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 - Mayer, Dennis
A1 - Lever, Fabiano
A1 - Picconi, David
A1 - Metje, Jan
A1 - Ališauskas, Skirmantas
A1 - Calegari, Francesca
A1 - Düsterer, Stefan
A1 - Ehlert, Christopher
A1 - Feifel, Raimund
A1 - Niebuhr, Mario
A1 - Manschwetus, Bastian
A1 - Kuhlmann, Marion
A1 - Mazza, Tommaso
A1 - Robinson, Matthew Scott
A1 - Squibb, Richard J.
A1 - Trabattoni, Andrea
A1 - Wallner, Måns
A1 - Saalfrank, Peter
A1 - Wolf, Thomas J. A.
A1 - Gühr, Markus
T1 - Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy
JF - Nature communications
N2 - Imaging the charge flow in photoexcited molecules would provide key information on photophysical and photochemical processes. Here the authors demonstrate tracking in real time after photoexcitation the change in charge density at a specific site of 2-thiouracil using time-resolved X-ray photoelectron spectroscopy. The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220-250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.
Y1 - 2022
U6 - https://doi.org/10.1038/s41467-021-27908-y
SN - 2041-1723
N1 - Publisher correction: https://doi.org/10.1038/s41467-022-28584-2
VL - 13
IS - 1
PB - Nature Research
CY - Berlin
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 -
TY - JOUR
A1 - Lau, Skadi
A1 - Liu, Yue
A1 - Maier, Anna
A1 - Braune, Steffen
A1 - Gossen, Manfred
A1 - Neffe, Axel T.
A1 - Lendlein, Andreas
T1 - Establishment of an in vitro thrombogenicity test system with cyclic olefin copolymer substrate for endothelial layer formation
JF - MRS communications / a publication of the Materials Research Society
N2 - In vitro thrombogenicity test systems require co-cultivation of endothelial cells and platelets under blood flow-like conditions. Here, a commercially available perfusion system is explored using plasma-treated cyclic olefin copolymer (COC) as a substrate for the endothelial cell layer. COC was characterized prior to endothelialization and co-cultivation with platelets under static or flow conditions. COC exhibits a low roughness and a moderate hydrophilicity. Flow promoted endothelial cell growth and prevented platelet adherence. These findings show the suitability of COC as substrate and the importance of blood flow-like conditions for the assessment of the thrombogenic risk of drugs or cardiovascular implant materials.
Y1 - 2021
U6 - https://doi.org/10.1557/s43579-021-00072-6
SN - 2159-6867
VL - 11
IS - 5
SP - 559
EP - 567
PB - Springer
CY - Berlin
ER -
TY - JOUR
A1 - Neusser, David
A1 - Sun, Bowen
A1 - Tan, Wen Liang
A1 - Thomsen, Lars
A1 - Schultz, Thorsten
A1 - Perdigon-Toro, Lorena
A1 - Koch, Norbert
A1 - Shoaee, Safa
A1 - McNeill, Christopher R.
A1 - Neher, Dieter
A1 - Ludwigs, Sabine
T1 - Spectroelectrochemically determined energy levels of PM6:Y6 blends and their relevance to solar cell performance
JF - Journal of materials chemistry : C, Materials for optical and electronic devices
N2 - Recent advances in organic solar cell performance have been mainly driven forward by combining high-performance p-type donor-acceptor copolymers (e.g.PM6) and non-fullerene small molecule acceptors (e.g.Y6) as bulk-heterojunction layers. A general observation in such devices is that the device performance, e.g., the open-circuit voltage, is strongly dependent on the processing solvent. While the morphology is a typically named key parameter, the energetics of donor-acceptor blends are equally important, but less straightforward to access in the active multicomponent layer. Here, we propose to use spectral onsets during electrochemical cycling in a systematic spectroelectrochemical study of blend films to access the redox behavior and the frontier orbital energy levels of the individual compounds. Our study reveals that the highest occupied molecular orbital offset (Delta E-HOMO) in PM6:Y6 blends is similar to 0.3 eV, which is comparable to the binding energy of Y6 excitons and therefore implies a nearly zero driving force for the dissociation of Y6 excitons. Switching the PM6 orientation in the blend films from face-on to edge-on in bulk has only a minor influence on the positions of the energy levels, but shows significant differences in the open circuit voltage of the device. We explain this phenomenon by the different interfacial molecular orientations, which are known to affect the non-radiative decay rate of the charge-transfer state. We compare our results to ultraviolet photoelectron spectroscopy data, which shows distinct differences in the HOMO offsets in the PM6:Y6 blend compared to neat films. This highlights the necessity to measure the energy levels of the individual compounds in device-relevant blend films.
Y1 - 2022
U6 - https://doi.org/10.1039/d2tc01918c
SN - 2050-7526
SN - 2050-7534
VL - 10
IS - 32
SP - 11565
EP - 11578
PB - Royal Society of Chemistry
CY - Cambridge
ER -
TY - JOUR
A1 - Tung, Wing Tai
A1 - Sun, Xianlei
A1 - Wang, Weiwei
A1 - Xu, Xun
A1 - Ma, Nan
A1 - Lendlein, Andreas
T1 - Structure, mechanical properties and degradation behavior of electrospun PEEU fiber meshes and films
JF - MRS advances : a journal of the Materials Research Society (MRS)
N2 - The capability of a degradable implant to provide mechanical support depends on its degradation behavior. Hydrolytic degradation was studied for a polyesteretherurethane (PEEU70), which consists of poly(p-dioxanone) (PPDO) and poly(epsilon-caprolactone) (PCL) segments with a weight ratio of 70:30 linked by diurethane junction units. PEEU70 samples prepared in the form of meshes with average fiber diameters of 1.5 mu m (mesh1.5) and 1.2 mu m (mesh1.2), and films were sterilized and incubated in PBS at 37 degrees C with 5 vol% CO2 supply for 1 to 6 weeks. Degradation features, such as cracks or wrinkles, became apparent from week 4 for all samples. Mass loss was found to be 11 wt%, 6 wt%, and 4 wt% for mesh1.2, mesh1.5, and films at week 6. The elongation at break decreased to under 20% in two weeks for mesh1.2. In case of the other two samples, this level of degradation was achieved after 4 weeks. The weight average molecular weight of both PEEU70 mesh and film samples decreased to below 30 kg/mol when elongation at break dropped below 20%. The time period of sustained mechanical stability of PEEU70-based meshes depends on the fiber diameter and molecular weight.
Y1 - 2021
U6 - https://doi.org/10.1557/s43580-020-00001-0
SN - 2059-8521
VL - 6
IS - 10
SP - 276
EP - 282
PB - Springer Nature Switzerland AG
CY - Cham
ER -
TY - JOUR
A1 - Stefancu, Andrei
A1 - Nan, Lin
A1 - Zhu, Li
A1 - Chis, Vasile
A1 - Bald, Ilko
A1 - Liu, Min
A1 - Leopold, Nicolae
A1 - Maier, Stefan A.
A1 - Cortes, Emiliano
T1 - Controlling plasmonic chemistry pathways through specific ion effects
JF - Advanced optical materials
N2 - Plasmon-driven dehalogenation of brominated purines has been recently explored as a model system to understand fundamental aspects of plasmon-assisted chemical reactions. Here, it is shown that divalent Ca2+ ions strongly bridge the adsorption of bromoadenine (Br-Ade) to Ag surfaces.
Such ion-mediated binding increases the molecule's adsorption energy leading to an overlap of the metal energy states and the molecular states, enabling the chemical interface damping (CID) of the plasmon modes of the Ag nanostructures (i.e., direct electron transfer from the metal to Br-Ade).
Consequently, the conversion of Br-Ade to adenine almost doubles following the addition of Ca2+.
These experimental results, supported by theoretical calculations of the local density of states of the Ag/Br-Ade complex, indicate a change of the charge transfer pathway driving the dehalogenation reaction, from Landau damping (in the lack of Ca2+ ions) to CID (after the addition of Ca2+).
The results show that the surface dynamics of chemical species (including water molecules) play an essential role in charge transfer at plasmonic interfaces and cannot be ignored. It is envisioned that these results will help in designing more efficient nanoreactors, harnessing the full potential of plasmon-assisted chemistry.
KW - chemical interface damping
KW - Hofmeister effect
KW - hydration layer
KW - plasmonic chemistry
KW - specific ion effects
KW - surface-enhanced Raman scattering
Y1 - 2022
U6 - https://doi.org/10.1002/adom.202200397
SN - 2195-1071
VL - 10
IS - 14
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Zhao, Yuhang
A1 - Opitz, Andreas
A1 - Eljarrat, Alberto
A1 - Kochovski, Zdravko
A1 - Koch, Christoph
A1 - Koch, Norbert
A1 - Lu, Yan
T1 - Kinetic study on the adsorption of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane on Ag nanoparticles in chloroform
BT - implications for the charge transfer complex of Ag-F(4)TCNQ
JF - ACS applied nano materials
N2 - In this study, the kinetics of the adsorption of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ) on the surface of Ag nanoparticles (Ag NPs) in chloroform has been intensively investigated, as molecular doping is known to play a crucial role in organic electronic devices. Based on the results obtained from UV-visible (vis)-near-infrared (NIR) absorption spectroscopy, cryogenic transmission electron microscopy, scanning nanobeam electron diffraction, and electron energy loss spectroscopy, a two-step interaction kinetics has been proposed for the Ag NPs and F(4)TCNQ molecules, which includes the first step of electron transfer from Ag NPs to F(4)TCNQ indicated by the ionization of F(4)TCNQ and the second step of the formation of a Ag-F(4)TCNQ complex. The whole process has been followed via UV-vis-NIR absorption spectroscopy, which reveals distinct kinetics at two stages: the instantaneous ionization and the long-term complex formation. The kinetics and the influence of the molar ratio of Ag NPs/F(4)TCNQ molecules on the interaction between Ag NPs and F(4)TCNQ molecules in an organic solution are reported herein for the first time. Furthermore, the control experiment with silica-coated Ag NPs manifests that the charge transfer at the surface between Ag NPs and F(4)TCNQ molecules is prohibited by a silica layer of 18 nm.
KW - Ag nanoparticles
KW - F(4)TCNQ
KW - phase transfer
KW - kinetics
KW - electron transfer
KW - surface interaction
Y1 - 2021
U6 - https://doi.org/10.1021/acsanm.1c02153
SN - 2574-0970
VL - 4
IS - 11
SP - 11625
EP - 11635
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Zhou, Shuo
A1 - Xu, Xun
A1 - Ma, Nan
A1 - Jung, Friedrich
A1 - Lendlein, Andreas
T1 - Influence of sterilization conditions on sulfate-functionalized polyGGE
JF - Clinical hemorheology and microcirculation : blood flow and vessels
N2 - Sulfated biomolecules are known to influence numerous biological processes in all living organisms. Particularly, they contribute to prevent and inhibit the hypercoagulation condition. The failure of polymeric implants and blood contacting devices is often related to hypercoagulation and microbial contamination. Here, bioactive sulfated biomacromolecules are mimicked by sulfation of poly(glycerol glycidyl ether) (polyGGE) films. Autoclaving, gamma-ray irradiation and ethylene oxide (EtO) gas sterilization techniques were applied to functionalized materials. The sulfate group density and hydrophilicity of sulfated polymers were decreased while chain mobility and thermal degradation were enhanced post autoclaving when compared to those after EtO sterilization. These results suggest that a quality control after sterilization is mandatory to ensure the amount and functionality of functionalized groups are retained.
KW - Sulfated polymer
KW - sulfation
KW - sterilization
KW - ethylene oxide
Y1 - 2021
U6 - https://doi.org/10.3233/CH-211241
SN - 1386-0291
SN - 1875-8622
VL - 79
IS - 4
SP - 597
EP - 608
PB - IOS Press
CY - Amsterdam
ER -
TY - THES
A1 - Mostafa, Amr
T1 - DNA origami nanoforks: A platform for cytochrome c single molecule surface enhanced Raman spectroscopy
N2 - This thesis presents a comprehensive exploration of the application of DNA origami nanofork antennas (DONAs) in the field of spectroscopy, with a particular focus on the structural analysis of Cytochrome C (CytC) at the single-molecule level. The research encapsulates the design, optimization, and application of DONAs in enhancing the sensitivity and specificity of Raman spectroscopy, thereby offering new insights into protein structures and interactions.
The initial phase of the study involved the meticulous optimization of DNA origami structures. This process was pivotal in developing nanoscale tools that could significantly enhance the capabilities of Raman spectroscopy. The optimized DNA origami nanoforks, in both dimer and aggregate forms, demonstrated an enhanced ability to detect and analyze molecular vibrations, contributing to a more nuanced understanding of protein dynamics.
