Pyridinic-N Coordination Effect on the Adsorption and Activation of CO2 by Single Vacancy Iron-Doped Graphene.

Graphene doped with different transition metals has been recently proposed to adsorb CO2 and help reduce the greenhouse effect. Iron-doped graphene is one of the most promising candidates for this task, but there is still a lack of full understanding of the adsorption mechanism. In this work, we analyze the electronic structure, geometry, and charge redistribution during adsorption of CO2 molecules by single vacancy iron-doped graphene by DFT calculations using the general gradient approximation of Perdew, Burke, and Ernzernhof functional (PBE) and the van der Waals density functional (vdW). To understand the impact of the pyridinic-N coordination of the iron atom, we gradually replaced the neighboring carbon atoms by nitrogen atoms. The analysis indicates that chemisorption and physisorption occur when the molecule is adsorbed in the side-on and end-on orientation, respectively. Adsorption is stronger when pyridinic-N coordination increases, and the vdW functional describes the chemical interactions and adsorption energy differently in relation to PBE without significant structural changes. The development of the chemical interactions with the change of coordination in the system is further investigated in this work with crystal overlap Hamilton population (COHP) analysis.

Charge Transport in Conjugated and Saturated Hydrocarbons: Comparing Ballistic and Cotunneling Contributions.

The comparison between electrical transport in CnH2n+2S2 alkane and CnHn+2S2 alkene (n = 4, 6, 8, 10) is studied by using a generalized Breit-Wigner approach and considering coherent transport mechanisms and eventual changes in the state of charge (i.e., cotunneling processes) for both molecules. In general, the conductance of alkanes tends to be smaller than that of similar-sized alkenes. However, cotunneling processes have an important participation in the overall transport in the case of alkanes but not for the alkene family. The progressive changes in both the eigenenergies of the relevant frontier molecular orbitals of the charged species and their spatial localization play decisive roles in the observed differences. While the molecular orbitals of the charged species of the conjugated molecules are hardly affected by the applied voltage, their saturated counterparts are quite sensitive to the external field. With this, successive avoided-crossing events between the molecular orbitals of the single-charged alkane molecules can lead to the appearance of nonballistic conduction channels that make no negligible contributions to the molecular transport.

Exchange Bias in Magnetic Topological Insulator Superlattices.

Magnetic doping and proximity coupling can open a band gap in a topological insulator (TI) and give rise to dissipationless quantum conduction phenomena. Here, by combining these two approaches, we demonstrate a novel TI superlattice structure that is alternately doped with transition and rare earth elements. An unexpected exchange bias effect is unambiguously confirmed in the superlattice with a large exchange bias field using magneto-transport and magneto-optical techniques. Further, the Curie temperature of the Cr-doped layers in the superlattice is found to increase by 60 K compared to a Cr-doped single-layer film. This result is supported by density-functional-theory calculations, which indicate the presence of antiferromagnetic ordering in Dy:Bi2Te3 induced by proximity coupling to Cr:Sb2Te3 at the interface. This work provides a new pathway to realizing the quantum anomalous Hall effect at elevated temperatures and axion insulator state at zero magnetic field by interface engineering in TI heterostructures.

Visualizing Magnetic Structure in 3D Nanoscale Ni-Fe Gyroid Networks.

Arrays of interacting 2D nanomagnets display unprecedented electromagnetic properties via collective effects, demonstrated in artificial spin ices and magnonic crystals. Progress toward 3D magnetic metamaterials is hampered by two challenges: fabricating 3D structures near intrinsic magnetic length scales (sub-100 nm) and visualizing their magnetic configurations. Here, we fabricate and measure nanoscale magnetic gyroids, periodic chiral networks comprising nanowire-like struts forming three-connected vertices. Via block copolymer templating, we produce Ni75Fe25 single-gyroid and double-gyroid (an inversion pair of single-gyroids) nanostructures with a 42 nm unit cell and 11 nm diameter struts, comparable to the exchange length in Ni-Fe. We visualize their magnetization distributions via off-axis electron holography with nanometer spatial resolution and interpret the patterns using finite-element micromagnetic simulations. Our results suggest an intricate, frustrated remanent state which is ferromagnetic but without a unique equilibrium configuration, opening new possibilities for collective phenomena in magnetism, including 3D magnonic crystals and unconventional computing.

Kerr effect anomaly in magnetic topological insulator superlattices.

