Instytut Podstawowych Problemów Techniki

Streszczenie:

Atopic dermatitis (AD) is a chronic inflammatory skin disease with a complex etiology that lacks effective treatment. The therapeutic goals include alleviating symptoms, such as moisturizing and applying antibacterial and anti-inflammatory medications. Hence, there is an urgent need to develop a patch that effectively alleviates most of the AD symptoms. In this study, we employed a “green” cross-linking approach of poly(vinyl alcohol) (PVA) using glycerol, and we combined it with polyacrylonitrile (PAN) to fabricate core–shell (CS) nanofibers through electrospinning. Our designed structure offers multiple benefits as the core ensures controlled drug release and increases the strength of the patch, while the shell provides skin moisturization and exudate absorption. The efficient PVA cross-linking method facilitates the inclusion of sensitive molecules such as fermented oils. In vitro studies demonstrate the patches’ exceptional biocompatibility and efficacy in minimizing cell ingrowth into the CS structure containing argan oil, a property highly desirable for easy removal of the patch. Histological examinations conducted on an ex vivo model showed the nonirritant properties of developed patches. Furthermore, the eradication of Staphylococcus aureus bacteria confirms the potential use of CS nanofibers loaded with argan oil or norfloxacin, separately, as an antibacterial patch for infected AD wounds. In vivo patch application studies on patients, including one with AD, demonstrated ideal patches’ moisturizing effect. This innovative approach shows significant promise in enhancing life quality for AD sufferers by improving skin hydration and avoiding infections.

Słowa kluczowe:

atopic dermatitis, core−shell electrospun nanofibers, antibacterial, mucoadhesive, moisturizing patch

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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.

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Hierarchical nanostructures fabricate by electrospinning in combination with light-responsive agents offer promising scenarios for developing novel activable antibacterial interfaces. This study introduces an innovative antibacterial face mask developed from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers integrated with indocyanine green (ICG), targeting the urgent need for effective antimicrobial protection for community health workers. The research focuses on fabricating and characterizing this nanofibrous material, evaluating the mask's mechanical and chemical properties, investigating its particle filtration, and assessing antibacterial efficacy under photothermal conditions for reactive oxygen species (ROS) generation. The PHBV/ICG nanofibers are produced using an electrospinning process, and the nanofibrous construct's morphology, structure, and photothermal response are investigated. The antibacterial efficacy of the nanofibers is tested, and substantial bacterial inactivation under both near-infrared (NIR) and solar irradiation is demonstrated due to the photothermal response of the nanofibers. The material's photothermal response is further analyzed under cyclic irradiation to simulate real-world conditions, confirming its durability and consistency. This study highlights the synergistic impact of PHBV and ICG in enhancing antibacterial activity, presenting a biocompatible and environmentally friendly solution. These findings offer a promising path for developing innovative face masks that contribute significantly to the field of antibacterial materials and solve critical public health challenges.

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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.

Słowa kluczowe:

photothermal materials, organic waste valorization, bioderived materials

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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%.

Słowa kluczowe:

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

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Polycaprolactone (PCL), a recognized biopolymer, has emerged as a prominent choice for diverse biomedical endeavors due to its good mechanical properties, exceptional biocompatibility, and tunable properties. These attributes render PCL a suitable alternative biomaterial to use in biofabrication, especially the electrospinning technique, facilitating the production of nanofibers with varied dimensions and functionalities. However, the inherent hydrophobicity of PCL nanofibers can pose limitations. Conversely, acrylamide-based hydrogels, characterized by their interconnected porosity, significant water retention, and responsive behavior, present an ideal matrix for numerous biomedical applications. By merging these two materials, one can harness their collective strengths while potentially mitigating individual limitations. A robust interface and effective anchorage during the composite fabrication are pivotal for the optimal performance of the nanoplatforms. Nanoplatforms are subject to varying degrees of tension and physical alterations depending on their specific applications. This is particularly pertinent in the case of layered nanostructures, which require careful consideration to maintain structural stability and functional integrity in their intended applications. In this study, we delve into the influence of the fiber dimensions, orientation and surface modifications of the nanofibrous layer and the hydrogel layer's crosslinking density on their intralayer interface to determine the optimal approach. Comprehensive mechanical pull-out tests offer insights into the interfacial adhesion and anchorage between the layers. Notably, plasma treatment of the hydrophobic nanofibers and the stiffness of the hydrogel layer significantly enhance the mechanical effort required for fiber extraction from the hydrogels, indicating improved anchorage. Furthermore, biocompatibility assessments confirm the potential biomedical applications of the proposed nanoplatforms.