A key aspect of this research was the comparative analysis between the dimer and aggregate forms of DONAs. This comparison revealed that while both configurations effectively identified oxidation and spin states of CytC, the aggregate form offered a broader range of detectable molecular states due to its prolonged signal emission and increased number of molecules. This extended duration of signal emission in the aggregates was attributed to the collective hotspot area, enhancing overall signal stability and sensitivity.
Furthermore, the study delved into the analysis of the Amide III band using the DONA system. Observations included a transient shift in the Amide III band's frequency, suggesting dynamic alterations in the secondary structure of CytC. These shifts, indicative of transitions between different protein structures, were crucial in understanding the protein’s functional mechanisms and interactions.
The research presented in this thesis not only contributes significantly to the field of spectroscopy but also illustrates the potential of interdisciplinary approaches in biosensing. The use of DNA origami-based systems in spectroscopy has opened new avenues for research, offering a detailed and comprehensive understanding of protein structures and interactions. The insights gained from this research are expected to have lasting implications in scientific fields ranging from drug development to the study of complex biochemical pathways. This thesis thus stands as a testament to the power of integrating nanotechnology, biochemistry, and spectroscopic techniques in addressing complex scientific questions.
N2 - Diese Dissertation präsentiert eine umfassende Untersuchung der Anwendung von DNA-Origami-Nanogabelantennen (DONAs) im Bereich der Spektroskopie, mit einem besonderen Fokus auf der strukturellen Analyse von Cytochrom C (CytC) auf Einzelmolekülebene. Die Forschung umfasst das Design, die Optimierung und die Anwendung von DONAs zur Steigerung der Sensitivität und Spezifität der Raman-Spektroskopie und bietet somit neue Einblicke in Proteinstrukturen und -interaktionen.
Die erste Phase der Studie beinhaltete die sorgfältige Optimierung von DNA-Origami-Strukturen. Dieser Prozess war entscheidend für die Entwicklung von Nanowerkzeugen, die die Fähigkeiten der Raman-Spektroskopie erheblich verbessern könnten. Die optimierten DNA-Origami-Nanogabeln, sowohl in Dimer- als auch in Aggregatform, zeigten eine verbesserte Fähigkeit, molekulare Schwingungen zu detektieren und zu analysieren, was zu einem nuancierteren Verständnis der Proteindynamik beitrug.
Ein Schlüsselaspekt dieser Forschung war die vergleichende Analyse zwischen den Dimer- und Aggregatformen von DONAs. Dieser Vergleich zeigte, dass beide Konfigurationen effektiv Oxidations- und Spin-Zustände von CytC identifizieren konnten, wobei die Aggregatform aufgrund ihrer längeren Signalemission und der erhöhten Anzahl von Molekülen ein breiteres Spektrum an detektierbaren molekularen Zuständen bot. Die verlängerte Dauer der Signalemission in den Aggregaten wurde auf den kollektiven Hotspot-Bereich zurückgeführt, der die Gesamtsignalstabilität und -empfindlichkeit erhöhte.
Darüber hinaus ging die Studie auf die Analyse der Amid-III-Bande unter Verwendung des DONA-Systems ein. Zu den Beobachtungen gehörte eine vorübergehende Verschiebung der Frequenz der Amid-III-Bande, was auf dynamische Veränderungen in der Sekundärstruktur von CytC hindeutete. Diese Verschiebungen, die auf Übergänge zwischen verschiedenen Proteinstrukturen hindeuteten, waren entscheidend für das Verständnis der funktionellen Mechanismen und Interaktionen des Proteins.
Die in dieser Dissertation präsentierte Forschung leistet nicht nur einen bedeutenden Beitrag zum Gebiet der Spektroskopie, sondern veranschaulicht auch das Potenzial interdisziplinärer Ansätze in der Biosensorik. Der Einsatz von DNA-Origami-basierten Systemen in der Spektroskopie hat neue Wege für die Forschung eröffnet und bietet ein detailliertes und umfassendes Verständnis von Proteinstrukturen und -interaktionen. Die aus dieser Forschung gewonnenen Erkenntnisse werden voraussichtlich langfristige Auswirkungen auf wissenschaftliche Bereiche haben, die von der Arzneimittelentwicklung bis hin zur Untersuchung komplexer biochemischer Prozesse reichen. Diese Dissertation steht somit als Zeugnis für die Kraft der Integration von Nanotechnologie, Biochemie und spektroskopischen Techniken bei der Beantwortung komplexer wissenschaftlicher Fragen.
KW - DNA origami
KW - DNA origami nanoantennas (DONA)
KW - SERS
KW - Cytochrome C
Y1 - 2024
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-635482
ER -
TY - JOUR
A1 - Michaelis, Vivien
A1 - Aengenheister, Leonie
A1 - Tuchtenhagen, Max
A1 - Rinklebe, Jörg
A1 - Ebert, Franziska
A1 - Schwerdtle, Tanja
A1 - Buerki-Thurnherr, Tina
A1 - Bornhorst, Julia
T1 - Differences and interactions in placental manganese and iron transfer across an in vitro model of human villous trophoblasts
JF - International journal of molecular sciences
N2 - Manganese (Mn) as well as iron (Fe) are essential trace elements (TE) important for the maintenance of physiological functions including fetal development. However, in the case of Mn, evidence suggests that excess levels of intrauterine Mn are associated with adverse pregnancy outcomes. Although Mn is known to cross the placenta, the fundamentals of Mn transfer kinetics and mechanisms are largely unknown. Moreover, exposure to combinations of TEs should be considered in mechanistic transfer studies, in particular for TEs expected to share similar transfer pathways. Here, we performed a mechanistic in vitro study on the placental transfer of Mn across a BeWo b30 trophoblast layer. Our data revealed distinct differences in the placental transfer of Mn and Fe. While placental permeability to Fe showed a clear inverse dose-dependency, Mn transfer was largely independent of the applied doses. Concurrent exposure of Mn and Fe revealed transfer interactions of Fe and Mn, indicating that they share common transfer mechanisms. In general, mRNA and protein expression of discussed transporters like DMT1, TfR, or FPN were only marginally altered in BeWo cells despite the different exposure scenarios highlighting that Mn transfer across the trophoblast layer likely involves a combination of active and passive transport processes.
KW - manganese
KW - iron
KW - placental transfer
KW - TE interactions
KW - BeWo b30
KW - trophoblasts
Y1 - 2022
U6 - https://doi.org/10.3390/ijms23063296
SN - 1422-0067
VL - 23
IS - 6
PB - MDPI
CY - Basel
ER -
TY - GEN
A1 - Bande, Annika
A1 - González, Leticia
A1 - Klamroth, Tillmann
A1 - Tremblay, Jean Christophe
T1 - Theoretical chemistry and quantum dynamics at interfaces
BT - Celebrating the career of Peter Saalfrank on the occasion of his 60th birthday
T2 - Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature
Y1 - 2022
U6 - https://doi.org/10.1016/j.chemphys.2022.111509
SN - 0301-0104
SN - 1873-4421
VL - 558
PB - Elsevier Science
CY - Amsterdam [u.a.]
ER -
TY - JOUR
A1 - Crovetto, Andrea
A1 - Kojda, Danny
A1 - Yi, Feng
A1 - Heinselman, Karen N.
A1 - LaVan, David A.
A1 - Habicht, Klaus
A1 - Unold, Thomas
A1 - Zakutayev, Andriy
T1 - Crystallize It before It diffuses
BT - kinetic stabilization of thin-film phosphorus-rich semiconductor CuP2
JF - Journal of the american chemical society
N2 - Numerous phosphorus-rich metal phosphides containing both P-P bonds and metal-P bonds are known from the solid-state chemistry literature. A method to grow these materials in thin-film form would be desirable, as thin films are required in many applications and they are an ideal platform for high-throughput studies. In addition, the high density and smooth surfaces achievable in thin films are a significant advantage for characterization of transport and optical properties. Despite these benefits, there is hardly any published work on even the simplest binary phosphorus-rich phosphide films. Here, we demonstrate growth of single-phase CuP2 films by a two-step process involving reactive sputtering of amorphous CuP2+x and rapid annealing in an inert atmosphere. At the crystallization temperature, CuP2 is thermodynamically unstable with respect to Cu3P and P-4. However, CuP2 can be stabilized if the amorphous precursors are mixed on the atomic scale and are sufficiently close to the desired composition (neither too P poor nor too P rich). Fast formation of polycrystalline CuP2, combined with a short annealing time, makes it possible to bypass the diffusion processes responsible for decomposition. We find that thin-film CuP2 is a 1.5 eV band gap semiconductor with interesting properties, such as a high optical absorption coefficient (above 10(5) cm(-1)), low thermal conductivity (1.1 W/(K m)), and composition-insensitive electrical conductivity (around 1 S/cm). We anticipate that our processing route can be extended to other phosphorus-rich phosphides that are still awaiting thin-film synthesis and will lead to a more complete understanding of these materials and of their potential applications.
Y1 - 2022
U6 - https://doi.org/10.1021/jacs.2c04868
SN - 0002-7863
SN - 1520-5126
VL - 144
IS - 29
SP - 13334
EP - 13343
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Tung, Wing Tai
A1 - Maring, Janita A.
A1 - Xu, Xun
A1 - Liu, Yue
A1 - Becker, Matthias
A1 - Somesh, Dipthi Bachamanda
A1 - Klose, Kristin
A1 - Wang, Weiwei
A1 - Sun, Xianlei
A1 - Ullah, Imran
A1 - Kratz, Karl
A1 - Neffe, Axel T.
A1 - Stamm, Christof
A1 - Ma, Nan
A1 - Lendlein, Andreas
T1 - In vivo performance of a cell and factor free multifunctional fiber mesh modulating postinfarct myocardial remodeling
JF - Advanced Functional Materials
N2 - Guidance of postinfarct myocardial remodeling processes by an epicardial patch system may alleviate the consequences of ischemic heart disease. As macrophages are highly relevant in balancing immune response and regenerative processes their suitable instruction would ensure therapeutic success. A polymeric mesh capable of attracting and instructing monocytes by purely physical cues and accelerating implant degradation at the cell/implant interface is designed. In a murine model for myocardial infarction the meshes are compared to those either coated with extracellular matrix or loaded with induced cardiomyocyte progenitor cells. All implants promote macrophage infiltration and polarization in the epicardium, which is verified by in vitro experiments. 6 weeks post-MI, especially the implantation of the mesh attenuates left ventricular adverse remodeling processes as shown by reduced infarct size (14.7% vs 28-32%) and increased wall thickness (854 mu m vs 400-600 mu m), enhanced angiogenesis/arteriogenesis (more than 50% increase compared to controls and other groups), and improved heart function (ejection fraction = 36.8% compared to 12.7-31.3%). Upscaling as well as process controls is comprehensively considered in the presented mesh fabrication scheme to warrant further progression from bench to bedside.
KW - bioinstructive materials
KW - cardiac regeneration
KW - function by structure;
KW - modulation of in vivo regeneration
KW - multifunctional biomaterials
Y1 - 2022
U6 - https://doi.org/10.1002/adfm.202110179
SN - 1616-301X
SN - 1616-3028
VL - 32
IS - 31
PB - Wiley
CY - Weinheim
ER -
TY - JOUR
A1 - Breternitz, Joachim
A1 - Schorr, Susan
T1 - Symmetry relations in wurtzite nitrides and oxide nitrides and the curious case of Pmc2(1)
JF - Acta crystallographica / International Union of Crystallography. Section A, Foundations and advances
N2 - Binary III-V nitrides such as AlN, GaN and InN in the wurtzite-type structure have long been considered as potent semiconducting materials because of their optoelectronic properties, amongst others. With rising concerns over the utilization of scarce elements, a replacement of the trivalent cations by others in ternary and multinary nitrides has led to the development of different variants of nitrides and oxide nitrides crystallizing in lower-symmetry variants of wurtzite. This work presents the symmetry relationships between these structural types specific to nitrides and oxide nitrides and updates some prior work on this matter. The non-existence of compounds crystallizing in Pmc2(1), formally the highest subgroup of the wurtzite type fulfilling Pauling's rules for 1:1:2 stoichiometries, has been puzzling scientists for a while; a rationalization is given, from a crystallographic basis, of why this space group is unlikely to be adopted.
KW - group-subgroup relationships
KW - nitride materials
KW - wurtzite type
Y1 - 2021
U6 - https://doi.org/10.1107/S2053273320015971
SN - 2053-2733
VL - 77
IS - 3
SP - 208
EP - 216
PB - Blackwell
CY - Oxford [u.a.]
