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1.
Air-water interface-assisted synthesis and charge transport characterization of quasi-2d polyacetylene films with enhanced electron mobility via ring-opening polymerization of pyrrole
Kejun Liu, Nadiia Pastukhova, Egon Pavlica, Gvido Bratina, Xinliang Feng, 2024, other component parts

Abstract: Water surfaces catalyze some organic reactions more effectively, making them unique for 2D organic material synthesis. This report introduces a new synthesis method via surfactant-monolayer-assisted interfacial synthesis on water surfaces for ring-opening polymerization of pyrrole, producing distinct polypyrrole derivatives with polyacetylene backbones and ionic substitutions. The synthesis result in quasi 2D polyacetylene (q2DPA) film with enhanced charge transport behavior. We employed time-of-flight photoconductivity (TOFP) measurements using pulsed laser light of tunable wavelength for photoexcitation of the charge carriers within the q2DPA film. The charge transport was measured in the lateral direction as a function of external bias voltage ranging from 0 V to 200 V. We observed high electron mobility ({\mu}) of q2DPA reaching values of 375 cm2 V-1 s-1 at bias voltage Vb = -20V and photon energy of 3.8 eV.
Keywords: air-water interface-assisted synthesis, time-of-flight photoconductivity, 2D polymers, quasi 2D polyacetylene, q2DPA
Published in RUNG: 09.04.2024; Views: 409; Downloads: 2
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2.
High charge carrier mobility in thin films of quasi-two-dimensional polyacetylenes with sulphuric inter-chain linkers
Nadiia Pastukhova, Gvido Bratina, Egon Pavlica, 2023, published scientific conference contribution abstract

Abstract: Quasi-two-dimensional conjugated polymers (q2DCP) have been described and recognised as crystalline, one- or two-layer polymer nanosheets prepared by arranging linear conjugated polymer chains in a 2D plane via non-covalent interchain interactions.[1,2] The extension of polymer dimensionality to two dimensions improves the alignment of individual polymer layers and overcomes the limitations associated with charge carrier hopping between polymer chains in one-dimensional and crosslinked polymers [3] Compared to other two-dimensional materials such as graphene or transition metal dichalcogenides, q2DCPs offer a high degree of flexibility in chemical design and are compatible with liquid-based processing methods. Various q2DCPs have been synthesized by surface active monolayer-assisted interfacial synthesis (SMAIS) [5] The photoreaction of these materials is of particular interest due to their tunable properties such as band gap and associated wavelength-dependent photoexcitation, which enables a wide range of applications in optoelectronic devices. Using time-of-flight photoconductivity measurements (TOF-PC) [4], we investigate the charge transport properties of 2D polyacetylene prepared by the SMAIS method. A typical TOFP measurement of q2D polyacetylene is shown in Figure 1, using a focused nanosecond pulse laser at 325 nm and an electrode spacing of 250 µm. From the polarity of the bias voltage and the duration of the photocurrent, we can determine the polarity, velocity, and mobility of the photo-excited carriers as a function of the applied bias voltage and excitation wavelength. and observed electron mobility of 250 cm2/Vs, which is in the range of the most advanced organic single-crystal small-molecule semiconductors and almost an order of magnitude higher than linear polymeric semiconductors. We investigated the optical absorption and transmission on a lateral scale using scanning near-field optical microscopy (SNOM).
Keywords: 2D polymers, organic semiconductors, q2DPA, SNOM, time-of-flight photoconductivity
Published in RUNG: 25.03.2024; Views: 405; Downloads: 1
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3.
4.
Organic and flexible : lecture at Ženske v znanosti in za znanost, Ljubljana, 12. 2. 2024
Nadiia Pastukhova, 2024, unpublished conference contribution

Abstract: The development of organic semiconductors (OS) opens a new perspective and possibilities for novel device architectures including flexible and wearable electronics. One of the key parameters is the charge carriers' mobility. In OSs, it is affected by many factors, including molecular stacking, chemical impurities, temperature, pressure, electric field, and charge carrier density. These factors can affect the structural or energetic disorder. To overcome limitations, new polymers that extend the π-conjugation to two dimensions were developed. The two-dimensional network structure provides a high degree of structural stability and tunability of properties, while the organic molecules can be engineered to exhibit specific chemical and physical properties such as large surface area, pore size, and electronic properties. I will present our recent research, where quasi-2D polyacetylene (q2DPA) demonstrates high electron mobility along the direction of the layer, measured by the lateral time-of-flight photoconductivity (TOF) method.
Keywords: 2D polymers, time-of-flight photoconductivity, TOF, organic semiconductors
Published in RUNG: 22.03.2024; Views: 432; Downloads: 2
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5.
Sustained delivery of Cu(II)-based DNA intercalators by nanometer-sized cyclodextrin-based porous polymers
Tina Škorjanc, Julian Heinrich, Damjan Makuc, Nora Kulak, Matjaž Valant, 2023, original scientific article

