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Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based...
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Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials

A special issue of Chemosensors (ISSN 2227-9040). This special issue belongs to the section "Applied Chemical Sensors".

Deadline for manuscript submissions: closed (15 February 2022) | Viewed by 19571

Special Issue Editors

Dr. Eugenia-Lenuta Fagadar-Cosma

E-Mail Website
Chief Guest Editor
“Coriolan Dragulescu” Institute of Chemistry, 24 Mihai Viteazu Ave., 300223 Timisoara, Romania
Interests: organic chemistry; porphyrins; metalloporphyrins; colloid chemistry; material chemistry; sol-gel processes; nanomaterials; silica matrices; hybrid nanomaterials; aggregates; sensors; electrochemical mediators; catalysts; corrosion inhibitors; adsorbents
Special Issues, Collections and Topics in MDPI journals
Dr. Stela-Maria Pruneanu

E-Mail Website
Co-Guest Editor
National Institute for Research and Development of Isotopic and Molecular Technologies, Donat Street, No. 67-103, RO-400293 Cluj-Napoca, Romania
Interests: graphene synthesis by electrochemical methods; graphene-modified electrodes; electrochemical detection of biomolecules (e.g., adenine; guanine; dopamine); pharmaceutical drugs and organic polutants
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Porphyrins, π-conjugated organic macrocycles, are well-known for their interesting architectural/conformational flexibility and optical, electronic, and versatile metal complexation properties; therefore, their derivatives find applications in a variety of sensors/biosensors.

On the other hand, graphene is an excellent immobilizing matrix in electrochemical sensor applications due to its large surface area, high conductivity and stability, biocompatibility, inertness, and good adhesion. Increasing the sensitivity and selectivity of graphene through functionalization with attractive building blocks such as porphyrins, metalloporphyrins, and heavy metal-binding proteins will bring remarkable advances.

This Special Issue is addressed to all types of sensors for pH, biomolecules, and other analytes with medical relevance using as sensing materials porphyrins, porphyrin-based hybrid materials, as well as graphene, functionalized graphene, and graphene-based materials.

An expected approach will be that of design and tailoring of required properties of novel hybrid/composite sensitive materials based on porphyrins and graphene and inorganic partners, such as: silica matrices, plasmonic nanomaterials, polymers or calcogenides. Functionalization and assembly in chemo-bio sensitive structures, such as conjugated systems of porphyrins dimmers/trimers for fluorimetric detection or porphyrin–calixarene systems are in the scope of this issue.

Other targeted aspects would cover the obtaining and full characterization through state-of-the-art techniques of the sensitive materials, the description of methods for thin layer deposition to obtain modified electrodes or composite layers, the integration, optical and electrochemical investigation, and selection of the most promising for sensing capacity systems, and the increasing knowledge in supramolecular occurring phenomena and in providing a mechanism for detection.

The main aim of this issue is to acknowledge simple and fast analysis of several health parameters, such as pH, 8-OHdG, dopamine, histamine, β-carotene, ascorbic acid, uric acid, hydrogen peroxide, and heavy metals, from different biological samples, which allows the identification of possible diseases at an early stage (diabetes, cardio and hormone diseases, incipient cancer).

Prof. Eugenia Fagadar-Cosma
Dr. Stela-Maria Pruneanu
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Chemosensors is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Porphyrins
  • Porphyrin-based hybrid materials
  • Graphene
  • Graphene–nanoparticles composites
  • Heteroatom-doped graphene
  • pH sensors
  • Detection of analytes with medical relevance
  • Electrochemical detection of biomolecules
  • Optical chemical sensors
  • Electrochemical mediators
  • Screen-printed microelectrodes

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Published Papers (6 papers)