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In neuroscience, the acquisition of neural signals from the brain cortex is crucial to analyze brain processes, detect neurological disorders, and offer therapeutic brain–computer interfaces. The design of neural interfaces conformable to the brain tissue is one of today’s major challenges since the insufficient biocompatibility of those systems provokes a fibrotic encapsulation response, leading to an inaccurate signal recording and tissue damage precluding long-term/permanent implants. The design and production of a novel soft neural biointerface made of polyacrylamide hydrogels loaded with plasmonic silver nanocubes are reported herein. Hydrogels are surrounded by a silicon-based template as a supporting element for guaranteeing an intimate neural-hydrogel contact while making possible stable recordings from specific sites in the brain cortex. The nanostructured hydrogels show superior electroconductivity while mimicking the mechanical characteristics of the brain tissue. Furthermore, in vitro biological tests performed by culturing neural progenitor cells demonstrate the biocompatibility of hydrogels along with neuronal differentiation. In vivo chronic neuroinflammation tests on a mouse model show no adverse immune response toward the nanostructured hydrogel-based neural interface. Additionally, electrocorticography acquisitions indicate that the proposed platform permits long-term efficient recordings of neural signals, revealing the suitability of the system as a chronic neural biointerface.

Słowa kluczowe:

brain−machine interface,conductive hydrogels,nanostructured biomaterials,in vitro and in vivo biocompatibility,long-term neural recording

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As scientists discovered that raw neurological signals could translate into bioelectric information, brain–machine interfaces (BMI) for experimental and clinical studies have experienced massive growth. Developing suitable materials for bioelectronic devices to be used for real-time recording and data digitalizing has three important necessitates which should be covered. Biocompatibility, electrical conductivity, and having mechanical properties similar to soft brain tissue to decrease mechanical mismatch should be adopted for all materials. In this review, inorganic nanoparticles and intrinsically conducting polymers are discussed to impart electrical conductivity to systems, where soft materials such as hydrogels can offer reliable mechanical properties and a biocompatible substrate. Interpenetrating hydrogel networks offer more mechanical stability and provide a path for incorporating polymers with desired properties into one strong network. Promising fabrication methods, like electrospinning and additive manufacturing, allow scientists to customize designs for each application and reach the maximum potential for the system. In the near future, it is desired to fabricate biohybrid conducting polymer-based interfaces loaded with cells, giving the opportunity for simultaneous stimulation and regeneration. Developing multi-modal BMIs, Using artificial intelligence and machine learning to design advanced materials are among the future goals for this field.

Słowa kluczowe:

3D printing,brain–machine interface,conductive hydrogels,electrospinning,neural recording

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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.

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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.

