Lead(II)-Based Coordination Polymer Exhibiting Reversible Color Switching and Selective CO2 Photoreduction Properties.

Herein, we report a new photofunctional Pb-S-based coordination polymer (CP) with the formula [Pb(ATAT)(OAc)]n (ATAT = 3-amino-5-mercapto-1,2,4-triazole, OAc = acetate, CP1). Apart from its photoactive one-dimensional (1D) (-Pb-S-)n chain, CP1 is also composed of another 1D (-Pb-O-)n chain that originates from the coordination with acetate. The coordinated acetate can be exchanged with water (H2O) or dimethyl sulfoxide (DMSO), leading to the formation of a CP1-H2O or CP1-DMSO structure that exhibits a distinct change in optical properties, including a white-to-yellow color change. The structural transformation of CP1 to CP1-H2O and CP1-DMSO, and its subsequent recovery to the original CP1 structure could be controlled by the presence or absence of acetic acid vapor; the transformation was completely reversible. CP1 absorbed light with wavelengths shorter than 390 nm, with an estimated bandgap of 3.18 eV. Density functional theory calculations indicated that the valence band of CP1 is mainly formed by N and S orbitals originating from the ATAT unit, whereas the conduction band is composed of the Pb orbitals. Even without any modification, such as the incorporation of a molecular catalyst, CP1 reduced CO2 into formate under UV light with >99% selectivity.

Synthesis of N-ß-brominated alkenyl isothiocyanates via dehydrogenation of alkyl isothiocyanates.

This study presents a new dehydrogenative synthesis of alkenyl isothiocyanates, providing compounds with bromo and isothiocyanate groups. These reactive functionalities offer versatility for further transformations. Application in an amine sensor utilizing a coumarin-attached product demonstrates practical utility. This streamlined approach facilitates access to alkenyl isothiocyanates, valuable tools for biological studies.

Polymorphism of Two-Dimensional Semiconducting Coordination Polymers: Impact of a Lead-Sulfur Network on Photoconductivity.

Sulfur-coordinated coordination polymers (S-CPs) have unique optoelectrical properties that originate from infinite M-S bond networks. In this study, we synthesized and characterized two polymorphs of a two-dimensional (2D) Pb(II) S-CP with a formula of [Pb(tzdt)(OAc)] (Htzdt=1,3-thiazolidine-2-thione, OAc=acetate). Our findings revealed that the thermodynamic product (KGF-26) possesses quasi-2D (-Pb-S-)n layers with weak nonbonded Pb-S bonds, whereas the kinetic product (KGF-27) has intrinsic 2D (-Pb-S-)n layers with Pb-S bonds. The results of time-resolved microwave conductivity measurements and first-principles calculations confirmed that KGF-27 exhibits higher photoconductivity than KGF-26, which establishes that the inorganic (-Pb-S-)n networks with Pb-S bonds are crucial for achieving high photoconductivity. This is the first experimental demonstration of the impact of the (-M-S-)n networks in S-CPs on photoconductivity through the comparison of crystal polymorphisms.

Functionalized Polyamine Synthesis with Photoredox Catalysis.

Polyamines, such as putrescine and spermidine, are pivotal in various biological processes across living organisms. Despite their significance, structurally modified polyamines offer a less-explored avenue for discovering bioactive compounds. The limitation is attributed to the synthetic difficulty of accessing functionalized polyamines. In this study, we accomplished photoredox-catalyzed functionalization of polyamines to diversify their structure. The rapid functionalization allows attaching fluorophores to the target polyamine, facilitating the development of molecular probes for advancing chemical biology studies.

Engineering of CdS-chain arrays assembled through S⋯S interactions in 1D semiconductive coordination polymers.

One-dimensional (1D) Cd(II) coordination polymers [Cd(x-SPhOMe)2]n (x = ortho, meta, and para; HSPhOMe = methoxybenzenethiol) containing inorganic 1D (-Cd-S-)n chains were synthesized. Among these, the KGF-31 polymer bearing para-SPhOMe featured a three-strand chain structure assembled via interchain S⋯S interactions and exhibited high photoconductivity and longevity.

Coupling Dielectric Functionality with Magnetic Properties in Coordination Metal Complexes.