ER -
TY - JOUR
A1 - Mei, Shilin
A1 - Siebert, Andreas
A1 - Xu, Yaolin
A1 - Quan, Ting
A1 - Garcia-Diez, Raul
A1 - Bär, Marcus
A1 - Härtel, Paul
A1 - Abendroth, Thomas
A1 - Dörfler, Susanne
A1 - Kaskel, Stefan
A1 - Lu, Yan
T1 - Large-Scale Synthesis of Nanostructured Carbon-Ti4O7 Hollow Particles as Efficient Sulfur Host Materials for Multilayer Lithium-Sulfur Pouch Cells
JF - Batteries & supercaps
N2 - Applications of advanced cathode materials with well-designed chemical components and/or optimized nanostructures promoting the sulfur redox kinetics and suppressing the shuttle effect of polysulfides are highly valued. However, in the case of actual lithium-sulfur (Li-S) batteries under practical working conditions, one long-term obstacle still exists, which is mainly due to the difficulties in massive synthesis of such nanomaterials with low cost and ease of control on the nanostructure. Herein, we develop a facile synthesis of carbon coated Ti4O7 hollow nanoparticles (Ti4O7) using spherical polymer electrolyte brush as soft template, which is scalable via utilizing a minipilot reactor. The C Ti4O7 hollow nanoparticles provide strong chemical adsorption to polysulfides through the large polar surface and additional physical confinement by rich micro- & mesopores and have successfully been employed as an efficient sulfur host for multilayer pouch cells. Besides, the sluggish kinetics of the sulfur and lithium sulfide redox mechanism can be improved by the highly conductive Ti4O7 via catalyzation of the conversion of polysulfides. Consequently, the C-Ti4O7 based pouch cell endows a high discharge capacity of 1003 mAhg(-1) at 0.05 C, a high-capacity retention of 83.7% after 100 cycles at 0.1 C, and a high Coulombic efficiency of 97.5% at the 100th cycle. This work proposes an effective approach to transfer the synthesis of hollow Ti4O7 nanoparticles from lab- to large-scale production, paving the way to explore a wide range of advanced nanomaterials for multilayer Li-S pouch cells.
KW - lithium-sulfur batteries
KW - pouch cell
KW - spherical polyelectrolyte brushes (SPB)
KW - Ti4O7
Y1 - 2022
U6 - https://doi.org/10.1002/batt.202100398
SN - 2566-6223
VL - 5
IS - 6
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Lepre, Enrico
A1 - Heske, Julian
A1 - Nowakowski, Michal
A1 - Scoppola, Ernesto
A1 - Zizak, Ivo
A1 - Heil, Tobias
A1 - Kühne, Thomas D.
A1 - Antonietti, Markus
A1 - Lopez-Salas, Nieves
A1 - Albero, Josep
T1 - Ni-based electrocatalysts for unconventional CO2 reduction reaction to formic acid
JF - Nano energy
N2 - Electrochemical reduction stands as an alternative to revalorize CO2. Among the different alternatives, Ni single atoms supported on carbonaceous materials are an appealing catalytic solution due to the low cost and versatility of the support and the optimal usage of Ni and its predicted selectivity and efficiency (ca. 100% towards CO). Herein, we have used noble carbonaceous support derived from cytosine to load Ni subnanometric sites. The large heteroatom content of the support allows the stabilization of up to 11 wt% of Ni without the formation of nanoparticles through a simple impregnation plus calcination approach, where nickel promotes the stabilization of C3NOx frameworks and the oxidative support promotes a high oxidation state of nickel. EXAFS analysis points at nickel single atoms or subnanometric clusters coordinated by oxygen in the material surface. Unlike the wellknown N-coordinated Ni single sites selectivity towards CO2 reduction, O-coordinated-Ni single sites (ca. 7 wt% of Ni) reduced CO2 to CO, but subnanometric clusters (11 wt% of Ni) foster the unprecedented formation of HCOOH with 27% Faradaic efficiency at - 1.4 V. Larger Ni amounts ended up on the formation of NiO nanoparticles and almost 100% selectivity towards hydrogen evolution.
KW - CO 2 reduction reaction
KW - Noble carbon
KW - Ni-O4 electrocatalysts
KW - Formic acid
Y1 - 2022
U6 - https://doi.org/10.1016/j.nanoen.2022.107191
SN - 2211-2855
SN - 2211-3282
VL - 97
PB - Elsevier
CY - Amsterdam
ER -
TY - JOUR
A1 - Haubitz, Toni
A1 - Drobot, Björn
A1 - Tsushima, Satoru
A1 - Steudtner, Robin
A1 - Stumpf, Thorsten
A1 - Kumke, Michael Uwe
T1 - Quenching mechanism of uranyl(VI) by chloride and bromide in aqueous and non-aqueous solutions
JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory
N2 - A major hindrance in utilizing uranyl(VI) luminescence as a standard analytical tool, for example, in environmental monitoring or nuclear industries, is quenching by other ions such as halide ions, which are present in many relevant matrices of uranyl(VI) speciation. Here, we demonstrate through a combination of time-resolved laser-induced fluorescence spectroscopy, transient absorption spectroscopy, and quantum chemistry that coordinating solvent molecules play a crucial role in U(VI) halide luminescence quenching. We show that our previously suggested quenching mechanism based on an internal redox reaction of the 1:2-uranyl-halide-complex holds also true for bromide-induced quenching of uranyl(VI). By adopting specific organic solvents, we were able to suppress the separation of the oxidized halide ligand X-2(center dot-) and the formed uranyl(V) into fully solvated ions, thereby "reigniting" U(VI) luminescence. Time-dependent density functional theory calculations show that quenching occurs through the outer-sphere complex of U(VI) and halide in water, while the ligand-to-metal charge transfer is strongly reduced in acetonitrile.
Y1 - 2021
U6 - https://doi.org/10.1021/acs.jpca.1c02487
SN - 1089-5639
SN - 1520-5215
VL - 125
IS - 20
SP - 4380
EP - 4389
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Pham, Duong Tung
A1 - Quan, Ting
A1 - Mei, Shilin
A1 - Lu, Yan
T1 - Colloidal metal sulfide nanoparticles for high performance electrochemical energy storage systems
JF - Current opinion in green and sustainable chemistry
N2 - Transition metal sulfides have emerged as excellent replacement candidates of traditional insertion electrode materials based on their conversion or alloying mechanisms, facilitating high specific capacity and rate ability. However, parasitic reactions such as massive volume change during the discharge/ charge processes, intermediate polysulfide dissolution, and passivating solid electrolyte interface formation have led to poor cyclability, hindering their feasibility and applicability in energy storage systems. Colloidal metal sulfide nanoparticles, a special class that integrates the intrinsic chemical properties of metal sulfides and their specified structural features, have fairly enlarged their contribution due to the synergistic effect. This review highlights the latest synthetic approaches based on colloidal process. Their corresponding electrochemical outcomes will also be discussed, which are thoroughly updated along with their insight scientific standpoints.
Y1 - 2022
U6 - https://doi.org/10.1016/j.cogsc.2022.100596
SN - 2452-2236
VL - 34
PB - Elsevier
CY - Amsterdam
ER -
TY - JOUR
A1 - Reitenbach, Julija
A1 - Geiger, Christina
A1 - Wang, Peixi
A1 - Vagias, Apostolos N.
A1 - Cubitt, Robert
A1 - Schanzenbach, Dirk
A1 - Laschewsky, André
A1 - Papadakis, Christine M.
A1 - Müller-Buschbaum, Peter
T1 - Effect of magnesium salts with chaotropic anions on the swelling behavior of PNIPMAM thin films
JF - Macromolecules : a publication of the American Chemical Society
N2 - Poly(N-isopropylmethacrylamide) (PNIPMAM) is a stimuli responsive polymer, which in thin film geometry exhibits a volume-phase transition upon temperature increase in water vapor. The swelling behavior of PNIPMAM thin films containing magnesium salts in water vapor is investigated in view of their potential application as nanodevices. Both the extent and the kinetics of the swelling ratio as well as the water content are probed with in situ time-of-flight neutron reflectometry. Additionally, in situ Fourier-transform infrared (FTIR) spectroscopy provides information about the local solvation of the specific functional groups, while two-dimensional FTIR correlation analysis further elucidates the temporal sequence of solvation events. The addition of Mg(ClO4)2 or Mg(NO3)2 enhances the sensitivity of the polymer and therefore the responsiveness of switches and sensors based on PNIPMAM thin films. It is found that Mg(NO3)2 leads to a higher relative water uptake and therefore achieves the highest thickness gain in the swollen state.
Y1 - 2023
U6 - https://doi.org/10.1021/acs.macromol.2c02282
SN - 0024-9297
SN - 1520-5835
VL - 56
IS - 2
SP - 567
EP - 577
PB - American Chemical Society
CY - Washington
ER -
TY - CHAP
A1 - Breternitz, Joachim
A1 - Schorr, Susan
T1 - Halide perovskites
BT - structural systematisation and what we learn from it
T2 - Acta crystallographica / International Union of Crystallography. Section A, Foundations and advances
KW - halide perovskites
KW - semiconductors
KW - group-subgroup relations
KW - twinning
Y1 - 2021
U6 - https://doi.org/10.1107/S0108767321089479
SN - 2053-2733
VL - 77
IS - Suppl.
SP - C750
EP - C750
PB - Blackwell
CY - Oxford [u.a.]
ER -
TY - JOUR
A1 - Nchiozem-Ngnitedem, Vaderament-Alexe
A1 - Sperlich, Eric
A1 - Matieta, Valaire Yemene
A1 - Kuete, Jenifer Reine Ngnouzouba
A1 - Kuete, Victor
A1 - Omer, Ejlal A. A.
A1 - Efferth, Thomas
A1 - Schmidt, Bernd
T1 - Synthesis and bioactivity of isoflavones from ficus carica and some non-natural analogues
JF - Journal of natural products : Lloydia
N2 - FicucariconeD (1) and its 4 '-demethyl congener 2 are isoflavones isolated from fruits of Ficus carica that share a 5,7-dimethoxy-6-prenyl-substituted A-ring. Both naturalproducts were, for the first time, obtained by chemical synthesisin six steps, starting from 2,4,6-trihydroxyacetophenone. Key stepsare a microwave-promoted tandem sequence of Claisen- and Cope-rearrangementsto install the 6-prenyl substituent and a Suzuki-Miyaura crosscoupling for installing the B-ring. By using various boronic acids,non-natural analogues become conveniently available. All compoundswere tested for cytotoxicity against drug-sensitive and drug-resistanthuman leukemia cell lines, but were found to be inactive. The compoundswere also tested for antimicrobial activities against a panel of eightGram-negative and two Gram-positive bacterial strains. Addition ofthe efflux pump inhibitor phenylalanine-arginine-beta-naphthylamide(PA beta N) significantly improved the antibiotic activity in mostcases, with MIC values as low as 2.5 mu M and activity improvementfactors as high as 128-fold.
KW - Antimicrobial activity
KW - Bacteria
KW - Ethers
KW - Flavonoids
KW - Mixtures
Y1 - 2023
U6 - https://doi.org/10.1021/acs.jnatprod.3c00219
SN - 0163-3864
SN - 1520-6025
VL - 86
IS - 6
SP - 1520
EP - 1528
PB - American Chemical Society
CY - Washington, DC
ER -
TY - JOUR
A1 - Geiger, Christina
A1 - Reitenbach, Julija
A1 - Henschel, Cristiane
A1 - Kreuzer, Lucas
A1 - Widmann, Tobias
A1 - Wang, Peixi
A1 - Mangiapia, Gaetano
A1 - Moulin, Jean-François
A1 - Papadakis, Christine M.
A1 - Laschewsky, André
A1 - Müller-Buschbaum, Peter
T1 - Ternary nanoswitches realized with multiresponsive PMMA-b-PNIPMAM films in mixed water/acetone vapor atmospheres
JF - Advanced engineering materials
N2 - To systematically add functionality to nanoscale polymer switches, an understanding of their responsive behavior is crucial. Herein, solvent vapor stimuli are applied to thin films of a diblock copolymer consisting of a short poly(methyl methacrylate) (PMMA) block and a long poly(N-isopropylmethacrylamide) (PNIPMAM) block for realizing ternary nanoswitches. Three significantly distinct film states are successfully implemented by the combination of amphiphilicity and co-nonsolvency effect. The exposure of the thin films to nitrogen, pure water vapor, and mixed water/acetone (90 vol%/10 vol%) vapor switches the films from a dried to a hydrated (solvated and swollen) and a water/acetone-exchanged (solvated and contracted) equilibrium state. These three states have distinctly different film thicknesses and solvent contents, which act as switch positions "off," "on," and "standby." For understanding the switching process, time-of-flight neutron reflectometry (ToF-NR) and spectral reflectance (SR) studies of the swelling and dehydration process are complemented by information on the local solvation of functional groups probed with Fourier-transform infrared (FTIR) spectroscopy. An accelerated responsive behavior beyond a minimum hydration/solvation level is attributed to the fast build-up and depletion of the hydration shell of PNIPMAM, caused by its hydrophobic moieties promoting a cooperative hydration character.
