@article{LiebigSarhanPrietzeletal.2018, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Prietzel, Claudia Christina and Th{\"u}nemann, Andreas F. and Bargheer, Matias and Koetz, Joachim}, title = {Undulated Gold Nanoplatelet Superstructures}, series = {Langmuir}, volume = {34}, journal = {Langmuir}, number = {15}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.7b02898}, pages = {4584 -- 4594}, year = {2018}, abstract = {Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 degrees C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV-vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of similar to 6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor.}, language = {en} } @article{KleinpeterKoch2019, author = {Kleinpeter, Erich and Koch, Andreas}, title = {The 13 C chemical shift and the anisotropy effect of the carbene electron-deficient centre}, series = {Magnetic resonance in chemistry}, volume = {58}, journal = {Magnetic resonance in chemistry}, number = {3}, publisher = {Wiley}, address = {Hoboken}, issn = {0749-1581}, doi = {10.1002/mrc.4979}, pages = {280 -- 292}, year = {2019}, abstract = {Both the C-13 chemical shift and the calculated anisotropy effect (spatial magnetic properties) of the electron-deficient centre of stable, crystalline, and structurally characterized carbenes have been employed to unequivocally characterize potential resonance contributors to the present mesomerism (carbene, ylide, betaine, and zwitter ion) and to determine quantitatively the electron deficiency of the corresponding carbene carbon atom. Prior to that, both structures and C-13 chemical shifts were calculated and compared with the experimental delta(C-13)/ppm values and geometry parameters (as a quality criterion for obtained structures).}, language = {en} } @article{DoeringGrigorievTapioetal.2022, author = {Doering, Ulrike and Grigoriev, Dmitry and Tapio, Kosti and Bald, Ilko and B{\"o}ker, Alexander}, title = {Synthesis of nanostructured protein-mineral-microcapsules by sonication}, series = {Soft matter}, volume = {18}, journal = {Soft matter}, number = {13}, publisher = {Royal Society of Chemistry}, address = {London}, issn = {1744-6848}, doi = {10.1039/d1sm01638e}, pages = {2558 -- 2568}, year = {2022}, abstract = {We propose a simple and eco-friendly method for the formation of composite protein-mineral-microcapsules induced by ultrasound treatment. Protein- and nanoparticle-stabilized oil-in-water (O/W) emulsions loaded with different oils are prepared using high-intensity ultrasound. The formation of thin composite mineral proteinaceous shells is realized with various types of nanoparticles, which are pre-modified with Bovine Serum Albumin (BSA) and subsequently characterized by EDX, TGA, zeta potential measurements and Raman spectroscopy. Cryo-SEM and EDX mapping visualizations show the homogeneous distribution of the densely packed nanoparticles in the capsule shell. In contrast to the results reported in our previous paper,(1) the shell of those nanostructured composite microcapsules is not cross-linked by the intermolecular disulfide bonds between BSA molecules. Instead, a Pickering-Emulsion formation takes place because of the amphiphilicity-driven spontaneous attachment of the BSA-modified nanoparticles at the oil/water interface. Using colloidal particles for the formation of the shell of the microcapsules, in our case silica, hydroxyapatite and calcium carbonate nanoparticles, is promising for the creation of new functional materials. The nanoparticulate building blocks of the composite shell with different chemical, physical or morphological properties can contribute to additional, sometimes even multiple, features of the resulting capsules. Microcapsules with shells of densely packed nanoparticles could find interesting applications in pharmaceutical science, cosmetics or in food technology.}, language = {en} } @article{FriessLendleinWischke2021, author = {Frieß, Fabian and Lendlein, Andreas and Wischke, Christian}, title = {Switching microobjects from low to high aspect ratios using a shape-memory effect}, series = {Soft matter}, volume = {17}, journal = {Soft matter}, number = {41}, publisher = {Royal Society of Chemistry}, address = {London}, issn = {1744-6848}, doi = {10.1039/d1sm00947h}, pages = {9326 -- 9331}, year = {2021}, abstract = {Spherical particles from shape-memory polymers (SMP) can be stretched to ellipsoids with high aspect ratio (AR) and temporarily stabilized. They can switch back to low AR upon thermal stimulation. Here, the creation of an alternative shape-switching capability of particles from low to high AR is introduced, where a SMP matrix from polyvinyl alcohol (PVA) is used to create crosslinked high AR particles and to program the embedded micrometer-sized particles from a second SMP (oligo(epsilon-caprolactone) micronetworks, MN) with a low switching temperature T-sw. This programming proceeds through shape-recovery of the PVA matrix, from which the MN are harvested by PVA matrix dissolution. The use of a dissolvable SMP matrix may be a general strategy to efficiently create systems with complex moving capabilities.