We report the magneto-optical Kerr effect (MOKE) study of magnetic topological insulator superlattice films with alternating transition-metal and rare-earth doping. We observe an unexpected hump in the MOKE hysteresis loops upon magnetization reversal at low temperatures, reminiscent of the topological Hall effect (THE) reported in transport measurements. The THE is commonly associated with the existence of magnetic skyrmions, i.e. chiral spin textures originating from topological defects in real space. Here, the observation of the effect is tied to ferromagnetic ordering in the rare-earth-doped layers of the superlattice. Our study may provide a new approach for the non-invasive optical investigation of skyrmions in magnetic films, complementary to electrical transport measurements, where the topological Hall signal is often the only hint of non-trivial magnetization patterns.

The comparison between superparamagnetic and ferromagnetic iron oxide nanoparticles for cancer nanotherapy in the magnetic resonance system.

The paper aims to compare zeta potentials, magnetic properties, electron spin resonance, photoluminescence (PL) spectra and antitumor effect of magneto-mechano-chemically synthesized magneto-sensitive nanocomplexes loaded with the anticancer drug doxorubicin (DOXO) during nanotherapy of Walker-256 carcinosarcoma carried out by a magnetic resonance system. Diamagnetic DOXO acquired the properties of a paramagnetic substance after synthesis. MNC comprising superparamagnetic nanoparticles (NP) and DOXO had different g-factors, zeta potentials, a lower saturation magnetic moment, area of the hysteresis loop, and a higher coercivity compared to similar MNC with ferromagnetic NP. The main PL peak of MNC spectrum was defined by DOXO at 598 nm. MNC composed of superparamagnetic NP and DOXO showed a lower standard deviation of the normal PL spectral distribution than MNC based on ferromagnetic NP in relation to conventional DOXO. MNC containing superparamagnetic NP responded to resonance conditions leading to a more pronounced antitumor effect compared to MNC with ferromagnetic NP in the course of magnetic nanotherapy for Walker-256 carcinosarcoma bearing animals (temperature inside the tumor did not exceed 40 °C). Therefore, these findings are associated with differences in chemotherapeutic effect between MNC due to a different surface charge and conformational changes in DOXO molecules during its magnetoelectric interaction with single- and multidomain NP.

Paramagnetism in Bacillus spores: Opportunities for novel biotechnological applications.

Spores of Bacillus megaterium, Bacillus cereus, and Bacillus subtilis were found to exhibit intrinsic paramagnetic properties as a result of the accumulation of manganese ions. All three Bacillus species displayed strong yet distinctive magnetic properties arising from differences in manganese quantity and valency. Manganese ions were found to accumulate both within the spore core as well as being associated with the surface of the spore. Bacillus megaterium spores accumulated up to 1 wt.% manganese (II) within, with a further 0.6 wt.% adsorbed onto the surface. At room temperature, Bacillus spores possess average magnetic susceptibilities in the range of 10-6 to 10-5 . Three spore-related biotechnological applications-magnetic sensing, magnetic separation and metal ion adsorption-were assessed subsequently, with the latter two considered as having the most potential for development.

Nanomagnetic Modulation of Tumor Redox State.

Modulation of reactive oxygen and nitrogen species in a tumor could be exploited for nanotherapeutic benefits. We investigate the antitumor effect in Walker-256 carcinosarcoma of magnetic nanodots composed of doxorubicin-loaded Fe3O4 nanoparticles combined with electromagnetic fields. Treatment using the magnetic nanodot with the largest hysteresis loop area (3402 erg/g) had the greatest antitumor effect with the minimum growth factor 0.49 ± 0.02 day-1 (compared to 0.58 ± 0.02 day-1 for conventional doxorubicin). Electron spin resonance spectra of Walker-256 carcinosarcoma treated with the nanodots, indicate an increase of 2.7 times of free iron (that promotes the formation of highly reactive oxygen species), using the nanodot with the largest hysteresis loop area, compared to conventional doxorubicin treatment as well as increases in ubisemiquinone, lactoferrin, NO-FeS-proteins. Hence, we provide evidence that the designed magnetic nanodots can modulate the tumor redox state. We discuss the implications of these results for cancer nanotherapy.

Magnetic properties and antitumor effect of nanocomplexes of iron oxide and doxorubicin.