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Research

12 pages, 2935 KiB  
Article
Phosphorous (V) Corrole Fluorophores for Nitrite Assessment in Environmental and Biological Samples
by Fabrizio Caroleo, Giovanni Diedenhofen, Alexandro Catini, Corrado Di Natale, Roberto Paolesse and Larisa Lvova
Chemosensors 2022, 10(3), 107; https://doi.org/10.3390/chemosensors10030107 - 10 Mar 2022
Cited by 8 | Viewed by 2487
Abstract
Two phosphorous (V) corrole complexes, [5,10,15-pentafluorophenyl corrole] phosphorous (V) (PFCorr) and [10-(4-trimethylsilylphenyl)-5,15-dimesityl-corrole] phosphorous (V) (PCorr) were synthesized and tested as nitrite-sensitive fluorophores. Fluorimetry studies on ligand sensitivity towards anions were carried out in solution, then inside polymeric membrane optodes [...] Read more.
Two phosphorous (V) corrole complexes, [5,10,15-pentafluorophenyl corrole] phosphorous (V) (PFCorr) and [10-(4-trimethylsilylphenyl)-5,15-dimesityl-corrole] phosphorous (V) (PCorr) were synthesized and tested as nitrite-sensitive fluorophores. Fluorimetry studies on ligand sensitivity towards anions were carried out in solution, then inside polymeric membrane optodes deposited on glass, and finally by functionalized SiO2 nanoparticles deposited on a paper support. The selective fluorescence quenching was registered upon addition of an increasing amount of NO2− ions for both ligands. The influence on the PFCorr optode’s response of the lipophilic sites’ functionalization was investigated. The sensors’ suitability for nitrite assessment in natural waters at levels 10-fault lower than the WHO’s recommended maximum concentration level of 3 mg/L was demonstrated. Full article
(This article belongs to the Special Issue Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials)
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16 pages, 5991 KiB  
Article
Nitrogen and Sulfur Co-Doped Graphene as Efficient Electrode Material for L-Cysteine Detection
by Codruța Varodi, Florina Pogăcean, Alexandra Cioriță, Ovidiu Pană, Cristian Leoștean, Bogdan Cozar, Teodora Radu, Maria Coroș, Raluca Ioana Ștefan-van Staden and Stela-Maria Pruneanu
Chemosensors 2021, 9(6), 146; https://doi.org/10.3390/chemosensors9060146 - 16 Jun 2021
Cited by 27 | Viewed by 3429
Abstract
Two graphene samples co-doped with nitrogen and sulfur were synthesized by the hydrothermal method using thiourea as doping and reducing agent for graphene oxide (GO). An appropriate amount of thiourea was added to the aqueous dispersion of GO, previously sonicated for 30 min. [...] Read more.
Two graphene samples co-doped with nitrogen and sulfur were synthesized by the hydrothermal method using thiourea as doping and reducing agent for graphene oxide (GO). An appropriate amount of thiourea was added to the aqueous dispersion of GO, previously sonicated for 30 min. The mixture was poured into an autoclave and placed in the oven for 3 h, at 120 and 200 °C. The samples were denoted NSGr-120 and NSGr-200, respectively, in agreement with the reaction temperatures. They were next morphologically and structurally characterized by advanced techniques, such as SEM/TEM, XPS, XRD, and FTIR. According to XPS analysis, the NSGr-120 sample has higher amounts of heteroatoms in comparison with NSGr-200, indicating that the reaction temperature is a crucial factor that affects the doping degree. In order to reveal the influence of the doping degree on the electrochemical performances of graphene-modified electrodes, they were tested in solutions containing L-cysteine molecules. The electrode with the best electrocatalytic performances, GC/NSGr-120, was tested to detect L-cysteine in a pharmaceutical drug, proving its applicability in real sample analysis. Full article
(This article belongs to the Special Issue Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials)
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19 pages, 5621 KiB  
Article
Efficient Oxidase Biosensors Based on Bioelectrocatalytic Surfaces of Electrodeposited Ferrocenyl Polycyclosiloxanes—Pt Nanoparticles
by Alvaro Boluda, Carmen M. Casado, Beatriz Alonso and M. Pilar García Armada
Chemosensors 2021, 9(4), 81; https://doi.org/10.3390/chemosensors9040081 - 15 Apr 2021
Cited by 8 | Viewed by 2604
Abstract
