair of specific monoclonal antibodies, one for detection and the other for capture. The detection antibody was biotinylated and combined with streptavidin labeled with rhodamine for the detection of surface-enhanced fluorescence, while, for the detection via Raman spectroscopy, streptavidin labeled with peroxidase was used and the signal was obtained after the application of 3,3′,5,5′-tetramethylbenzidine (TMB) precipitating substrate. It was found that the substrate with the silver dendrites provided higher fluorescence signal intensity compared to the substrate with the silver aggregates, while the opposite was observed for the Raman signal. Thus, the best substrate was used for each detection method. A detection limit of 12.5 pg/mL was achieved with both detection approaches along with a linear dynamic range up to 500 pg/mL, enabling survivin determination in human serum samples from both healthy and ovarian cancer patients for cancer diagnosis and monitoring purposes.
Kanioura A, Geka G, Kochylas I, Likodimos V, Gardelis S, Dimitriou A, Papanikolaou N, Kakabakos S, Petrou P. Superoxide Dismutase Determination on Silver Nanostructured Substrates through Surface-Enhanced Photoluminescence. Proceedings [Internet]. 2024;104. WebsiteAbstract
Oxidative stress is defined by an imbalance between the generation of reactive oxygen species and the biological system’s ability to neutralize them. This condition is commonly linked to various pathological conditions [1]. Superoxide dismutase (SOD) is a widely used enzyme to assess oxidative stress, and various techniques have been developed for its detection in biological samples such as blood, urine, and saliva [2]. Surface-enhanced photoluminescence (PL) is a particularly sensitive method, offering minimal interference from the sample matrix [3]. In this work, silver nanostructured surfaces were implemented as substrates for the immunochemical determination of SOD in synthetic saliva through PL. The substrates were prepared using a single-step metal-assisted chemical etching method (MACE), resulting in the formation of silicon nanowires decorated with silver dendrites of approximately 1.5 μm in height [4]. For SOD detection, a three-step competitive immunoassay configuration was followed. Briefly, SOD was immobilized onto the substrates and then the functionalized substrates were incubated with mixtures of SOD with anti-SOD primary antibody, prepared either in assay buffer or synthetic saliva. Then, a solution of biotinylated anti-species specific antibody was added, followed by a reaction with streptavidin labelled with the fluorescent dye Rhodamine Red-X, and the signal was determined through an in-house developed optical set-up. The developed method presents similar or slightly lower sensitivity (detection limit 0.05 μg/mL) compared to the literature; however, it does not require labor-intensive sample pretreatment steps [5,6]. The aforementioned findings demonstrate the capability of the developed method to detect superoxide dismutase in natural saliva, in order to evaluate the oxidative stress status of an organism.
Kanioura A, Geka G, Kochylas I, Likodimos V, Gardelis S, Dimitriou A, Papanikolaou N, Kakabakos S, Petrou P. Superoxide Dismutase Detection on Silver Nanostructured Substrates through Surface-Enhanced Spectroscopic Techniques. Chemosensors [Internet]. 2024;12. WebsiteAbstract
Oxidative stress refers to the overproduction of reactive oxygen species and is often associated with numerous pathological conditions. Superoxide dismutase (SOD) is a widely used enzyme for evaluating oxidative stress, with numerous methods being developed for its detection in biological specimens like blood, urine, and saliva. In this study, a simple metal-assisted chemical etching method was employed for the fabrication of nanostructured silicon surfaces decorated with either silver dendrites or silver aggregates. Those surfaces were used as substrates for the immunochemical determination of SOD in synthetic saliva through surface-enhanced Raman spectroscopy (SERS) and surface-enhanced fluorescence (SEF). The immunoassay was based on a 3-step competitive assay format, which included, after the immunoreaction with the specific anti-SOD antibody, a reaction with a biotinylated secondary antibody and streptavidin. Streptavidin labeled with peroxidase was used in combination with a precipitating tetramethylbenzidine substrate for detection through SERS, whereas for SEF measurements, streptavidin labeled with the fluorescent dye Rhodamine Red-X was utilized. Both immunoassays were sensitive, with a detection limit of 0.01 μg/mL and a linear dynamic range from 0.03 to 3.3 μg/mL, enabling the evaluation of the oxidative stress status of an organism.
