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Glycerylphytate as an ionic crosslinker for 3D printing of multi-layered scaffolds with improved shape fidelity and biological features

2020, Mora-Boza, A., Włodarczyk-Biegun, M.K., Del Campo, A., Vázquez-Lasa, B., Román, J.S.

The fabrication of intricate and long-term stable 3D polymeric scaffolds by a 3D printing technique is still a challenge. In the biomedical field, hydrogel materials are very frequently used because of their excellent biocompatibility and biodegradability, however the improvement of their processability and mechanical properties is still required. This paper reports the fabrication of dual crosslinked 3D scaffolds using a low concentrated (<10 wt%) ink of gelatin methacryloyl (GelMA)/chitosan and a novel crosslinking agent, glycerylphytate (G1Phy) to overcome the current limitations in the 3D printing field using hydrogels. The applied methodology consisted of a first ultraviolet light (UV) photopolymerization followed by a post-printing ionic crosslinking treatment with G1Phy. This crosslinker provides a robust framework and avoids the necessity of neutralization with strong bases. The blend ink showed shear-thinning behavior and excellent printability in the form of a straight and homogeneous filament. UV curing was undertaken simultaneously to 3D deposition, which enhanced precision and shape fidelity (resolution ≈150 μm), and prevented the collapse of the subsequent printed layers (up to 28 layers). In the second step, the novel G1Phy ionic crosslinker agent provided swelling and long term stability properties to the 3D scaffolds. The multi-layered printed scaffolds were mechanically stable under physiological conditions for at least one month. Preliminary in vitro assays using L929 fibroblasts showed very promising results in terms of adhesion, spreading, and proliferation in comparison to other phosphate-based traditional crosslinkers (i.e. TPP). We envision that the proposed combination of the blend ink and 3D printing approach can have widespread applications in the regeneration of soft tissues.

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Hydrophilic non-precious metal nitrogen-doped carbon electrocatalysts for enhanced efficiency in oxygen reduction reaction

2015, Hao, Guang-Ping, Sahraie, Nastaran Ranjbar, Zhang, Qiang, Krause, Simon, Oschatz, Martin, Bachmatiuk, Alicja, Strasser, Peter, Kaskel, Stefan

Exploring the role of surface hydrophilicity of non-precious metal N-doped carbon electrocatalysts in electrocatalysis is challenging. Herein we discover an ultra-hydrophilic non-precious carbon electrocatalyst, showing enhanced catalysis efficiency on both gravimetric and areal basis for oxygen reduction reaction due to a high dispersion of active centres.

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Local difference measures between complex networks for dynamical system model evaluation

2015, Lange, S., Donges, J.F., Volkholz, J., Kurths, J.

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Promoting abnormal grain growth in Fe-based shape memory alloys through compositional adjustments

2019, Vollmer, M., Arold, T., Kriegel, M.J., Klemm, V., Degener, S., Freudenberger, J., Niendorf, T.

Iron-based shape memory alloys are promising candidates for large-scale structural applications due to their cost efficiency and the possibility of using conventional processing routes from the steel industry. However, recently developed alloy systems like Fe–Mn–Al–Ni suffer from low recoverability if the grains do not completely cover the sample cross-section. To overcome this issue, here we show that small amounts of titanium added to Fe–Mn–Al–Ni significantly enhance abnormal grain growth due to a considerable refinement of the subgrain sizes, whereas small amounts of chromium lead to a strong inhibition of abnormal grain growth. By tailoring and promoting abnormal grain growth it is possible to obtain very large single crystalline bars. We expect that the findings of the present study regarding the elementary mechanisms of abnormal grain growth and the role of chemical composition can be applied to tailor other alloy systems with similar microstructural features.

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Sc3CH@C80: selective 13C enrichment of the central carbon atom

2016, Junghans, Katrin, Rosenkranz, Marco, Popov, Alexey A.

Sc3CH@C80 is synthesized and characterized by 1H, 13C, and 45Sc NMR. A large negative chemical shift of the proton, -11.73 ppm in the Ih and -8.79 ppm in the D5h C80 cage isomers, is found. 13C satellites in the 1H NMR spectrum enabled indirect determination of the 13C chemical shift for the central carbon at 173 ± 1 ppm. Intensity of the satellites allowed determination of the 13C content for the central carbon atom. This unique possibility is applied to analyze the cluster/cage 13C distribution in mechanistic studies employing either 13CH4 or 13C powder to enrich Sc3CH@C80 with 13C.

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Femtosecond stimulated Raman spectroscopy of the cyclobutane thymine dimer repair mechanism: A computational study

2014, Ando, H., Fingerhut, B.P., Dorfman, K.E., Biggs, J.D., Mukamel, S.

Cyclobutane thymine dimer, one of the major lesions in DNA formed by exposure to UV sunlight, is repaired in a photoreactivation process, which is essential to maintain life. The molecular mechanism of the central step, i.e., intradimer C-C bond splitting, still remains an open question. In a simulation study, we demonstrate how the time evolution of characteristic marker bands (C=O and C=C/C-C stretch vibrations) of cyclobutane thymine dimer and thymine dinucleotide radical anion, thymidylyl(3′→5′)-thymidine, can be directly probed with femtosecond stimulated Raman spectroscopy (FSRS). We construct a DFT(M05-2X) potential energy surface with two minor barriers for the intradimer C5-C′5 splitting and a main barrier for the C6-C′6 splitting, and identify the appearance of two C5=C6 stretch vibrations due to the C6-C′6 splitting as a spectroscopic signature of the underlying bond splitting mechanism. The sequential mechanism shows only absorptive features in the simulated FSRS signals, whereas the fast concerted mechanism shows characteristic dispersive line shapes. (Figure Presented).

