TY - THES A1 - Martin, Johannes T1 - Synthesis of protein-polymer conjugates and block copolymers via sortase-mediated ligation N2 - In den vergangenen Jahrzehnten haben therapeutische Proteine in der pharmazeutischen Industrie mehr und mehr an Bedeutung gewonnen. Werden Proteine nichtmenschlichen Ursprungs verwendet, kann es jedoch zu einer Immunreaktion kommen, sodass das Protein sehr schnell aus dem Körper ausgeschieden oder abgebaut wird. Um die Zirkulationszeit im Blut signifikant zu verlängern, werden die Proteine mit synthetischen Polymeren modifiziert (Protein-Polymer-Konjugate). Die Proteine aller heute auf dem Markt erhältlichen Medikamente dieser Art tragen eine oder mehrere Polymerketten aus Poly(ethylenglycol) (PEG). Ein Nachteil der PEGylierung ist, dass viele Patienten bei regelmäßiger Einnahme dieser Medikamente Antikörper gegen PEG entwickeln, die den effizienzsteigernden Effekt der PEGylierung wieder aufheben. Ein weiterer Nachteil der PEGylierung ist die oftmals deutlich verringerte Aktivität der Konjugate im Vergleich zum nativen Protein. Der Grund dafür ist die Herstellungsmethode der Konjugate, bei der meist die primären Amine der Lysin-Seitenketten und der N-Terminus des Proteins genutzt werden. Da die meisten Proteine mehrere gut zugängliche Lysine aufweisen, werden oft unterschiedliche und teilweise mehrere Lysine mit PEG funktionalisiert, was zu einer Mischung an Regioisomeren führt. Je nach Position der PEG-Kette kann das aktive Zentrum abgeschirmt oder die 3D-Struktur des Proteins verändert werden, was zu einem teilweise drastischen Aktivitätsabfall führt. In dieser Arbeit wurde eine neuartige Methode zur Ligation von Makromolekülen untersucht. Die Verwendung eines Enzyms als Katalysator zur Verbindung zweier Makromoleküle ist bisher wenig untersucht und ineffizient. Als Enzym wurde Sortase A ausgewählt, eine gut untersuchte Ligase aus der Familie der Transpeptidasen, welche die Ligation zweier Peptide katalysieren kann. Ein Nachteil dieser Sortase-vermittelten Ligation ist, dass es sich um eine Gleichgewichtsreaktion handelt, wodurch hohe Ausbeuten schwierig zu erreichen sind. Im Rahmen dieser Dissertation wurden zwei zuvor entwickelte Methoden zur Verschiebung des Gleichgewichts ohne Einsatz eines großen Überschusses von einem Edukt für Makromoleküle überprüft. Zur Durchführung der Sortase-vermittelten Ligation werden zwei komplementäre Peptidsequenzen verwendet, die Erkennungssequenz und das Nukleophil. Um eine systematische Untersuchung durchführen zu können, wurden alle nötigen Bausteine (Protein-Erkennungssequenz zur Reaktion mit Nukleophil-Polymer und Polymer-Erkennungssequenz mit Nukleophil-Protein) hergestellt. Als Polymerisationstechnik wurde die radikalische Polymerisation mit reversibler Deaktivierung (im Detail, Atom Transfer Radical Polymerization, ATRP und Reversible Addition-Fragmentation Chain Transfer, RAFT polymerization) gewählt, um eine enge Molmassenverteilung zu erreichen. Die Herstellung der Bausteine begann mit der Synthese der Peptide via automatisierter Festphasen-Peptidsynthese, um eine einfache Änderung der Peptidsequenz zu gewährleisten und um eine Modifizierung der Polymerkette nach der Polymerisation zu umgehen. Um die benötigte unterschiedliche Funktionalität der zwei Peptidsequenzen (freier C-Terminus bei der Erkennungssequenz bzw. freier N-Terminus bei dem Nukleophil) zu erreichen, wurden verschiedene Linker zwischen Harz und Peptid verwendet. Danach wurde der Kettenüberträger (chain transfer agent, CTA) zur Kontrolle der Polymerisation mit dem auf dem Harz befindlichen Peptid gekoppelt. Die für die anschließende Polymerisation verwendeten Monomere basierten auf Acrylamiden und Acrylaten und wurden anhand ihrer Eignung als Alternativen zu PEG ausgewählt. Es wurde eine kürzlich entwickelte Technik basierend auf der RAFT-Polymerisation (xanthate-supported photo-iniferter RAFT, XPI-RAFT) verwendet um eine Reihe an Peptid-Polymeren mit unterschiedlichen Molekulargewichten und engen Molekulargewichtsverteilungen herzustellen. Nach Entfernung der Schutzgruppen der Peptid-Seitenketten wurden die Peptid-Polymere zunächst genutzt, um mittels Sortase-vermittelter Ligation zwei Polymerketten zu einem Blockcopolymer zu verbinden. Unter Verwendung von Ni2+-Ionen in Kombination mit einer Verlängerung der Erkennungssequenz um ein Histidin zur Unterdrückung der Rückreaktion konnte ein maximaler Umsatz von 70 % erreicht werden. Dabei zeigte sich ein oberes Limit von