Significant research has been conducted on molecular ferroelectric materials, including pure organic and inorganic compounds; however, studies on ferroelectric materials based on coordination metal complexes are scarce. Ferroelectric materials based on coordination metal complexes have tunable structures and designs, with coexistence or synergy between the ferroelectric behavior and magnetic properties. Compared to inorganic compounds, few coordination metal complexes exhibit coupling between the magnetic and dielectric properties. Coordination metal complexes with strong coupling between the magnetic and dielectric properties exhibit dielectric permittivity variations under external magnetic fields. Therefore, they have attracted substantial interest for their potential use in magnetoelectric devices. In this review, we discuss recent advances in coordination metal complexes, that exhibit coupled magnetic functionalities and ferroelectricity or dielectric properties, including single-molecule magnets, electron delocalization systems, and external stimuli responsive compounds.

Ferroelectric coordination metal complexes based on structural and electron dynamics.

Ferroelectrics that display electrically invertible polarisation are attractive materials because of their potential for wide-ranging applications. To date, considerable effort has thus been devoted towards developing ferroelectric materials, particularly those comprising organic/inorganic compounds. In these systems, structural dynamics such as atomic displacement and reorientation of polar ions/molecules play a key role in the generation of reversible spontaneous polarisation. Although there are many reports concerned with organic/inorganic ferroelectrics, ferroelectrics based on coordination metal complexes have been largely unexplored despite their often unique electronic and spin state properties. In this feature article, we discuss recent progress involving coordination metal complex-based ferroelectrics where the reversible polarisation originates not only from structural dynamics (represented by proton transfer, molecular motion, and liquid crystalline behaviour) but also from electron dynamics (represented by electron transfer and spin crossover phenomena) occurring at the metal centre. Furthermore, unique synergy effects (i.e. magnetoelectric coupling) resulting from the structural and electron dynamics are described. We believe that this review pertaining to ferroelectric coordination metal complexes provides new insights for fabricating further advanced functional materials such as multiferroics and spintronics.

Synthesis and Strong π-π Interaction of Hexaazatriphenylene Derivatives with Alternating Electron-Withdrawing and -Donating Groups.

Hexaazatriphenylene (HAT) derivatives have attracted wide attention because of their electron-deficient nature and unique self-assembly properties. In this work, a facile synthesis method for obtaining HAT derivatives with alternating electron-withdrawing nitrile and electron-donating alkoxy groups (HATCNOCn) is proposed. Crystal structure analysis indicated that HATCNOCn forms a one-dimensional columnar structure via strong π-π interactions. Density functional theory calculations revealed that the edge of HATCNOCn is divided into positively and negatively charged sites owing to the presence of alternating nitrile and alkoxy groups, which would induce strong π-π interactions. Thermal analysis and polarizing optical microscopy revealed that HATCNOCn exhibits columnar liquid-crystal phases. Time-resolved microwave conductivity measurements further demonstrated the photoconductive nature of HATCNOCn. The proposed strategy could provide a new strategy for the design of novel organic semiconductive materials.

A Ferroelectric Metallomesogen Exhibiting Field-Induced Slow Magnetic Relaxation.

Magnetoelectric (ME) materials exhibiting coupled electric and magnetic properties are of significant interest because of their potential use in memory storage devices, new sensors, or low-consumption devices. Herein, we report a new category of ME material that shows liquid crystal (LC), ferroelectric (FE), and field-induced single molecule magnet (SMM) behaviors. Co(II) complex incorporating alkyl chains of type [Co(3C16 -bzimpy)2 ](BF4 )2 (1; 3C16 -bzimpy=2,2'-(4-hexadecyloxy-2,6-diyl)bis(1-hexadecyl-1H-benzo[d]imidazole)) displayed a chiral smectic C mesophase in the temperature range 321 K-458 K, in which distinct FE behavior was observed, with a remnant polarization (88.3 nC cm-2 ). Complex 1 also exhibited field-induced slow magnetic relaxation behavior that reflects the large magnetic anisotropy of the Co(II) center. Furthermore, the dielectric property of 1 was able to be tuned by an external magnetic field occurring from both spin-lattice coupling and molecular orientational variation. Clearly, this multifunctional compound, combining LC, FE, and SMM properties, represents an entry to the development of a range of next-generation ME materials.

Clinical Diagnosis of Central Vertigo in Patients With Dizziness in Emergency Practice.

