Spin-Polarized Photocatalytic CO2 Reduction of Mn-Doped Perovskite Nanoplates.

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance of electrocatalysts and photocatalysts. This work demonstrates the manipulations of spin-polarized electrons in CsPbBr3 halide perovskite nanoplates (NPLs) to boost the photocatalytic CO2 reduction reaction (CO2RR) efficiencies by doping manganese cations (Mn2+) and applying an external magnetic field. Mn-doped CsPbBr3 (Mn-CsPbBr3) NPLs exhibit an outstanding photocatalytic CO2RR compared to pristine CsPbBr3 NPLs due to creating spin-polarized electrons after Mn doping. Notably, the photocatalytic CO2RR of Mn-CsPbBr3 NPLs is significantly enhanced by applying an external magnetic field. Mn-CsPbBr3 NPLs exhibit 5.7 times improved performance of photocatalytic CO2RR under a magnetic field of 300 mT with a permanent magnet compared to pristine CsPbBr3 NPLs. The corresponding mechanism is systematically investigated by magnetic circular dichroism spectroscopy, ultrafast transient absorption spectroscopy, and density functional theory simulation. The origin of enhanced photocatalytic CO2RR efficiencies of Mn-CsPbBr3 NPLs is due to the increased number of spin-polarized photoexcited carriers by synergistic doping of the magnetic elements and applying a magnetic field, resulting in prolonged carrier lifetime and suppressed charge recombination. Our result shows that manipulating spin-polarized electrons in photocatalytic semiconductors provides an effective strategy to boost photocatalytic CO2RR efficiencies.

Field-Free Magnetoplasmon-Induced Ultraviolet Circular Dichroism Switching in Premagnetized Magnetic Nanowires.

Broadband modulation of magnetic circular dichroism (MCD) using a relatively low magnetic field or by producing a field-free magnetoplasmonic effect in the remnant magnetic state was achieved by the integration of the noble metals (NMs) Au and Ag and the perpendicular magnetic anisotropy of Co with ZnO nanowires (NWs) used as the template. The samples containing NMs revealed MCD sign reversals and enhancements when compared with the original Co/ZnO NWs. The magnetoplasmonic effect of Au close to the visible light spectrum could induce the CD change in the visible region. Notably, the ultraviolet (UV) CD in Ag/Co/ZnO NWs is 12.5 times larger under a magnetic field (∼0.2 T) and 10 times greater in the remnant state (field-free) than those of the original Co/ZnO NWs because of the magnetoplasmonic effect of Ag in the UV spectrum. These results are attributable to the coupling of the remnant magnetic state of Co magnetization, the magnetoplasmons of the NMs, and the excitons of the ZnO NWs. The findings are potentially applicable in magneto-optical recording, biosensing, and energy contexts involving magnetoplasmonic functionalization.

Enhanced Photodegradation in Metal Oxide Nanowires with Co-Doped Surfaces under a Low Magnetic Field.

This work demonstrated the enhanced photodegradation (PD) resulting from Co-rich doping of ZnO nanowire (NW) surfaces (Co2+/ZnO NWs) prepared by combining Co sputtering on ZnO NWs and immersion in deionized water to exploit the hydrophilic-hydrophobic transitions on the ZnO surfaces resulting from Co atom diffusion. Because of the controllable spin-dependent density of states (DOS) induced by Co2+, the PD of methylene blue dye can be enhanced by approximately 90% (when compared with bare ZnO NWs) by using a conventional permanent magnet with a relatively low magnetic field strength of approximately 0.15 T. The reliability of spin polarization-modulation attained through surface doping, based on the magnetic response observed from X-ray absorption measurements and magnetic circular dichroism, provides an opportunity to create highly efficient catalysts by engineering surfaces and tailoring their spin-dependent DOS.

Comparison of the chronic toxicities of graphene and graphene oxide toward adult zebrafish by using biochemical and phenomic approaches.

Graphene (GR) and graphene oxide (GO) are widely being used as promising candidates for biomedical applications, as well as for bio-sensing, drug delivery, and anticancer therapy. However, their undesirable side effects make it necessary to assess further the toxicity and safety of using these materials. The main objective of the current study was to investigate the toxicities of GR and GO in predicted environmental relevant concentrations in adult zebrafish (Danio rerio), particularly on their behaviors, and conducted biochemical assays to elucidate the possible mechanism that underlies their toxicities. Zebrafish was chronically (∼14 days) exposed to two different doses of GR (0.1 and 0.5 ppm) or GO (0.1 and 1 ppm). At 14 ± 1 days, a battery of behavioral tests was conducted, followed by enzyme-linked immunosorbent assays (ELISA) test on the following day to inspect the alterations in antioxidant activity, oxidative stress, and neurotransmitters in the treated zebrafish brain. An alteration in predator avoidance behavior was observed in all treated groups, while GR-treated fish exhibited abnormal exploratory behavior. Furthermore, altered locomotor activity was displayed by most of the treated groups, except for the high concentration of the GR group. From the ELISA results, we discovered a high concentration of GR exposure significantly decreased several neurotransmitters and cortisol levels. Meanwhile, elevated reactive oxygen species (ROS) were displayed by the group treated with low and high doses of GR and GO, respectively. These significant changes would possibly affect zebrafish behaviors and might suggest the potential toxicity from GR and GO exposures. To sum up, the present study presented new evidence for the effects of GR and GO in zebrafish behavioral dysregulation. We hope these assessments can contribute to our understanding of graphene and graphene oxide biosafety.