}, language = {en} } @article{RietzeTitovGranuccietal.2020, author = {Rietze, Clemens and Titov, Evgenii and Granucci, Giovanni and Saalfrank, Peter}, title = {Surface hopping dynamics for azobenzene photoisomerization}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {124}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {48}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.0c08052}, pages = {26287 -- 26295}, year = {2020}, abstract = {Azobenzenes easily photoswitch in solution, while their photoisomerization at surfaces is often hindered. In recent work, it was demonstrated by nonadiabatic molecular dynamics with trajectory surface hopping [Titov et al., J. Phys. Chem. Lett. 2016, 7, 3591-3596] that the experimentally observed suppression of trans -> cis isomerization yields in azobenzenes in a densely packed SAM (self-assembled monolayer) [Gahl et al., J. Am. Chem. Soc. 2010, 132, 1831-1838] is dominated by steric hindrance. In the present work, we systematically study by ground-state Langevin and nonadiabatic surface hopping dynamics, the effects of decreasing packing density on (i) UV/vis absorption spectra, (ii) trans -> cis isomerization yields, and (iii) excited-state lifetimes of photoexcited azobenzene. Within the quantum mechanics/ molecular mechanics models adopted here, we find that above a packing density of similar to 3 molecules/nm(2), switching yields are strongly reduced, while at smaller packing densities, the "monomer limit" is quickly approached. The UV/vis absorption spectra, on the other hand, depend on packing density over a larger range (down to at least similar to 1 molecule/nm(2)). Trends for excited-state lifetimes are less obvious, but it is found that lifetimes of pi pi* excited states decay monotonically with decreasing coverage. Effects of fluorination of the switches are also discussed for single, free molecules. Fluorination leads to comparatively large trans -> cis yields, in combination with long pi pi* lifetimes. Furthermore, for selected systems, also the effects of n pi* excitation at longer excitation wavelengths have been studied, which is found to enhance trans -> cis yields for free molecules but can lead to an opposite behavior in densely packed SAMs.}, language = {en} } @article{YestePrimusAlcantaraetal.2020, author = {Yeste, Maria Pilar and Primus, Philipp-Alexander and Alcantara, Rodrigo and Cauqui, Miguel Angel and Calvino, Juan Jose and Pintado, Jos{\´e} Mar{\´i}a and Blanco, Ginesa}, title = {Surface characterization of two Ce0.62Zr0.38O2 mixed oxides with different reducibility}, series = {Applied surface science : a journal devoted to applied physics and chemistry of surfaces and interfaces}, volume = {503}, journal = {Applied surface science : a journal devoted to applied physics and chemistry of surfaces and interfaces}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0169-4332}, doi = {10.1016/j.apsusc.2019.144255}, pages = {9}, year = {2020}, abstract = {This paper presents a study of the surface properties of two Ce/Zr mixed oxides with different reducibility, obtained by applying distinct thermal ageing treatments to an oxide with the composition Ce0.62Zr0.38O2. The surface composition was investigated by XPS. Chemical reactivity of the surface was studied by adsorption of the probe molecules CO2, D-2 and methanol. Nanostructural characterization was carried out by XRD, Raman and high-resolution Eu3+ spectroscopy (FLNS). The characterization showed only slight variations in surface composition and bulk Ce-Zr distribution, but hardy differences concerning the type and strength of acidic surface centres, as well as strong differences in the ability to dissociate hydrogen. Structural variations between both samples were identified by comparing the optical spectra of Eu3+ in surface doped samples.}, language = {en} } @article{IhlenburgMaiThuenemannetal.2021, author = {Ihlenburg, Ramona and Mai, Tobias and Th{\"u}nemann, Andreas F. and Baerenwald, Ruth and Saalw{\"a}chter, Kay and Koetz, Joachim and Taubert, Andreas}, title = {Sulfobetaine hydrogels with a complex multilength-scale hierarchical structure}, series = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, volume = {125}, journal = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, number = {13}, publisher = {American Chemical Society}, address = {Washington}, issn = {1520-6106}, doi = {10.1021/acs.jpcb.0c10601}, pages = {3398 -- 3408}, year = {2021}, abstract = {Hydrogels with a hierarchical structure were prepared from a new highly water-soluble crosslinker N,N,N',N'-tetramethyl-N,N'-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and from the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The free radical polymerization of the two compounds is rapid and yields near-transparent hydrogels with sizes up to 5 cm in diameter. Rheology shows a clear correlation between the monomer-to-crosslinker ratio and the storage and loss moduli of the hydrogels. Cryo-scanning electron microscopy, low-field nuclear magnetic resonance (NMR) spectroscopy, and small-angle X-ray scattering show that the gels have a hierarchical structure with features spanning the nanometer to the sub-millimeter scale. The NMR study is challenged by the marked inhomogeneity of the gels and the complex chemical structure of the sulfobetaine monomer. NMR spectroscopy shows how these complications can be addressed via a novel fitting approach that considers the mobility gradient along the side chain of methacrylate-based monomers.