KW - co-nonsolvency
KW - diblock copolymers
KW - nanoswitches
KW - neutron reflectometry
KW - thin films
Y1 - 2021
U6 - https://doi.org/10.1002/adem.202100191
SN - 1438-1656
SN - 1527-2648
VL - 23
IS - 11
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Melani, Giacomo
A1 - Nagata, Yuki
A1 - Saalfrank, Peter
T1 - Vibrational energy relaxation of interfacial OH on a water-covered alpha-Al2O3(0001) surface
BT - a non-equilibrium ab initio molecular dynamics study
JF - Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies
N2 - Vibrational relaxation of adsorbates is a sensitive tool to probe energy transfer at gas/solid and liquid/solid interfaces. The most direct way to study relaxation dynamics uses time-resolved spectroscopy. Here we report on a non-equilibrium ab initio molecular dynamics (NE-AIMD) methodology to model vibrational relaxation of OH vibrations on a hydroxylated, water-covered alpha-Al2O3(0001) surface. In our NE-AIMD approach, after exciting selected O-H bonds their coupling to surface phonons and to the water adlayer is analyzed in detail, by following both the energy flow in time, as well as the time-evolution of Vibrational Density of States (VDOS) curves. The latter are obtained from Time-dependent Correlation Functions (TCFs) and serve as prototypical, generic representatives of time-resolved vibrational spectra. As most important results, (i) we find a few-picosecond lifetime of the excited modes and (ii) identify both hydrogen-bonded aluminols and water molecules in the adsorbed water layer as main dissipative channels, while the direct coupling to Al2O3 surface phonons is of minor importance on the timescales of interest. Our NE-AIMD/TCF methodology is powerful for complex adsorbate systems, in principle even reacting ones, and opens a way towards time-resolved vibrational spectroscopy.
Y1 - 2021
U6 - https://doi.org/10.1039/d0cp03777j
SN - 1463-9076
SN - 1463-9084
VL - 23
IS - 13
SP - 7714
EP - 7723
PB - Royal Society of Chemistry
CY - Cambridge
ER -
TY - JOUR
A1 - Wang, Zhenyu
A1 - Fritsch, Daniel
A1 - Berendts, Stefan
A1 - Lerch, Martin
A1 - Breternitz, Joachim
A1 - Schorr, Susan
T1 - Elucidation of the reaction mechanism for the synthesis of ZnGeN2 through Zn2GeO4 ammonolysis
JF - Chemical science / RSC, Royal Society of Chemistry
N2 - Ternary II-IV-N-2 materials have been considered as a promising class of materials that combine photovoltaic performance with earth-abundance and low toxicity. When switching from binary III-V materials to ternary II-IV-N-2 materials, further structural complexity is added to the system that may influence its optoelectronic properties. Herein, we present a systematic study of the reaction of Zn2GeO4 with NH3 that produces zinc germanium oxide nitrides, and ultimately approach stoichiometric ZnGeN2, using a combination of chemical analyses, X-ray powder diffraction and DFT calculations. Elucidating the reaction mechanism as being dominated by Zn and O extrusion at the later reaction stages, we give an insight into studying structure-property relationships in this emerging class of materials.
Y1 - 2021
U6 - https://doi.org/10.1039/d1sc00328c
SN - 2041-6539
VL - 12
IS - 24
SP - 8493
EP - 8500
PB - Royal Society of Chemistry
CY - Cambridge
ER -
TY - JOUR
A1 - Saeedi Garakani, Sadaf
A1 - Xie, Dongjiu
A1 - Khorsand Kheirabad, Atefeh
A1 - Lu, Yan
A1 - Yuan, Jiayin
T1 - Template-synthesis of a poly(ionic liquid)-derived Fe1-xS/nitrogen-doped porous carbon membrane and its electrode application in lithium-sulfur batteries
JF - Materials advances
N2 - This study deals with the facile synthesis of Fe1-xS nanoparticle-containing nitrogen-doped porous carbon membranes (denoted as Fe1-xS/N-PCMs) via vacuum carbonization of hybrid porous poly(ionic liquid) (PIL) membranes, and their successful use as a sulfur host material to mitigate the shuttle effect in lithium-sulfur (Li-S) batteries. The hybrid porous PIL membranes as the sacrificial template were prepared via ionic crosslinking of a cationic PIL with base-neutralized 1,1 '-ferrocenedicarboxylic acid, so that the iron source was molecularly incorporated into the template. The carbonization process was investigated in detail at different temperatures, and the chemical and porous structures of the carbon products were comprehensively analyzed. The Fe1-xS/N-PCMs prepared at 900 degrees C have a multimodal pore size distribution with a satisfactorily high surface area and well-dispersed iron sulfide nanoparticles to physically and chemically confine the LiPSs. The sulfur/Fe1-xS/N-PCM composites were then tested as electrodes in Li-S batteries, showing much improved capacity, rate performance and cycle stability, in comparison to iron sulfide-free, nitrogen-doped porous carbon membranes.
Y1 - 2021
U6 - https://doi.org/10.1039/d1ma00441g
SN - 2633-5409
VL - 2
IS - 15
SP - 5203
EP - 5212
PB - Royal Society of Chemistry
CY - Cambridge
ER -
TY - JOUR
A1 - Xu, Xun
A1 - Nie, Yan
A1 - Wang, Weiwei
A1 - Ma, Nan
A1 - Lendlein, Andreas
T1 - Periodic thermomechanical modulation of toll-like receptor expression and distribution in mesenchymal stromal cells
JF - MRS communications / a publication of the Materials Research Society
N2 - Toll-like receptor (TLR) can trigger an immune response against virus including SARS-CoV-2. TLR expression/distribution is varying in mesenchymal stromal cells (MSCs) depending on their culture environments. Here, to explore the effect of periodic thermomechanical cues on TLRs, thermally controlled shape-memory polymer sheets with programmable actuation capacity were created. The proportion of MSCs expressing SARS-CoV-2-associated TLRs was increased upon stimulation. The TLR4/7 colocalization was promoted and retained in the endoplasmic reticula. The TLR redistribution was driven by myosin-mediated F-actin assembly. These results highlight the potential of boosting the immunity for combating COVID-19 via thermomechanical preconditioning of MSCs.
KW - Actuation
KW - Antiviral
KW - Biomaterial
KW - COVID-19
KW - Shape memory
Y1 - 2021
U6 - https://doi.org/10.1557/s43579-021-00049-5
SN - 2159-6859
SN - 2159-6867
VL - 11
IS - 4
SP - 425
EP - 431
PB - Springer
CY - Berlin
ER -
TY - JOUR
A1 - Schulze, Nicole
A1 - Koetz, Joachim
T1 - Kinetically controlled growth of gold nanotriangles in a vesicular template phase by adding a strongly alternating polyampholyte
JF - Journal of dispersion science and technology
N2 - This paper is focused on the temperature-dependent synthesis of gold nanotriangles in a vesicular template phase, containing phosphatidylcholine and AOT, by adding the strongly alternating polyampholyte PalPhBisCarb.
UV-vis absorption spectra in combination with TEM micrographs show that flat gold nanoplatelets are formed predominantly in the presence of the polyampholyte at 45°C. The formation of triangular and hexagonal nanoplatelets can be directly influenced by the kinetic approach, i.e., by varying the polyampholyte dosage rate at 45°C. Corresponding zeta potential measurements indicate that a temperature-dependent adsorption of the polyampholyte on the {111} faces will induce the symmetry breaking effect, which is responsible for the kinetically controlled hindered vertical and preferred lateral growth of the nanoplatelets.
KW - Kinetically controlled nanocrystal growth
KW - nanotriangles
KW - polyampholytes
Y1 - 2016
U6 - https://doi.org/10.1080/01932691.2016.1220318
SN - 0193-2691
SN - 1532-2351
VL - 38
IS - 8
SP - 1073
EP - 1078
PB - Taylor & Francis
CY - Philadelphia
ER -
TY - THES
A1 - Margraf, Johannes T.
T1 - Science-driven chemical machine learning
Y1 - 2023
ER -
TY - JOUR
A1 - Deng, Zijun
A1 - Wang, Weiwei
A1 - Xu, Xun
A1 - Ma, Nan
A1 - Lendlein, Andreas
T1 - Polydopamine-based biofunctional substrate coating promotes mesenchymal stem cell migration
JF - MRS advances : a journal of the Materials Research Society (MRS)
N2 - Rapid migration of mesenchymal stem cells (MSCs) on device surfaces could support in vivo tissue integration and might facilitate in vitro organoid formation. Here, polydopamine (PDA) is explored as a biofunctional coating to effectively promote MSC motility. It is hypothesized that PDA stimulates fibronectin deposition and in this way enhances integrin-mediated migration capability. The random and directional cell migration was investigated by time-lapse microscopy and gap closure assay respectively, and analysed with softwares as computational tools. A higher amount of deposited fibronectin was observed on PDA substrate, compared to the non-coated substrate. The integrin beta 1 activation and focal adhesion kinase (FAK) phosphorylation at Y397 were enhanced on PDA substrate, but the F-actin cytoskeleton was not altered, suggesting MSC migration on PDA was regulated by integrin initiated FAK signalling. This study strengthens the biofunctionality of PDA coating for regulating stem cells and offering a way of facilitating tissue integration of devices.
Y1 - 2021
U6 - https://doi.org/10.1557/s43580-021-00091-4
SN - 2059-8521
VL - 6
IS - 31
SP - 739
EP - 744
PB - Springer Nature Switzerland AG
CY - Cham
ER -
TY - JOUR
A1 - Machatschek, Rainhard Gabriel
A1 - Saretia, Shivam
A1 - Lendlein, Andreas
T1 - Assessing the influence of temperature-memory creation on the degradation of copolyesterurethanes in ultrathin films
JF - Advanced materials interfaces
N2 - Copolyesterurethanes (PDLCLs) based on oligo(epsilon-caprolactone) (OCL) and oligo(omega-pentadecalactone) (OPDL) segments are biodegradable thermoplastic temperature-memory polymers. The temperature-memory capability in these polymers with crystallizable control units is implemented by a thermomechanical programming process causing alterations in the crystallite arrangement and chain organization. These morphological changes can potentially affect degradation. Initial observations on the macroscopic level inspire the hypothesis that switching of the controlling units causes an accelerated degradation of the material, resulting in programmable degradation by sequential coupling of functions. Hence, detailed degradation studies on Langmuir films of a PDLCL with 40 wt% OPDL content are carried out under enzymatic catalysis. The temperature-memory creation procedure is mimicked by compression at different temperatures. The evolution of the chain organization and mechanical properties during the degradation process is investigated by means of polarization-modulated infrared reflection absorption spectroscopy, interfacial rheology and to some extend by X-ray reflectivity. The experiments on PDLCL Langmuir films imply that degradability is not enhanced by thermal switching, as the former depends on the temperature during cold programming. Nevertheless, the thin film experiments show that the leaching of OCL segments does not induce further crystallization of the OPDL segments, which is beneficial for a controlled and predictable degradation.
KW - block copolymers
KW - degradation
KW - Langmuir monolayers
KW - rheology
KW - temperature-memory polymers
Y1 - 2021
U6 - https://doi.org/10.1002/admi.202001926
SN - 2196-7350
VL - 8
IS - 6
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Sperlich, Eric
A1 - Köckerling, Martin
T1 - The double cluster compound [Nb6Cl14(MeCN)(4)] [Nb6Cl14(pyz)(4)].6MeCN (Me: methyl, pyz: pyrazine) with a layered structure resulting from weak intermolecular interactions
JF - Zeitschrift für Naturforschung
N2 - The synthesis and the crystal structure of the double cluster compound [Nb6Cl14(MeCN)(4)][Nb6Cl14(pyz)(4)]middot6CH(3)CN are described. The synthesis is based on a partial ligand exchange reaction, which proceeds upon dissolving [Nb6Cl14(pyz)(4)]middot2CH(2)Cl(2) in acetonitrile. The compound is built up of two discrete neutral cluster units, which consist of octahedra of Nb-6 atoms coordinated by 12 edge-bridging chlorido and two terminal chlorido ligands, and four acetonitrile ligands on one and four pyrazine ligands on the other cluster unit. Co-crystallized acetonitrile molecules are also present. The single-crystal structure determination has revealed a cluster arrangement in which the [Nb6Cl14(pyz)(4)] units are connected by (halogen) lone-pair-(pyrazine) pi interactions. These lead to chains of [Nb6Cl14(pyz)(4)] clusters. These chains are further connected to cluster layers by (nitrile-halogen) dipole-dipole interactions, in which the [Nb6Cl14(MeCN)(4)] and co-crystallized MeCN molecules are also involved. These cluster layers are arranged parallel to the crystallographic {011} plane.