durchschnittlich 100 Wiederholungseinheiten; die Ligation von längeren Polymeren war nicht erfolgreich. Danach wurden ein Modellprotein und ein Nanobody mit vielversprechenden medizinischen Eigenschaften mit den für die enzymkatalysierte Ligation benötigten Peptidsequenzen für die Kopplung mit den zuvor hergestellten Peptid-Polymeren verwendet. Dabei konnte bei Verwendung des Modellproteins keine Bildung von Protein-Polymer-Konjugaten beobachtet werden. Der Nanobody konnte dagegen C-terminal mit einem Polymer funktionalisiert werden. Dabei wurde eine ähnliche Limitierung in der Polymer-Kettenlänge beobachtet wie zuvor. Die auf Ni-Ionen basierte Strategie zur Gleichgewichtsverschiebung hatte hier keinen ausschlaggebenden Effekt, während die Verwendung von einem Überschuss an Polymer zur vollständigen Umsetzung des Edukt-Nanobody führte. Die erhaltenen Daten aus diesem Projekt bilden eine gute Basis für weitere Forschung in dem vielversprechenden Feld der enzymkatalysierten Herstellung von Protein-Polymer-Konjugaten und Blockcopolymeren. Langfristig könnte diese Herangehensweise eine vielseitig einsetzbare Herstellungsmethode von ortsspezifischen therapeutischen Protein-Polymer Konjugaten darstellen, welche sowohl eine hohe Aktivität als auch eine lange Zirkulationszeit im Blut aufweisen. N2 - During the last decades, therapeutical proteins have risen to great significance in the pharmaceutical industry. As non-human proteins that are introduced into the human body cause a distinct immune system reaction that triggers their rapid clearance, most newly approved protein pharmaceuticals are shielded by modification with synthetic polymers to significantly improve their blood circulation time. All such clinically approved protein-polymer conjugates contain polyethylene glycol (PEG) and its conjugation is denoted as PEGylation. However, many patients develop anti-PEG antibodies which cause a rapid clearance of PEGylated molecules upon repeated administration. Therefore, the search for alternative polymers that can replace PEG in therapeutic applications has become important. In addition, although the blood circulation time is significantly prolonged, the therapeutic activity of some conjugates is decreased compared to the unmodified protein. The reason is that these conjugates are formed by the traditional conjugation method that addresses the protein's lysine side chains. As proteins have many solvent exposed lysines, this results in a somewhat uncontrolled attachment of polymer chains, leading to a mixture of regioisomers, with some of them eventually affecting the therapeutic performance. This thesis investigates a novel method for ligating macromolecules in a site-specific manner, using enzymatic catalysis. Sortase A is used as the enzyme: It is a well-studied transpeptidase which is able to catalyze the intermolecular ligation of two peptides. This process is commonly referred to as sortase-mediated ligation (SML). SML constitutes an equilibrium reaction, which limits product yield. Two previously reported methods to overcome this major limitation were tested with polymers without using an excessive amount of one reactant. Specific C- or N-terminal peptide sequences (recognition sequence and nucleophile) as part of the protein are required for SML. The complementary peptide was located at the polymer chain end. Grafting-to was used to avoid damaging the protein during polymerization. To be able to investigate all possible combinations (protein-recognition sequence and nucleophile-protein as well as polymer-recognition sequence and nucleophile-polymer) all necessary building blocks were synthesized. Polymerization via reversible deactivation radical polymerization (RDRP) was used to achieve a narrow molecular weight distribution of the polymers, which is required for therapeutic use. The synthesis of the polymeric building blocks was started by synthesizing the peptide via automated solid-phase peptide synthesis (SPPS) to avoid post-polymerization attachment and to enable easy adaptation of changes in the peptide sequence. To account for the different functionalities (free N- or C-terminus) required for SML, different linker molecules between resin and peptide were used. To facilitate purification, the chain transfer agent (CTA) for reversible addition-fragmentation chain-transfer (RAFT) polymerization was coupled to the resin-immobilized recognition sequence peptide. The acrylamide and acrylate-based monomers used in this thesis