Spin Filtering and Amplification in Self-Assembled Nanofibers Based on Chiral Asymmetric Building Blocks.

The cooperativity in artificial self-assembling systems can be enhanced to expand their applications and redesign their properties. Recently, chiral molecules have garnered renewed attention due to their potential as highly efficient spin filters through the chiral-induced spin selectivity (CISS) effect. However, the potential of asymmetric building blocks based on chiral perylene diimides (PDIs) self-assembled materials to generate a spin-polarized current is still not widely acknowledged. In this work, we have demonstrated that nanofibers derived from "asymmetric PDIs" molecules have been found to exhibit promising spin-filtering property and the amplification of spin polarization at room temperature. Also, the exploration of chiral amplification and correlating it with the amplification of spin polarization have been reported for the first time through this work. These findings underscore the significance of self-assembled materials in the realm of spintronics, as they offer fascinating platforms with evolving structure-property relationship. It also provides the feasible possibility of enhancing the CISS-based spintronic devices that can accomplish controllability and high spin-filtering efficiency simultaneously.

Spin-induced electron transmission through metal-organic chiral crystals.

Metal-organic Co(II)-phenylalanine crystals were studied and were found to possess magnetic properties and long-range spin transport. Magnetic measurements confirmed that in the crystals there are antiferromagnetic interactions between Co(II) and the lattice. The metal-organic crystals (MOCs) also present the chirality-induced spin selectivity (CISS) effect at room temperature. A long-range spin polarization is observed using a magnetic conductive-probe atomic force microscope. The spin polarization is found to be in the range of 35-45%.

Degradation Analysis of Organic Light-Emitting Diodes through Dispersive Magneto-Electroluminescence Response.

Understanding the stability and degradation of organic light-emitting diodes (OLEDs) under working conditions is a significant area of research for developing more effective OLEDs and further improving their performance. However, studies of degradation processes by in situ noninvasive methods have not been adequately developed. In this work, tris-(8-hydroxyquinolino) aluminum (Alq3)-based OLED degradation processes have been analyzed through the investigation of the device dispersive magneto-electroluminescence (MEL(B)) response measured at room temperature. By studying the change in the MEL(B) response during the device degradation under different external stimuli, such as exposing the device to the atmosphere and prolonged illumination by a strong visible light source, we have gained insight into the microscopic spin-dependent phenomena that control the recombination of e-h polaron pairs in the device. We found that the device degradation leads to a shorter e-h polaron lifetime, smaller dispersive parameter, and broader lifetime distribution function that shows increased disorder in the active layer. This study could offer a potential tool that may be beneficial for assessing the degradation of OLED devices based on various active layers.

A randomised, double-blind, comparative study of preoperative magnesium sulphate versus zinc sulphate gargle for prevention of postoperative sore throat following endotracheal intubation.

Background and Aims: Magnesium sulphate and zinc sulphate have been reported to attenuate postoperative sore throat (POST). The study aims to compare the effect of preoperative magnesium sulphate and zinc sulphate gargle on the incidence and severity of POST following endotracheal intubation within 24 h. Methods: After ethics committee approval, 132 patients were randomly allocated to three groups (M, Z and D). Fifteen minutes before laryngoscopy and tracheal intubation, patients assigned to groups M and Z received a solution for gargle containing magnesium sulphate 20 mg/kg and zinc sulphate containing 40 mg of elemental zinc dissolved in 20 ml of 5% dextrose solution, respectively. Group D received 20 ml of 5% dextrose solution. Incidence and severity of POST (4-point score: Grade 0- no sore throat, Grade 1- mild sore throat, Grade 2- moderate sore throat, Grade 3- severe sore throat) was assessed for 24 h after extubation. Statistica, Version 8.0 (StatSoft, Inc., Tulsa, Oklahoma, USA) was used for analysing the data. Results: The lowest incidence of POST in group M was 13.6% (95% confidence interval [CI] 3.5-23.7) compared to 0% in group Z, whereas the highest incidence recorded in group M was 25% (95% CI 12.2-37.7) in contrast to 13.6% (95% CI 3.5-23.7) in group Z during the first 24 h after operation. It was observed that the incidence of mild POST (POST score 1) was significantly lower (P < 0.05) in group Z compared to group M in the first 4 h postoperatively. Conclusion: Zinc sulphate gargle before laryngoscopy and tracheal intubation is more effective for reducing the incidence of POST than magnesium sulphate gargle.

Spin-induced asymmetry reaction-The formation of asymmetric carbon by electropolymerization.