Pylarinou M, Sakellis I, Tsipas P, Gardelis S, Psycharis V, Dimoulas A, Stergiopoulos T, Likodimos V. Light trapping and electron transfer in plasmonic–photonic Ag{,} Au modified Mo-BiVO4 inverse opal photoelectrocatalysts. Nanoscale [Internet]. 2024:-. WebsiteAbstract
Plasmonic photocatalysis based on metal-semiconductor heterojunctions is considered a key strategy to evade the inherent limitations of poor light harvesting and charge separation of semiconductor photocatalysts. It can be profitably combined with three-dimensional photonic crystals (PCs) that offer an ideal scaffold for loading plasmonic nanoparticles and a unique architecture to intensify photon capture. In this work{,} Mo-doped BiVO4 inverse opals were applied as visible light-responsive photonic hosts of Ag and/or Au plasmonic nanoparticles in order to exploit the synergy of plasmonic and photonic amplification effects with interfacial charge transfer for the photoelectrocatalytic degradation of recalcitrant pharmaceutical contaminants under visible light. Photoelectrochemical evaluation indicated a major contribution from hot spot-assisted local field enhancement{,} most pronounced for Ag/Mo-BiVO4 PCs due to the spectral overlap of the localized surface plasmon resonance with the electronic absorption and blue-edge slow photon region of Mo-BiVO4 PCs{,} in contrast to weak plasmonic sensitization effects for the Au-modified PCs. The diverse band alignment at the metal-semiconductor interfaces resulted in the enhanced photoelectrocatalytic degradation of tetracycline broad spectrum antibiotic by Ag/Mo-BiVO4 and the refractory ibuprofen drug by (Ag{,}Au)/Mo-BiVO4{,} attributed to the enhanced charge separation by electron transfer toward Ag nanoparticles. Combination of visible light activated semiconductor PCs and plasmonic nanoparticles with suitable band alignment and photonic band gap may provide a versatile approach for the rational design of efficient plasmonic-photonic photoeletrocatalysts.
Giannakopoulos K, Lasithiotakis M, Karakasis C, Gini M, Gardelis S, Karakassiliotis I, Mouti N, Xesfyngi Y, Manolis G, georgoutsou spyridonos M, et al. Spark Discharge Aerosol-generated copper-based nanoparticles: Structural & optical properties; application on the antiviral (SARS-CoV-2) and antibacterial improvement of face masks. ChemPlusChem [Internet]. 2024;n/a:e202400194. Publisher's VersionAbstract
Nanoparticle formation by Spark Discharge Aerosol Generation offers low-cost fabrication of nanoparticles, without the use of chemicals or vacuum. It produces aerosol particles of a few nanometers in size with high purity. In this work, copper-based - CuO (tenorite) and Cu- nanoparticles are produced, characterized and used to modify face mask air filters, achieving the introduction of antibacterial and antiviral properties. A range of characterization techniques have been employed, down to the atomic level. The majority of the particles are CuO (of a few nanometers in size that agglomerate to form aggregates), the remainder being a small number of larger Cu particles. The particles were deposited on various substrates, mainly fiber filters in order to study them and use them as biocidal agents. On face masks, their antibacterial activity against Escherichia coli (E.coli) results in a 100% decrease in bacteria cell viability. Their antiviral activity on face masks results in a 90% reduction of the Severe Acute Respiratory Syndrome Corona Virus 2 (SARS-CoV-2) viability, 15 minutes post the application of the virus stock solution. This highlights the effectiveness of this approach, its simplicity, its low cost and its excellent environmental credentials.
Apostolaki M-A, Sakellis E, Tsipas P, Gardelis S, Likodimos V. Surface-Enhanced Raman Spectroscopy on Ag−WO3/TiO2 Inverse Opal Film Substrates. Proceedings [Internet]. 2024;97. WebsiteAbstract
The synergetic effects of electromagnetic and chemical enhancements via the combination of semiconductor nanomaterials with noble metal nanoparticles is crucial to the performance of surface-enhanced Raman scattering (SERS). Here, WO3/TiO2 photonic crystal films in the form of three-dimensional inverse opals were fabricated via the co-assembly of polymer colloidal templates with water-soluble precursors in order to simultaneously grow both constituent metal oxides with tailored electronic properties and photonic band gaps. The surface modification of compositionally tuned WO3/TiO2 inverse opals by Ag nanoparticles is demonstrated to be an efficient method to boost SERS efficiency in the detection of 4−mercaptobenzoic acid via the synergy of plasmonic effects with charge transfer and slow-light trapping.
Kochylas I, Kanioura A, Geka G, Likodimos V, Gardelis S, Dimitriou A, Papanikolaou N, Kakabakos S, Petrou P. Surface Enhanced Raman Scattering (SERS) for the Detection of Oxidative Stress Markers Using Si Nanowires (SiNWs)/Ag Nanostructures Fabricated by Metal Assisted Chemical Etching (MACE). Proceedings [Internet]. 2024;97. WebsiteAbstract
In this work, silicon nanowires were constructed by metal-assisted chemical etching and decorated with silver nanoparticles and used as substrates for the SERS determination of oxidative stress markers, namely glutathione, malondialdehyde and catalase. The assays were sensitive, with detection limits of 50 and 3.2 nM for glutathione and malondialdehyde, respectively, and 0.5 μg/mL for catalase, indicating the capability of the proposed substrates to be implemented for the determination of various oxidative stress markers.