Abstract: DNA intercalators are small molecules that insert between adjacent DNA base pairs and thus disturb DNA replication and transcription, which can lead to cell death. Certain metal complexes are excellent DNA intercalators, and have shown promise in chemotherapy. Here, a cyclodextrin porous polymer was prepared, characterized, exfoliated to form nanometer-sized particles, and used as a delivery vehicle for metal-free and Cu(II)-metalated anthraquinone-based DNA intercalators with a goal to minimize side effects of the highly toxic DNA intercalators. NMR experiments, including DOSY NMR, have shown the interaction between the cyclodextrin building block and the studied DNA intercalators. Porous nature of the delivery vehicle provided ample surface area for interaction with the drug candidates, resulting in encapsulation rates of up to 56%. Sustained cargo release from the polymer was achieved over eight days, and time-dependent cytotoxicity was observed. Furthermore, optical microscopy images indicated delivery vehicle internalization as well as disturbed cellular morphology within 24 hours of incubation. We anticipate that this study will stimulate further interest in the development of polymeric delivery systems for metal complexes.
Keywords: porous organic polymers, cyclodextrin, DNA intercalators, Cu(II) complexes, metal complexes
Published in RUNG: 10.11.2023; Views: 862; Downloads: 4
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6.
A rational design of isoindigo-based conjugated microporous n-type semiconductors for high electron mobility and conductivity
Kayaramkodath C. Ranjeesh, Ayman Rezk, Jose Ignacio Martinez, Safa Gaber, Areej Merhi, Tina Škorjanc, Matjaž Finšgar, Gisha Elizabeth Luckachan, Ali Trabolsi, Bilal R. Kaafarani, 2023, original scientific article

Abstract: The development of n-type organic semiconductors has evolved significantly slower in comparison to that of p-type organic semiconductors mainly due to the lack of electron-deficient building blocks with stability and processability. However, to realize a variety of organic optoelectronic devices, high-performance n-type polymer semiconductors are essential. Herein, conjugated microporous polymers (CMPs) comprising isoindigo acceptor units linked to benzene or pyrene donor units (BI and PI) showing n-type semiconducting behavior are reported. In addition, considering the challenges of deposition of a continuous and homogeneous thin film of CMPs for accurate Hall measurements, a plasma-assisted fabrication technique is developed to yield uniform thin films. The fully conjugated 2D networks in PI- and BI-CMP films display high electron mobility of 6.6 and 3.5 cm2 V−1 s−1, respectively. The higher carrier concentration in PI results in high conductivity (5.3 mS cm−1). Both experimental and computational studies are adequately combined to investigate structure–property relations for this intriguing class of materials in the context of organic electronics.
Keywords: conjugated microporous polymers, isoindigo, semiconductors, conductivity, electron mobility
Published in RUNG: 18.08.2023; Views: 937; Downloads: 7
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7.
Biological applications of porous polymers and covalent organic frameworks : lecture at the Otto-von-Guericke Universität Magdeburg, Tuesday, 27th June 2023, Magdeburg, Germany
Tina Škorjanc, 2023, unpublished conference contribution

Abstract: Porous organic polymers (POPs) and covalent organic frameworks (COFs) have gained significant attention in the scientific community for a wide array of applications because of their attractive physical and chemical properties. Porosity of these materials provides ample surface area for interaction with targets, while crystallinity allows for highly specific structural tuning. In this seminar, I will present two strategies of utilizing these features of newly prepared materials in biosensing. Firstly, a cationic POP was synthesized, deposited onto interdigitated electrode arrays via a nontraditional electrophoresis technique, and utilized for electrochemical sensing of bacterial cells. As the principle of detection relied on electrostatic interactions between the cationic POP and the anionic bacterial surface, the sensor operated for both Gram-positive and Gram-negative bacteria. Secondly, a small-molecule nitroimidazole target for hypoxia, a low oxygen environment present in tumors, was post-synthetically conjugated to the pores of a fluorescent COF. This material served as a useful hypoxia imaging agent in cancerous cells. The seminar will conclude with some future perspectives on POPs and COFs in biological applications followed by Q & A.
Keywords: Porous organic polymers, covalent organic frameworks, biosensors, hypoxia
Published in RUNG: 13.07.2023; Views: 981; Downloads: 0
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8.
9.
Photoexcited charge mobility in quasi two-dimensional polyacetylene
Nadiia Pastukhova, Kejun Liu, Renhao Dong, Gvido Bratina, Xinliang Feng, Egon Pavlica, 2022, published scientific conference contribution abstract

Abstract: Two-dimensional conjugated polymers (2DCPs) have been described and recognised as crystalline, one- to two-layer polymer nanosheets prepared by 2D covalent polymerization exhibiting strong in-plane π-electron delocalization with two orthogonal directions and weak out-of-plane π-π stacking.[1,2] The extension of polymer dimensionality into two dimensions improves the alignment of individual polymer sheets and overcomes the limitations associated with charge carrier hopping between polymer chains in one-dimensional and crosslinked polymers.[3] Compared to other two-dimensional materials such as graphene or transition metal dichalcogenides, 2DCPs offer a high degree of flexibility in chemical design and are compatible with liquid-based processing methods. Various 2DCPs have been synthesised by surfactant monolayer-assisted interfacial synthesis (SMAIS).[5] Of particular interest is the photoresponse of these materials due to their tunable properties, such as bandgap and associated wavelength-dependent photoexcitation, which enables a wide range of applications in optoelectronic devices. Using time-of-flight photoconductivity (TOF-PC) measurements [4], we investigate the charge transport properties of 2D polyacetylene prepared by SMAIS method. We preform TOF-PC measurement of 2D polyacetylene using a focused nanosecond pulse laser at 325 nm and electrode separation of 250 µm. From the bias polarity and time duration of the photocurrent, we can determine the polarity, velocity and mobility of photoexcited charge carriers as a function of applied bias voltage and excitation wavelength. Using excitation at 325 m, we observed an electron mobility in the range of 150 cm2 V-1 s-1, which is in the realm of most advances small-molecule single-crystal organic semiconductors and almost an order of magnitude higher than linear polymeric semiconductors.
Keywords: Two-dimensional conjugated polymers, 2DCPs, 2Dpolymers, charge mobility, time-of-flight photoconductivity
Published in RUNG: 29.11.2022; Views: 1110; Downloads: 0
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10.
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