Słowa kluczowe:

conjugated polyelectrolyte,electron transport layers,polythiophene

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Cross-linking of poly(vinyl alcohol) (PVA) creates a three-dimensional network by bonding adjacent polymer chains. The cross-linked structure, upon immersion in water, turns into a hydrogel, which exhibits unique absorption properties due to the presence of hydrophilic groups within the PVA polymer chains and, simultaneously, ceases to be soluble in water. The properties of PVA can be adjusted by chemical modification or blending with other substances, such as polymers, e.g., conductive poly[3-(potassium-5-butanoate)thiophene-2,5-diyl] (P3KBT). In this work, PVA-based conductive semi-interpenetrating polymer networks (semi-IPNs) are successfully fabricated. The systems are obtained as a result of electrospinning of PVA/P3KBT precursor solutions with different polymer concentrations and then cross-linking using “green”, environmentally safe methods. One approach consists of thermal treatment (H), while the second approach combines stabilization with ethanol and heating (E). The comprehensive characterization allows to evaluate the correlation between the cross-linking methods and properties of nanofibrous hydrogels. While both methods are successful, the cross-linking density is higher in the thermally cross-linked samples, resulting in lower conductivity and swelling ratio compared to the E-treated samples. Moreover, the H-cross-linked systems have better mechanical properties─lower stiffness and greater tensile strength. All the tested systems are biocompatible, and interestingly, due to the presence of P3KBT, they show photoresponsivity to solar radiation generated by the simulator. The results indicate that both methods of PVA cross-linking are highly effective and can be applied to a specific system depending on the target, e.g., biomedical or electronic applications.

Słowa kluczowe:

poly(vinyl alcohol),poly[3-(potassium-5-butanoate)thiophene-2.5-diyl],electrospun nanofibers,cross-linking,fibrous hydrogel,semi-IPN

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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.

Słowa kluczowe:

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

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Intrinsically conducting polymers (ICPs) are widely used to fabricate biomaterials; their application in neural tissue engineering, however, is severely limited because of their hydrophobicity and insufficient mechanical properties. For these reasons, soft conductive polymer hydrogels (CPHs) are recently developed, resulting in a water-based system with tissue-like mechanical, biological, and electrical properties. The strategy of incorporating ICPs as a conductive component into CPHs is recently explored by synthesizing the hydrogel around ICP chains, thus forming a semi-interpenetrating polymer network (semi-IPN). In this work, a novel conductive semi-IPN hydrogel is designed and synthesized. The hybrid hydrogel is based on a poly(N-isopropylacrylamide-co-N-isopropylmethacrylamide) hydrogel where polythiophene is introduced as an ICP to provide the system with good electrical properties. The fabrication of the hybrid hydrogel in an aqueous medium is made possible by modifying and synthesizing the monomers of polythiophene to ensure water solubility. The morphological, chemical, thermal, electrical, electrochemical, and mechanical properties of semi-IPNs were fully investigated. Additionally, the biological response of neural progenitor cells and mesenchymal stem cells in contact with the conductive semi-IPN was evaluated in terms of neural differentiation and proliferation. Lastly, the potential of the hydrogel solution as a 3D printing ink was evaluated through the 3D laser printing method. The presented results revealed that the proposed 3D printable conductive semi-IPN system is a good candidate as a scaffold for neural tissue applications.

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Over the last decade, nanotechnology and nanomaterials have attracted enormous interest due to the rising number of their applications in solar cells. A fascinating strategy to increase the efficiency of organic solar cells is the use of tailor-designed buffer layers to improve the charge transport process. High-efficiency bulk heterojunction (BHJ) solar cells have been obtained by introducing hollow core polyaniline (PANI) nanofibers as a buffer layer. An improved power conversion efficiency in polymer solar cells (PSCs) was demonstrated through the incorporation of electrospun hollow core PANI nanofibers positioned between the active layer and the electrode. PANI hollow nanofibers improved buffer layer structural properties, enhanced optical absorption, and induced a more balanced charge transfer process. Solar cell photovoltaic parameters also showed higher open-circuit voltage (+ 40.3%) and higher power conversion efficiency (+ 48.5%) than conventional architecture BHJ solar cells. Furthermore, the photovoltaic cell developed achieved the highest reported efficiency value ever reached for an electrospun fiber-based solar cell (PCE = 6.85%). Our results indicated that PANI hollow core nanostructures may be considered an effective material for high-performance PSCs and potentially applicable to other fields, such as fuel cells and sensors.

