@article{LeverMayerMetjeetal.2021, author = {Lever, Fabiano and Mayer, Dennis and Metje, Jan and Alisauskas, Skirmantas and Calegari, Francesca and D{\"u}sterer, Stefan and Feifel, Raimund and Niebuhr, Mario and Manschwetus, Bastian and Kuhlmann, Marion and Mazza, Tommaso and Robinson, Matthew Scott and Squibb, Richard J. and Trabattoni, Andrea and Wallner, M{\aa}ns and Wolf, Thomas J. A. and G{\"u}hr, Markus}, title = {Core-level spectroscopy of 2-thiouracil at the sulfur L1 and L2,3 edges utilizing a SASE free-electron-laser}, series = {Molecules}, volume = {26}, journal = {Molecules}, number = {21}, publisher = {MDPI}, address = {Basel}, issn = {1420-3049}, doi = {10.3390/molecules26216469}, pages = {11}, year = {2021}, abstract = {In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L1- and L2,3-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster-Kronig and Auger-Meitner emission at the L1- and L2,3-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy.}, language = {en} } @article{TianLiang2022, author = {Tian, Peibo and Liang, Yingjie}, title = {Material coordinate driven variable-order fractal derivative model of water anomalous adsorption in swelling soil}, series = {Chaos, solitons \& fractals}, volume = {164}, journal = {Chaos, solitons \& fractals}, publisher = {Elsevier}, address = {Oxford}, issn = {0960-0779}, doi = {10.1016/j.chaos.2022.112754}, pages = {8}, year = {2022}, abstract = {The diffusion process of water in swelling (expansive) soil often deviates from normal Fick diffusion and belongs to anomalous diffusion. The process of water adsorption by swelling soil often changes with time, in which the microstructure evolves with time and the absorption rate changes along a fractal dimension gradient function. Thus, based on the material coordinate theory, this paper proposes a variable order derivative fractal model to describe the cumulative adsorption of water in the expansive soil, and the variable order is time dependent linearly. The cumulative adsorption is a power law function of the anomalous sorptivity, and patterns of the variable order. The variable-order fractal derivative model is tested to describe the cumulative adsorption in chernozemic surface soil, Wunnamurra clay and sandy loam. The results show that the fractal derivative model with linearly time dependent variable-order has much better accuracy than the fractal derivative model with a constant derivative order and the integer order model in the application cases. The derivative order can be used to distinguish the evolution of the anomalous adsorption process. The variable-order fractal derivative model can serve as an alternative approach to describe water anomalous adsorption in swelling soil.}, language = {en} } @article{SchneiderBytyqiKohautetal.2022, author = {Schneider, Sebastian and Bytyqi, Kushtrim and Kohaut, Stephan and B{\"u}gel, Patrick and Weinschenk, Benjamin and Marz, Michael and Kimouche, Amina and Fink, Karin and Hoffmann-Vogel, Regina}, title = {Molecular self-assembly of DBBA on Au(111) at room temperature}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {24}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {46}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/d2cp02268k}, pages = {28371 -- 28380}, year = {2022}, abstract = {We have investigated the self-assembly of the graphene nanoribbon molecular precursor 10,10'-dibromo-9,9'-bianthryl (DBBA) on Au(111) with frequency modulation scanning force microscopy (FM-SFM) at room temperature combined with ab initio calculations. For low molecular coverages, the molecules aggregate along the substrate herringbone reconstruction main directions while remaining mobile. At intermediate coverage, two phases coexist, zigzag stripes of monomer chains and decorated herringbones. For high coverage, the molecules assemble in a dimer-striped phase. The adsorption behaviour of DBBA molecules and their interactions are discussed and compared with the results from ab initio calculations.