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Erratum: Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging (Nanoscale (2021) DOI: 10.1039/D1NR01806J)

2021, Carnis, Jerome, Kirner, Felizitas, Lapkin, Dmitry, Sturm, Sebastian, Kim, Young Yong, Baburin, Igor A., Khubbutdinov, Ruslan, Ignatenko, Alexandr, Iashina, Ekaterina, Mistonov, Alexander, Steegemans, Tristan, Wieck, Thomas, Gemming, Thomas, Lubk, Axel, Lazarev, Sergey, Sprung, Michael, Vartanyants, Ivan A., Sturm, Elena V.

Correction for ‘Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging’ by Jerome Carnis et al., Nanoscale, 2021, DOI: 10.1039/D1NR01806J.

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Human spermbots for patient-representative 3D ovarian cancer cell treatment

2020, Xu, Haifeng, Medina-Sánchez, Mariana, Zhang, Wunan, Seaton, Melanie P. H., Brison, Daniel R., Edmondson, Richard J., Taylor, Stephen S., Nelson, Louisa, Zeng, Kang, Bagley, Steven, Ribeiro, Carla, Restrepo, Lina P., Lucena, Elkin, Schmidt, Christine K., Schmidt, Oliver G.

Cellular micromotors are attractive for locally delivering high concentrations of drug, and targeting hard-to-reach disease sites such as cervical cancer and early ovarian cancer lesions by non-invasive means. Spermatozoa are highly efficient micromotors perfectly adapted to traveling up the female reproductive system. Indeed, bovine sperm-based micromotors have shown potential to carry drugs toward gynecological cancers. However, due to major differences in the molecular make-up of bovine and human sperm, a key translational bottleneck for bringing this technology closer to the clinic is to transfer this concept to human material. Here, we successfully load human sperm with Doxorubicin (DOX) and perform treatment of 3D cervical cancer and patient-representative ovarian cancer cell cultures, resulting in strong anticancer cell effects. Additionally, we define the subcellular localization of the chemotherapeutic drug within human sperm, using high-resolution optical microscopy. We also assess drug effects on sperm motility and viability over time, employing sperm samples from healthy donors as well as assisted reproduction patients. Finally, we demonstrate guidance and release of human drug-loaded sperm onto cancer tissues using magnetic microcaps, and show the sperm microcap loaded with a second anticancer drug, camptothecin (CPT), which unlike DOX is not suitable for directly loading into sperm due to its hydrophobic nature. This co-drug delivery approach opens up novel targeted combinatorial drug therapies for future applications. © 2020 The Royal Society of Chemistry.

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Exploiting flux shadowing for strain and bending engineering in core-shell nanowires

2022, Al Humaidi, Mahmoud, Jakob, Julian, Al Hassan, Ali, Davtyan, Arman, Schroth, Philipp, Feigl, Ludwig, Herranz, Jesús, Novikov, Dmitri, Geelhaar, Lutz, Baumbach, Tilo, Pietsch, Ullrich

Here we report on the non-uniform shell growth of InxGa1−xAs on the GaAs nanowire (NW) core by molecular beam epitaxy (MBE). The growth was realized on pre-patterned silicon substrates with the pitch size (p) ranging from 0.1 μm to 10 μm. Considering the preferable bending direction with respect to the MBE cells as well as the layout of the substrate pattern, we were able to modify the strain distribution along the NW growth axis and the subsequent bending profile. For NW arrays with a high number density, the obtained bending profile of the NWs is composed of straight (barely-strained) and bent (strained) segments with different lengths which depend on the pitch size. A precise control of the bent and straight NW segment length provides a method to design NW based devices with length selective strain distribution.

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STM induced manipulation of azulene-based molecules and nanostructures: the role of the dipole moment

2020, Kühne, Tim, Au-Yeung, Kwan Ho, Eisenhut, Frank, Aiboudi, Oumaima, Ryndyk, Dmitry A., Cuniberti, Gianaurelio, Lissel, Franziska, Moresco, Francesca

Among the different mechanisms that can be used to drive a molecule on a surface by the tip of a scanning tunneling microscope at low temperature, we used voltage pulses to move azulene-based single molecules and nanostructures on Au(111). Upon evaporation, the molecules partially cleave and form metallo-organic dimers while single molecules are very scarce, as confirmed by simulations. By applying voltage pulses to the different structures under similar conditions, we observe that only one type of dimer can be controllably driven on the surface, which has the lowest dipole moment of all investigated structures. Experiments under different bias and tip height conditions reveal that the electric field is the main driving force of the directed motion. We discuss the different observed structures and their movement properties with respect to their dipole moment and charge distribution on the surface.