KW - cluster
KW - crystal structure
KW - dipole-dipole interaction
KW - halide
KW - lone-pair-pi interactions
KW - niobium
Y1 - 2023
U6 - https://doi.org/10.1515/znb-2023-0001
SN - 0932-0776
SN - 1865-7117
VL - 78
IS - 5
SP - 279
EP - 283
PB - De Gruyter
CY - Berlin
ER -
TY - JOUR
A1 - Kreuzer, Lucas
A1 - Widmann, Tobias
A1 - Geiger, Christina
A1 - Wang, Peixi
A1 - Vagias, Apostolos N.
A1 - Heger, Julian Eliah
A1 - Haese, Martin
A1 - Hildebrand, Viet
A1 - Laschewsky, André
A1 - Papadakis, Christine M.
A1 - Müller-Buschbaum, Peter
T1 - Salt-dependent phase transition behavior of doubly thermoresponsive poly(sulfobetaine)-based diblock copolymer thin films
JF - Langmuir : the ACS journal of surfaces and colloids / American Chemical Society
N2 - The water vapor-induced swelling, as well as subsequent phase-transition kinetics, of thin films of a diblock copolymer (DBC) loaded with different amounts of the salt NaBr, is investigated in situ. In dilute aqueous solution, the DBC features an orthogonally thermoresponsive behavior. It consists of a zwitterionic poly(sulfobetaine) block, namely, poly(4-(N-(3'-methacrylamidopropyl)-N, N-dimethylammonio) butane-1-sulfonate) (PSBP), showing an upper critical solution temperature, and a nonionic block, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), exhibiting a lower critical solution temperature. The swelling kinetics in D2O vapor at 15 degrees C and the phase transition kinetics upon heating the swollen film to 60 degrees C and cooling back to 15 degrees C are followed with simultaneous time-of-flight neutron reflectometry and spectral reflectance measurements. These are complemented by Fourier transform infrared spectroscopy. The collapse temperature of PNIPMAM and the swelling temperature of PSBP are found at lower temperatures than in aqueous solution, which is attributed to the high polymer concentration in the thin-film geometry. Upon inclusion of sub-stoichiometric amounts (relative to the monomer units) of NaBr in the films, the water incorporation is significantly increased. This increase is mainly attributed to a salting-in effect on the zwitterionic PSBP block. Whereas the addition of NaBr notably shifts the swelling temperature of PSBP to lower temperatures, the collapse temperature of PNIPMAM remains unaffected by the presence of salt in the films.
Y1 - 2021
U6 - https://doi.org/10.1021/acs.langmuir.1c01342
SN - 0743-7463
SN - 1520-5827
VL - 37
IS - 30
SP - 9179
EP - 9191
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Pessanha, Tatiana
A1 - Paschoalino, Waldemir J.
A1 - Deroco, Patricia B.
A1 - Kogikoski Junior, Sergio
A1 - Moraes, Ana C. M. de
A1 - Carvalho Castro de Silva, Cecilia de
A1 - Kubota, Lauro T.
T1 - Interfacial capacitance of graphene oxide films electrodes
BT - Fundamental studies on electrolytes interface aiming (bio)sensing applications
JF - Electroanalysis : an internatinal journal devoted to electroanalysis, sensors and bioelectronic devices
N2 - The understanding of bidimensional materials dynamics and its electrolyte interface equilibrium, such as graphene oxide (GO), is critical for the development of a capacitive biosensing platform. The interfacial capacitance (C-i) of graphene-based materials may be tuned by experimental conditions such as pH optimization and cation size playing key roles at the enhancement of their capacitive properties allowing their application as novel capacitive biosensors. Here we reported a systematic study of C-i of multilayer GO films in different aqueous electrolytes employing electrochemical impedance spectroscopy for the application in a capacitive detection system. We demonstrated that the presence of ionizable oxygen-containing functional groups within multilayer GO film favors the interactions and the accumulation of cations in the structure of the electrodes enhancing the GO C-i in aqueous solutions, where at pH 7.0 (the best condition) the C-i was 340 mu F mg(-1) at -0.01 V vs Ag/AgCl. We also established that the hydrated cation radius affects the mobility and interaction with GO functional groups and it plays a critical role in the Ci, as demonstrated in the presence of different cations Na+=640 mu F mg(-1), Li+=575 mu F mg(-1) and TMA(+)=477 mu F mg(-1). As a proof-of-concept, the capacitive behaviour of GO was explored as biosensing platform for standard streptavidin-biotin systems. For this system, the C-i varied linearly with the log of the concentration of the targeting analyte in the range from 10 pg mL(-1) to 100 ng mL(-1), showing the promising applicability of capacitive GO based sensors for label-free biosensing.
KW - Interfacial capacitance
KW - Graphene oxide
KW - Functional groups
KW - Electrochemical impedance
KW - Graphene derivates
Y1 - 2021
U6 - https://doi.org/10.1002/elan.202100220
SN - 1521-4109
SN - 1040-0397
VL - 34
IS - 4
SP - 692
EP - 700
PB - Wiley-VCH
CY - Weinheim
ER -
TY - THES
A1 - Savatieiev, Oleksandr
T1 - Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis
N2 - Graphitic carbon nitrides (g-CNs) are represented by melon-type g-CN, poly(heptazine imides) (PHIs), triazine-based g-CN and poly(triazine imide) with intercalated LiCl (PTI/Li+Cl‒). These materials are composed of sp2-hybridized carbon and nitrogen atoms; C:N ratio is close to 3:4; the building unit is 1,3,5-triazine or tri-s-triazine; the building units are interconnected covalently via sp2-hybridized nitrogen atoms or NH-moieties; the layers are assembled into a stack via weak van der Waals forces as in graphite. Due to medium band gap (~2.7 eV) g-CNs, such as melon-type g-CN and PHIs, are excited by photons with wavelength ≤ 460 nm. Since 2009 g-CNs have been actively studied as photocatalysts in evolution of hydrogen and oxygen – two half-reactions of full water splitting, by employing corresponding sacrificial agents. At the same time application of g-CNs as photocatalysts in organic synthesis has been remaining limited to few reactions only. Cumulative Habilitation summarizes research work conducted by the group ‘Innovative Heterogeneous Photocatalysis’ between 2017-2023 in the field of carbon nitride organic photocatalysis, which is led by Dr. Oleksandr Savatieiev.
g-CN photocatalysts activate molecules, i.e. generate their more reactive open-shell intermediates, via three modes: i) Photoinduced electron transfer (PET); ii) Excited state proton-coupled electron transfer (ES-PCET) or direct hydrogen atom transfer (dHAT); iii) Energy transfer (EnT). The scope of reactions that proceed via oxidative PET, i.e. one-electron oxidation of a substrate to the corresponding radical cation, are represented by synthesis of sulfonylchlorides from S-acetylthiophenols. The scope of reactions that proceed via reductive PET, i.e. one-electron reduction of a substrate to the corresponding radical anion, are represented by synthesis of γ,γ-dichloroketones from the enones and chloroform.
Due to abundance of sp2-hybridized nitrogen atoms in the structure of g-CN materials, they are able to cleave X-H bonds in organic molecules and store temporary hydrogen atom. ES-PCET or dHAT mode of organic molecules activation to the corresponding radicals is implemented for substrates featuring relatively acidic X-H bonds and those that are characterized by low bond dissociation energy, such as C-H bond next to the heteroelements. On the other hand, reductively quenched g-CN carrying hydrogen atom reduces a carbonyl compound to the ketyl radical via PCET that is thermodynamically more favorable pathway compared to the electron transfer. The scope of these reactions is represented by cyclodimerization of α,β-unsaturated ketones to cyclopentanoles.
g-CN excited state demonstrates complex dynamics with the initial formation of singlet excited state, which upon intersystem crossing produces triplet excited state that is characterized by the lifetime > 2 μs. Due to long lifetime, g-CN activate organic molecules via EnT. For example, g-CN sensitizes singlet oxygen, which is the key intermediate in the dehydrogenation of aldoximes to nitrileoxides. The transient nitrileoxide undergoes [3+2]-cycloaddition to nitriles and gives oxadiazoles-1,2,4.
PET, ES-PCET and EnT are fundamental phenomena that are applied beyond organic photocatalysis. Hybrid composite is formed by combining conductive polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) with potassium poly(heptazine imide) (K-PHI). Upon PET, K-PHI modulated population of polarons and therefore conductivity of PEDOT:PSS. The initial state of PEDOT:PSS is recovered upon material exposure to O2. K-PHI:PEDOT:PSS may be applied in O2 sensing.
In the presence of electron donors, such as tertiary amines and alcohols, and irradiation with light, K-PHI undergoes photocharging – the g-CN material accumulates electrons and charge-compensating cations. Such photocharged state is stable under anaerobic conditions for weeks, but at the same time it is a strong reductant. This feature allows decoupling in time light harvesting and energy storage in the form of electron-proton couples from utilization in organic synthesis. The photocharged state of K-PHI reduces nitrobenzene to aniline, and enables dimerization of α,β-unsaturated ketones to hexadienones in dark.
N2 - Graphitische Kohlenstoffnitride (g-CNs) werden durch g-CN vom Melonen-Typ, Poly(heptazinimide) (PHIs), g-CN auf Triazinbasis und Poly(triazinimid) mit interkaliertem LiCl (PTI/Li+Cl-) repräsentiert. Diese Materialien bestehen aus sp2-hybridisierten Kohlenstoff- und Stickstoffatomen; das C:N-Verhältnis liegt nahe bei 3:4; das Grundgerüst ist 1,3,5-Triazin oder Tri-s-Triazin; die Grundgerüste sind kovalent über sp2-hybridisierte Stickstoffatome oder NH-Moleküle miteinander verbunden; die Schichten werden über schwache van-der-Waals-Kräfte wie in Graphit zu einem Stapel zusammengefügt. Aufgrund der mittleren Bandlücke (~2,7 eV) werden g-CNs, wie z. B. g-CN vom Melonen-Typ und PHIs, durch Photonen mit einer Wellenlänge ≤ 460 nm angeregt. Seit 2009 werden g-CNs aktiv als Photokatalysatoren für die Entwicklung von Wasserstoff und Sauerstoff - zwei Halbreaktionen der vollständigen Wasserspaltung - untersucht, indem entsprechende Opferstoffe eingesetzt werden. Gleichzeitig ist die Anwendung von g-CNs als Photokatalysatoren in der organischen Synthese auf wenige Reaktionen beschränkt geblieben. Die kumulative Habilitation fasst die Forschungsarbeiten zusammen, die von der Gruppe "Innovative heterogene Photokatalyse" zwischen 2017 und 2023 auf dem Gebiet der organischen Photokatalyse mit Kohlenstoffnitrid durchgeführt wurden, die von Dr. Oleksandr Savatieiev geleitet wird.
g-CN-Photokatalysatoren aktivieren Moleküle, d. h. sie erzeugen ihre reaktiveren Zwischenprodukte mit offener Schale über drei Modi: i) photoinduzierter Elektronentransfer (PET); ii) protonengekoppelter Elektronentransfer im angeregten Zustand (ES-PCET) oder direkter Wasserstoffatomtransfer (dHAT); iii) Energietransfer (EnT). Der Bereich der Reaktionen, die über oxidativen PET ablaufen, d. h. die Ein-Elektronen-Oxidation eines Substrats zum entsprechenden Radikalkation, wird durch die Synthese von Sulfonylchloriden aus S-Acetylthiophenolen dargestellt. Der Bereich der Reaktionen, die über reduktive PET ablaufen, d. h. Reduktion eines Substrats mit einem Elektron zum entsprechenden radikalischen Anion, wird durch die Synthese von γ,γ-Dichloroketonen aus Enonen und Chloroform repräsentiert.