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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%.

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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.

Słowa kluczowe:

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

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A new regioregular polythiophene derivative, called poly[3-(12-hydroxydodecyl)thiophene] (PT12OH), was synthesized by post-functionalizing its ω-brominated precursor poly[3-(12-bromododecyl)thiophene] (PT12Br) prepared using the Grignard metathesis route. Thanks to the optimal balance between hydrophilic and hydrophobic groups within its structure, PT12OH was highly soluble and easily filmable from common organic solvents allowing for its complete characterization. It also showed enhanced thermal properties, crystallinity, and self-assembling capabilities by the formation of strong inter- and intrachain hydrogen bonds. Bulk heterojunction photovoltaic cells with PT12OH and PC61BM showed a PCE of 4.83% and a remarkable over-time stability, offering good photoconversion efficiency even after 120 h of accelerated aging. Indeed, the PCE decrease was 34% for the hydroxylated polymer and 65% for its brominated precursor. It should also be pointed out that the enhanced thermal stability of PT12OH was achieved without resorting to any complex post-annealing photochemical, thermal, or chemical treatment and was thus directly ascribable to the polymer chemical structure. The simple and effective synthetic procedure, photovoltaic efficiency, and enhanced stability revealed the potential of PT12OH for large-scale organic solar cell applications.

Słowa kluczowe:

bulk heterojunction solar cell, regioregular polythiophene derivatives, post-polymerization functionalization, over-time stability

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Multifunctional nanomaterials with the ability torespond to near-infrared (NIR) light stimulation are vital for thedevelopment of highly efficient biomedical nanoplatforms with apolytherapeutic approach. Inspired by the mesoglea structure ofjellyfish bells, a biomimetic multifunctional nanostructured pillowwith fast photothermal responsiveness for NIR light-controlled on-demand drug delivery is developed. We fabricate a nanoplatformwith several hierarchical levels designed to generate a series ofcontrolled, rapid, and reversible cascade-like structural changesupon NIR light irradiation. The mechanical contraction of thenanostructured platform, resulting from the increase of temper-ature to 42°C due to plasmonic hydrogel−light interaction, causesa rapid expulsion of water from the inner structure, passing through an electrospun membrane anchored onto the hydrogel core. Themutual effects of the rise in temperature and waterflow stimulate the release of molecules from the nanofibers. To expand thepotential applications of the biomimetic platform, the photothermal responsiveness to reach the typical temperature level forperforming photothermal therapy (PTT) is designed. The on-demand drug model penetration into pig tissue demonstrates theefficiency of the nanostructured platform in the rapid and controlled release of molecules, while the high biocompatibility confirmsthe pillow potential for biomedical applications based on the NIR light-driven multitherapy strategy.

Słowa kluczowe:

bioinspired materials, NIR-light responsive nanomaterials, multifunctional platforms, electrospun nanofibers, plasmonic hydrogel, photothermal-based polytherapy, on-demand drug delivery

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This work describes the morphological, optical, and thermo‐optical properties of a temperature‐sensitive hydrogel poly(N‐isopropylacrylamide‐co‐N‐isopropylmethacrylamide) [P(NIPAm‐co‐NIPMAm]) film containing a specific amount of gold nanorods (GNRs). The light‐induced thermoplasmonic heating of GNRs is used to control the optical scattering of an initially transparent hydrogel film. A hydrated P(NIPAm‐co‐NIPMAm) film is optically clear at room temperature. When heated to temperatures over 37 °C via light irradiation with a resonant source (λ = 810 nm) to the GNRs, a reversible phase transition from a swollen hydrated state to a shrunken dehydrated state occurs. This phenomenon causes a drastic and reversible change in the optical transparency from a clear to an opaque state. A significant red shift (≈30 nm) of the longitudinal band can also be seen due to an increased average refractive index surrounding the GNRs. This change is in agreement with an ad hoc theoretical model which uses a modified Gans theory for ellipsoidal nanoparticles. Morphological analysis of the composite film shows the presence of well‐isolated and randomly dispersed GNRs. Thermo‐optical experiments demonstrate an all‐optically controlled light attenuator (65% contrast ratio) which can be easily integrated in several modern optical applications such as smart windows and light‐responsive optical attenuators.

