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Synthesis and Characterization of Oxide Chloride Sr2VO3Cl, a Layered S = 1 Compound
The mixed-anion compound with composition Sr2VO3Cl has been synthesized for the first time, using the conventional high-temperature solid-state synthesis technique in a closed silica ampule under inert conditions. This compound belongs to the known Sr2TmO3Cl (Tm = Sc, Mn, Fe, Co, Ni) family, but with Tm = V. All homologues within this family can be described with the tetragonal space group P4/nmm (No. 129); from a Rietveld refinement of powder X-ray diffraction data on the Tm = V homologue, the unit cell parameters were determined to a = 3.95974(8) and c = 14.0660(4) Å, and the atomic parameters in the crystal structure could be estimated. The synthesized powder is black, implying that the compound is a semiconductor. The magnetic investigations suggest that Sr2VO3Cl is a paramagnet at high temperatures, exhibiting a μeff = 2.0 μB V-1 and antiferromagnetic (AFM) interactions between the magnetic vanadium spins (θCW = −50 K), in line with the V-O-V advantageous super-exchange paths in the V-O layers. Specific heat capacity studies indicate two small anomalies around 5 and 35 K, which however are not associated with long-range magnetic ordering. 35Cl ss-NMR investigations suggest a slow spin freezing below 4.2 K resulting in a glassy-like spin ground state.
Persistent peri-Heptacene: Synthesis and In Situ Characterization
n-peri-Acenes (n-PAs) have gained interest as model systems of zigzag-edged graphene nanoribbons for potential applications in nanoelectronics and spintronics. However, the synthesis of n-PAs larger than peri-tetracene remains challenging because of their intrinsic open-shell character and high reactivity. Presented here is the synthesis of a hitherto unknown n-PA, that is, peri-heptacene (7-PA), in which the reactive zigzag edges are kinetically protected with eight 4-tBu-C6H4 groups. The formation of 7-PA is validated by high-resolution mass spectrometry and in situ FT-Raman spectroscopy. 7-PA displays a narrow optical energy gap of 1.01 eV and exhibits persistent stability (t1/2≈25 min) under inert conditions. Moreover, electron-spin resonance measurements and theoretical studies reveal that 7-PA exhibits an open-shell feature and a significant tetraradical character. This strategy could be considered a modular approach for the construction of next-generation (3 N+1)-PAs (where N≥3). © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
A Rotating Spiral Micromotor for Noninvasive Zygote Transfer
Embryo transfer (ET) is a decisive step in the in vitro fertilization process. In most cases, the embryo is transferred to the uterus after several days of in vitro culture. Although studies have identified the beneficial effects of ET on proper embryo development in the earlier stages, this strategy is compromised by the necessity to transfer early embryos (zygotes) back to the fallopian tube instead of the uterus, which requires a more invasive, laparoscopic procedure, termed zygote intrafallopian transfer (ZIFT). Magnetic micromotors offer the possibility to mitigate such surgical interventions, as they have the potential to transport and deliver cellular cargo such as zygotes through the uterus and fallopian tube noninvasively, actuated by an externally applied rotating magnetic field. This study presents the capture, transport, and release of bovine and murine zygotes using two types of magnetic micropropellers, helix and spiral. Although helices represent an established micromotor architecture, spirals surpass them in terms of motion performance and with their ability to reliably capture and secure the cargo during both motion and transfer between different environments. Herein, this is demonstrated with murine oocytes/zygotes as the cargo; this is the first step toward the application of noninvasive, magnetic micromotor‐assisted ZIFT.
Symmetry‐Induced Selective Excitation of Topological States in Su–Schrieffer–Heeger Waveguide Arrays
The investigation of topological state transition in carefully designed photonic lattices is of high interest for fundamental research, as well as for applied studies such as manipulating light flow in on-chip photonic systems. Herein, the topological phase transition between symmetric topological zero modes (TZM) and antisymmetric TZMs in Su–Schrieffer–Heeger mirror symmetric waveguides is reported. The transition of TZMs is realized by adjusting the coupling ratio between neighboring waveguide pairs, which is enabled by selective modulation of the refractive index in the waveguide gaps. Bidirectional topological transitions between symmetric and antisymmetric TZMs can be achieved with proposed switching strategy. Selective excitation of topological edge mode is demonstrated owing to the symmetry characteristics of the TZMs. The flexible manipulation of topological states is promising for on-chip light flow control and may spark further investigations on symmetric/antisymmetric TZM transitions in other photonic topological frameworks.
Segregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDFTFE), UHMWPE, and rGO
The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc. © 2020 American Chemical Society.