The in-situ synthesis of catalytic surfaces with metallic nanoparticles must overcome the issues related to particle aggregation and polydispersity in the particle size. This work achieves it by using two electrodeposited ferrocenyl polycyclosiloxane polymers (MFPP and FPP) as templates for electro-synthesize Pt nanoparticles [...] Read more.
The in-situ synthesis of catalytic surfaces with metallic nanoparticles must overcome the issues related to particle aggregation and polydispersity in the particle size. This work achieves it by using two electrodeposited ferrocenyl polycyclosiloxane polymers (MFPP and FPP) as templates for electro-synthesize Pt nanoparticles (PtNPS). In addition, this new electrode surface combines two efficient electrocatalysts: Ferrocene and Pt nanoparticles, with synergistic biocatalytic properties that constitute an electrocatalytic framework for the covalent immobilization of xanthine oxidase. In this work, we present the results of the kinetic, electrochemical and analytical studies of the prepared electrodes. These results showed that the PtNPs/FPP system is the best bioelectrocatalytic surface and improves other more complex xanthine oxidase devices based on the hydrogen peroxide oxidation, allowing the use of lower measuring potential with good sensitivity, wider linear ranges and low detection limits. In addition, this electrode provides the novelty of allowing the measurement of xanthine through the enzymatic consumption of oxygen at potential −0.1 V with a sensitivity of 1.10 A M−1 cm−2, linear ranges of 0.01–0.1 and 0.1–1.4 mM, low detection limit (48 nM) and long-term stability. The new device has been successfully applied to the determination of xanthine in fish meat. Full article
(This article belongs to the Special Issue Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials)
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17 pages, 5219 KiB  
Article
SnSe2-Zn-Porphyrin Nanocomposite Thin Films for Threshold Methane Concentration Detection at Room Temperature
by Adam Lőrinczi, Eugenia Fagadar-Cosma, Gabriel Socol, Andreea Mihăilescu, Elena Matei, Florinel Sava and Mariana Ştefan
Chemosensors 2020, 8(4), 134; https://doi.org/10.3390/chemosensors8040134 - 18 Dec 2020
Cited by 6 | Viewed by 3552
Abstract
Nanocomposite thin films, sensitive to methane at the room temperature (25–30 °C), have been prepared, starting from SnSe2 powder and Zn(II)-5,10,15,20-tetrakis-(4-aminophenyl)- -porphyrin (ZnTAPP) powder, that were fully characterized by XRD, UV-VIS, FT-IR, Nuclear Magnetic Resonance (1H-NMR and 13C-NMR), Atomic [...] Read more.
Nanocomposite thin films, sensitive to methane at the room temperature (25–30 °C), have been prepared, starting from SnSe2 powder and Zn(II)-5,10,15,20-tetrakis-(4-aminophenyl)- -porphyrin (ZnTAPP) powder, that were fully characterized by XRD, UV-VIS, FT-IR, Nuclear Magnetic Resonance (1H-NMR and 13C-NMR), Atomic Force Microscopy (AFM), SEM and Electron Paramagnetic Resonance (EPR) techniques. Film deposition was made by drop casting from a suitable solvent for the two starting materials, after mixing them in an ultrasonic bath. The thickness of these films were estimated from SEM images, and found to be around 1.3 μm. These thin films proved to be sensitive to a threshold methane (CH4) concentration as low as 1000 ppm, at a room temperature of about 25 °C, without the need for heating the sensing element. The nanocomposite material has a prompt and reproducible response to methane in the case of air, with 50% relative humidity (RH) as well. A comparison of the methane sensing performances of our new nanocomposite film with that of other recently reported methane sensitive materials is provided. It is suitable for signaling gas presence before reaching the critical lower explosion limit concentration of methane at 50,000 ppm. Full article
(This article belongs to the Special Issue Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials)
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13 pages, 3376 KiB  
Article
Sensing and Interaction of His-Tagged CA19-9 Antigen with Graphene-Modified Electrodes
by Mihaela Mic, Codruta Varodi, Florina Pogacean, Crina Socaci, Maria Coros, Raluca-Ioana Stefan-van Staden and Stela Pruneanu
