Federica Mandoj

The development of novel sensing materials and analytical systems remains challenging nowadays. Among various transduction principles employed in chemical sensors, the optical transduction is often preferred, due to the fast response time, simplicity of preparation, and easy signal acquisition of optodes. In this contribution, the main aspects of novel optical sensor development and their application in both single and array configurations for liquid sample analysis will be discussed. The applications of fluorimetric and colorimetric all-solid-state optical sensors and sensory arrays recently developed or under investigation for ecological monitoring, quality assessment, and medical and health care will be illustrated.

In this work, we have described the synthesis and characterization of novel zinc (II) phthalocyanine bearing four 2-(2,4-dichloro-benzyl)-4-(1,1,3,3-tetramethyl-butyl)-phenoxy substituents on the peripheral positions. The compound was characterized by elemental analysis and different spectroscopic techniques, such as FT-IR, ¹H NMR, MALDI-TOF, and UV-Vis. The Zn (II) phthalocyanine shows excellent solubility in organic solvents such as dichloromethane (DCM), n-hexane, chloroform, tetrahydrofuran (THF), and toluene. Photochemical and electrochemical characterizations of the complex were performed by UV-Vis, fluorescence spectroscopy, and cyclic voltammetry. Its good solubility allows a direct deposition of this compound as film, which has been tested as a solid-state sensing material in gravimetric chemical sensors for gas detection, and the obtained results indicate its potential for qualitative discrimination and quantitative assessment of various volatile organic compounds, among them methanol, n-hexane, triethylamine (TEA), toluene and DCM, in a wide concentration range.

Optical chemical sensors are widely applied in many fields of modern analytical practice, due to their simplicity in preparation and signal acquisition, low costs, and fast response time. Moreover, the construction of most modern optical sensors requires neither wire connections with the detector nor sophisticated and energy-consuming hardware, enabling wireless sensor development for a fast, in-field and online analysis. In this review, the last five years of progress (from 2017 to 2021) in the field of optical chemical sensors development for persistent organic pollutants (POPs) is provided. The operating mechanisms, the transduction principles and the types of sensing materials employed in single selective optical sensors and in multisensory systems are reviewed. The selected examples of optical sensors applications are reported to demonstrate the benefits and drawbacks of optical chemical sensor use for POPs assessment.

Porphyrins and carbon nanomaterials are among the most widely investigated and applied compounds, both offering multiple options to modulate their optical, electronic and magnetic properties by easy and well-established synthetic manipulations. Individually, they play a leading role in the development of efficient and robust chemical sensors, where they detect a plethora of analytes of practical relevance. But even more interesting, the merging of the peculiar features of these single components into hybrid nanostructures results in novel materials with amplified sensing properties exploitable in different application fields, covering the areas of health, food, environment and so on. In this contribution, we focused on recent examples reported in literature illustrating the integration of different carbon materials (i.e., graphene, nanotubes and carbon dots) and (metallo)porphyrins in heterostructures exploited in chemical sensors operating in liquid as well as gaseous phase, with particular focus on research performed in the last four years.

An overview of the solvent-driven aggregation of a series of chiral porphyrin derivatives studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and solubility in aqueous media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent composition, forming architectures with supramolecular chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the number and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concentration. Additionally, Molecular Mechanics calculations can give insights into the intimate nature of the driving forces governing the self-assembly process. The critical use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials.

A novel porphyrin ligand, Zn(II)TPP-BPI-crown (ZnPC), functionalized with two dibenzo-crown-ether moieties was synthesized and tested as cation-sensitive ionophore. Fluorescence studies on ligand sensitivity towards a number of different metal cations (Na⁺, K⁺, Li⁺, Ca²⁺, Mg²⁺, Co²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Zn²⁺ and NH₄⁺) were carried out first in solution and then inside polymeric membrane optodes. Emission light signal was sufficiently brilliant to be captured by a low-cost computer webcam, while a commercial blue-light LED served as monochromic excitation light source. The influence on the ZnPC optode response of the lipophilic sites functionalization was investigated. The visibly (naked eye) observed color change of sensing material from green to red demonstrated the suitability of the ZnPC-based optodes to perform fast monitoring of Cu(II) ions in the concentration range between 6.6 × 10⁻⁷ and 2.4 × 10⁻² mol/L with a low detection limit (estimated by s/n = 3 method) of 0.3 mg/L, which is lower than WHO guideline value of 2 mg/L.