BACKGROUND: Life-threatening diseases should be promptly identified to provide appropriate medical care for emergency outpatients experiencing dizziness. However, dizziness is associated with various medical conditions; thus, a definitive diagnosis is challenging. To accurately diagnose vertigo in an emergency outpatient, we conducted a survey on the need to identify vertigo patients in the current outpatient departments. MATERIALS AND METHODS: The participants included 509 patients who visited the outpatient department at our hospital from February 2014 to May 2017. Overall, 12 characteristics were retrospectively extracted from the patients' medical records: age, sex, visit method, medical history (diabetes, hypertension, cardiac, or cerebrovascular disease), dizziness history, vertigo characteristics, concomitant symptoms, systolic blood pressure, nystagmus, imaging history, diagnosis, and hospitalization department. Univariate and multivariate analyses were performed to identify factors related to central vertigo. RESULTS: The diagnosis of central vertigo was confirmed when intracranial lesions were detected through imaging. In multivariate analysis, the presence/absence of a history of headache and cardiovascular disease were significantly correlated with central vertigo (P=0.002 and 0.006, respectively), with odds ratios of 5.18 and 4.38, respectively. CONCLUSIONS: To avoid missing central dizziness in a patient, diagnostic abilities should be improved by including careful interviews and confirmation of the presence/absence of accompanying symptoms. Furthermore, collaboration with neurology and neurosurgery departments is important for improving the diagnosis in suspected cases.

Spin crossover phenomena in long chain alkylated complexes.

Soft materials represented by polymers, liquid crystals, and colloids are a class of materials that exhibit a variety of unique functionalities which derive from their non-rigid structures. In particular, soft metal complexes incorporating flexible long alkyl chains in their structures have been shown to display synergy between the structural dynamics of the long alkyl chain moieties and the electron dynamics occurring at the metal centre. This review presents a discussion of such soft metal complexes with a focus on spin crossover (SCO) behaviours that are associated with a structural phase transition, including a liquid crystal (LC) transition, arising from the flexible natures of the respective complexes. We also discuss how to fabricate soft materials based on SCO complexes.

Ferroelectric and Spin Crossover Behavior in a Cobalt(II) Compound Induced by Polar-Ligand-Substituent Motion.

Ferroelectric spin crossover (SCO) behavior is demonstrated to occur in the cobalt(II) complex, [Co(FPh-terpy)2 ](BPh4 )2 ⋅3ac (1⋅3 ac; FPh-terpy=4'-((3-fluorophenyl)ethynyl)-2,2':6',2''-terpyridine) and is dependent on the degree of 180° flip-flop motion of the ligand's polar fluorophenyl ring. Single crystal X-ray structures at several temperatures confirmed the flip-flop motion of fluorobenzene ring and also gave evidence for the SCO behavior with the latter behavior also confirmed by magnetic susceptibility measurements. The molecular motion of the fluorobenzene ring was also revealed using solid-state 19 F NMR spectroscopy. Thus the SCO behavior is accompanied by the flip-flop motion of the fluorobenzene ring, leading to destabilization of the low spin cobalt(II) state; with the magnitude of rotation able to be controlled by an electric field. This first example of spin-state conversion being dependent on the molecular motion of a ligand-appended fluorobenzene ring in a SCO cobalt(II) compound provides new insight for the design of a new category of molecule-based magnetoelectric materials.

Subcortical deafness as a subtype of auditory agnosia after injury of bilateral auditory radiations caused by two cerebrovascular accidents - normal auditory brainstem responses with I-VII waves and abolished consciousness of hearing.

BACKGROUND: In central auditory disorders caused by damage of the cerebral hemispheres, there are cortical deafness and auditory agnosia. Although clinical cases of cortical deafness have been reported, little is known about the hearing problems and localized lesions associated with cortical deafness. AIMS/OBJECTIVES: The aims of our research are to elucidate lesion sites associated with cortical deafness and to clarify why patients with cerebral lesions are not aware of any sound at all. MATERIALS AND METHODS: Three patients diagnosed as having total loss of hearing participated in this study. We conducted pure-tone audiometry, speech audiometry, distortion product otoacoustic emission (DPOAE), auditory brainstem response (ABR), and brain magnetic resonance imaging (MRI) to diagnose cortical deafness with aphasia tests of these patients. RESULTS: Our studies showed that waves VI and VII as well as waves I to V have normal peak latencies in ABRs in all three patients. In brain MRI, we found complete damage of proximal parts of bilateral auditory radiations in the three patients. CONCLUSIONS: We propose 'subcortical deafness' as a subtype of auditory agnosia.