Aufgrund der zahlreichen sp2-hybridisierten Stickstoffatome in der Struktur der g-CN-Materialien können sie X-H-Bindungen in organischen Molekülen spalten und temporäre Wasserstoffatome speichern. Der ES-PCET- oder dHAT-Modus der Aktivierung organischer Moleküle zu den entsprechenden Radikalen wird bei Substraten mit relativ sauren X-H-Bindungen und solchen, die sich durch eine niedrige Bindungsdissoziationsenergie auszeichnen, wie z. B. die C-H-Bindung neben den Heteroelementen, durchgeführt. Andererseits reduziert reduktiv gequenchtes g-CN, das ein Wasserstoffatom trägt, eine Carbonylverbindung über PCET zum Ketylradikal, was im Vergleich zum Elektronentransfer der thermodynamisch günstigere Weg ist. Der Umfang dieser Reaktionen wird durch die Cyclodimerisierung von α,β-ungesättigten Ketonen zu Cyclopentanolen dargestellt.
Der angeregte Zustand von g-CN zeigt eine komplexe Dynamik mit der anfänglichen Bildung eines angeregten Singulett-Zustands, der beim Übergang zwischen den Systemen einen angeregten Triplett-Zustand erzeugt, der durch eine Lebensdauer von > 2 μs gekennzeichnet ist. Aufgrund der langen Lebensdauer aktivieren g-CN organische Moleküle über EnT. So sensibilisiert g-CN beispielsweise Singulett-Sauerstoff, der das wichtigste Zwischenprodukt bei der Dehydrierung von Aldoximen zu Nitriloxiden ist. Das transiente Nitriloxid unterliegt einer [3+2]-Cycloaddition zu Nitrilen und ergibt Oxadiazole-1,2,4.
PET, ES-PCET und EnT sind grundlegende Phänomene, die über die organische Photokatalyse hinaus Anwendung finden. Hybridkomposit wird durch die Kombination von leitfähigen Polymeren wie Poly(3,4-ethylendioxythiophen)polystyrolsulfonat (PEDOT:PSS) mit Kaliumpoly(heptazinimid) (K-PHI) gebildet. Nach PET modulierte K-PHI die Population der Polaronen und damit die Leitfähigkeit von PEDOT:PSS. Der Ausgangszustand von PEDOT:PSS wird wiederhergestellt, wenn das Material O2 ausgesetzt wird. K-PHI:PEDOT:PSS kann für die O2-Sensorik verwendet werden.
In Gegenwart von Elektronendonatoren, wie tertiären Aminen und Alkoholen, und bei Lichteinstrahlung wird K-PHI photogeladen - das g-CN-Material sammelt Elektronen und ladungsausgleichende Kationen an. Dieser photogeladene Zustand ist unter anaeroben Bedingungen wochenlang stabil, gleichzeitig ist er aber ein starkes Reduktionsmittel. Diese Eigenschaft ermöglicht die zeitliche Entkopplung von Lichtsammlung und Energiespeicherung in Form von Elektron-Protonen-Paaren von der Nutzung in der organischen Synthese. Der photogeladene Zustand von K-PHI reduziert Nitrobenzol zu Anilin und ermöglicht die Dimerisierung von α,β-ungesättigten Ketonen zu Hexadienonen im Dunkeln.
KW - carbon nitride
KW - photocatalysis
KW - photochemistry
KW - photocharging
KW - organic synthesis
Y1 - 2023
ER -
TY - GEN
A1 - Hechenbichler, Michelle
A1 - Laschewsky, Andre
A1 - Gradzielski, Michael
T1 - Poly(N,N-bis(2-methoxyethyl)acrylamide), a thermoresponsive non-ionic polymer combining the amide and the ethyleneglycolether motifs
T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe
N2 - Poly(N,N-bis(2-methoxyethyl)acrylamide) (PbMOEAm) featuring two classical chemical motifs from non-ionic water-soluble polymers, namely, the amide and ethyleneglycolether moieties, was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. This tertiary polyacrylamide is thermoresponsive exhibiting a lower critical solution temperature (LCST)-type phase transition. A series of homo- and block copolymers with varying molar masses but low dispersities and different end groups were prepared. Their thermoresponsive behavior in aqueous solution was analyzed via turbidimetry and dynamic light scattering (DLS). The cloud points (CP) increased with increasing molar masses, converging to 46 degrees C for 1 wt% solutions. This rise is attributed to the polymers' hydrophobic end groups incorporated via the RAFT agents. When a surfactant-like strongly hydrophobic end group was attached using a functional RAFT agent, CP was lowered to 42 degrees C, i.e., closer to human body temperature. Also, the effect of added salts, in particular, the role of the Hofmeister series, on the phase transition of PbMOEAm was investigated, exemplified for the kosmotropic fluoride, intermediate chloride, and chaotropic thiocyanate anions. A pronounced shift of the cloud point of about 10 degrees C to lower or higher temperatures was observed for 0.2 M fluoride and thiocyanate, respectively. When PbMOEAm was attached to a long hydrophilic block of poly(N,N-dimethylacrylamide) (PDMAm), the cloud points of these block copolymers were strongly shifted towards higher temperatures. While no phase transition was observed for PDMAm-b-pbMOEAm with short thermoresponsive blocks, block copolymers with about equally sized PbMOEAm and PDMAm blocks underwent the coil-to-globule transition around 60 degrees C.
T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1345
KW - polyacrylamide
KW - water-soluble polymers
KW - responsive systems
KW - lower
KW - critical solution temperature
KW - polymer amphiphile
Y1 - 2020
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-598378
SN - 0303-402X
SN - 1435-1536
SN - 1866-8372
VL - 299
IS - 2
PB - Springer
CY - Berlin; Heidelberg
ER -
TY - THES
A1 - Hussein, Mahmoud
T1 - Solvent engineering for highly-efficiency lead-free perovskite solar cells
T1 - Lösungsmitteltechnik für hocheffiziente Zinn-Perowskit-Solarzellen
N2 - Global warming, driven primarily by the excessive emission of greenhouse gases such as carbon dioxide into the atmosphere, has led to severe and detrimental environmental impacts. Rising global temperatures have triggered a cascade of adverse effects, including melting glaciers and polar ice caps, more frequent and intense heat waves disrupted weather patterns, and the acidification of oceans. These changes adversely affect ecosystems, biodiversity, and human societies, threatening food security, water availability, and livelihoods. One promising solution to mitigate the harmful effects of global warming is the widespread adoption of solar cells, also known as photovoltaic cells. Solar cells harness sunlight to generate electricity without emitting greenhouse gases or other pollutants. By replacing fossil fuel-based energy sources, solar cells can significantly reduce CO2 emissions, a significant contributor to global warming. This transition to clean, renewable energy can help curb the increasing concentration of greenhouse gases in the atmosphere, thereby slowing down the rate of global temperature rise.
Solar energy’s positive impact extends beyond emission reduction. As solar panels become more efficient and affordable, they empower individuals, communities, and even entire nations to generate electricity and become less dependent on fossil fuels. This decentralized energy generation can enhance resilience in the face of climate-related challenges. Moreover, implementing solar cells creates green jobs and stimulates technological innovation, further promoting sustainable economic growth. As solar technology advances, its integration with energy storage systems and smart grids can ensure a stable and reliable energy supply, reducing the need for backup fossil fuel power plants that exacerbate environmental degradation.
The market-dominant solar cell technology is silicon-based, highly matured technology with a highly systematic production procedure. However, it suffers from several drawbacks, such as: 1) Cost: still relatively high due to high energy consumption due to the need to melt and purify silicon, and the use of silver as an electrode, which hinders their widespread availability, especially in low-income countries. 2) Efficiency: theoretically, it should deliver around 29%; however, the efficiency of most of the commercially available silicon-based solar cells ranges from 18 – 22%. 3) Temperature sensitivity: The efficiency decreases with the increase in the temperature, affecting their output. 4) Resource constraints: silicon as a raw material is unavailable in all countries, creating supply chain challenges.
Perovskite solar cells arose in 2011 and matured very rapidly in the last decade as a highly efficient and versatile solar cell technology. With an efficiency of 26%, high absorption coefficients, solution processability, and tunable band gap, it attracted the attention of the solar cells community. It represented a hope for cheap, efficient, and easily processable next-generation solar cells. However, lead toxicity might be the block stone hindering perovskite solar cells’ market reach. Lead is a heavy and bioavailable element that makes perovskite solar cells environmentally unfriendly technology. As a result, scientists try to replace lead with a more environmentally friendly element. Among several possible alternatives, tin was the most suitable element due to its electronic and atomic structure similarity to lead.
Tin perovskites were developed to alleviate the challenge of lead toxicity. Theoretically, it shows very high absorption coefficients, an optimum band gap of 1.35 eV for FASnI3, and a very high short circuit current, which nominates it to deliver the highest possible efficiency of a single junction solar cell, which is around 30.1% according to Schockly-Quisser limit. However, tin perovskites’ efficiency still lags below 15% and is irreproducible, especially from lab to lab. This humble performance could be attributed to three reasons: 1) Tin (II) oxidation to tin (IV), which would happen due to oxygen, water, or even by the effect of the solvent, as was discovered recently. 2) fast crystallization dynamics, which occurs due to the lateral exposure of the P-orbitals of the tin atom, which enhances its reactivity and increases the crystallization pace. 3) Energy band misalignment: The energy bands at the interfaces between the perovskite absorber material and the charge selective layers are not aligned, leading to high interfacial charge recombination, which devastates the photovoltaic performance. To solve these issues, we implemented several techniques and approaches that enhanced the efficiency of tin halide perovskites, providing new chemically safe solvents and antisolvents. In addition, we studied the energy band alignment between the charge transport layers and the tin perovskite absorber.
Recent research has shown that the principal source of tin oxidation is the solvent known as dimethylsulfoxide, which also happens to be one of the most effective solvents for processing perovskite. The search for a stable solvent might prove to be the factor that makes all the difference in the stability of tin-based perovskites. We started with a database of over 2,000 solvents and narrowed it down to a series of 12 new solvents that are suitable for processing FASnI3 experimentally. This was accomplished by looking into 1) the solubility of the precursor chemicals FAI and SnI2, 2) the thermal stability of the precursor solution, and 3) the potential to form perovskite. Finally, we show that it is possible to manufacture solar cells using a novel solvent system that outperforms those produced using DMSO. The results of our research give some suggestions that may be used in the search for novel solvents or mixes of solvents that can be used to manufacture stable tin-based perovskites.
Due to the quick crystallization of tin, it is more difficult to deposit tin-based perovskite films from a solution than manufacturing lead-based perovskite films since lead perovskite is more often utilized. The most efficient way to get high efficiencies is to deposit perovskite from dimethyl sulfoxide (DMSO), which slows down the quick construction of the tin-iodine network that is responsible for perovskite synthesis. This is the most successful approach for achieving high efficiencies. Dimethyl sulfoxide, which is used in the processing, is responsible for the oxidation of tin, which is a disadvantage of this method. This research presents a potentially fruitful alternative in which 4-(tert-butyl) pyridine can substitute dimethyl sulfoxide in the process of regulating crystallization without causing tin oxidation to take place. Perovskite films that have been formed from pyridine have been shown to have a much-reduced defect density. This has resulted in increased charge mobility and better photovoltaic performance, making pyridine a desirable alternative for use in the deposition of tin perovskite films.
The precise control of perovskite precursor crystallization inside a thin film is of utmost importance for optimizing the efficiency and manufacturing of solar cells. The deposition process of tin-based perovskite films from a solution presents difficulties due to the quick crystallization of tin compared to the more often employed lead perovskite. The optimal approach for attaining elevated efficiencies entails using dimethyl sulfoxide (DMSO) as a medium for depositing perovskite. This choice of solvent impedes the tin-iodine network’s fast aggregation, which plays a crucial role in the production of perovskite. Nevertheless, this methodology is limited since the utilization of dimethyl sulfoxide leads to the oxidation of tin throughout the processing stage. In this thesis, we present a potentially advantageous alternative approach wherein 4-(tert-butyl) pyridine is proposed as a substitute for dimethyl sulfoxide in regulating crystallization processes while avoiding the undesired consequence of tin oxidation. Films of perovskite formed using pyridine as a solvent have a notably reduced density of defects, resulting in higher mobility of charges and improved performance in solar applications. Consequently, the utilization of pyridine for the deposition of tin perovskite films is considered advantageous.