We present a technology and magneto-mechanical milling chamber for the magneto-mechano-chemical synthesis (MMCS) of magneto-sensitive complex nanoparticles (MNC) comprising nanoparticles Fe3O4 and anticancer drug doxorubicin (DOXO). Magnetic properties of MNC were studied with vibrating magnetometer and electron paramagnetic resonance. Under the influence of mechano-chemical and MMCS, the complex show a hysteresis curve, which is typical for soft ferromagnetic materials. We also demonstrate that Lewis lung carcinoma had a hysteresis loop typical for a weak soft ferromagnet in contrast to surrounding tissues, which were diamagnetic. Combined action of constant magnetic field and radio frequency moderate inductive hyperthermia (RFH) below 40°C and MNC was found to induce greater antitumor and antimetastatic effects as compared to conventional DOXO. Radiospectroscopy shows minimal activity of FeS-protein electron transport chain of mitochondria, and an increase in the content of non-heme iron complexes with nitric oxide in the tumor tissues under the influence of RFH and MNC.

Spatially homogeneous ferromagnetism below the enhanced Curie temperature in EuO(1-x) thin films.

We have used low-energy implanted muons as a volume sensitive probe of the magnetic properties of EuO(1-x) thin films. We find that static and homogeneous magnetic order persists up to the elevated T(C) in the doped samples, and the muon signal displays the double dome feature also observed in the sample magnetization. Our results appear incompatible with either the magnetic phase separation or bound magnetic polaron descriptions previously suggested to explain the elevated T(C), but are compatible with an RKKY-like interaction mediating magnetic interactions above 69 K.

Pulse-controlled qubit in semiconductor double quantum dots.

We present a numerically-optimized multipulse framework for the quantum control of a single-electron double quantum dot qubit. Our framework defines a set of pulse sequences, necessary for the manipulation of the ideal qubit basis, that avoids errors associated with excitations outside the computational subspace. A novel control scheme manipulates the qubit adiabatically, while also retaining high speed and ability to perform a general single-qubit rotation. This basis generates spatially localized logical qubit states, making readout straightforward. We consider experimentally realistic semiconductor qubits with finite pulse rise and fall times and determine the fastest pulse sequence yielding the highest fidelity. We show that our protocol leads to improved control of a qubit. We present simulations of a double quantum dot in a semiconductor device to visualize and verify our protocol. These results can be generalized to other physical systems since they depend only on pulse rise and fall times and the energy gap between the two lowest eigenstates.

Efficient One-Pot Solvothermal Synthesis and Characterization of Zirconia Nanoparticle-Decorated Reduced Graphene Oxide Nanocomposites: Evaluation of Their Enhanced Anticancer Activity toward Human Cancer Cell Lines.

This study mainly deals with an effective one-pot solvothermal synthetic pathway for the preparation of uniformly dispersed zirconium oxide nanoparticles on the flattened rough surface of reduced graphene oxide (ZrO2/rGO NCs) using the aqueous leaf extract of Andrographis paniculata. After obtaining detailed information on the preparation and characterization, the anticancer activity of the synthesized ZrO2/rGO nanocrystals (NCs) was evaluated on two human cancer cell lines (A549 and HCT116) along with one normal human cell line (hMSC). The 3-[4,5-dimethylthiazole-2-yl]-2,5-diphenyltetrazolium bromide assays revealed that ZrO2/rGO NCs exhibited a dose-dependent cytotoxicity pattern. The cell viability (%) drastically decreases up to 96-98% after exposure to an optimal concentration of 10 ppm nanocomposites. Analysis of both the reactive oxygen species generation and the Annexin V-FTIC staining assays reveal that ZrO2/rGO NCs have the ability to induce apoptosis in A549 and HCT116 cell lines. Thus, the green synthesis of ZrO2/rGO NCs shows potential in developing efficient therapeutic agents for cancer therapy.

Biofabricated Palladium Nanoparticle-Decorated Reduced Graphene Oxide Nanocomposite Using the Punica granatum (Pomegranate) Peel Extract: Investigation of Potent In Vivo Hepatoprotective Activity against Acetaminophen-Induced Liver Injury in Wistar Albino Rats.