Słowa kluczowe:

active plasmonics, gold nanorods, hydrogels, optical attenuators, optical transparency, plasmonic nanoparticles, polymers

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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.

Słowa kluczowe:

conjugated polymers, fullerenes, functionalization of polymers, metathesis

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Three regioregular thiophenic copolymers, characterized by a bromine atom or a C60-fullerene group at different molar ratios at the end of a decamethylenic plastifying side chain, have been successfully synthesized using a straightforward postpolymerization functionalization procedure based on a Grignard coupling reaction. Owing to their good solubility in common organic solvents, the products were fully characterized using chromatographic, spectroscopic, thermal, and morphological techniques and used as single materials in the photoactive layers of organic solar cells. The photoconversion efficiencies obtained with copolymers were compared with those of a reference cell prepared using a physical blend of the precursor homopolymer and [6,6]-phenyl-C61-butyric acid methyl ester. The best results were obtained with COP2, the copolymer with a 21% molar content of C60-functionalized side chains. The use of the double-cable polymer made possible an enhanced 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, yielding a power conversion efficiency higher than that of the reference cell (4.05 vs 3.68%). Moreover, the presence of the halogen group was exploited for the photo-cross-linking of the active layer immediately after the thermal annealing procedure. The cross-linked samples showed an increased stability over time, leading to good efficiencies even after 120 h of accelerated aging: this was a key feature for the widespread practical applicability of the prepared devices.

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Materials for the treatment of cancer have been studied comprehensively over the past few decades. Among the various kinds of biomaterials, polymer-based nanomaterials represent one of the most interesting research directions in nanomedicine because their controlled synthesis and tailored designs make it possible to obtain nanostructures with biomimetic features and outstanding biocompatibility. Understanding the chemical and physical mechanisms behind the cascading stimuli-responsiveness of smart polymers is fundamental for the design of multifunctional nanomaterials to be used as photothermal agents for targeted polytherapy. In this review, we offer an in-depth overview of the recent advances in polymer nanomaterials for photothermal therapy, describing the features of three different types of polymer-based nanomaterials. In each case, we systematically show the relevant benefits, highlighting the strategies for developing light-controlled multifunctional nanoplatforms that are responsive in a cascade manner and addressing the open issues by means of an inclusive state-of-the-art review. Moreover, we face further challenges and provide new perspectives for future strategies for developing novel polymeric nanomaterials for photothermally assisted therapies.

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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%.

Słowa kluczowe:

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

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Highly efficient single-material organic solar cells (SMOCs) based on fullerene-grafted polythiophenes were fabricated by incorporating electrospun one-dimensional (1D) nanostructures obtained from polymer chain stretching. Poly(3-alkylthiophene) chains were chemically tailored in order to reduce the side effects of charge recombination which severely affected SMOC photovoltaic performance. This enabled us to synthesize a donor–acceptor conjugated copolymer with high solubility, molecular weight, regioregularity, and fullerene content. We investigated the correlations among the active layer hierarchical structure given by the inclusion of electrospun nanofibers and the solar cell photovoltaic properties. The results indicated that SMOC efficiency can be strongly increased by optimizing the supramolecular and nanoscale structure of the active layer, while achieving the highest reported efficiency value (PCE = 5.58%). The enhanced performance may be attributed to well-packed and properly oriented polymer chains. Overall, our work demonstrates that the active material structure optimization obtained by including electrospun nanofibers plays a pivotal role in the development of efficient SMOCs and suggests an interesting perspective for the improvement of copolymer-based photovoltaic device performance using an alternative pathway.