}, language = {en} } @article{ScharsichLohwasserSommeretal.2012, author = {Scharsich, Christina and Lohwasser, Ruth H. and Sommer, Michael and Asawapirom, Udom and Scherf, Ullrich and Thelakkat, Mukundan and Neher, Dieter and Koehler, Anna}, title = {Control of aggregate formation in poly(3-hexylthiophene) by solvent, molecular weight, and synthetic method}, series = {Journal of polymer science : B, Polymer physics}, volume = {50}, journal = {Journal of polymer science : B, Polymer physics}, number = {6}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0887-6266}, doi = {10.1002/polb.23022}, pages = {442 -- 453}, year = {2012}, abstract = {Aggregate formation in poly(3-hexylthiophene) depends on molecular weight, solvent, and synthetic method. The interplay of these parameters thus largely controls device performance. In order to obtain a quantitative understanding on how these factors control the resulting electronic properties of P3HT, we measured absorption in solution and in thin films as well as the resulting field effect mobility in transistors. By a detailed analysis of the absorption spectra, we deduce the fraction of aggregates formed, the excitonic coupling within the aggregates, and the conjugation length within the aggregates, all as a function of solvent quality for molecular weights from 5 to 19 kDa. From this, we infer in which structure the aggregated chains pack. Although the 5 kDa samples form straight chains, the 11 and 19 kDa chains are kinked or folded, with conjugation lengths that increase as the solvent quality reduces. There is a maximum fraction of aggregated chains (about 55 +/- 5\%) that can be obtained, even for poor solvent quality. We show that inducing aggregation in solution leads to control of aggregate properties in thin films. As expected, the field-effect mobility correlates with the propensity to aggregation. Correspondingly, we find that a well-defined synthetic approach, tailored to give a narrow molecular weight distribution, is needed to obtain high field effect mobilities of up to 0.01 cm2/Vs for low molecular weight samples (=11 kDa), while the influence of synthetic method is negligible for samples of higher molecular weight, if low molecular weight fractions are removed by extraction.}, language = {en} } @article{PuppeHoehnKaczoreketal.2017, author = {Puppe, Daniel and H{\"o}hn, Axel and Kaczorek, Danuta and Wanner, Manfred and Wehrhan, Marc and Sommer, Michael}, title = {How big is the influence of biogenic silicon pools on short-term changes in water-soluble silicon in soils? Implications from a study of a 10-year-old soil-plant system}, series = {Biogeosciences}, volume = {14}, journal = {Biogeosciences}, publisher = {Copernicus}, address = {G{\"o}ttingen}, issn = {1726-4170}, doi = {10.5194/bg-14-5239-2017}, pages = {14}, year = {2017}, abstract = {The significance of biogenic silicon (BSi) pools as a key factor for the control of Si fluxes from terrestrial to aquatic ecosystems has been recognized for decades. However, while most research has been focused on phytogenic Si pools, knowledge of other BSi pools is still limited. We hypothesized that different BSi pools influence short-term changes in the water-soluble Si fraction in soils to different extents. To test our hypothesis we took plant (Calamagrostis epigejos, Phragmites australis) and soil samples in an artificial catchment in a post-mining landscape in the state of Brandenburg, Germany. We quantified phytogenic (phytoliths), protistic (diatom frustules and testate amoeba shells) and zoogenic (sponge spicules) Si pools as well as Tironextractable and water-soluble Si fractions in soils at the beginning (t(0)) and after 10 years (t(10)) of ecosystem development. As expected the results of Tiron extraction showed that there are no consistent changes in the amorphous Si pool at Chicken Creek (Huhnerwasser) as early as after 10 years. In contrast to t(0) we found increased water-soluble Si and BSi pools at t(10); thus we concluded that BSi pools are the main driver of short-term changes in water-soluble Si. However, because total BSi represents only small proportions of water-soluble Si at t(0) (< 2 \%) and t(10) (2.8-4.3 \%) we further concluded that smaller (< 5 mu m) and/or fragile phytogenic Si structures have the biggest impact on short-term changes in water-soluble Si. In this context, extracted phytoliths (> 5 mu m) only amounted to about 16\% of total Si con-tents of plant materials of C. epigejos and P. australis at t(10); thus about 84\% of small-scale and/or fragile phytogenic Si is not quantified by the used phytolith extraction method. Analyses of small-scale and fragile phytogenic Si structures are urgently needed in future work as they seem to represent the biggest and most reactive Si pool in soils. Thus they are the most important drivers of Si cycling in terrestrial biogeosystems.