Strong Excitonic Magneto-Optic Effects in Two-Dimensional Organic-Inorganic Hybrid Perovskites.

This work demonstrates the strong excitonic magneto-optic (MO) effects of magnetic circular dichroism (MCD) and Faraday rotation (FR) in nonmagnetic two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (RPPs) at room temperature. Due to their strong and sharp excitonic absorption as a result of unique quantum well structures of 2D RPPs, sizeable linear excitonic MO effects of MCD and FR can be observed at room temperature under a low magnetic field (<1 T) compared with their three-dimensional counterpart. In addition, since the band gaps of 2D organic-inorganic hybrid perovskites can be manipulated either by changing the number n of inorganic octahedral slabs per unit cell or through halide engineering, linear excitonic MO effects of 2D-RPPs can be observed through the broadband spectral ranges of visible light. Our result may pave the way for the promising research field of MO and magneto-optoelectronic applications based on 2D organic-inorganic hybrid perovskites with facile solution processes.

Giant Zeeman Splitting for Monolayer Nanosheets at Room Temperature.

Giant Zeeman splitting and zero-field splitting (ZFS) are observed in 2D nanosheets that have monolayers of atomic thickness. In this study, single-crystalline CdSe(ethylenediamine)0.5 and Mn2+-doped nanosheets are synthesized via a solvothermal process. Tunable amounts of Mn2+(0.5-8.0%) are introduced, resulting in lattice contraction as well as phosphorescence from five unpaired electrons. The exciton dynamics are dominated by spin-related electronic transitions (4T1 → 6A1) with long lifetimes (20.5, 132, and 295 µs). Temperature-varied EPR spectroscopy with spectral simulation reveals large ZFS (D = 3850 MHz) due to axial distortion of substituted Mn2+ (S = 5/2). In the magnetic circular dichroism (MCD) measurements, we observed giant Zeeman splitting with large effective g values (up to 231 ± 21), which implies huge sp-d exchange interactions in 2D monolayer regimes, leading to diluted magnetic semiconductor (DMS) materials.

Manipulated Optical Absorption and Accompanied Photocurrent Using Magnetic Field in Charger Transfer Engineered C/ZnO Nanowires.

The rarely explored, spin-polarized band engineering, enables direct dynamic control of the magneto-optical absorption (MOA) and associated magneto-photocurrent (MPC) by a magnetic field, greatly enhancing the range of applicability of photosensitive semiconductor materials. It is demonstrated that large negative and positive MOA and MPC effects can be tuned alternately in amorphous carbon ( a-C )/ZnO nanowires by controlling the sp2/sp3 ratio of a-C . A sizeable enhancement of the MPC ratio (≈15%) appears at a relatively low magnetic field (≈0.2 T). Simulated two peaks spin-polarized density of states is applied to explain that the alternate sign switching of the MOA is mainly related to the charge transfer between ZnO and C. The results indicate that the enhanced magnetic field performance of ( a-C )/ZnO nanowires may have applications in renewable energy-related fields and tunable magneto-photonics.

An Updated Review of Toxicity Effect of the Rare Earth Elements (REEs) on Aquatic Organisms.

Rare earth elements (REEs) or "technology metals" were coined by the U.S. Department of Energy, a group of seventeen elements found in the Earth's crust. These chemical elements are vital and irreplaceable to the world of technology owing to their unique physical, chemical, and light-emitting properties, all of which are beneficial in modern healthcare, telecommunication, and defense. Rare earth elements are relatively abundant in Earth's crust, with critical qualities to the device performance. The reuse and recycling of rare earth elements through different technologies can minimize impacts on the environment; however, there is insufficient data about their biological, bioaccumulation, and health effects. The increasing usage of rare earth elements has raised concern about environmental toxicity, which may further cause harmful effects on human health. The study aims to review the toxicity analysis of these rare earth elements concerning aquatic biota, considering it to be the sensitive indicator of the environment. Based on the limited reports of REE effects, the review highlights the need for more detailed studies on the hormetic effects of REEs. Aquatic biota is a cheap, robust, and efficient platform to study REEs' toxicity, mobility of REEs, and biomagnification in water bodies. REEs' diverse effects on aquatic life forms have been observed due to the lack of safety limits and extensive use in the various sectors. In accordance with the available data, we have put in efforts to compile all the relevant research results in this paper related to the topic "toxicity effect of REEs on aquatic life".