We describe the spin polarization-induced chirogenic electropolymerization of achiral 2-vinylpyridine, which forms a layer of enantioenhanced isotactic polymer on the electrode. The product formed is enantioenriched in asymmetric carbon polymer. To confirm the chirality of the polymer film formed on the electrode, we also measured its electron spin polarization properties as a function of its thickness. Two methods were used: First, spin polarization was measured by applying magnetic contact atomic force microscopy, and second, magnetoresistance was assessed in a sandwich-like four-point contact structure. We observed high spin-selective electron transmission, even for a layer thickness of 120 nm. A correlation exists between the change in the circular dichroism signal and the change in the spin polarization, as a function of thickness. The spin-filtering efficiency increases with temperature.

Interrelation between Stress Management and Secretion Systems of Ralstonia solanacearum: An In Silico Assessment.

Ralstonia solanacearum (Rs), the causative agent of devastating wilt disease in several major and minor economic crops, is considered one of the most destructive bacterial plant pathogens. However, the mechanism(s) by which Rs counteracts host-associated environmental stress is still not clearly elucidated. To investigate possible stress management mechanisms, orthologs of stress-responsive genes in the Rs genome were searched using a reference set of known genes. The genome BLAST approach was used to find the distributions of these orthologs within different Rs strains. BLAST results were first confirmed from the KEGG Genome database and then reconfirmed at the protein level from the UniProt database. The distribution pattern of these stress-responsive factors was explored through multivariate analysis and STRING analysis. STRING analysis of stress-responsive genes in connection with different secretion systems of Rs was also performed. Initially, a total of 28 stress-responsive genes of Rs were confirmed in this study. STRING analysis revealed an additional 7 stress-responsive factors of Rs, leading to the discovery of a total of 35 stress-responsive genes. The segregation pattern of these 35 genes across 110 Rs genomes was found to be almost homogeneous. Increasing interactions of Rs stress factors were observed in six distinct clusters, suggesting six different types of stress responses: membrane stress response (MSR), osmotic stress response (OSR), oxidative stress response (OxSR), nitrosative stress response (NxSR), and DNA damage stress response (DdSR). Moreover, a strong network of these stress responses was observed with type 3 secretion system (T3SS), general secretory proteins (GSPs), and different types of pili (T4P, Tad, and Tat). To the best of our knowledge, this is the first report on overall stress response management by Rs and the potential connection with secretion systems.

Multistate Switching of Spin Selectivity in Electron Transport through Light-Driven Molecular Motors.

It is established that electron transmission through chiral molecules depends on the electron's spin. This phenomenon, termed the chiral-induced spin selectivity (CISS), effect has been observed in chiral molecules, supramolecular structures, polymers, and metal-organic films. Which spin is preferred in the transmission depends on the handedness of the system and the tunneling direction of the electrons. Molecular motors based on overcrowded alkenes show multiple inversions of helical chirality under light irradiation and thermal relaxation. The authors found here multistate switching of spin selectivity in electron transfer through first generation molecular motors based on the four accessible distinct helical configurations, measured by magnetic-conductive atomic force microscopy. It is shown that the helical state dictates the molecular organization on the surface. The efficient spin polarization observed in the photostationary state of the right-handed motor coupled with the modulation of spin selectivity through the controlled sequence of helical states, opens opportunities to tune spin selectivity on-demand with high spatio-temporal precision. An energetic analysis correlates the spin injection barrier with the extent of spin polarization.

Spin Filtering in Supramolecular Polymers Assembled from Achiral Monomers Mediated by Chiral Solvents.

In past studies, spin selective transport was observed in polymers and supramolecular structures that are based on homochiral building blocks possessing stereocenters. Here we address the question to what extent chiral building blocks are required for observing the chiral induced spin selectivity (CISS) effect. We demonstrate the CISS effect in supramolecular polymers exclusively containing achiral monomers, where the supramolecular chirality was induced by chiral solvents that were removed from the fibers before measuring. Spin-selective transport was observed for electrons transmitted perpendicular to the fibers' long axis. The spin polarization correlates with the intensity of the CD spectra of the polymers, indicating that the effect is nonlocal. It is found that the spin polarization increases with the samples' thickness and the thickness dependence is the result of at least two mechanisms: the first is the CISS effect, and the second reduces the spin polarization due to scattering. Temperature dependence studies provide the first support for theoretical work that suggested that phonons may contribute to the spin polarization.

Long term effects of stress on hippocampal function: Emphasis on early life stress paradigms and potential involvement of neuropeptide Y.