Tin perovskites are suffering from an apparent energy band misalignment. However, the band diagrams published in the current body of research display contradictions, resulting in a dearth of unanimity. Moreover, comprehensive information about the dynamics connected with charge extraction is lacking. This thesis aims to ascertain the energy band locations of tin perovskites by employing the kelvin probe and Photoelectron yield spectroscopy methods. This thesis aims to construct a precise band diagram for the often-utilized device stack. Moreover, a comprehensive analysis is performed to assess the energy deficits inherent in the current energetic structure of tin halide perovskites. In addition, we investigate the influence of BCP on the improvement of electron extraction in C60/BCP systems, with a specific emphasis on the energy factors involved. Furthermore, transient surface photovoltage was utilized to investigate the charge extraction kinetics of frequently studied charge transport layers, such as NiOx and PEDOT as hole transport layers and C60, ICBA, and PCBM as electron transport layers. The Hall effect, KP, and TRPL approaches accurately ascertain the p-doping concentration in FASnI3. The results consistently demonstrated a value of 1.5 * 1017 cm-3. Our research findings highlight the imperative nature of autonomously constructing the charge extraction layers for tin halide perovskites, apart from those used for lead perovskites.
The crystallization of perovskite precursors relies mainly on the utilization of two solvents. The first one dissolves the perovskite powder to form the precursor solution, usually called the solvent. The second one precipitates the perovskite precursor, forming the wet film, which is a supersaturated solution of perovskite precursor and in the remains of the solvent and the antisolvent. Later, this wet film crystallizes upon annealing into a full perovskite crystallized film. In our research context, we proposed new solvents to dissolve FASnI3, but when we tried to form a film, most of them did not crystallize. This is attributed to the high coordination strength between the metal halide and the solvent molecules, which is unbreakable by the traditionally used antisolvents such as Toluene and Chlorobenzene. To solve this issue, we introduce a high-throughput antisolvent screening in which we screened around 73 selected antisolvents against 15 solvents that can form a 1M FASnI3 solution. We used for the first time in tin perovskites machine learning algorithm to understand and predict the effect of an antisolvent on the crystallization of a precursor solution in a particular solvent. We relied on film darkness as a primary criterion to judge the efficacy of a solvent-antisolvent pair. We found that the relative polarity between solvent and antisolvent is the primary factor that affects the solvent-antisolvent interaction. Based on our findings, we prepared several high-quality tin perovskite films free from DMSO and achieved an efficiency of 9%, which is the highest DMSO tin perovskite device so far.
N2 - Zinn ist eine der vielversprechendsten Alternativen zu Blei, um bleifreie Halogenidperowskite für die Optoelektronik herzustellen. Die Stabilität von Perowskiten auf Zinnbasis wird jedoch durch die Oxidation von Sn(II) zu Sn(IV) beeinträchtigt. Jüngste Arbeiten haben ergeben, dass Dimethylsulfoxid, eines der besten Lösungsmittel für die Verarbeitung von Perowskiten, die Hauptquelle für die Oxidation von Zinn ist. Die Suche nach einem stabilen Lösungsmittel könnte den Ausschlag für die Stabilität von Perowskiten auf Zinnbasis geben. Ausgehend von einer Datenbank mit über 2000 Lösungsmitteln haben wir eine Reihe von 12 neuen Lösungsmitteln identifiziert, die für die Verarbeitung von Formamidinium-Zinniodid-Perowskit (FASnI3) geeignet sind, indem wir 1) die Löslichkeit der Vorläuferchemikalien FAI und SnI2, 2) die thermische Stabilität der Vorläuferlösung und 3) die Möglichkeit zur Bildung von Perowskit experimentell untersucht haben. Schließlich demonstrieren wir ein neues Lösungsmittelsystem zur Herstellung von Solarzellen, das die auf DMSO basierenden Zellen übertrifft. Unsere Arbeit liefert Leitlinien für die weitere Identifizierung neuer Lösungsmittel oder Lösungsmittelmischungen zur Herstellung stabiler Perowskite auf Zinnbasis.
Die genaue Steuerung der Kristallisation des Perowskit-Vorläufers in einer Dünnschicht ist entscheidend für die Effizienz und Produktion von Solarzellen. Die Abscheidung von Perowskit-Filmen auf Zinnbasis aus einer Lösung stellt aufgrund der schnellen Kristallisation von Zinn im Vergleich zu dem üblicherweise verwendeten Bleiperowskit eine Herausforderung dar. Die effektivste Methode zur Erzielung hoher Wirkungsgrade ist die Abscheidung von Perowskit aus Dimethylsulfoxid (DMSO), das den schnellen Aufbau des für die Perowskitbildung verantwortlichen Zinn-Jod-Netzwerks behindert. Dieser Ansatz hat jedoch einen Nachteil, da Dimethylsulfoxid während der Verarbeitung eine Zinnoxidation verursacht. In dieser Studie wird eine vielversprechende Alternative vorgestellt, bei der 4-(tert-Butyl)-pyridin Dimethylsulfoxid bei der Steuerung der Kristallisation ersetzen kann, ohne eine Zinnoxidation zu verursachen. Aus Pyridin abgeschiedene Perowskit-Filme weisen eine deutlich geringere Defektdichte auf, was zu einer erhöhten Ladungsbeweglichkeit und einer verbesserten photovoltaischen Leistung führt und es zu einer günstigen Wahl für die Abscheidung von Zinn-Perowskit-Filmen macht.
Zinnperowskite haben sich als vielversprechender, umweltverträglicher Ersatz für Bleiperowskite erwiesen, vor allem wegen ihrer besseren optoelektronischen Eigenschaften und ihrer geringeren Bioverfügbarkeit. Dennoch gibt es mehrere Gründe, warum die Leistung von Zinnperowskiten nicht mit der von Bleiperowskiten verglichen werden kann. Einer dieser Gründe ist die Nichtübereinstimmung der Energiebänder zwischen dem Perowskit-Absorberfilm und den ladungstransportierenden Schichten (CTLs). Die in der vorhandenen Literatur dargestellten Banddiagramme sind jedoch uneinheitlich, was zu einem Mangel an Konsens führt. Außerdem ist das Verständnis der mit der Ladungsextraktion verbundenen Dynamik noch unzureichend. In dieser Studie sollen die Energiebandpositionen von Zinnperowskiten mit Hilfe der Kelvinsonde (KP) und der Photoelektronenausbeutespektroskopie (PYS) bestimmt werden. Ziel ist es, ein genaues Banddiagramm für den üblicherweise verwendeten Bauelementestapel zu erstellen. Darüber hinaus führen wir eine Diagnose der energetischen Unzulänglichkeiten durch, die im bestehenden energetischen Rahmen von Zinnhalogenid-Perowskiten vorhanden sind. Unser Ziel ist es, Folgendes zu klären den Einfluss von BCP auf die Verbesserung der Elektronenextraktion in C60/BCP-Systemen, wobei der Schwerpunkt auf den energetischen Aspekten liegt. Darüber hinaus haben wir die transiente Oberflächenphotospannung (tr-SPV) eingesetzt, um Einblicke in die Ladungsextraktionskinetik von allgemein bekannten CTLs zu gewinnen, einschließlich NiOx und PEDOT als Lochtransportschichten (HTLs) und C60, ICBA und PCBM als Elektronentransportschichten (ETLs). In diesem Kapitel verwenden wir den Halleffekt, KP- und TRPL-Techniken, um die genaue p-Dotierungskonzentration in FASnI3 zu bestimmen. Unsere Ergebnisse ergaben durchweg einen Wert von 1.5 * 1017 cm-3. Die Ergebnisse unserer Studie zeigen, dass es notwendig ist, die Ladungsextraktionsschichten von Zinnhalogenidperowskiten unabhängig von den Bleiperowskiten zu entwickeln.
Die Kristallisation von Perowskit-Vorstufen beruht hauptsächlich auf der Verwendung von zwei Lösungsmitteln. Das erste löst das Perowskit-Pulver auf und bildet die Vorläuferlösung, die üblicherweise als Lösungsmittel bezeichnet wird. Mit dem zweiten wird der Perowskit-Precursor ausgefällt, wobei sich der Nassfilm bildet, der eine übersättigte Lösung des Perowskit-Precursors und der Reste des Lösungsmittels und des Antisolierungsmittels ist. Später kristallisiert dieser nasse Film beim Ausglühen zu einem vollständig kristallisierten Perowskit-Film. In unserem Forschungskontext haben wir neue Lösungsmittel vorgeschlagen, um FASnI3 aufzulösen, aber als wir versuchten, einen Film zu bilden, kristallisierten die meisten von ihnen nicht. Dies ist auf die hohe Koordinationsstärke zwischen dem Metallhalogenid und den Lösungsmittelmolekülen zurückzuführen, die von den traditionell verwendeten Antisolierungsmitteln wie Toluol und Chlorbenzol nicht aufgebrochen werden kann. Um dieses Problem zu lösen, haben wir ein Hochdurchsatz-Screening von Antisolventien durchgeführt, bei dem wir 73 ausgewählte Antisolventien mit 15 Lösungsmitteln verglichen haben, die eine 1M FASnI3-Lösung bilden können. Wir haben zum ersten Mal bei Zinnperowskiten einen Algorithmus für maschinelles Lernen verwendet, um die Wirkung eines Antisolvens auf die Kristallisation einer Vorläuferlösung in einem bestimmten Lösungsmittel zu verstehen und vorherzusagen. Wir stützten uns auf die Schwärzung des Films als primäres Kriterium zur Beurteilung der Wirksamkeit eines Lösungsmittel-Antisolierungsmittel-Paares. Wir fanden heraus, dass die relative Polarität zwischen Lösungsmittel und Antisolvent der wichtigste Faktor ist, der die Wechselwirkung zwischen Lösungsmittel und Antisolvent beeinflusst. Auf der Grundlage unserer Erkenntnisse haben wir mehrere hochwertige Zinn-Perowskit-Filme ohne DMSO hergestellt und einen Wirkungsgrad von 9 % erzielt, was die bisher höchste DMSO-Zinn-Perowskit-Vorrichtung darstellt.
KW - perovskite solar cells
KW - lead-free perovskites
KW - tin perovskites
KW - solar cells
KW - perovskite
KW - Perowskit-Solarzellen
KW - photovoltaische Materialien
KW - Solarzellen
KW - Lösungsmittel
KW - bleifreie Perowskit-Solarzellen
Y1 - 2024
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-630375
ER -
TY - JOUR
A1 - Wang, Peixi
A1 - Geiger, Christina
A1 - Kreuzer, Lucas
A1 - Widmann, Tobias
A1 - Reitenbach, Julija
A1 - Liang, Suzhe
A1 - Cubitt, Robert
A1 - Henschel, Cristiane
A1 - Laschewsky, André
A1 - Papadakis, Christine M.
A1 - Müller-Buschbaum, Peter
T1 - Poly(sulfobetaine)-based diblock copolymer thin films in water/acetone atmosphere: modulation of water hydration and co-nonsolvency-triggered film contraction
JF - Langmuir : the ACS journal of surfaces and colloids
N2 - The water swelling and subsequent solvent exchange including co-nonsolvency behavior of thin films of a doubly thermo-responsive diblock copolymer (DBC) are studied viaspectral reflectance, time-of-flight neutron reflectometry, and Fourier transform infrared spectroscopy.
The DBC consists of a thermo-responsive zwitterionic (poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate)) (PSBP) block, featuring an upper critical solution temperature transition in aqueous media but being insoluble in acetone, and a nonionic poly(N-isopropylmethacrylamide) (PNIPMAM) block, featuring a lower critical solution temperature transition in water, while being soluble in acetone.
Homogeneous DBC films of 50-100 nm thickness are first swollen in saturated water vapor (H2OorD2O), before they are subjected to a contraction process by exposure to mixed saturated water/acetone vapor (H2OorD2O/acetone-d6 = 9:1 v/v).
The affinity of the DBC film toward H2O is stronger than for D2O, as inferred from the higher film thickness in the swollen state and the higher absorbed water content, thus revealing a pronounced isotope sensitivity.
During the co-solvent-induced switching by mixed water/acetone vapor, a two-step film contraction is observed, which is attributed to the delayed expulsion of water molecules and uptake of acetone molecules.
The swelling kinetics are compared for both mixed vapors (H2O/acetone-d6 and D2O/acetone-d6) and with those of the related homopolymer films.
Moreover, the concomitant variations of the local environment around the hydrophilic groups located in the PSBP and PNIPMAM blocks are followed.
The first contraction step turns out to be dominated by the behavior of the PSBP block, where as the second one is dominated by the PNIPMAM block.
The unusual swelling and contraction behavior of the latter block is attributed to its co-nonsolvency behavior.
Furthermore, we observe cooperative hydration effects in the DBC films, that is, both polymer blocks influence each other's solvation behavior.