Surface Modification of Magnetic Nanoparticles by Carbon-Coating Can Increase Its Biosafety: Evidences from Biochemical and Neurobehavioral Tests in Zebrafish.

Recently, magnetic nanoparticles (MNPs) have gained much attention in the field of biomedical engineering for therapeutic as well as diagnostic purposes. Carbon magnetic nanoparticles (C-MNPs) are a class of MNPs categorized as organic nanoparticles. C-MNPs have been under considerable interest in studying in various applications such as magnetic resonance imaging, photothermal therapy, and intracellular transportof drugs. Research work is still largely in progress for testing the efficacy of C-MNPs on the theranostics platform in cellular studies and animal models. In this study, we evaluated the neurobehavioral toxicity parameters on the adult zebrafish (Danio rerio) at either low (1 ppm) or high (10 ppm) concentration level of C-MNPs over a period of two weeks by waterborne exposure. The physical properties of the synthesized C-MNPs were characterized by transmission electron microscopy, Raman, and XRD spectrum characterization. Multiple behavior tests for the novel tank, mirror biting, predator avoidance, conspecific social interaction, shoaling, and analysis of biochemical markers were also conducted to elucidate the corresponding mechanism. Our data demonstrate the waterborne exposure of C-MNPs is less toxic than the uncoated MNPs since neither low nor high concentration C-MNPs elicit toxicity response in behavioral and biochemical tests in adult zebrafish. The approach combining biochemical and neurobehavioral approaches would be helpful for understanding C-MNPs association affecting the bioavailability, biosafety, interaction, and uptake of these C-MNPs in the living organism.

Theoretical model investigating the magnetic properties of cobalt-doped ZnO.

We propose a theoretical model to investigate the magnetic properties of cobalt-doped ZnO (ZnO:Co) thin films qualitatively. The model was built on the dilute Co dopants in the host of ZnO forming the magnetic Co+2 ions and the energy level of the magnetic ions crossing the band edge of ZnO resulting in a magnetic interaction between the Co+2 spins and the spins of the electrons from the conduction band of ZnO. The mechanism of the ferromagnetism revealed in the studied system is proposed here to be induced not only by the mediated conducting electrons via spin interactions but also by the Coulomb excitations, arising from the electrons localized by the oxygen vacancies. This approach of including Coulomb excitation in the modified carrier-mediated model could explain well the magnetic properties of ZnO:Co and solves the drawback of the carrier-mediated model in interpreting the appearance of ferromagnetism in the insulating ZnO:Co. We propose that the Coulomb excitations induced by the electrons captured by the oxygen vacancies are an essential element in the magnetic ZnO, which reveals the fact that the bound magnetic polaron model without considering the Coulomb excitation is insufficient to describe the magnetic properties of ZnO.

Extraction of magnetic circular dichroism effects from blended mixture of magnetic linear dichroism signals in the cobalt/Scotch tape system.

Circular dichroism (CD) signals revealed in some materials may arise from different origins during measurements. Magnetic field dependent CD (MCD) emanating from the spin-polarized band provides direct insight into the spin-spin interband transitions in magnetic materials. On the contrary, natural CD effects which are artefactual signals resulting from the linear polarization (LP) components during the polarization modulation with a photo-elastic modulator in anisotropic polymer systems were usually observed. There is no simple method to reliably distinguish MCD effect due to spin polarized band structures from natural CD effect, which limits our understanding of the magnetic material/polymer hybrid structures. This paper aims to introduce a general strategy of averaging out the magnetic linear dichroism (MLD) contributions due to the anisotropic structure and disentangling MCD signal(s) from natural MCD signal(s). We demonstrate the effectiveness of separating MCD from natural MCD using rotational MCD measurement and presented the results of a sample with Co thin film on polymer Scotch tape (unplasticized polyvinyl chloride) glued on a quartz substrate. We demonstrate that the proposed method can be used as an effective tool in disentangling MCD and natural MCD effects, and it opens prospects to study the magnetic material /polymer hybrid systems.

Two new polymorphs of cis-perinone: crystal structures, physical and electric properties.

The crystal structures of two polymorphs of cis-perinone (bisbenzimidazo[2,1-b:1',2'-j]benzo[lmn][3,8]phenanthroline-6,9-dione, Pigment Red 194) were solved from single crystals obtained solvothermally from 1,2-dichlorobenzene or n-butanol at 220°C. Both crystal structures (space group P21/c) derive from stacking of flat molecules arranged due to π-π interaction. The melting points of these two polymorphs are 471°C and 468°C and their respective optical bandgaps are 1.94 eV and 1.71 eV. One of the polymorphs demonstrates drift and hopping mechanisms of electric conductivity, whereas the other one is dominated by the drift conductivity. The direct current (DC) electric conductivity of the samples are 4.77 × 10-13 S m-1 and 6.84 × 10-10 S m-1 at room temperature. The significant difference in DC conductivities can be explained by the dependence of the mobility and concentration of charge carriers on the structure of the samples.