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.

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.

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.

2019, Liu, F., Velkos, G., Krylov, D.S., Spree, L., Zalibera, M., Ray, R., Samoylova, N.A., Chen, C.-H., Rosenkranz, M., Schiemenz, S., Ziegs, F., Nenkov, K., Kostanyan, A., Greber, T., Wolter, A.U.B., Richter, M., Büchner, B., Avdoshenko, S.M., Popov, A.A.

Engineering intramolecular exchange interactions between magnetic metal atoms is a ubiquitous strategy for designing molecular magnets. For lanthanides, the localized nature of 4f electrons usually results in weak exchange coupling. Mediating magnetic interactions between lanthanide ions via radical bridges is a fruitful strategy towards stronger coupling. In this work we explore the limiting case when the role of a radical bridge is played by a single unpaired electron. We synthesize an array of air-stable Ln 2 @C 80 (CH 2 Ph) dimetallofullerenes (Ln 2 = Y 2 , Gd 2 , Tb 2 , Dy 2 , Ho 2 , Er 2 , TbY, TbGd) featuring a covalent lanthanide-lanthanide bond. The lanthanide spins are glued together by very strong exchange interactions between 4f moments and a single electron residing on the metal–metal bonding orbital. Tb 2 @C 80 (CH 2 Ph) shows a gigantic coercivity of 8.2 Tesla at 5 K and a high 100-s blocking temperature of magnetization of 25.2 K. The Ln-Ln bonding orbital in Ln 2 @C 80 (CH 2 Ph) is redox active, enabling electrochemical tuning of the magnetism.

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.

2014, Lin, Gungun, Makarov, Denys, Medina-Sánchez, Mariana, Guix, Maria, Baraban, Larysa, Cuniberti, Gianaurelio, Schmidt, Oliver G.

We present a concept of multidimensional magnetic and optical barcoding of droplets based on a magnetofluidic platform. The platform comprises multiple functional areas, such as an encoding area, an encoded droplet pool and a magnetic decoding area with integrated giant magnetoresistive (GMR) sensors. To prove this concept, penicillin functionalized with fluorescent dyes is coencapsulated with magnetic nanoparticles into droplets. While fluorescent dyes are used as conventional optical barcodes which are decoded with an optical decoding setup, an additional dimensionality of barcodes is created by using magnetic nanoparticles as magnetic barcodes for individual droplets and integrated micro-patterned GMR sensors as the corresponding magnetic decoding devices. The strategy of incorporating a magnetic encoding scheme provides a dynamic range of ~40 dB in addition to that of the optical method. When combined with magnetic barcodes, the encoding capacity can be increased by more than 1 order of magnitude compared with using only optical barcodes, that is, the magnetic platform provides more than 10 unique magnetic codes in addition to each optical barcode. Besides being a unique magnetic functional element for droplet microfluidics, the platform is capable of on-demand facile magnetic encoding and real-time decoding of droplets which paves the way for the development of novel non-optical encoding schemes for highly multiplexed droplet-based biological assays.

2019, Li, Y., Kovačič, M., Westphalen, J., Oswald, S., Ma, Z., Hänisch, C., Will, P.-A., Jiang, L., Junghaehnel, M., Scholz, R., Lenk, S., Reineke, S.

Organic light-emitting diodes (OLEDs) suffer from notorious light trapping, resulting in only moderate external quantum efficiencies. Here, we report a facile, scalable, lithography-free method to generate controllable nanostructures with directional randomness and dimensional order, significantly boosting the efficiency of white OLEDs. Mechanical deformations form on the surface of poly(dimethylsiloxane) in response to compressive stress release, initialized by reactive ions etching with periodicity and depth distribution ranging from dozens of nanometers to micrometers. We demonstrate the possibility of independently tuning the average depth and the dominant periodicity. Integrating these nanostructures into a two-unit tandem white organic light-emitting diode, a maximum external quantum efficiency of 76.3% and a luminous efficacy of 95.7 lm W−1 are achieved with extracted substrate modes. The enhancement factor of 1.53 ± 0.12 at 10,000 cd m−2 is obtained. An optical model is built by considering the dipole orientation, emitting wavelength, and the dipole position on the sinusoidal nanotexture.

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.

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.

2019, Zhang, Y., Holder, T., Ishizuka, H., de Juan, F., Nagaosa, N., Felser, C., Yan, B.

The bulk photovoltaic effect (BPVE) rectifies light into the dc current in a single-phase material and attracts the interest to design high-efficiency solar cells beyond the pn junction paradigm. Because it is a hot electron effect, the BPVE surpasses the thermodynamic Shockley–Queisser limit to generate above-band-gap photovoltage. While the guiding principle for BPVE materials is to break the crystal centrosymmetry, here we propose a magnetic photogalvanic effect (MPGE) that introduces the magnetism as a key ingredient and induces a giant BPVE. The MPGE emerges from the magnetism-induced asymmetry of the carrier velocity in the band structure. We demonstrate the MPGE in a layered magnetic insulator CrI3, with much larger photoconductivity than any previously reported results. The photocurrent can be reversed and switched by controllable magnetic transitions. Our work paves a pathway to search for magnetic photovoltaic materials and to design switchable devices combining magnetic, electronic, and optical functionalities.