The brain is both central in orchestrating the response to stress, and, a very sensitive target when such response is not controlled. In fact, stress has long been associated with the onset and/or exacerbation of several neuropsychiatric disorders such as anxiety, depression, and drug addiction. The hippocampus is a key brain region involved in the response to stress, not only due to its anatomical connections with the hypothalamic-pituitary-adrenal axis but also as a major target of stress mediators. The hippocampal dentate gyrus (DG)-CA3 circuit, composed of DG granule cells axons (mossy fibers) synapsing onto CA3 pyramidal cells, plays an essential role in memory encoding and retrieval, functions that are vulnerable to stress. Although naturally excitatory, this circuit is under the inhibitory control of GABAergic interneurons that maintain the excitation/inhibition balance. One subgroup of such interneurons produces neuropeptide Y (NPY), which has emerged as a promising endogenous stress "resilience molecule" due to its anxiolytic and anti-epileptic properties. Here we examine existing evidence that reveals a potential role for hilar NPY+ interneurons in mediating stress-induced changes in hippocampal function. We will focus specifically on rodent models of early life stress (ELS), defined as adverse conditions during the early postnatal period that can have profound consequences for neurodevelopment. Collectively, these findings suggest that the long-lasting effects of ELS might stem from the loss of GABAergic NPY+ cells, which then can lead to reduced inhibition in the DG-CA3 pathway. Such change might then lead to hyperexcitability and concomitant hippocampal-dependent behavioral deficits.

Long-Range Spin-Selective Transport in Chiral Metal-Organic Crystals with Temperature-Activated Magnetization.

Room-temperature, long-range (300 nm), chirality-induced spin-selective electron conduction is found in chiral metal-organic Cu(II) phenylalanine crystals, using magnetic conductive-probe atomic force microscopy. These crystals are found to be also weakly ferromagnetic and ferroelectric. Notably, the observed ferromagnetism is thermally activated, so that the crystals are antiferromagnetic at low temperatures and become ferromagnetic above ∼50 K. Electron paramagnetic resonance measurements and density functional theory calculations suggest that these unusual magnetic properties result from indirect exchange interaction of the Cu(II) ions through the chiral lattice.

Spin Filtering Along Chiral Polymers.

Spin-dependent conduction and polarization in chiral polymers were studied for polymers organized as self-assembled monolayers with conduction along the polymer backbone, namely, along its longer axis. Large spin polarization and magnetoresistance effects were observed, showing a clear dependence on the secondary structure of the polymer. The results indicate that the spin polarization process does not include spin flipping and hence it results from backscattering probabilities for the two spin states.

Highly Efficient and Tunable Filtering of Electrons' Spin by Supramolecular Chirality of Nanofiber-Based Materials.

Organic semiconductors and organic-inorganic hybrids are promising materials for spintronic-based memory devices. Recently, an alternative route to organic spintronic based on chiral-induced spin selectivity (CISS) is suggested. In the CISS effect, the chirality of the molecular system itself acts as a spin filter, thus avoiding the use of magnets for spin injection. Here, spin filtering in excess of 85% in helical π-conjugated materials based on supramolecular nanofibers at room temperature is reported. The high spin-filtering efficiency can even be observed in nanofibers assembled from mixtures of chiral and achiral molecules through chiral amplification effect. Furthermore and most excitingly, it is shown that both "up" and "down" orientations of filtered spins can be obtained in a single enantiopure system via the temperature-dependent helicity (P and M) inversion of supramolecular nanofibers. The findings showcase that materials based on helical noncovalently assembled systems are modular platforms with an emerging structure-property relationship for spintronic applications.

Spin-Dependent Electron Transport through Bacterial Cell Surface Multiheme Electron Conduits.

Multiheme cytochromes, located on the bacterial cell surface, function as long-distance (>10 nm) electron conduits linking intracellular reactions to external surfaces. This extracellular electron transfer process, which allows microorganisms to gain energy by respiring solid redox-active minerals, also facilitates the wiring of cells to electrodes. While recent studies have suggested that a chiral induced spin selectivity effect is linked to efficient electron transmission through biomolecules, this phenomenon has not been investigated in extracellular electron conduits. Using magnetic conductive probe atomic force microscopy, Hall voltage measurements, and spin-dependent electrochemistry of the decaheme cytochromes MtrF and OmcA from the metal-reducing bacterium Shewanella oneidensis MR-1, we show that electron transport through these extracellular conduits is spin-selective. Our study has implications for understanding how spin-dependent interactions and magnetic fields may control electron transport across biotic-abiotic interfaces in both natural and biotechnological systems.

Low-Resistance Molecular Wires Propagate Spin-Polarized Currents.