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Water-soluble regioregular poly{3-[(6-sodium sulfonate)hexyl]thiophene} (PT6S) and poly{3-[(6-trimethylammoniumbromide)hexyl]thiophene} (PT6N) have been synthesized and employed both as photoactive layers for the assembling of “green” bulk-heterojunction organic solar cells and as charge-collection layers in a cell with “classic” architecture. While the photovoltaic performances obtained with the two aforementioned polymers were lower than the reference cell, their latter use allowed to notably increase the inherent J-V properties, leading to a considerable enhancement in the overall photovoltaic output. The power conversion efficiency of the optimized multilayer BHJ solar cell reached 4.78%, revealing a higher efficiency than the reference cell (3.63%).

Słowa kluczowe:

Water-soluble polymer, Polythiophene derivative, Bulk heterojunction, Organic photovoltaic, Interfacial layer

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A novel thiophenic tetramer containing a cinnamate group in the side chain with a functionalization degree of 50% is reported. The tetramer was obtained by means of a simple and straightforward procedure involving the functionalization of a p-methoxyphenoxy substituted thiophenic precursor, which led to a soluble product with a good yield. The oligomer was fully characterized from a structural and chemical point of view and employed for the fabrication of small molecule organic solar cells exploiting the bulk heterojunction (BHJ) architecture. The presence of an UV-light sensitive group in the tetramer allowed the photocrosslinking of tetramer/PCBM blends, giving high values of photocurrent and conversion efficiency for the exposed samples. Moreover, the UV-treated devices showed improved stability, even upon heating for three days at 130 °C, thus confirming that photocrosslinking can strongly reduce phase segregation under severe operational conditions.

Słowa kluczowe:

electronic materials, polymers, fullerenes, nanostructures, electrical characterization, semiconductors

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Composite nanofibers made of a polyaniline-based polymer blend and different thiol-capped metal nanoparticles were prepared using ex situ synthesis and electrospinning technique. The effects of the nanoparticle composition and chemical structure on the electrical properties of the nanocomposites were investigated. This study confirmed that Brust's procedure is an effective method for the synthesis of sub-10 nm silver, gold, and silver-gold alloy nanoparticles protected with different types of thiols. Electron microscopy results demonstrated that electrospinning is a valuable technique for the production of composite nanofibers with similar morphology and revealed that nanofillers are well-dispersed into the polymer matrix. X-ray diffraction tests proved the lack of a significant influence of the nanoparticle chemical structure on the polyaniline chain arrangement. However, the introduction of conductive nanofillers in the polymer matrix influences the charge transport noticeably improving electrical conductivity. The enhancement of electrical properties is mediated by the nanoparticle capping layer structure. The metal nanoparticle core composition is a key parameter, which exerted a significant influence on the conductivity of the nanocomposites. These results prove that the proposed method can be used to tune the electrical properties of nanocomposites.

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In this article, we report on the production by electrospinning of P3HT/PEO, P3HT/PEO/GO, and P3HT/PEO/rGO nanofibers in which the filler is homogeneously dispersed and parallel oriented along the fibers axis. The effect of nanofillers' presence inside nanofibers and GO reduction was studied, in order to reveal the influence of the new hierarchical structure on the electrical conductivity and mechanical properties. An in-depth characterization of the purity and regioregularity of the starting P3HT as well as the morphology and chemical structure of GO and rGO was carried out. The morphology of the electrospun nanofibers was examined by both scanning and transmission electron microscopy. The fibrous nanocomposites are also characterized by differential scanning calorimetry to investigate their chemical structure and polymer chains arrangements. Finally, the electrical conductivity of the electrospun fibers and the elastic modulus of the single fibers are evaluated using a four-point probe method and atomic force microscopy nanoindentation, respectively. The electrospun materials crystallinity as well as the elastic modulus increase with the addition of the nanofillers while the electrical conductivity is positively influenced by the GO reduction.

