Martina Marinelli, MSc


Recent publications
1.Nakielski P., Kosik-Kozioł A., Rinoldi C., Rybak D., Namdev M., Jacob W., Lehmann T., Głowacki M., Bogusz S., Rzepna M., Marinelli M., Lanzi M., Dror S., Sarah M., Dmitriy S., Pierini F., Injectable PLGA Microscaffolds with Laser-Induced Enhanced Microporosity for Nucleus Pulposus Cell Delivery, Small, ISSN: 1613-6810, DOI: 10.1002/smll.202404963, pp.2404963-1-15, 2024
Abstract:

Intervertebral disc (IVD) degeneration is a leading cause of lower back pain (LBP). Current treatments primarily address symptoms without halting the degenerative process. Cell transplantation offers a promising approach for early-stage IVD degeneration, but challenges such as cell viability, retention, and harsh host environments limit its efficacy. This study aimed to compare the injectability and biocompatibility of human nucleus pulposus cells (hNPC) attached to two types of microscaffolds designed for minimally invasive delivery to IVD. Microscaffolds are developed from poly(lactic-co-glycolic acid) (PLGA) using electrospinning and femtosecond laser structuration. These microscaffolds are tested for their physical properties, injectability, and biocompatibility. This study evaluates cell adhesion, proliferation, and survival in vitro and ex vivo within a hydrogel-based nucleus pulposus model. The microscaffolds demonstrate enhanced surface architecture, facilitating cell adhesion and proliferation. Laser structuration improved porosity, supporting cell attachment and extracellular matrix deposition. Injectability tests show that microscaffolds can be delivered through small-gauge needles with minimal force, maintaining high cell viability. The findings suggest that laser-structured PLGA microscaffolds are viable for minimally invasive cell delivery. These microscaffolds enhance cell viability and retention, offering potential improvements in the therapeutic efficiency of cell-based treatments for discogenic LBP.

Affiliations:
Nakielski P.-IPPT PAN
Kosik-Kozioł A.-IPPT PAN
Rinoldi C.-IPPT PAN
Rybak D.-IPPT PAN
Namdev M.-other affiliation
Jacob W.-other affiliation
Lehmann T.-other affiliation
Głowacki M.-Jagiellonian University (PL)
Bogusz S.-other affiliation
Rzepna M.-other affiliation
Marinelli M.-other affiliation
Lanzi M.-University of Bologna (IT)
Dror S.-other affiliation
Sarah M.-other affiliation
Dmitriy S.-other affiliation
Pierini F.-IPPT PAN
2.Zargarian S., Zakrzewska A., Kosik-Kozioł A., Bartolewska M., Shah S., Li X., Su Q., Petronella F., Marinelli M., De Sio L., Lanzi M., Ding B., Pierini F., Advancing resource sustainability with green photothermal materials: Insights from organic waste-derived and bioderived sources, nanotechnology reviews, ISSN: 2191-9097, DOI: 10.1515/ntrev-2024-0100, Vol.13, No.1, pp.20240100-1-39, 2024
Abstract:

Recently, there has been a surge of interest in developing new types of photothermal materials driven by the ongoing demand for efficient energy conversion, environmental concerns, and the need for sustainable solutions. However, many existing photothermal materials face limitations such as high production costs or narrow absorption bands, hindering their widespread application. In response to these challenges, researchers have redirected their focus toward harnessing the untapped potential of organic waste-derived and bioderived materials. These materials, with photothermal properties derived from their intrinsic composition or transformative processes, offer a sustainable and cost-effective alternative. This review provides an extended categorization of organic waste-derived and bioderived materials based on their origin. Additionally, we investigate the mechanisms underlying the photothermal properties of these materials. Key findings highlight their high photothermal efficiency and versatility in applications such as water and energy harvesting, desalination, biomedical applications, deicing, waste treatment, and environmental remediation. Through their versatile utilization, they demonstrate immense potential in fostering sustainability and support the transition toward a greener and more resilient future. The authors’ perspective on the challenges and potentials of platforms based on these materials is also included, highlighting their immense potential for real-world implementation.