}, language = {en} } @article{BouaklineSaalfrank2021, author = {Bouakline, Foudhil and Saalfrank, Peter}, title = {Seemingly asymmetric atom-localized electronic densities following laser-dissociation of homonuclear diatomics}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry}, volume = {154}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry}, number = {23}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/5.0049710}, pages = {10}, year = {2021}, abstract = {Recent experiments on laser-dissociation of aligned homonuclear diatomic molecules show an asymmetric forward-backward (spatial) electron-localization along the laser polarization axis. Most theoretical models attribute this asymmetry to interference effects between gerade and ungerade vibronic states. Presumably due to alignment, these models neglect molecular rotations and hence infer an asymmetric (post-dissociation) charge distribution over the two identical nuclei. In this paper, we question the equivalence that is made between spatial electron-localization, observed in experiments, and atomic electron-localization, alluded by these theoretical models. We show that (seeming) agreement between these models and experiments is due to an unfortunate omission of nuclear permutation symmetry, i.e., quantum statistics. Enforcement of the latter requires mandatory inclusion of the molecular rotational degree of freedom, even for perfectly aligned molecules. Unlike previous interpretations, we ascribe spatial electron-localization to the laser creation of a rovibronic wavepacket that involves field-free molecular eigenstates with opposite space-inversion symmetry i.e., even and odd parity. Space-inversion symmetry breaking would then lead to an asymmetric distribution of the (space-fixed) electronic density over the forward and backward hemisphere. However, owing to the simultaneous coexistence of two indistinguishable molecular orientational isomers, our analytical and computational results show that the post-dissociation electronic density along a specified space-fixed axis is equally shared between the two identical nuclei-a result that is in perfect accordance with the principle of the indistinguishability of identical particles. Published under an exclusive license by AIP Publishing.}, language = {en} } @article{KleinpeterKoch2021, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Quantification of sigma-acceptor and pi-donor stabilization in O, S and Hal analogues of N-heterocyclic carbenes (NHCs) on the magnetic criterion}, series = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, volume = {125}, journal = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, number = {33}, publisher = {American Chemical Society}, address = {Washington}, issn = {1089-5639}, doi = {10.1021/acs.jpca.1c05257}, pages = {7235 -- 7245}, year = {2021}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.}, language = {en} } @article{SchimkaKlierdeGuerenuetal.2019, author = {Schimka, Selina and Klier, Dennis Tobias and de Guerenu, Anna Lopez and Bastian, Philipp and Lomadze, Nino and Kumke, Michael Uwe and Santer, Svetlana}, title = {Photo-isomerization of azobenzene containing surfactants induced by near-infrared light using upconversion nanoparticles as mediator}, series = {Journal of physics : Condensed matter}, volume = {31}, journal = {Journal of physics : Condensed matter}, number = {12}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {0953-8984}, doi = {10.1088/1361-648X/aafcfa}, pages = {9}, year = {2019}, abstract = {Here we report on photo-isomerization of azobenzene containing surfactants induced during irradiation with near-infrared (NIR) light in the presence of upconversion nanoparticles (UCNPs) acting as mediator. The surfactant molecule consists of charged head group and hydrophobic tail with azobenzene group incorporated in alkyl chain. The azobenzene group can be reversible photo-isomerized between two states: trans- and cis- by irradiation with light of an appropriate wavelength. The trans-cis photo-isomerization is induced by UV light, while cis-trans isomerization proceeds either thermally in darkness, or can be accelerated by exposure to illumination with a longer wavelength typically in a blue/green range. We present the application of lanthanide doped UCNPs to successfully switch azobenzene containing surfactants from cis to trans conformation in bulk solution using NIR light. Using Tm-3(+) or Er-3(+) as activator ions, the UCNPs provide emissions in the spectral range of 450 nm < lambda(em) < 480 nm (for Tm-3(+), three and four photon induced emission) or 525 nm < lambda(em) < 545 nm (for Er-3(+), two photon induced emission), respectively. Especially for UCNPs containing Tm-3(+) a good overlap of the emissions with the absorption bands of the azobenzene is present. Under illumination of the surfactant solution with NIR light (lambda(ex) = 976 nm) in the presence of the Tm-3(+)-doped UCNPs, the relaxation time of cis-trans photo-isomerization was increased by almost 13 times compared to thermally induced isomerization. The influence of thermal heating due to the irradiation using NIR light was shown to be minor for solvents not absorbing in NIR spectral range (e.g. CHCl3) in contrast to water, which shows a distinct absorption in the NIR.}, language = {en} }