were chosen for their potential to replace PEG. Following that, surface-initiated (SI) ATRP and RAFT polymerization were attempted, but failed. As a result, the newly developed method of xanthate-supported photo-iniferter (XPI) RAFT polymerization in solution was used successfully to obtain a library of various peptide-polymer conjugates with different chain lengths and narrow molar mass distributions. After peptide side chain deprotection, these constructs were used first to ligate two polymers via SML, which was successful but revealed a limit in polymer chain length (max. 100 repeat units). When utilizing equimolar amounts of reactants, the use of Ni2+ ions in combination with a histidine after the recognition sequence to remove the cleaved peptide from the equilibrium maximized product formation with conversions of up to 70 %. Finally, a model protein and a nanobody with promising properties for therapeutical use were biotechnologically modified to contain the peptide sequences required for SML. Using the model protein for C- or N-terminal SML with various polymers did not result in protein-polymer conjugates. The reason is most likely the lack of accessibility of the protein termini to the enzyme. Using the nanobody for C-terminal SML, on the other hand, was successful. However, a similar polymer chain length limit was observed as in polymer-polymer SML. Furthermore, in case of the synthesis of protein-polymer conjugates, it was more effective to shift the SML equilibrium by using an excess of polymer than by employing the Ni2+ ion strategy. Overall, the experimental data from this work provides a good foundation for future research in this promising field; however, more research is required to fully understand the potential and limitations of using SML for protein-polymer synthesis. In future, the method explored in this dissertation could prove to be a very versatile pathway to obtain therapeutic protein-polymer conjugates that exhibit high activities and long blood circulation times. KW - biohybrid molecules KW - sortaseA KW - polymerization KW - RAFT KW - ATRP KW - peptide synthesis KW - enzymatic conjugation KW - sortagging Y1 - 2024 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-645669 ER - TY - CHAP A1 - Wang, Zhenyu A1 - Breternitz, Joachim A1 - Schorr, Susan T1 - Cation disorder in zinc-group IV- nitride and oxide nitride semiconductor materials revealed through neutron diffraction T2 - Acta crystallographica / International Union of Crystallography. Section A, Foundations and advances KW - nitride materials KW - semiconductors KW - structure-property relationships Y1 - 2021 U6 - https://doi.org/10.1107/S0108767321086256 SN - 2053-2733 VL - 77 IS - Suppl. SP - C1077 EP - C1077 PB - Blackwell CY - Oxford [u.a.] ER - TY - JOUR A1 - Erler, Alexander A1 - Riebe, Daniel A1 - Beitz, Toralf A1 - Löhmannsröben, Hans-Gerd A1 - Leenen, Mathias A1 - Pätzold, Stefan A1 - Ostermann, Markus A1 - Wójcik, Michał T1 - Mobile laser-induced breakdown spectroscopy for future application in precision agriculture BT - a case study JF - Sensors N2 - In precision agriculture, the estimation of soil parameters via sensors and the creation of nutrient maps are a prerequisite for farmers to take targeted measures such as spatially resolved fertilization. In this work, 68 soil samples uniformly distributed over a field near Bonn are investigated using laser-induced breakdown spectroscopy (LIBS). These investigations include the determination of the total contents of macro- and micronutrients as well as further soil parameters such as soil pH, soil organic matter (SOM) content, and soil texture. The applied LIBS instruments are a handheld and a platform spectrometer, which potentially allows for the single-point measurement and scanning of whole fields, respectively. Their results are compared with a high-resolution lab spectrometer. The prediction of soil parameters was based on multivariate methods. Different feature selection methods and regression methods like PLS, PCR, SVM, Lasso, and Gaussian processes were tested and compared. While good predictions were obtained for Ca, Mg, P, Mn, Cu, and silt content, excellent predictions were obtained for K, Fe, and clay content. The comparison of the three different spectrometers showed that although the lab spectrometer gives the best results, measurements with both field spectrometers also yield good results. This allows for a method transfer to the in-field measurements. KW - LIBS KW - precision agriculture KW - soil KW - multivariate methods KW - feature selection Y1 - 2023 U6 - https://doi.org/10.3390/s23167178 SN - 1424-8220 VL - 23 IS - 16 PB - MDPI CY - Basel ER - TY - JOUR A1 - Adesina, Morenike O. A1 - Block, Inga A1 - Günter, Christina A1 - Unuabonah, Emmanuel Iyayi A1 - Taubert, Andreas T1 - Efficient Removal of Tetracycline and Bisphenol A from Water with a New Hybrid Clay/TiO2 Composite JF - ACS Omega N2 - New TiO2 hybrid composites were prepared fromkaolinclay, predried and carbonized biomass, and titanium tetraisopropoxideand explored for tetracycline (TET) and bisphenol A (BPA) removalfrom water. Overall, the removal rate is 84% for TET and 51% for BPA.The maximum adsorption capacities (q (m))are 30 and 23 mg/g for TET and BPA, respectively. These capacitiesare far greater than those obtained for unmodified TiO2. Increasing the ionic strength of the solution does not change theadsorption capacity of the adsorbent. pH changes only slightly changeBPA adsorption, while a pH > 7 significantly reduces the adsorptionof TET on the material. The Brouers-Sotolongo fractal modelbest describes the kinetic data for both TET and BPA adsorption, predictingthat the adsorption process occurs via a complex mechanism involvingvarious forces of attraction. Temkin and Freundlich isotherms, whichbest fit the equilibrium adsorption data for TET and BPA, respectively,suggest that adsorption sites are heterogeneous in nature. Overall,the composite materials are much more effective for TET removal fromaqueous solution than for BPA. This phenomenon is assigned to a differencein the TET/adsorbent interactions vs the BPA/adsorbent interactions:the decisive factor appears to be favorable electrostatic interactionsfor TET yielding a more effective TET removal. Y1 - 2023 U6 - https://doi.org/10.1021/acsomega.3c00184 SN - 2470-1343 VL - 8 IS - 24 SP - 21594 EP - 21604 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Mazarei, Elham A1 - Penschke, Christopher A1 - Saalfrank, Peter T1 - Band gap engineering in two-dimensional materials by functionalization BT - Methylation of graphene and graphene bilayers JF - ACS Omega N2 - Graphene is well-knownfor its unique combination of electricaland mechanical properties. However, its vanishing band gap limitsthe use of graphene in microelectronics. Covalent functionalizationof graphene has been a common approach to address this critical issueand introduce a band gap. In this Article, we systematically analyzethe functionalization of single-layer graphene (SLG) and bilayer graphene(BLG) with methyl (CH3) using periodic density functionaltheory (DFT) at the PBE+D3 level of theory. We also include a comparisonof methylated single-layer and bilayer graphene, as well as a discussionof different methylation options (radicalic, cationic, and anionic).For SLG, methyl coverages ranging from 1/8 to 1/1, (i.e.,the fully methylated analogue of graphane) are considered. We findthat up to a coverage theta of 1/2, graphene readily accepts CH3, with neighbor CH3 groups preferring trans positions. Above theta = 1/2, the tendency to accept further CH3 weakens and the lattice constant increases. The band gapbehaves less regularly, but overall it increases with increasing methylcoverage. Thus, methylated graphene shows potential for developingband gap-tuned microelectronics devices and may offer further functionalizationoptions. To guide in the interpretation of methylation experiments,vibrational signatures of various species are characterized by normal-modeanalysis (NMA), their vibrational density of states (VDOS), and infrared(IR) spectra, the latter two are obtained from ab initio moleculardynamics (AIMD) in combination with a velocity-velocity autocorrelationfunction (VVAF) approach. KW - Adsorption KW - Alkyls KW - Band structure KW - Electrical conductivity KW - Two dimensional materials Y1 - 2023 U6 - https://doi.org/10.1021/acsomega.3c02068 SN - 2470-1343 VL - 8 IS - 24 SP - 22026 EP - 22041 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - The multiple bond character of the carbon-boron bond in boron trapped N-heterocyclic carbenes (NHCs) and cyclic(alkyl)(amino) carbenes (CAACs) on the magnetic criterion JF - Tetrahedron N2 - Geometry, 11B, 13C chemical shifts and the spatial magnetic properties (Through-Space NMR Shieldings -TSNMRS) of both cations and anions of boron-trapped N-heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) and of the corresponding