Keywords:

photothermal materials, organic waste valorization, bioderived materials

Affiliations:
Zargarian S.-IPPT PAN
Zakrzewska A.-IPPT PAN
Kosik-Kozioł A.-IPPT PAN
Bartolewska M.-IPPT PAN
Shah S.-IPPT PAN
Li X.-Donghua University (CN)
Su Q.-other affiliation
Petronella F.-other affiliation
Marinelli M.-other affiliation
De Sio L.-other affiliation
Lanzi M.-University of Bologna (IT)
Ding B.-Donghua University (CN)
Pierini F.-IPPT PAN
3.Marinelli M., Lanzi M., Quadretti D., Ziai Y., Pierini F., Zanelli A., Riccardo M., Salatelli E., A new alcohol-soluble dye-tetraphenyl porphyrin functionalized copolymer: Inside the role as a third component/cathode interlayer in halogen-free OSCs, REACTIVE AND FUNCTIONAL POLYMERS, ISSN: 1381-5148, DOI: 10.1016/j.reactfunctpolym.2024.105928, Vol.200, pp.105928-1-10, 2024
Abstract:

Development and step-by-step characterizations of a novel cationic thiophene based copolymer (P1buP), including ionic phosphonium salt and dye-tetraphenylporphyrin (TPP) moiety in side chains, with an iconic property of solubility in a wide range of polar solvents is reported. Synthesized by using simple, low-cost, and straightforward procedures, the material is used to fabricate completely halogen-free (i.e., from ethanol) ternary organic solar cells (OSCs), in the presence of an alcohol-soluble ionic 3,4-dialkoxythiophene based homopolymer (P2buP) and a serinol-fullerene derivative (C60-Ser). Indeed, thanks to co-sensitization techniques, where multiple dyes harvest different parts of the solar spectrum, the power conversion efficiency of the best final device dramatically increases up to nearly 5.0%, as the light absorption is usually optimized. Additionally, since the use of a cathode interlayer in OSCs also plays a pivotal role in electron extraction and device stability, a possible application of the ionic TPP material as the interfacial layer is also investigated. Furthermore, to improve and optimize the best performing device, a successful post-metalation with Zn of the porphyrin core is carried out, and a ternary OSC (P1buP:P2buP:C60-Ser = 0.33:0.67:1 w/w) is fabricated, resulting in a photoconversion efficiency (PCE) of ∼6.0%.

Keywords:

Ionic dye-tetraphenylporphyrin, Co-sensitization, Ternary OSCs, Cathode interlayers, Halogen-free deposition

Affiliations:
Marinelli M.-other affiliation
Lanzi M.-University of Bologna (IT)
Quadretti D.-University of Bologna (IT)
Ziai Y.-IPPT PAN
Pierini F.-IPPT PAN
Zanelli A.-CNR-ISOF (IT)
Riccardo M.-other affiliation
Salatelli E.-University of Bologna (IT)
4.Zangoli M., Monti F., Zanelli A., Marinelli M., Flammini S., Spallacci N., Zakrzewska A., Lanzi M., Salatelli E., Pierini F., Di Maria F., Multifunctional Photoelectroactive Materials for Optoelectronic Applications Based on Thieno[3,4-b]pyrazines and Thieno[1,2,5]thiadiazoles, Chemistry - A European Journal, ISSN: 0947-6539, DOI: 10.1002/chem.202303590, pp.1-18, 2023
Abstract:

In this study, we introduce a novel family of symmetrical thiophene-based small molecules with a Donor–Acceptor–Donor structure. These compounds feature three different acceptor units: benzo[c][1,2,5]thiadiazole (Bz), thieno[3,4-b]pyrazine (Pz), and thieno[1,2,5]thiadiazole (Tz), coupled with electron donor units based on a carbazole-thiophene derivative. Using Density Functional Theory (DFT), we investigate how the molecular geometry and strength of the central acceptor unit impact the redox and spectroscopic properties. Notably, the incorporation of Pz and Tz moieties induces a significant redshift in the absorption and emission spectra, which extend into the near-infrared (NIR) region, simultaneously reducing their energy gaps (~1.4-1.6 eV). This shift is attributed to the increased coplanarity of the oligomeric inner core, both in the ground (S0) and excited (S1) states, due to the enhanced quinoidal character as supported by bond-length alternation (BLA) analysis. These structural changes promote better π-electron delocalization and facilitate photoinduced charge transfer processes in optoelectronic devices. Notably, we show that Pz- and Tz-containing molecules exhibit NIR electrochromic behavior and present ambivalent character in bulk heterojunction (BHJ) solar cells. Finally, theoretical calculations suggest that these molecules could serve as effective two-photon absorption (2PA) probes, further expanding their potential in optoelectronic applications.

Affiliations:
Zangoli M.-CNR-ISOF (IT)
Monti F.-CNR-ISOF (IT)
Zanelli A.-CNR-ISOF (IT)
Marinelli M.-other affiliation
Flammini S.-other affiliation
Spallacci N.-other affiliation
Zakrzewska A.-IPPT PAN
Lanzi M.-University of Bologna (IT)
Salatelli E.-University of Bologna (IT)
Pierini F.-IPPT PAN
Di Maria F.-CNR-ISOF (IT)
5.Quadretti D., Marinelli M., Salatelli E., Pierini F., Zanelli A., Lanzi M., Effects of Water/Alcohol Soluble Cationic Polythiophenes as Cathode Interlayers for Eco-Friendly Solar Cells, Macromolecular Chemistry and Physics, ISSN: 1022-1352, DOI: 10.1002/macp.202200422, Vol.224, No.6, pp.2200422-1-14, 2023
Abstract:

Three new ionic polythiophene derivatives, soluble in polar solvents, are synthesized with good yields using simple, low-cost, and straightforward procedures. They are investigated as interfacial cationic conjugated
polyelectrolyte (CPE) layers for halogen-free bulk heterojunction polymeric solar cells, based on a water-soluble electron-donor polymer
(poly[3-(6-diethanolaminohexyl)thiophene]) and a water-soluble electron-acceptor fullerene derivative (malonodiserinolamide fullerene). The simple insertion of the CPE interlayer between the active layer and the aluminum cathode dramatically increases the power conversion efficiency of the final device up to nearly 5%, resulting from a decrease of the electrode work function, improved electron extraction, and optimization of the morphology of the layers. The obtained results demonstrate that the incorporation of CPE layer is a powerful and convenient methodology for the
development of highly efficient and eco-friendly processable polymeric solar cells.

Keywords:

conjugated polyelectrolyte,electron transport layers,polythiophene

Affiliations:
Quadretti D.-University of Bologna (IT)
Marinelli M.-other affiliation
Salatelli E.-University of Bologna (IT)
Pierini F.-IPPT PAN
Zanelli A.-CNR-ISOF (IT)
Lanzi M.-University of Bologna (IT)
6.Marinelli M., Lanzi M., Pierini F., Ziai Y., Zanelli A., Quadretti D., Di Maria F., Salatelli E., Ionic Push–Pull Polythiophenes: A Further Step towards Eco-Friendly BHJ Organic Solar Cells, Polymers, ISSN: 2073-4360, DOI: 10.3390/polym14193965, Vol.14, No.19, pp.3965-1-17, 2022
Abstract:

Four new conjugated polymers alternating benzothiadiazole units and thiophene moieties functionalized with ionic phosphonium or sulfonic acid salts in the side chains were synthesized by a postfunctionalization approach of polymeric precursors. The introduction of ionic groups makes the conjugated polymers soluble in water and/or polar solvents, allowing for the fabrication of bulk heterojunction (BHJ) solar cells using environmentally friendly conditions. All polymers were fully characterized by spectroscopic, thermal, electrochemical, X-ray diffraction, scanning electron, and atomic force techniques. BHJ solar cells were obtained from halogen-free solvents (i.e., ethanol and/or anisole) by blending the synthesized ionic push–pull polymers with a serinol-fullerene derivative or an ionic homopolymer acting as electron-acceptor (EA) or electron-donor (ED) counterparts, respectively. The device with the highest optical density and the smoothest surface of the active layer was the best-performing, showing a 4.76% photoconversion efficiency.