Spin based properties, applications, and devices are typically related to inorganic ferromagnetic materials. The development of organic materials for spintronic applications has long been encumbered by its reliance on ferromagnetic electrodes for polarized spin injection. The discovery of the chirality-induced spin selectivity (CISS) effect, in which chiral organic molecules serve as spin filters, defines a marked departure from this paradigm because it exploits soft materials, operates at ambient temperature, and eliminates the need for a magnetic electrode. To date, the CISS effect has been explored exclusively in molecular insulators. Here we combine chiral molecules, which serve as spin filters, with molecular wires that despite not being chiral, function to preserve spin polarization. Self-assembled monolayers (SAMs) of right-handed helical (l-proline)8 (Pro8) and corresponding peptides, N-terminal conjugated to (porphinato)zinc or meso-to-meso ethyne-bridged (porphinato)zinc structures (Pro8PZnn), were interrogated via magnetic conducting atomic force microscopy (mC-AFM), spin-dependent electrochemistry, and spin Hall devices that measure the spin polarizability that accompanies the charge polarization. These data show that chiral molecules are not required to transmit spin-polarized currents made possible by the CISS mechanism. Measured Hall voltages for Pro8PZn1-3 substantially exceed that determined for the Pro8 control and increase dramatically as the conjugation length of the achiral PZnn component increases; mC-AFM data underscore that measured spin selectivities increase with an increasing Pro8PZn1-3 N-terminal conjugation. Because of these effects, spin-dependent electrochemical data demonstrate that spin-polarized currents, which trace their genesis to the chiral Pro8 moiety, propagate with no apparent dephasing over the augmented Pro8PZnn length scales, showing that spin currents may be transmitted over molecular distances that greatly exceed the length of the chiral moiety that makes possible the CISS effect.

Single-ion magnetic anisotropy in a vacant octahedral Co(ii) complex.

The first example of a pentacoordinate CoII single-ion magnet based on a P-donor ligand with vacant octahedral coordination geometry is reported here. Thorough magnetic measurements reveal the presence of field induced slow relaxation behavior with an easy-plane magnetic anisotropy. The combined theoretical and experimental studies disclose that direct and quantum tunneling processes become dominant at low temperature to relax the magnetization; however, from the thermal dependence of relaxation time it can be observed that the optical or acoustic Raman processes become important to the overall relaxation process.

Influence of the Coordination Environment on Easy-Plane Magnetic Anisotropy of Pentagonal Bipyramidal Cobalt(II) Complexes.

A rational approach of modulating the easy-plane magnetic anisotropy of mononuclear pentagonal bipyramidal CoII single molecule magnets (SMMs) has been revealed in this paper. A class of three new pentagonal-bipyramidal complexes with formulas [Co(H2daps)(MeOH)2] (1), [Co(H4daps)(NCS)(MeOH)]·(ClO4)·(MeOH) (2), and [Co(H4daps)(NCS)2]·(MeOH)2 (3) (H4daps = 2,6-bis(1-salicyloylhydrazonoethyl) pyridine) were studied. In these complexes, the axial positions are successively replaced by different O and N donar ligands in a systematic way. Detailed magnetic measurements disclose the existence of large easy-plane magnetic anisotropy and field-induced slow magnetic relaxation behavior. Both experimental and ab initio theoretical calculations display that easy-plane magnetic anisotropy is maintained upon variation of coordination environments. Nevertheless, the magnitude of the D value was found to be increased in the case of weaker axially coordinated σ-donor ligands and a more symmetrical equatorial ligand. Additionally, the detailed investigation of field and temperature dependence of relaxation time revealed that quantum tunnelling of magnetization is the predominant process for slow magnetic relaxation and the Raman process is significant which explicates the thermal dependence. Magnetic dilution experiments have been performed to eliminate the possible influence of intermolecular interactions on magnetic behaviors of adjacent CoII centers.

A new series of tetrahedral Co(ii) complexes [CoLX2] (X = NCS, Cl, Br, I) manifesting single-ion magnet features.

A series of tetrahedral CoII complexes [CoLX2] (X = NCS (1), Cl (2), Br (3) and I (4); L = 9,9-dimethyl-4,5-bis(diphenylphosphino) xanthene) based on a P-donor ligand has been prepared to investigate the influence of terminal ligand field strength on the anisotropy of CoII single-ion magnets. It has been observed that heavier and softer terminal ligands are able to decrease the anisotropy of the tetrahedral CoII centers. Thorough analyses of experimental and theoretical studies show that all complexes have an easy-axis type magnetic anisotropy and slow relaxation behaviors of tetrahedral CoII centers. Detailed ab initio theory studies disclose that the changes in the ligand field strength imposed by the terminal ligands result in modifying the single ion anisotropy (D) of polyhedra 1-4. Furthermore, the isostructural ZnII analogue (5) has been prepared to examine the influence of dipolar interactions between adjacent CoII centres and magnetic dilution experiments were performed.