Acute acetaminophen (APAP) toxicity is a predominant clinical problem, which causes serious liver injury in both humans and experimental animals. This study presents the histological and biochemical factor and antioxidant enzyme level changes induced by an acute acetaminophen overdose in Wistar albino rat livers to elucidate the effective hepatoprotective potential of biofabricated palladium nanoparticle-decorated reduced graphene oxide nanocomposites (rGO/PdNPs-NC) compared to silymarin. After detailed characterization of the hepatoprotective potential of the synthesized rGO/PdNPs-NC, the rats were divided into eight groups (n = 6): control group (normal saline, 1 mL/kg b.w.), silymarin, Punica granatum (pomegranate) peel extract, PdNPs, reduced graphene oxide (rGO-PG), and reduced graphene oxide palladium nanocomposites (rGO/PdNPs-NC, low and high doses) for 7 successive days. The acetaminophen (APAP)-treated group was administered a single dose of acetaminophen (2 g/kg b.w.) on the 8th day. The histopathological results showed that the acetaminophen overdose group exhibited massive intrahepatic hemorrhagic necrosis around the centrilobular region with hepatocytes with vacuolization and swollen cytoplasm found in the liver architecture. This hepatopotential was further assessed by various biochemical parameters such as SGOT, SGPT, ALB, ALP, LDH, direct bilirubin, total bilirubin, and total protein. Also, the antioxidant parameters such as SOD, CAT, MDA, GSH, GRD, and GST were assayed. Rats of groups 7 and 8 showed a significant decrease in SGOT, SGPT, ALP, LDH, direct bilirubin, and total bilirubin (p < 0.001), while a significant increase in the final total protein and ALB as compared to group 2 rats (p < 0.001) was observed. The antioxidant parameters exhibited that rats of groups 7 and 8 showed a significant (p < 0.001) increase in the level of SOD, CAT, GSH, GRD, and GST without affecting the MDA as compared to group 2 rats. Also, the hepatoprotective potential of rGO/PdNPs-NC (low and high doses) was comparable to that of the standard reference drug silymarin. The present study reveals that the rGO/PdNPs-NC possesses significant hepatoprotective activity and acts as an effective and promising curative agent against acetaminophen-induced hepatotoxicity.

One-Pot Solvothermal Synthetic Route of a Zinc Oxide Nanoparticle-Decorated Reduced Graphene Oxide Nanocomposite: An Advanced Material with a Novel Anticancer Theranostic Approach.

This study focuses on a one-pot solvothermal synthetic route for the preparation of uniformly decorated zinc oxide nanoparticles on the surface of reduced graphene oxide (rGO/ZnO-NC) by using Andrographis paniculata leaf aqueous extract as an eco-friendly reducing agent. After characterizing the samples by different physical and chemical techniques, the anticancer activity of the synthesized rGO/ZnO-NC was examined on two human cancerous cell lines (HCT116 and A549) and one normal cell line (hMSCs). The MTT assays revealed that rGO/ZnO-NC exhibited dose-dependent cytotoxicity at a maximum concentration range of 10 ppm and the viability of the cells was drastically decreased to 95-96%. Measurement of reactive oxygen species (ROS) generation and Annexin V-FTIC staining assay revealed that rGO/ZnO-NC induced apoptosis in HCT116 and A549 cell lines. Thus, this study shows that the green-synthesized rGO/ZnO-NC has great potential in developing an efficacious novel therapeutic agent for cancers.

Determining the Proximity Effect-Induced Magnetic Moment in Graphene by Polarized Neutron Reflectivity and X-ray Magnetic Circular Dichroism.

We report the magnitude of the induced magnetic moment in CVD-grown epitaxial and rotated-domain graphene in proximity with a ferromagnetic Ni film, using polarized neutron reflectivity (PNR) and X-ray magnetic circular dichroism (XMCD). The XMCD spectra at the C K-edge confirm the presence of a magnetic signal in the graphene layer, and the sum rules give a magnetic moment of up to ∼0.47 µB/C atom induced in the graphene layer. For a more precise estimation, we conducted PNR measurements. The PNR results indicate an induced magnetic moment of ∼0.41 µB/C atom at 10 K for epitaxial and rotated-domain graphene. Additional PNR measurements on graphene grown on a nonmagnetic Ni9Mo1 substrate, where no magnetic moment in graphene is measured, suggest that the origin of the induced magnetic moment is due to the opening of the graphene's Dirac cone as a result of the strong C pz-Ni 3d hybridization.

Biogenic Photo-Catalyst TiO2 Nanoparticles for Remediation of Environment Pollutants.

