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- ItemStrong out-of-plane magnetic anisotropy in ion irradiated anatase TiO2 thin films(New York, NY : American Inst. of Physics, 2016) Stiller, M.; Barzola-Quiquia, J.; Esquinazi, P.; Spemann, D.; Meijer, J.; Lorenz, M.; Grundmann, M.The temperature and field dependence of the magnetization of epitaxial, undoped anatase TiO2 thin films on SrTiO3 substrates was investigated. Low-energy ion irradiation was used to modify the surface of the films within a few nanometers, yet with high enough energy to produce oxygen and titanium vacancies. The as-prepared thin film shows ferromagnetism which increases after irradiation with low-energy ions. An optimal and clear magnetic anisotropy was observed after the first irradiation, opposite to the expected form anisotropy. Taking into account the experimental parameters, titanium vacancies as di-Frenkel pairs appear to be responsible for the enhanced ferromagnetism and the strong anisotropy observed in our films. The magnetic impurities concentrations was measured by particle-induced X-ray emission with ppm resolution. They are ruled out as a source of the observed ferromagnetism before and after irradiation.
- ItemA Diverse View of Science to Catalyse Change(Weinheim : Wiley-VCH, 2020) Urbina-Blanco, César A.; Jilani, Safia Z.; Speight, Isaiah R.; Bojdys, Michael J.; Friščić, Tomislav; Stoddart, J. Fraser; Nelson, Toby L.; Mack, James; Robinson, Renã A.S.; Waddell, Emanuel A.; Lutkenhaus, Jodie L.; Godfrey, Murrell; Abboud, Martine I.; Aderinto, Stephen O.; Aderohunmu, Damilola; Bibič, Lučka; Borges, João; Dong, Vy M.; Ferrins, Lori; Fung, Fun Man; John, Torsten; Lim, Felicia P.L.; Masters, Sarah L.; Mambwe, Dickson; Thordarson, Pall; Titirici, Maria-Magdalena; Tormet-González, Gabriela D.; Unterlass, Miriam M.; Wadle, Austin; Yam, Vivian W.-W.; Yang, Ying-WeiValuing diversity leads to scientific excellence, the progress of science and most importantly, it is simply the right thing to do. We can value diversity not only in words, but also in actions. From the structure of DNA,1 to computer science,2 and space-station batteries,3 several key scientific discoveries that enhance our lives today, were made by marginalized scientists. These three scientists, Rosalind E. Franklin, Alan M. Turing and Olga D. González-Sanabria, did not conform to the cultural expectations of how scientists should look and behave. Unfortunately, marginalized scientists are often viewed as just a resource rather than the lifeblood that constitutes science itself. We need to embrace scientists from all walks of life and corners of the globe; this will also mean that nobody is excluded from tackling the life-threatening societal challenges that lie ahead. An awareness of science policy is essential to safeguarding our future. Science policy deals with creating the framework and codes of conduct that determine how science can best serve society.4-6 Discussions around science policy are often accompanied by anecdotes of “good” and “bad” practices regarding the merits of diversity and inclusion. Excellence and truth, which flow inexorably from diversity and inclusion, are the bedrocks upon which science should influence political and economic outcomes. A vital area of science policy is to support the professional development of marginalized scientists, an objective that must be acted upon by scientific leaders and communicators...
- ItemBenchmark of Simplified Time-Dependent Density Functional Theory for UV–Vis Spectral Properties of Porphyrinoids(Weinheim : Wiley-VCH Verlag, 2019) Batra, Kamal; Zahn, Stefan; Heine, ThomasTime-dependent density functional theory is thoroughly benchmarked for the predictive calculation of UV–vis spectra of porphyrin derivatives. With the aim to provide an approach that is computationally feasible for large-scale applications such as biological systems or molecular framework materials, albeit performing with high accuracy for the Q-bands, the results given by various computational protocols, including basis sets, density-functionals (including gradient corrected local functionals, hybrids, double hybrids and range-separated functionals), and various variants of time-dependent density functional theory, including the simplified Tamm–Dancoff approximation, are compared. An excellent choice for these calculations is the range-separated functional CAM-B3LYP in combination with the simplified Tamm–Dancoff approximation and a basis set of double-ζ quality def2-SVP (mean absolute error [MAE] of ≈0.05 eV). This is not surpassed by more expensive approaches, not even by double hybrid functionals, and solely systematic excitation energy scaling slightly improves the results (MAE ≈0.04 eV).