Magnetism in a helicate complexes arising with the tetradentate ligand.

The synthesis of [M(dimphen)(NCS)2] (1; M = FeII), (2; M = CoII), (3; M = MnII) and [Fe(dimphen)(NCSe)2] (4), where dimphen = [1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane], are reported. The crystal packing structures of 1-3, show intermolecular π-π stacking and NCSSCN interactions. The complex 1 shows ferromagnetic interaction, and the complex 2 displays single-molecular magnet behaviour.

Ingredients of Jelly Products Affect Aspiration-Related Pulmonary Inflammation; in an Animal Study.

Diet modification is an important intervention in the management of patients with dysphagia. Food entering the airway, same as oral bacterium, causes pulmonary inflammation; therefore, the elucidation of inflammatory responses to different foods is important. This study aimed to investigate the differences in the severity of inflammatory response induced by intratrachial injection of foods with different nutritional components. Two jelly products, the one containing only carbohydrates (KURIN jelly: Isocal Jelly KURIN®) and the other containing carbohydrates, proteins, and lipids (HC jelly: Isocal Jelly HC®), were prepared. These jelly products (dilution with saline, 50% volume/volume) and saline, as control, were intratracheally administered to Sprague-Dawley rats at a dose of 1 ml/kg (KURIN group (n = 15), HC group (n = 15), Saline group (n = 15)). At 1, 2 and 7 days after administration, lungs were harvested and histological analysis was performed. The severity of induced inflammation was evaluated using the Acute Lung Injury (ALI) score with hematoxylin-eosin staining, and the expression of IL-1ß, IL-6 and TNF-α, markers of airway inflammation, were observed with immunostaining. The ALI score in the HC jelly group was significantly higher than the KURIN jelly group and the Saline group (P < 0.01) at 1 and 2 days after administration, while the ALI score in the KURIN jelly group was higher than Saline group only at 2 day after administration. Numerous positive cells for IL-1ß, IL-6 and TNF-α were observed only in the HC jelly group at 1 and 2 days after administration. There were no significant histological differences between the three groups at 7 days after administration. Our data suggests that the severity of inflammation caused by aspiration differs depending on the ingredients of the foods, and the nutrients contained in foods might be considered in dietary management for the patients with dysphagia.

Water Molecule-Induced Reversible Magnetic Switching in a Bis-Terpyridine Cobalt(II) Complex Exhibiting Coexistence of Spin Crossover and Orbital Transition Behaviors.

The development of molecule-based switchable materials remains an important challenge in the field of molecular science. Achievement of a structural phase transition induced by adsorption/desorption of guest molecules in spin crossover (SCO) Co(II) compounds is of significant interest because of the possibility that the spin state of the magnetic anisotropic high-spin (HS, S = 3/2) and low-spin (LS, S = 1/2) states can be switched via the induced changes in associated intermolecular interactions. In this study, we demonstrated a reversible magnetic switching associated with spin state conversion, along with a single-crystal to single-crystal (SCSC) phase transition induced by dehydration/rehydration. [Co(terpy)2](BF4)2·H2O (1·H2O; terpy = 2,2':6',2''-terpyridine) assembles in the solid state via π-π and CH-π interactions involving adjacent terpyridine cores along the ab direction to form two-dimensional (2D) layered domains. 1·H2O exhibits gradual and incomplete SCO, from fully HS to ca. 0.5 HS, and the field-induced single-molecule magnet (SMM) behavior attributed to the presence of the anisotropic partial high-spin Co(II) species. 1·H2O undergoes a SCSC transformation accompanied by a change from the tetragonal space group I41/a to P42/n via a dehydration process. Dehydrated 1 exhibits a reverse thermal hysteresis behavior (T1/2↑ = 287 K; T1/2↓ = 270 K) in the gradual SCO region from fully HS to ca. 0.5 HS, followed by an ordinary thermal hysteresis (T'1/2↑ = 195 K; T'1/2↓ = 155 K) to fully LS Co(II). A temperature-dependent single-crystal X-ray structural analysis revealed that the reverse hysteresis can be attributed to an order/disorder structural phase transition of the BF4- anions involving a symmetry breaking to yield the monoclinic space group P21/n and orbital (angular momentum) transition (LT). Both the SCSC phase transition and magnetic behavior are switchable by dehydration/rehydration processes; thus 1 again adsorbs water at room temperature to give both the original structure and its magnetic behavior.