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Anti-correlation of HER2 and focal adhesion complexes in the plasma membrane

2020, Weinberg, F., Han, M.K.L., Dahmke, I.N., Campo, A.D., de Jonge, N.

Excess presence of the human epidermal growth factor receptor 2 (HER2) as well as of the focal adhesion protein complexes are associated with increased proliferation, migratory, and invasive behavior of cancer cells. A cross-regulation between HER2 and integrin signaling pathways has been found, but the exact mechanism remains elusive. Here, we investigated whether HER2 colocalizes with focal adhesion complexes on breast cancer cells overexpressing HER2. For this purpose, vinculin or talin green fluorescent protein (GFP) fusion proteins, both key constituents of focal adhesions, were expressed in breast cancer cells. HER2 was either extracellularly or intracellularly labeled with fluorescent quantum dots nanoparticles (QDs). The cell-substrate interface was analyzed at the location of the focal adhesions by means of total internal reflection fluorescent microscopy or correlative fluorescence- and scanning transmission electron microscopy. Expression of HER2 at the cell-substrate interface was only observed upon intracellular labeling, and was heterogeneous with both HER2-enriched and -low regions. In contrast to an expected enrichment of HER2 at focal adhesions, an anti-correlated expression pattern was observed for talin and HER2. Our findings suggest a spatial anti-correlation between HER2 and focal adhesion complexes for adherent cells.

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A crystalline anionic complex of scandium nitride endometallofullerene: Experimental observation of single-bonded (Sc3N@Ih-C80−)2 dimers

2016, Konarev, Dmitri V., Zorina, Leokadiya V., Khasanov, Salavat S., Popov, Alexey A., Otsuka, Akihiro, Yamochi, Hideki, Saito, Gunzi, Lyubovskaya, Rimma N.

Reduction of scandium nitride clusterfullerene, Sc3N@Ih-C80, by sodium fluorenone ketyl in the presence of cryptand[2,2,2] allows the crystallization of the {cryptand[2,2,2](Na+)}2(Sc3N@Ih-C80−)2·2.5C6H4Cl2 (1) salt. The Sc3N@Ih-C80˙− radical anions are dimerized to form single-bonded (Sc3N@Ih-C80−)2 dimers.

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A highly flexible and compact magnetoresistive analytic device

2014, Lin, G., Makarov, D., Melzer, M., Si, W., Yan, C., Schmidt, O.G.

A grand vision of realization of smart and compact multifunctional microfluidic devices for wearable health monitoring, environment sensing and point-of-care tests emerged with the fast development of flexible electronics. As a vital component towards this vision, magnetic functionality in flexible fluidics is still missing although demanded by the broad utility of magnetic nanoparticles in medicine and biology. Here, we demonstrate the first flexible microfluidic analytic device with integrated high-performance giant magnetoresistive (GMR) sensors. This device can be bent to a radius of 2 mm while still retaining its full performance. Various dimensions of magnetic emulsion droplets can be probed with high precision using a limit of detection of 0.5 pl, providing broad applicability in high-throughput droplet screening, flow cytometry and drug development. The flexible feature of this analytic device holds great promise in the realization of wearable, implantable multifunctional platforms for biomedical, pharmaceutical and chemical applications.

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Graphene oxide functional nanohybrids with magnetic nanoparticles for improved vectorization of doxorubicin to neuroblastoma cells

2019, Lerra, L., Farfalla, A., Sanz, B., Cirillo, G., Vittorio, O., Voli, F., Grand, M.L., Curcio, M., Nicoletta, F.P., Dubrovska, A., Hampel, S., Iemma, F., Goya, G.F.

With the aim to obtain a site-specific doxorubicin (DOX) delivery in neuroblastoma SH-SY5Y cells, we designed an hybrid nanocarrier combining graphene oxide (GO) and magnetic iron oxide nanoparticles (MNPs), acting as core elements, and a curcumin–human serum albumin conjugate as functional coating. The nanohybrid, synthesized by redox reaction between the MNPs@GO system and albumin bioconjugate, consisted of MNPs@GO nanosheets homogeneously coated by the bioconjugate as verified by SEM investigations. Drug release experiments showed a pH-responsive behavior with higher release amounts in acidic (45% at pH 5.0) vs. neutral (28% at pH 7.4) environments. Cell internalization studies proved the presence of nanohybrid inside SH-SY5Y cytoplasm. The improved efficacy obtained in viability assays is given by the synergy of functional coating and MNPs constituting the nanohybrids: while curcumin moieties were able to keep low DOX cytotoxicity levels (at concentrations of 0.44–0.88 µM), the presence of MNPs allowed remote actuation on the nanohybrid by a magnetic field, increasing the dose delivered at the target site.