Thiophene-Based Conjugated Acetylenic Polymers with Dual Active Sites for Efficient Co-Catalyst-Free Photoelectrochemical Water Reduction in Alkaline Medium
Although being attractive materials for photoelectrochemical hydrogen evolution reaction (PEC HER) under neutral or acidic conditions, conjugated polymers still show poor PEC HER performance in alkaline medium due to the lack of water dissociation sites. Herein, we demonstrate that tailoring the polymer skeleton from poly(diethynylthieno[3,2-b]thiophene) (pDET) to poly(2,6-diethynylbenzo[1,2-b:4,5-b′]dithiophene (pBDT) and poly(diethynyldithieno[3,2-b:2′,3′-d]thiophene) (pDTT) in conjugated acetylenic polymers (CAPs) introduces highly efficient active sites for water dissociation. As a result, pDTT and pBDT, grown on Cu substrate, demonstrate benchmark photocurrent densities of 170 μA cm−2 and 120 μA cm−2 (at 0.3 V vs. RHE; pH 13), which are 4.2 and 3 times higher than that of pDET, respectively. Moreover, by combining DFT calculations and electrochemical operando resonance Raman spectroscopy, we propose that the electron-enriched Cβ of the outer thiophene rings of pDTT are the water dissociation active sites, while the −C≡C− bonds function as the active sites for hydrogen evolution. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
Quinoidal Azaacenes: 99 % Diradical Character
Quinoidal azaacenes with almost pure diradical character (y=0.95 to y=0.99) were synthesized. All compounds exhibit paramagnetic behavior investigated by EPR and NMR spectroscopy, and SQUID measurements, revealing thermally populated triplet states with an extremely low-energy gap ΔEST′ of 0.58 to 1.0 kcal mol−1. The species are persistent in solution (half-life≈14–21 h) and in the solid state they are stable for weeks.
Origami-Inspired Shape Memory Folding Microactuator
This paper presents the design, fabrication and performance of origami-based folding microactuators based on a cold-rolled NiTi foil of 20 µm thickness showing the one-way shape memory effect. Origami refers to a variety of techniques of transforming planar sheets into three-dimensional (3D) structures by folding, which has been introduced in science and engineering for, e.g., assembly and robotics. Here, NiTi microactuators are interconnected to rigid sections (tiles) forming an initial planar system that self-folds into a set of predetermined 3D shapes upon heating. While this concept has been demonstrated at the macro scale, we intend to transfer this concept into microtechnology by combining state-of-the art methods of micromachining. NiTi foils are micromachined by laser cutting or photolithography to achieve double-beam structures allowing for direct Joule heating with an electrical current. A thermo-mechanical treatment is used for shape setting of as-received specimens to reach a maximum folding angle of 180°. The bending moments, bending radii and load-dependent folding angles upon Joule heating are evaluated. The shape setting process is particularly effective for small bending radii, which, however generates residual plastic strain. After shape setting, unloaded beam structures show recoverable bending deflection between 0° and 140° for a maximum heating power of 900 mW. By introducing additional loads to account for the effect of the tiles, the smooth folding characteristic evolves into a sharp transition, whereby full deflection up to 180° is reached. The achieved results are an important step towards the development of cooperative multistable microactuator systems for 3D self-assembly.
Saturation of the anomalous Hall effect at high magnetic fields in altermagnetic RuO2
Observations of the anomalous Hall effect in RuO2 and MnTe have demonstrated unconventional time-reversal symmetry breaking in the electronic structure of a recently identified new class of compensated collinear magnets, dubbed altermagnets. While in MnTe, the unconventional anomalous Hall signal accompanied by a vanishing magnetization is observable at remanence, the anomalous Hall effect in RuO2 is excluded by symmetry for the Néel vector pointing along the zero-field [001] easy-axis. Guided by a symmetry analysis and ab initio calculations, a field-induced reorientation of the Néel vector from the easy-axis toward the [110] hard-axis was used to demonstrate the anomalous Hall signal in this altermagnet. We confirm the existence of an anomalous Hall effect in our RuO2 thin-film samples, whose set of magnetic and magneto-transport characteristics is consistent with the earlier report. By performing our measurements at extreme magnetic fields up to 68 T, we reach saturation of the anomalous Hall signal at a field Hc ≃ 55 T that was inaccessible in earlier studies but is consistent with the expected Néel-vector reorientation field.
Magnetic Micromotors for Multiple Motile Sperm Cells Capture, Transport, and Enzymatic Release
An integrated system combining a magnetically-driven micromotor and a synthetized protein-based hyaluronic acid (HA) microflake is presented for the in situ selection and transport of multiple motile sperm cells (ca. 50). The system appeals for targeted sperm delivery in the reproductive system to assist fertilization or to deliver drugs. The binding mechanism between the HA microflake and sperm relies on the interactions between HA and the corresponding sperm HA receptors. Once sperm are captured within the HA microflake, the assembly is trapped and transported by a magnetically-driven helical microcarrier. The trapping of the sperm-microflake occurs by a local vortex induced by the microcarrier during rotation-translation under a rotating magnetic field. After transport, the microflake is enzymatically hydrolyzed by local proteases, allowing sperm to escape and finally reach the target location. This cargo-delivery system represents a new concept to transport not only multiple motile sperm but also other actively moving biological cargoes.