Chemosensors 2020, 8(4), 112; https://doi.org/10.3390/chemosensors8040112 - 5 Nov 2020
Cited by 6 | Viewed by 2339
Abstract
The electrochemical oxidation of CA19-9 tagged with L-Histidine (CA199-His) was investigated for the first time with screen-printed electrodes (DS) modified with graphene oxide (DS/GO) or thermally reduced graphene oxide (DS/TRGO). Successive cyclic voltammograms (CV) measurements performed with bare and DS/TRGO electrodes proved that [...] Read more.
The electrochemical oxidation of CA19-9 tagged with L-Histidine (CA199-His) was investigated for the first time with screen-printed electrodes (DS) modified with graphene oxide (DS/GO) or thermally reduced graphene oxide (DS/TRGO). Successive cyclic voltammograms (CV) measurements performed with bare and DS/TRGO electrodes proved that the intensity of the oxidation peak (I peak) is time-dependent. In fact, the oxidation signal increased over time, reached a maximum and then decreased due to the saturation of the surface with CA199-His molecules. The interaction of CA199-His with GO, TRGO, or graphite was additionally studied by isothermal calorimetry, a useful tool for accessing information regarding the biomolecule adsorption on graphene surface. The adsorption of CA199-His on TRGO was generating a higher heat, suggesting quantitative and efficient interactions. At the same time, in the case of TRGO, the saturation was not reached, indicating the existence of more free binding sites than in the case of GO and graphite. As such, the carbohydrate marker CA199-His showed a higher affinity for the TRGO surface than for the graphite or GO surfaces. The lack of saturation in the case of TRGO may indicate a continuous structural modification of the antigen when interacting with the graphene surface. Full article
(This article belongs to the Special Issue Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials)
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15 pages, 3719 KiB  
Article
Novel Platinum-Porphyrin as Sensing Compound for Efficient Fluorescent and Electrochemical Detection of H2O2
by Eugenia Fagadar-Cosma, Nicoleta Plesu, Anca Lascu, Diana Anghel, Maria Cazacu, Catalin Ianasi, Gheorghe Fagadar-Cosma, Ion Fratilescu and Camelia Epuran
Chemosensors 2020, 8(2), 29; https://doi.org/10.3390/chemosensors8020029 - 23 Apr 2020
Cited by 12 | Viewed by 4065
Abstract
Metalloporphyrins are highly recognized for their capacity to act as sensitive substances used in formulation of optical, fluorescent, and electrochemical sensors. A novel compound, namely Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl) porphyrin, was synthesized by metalation with PtCl2(PhCN)2 of the corresponding porphyrin base and was [...] Read more.
Metalloporphyrins are highly recognized for their capacity to act as sensitive substances used in formulation of optical, fluorescent, and electrochemical sensors. A novel compound, namely Pt(II)-5,10,15,20-tetra-(4-allyloxy-phenyl) porphyrin, was synthesized by metalation with PtCl2(PhCN)2 of the corresponding porphyrin base and was fully characterized by UV-vis, fluorimetry, FT-IR, 1H-NMR, and 13C-NMR methods. The fluorescence response of this Pt-porphyrin in the presence of different concentrations of hydrogen peroxide was investigated. Besides, modified glassy carbon electrodes with this Pt-porphyrin (Pt-Porf-GCE) were realized and several electrochemical characterizations were comparatively performed with bare glassy carbon electrodes (GCE), in the absence or presence of hydrogen peroxide. The Pt-porphyrin demonstrated to be a successful sensitive material for the detection of hydrogen peroxide both by fluorimetric method in a concentration range relevant for biological samples (1.05–3.9 × 10−7 M) and by electrochemical method, in a larger concentration range from 1 × 10−6 M to 5 × 10−5 M. Based on different methods, this Pt-porphyrin can cover detection in diverse fields, from medical tests to food and agricultural monitoring, proving high accuracy (correlation coefficients over 99%) in both fluorimetric and electrochemical measurements. Full article
(This article belongs to the Special Issue Detection of Analytes with Medical Relevance Using Porphyrins and/or Graphene-Based Materials)
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