diborane/diborene/diboryne dis-carbene adducts have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept; the TSNMRS results are visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The ICSS of the TSNMRS (actually the anisotropy effects measurable in 1H NMR spectroscopy) are employed to qualify and quantify the present multiple bond character of the Carbene-Boron bond in the trapped NHCs and CAACs. Results are confirmed by bond length and 11B/13C chemical shift variations. Thus the partial multiple bond character of the Carbene-Boron bond cannot be expressed by the arrow of weak, much longer dative bonds and should be omitted as in other covalent lone pair-it or triel bonds. & COPY; 2023 Elsevier Ltd. All rights reserved. KW - NHCs KW - CAACs KW - Multiple NHC(CAAC)-Boron bonds KW - Through -space NMR KW - shieldings (TSNMRS) KW - NICS KW - Anisotropy effect KW - Ring current effect Y1 - 2023 U6 - https://doi.org/10.1016/j.tet.2023.133469 SN - 0040-4020 SN - 1464-5416 VL - 140 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Schlappa, Stephanie A1 - Bressel, Lena A1 - Reich, Oliver A1 - Münzberg, Marvin T1 - Advanced particle size analysis in high-solid-content polymer dispersions using photon density wave spectroscopy JF - Polymers N2 - High-solid-content polystyrene and polyvinyl acetate dispersions of polymer particles with a 50 nm to 500 nm mean particle diameter and 12-55% (w/w) solid content have been produced via emulsion polymerization and characterized regarding their optical and physical properties. Both systems have been analyzed with common particle-size-measuring techniques like dynamic light scattering (DLS) and static light scattering (SLS) and compared to inline particle size distribution (PSD) measurements via photon density wave (PDW) spectroscopy in undiluted samples. It is shown that particle size measurements of undiluted polystyrene dispersions are in good agreement between analysis methods. However, for polyvinyl acetate particles, size determination is challenging due to bound water in the produced polymer. For the first time, water-swelling factors were determined via an iterative approach of PDW spectroscopy error (X-2) minimization. It is shown that water-swollen particles can be analyzed in high-solid-content solutions and their physical properties can be assumed to determine the refractive index, density, and volume fraction in dispersion. It was found that assumed water swelling improved the reduced scattering coefficient fit by PDW spectroscopy by up to ten times and particle size determination was refined and enabled. Particle size analysis of the water-swollen particles agreed well with offline-based state-of-the-art techniques. KW - emulsion polymerization KW - multiple light scattering KW - photon density wave KW - spectroscopy KW - particle sizing KW - swelling of polymers Y1 - 2023 U6 - https://doi.org/10.3390/polym15153181 SN - 2073-4360 VL - 15 IS - 15 PB - MDPI CY - Basel ER - TY - JOUR A1 - Xu, Yaolin A1 - Dong, Kang A1 - Jie, Yulin A1 - Adelhelm, Philipp A1 - Chen, Yawei A1 - Xu, Liang A1 - Yu, Peiping A1 - Kim, Junghwa A1 - Kochovski, Zdravko A1 - Yu, Zhilong A1 - Li, Wanxia A1 - LeBeau, James A1 - Shao-Horn, Yang A1 - Cao, Ruiguo A1 - Jiao, Shuhong A1 - Cheng, Tao A1 - Manke, Ingo A1 - Lu, Yan T1 - Promoting mechanistic understanding of lithium deposition and solid-electrolyte interphase (SEI) formation using advanced characterization and simulation methods: recent progress, limitations, and future perspectives JF - Avanced energy materials N2 - In recent years, due to its great promise in boosting the energy density of lithium batteries for future energy storage, research on the Li metal anode, as an alternative to the graphite anode in Li-ion batteries, has gained significant momentum. However, the practical use of Li metal anodes has been plagued by unstable Li (re)deposition and poor cyclability. Although tremendous efforts have been devoted to the stabilization of Li metal anodes, the mechanisms of electrochemical (re-)deposition/dissolution of Li and solid-electrolyte-interphase (SEI) formation remain elusive. This article highlights the recent mechanistic understandings and observations of Li deposition/dissolution and SEI formation achieved from advanced characterization techniques and simulation methods, and discusses major limitations and open questions in these processes. In particular, the authors provide their perspectives on advanced and emerging/potential