Multifunctional Properties of a 1D Helical Co(II) Coordination Polymer: Toward Single-Ion Magnetic Behavior and Efficient Dye Degradation.

This contribution deals with the synthesis and utilization of a new pyrazole-based unsymmetrical ligand, 3-(3-carboxyphenyl)-1H-pyrazole-5-carboxylic acid (H2CPCA), for generating multifunctional materials. The reaction with the Co(II) salt in the presence of a co-ligand 2,9-dimethyl phenanthroline (dmphen) results in the formation of the helical compound {[Co2(dmphen)2(CPCA)2]DMF} n (1). However, two isostructural monomeric complexes are formed {[M(HCPCA)2(H2O)2], M = Co(II), (2) and Mn(II) (3)} when reactions were carried out in the absence of dmphen. Compound 1 shows some highly encouraging single-ion magnetic (SIM) properties. Detailed magnetic studies unveil slow relaxation of magnetization of compound 1, driven by the higher magnetic anisotropy of the cobalt ion, with the energy barrier of ∼9.2 K and relaxation time of 9.1 × 10-5 s, suggesting a SIM behavior. Moreover, UV-vis and fluorescence studies confirm the selective dye degradation of compound 1 with methylene blue both in the presence and absence of H2O2, with the remarkable degradation efficiency of ∼98 and ∼82%, respectively.

Quantitative Estimation of Ising-Type Magnetic Anisotropy in a Family of C3 -Symmetric CoII Complexes.

In this paper, the influence of the structural and chemical effects on the Ising-type magnetic anisotropy of pentacoordinate CoII complexes has been investigated by using a combined experimental and theoretical approach. For this, a deliberate design and synthesis of four pentacoordinate CoII complexes [Co(tpa)Cl]⋅ClO4 (1), [Co(tpa)Br]⋅ClO4 (2), [Co(tbta)Cl]⋅(ClO4 )⋅(MeCN)2 ⋅(H2 O) (3) and [Co(tbta)Br]⋅ClO4 (4) by using the tripodal ligands tris(2-methylpyridyl)amine (tpa) and tris[(1-benzyl-1 H-1,2,3-triazole-4-yl)methyl]amine) (tbta) have been carried out. Detailed dc and ac measurements show the existence of field-induced slow magnetic relaxation behavior of CoII centers with Ising-type magnetic anisotropy. A quantitative estimation of the zero-field splitting (ZFS) parameters has been effectively achieved by using detailed ab initio theory calculations. Computational studies reveal that the wavefunction of all the studied complexes has a very strong multiconfigurational character that stabilizes the largest ms =±3/2 components of the quartet state and hence produce a large negative contribution to the ZFS parameters. The difference in the magnitudes of the Ising-type anisotropy can be explained through ligand field theory considerations, that is, D is larger and negative in the case of weak equatorial σ-donating and strong apical π-donating ligands. To elucidate the role of intermolecular interactions in the magnetic relaxation behavior between adjacent CoII centers, a diamagnetic isostructural ZnII analog (5) was synthesized and the magnetic dilution experiment was performed.

Probing the Effects of Ligand Field and Coordination Geometry on Magnetic Anisotropy of Pentacoordinate Cobalt(II) Single-Ion Magnets.

In this work, the effects of ligand field strength as well as the metal coordination geometry on magnetic anisotropy of pentacoordinated CoII complexes have been investigated using a combined experimental and theoretical approach. For that, a strategic design and synthesis of three pentacoordinate CoII complexes [Co(bbp)Cl2]·(MeOH) (1), [Co(bbp)Br2]·(MeOH) (2), and [Co(bbp)(NCS)2] (3) has been achieved by using the tridentate coordination environment of the ligand in conjunction with the accommodating terminal ligands (i.e., chloride, bromide, and thiocyanate). Detailed magnetic studies disclose the occurrence of slow magnetic relaxation behavior of CoII centers with an easy-plane magnetic anisotropy. A quantitative estimation of ZFS parameters has been successfully performed by density functional theory (DFT) calculations. Both the sign and magnitude of ZFS parameters are prophesied well by this DFT method. The theoretical results also reveal that the α → ß (SOMO-SOMO) excitation contributes almost entirely to the total ZFS values for all complexes. It is worth noting that the excitation pertaining to the most positive contribution to the ZFS parameter is the dxy → dx2-y2 excitation for complexes 1 and 2, whereas for complex 3 it is the dz2 → dx2-y2 excitation.