Y1 - 2022
U6 - https://doi.org/10.1021/acs.langmuir.2c00451
SN - 0743-7463
SN - 1520-5827
VL - 38
IS - 22
SP - 6934
EP - 6948
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Kuntze, Kim
A1 - Viljakka, Jani
A1 - Titov, Evgenii
A1 - Ahmed, Zafar
A1 - Kalenius, Elina
A1 - Saalfrank, Peter
A1 - Priimagi, Arri
T1 - Towards low-energy-light-driven bistable photoswitches
BT - ortho-fluoroaminoazobenzenes
JF - Photochemical & photobiological sciences / European Society for Photobiology
N2 - Thermally stable photoswitches that are driven with low-energy light are rare, yet crucial for extending the applicability of photoresponsive molecules and materials towards, e.g., living systems. Combined ortho-fluorination and -amination couples high visible light absorptivity of o-aminoazobenzenes with the extraordinary bistability of o-fluoroazobenzenes. Herein, we report a library of easily accessible o-aminofluoroazobenzenes and establish structure-property relationships regarding spectral qualities, visible light isomerization efficiency and thermal stability of the cis-isomer with respect to the degree of o-substitution and choice of amino substituent. We rationalize the experimental results with quantum chemical calculations, revealing the nature of low-lying excited states and providing insight into thermal isomerization. The synthesized azobenzenes absorb at up to 600 nm and their thermal cis-lifetimes range from milliseconds to months. The most unique example can be driven from trans to cis with any wavelength from UV up to 595 nm, while still exhibiting a thermal cis-lifetime of 81 days.
[GRAPHICS]
.
Y1 - 2022
U6 - https://doi.org/10.1007/s43630-021-00145-4
SN - 1474-905X
SN - 1474-9092
VL - 21
IS - 2
SP - 159
EP - 173
PB - Springer
CY - Heidelberg
ER -
TY - JOUR
A1 - Xie, Dongjiu
A1 - Xu, Yaolin
A1 - Wang, Yonglei
A1 - Pan, Xuefeng
A1 - Härk, Eneli
A1 - Kochovski, Zdravko
A1 - Eljarrat, Alberto
A1 - Müller, Johannes
A1 - Koch, Christoph T.
A1 - Yuan, Jiayin
A1 - Lu, Yan
T1 - Poly(ionic liquid) nanovesicle-templated carbon nanocapsules functionalized with uniform iron nitride nanoparticles as catalytic sulfur host for Li-S batteries
JF - ACS nano
N2 - Poly(ionic liquid)s (PIL) are common precursors for heteroatom-doped carbon materials. Despite a relatively higher carbonization yield, the PIL-to-carbon conversion process faces challenges in preserving morphological and structural motifs on the nanoscale. Assisted by a thin polydopamine coating route and ion exchange, imidazoliumbased PIL nanovesicles were successfully applied in morphology-maintaining carbonization to prepare carbon composite nanocapsules. Extending this strategy further to their composites, we demonstrate the synthesis of carbon composite nanocapsules functionalized with iron nitride nanoparticles of an ultrafine, uniform size of 3-5 nm (termed "FexN@C "). Due to its unique nanostructure, the sulfur-loaded FexN@C electrode was tested to efficiently mitigate the notorious shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. The cavity of the carbon nanocapsules was spotted to better the loading content of sulfur. The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electronic conductivity and strong binding power to LiPSs. Benefiting from this well-crafted composite nanostructure, the constructed FexN@C/S cathode demonstrated a fairly high discharge capacity of 1085 mAh g(-1) at 0.5 C initially, and a remaining value of 930 mAh g(-1 )after 200 cycles. In addition, it exhibits an excellent rate capability with a high initial discharge capacity of 889.8 mAh g(-1) at 2 C. This facile PIL-to-nanocarbon synthetic approach is applicable for the exquisite design of complex hybrid carbon nanostructures with potential use in electrochemical energy storage and conversion.
KW - poly(ionic liquid)s
KW - nanovesicles
KW - sulfur host
KW - iron nitride
KW - Li-S
KW - batteries
Y1 - 2022
U6 - https://doi.org/10.1021/acsnano.2c01992
SN - 1936-0851
SN - 1936-086X
VL - 16
IS - 7
SP - 10554
EP - 10565
PB - American Chemical Society
CY - Washington
ER -
TY - JOUR
A1 - Neffe, Axel T.
A1 - Löwenberg, Candy
A1 - Julich-Gruner, Konstanze K.
A1 - Behl, Marc
A1 - Lendlein, Andreas
T1 - Thermally-induced shape-memory behavior of degradable gelatin-based networks
JF - International journal of molecular sciences
N2 - Shape-memory hydrogels (SMH) are multifunctional, actively-moving polymers of interest in biomedicine. In loosely crosslinked polymer networks, gelatin chains may form triple helices, which can act as temporary net points in SMH, depending on the presence of salts. Here, we show programming and initiation of the shape-memory effect of such networks based on a thermomechanical process compatible with the physiological environment. The SMH were synthesized by reaction of glycidylmethacrylated gelatin with oligo(ethylene glycol) (OEG) alpha,omega-dithiols of varying crosslinker length and amount. Triple helicalization of gelatin chains is shown directly by wide-angle X-ray scattering and indirectly via the mechanical behavior at different temperatures. The ability to form triple helices increased with the molar mass of the crosslinker. Hydrogels had storage moduli of 0.27-23 kPa and Young's moduli of 215-360 kPa at 4 degrees C. The hydrogels were hydrolytically degradable, with full degradation to water-soluble products within one week at 37 degrees C and pH = 7.4. A thermally-induced shape-memory effect is demonstrated in bending as well as in compression tests, in which shape recovery with excellent shape-recovery rates R-r close to 100% were observed. In the future, the material presented here could be applied, e.g., as self-anchoring devices mechanically resembling the extracellular matrix.
KW - shape-memory hydrogel
KW - active polymer
KW - biopolymer
KW - mechanical
KW - properties
KW - degradation
Y1 - 2021
U6 - https://doi.org/10.3390/ijms22115892
SN - 1422-0067
SN - 1661-6596
VL - 22
IS - 11
PB - Molecular Diversity Preservation International
CY - Basel
ER -
TY - JOUR
A1 - Bochove, Bas van
A1 - Grijpma, Dirk W.
A1 - Lendlein, Andreas
A1 - Seppälä, Jukka
T1 - Designing advanced functional polymers for medicine
JF - European polymer journal : EPJ
Y1 - 2021
U6 - https://doi.org/10.1016/j.eurpolymj.2021.110573
SN - 0014-3057
VL - 155
PB - Elsevier
CY - Oxford
ER -
TY - JOUR
A1 - Hwang, Jinyeon
A1 - Zhang, Wuyong
A1 - Youk, Sol
A1 - Schutjajew, Konstantin
A1 - Oschatz, Martin
T1 - Understanding structure-property relationships under experimental conditions for the optimization of lithium-ion capacitor anodes based on all-carbon-composite materials
JF - Energy technology : generation, conversion, storage, distribution
N2 - The nanoscale combination of a conductive carbon and a carbon-based material with abundant heteroatoms for battery electrodes is a method to overcome the limitation that the latter has high affinity to alkali metal ions but low electronic conductivity. The synthetic protocol and the individual ratios and structures are important aspects influencing the properties of such multifunctional compounds. Their interplay is, herein, investigated by infiltration of a porous ZnO-templated carbon (ZTC) with nitrogen-rich carbon obtained by condensation of hexaazatriphenylene-hexacarbonitrile (HAT-CN) at 550-1000 degrees C. The density of lithiophilic sites can be controlled by HAT-CN content and condensation temperature. Lithium storage properties are significantly improved in comparison with those of the individual compounds and their physical mixtures. Depending on the uniformity of the formed composite, loading ratio and condensation temperature have different influence. Most stable operation at high capacity per used monomer is achieved with a slowly dried composite with an HAT-CN:ZTC mass ratio of 4:1, condensed at 550 degrees C, providing more than 400 mAh g(-1) discharge capacity at 0.1 A g(-1) and a capacity retention of 72% after 100 cycles of operation at 0.5 A g(-1) due to the homogeneity of the composite and high content of lithiophilic sites.
KW - anodes
KW - hybrid materials
KW - nitrogen-doped carbon
KW - porous carbon
KW - lithium-ion capacitors
Y1 - 2021
U6 - https://doi.org/10.1002/ente.202001054
SN - 2194-4296
VL - 9
IS - 3
PB - Wiley-VCH
CY - Weinheim
ER -
TY - JOUR
A1 - Pan, Xuefeng
A1 - Sarhan, Radwan Mohamed
A1 - Kochovski, Zdravko
A1 - Chen, Guosong
A1 - Taubert, Andreas
A1 - Mei, Shilin
A1 - Lu, Yan
T1 - Template synthesis of dual-functional porous MoS2 nanoparticles with photothermal conversion and catalytic properties
JF - Nanoscale
N2 - Advanced catalysis triggered by photothermal conversion effects has aroused increasing interest due to its huge potential in environmental purification.
In this work, we developed a novel approach to the fast degradation of 4-nitrophenol (4-Nip) using porous MoS2 nanoparticles as catalysts, which integrate the intrinsic catalytic property of MoS2 with its photothermal conversion capability.
Using assembled polystyrene-b-poly(2-vinylpyridine) block copolymers as soft templates, various MoS 2 particles were prepared, which exhibited tailored morphologies (e.g., pomegranate-like, hollow, and open porous structures).
The photothermal conversion performance of these featured particles was compared under near-infrared (NIR) light irradiation.
Intriguingly, when these porous MoS2 particles were further employed as catalysts for the reduction of 4-Nip, the reaction rate constant was increased by a factor of 1.5 under NIR illumination.
We attribute this catalytic enhancement to the open porous architecture and light-to-heat conversion performance of the MoS2 particles. This contribution offers new opportunities for efficient photothermal-assisted catalysis.
Y1 - 2022
U6 - https://doi.org/10.1039/d2nr01040b
SN - 2040-3372
VL - 14
IS - 18
SP - 6888
EP - 6901
PB - RSC Publ. (Royal Society of Chemistry)
CY - Cambridge
ER -
TY - JOUR
A1 - Zhao, Yuhang
A1 - Sarhan, Radwan Mohamed
A1 - Eljarrat, Alberto
A1 - Kochovski, Zdravko
A1 - Koch, Christoph
A1 - Schmidt, Bernd
A1 - Koopman, Wouter-Willem Adriaan
A1 - Lu, Yan
T1 - Surface-functionalized Au-Pd nanorods with enhanced photothermal conversion and catalytic performance
JF - ACS applied materials & interfaces
N2 - Bimetallic nanostructures comprising plasmonic and catalytic components have recently emerged as a promising approach to generate a new type of photo-enhanced nanoreactors. Most designs however concentrate on plasmon-induced charge separation, leaving photo-generated heat as a side product.
This work presents a photoreactor based on Au-Pd nanorods with an optimized photothermal conversion, which aims to effectively utilize the photo-generated heat to increase the rate of Pd-catalyzed reactions. Dumbbell-shaped Au nanorods were fabricated via a seed-mediated growth method using binary surfactants. Pd clusters were selectively grown at the tips of the Au nanorods, using the zeta potential as a new synthetic parameter to indicate the surfactant remaining on the nanorod surface.
The photothermal conversion of the Au-Pd nanorods was improved with a thin layer of polydopamine (PDA) or TiO2.
As a result, a 60% higher temperature increment of the dispersion compared to that for bare Au rods at the same light intensity and particle density could be achieved.
The catalytic performance of the coated particles was then tested using the reduction of 4-nitrophenol as the model reaction. Under light, the PDA-coated Au-Pd nanorods exhibited an improved catalytic activity, increasing the reaction rate by a factor 3.
An analysis of the activation energy confirmed the photoheating effect to be the dominant mechanism accelerating the reaction. Thus, the increased photothermal heating is responsible for the reaction acceleration.
Interestingly, the same analysis shows a roughly 10% higher reaction rate for particles under illumination compared to under dark heating, possibly implying a crucial role of localized heat gradients at the particle surface.
Finally, the coating thickness was identified as an essential parameter determining the photothermal conversion efficiency and the reaction acceleration.
KW - Au-Pd nanorods
KW - PDA
KW - photothermal conversion
KW - surface plasmon
KW - 4-nitrophenol
Y1 - 2022
U6 - https://doi.org/10.1021/acsami.2c00221
SN - 1944-8244
SN - 1944-8252
VL - 14
IS - 15
SP - 17259
EP - 17272
PB - American Chemical Society
CY - Washington, DC
ER -