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Nanotopography mediated osteogenic differentiation of human dental pulp derived stem cells

2017, Bachhuka, Akash, Delalat, Bahman, Ghaemi, Soraya Rasi, Gronthos, Stan, Voelcker, Nicolas H., Vasilev, Krasimir

Advanced medical devices, treatments and therapies demand an understanding of the role of interfacial properties on the cellular response. This is particularly important in the emerging fields of cell therapies and tissue regeneration. In this study, we evaluate the role of surface nanotopography on the fate of human dental pulp derived stem cells (hDPSC). These stem cells have attracted interest because of their capacity to differentiate to a range of useful lineages but are relatively easy to isolate. We generated and utilized density gradients of gold nanoparticles which allowed us to examine, on a single substrate, the influence of nanofeature density and size on stem cell behavior. We found that hDPSC adhered in greater numbers and proliferated faster on the sections of the gradients with higher density of nanotopography features. Furthermore, greater surface nanotopography density directed the differentiation of hDPSC to osteogenic lineages. This study demonstrates that carefully tuned surface nanotopography can be used to manipulate and guide the proliferation and differentiation of these cells. The outcomes of this study can be important in the rational design of culture substrates and vehicles for cell therapies, tissue engineering constructs and the next generation of biomedical devices where control over the growth of different tissues is required.

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Modulating the luminance of organic light-emitting diodes: Via optical stimulation of a photochromic molecular monolayer at transparent oxide electrode

2020, Ligorio, Giovanni, Cotella, Giovanni F., Bonasera, Aurelio, Zorn Morales, Nicolas, Carnicella, Giuseppe, Kobin, Björn, Wang, Qiankun, Koch, Norbert, Hecht, Stefan, List-Kratochvil, Emil J.W., Cacialli, Franco

Self-assembled monolayers (SAMs) deposited on bottom electrodes are commonly used to tune charge carrier injection or blocking in optoelectronic devices. Beside the enhancement of device performance, the fabrication of multifunctional devices in which the output can be modulated by multiple external stimuli remains a challenging target. In this work, we report the functionalization of an indium tin oxide (ITO) electrode with a SAM of a diarylethene derivative designed for optically control the electronic properties. Following the demonstration of dense SAM formation and its photochromic activity, as a proof-of-principle, an organic light-emitting diode (OLED) embedding the light-responsive SAM-covered electrode was fabricated and characterized. Optically addressing the two-terminal device by irradiation with ultraviolet light doubles the electroluminescence. The original value can be restored reversibly by irradiation with visible light. This expanded functionality is based on the photoinduced modulation of the electronic structure of the diarylethene isomers, which impact the charge carriers' confinement within the emissive layer. This approach could be successfully exploited in the field of opto-communication technology, for example to fabricate opto-electronic logic circuits. © 2020 The Royal Society of Chemistry.

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Mixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-: I h and Dy2MN@C80- i h (M = Gd, Er, Tm, and Lu): Synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom

2019, Schlesier, C., Liu, F., Dubrovin, V., Spree, L., Büchner, B., Avdoshenko, S.M., Popov, A.A.