Solvent vapor-induced polarity and ferroelectricity switching.

Vapor-induced crystal to crystal transformation between non-polar [Fe(sap)(acac)(sol)] (H2sap = 2-salicylideneaminophenol, acac = acethylacetate, sol = MeOH, pyridine) and polar [Fe(sap)(acac)(DMSO)] was demonstrated. It provides an example of switchable ferroelectric behaviour attributted to the structural phase transition triggered by solvent vapour.

Double-layered honeycomb architectures constructed via hierarchical self-assembly of hexagonal spin crossover cobalt(ii) metallacycles.

A hexagonal cobalt(ii) metallacycle and its "lipid packaged" derivatives, [Co6(R-bisterpy)6]X12 (R = H, OC16H33, OC27H55; X = BF4, C12-Glu), have been synthesized and characterized. The compounds incorporating BF4- anions formed sphere-like aggregates while the compounds with C12-Glu lipid anions gave double-layered honeycomb architectures composed of hexagonal stacked tubular structures, which exhibit spin crossover behaviour.

Ferroelectric metallomesogens composed of achiral spin crossover molecules.

Ferroelectric liquid crystals (FLCs) are fascinating functional materials that have a remnant and electrically invertible polarization. To date, typical FLCs have been mainly realized by molecular design such as the incorporation of chirality into a given molecular structure. Here, we report for the first time ferroelectricity induced by spin transition associated with a crystal - liquid crystal phase transition in achiral molecules. Iron(ii) metallomesogens incorporating alkyl chains of type [Fe(3C n -bzimpy)2](BF4)2 (n = 8 (1), 10 (2), 12 (3), 14 (4), 16 (5) and 18 (6); bzimpy = 2,6-bis(benzimidazol-2'-yl)pyridine) that exhibit spin crossover (SCO) phenomena have been synthesized. Compounds 5 and 6 were each demonstrated to show SCO behaviour along with the occurrence of a phase transition between the crystalline (Cr) state and corresponding chiral smectic C (SmC*) state. The distortion of the coordination sphere in the high spin state is seen to trigger the generation of the SmC* state. The liquid crystalline compounds do not display ferroelectric behaviour in their Cr state but do exhibit ferroelectric hysteresis loops in their SmC* state. Ferroelectric switching was clearly confirmed by second harmonic generation (SHG) experiments involving the respective phases. These findings will undoubtedly lead to new strategies for the design of new FLCs based on metal-centred spin transitions.

Microglia Enhance Synapse Activity to Promote Local Network Synchronization.

Microglia are highly motile immunoreactive cells that play integral roles in the response to brain infection and damage, and in the progression of various neurological diseases. During development, microglia also help sculpt neural circuits, via both promoting synapse formation and by targeting specific synapses for elimination and phagocytosis. Microglia are also active surveyors of neural circuits in the mature, healthy brain, although the functional consequences of such microglia-neuron contacts under these conditions is unclear. Using in vivo imaging of neurons and microglia in awake mice, we report here the functional consequences of microglia-synapse contacts. Direct contact between a microglial process and a single synapse results in a specific increase in the activity of that contacted synapse, and a corresponding increase in back-propagating action potentials along the parent dendrite. This increase in activity is not seen for microglia-synapse contacts when microglia are activated by chronic lipopolysaccharide (LPS) treatment. To probe how this microglia-synapse contact affects neural circuits, we imaged across larger populations of motor cortical neurons. When microglia were again activated by LPS (or partially ablated), there was a decrease in the extent to which neuronal activity was synchronized. Together, our results demonstrate that interactions between physiological or resting microglia and synapses in the mature, healthy brain leads to an increase in neuronal activity and thereby helps to synchronize local populations of neurons. Our novel findings provide a plausible physical basis for understanding how alterations in immune status may impact on neural circuit plasticity and on cognitive behaviors such as learning.