This article reports a benign environmentally friendly fabrication method of titanium dioxide (TDO) nanoparticles (named TDO NPs3, TDO NPs5, and TDO NPs8) using aqueous extract of durva herb waste. This synthesis process avoids use of harmful substances and persistent chemicals throughout the order and enables us to control the size of the nanomaterials. Characterization of TDO nanoparticles was analyzed by ultraviolet-visible spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The morphological nature of the TDO samples was inspected by transmission electron microscopy, which indicated that the TDO NPs3, TDO NPs5, and TDO NPs8 were spherical in shape, with average sizes of 5.14, 12.54, and 29.61 nm, respectively. The stability of TDO nanoparticles was assessed using thermogravimetric analysis and dynamic light scattering analysis. These samples could be used for degradation of polluting industrial textile dyes, such as methylene blue (MB) and rhodamine B (Rh-B). Remarkably, the TDO NPs3 sample (5.14 nm size) exhibits a noticeable degradation of the MB dye in a shorter time period (50 min) than the TDO NPs8 sample with a size of 29.61 nm (120 min). The TDO NPs3 sample was also tested for degradation of Rh-B dye, showing high degradation efficiency over a short period of time (60 min). In contrast, the TDO NPs8 sample showed degradation of the Rh-B dye in 120 min. The effect of the dye concentration and the catalyst dose to remove dye pollutants has also been investigated. The synthesized TDO NPs act as exceptional catalysts for the degradation of dyes, and they are promising materials for the degradation of industrial polluting dyes.

Localized magnetic fields in arbitrary directions using patterned nanomagnets.

Control of the local magnetic fields desirable for spintronics and quantum information technology is not well developed. Existing methods produce either moderately small local fields or one field orientation. We present designs of patterned magnetic elements that produce remanent fields of 50 mT (potentially 200 mT) confined to chosen, submicrometer regions in directions perpendicular to an external initializing field. A wide variety of magnetic-field profiles on nanometer scales can be produced with the option of applying electric fields, for example, to move a quantum dot between regions where the magnetic-field direction or strength is different. We have confirmed our modeling by measuring the fields in one design using electron holography.

Growth and Characterisation Studies of Eu3O4 Thin Films Grown on Si/SiO2 and Graphene.

We report the growth, structural and magnetic properties of the less studied Eu-oxide phase, Eu3O4, thin films grown on a Si/SiO2 substrate and Si/SiO2/graphene using molecular beam epitaxy. The X-ray diffraction scans show that highly textured crystalline Eu3O4(001) films are grown on both substrates, whereas the film deposited on graphene has a better crystallinity than that grown on the Si/SiO2 substrate. The SQUID measurements show that both films have a Curie temperature of ∼5.5±0.1 K, with a magnetic moment of ∼320 emu/cm3 at 2 K. The mixed valence of the Eu cations has been confirmed by the qualitative analysis of the depth-profile X-ray photoelectron spectroscopy measurements with the Eu2+:Eu3+ ratio of 28:72. However, surprisingly, our films show no metamagnetic behaviour as reported for the bulk and powder form. Furthermore, the microscopic optical images and Raman measurements show that the graphene underlayer remains largely intact after the growth of the Eu3O4 thin films.

Non-Planar Geometrical Effects on the Magnetoelectrical Signal in a Three-Dimensional Nanomagnetic Circuit.

Expanding nanomagnetism and spintronics into three dimensions (3D) offers great opportunities for both fundamental and technological studies. However, probing the influence of complex 3D geometries on magnetoelectrical phenomena poses important experimental and theoretical challenges. In this work, we investigate the magnetoelectrical signals of a ferromagnetic 3D nanodevice integrated into a microelectronic circuit using direct-write nanofabrication. Due to the 3D vectorial nature of both electrical current and magnetization, a complex superposition of several magnetoelectrical effects takes place. By performing electrical measurements under the application of 3D magnetic fields, in combination with macrospin simulations and finite element modeling, we disentangle the superimposed effects, finding how a 3D geometry leads to unusual angular dependences of well-known magnetotransport effects such as the anomalous Hall effect. Crucially, our analysis also reveals a strong role of the noncollinear demagnetizing fields intrinsic to 3D nanostructures, which results in an angular dependent magnon magnetoresistance contributing strongly to the total magnetoelectrical signal. These findings are key to the understanding of 3D spintronic systems and underpin further fundamental and device-based studies.

Magnetically induced pattern formation in phase separating polymer-solvent-nanoparticle mixtures.

Permanent magnetic structures with controlled dimension and architecture (labyrinthine, hexagonal, or dispersed columnar) are formed in a partially miscible ferrofluid-nonferrofluid mixture under the influence of a perpendicular magnetic field. The origin of the permanent structures, which have characteristic lateral dimensions ranging from 1 to 10 µm, is the repartitioning of the ferrofluid carrier solvent into the nonferrofluid polymeric phase. This polymer-solvent phase separation under a magnetic field leads to departures from the expected final dimension of the magnetically stabilized ferrofluid droplet sizes.