}, language = {en} } @article{VoloskovMishurovaEvlashinetal.2022, author = {Voloskov, Boris and Mishurova, Tatiana and Evlashin, Stanislav and Akhatov, Iskander and Bruno, Giovanni and Sergeichev, Ivan}, title = {Artificial defects in 316L stainless steel produced by laser powder bed fusion: printability, microstructure, and effects on the very-high-cycle fatigue behavior}, series = {Advanced engineering materials}, volume = {25}, journal = {Advanced engineering materials}, number = {1}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1438-1656}, doi = {10.1002/adem.202200831}, pages = {13}, year = {2022}, abstract = {The printability of artificial defects inside the additively manufactured laser powder bed fusion (LPBF) 316L stainless steel is investigated. The printing parameters of the LPBF process are optimized to produce artificial defects with reproducible sizes at desired positions while minimizing redundant porosity. The smallest obtained artificial defect is 90 mu m in diameter. The accuracy of the geometry of the printed defect depends on both the height and the diameter in the input model. The effect of artificial defects on the very-high-cycle fatigue (VHCF) behavior of LPBF 316L stainless steel is also studied. The specimens printed with artificial defects in the center are tested under VHCF using an ultrasonic machine. Crack initiation is accompanied by the formation of a fine granular area (FGA), typical of VHCF. Despite the presence of relatively large artificial defects, FGA formation is observed around accidental natural printing defects closer to the surface, which can still be considered as internal. The causes for this occurrence are discussed.}, language = {en} } @article{UmlandtKopyshevPasechniketal.2022, author = {Umlandt, Maren and Kopyshev, Alexey and Pasechnik, Sergey and Zakharov, Alexandre and Lomadze, Nino and Santer, Svetlana}, title = {Light-triggered manipulations of droplets all in one: reversible wetting, transport, splitting, and merging}, series = {ACS applied materials \& interfaces}, volume = {14}, journal = {ACS applied materials \& interfaces}, number = {36}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.2c10710}, pages = {41412 -- 41420}, year = {2022}, abstract = {Here, we establish different ways of light-triggered droplet manipulation such as reversible wetting, splitting, merging, and transport. The unique features of our approach are that the changes in the wetting properties of microscopic droplets of isotropic (oil) or anisotropic (liquid crystalline) liquids adsorbed on photoswitchable films can be triggered just by application of soft optical stimuli, which lead to dynamical, reversible changes in the local morphology of the structured surfaces. The adaptive films consist of an azobenzene-containing surfactant ionically attached to oppositely charged polymer chains. Under exposure to irradiation with light, the azobenzene photoisomerizes between two states, nonpolar trans -isomer and polar cis-isomer, resulting in the corresponding changes in the surface energy and orientation of the surfactant tails at the interface. Additionally, the local increase in the surface temperature due to absorption of light by the azobenzene groups enables diverse processes of manipulation of the adsorbed small droplets, such as the reversible increase of the droplet basal area up to 5 times, anisotropic wetting during irradiation with modulated light, and precise partition of the droplet into many small pieces, which can then be merged on demand to the desired number of larger droplets. Moreover, using a moving focused light spot, we experimentally demonstrate and theoretically explain the locomotion of the droplet over macroscopic distances with a velocity of up to 150 mu m center dot s-1. Our findings could lead to the ultimate application of a programmable workbench for manipulating and operating an ensemble of droplets, just using simple and gentle optical stimuli.}, language = {en} } @article{LeproGrossmannPanahetal.2022, author = {Lepro, Valentino and Großmann, Robert and Panah, Setareh Sharifi and Nagel, Oliver and Klumpp, Stefan and Lipowsky, Reinhard and Beta, Carsten}, title = {Optimal cargo size for active diffusion of biohybrid microcarriers}, series = {Physical Review Applied}, volume = {18}, journal = {Physical Review Applied}, number = {3}, publisher = {American Physical Society}, address = {College Park}, issn = {2331-7019}, doi = {10.1103/PhysRevApplied.18.034014}, pages = {13}, year = {2022}, abstract = {As society paves its way towards device miniaturization and precision medicine, microscale actuation and transport become increasingly prominent research fields with high impact in both technological and clinical contexts. In order to accomplish movement of micron-sized objects towards specific target sites, active biohybrid transport systems, such as motile living cells that act as smart biochemically powered microcarriers, have been suggested as an alternative to synthetic microrobots. Inspired by the motility of leukocytes, we propose the amoeboid crawling of eukaryotic cells as a promising mechanism for transport of micron-sized cargoes and present an in-depth study of this type of composite