Słowa kluczowe:

electrospun composite nanofibers, poly(3-hexylthiophene), graphene oxide, electrical conductivity, mechanical properties

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The aim of this study was to examine the role of the nanofillers spatial arrangement in the electrical properties of hybrid organic-inorganic fibers. In this paper, we have presented experimental results for preparation of fibers with a nanometric diameter based on a polyaniline/poly(ethylene oxide) doped blend and geomimetic chrysotile nanotubes. The nanostructured material was prepared using electrospinning techniques. Electrospun fibers made by pristine polymers and by the same blend loaded with carbon nanotubes were used as reference materials to compare the structural, and electrical properties of the novel organic-inorganic material. Generally, electrical properties were improved by the addition of materials that have high conductivity. Electrospun fibers filled with a traditional insulator like chrysotile have shown higher electrical conductivity than the pristine materials. In order to fully understand how structural variations impact upon the electrical conductivity the materials were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (RS), differential scanning calorimetry (DSC) and four-point probe method. The results suggest that the occurred electrical conductivity gain could be attributed to parallel orientation of the chrysotile nanotubes and higher crystallinity induced by the one-dimensional nanostructured filler materials. The obtained results bring us one step closer to using intrinsically conducting polymers (ICPs) in the creation of functionalized polymeric nanocomposites for nanotechnology.

Słowa kluczowe:

Nanocomposites, Conductive polymer, Electrospinning, Chrysotile, Carbon nanotubes

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In this article we demonstrate the use of a blend made of two regioregular polythiophenic derivatives, namely poly(3-methylthio)thiophene and poly(3-hexyl)thiophene, to obtain conductive traces by the simple laser exposure of their thin films to a suitable laser source. The polymeric blend was also tested as a photoactive layer for BHJ solar cells, showing an improved surface morphology and a wider absorption spectrum, thus resulting in an enhanced photovoltaic performance. In the standard condition normally used for the cell preparation, we obtained a 3.16% power conversion efficiency. The device showed good reproducibility and stability over time.

Słowa kluczowe:

Electrical conductivity, Laser tracing, Bulk heterojunction polymeric solar cells, Regioregular polyalkylthiophenes, Polymer blends

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This article describes the preparation of thin films of conjugated polymers which can enhance their specific electrical conductivity by several orders of magnitude by changing their state from insulating to conducting materials. The examined polymers, i.e., a polyacetylenic and a polythiophenic derivative, are functionalized with thioalkylic side chains and are soluble in common organic solvents from which they lead to thick homogeneous films. The films can be deposited on different substrates, either rigid or flexible, and can be easily exposed to laser radiation to make them conductive. The process is irreversible, and the final conductivity is stable over time, even in the presence of high temperatures (up to 180°C), moisture, and air. The high stability of treated samples, easy polymer synthesis and quick and inexpensive suitably tailored laser tracing procedure make these materials very promising for applications in organic electronics and in the development of new electronic circuitry.

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Single-material organic solar cells (SMOCs) based on fullerene-grafted polythiophenes are considered promising devices for organic solar cells (OSCs). The main efforts in this field focus on the chemical tailoring of polymer molecules to reduce the side effects of charge recombination. These advances have made it possible to obtain a power conversion efficiency (PCE) close to conventional bulk heterojunction (BHJ) cells. So far, however, SMOCs still show inadequate efficiencies due to ineffective charge transport. Here we show how SMOC efficiency can be strongly increased by optimizing the supramolecular and nanoscale structure of the active layer, while achieving the highest reported efficiency value (PCE = 5.58%) [1]. The enhanced performance may be attributed to well-packed and properly oriented polymer chains. The hierarchical structure is given by the incorporation of electrospun one-dimensional nanostructures obtained from polymer chain stretching. Our results suggest that the active material optimization obtained by the use of electrospun nanofibers plays a key role in the development of efficient SMOCs.

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