- ItemBiocatalytic Degradation Efficiency of Postconsumer Polyethylene Terephthalate Packaging Determined by Their Polymer Microstructures(Weinheim : Wiley-VCH, 2019) Wei, Ren; Breite, Daniel; Song, Chen; Gräsing, Daniel; Ploss, Tina; Hille, Patrick; Schwerdtfeger, Ruth; Matysik, Jörg; Schulze, Agnes; Zimmermann, WolfgangPolyethylene terephthalate (PET) is the most important mass-produced thermoplastic polyester used as a packaging material. Recently, thermophilic polyester hydrolases such as TfCut2 from Thermobifida fusca have emerged as promising biocatalysts for an eco-friendly PET recycling process. In this study, postconsumer PET food packaging containers are treated with TfCut2 and show weight losses of more than 50% after 96 h of incubation at 70 °C. Differential scanning calorimetry analysis indicates that the high linear degradation rates observed in the first 72 h of incubation is due to the high hydrolysis susceptibility of the mobile amorphous fraction (MAF) of PET. The physical aging process of PET occurring at 70 °C is shown to gradually convert MAF to polymer microstructures with limited accessibility to enzymatic hydrolysis. Analysis of the chain-length distribution of degraded PET by nuclear magnetic resonance spectroscopy reveals that MAF is rapidly hydrolyzed via a combinatorial exo- and endo-type degradation mechanism whereas the remaining PET microstructures are slowly degraded only by endo-type chain scission causing no detectable weight loss. Hence, efficient thermostable biocatalysts are required to overcome the competitive physical aging process for the complete degradation of postconsumer PET materials close to the glass transition temperature of PET.
- ItemComparative study of sculptured metallic thin films deposited by oblique angle deposition at different temperatures(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2018) Liedtke, Susann; Grüner, Christoph; Gerlach, Jürgen W.; Rauschenbach, BerndMetals with a wide range of melting points are deposited by electron beam evaporation under oblique deposition geometry on thermally oxidized Si substrates. During deposition the sample holder is cooled down to 77 K. It is observed that all obliquely deposited metals grow as tilted, high aspect ratio columns and hence with a similar morphology. A comparison of such columns with those deposited at room temperature (300 K) reveals that shadowing dominates the growth process for columns deposited at 77 K, while the impact of surface diffusion is significantly increased at elevated substrate temperatures. Furthermore, it is discussed how the incidence angle of the incoming particle flux and the substrate temperature affect the columnar tilt angles and the porosity of the sculptured thin films. Exemplarily for tilted Al columns deposited at 77 K and at 300 K, in-plane pole figure measurements are carried out. A tendency to form a biaxial texture as well as a change in the crystalline structure depending on the substrate temperature is found for those films.
- ItemCoordination chemistry and photoswitching of dinuclear macrocyclic cadmium-, nickel-, and zinc complexes containing azobenzene carboxylato co-ligands(Frankfurt, Main : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2019) Klose, Jennifer; Severin, Tobias; Hahn, Peter; Jeremies, Alexander; Bergmann, Jens; Fuhrmann, Daniel; Griebel, Jan; Abel, Bernd; Kersting, BertholdThe synthesis of mixed-ligand complexes of the type [M2L(μ-L')]+, where L represents a 24-membered macrocyclic hexaaza-dithiophenolate ligand, L' is an azobenzene carboxylate co-ligand, and M = Cd(II), Ni(II) or Zn(II), is reported. A series of new complexes were synthesized, namely [M2L(μ-L')]+ (L' = azo-H, M = Cd (1), Ni (2); L' = azo-OH, M = Zn (3), Ni (4); L' = azo-NMe2, M = Zn (5), Cd (6), Ni (7); L' = azo-CO2Me, M = Cd (8), Ni (9)), and characterized by elemental analysis, electro-spray ionization mass spectrometry (ESIMS), IR, UV–vis and NMR spectroscopy (for diamagnetic Zn and Cd complexes) and X-ray single crystal structure analysis. The crystal structures of 3' and 5–8 display an isostructural series of compounds with bridging azobenzene carboxylates in the trans form. The paramagnetic Ni complexes 2, 4 and 7 reveal a weak ferromagnetic exchange interaction with magnetic exchange coupling constant values between 21 and 23 cm−1 (H = −2JS1S2). Irradiation of 1 with λ = 365 nm reveals a photoisomerization of the co-ligand from the trans to the cis form. © 2019 Klose et al.
- ItemDeposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2017) Börner, Martin; Blömer, Laura; Kischel, Marcus; Richter, Peter; Salvan, Georgeta; Zahn, Dietrich R. T.; Siles, Pablo F.; Fuentes, Maria E. N.; Bufon, Carlos C. B.; Grimm, Daniel; Schmidt, Oliver G.; Breite, Daniel; Abel, Bernd; Kersting, BertholdThe chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2− (6), HS(CH2)10CO2− (7), or HS(C6H4)2CO2− (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.
- ItemTopography evolution of germanium thin films synthesized by pulsed laser deposition(New York, NY : American Inst. of Physics, 2017) Schumacher, P.; Mayr, S.G.; Rauschenbach, B.Germanium thin films were deposited by Pulsed Laser Deposition (PLD) onto single crystal Ge (100) and Si (100) substrates with a native oxide film on the surface. The topography of the surface was investigated by Atomic Force Microscopy (AFM) to evaluate the scaling behavior of the surface roughness of amorphous and polycrystalline Ge films grown on substrates with different roughnesses. Roughness evolution was interpreted within the framework of stochastic rate equations for thin film growth. Here the Kardar-Parisi-Zhang equation was used to describe the smoothening process. Additionally, a roughening regime was observed in which 3-dimensional growth occurred. Diffusion of the deposited Ge adatoms controlled the growth of the amorphous Ge thin films. The growth of polycrystalline thin Ge films was dominated by diffusion processes only in the initial stage of the growth.
- ItemSynthesis of High Crystalline TiO2 Nanoparticles on a Polymer Membrane to Degrade Pollutants from Water(Basel : MDPI, 2018-9-5) Fischer, Kristina; Schulz, Paulina; Atanasov, Igor; Abdul Latif, Amira; Thomas, Isabell; Kühnert, Mathias; Prager, Andrea; Griebel, Jan; Schulze, AgnesTitanium dioxide (TiO2) is described as an established material to remove pollutants from water. However, TiO2 is still not applied on a large scale due to issues concerning, for example, the form of use or low photocatalytic activity. We present an easily upscalable method to synthesize high active TiO2 nanoparticles on a polyethersulfone microfiltration membrane to remove pollutants in a continuous way. For this purpose, titanium(IV) isopropoxide was mixed with water and hydrochloric acid and treated up to 210 °C. After cooling, the membrane was simply dip-coated into the TiO2 nanoparticle dispersion. Standard characterization was undertaken (i.e., X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, water permeance, contact angle). Degradation of carbamazepine and methylene blue was executed. By increasing synthesis temperature crystallinity and photocatalytic activity elevates. Both ultrasound modification of nanoparticles and membrane pre-modification with carboxyl groups led to fine distribution of nanoparticles. The ultrasound-treated nanoparticles gave the highest photocatalytic activity in degrading carbamazepine and showed no decrease in degradation after nine times of repetition. The TiO2 nanoparticles were strongly bound to the membrane. Photocatalytic TiO2 nanoparticles with high activity were synthesized. The innovative method enables a fast and easy nanoparticle production, which could enable the use in large-scale water cleaning.
- ItemDepth-Resolved Phase Analysis of Expanded Austenite Formed in Austenitic Stainless Steel(Basel : MDPI, 2020) Manova, Darina; Schlenz, Patrick; Gerlach, Jürgen W.; Mändl, StephanExpanded austenite γN formed after nitrogen insertion into austenitic stainless steel and CoCr alloys is known as a hard and very wear resistant phase. Nevertheless, no single composition and lattice expansion can describe this phase with nitrogen in solid solution. Using in situ X-ray diffraction (XRD) during ion beam sputtering of expanded austenite allows a detailed depth-dependent phase analysis, correlated with the nitrogen depth profiles obtained by time-of-flight secondary ion mass spectrometry (ToF-SIMS) or glow discharge optical emission spectroscopy (GDOES). Additionally, in-plane XRD measurements at selected depths were performed for strain analysis. Surprisingly, an anomalous peak splitting for the (200) expanded peak was observed for some samples during nitriding and sputter etching, indicating a layered structure only for {200} oriented grains. The strain analysis as a function of depth and orientation of scattering vector (parallel/perpendicular to the surface) is inconclusive. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.