methods for obtaining new insights into these questions. In addition, they give an outlook into cutting-edge interdisciplinary research topics for Li metal anodes. It pushes beyond the current knowledge and is expected to accelerate development toward a more in-depth and comprehensive understanding, in order to guide future research on Li metal anodes toward practical application. KW - advanced characterization KW - Li deposition KW - Li dissolution KW - Li metal KW - anodes KW - mechanistic understanding KW - solid-electrolyte-interphase KW - theoretical simulation Y1 - 2022 U6 - https://doi.org/10.1002/aenm.202200398 SN - 1614-6832 SN - 1614-6840 VL - 12 IS - 19 PB - Wiley CY - Weinheim ER - TY - JOUR A1 - Rothe, Martin A1 - Zhao, Yuhang A1 - Müller, Johannes A1 - Kewes, Günter A1 - Koch, Christoph T. A1 - Lu, Yan A1 - Benson, Oliver T1 - Self-assembly of plasmonic nanoantenna-waveguide structures for subdiffractional chiral sensing JF - ACS nano N2 - Spin-momentum locking is a peculiar effect in the near-field of guided optical or plasmonic modes. It can be utilized to map the spinning or handedness of electromagnetic fields onto the propagation direction. This motivates a method to probe the circular dichroism of an illuminated chiral object. In this work, we demonstrate local, subdiffraction limited chiral coupling of light and propagating surface plasmon polaritons in a self-assembled system of a gold nanoantenna and a silver nanowire. A thin silica shell around the nanowire provides precise distance control and also serves as a host for fluorescent molecules, which indicate the direction of plasmon propagation. We characterize our nanoantenna-nanowire systems comprehensively through correlated electron microscopy, energy-dispersive X-ray spectroscopy, dark-field, and fluorescence imaging. Three-dimensional numerical simulations support the experimental findings. Besides our measurement of far-field polarization, we estimate sensing capabilities and derive not only a sensitivity of 1 mdeg for the ellipticity of the light field, but also find 10(3) deg cm(2)/dmol for the circular dichroism of an analyte locally introduced in the hot spot of the antenna-wire system. Thorough modeling of a prototypical design predicts on-chip sensing of chiral analytes. This introduces our system as an ultracompact sensor for chiral response far below the diffraction limit. KW - plasmonics KW - nanoparticle assemblies KW - core-shell KW - spin-orbit coupling KW - chirality KW - circular dichroism KW - nano-optics Y1 - 2021 U6 - https://doi.org/10.1021/acsnano.0c05240 SN - 1936-0851 SN - 1936-086X VL - 15 IS - 1 SP - 351 EP - 361 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Ning, Jiaoyi A1 - Yu, Hongtao A1 - Mei, Shilin A1 - Schütze, Yannik A1 - Risse, Sebastian A1 - Kardjilov, Nikolay A1 - Hilger, André A1 - Manke, Ingo A1 - Bande, Annika A1 - Ruiz, Victor G. A1 - Dzubiella, Joachim A1 - Meng, Hong A1 - Lu, Yan T1 - Constructing binder- and carbon additive-free organosulfur cathodes based on conducting thiol-polymers through electropolymerization for lithium-sulfur batteries JF - ChemSusChem N2 - Herein, the concept of constructing binder- and carbon additive-free organosulfur cathode was proved based on thiol-containing conducting polymer poly(4-(thiophene-3-yl) benzenethiol) (PTBT). The PTBT featured the polythiophene-structure main chain as a highly conducting framework and the benzenethiol side chain to copolymerize with sulfur and form a crosslinked organosulfur polymer (namely S/PTBT). Meanwhile, it could be in-situ deposited on the current collector by electro-polymerization, making it a binder-free and free-standing cathode for Li-S batteries. The S/PTBT cathode exhibited a reversible capacity of around 870 mAh g(-1) at 0.1 C and improved cycling performance compared to the physically mixed cathode (namely S&PTBT). This multifunction cathode eliminated the influence of the additives (carbon/binder), making it suitable to be applied as a model electrode for operando analysis. Operando X-ray imaging revealed the remarkable effect in the suppression of polysulfides shuttle via introducing covalent bonds, paving the way for the study of the intrinsic mechanisms in Li-S batteries. KW - electrochemistry KW - energy storage KW - lithium-sulfur batteries KW - operando KW - studies KW - organosulfur Y1 - 2022 U6 - https://doi.org/10.1002/cssc.202200434 SN - 1864-5631 SN - 1864-564X VL - 15 IS - 14 PB - Wiley CY - Weinheim ER -