Systematic exploration of the synthesis of mixed-metal Dy-M nitride clusterfullerenes (NCFs, M = Gd, Er, Tm, Lu) is performed, and the impact of the second metal on the relative yield is evaluated. We demonstrate that the ionic radius of the metal appears to be the main factor allowing explanation of the relative yields in Dy-M mixed-metal systems with M = Sc, Lu, Er, and Gd. At the same time, Dy-Tm NCFs show anomalously low yields, which is not consistent with the relatively small ionic radius of Tm3+ but can be explained by the high third ionization potential of Tm. Complete separation of Dy-Gd and Dy-Er, as well as partial separation of Dy-Lu M3N@C80 nitride clusterfullerenes, is accomplished by recycling HPLC. The molecular structures of DyGd2N@C80 and DyEr2N@C80 are analyzed by means of single-crystal X-ray diffraction. A remarkable ordering of mixed-metal nitride clusters is found despite similar size and electronic properties of the metals. Possible pyramidalization of the nitride clusters in these and other nitride clusterfullerenes is critically analyzed with the help of DFT calculations and reconstruction of the nitrogen inversion barrier in M3N@C80 molecules is performed. Although a double-well potential with a pyramidal cluster structure is found to be common for most of them, the small size of the inversion barrier often leads to an apparent planar structure of the cluster. This situation is found for those M3N@C80 molecules in which the energy of the lowest vibrational level exceeds that of the inversion barrier, including Dy3N@C80 and DyEr2N@C80. The genuine pyramidal structure can be observed by X-ray diffraction only when the lowest vibrational level is below the inversion barrier, such as those found in Gd3N@C80 and DyGd2N@C80. The quantum nature of molecular vibrations becomes especially apparent when the size of the inversion barrier is comparable to the energy of the lowest vibrational levels.

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Colloidal PbS nanoplatelets synthesized via cation exchange for electronic applications

2019, Sonntag, Luisa, Shamraienko, Volodymyr, Fan, Xuelin, Samadi Khoshkhoo, Mahdi, Kneppe, David, Koitzsch, Andreas, Gemming, Thomas, Hiekel, Karl, Leo, Karl, Lesnyak, Vladimir, Eychmüller, Alexander

In this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 °C, 140 °C), and the amount of copper precursor. In a second step, Cu+ cations were replaced with Pb2+ ions within the crystal lattice via CE. While the shape and the size of parental CuS platelets were preserved, the crystal structure was rearranged from hexagonal covellite to PbS galena, accompanied by the fragmentation of the monocrystalline phase into polycrystalline one. Afterwards a halide mediated ligand exchange (LE) was carried out in order to remove insulating oleic acid residues from the PbS NPL surface and to form stable dispersions in polar organic solvents enabling thin-film fabrication. Both CE and LE processes were monitored by several characterization techniques. Furthermore, we measured the electrical conductivity of the resulting PbS NPL-based films before and after LE and compared the processing in ambient to inert atmosphere. Finally, we fabricated field-effect transistors with an on/off ratio of up to 60 and linear charge carrier mobility for holes of 0.02 cm2 V−1 s−1.

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Correction: Design and characterization of a plasmonic Doppler grating for azimuthal angle-resolved surface plasmon resonances

2021, See, Kel-Meng, Lin, Fan-Cheng, Huang, Jer-Shing

The authors regret that Fig. 1e of the original paper contained an error in the curves displayed for the silver, aluminium and palladium gratings. Specifically, a different value of the ‘index of the environment’ (1.65) was used in the calculation of these curves compared to that used for calculating the optical response of the gold grating (1.33). The correct Fig. 1 below, displays the curves calculated with the same value of the index of the environment (1.33). No amendments are made to the caption of Fig. 1 or the other sub-figures presented in the figure. This error does not affect any of the results or conclusions reported in the paper; only the display of the figure. (Figure Presented) The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

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SERS and plasmonic heating efficiency from anisotropic core/satellite superstructures

2019, Kuttner, Christian, Höller, Roland P. M., Quintanilla, Marta, Schnepf, Max J., Dulle, Martin, Fery, Andreas, Liz-Marzán, Luis M.

The optical properties of nanoparticle assemblies can be tailored via hybridization of plasmon modes. Isotropic core/satellite superstructures made of spherical nanoparticles are known to exhibit coupled modes with a strongly scattering (radiative) character, and provide hot spots yielding high activity in surface-enhanced Raman scattering (SERS). However, to complement this functionality with plasmonic heating, additional absorbing (non-radiative) modes are required. We introduce herein anisotropic superstructures formed by decorating a central nanorod with spherical satellite nanoparticles, which feature two coupled modes that allow application for both SERS and heating. On the basis of diffuse reflectance spectroscopy, small-angle X-ray scattering (SAXS), and electromagnetic simulations, the origin of the coupled modes is disclosed and thus serves as a basis toward alternative designs of functional superstructures. This work represents a proof-of-principle for the combination of high SERS efficiency with efficient plasmonic heating by near-infrared irradiation.