active matter. Its transport properties result from the interactions of an active element (cell) and a passive one (cargo) and reveal an optimal cargo size that enhances the locomotion of the load-carrying cells, even exceeding their motility in the absence of cargo. The experimental findings are rationalized in terms of a biohybrid active particle model that describes the emergent cell-cargo dynamics and enables us to derive the long-time diffusive transport of amoeboid microcarriers. As amoeboid locomotion is commonly observed for mammalian cells such as leukocytes, our results lay the foundations for the study of transport performance of other medically relevant cell types and for extending our findings to more advanced transport tasks in complex environments, such as tissues.}, language = {en} } @article{YanLiangXu2022, author = {Yan, Shengjie and Liang, Yingjie and Xu, Wei}, title = {Characterization of chloride ions diffusion in concrete using fractional Brownian motion run with power law clock}, series = {Fractals : complex geometry, patterns, and scaling in nature and society}, volume = {30}, journal = {Fractals : complex geometry, patterns, and scaling in nature and society}, number = {9}, publisher = {World Scient. Publ.}, address = {Singapore [u.a.]}, issn = {0218-348X}, doi = {10.1142/S0218348X22501778}, pages = {9}, year = {2022}, abstract = {In this paper, we propose a revised fractional Brownian motion run with a nonlinear clock (fBm-nlc) model and utilize it to illustrate the microscopic mechanism analysis of the fractal derivative diffusion model with variable coefficient (VC-FDM). The power-law mean squared displacement (MSD) links the fBm-nlc model and the VC-FDM via the two-parameter power law clock and the Hurst exponent is 0.5. The MSD is verified by using the experimental points of the chloride ions diffusion in concrete. When compared to the linear Brownian motion, the results show that the power law MSD of the fBm-nlc is much better in fitting the experimental points of chloride ions in concrete. The fBm-nlc clearly interprets the VC-FDM and provides a microscopic strategy in characterizing different types of non-Fickian diffusion processes with more different nonlinear functions.}, language = {en} } @article{SavchenkoLomadzeSanteretal.2022, author = {Savchenko, Vladyslav and Lomadze, Nino and Santer, Svetlana and Guskova, Olga}, title = {Spiropyran/merocyanine amphiphile in various solvents}, series = {International journal of molecular sciences}, volume = {23}, journal = {International journal of molecular sciences}, number = {19}, publisher = {MDPI}, address = {Basel}, issn = {1422-0067}, doi = {10.3390/ijms231911535}, pages = {24}, year = {2022}, abstract = {This joint experimental-theoretical work focuses on molecular and photophysical properties of the spiropyran-containing amphiphilic molecule in organic and aqueous solutions. Being dissolved in tested organic solvents, the system demonstrates positive photochromism, i.e., upon UV stimulus the colorless spiropyran form is transformed into colorful merocyanine isomer. However, the aqueous solution of the amphiphile possesses a negative photochromism: the orange-red merocyanine form becomes thermodynamically more stable in water, and both UV and vis stimuli lead to the partial or complete photobleaching of the solution. The explanation of this phenomenon is given on the basis of density functional theory calculations and classical modeling including thermodynamic integration. The simulations reveal that stabilization of merocyanine in water proceeds with the energy of ca. 70 kJ mol-1, and that the Helmholtz free energy of hydration of merocyanine form is 100 kJ mol-1 lower as compared to the behavior of SP isomer in water. The explanation of such a difference lies in the molecular properties of the merocyanine: after ring-opening reaction this molecule transforms into a zwitterionic form, as evidenced by the electrostatic potential plotted around the opened form. The presence of three charged groups on the periphery of a flat conjugated backbone stimulates the self-assembly of merocyanine molecules in water, ending up with the formation of elongated associates with stack-like building blocks, as shown in molecular dynamics simulations of the aqueous solution with the concentration above critical micelle concentration. Our quantitative evaluation of the hydrophilicity switching in spiropyran/merocyanine containing surfactants may prompt the search for new systems, including colloidal and polymeric ones, aiming at remote tuning of their morphology, which could give new promising shapes and patterns for the needs of modern nanotechnology.}, language = {en} }