Keywords:

donor–acceptor systems, bifunctional materials, phosphonium salts, eco-friendly BHJ solar cells, anisole

Affiliations:
Marinelli M.-other affiliation
Lanzi M.-University of Bologna (IT)
Pierini F.-IPPT PAN
Ziai Y.-IPPT PAN
Zanelli A.-CNR-ISOF (IT)
Quadretti D.-University of Bologna (IT)
Di Maria F.-CNR-ISOF (IT)
Salatelli E.-University of Bologna (IT)
7.Marinelli M., Candini A., Monti F., Boschi A., Zangoli M., Salatelli E., Pierini F., Lanzi M., Zanelli A., Gazzano M., Di Maria F., Push–pull thiophene-based small molecules with donor and acceptor units of varying strength for photovoltaic application: beyond P3HT and PCBM, Journal of Materials Chemistry C, ISSN: 2050-7526, DOI: 10.1039/d1tc02641k, Vol.9, No.34, pp.11216-11228, 2021
Abstract:

Here is reported an expedient synthesis implementing enabling technologies of a family of thiophene-based heptamers alternating electron donor (D) and acceptor (A) units in a D–A′–D–A–D–A′–D sequence. The nature of the peripheral A groups (benzothiadiazole vs. thienopyrrole-dione vs. thiophene-S,S-dioxide) and the strength of the donor units (alkyl vs. thioalkyl substituted thiophene ring) have been varied to finely tune the chemical-physical properties of the D–A oligomers, to affect the packing arrangement in the solid-state as well as to enhance the photovoltaic performances. The optoelectronic properties of all compounds have been studied by means of optical spectroscopy, electrochemistry, and density functional theory calculations. Electrochemical measurements and Kelvin probe force microscopy (KPFM) predicted a bifunctional behaviour for these oligomers, suggesting the possibility of using them as donor materials when blended with PCBM, and as acceptor materials when coupled with P3HT. Investigation of their photovoltaic properties confirmed this unusual characteristic, and it is shown that the performance can be tuned by the different substitution pattern. Furthermore, thanks to their ambivalent character, binary non-fullerene small-molecule organic solar cells with negligible values of HOMO and LUMO offsets were also fabricated, resulting in PCEs ranging between 2.54–3.96%.

Affiliations:
Marinelli M.-other affiliation
Candini A.-CNR-ISOF (IT)
Monti F.-CNR-ISOF (IT)
Boschi A.-CNR-ISOF (IT)
Zangoli M.-CNR-ISOF (IT)
Salatelli E.-University of Bologna (IT)
Pierini F.-IPPT PAN
Lanzi M.-University of Bologna (IT)
Zanelli A.-CNR-ISOF (IT)
Gazzano M.-CNR-ISOF (IT)
Di Maria F.-CNR-ISOF (IT)
8.Lanzi M., Quadretti D., Marinelli M., Ziai Y., Salatelli E., Pierini F., Influence of the active layer structure on the photovoltaic performance of water-soluble polythiophene-based solar cells, Polymers, ISSN: 2073-4360, DOI: 10.3390/polym13101640, Vol.13, No.10, pp.1640-1-20, 2021
Abstract:

A new side-chain C60-fullerene functionalized thiophene copolymer bearing tributylphosphine-substituted hexylic lateral groups was successfully synthesized by means of a fast and effective post-polymerization reaction on a regioregular ω-alkylbrominated polymeric precursor. The growth of the polymeric intermediate was followed by NMR spectrometry in order to determine the most convenient reaction time. The obtained copolymer was soluble in water and polar solvents and was used as a photoactive layer in single-material organic photovoltaic (OPV) solar cells. The copolymer photovoltaic efficiency was compared with that of an OPV cell containing a water-soluble polythiophenic homopolymer, functionalized with the same tributylphosphine-substituted hexylic side chains, in a blend with a water-soluble C60-fullerene derivative. The use of a water-soluble double-cable copolymer made it possible to enhance the control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena, as well as the macroscale separation between the electron acceptor and donor components. Indeed, the power conversion efficiency of OPV cells based on a single material was higher than that obtained with the classical architecture, involving the presence of two distinct ED and EA materials (PCE: 3.11% vs. 2.29%, respectively). Moreover, the synthetic procedure adopted to obtain single material-based cells is more straightforward and easier than that used for the preparation of the homopolymer-based BHJ solar cell, thus making it possible to completely avoid the long synthetic pathway which is required to prepare water-soluble fullerene derivatives.

Keywords:

water-soluble polymers, double-cable copolymers, polythiophenes, GRIM polymerization, tributylphosphine, water-soluble fullerenes, OPVs

Affiliations:
Lanzi M.-University of Bologna (IT)
Quadretti D.-University of Bologna (IT)
Marinelli M.-IPPT PAN
Ziai Y.-IPPT PAN
Salatelli E.-University of Bologna (IT)
Pierini F.-IPPT PAN
9.Lanzi M., Salatelli E., Marinelli M., Pierini F., Effect of photocrosslinking of D‐A thiophene copolymers on the performance of single‐material solar cells, Macromolecular Chemistry and Physics, ISSN: 1022-1352, DOI: 10.1002/macp.201900433, Vol.221, No.2, pp.1900433-1-12, 2020
Abstract:

Side‐chain C60‐fullerene functionalized alkylthiophene copolymers with different regioregularity and fullerene content are successfully synthesized using a simple and straightforward post‐polymerization functionalization procedure based on a Grignard coupling reaction. The products are employed as single materials in photoactive layers of organic photovoltaic solar cells. The use of double‐cable polymers allows an enhanced control on the nanomorphology of the active blend, reducing the phase‐segregation phenomena as well as the macroscale separation between the electron acceptor and donor components. With the insertion of a thin layer of gold nanoparticles between buffer and active layer of the cells, a conversion efficiency of 5.68% is obtained. Moreover, an increased stability over time is achieved when the copolymers are photocrosslinked immediately after the annealing procedure, leading to acceptable efficiencies even after 80 h of accelerated ageing, a key feature for widespread applicability of the prepared devices.

Keywords:

conjugated polymers, fullerenes, functionalization of polymers, metathesis

Affiliations:
Lanzi M.-University of Bologna (IT)
Salatelli E.-University of Bologna (IT)
Marinelli M.-other affiliation
Pierini F.-IPPT PAN
10.Lanzi M., Salatelli E., Giorgini L., Marinelli M., Pierini F., Effect of the incorporation of an Ag nanoparticle interlayer on the photovoltaic performance of green bulk heterojunction water-soluble polythiophene solar cells, POLYMER, ISSN: 0032-3861, DOI: 10.1016/j.polymer.2018.07.012, Vol.149, pp.273-285, 2018
Abstract:

Two water-soluble regioregular poly(3-alkylthiophene)s, incorporating aminic groups at the end of the side chains, have been synthesized using a post-polymerization functionalization procedure on a ω-bromine substituted polyalkylthiophene. The high solubility of the obtained polymers in water allowed for the preparation of “green” bulk heterojunction solar cells which reached a power conversion efficiency of 4.85% when PC61BM was used as electron-acceptor material. Improved optical absorption and photocurrent have been obtained by interposing a layer of Ag nanoparticles between the buffer and the photoactive layer, leading to a final power conversion efficiency of 5.51%.

Keywords:

Water-soluble polythiophene, Bulk heterojunction solar cell, Organic photovoltaic

Affiliations:
Lanzi M.-University of Bologna (IT)
Salatelli E.-University of Bologna (IT)
Giorgini L.-University of Bologna (IT)
Marinelli M.-other affiliation
Pierini F.-IPPT PAN