Self-assembly of Ni(II) with a chiral ligand pair vs. mixture of the chiral ligand pair: structural features and recognition ability of Ni2L4 cages.

The self-assembly of NiCl2 with a chiral bidentate ligand pair, (1R,2S)-(+)- and (1S,2R)-(-)-1-(nicotinamido)-2,3-dihydro-1H-inden-2-yl nicotinate (r,s-L and s,r-L) in a mixture of ethanol and dioxane, gives rise to stable crystals consisting of [2Cl@Ni2Cl2(s,r-L)4(H2O)2]·4C4H8O2·EtOH and [2Cl@Ni2Cl2(r,s-L)4(H2O)2]·4C4H8O2·EtOH chiral cages, respectively, with two encapsulated chloride anions in the cavities. The most interesting feature is that the self-assembly of NiCl2 with the mixture of r,s-L and s,r-L (1 : 1-1 : 4) produces crystals of thermodynamically stable achiral cages, [2Cl·2H2O@Ni2Cl2(s,r-L)2(r,s-L)2(H2O)2]·7C4H8O2, in the molar ratio range. Furthermore, the [2Cl@Ni2Cl2(s,r-L)4(H2O)2]·4C4H8O2·EtOH and [2Cl@Ni2Cl2(r,s-L)4(H2O)2]·4C4H8O2·EtOH chiral crystals can recognize the pairs of L-,D-tryptophan and L-,D-cysteine via cyclic voltammetry (CV) signals, in contrast to the [2Cl·2H2O@Ni2Cl2(s,r-L)2(r,s-L)2(H2O)2]·7C4H8O2 achiral crystal.

Association of immunotoxicological indices with lung cancer biomarkers in poultry, grape, and rose farming workers.

Exposure to occupational hazards like dust, pesticides, diesel emission particles, or physical hazards in the agricultural sector is known to cause adverse health effects on farm workers. Our study aimed at addressing the association of immunomodulatory status with plasma levels of lung cancer biomarkers in farming population, attempting to recognition of vulnerable farming group. Blood samples from apparently healthy 51 chicken husbandry, 19 grape orchard, and 21 rose greenhouse workers were subjected to evaluate plasma levels of two representative lung cancer biomarkers, pro-gastrin releasing peptide (Pro-GRP) and cytokeratin fragment 19 (CYFRA 21-1). Peripheral blood mononuclear cells obtained from farmers were used for natural killer (NK) cell phenotyping and cytokines (interferon-gamma, IFN-γ and interleukin-13, IL-13) profiling in the culture supernatant. Compared to the rose greenhouse farmers, the grape orchard and chicken husbandry workers revealed a significantly upregulated plasma Pro-GRP and CYFRA 21-1 level. A low proportion of NK cells was observed among the female grape orchard workers and a lowered IFN- γ:IL-13 ratio was seen in the grape and chicken husbandry workers than the rose workers. Our findings imply that grape orchard and chicken husbandry workers have more disturbed immune homeostasis implicated with augmentation in the levels of lung cancer biomarkers than the rose greenhouse workers.

Formation Process of SiF6@Cu2L4 Chiral Cage Pairs in a Glass Vessel: Catechol Oxidation Catalysis and Chiral Recognition.

Self-assembly of CuX2 (X- = BF4-, PF6-, and SbF6-) with a pair of chiral bidentate ligands, (1R,2S)-(+)- and (1S,2R)-(-)-1-(nicotinamido)-2,3-dihydro-1H-inden-2-yl-nicotinate (r,s-L or s,r-L), in a mixture solvent including ethanol in a glass vessel gives rise to SiF62--encapsulated Cu2L4 chiral cage products. The SiF62- anion from the reaction of X- with SiO2 of the glass-vessel surface acts as a cage template or cage bridge. One of the products, [SiF6@Cu2(SiF6)(s,r-L)4]·3CHCl3·4EtOH, is one of the most effective heterogeneous catalysts for the oxidation of 3,5-di-tert-butylcatechol. Furthermore, an l-DOPA/d-DOPA pair is recognizable by the cyclic voltammetry (CV) signals of its combination with chiral cages [SiF6@Cu2(BF4)2(s,r- or r,s-L)4]·4CHCl3·2EtOH pair and [SiF6@Cu2(SiF6)(s,r- or r,s-L)4]·3CHCl3·4EtOH pair.

Dopamine and serotonin alterations by Hizikia fusiformis extracts under in vitro cortical primary neuronal cell cultures.

BACKGROUND/OBJECTIVES: Hizikia fusiformis (HF) is a class of brown seaweeds whose active ingredients exert central nervous system protective effects, such as neuroprotection; however, the underlying mechanisms remain unknown. Given that dopamine (DA) and serotonin (5HT) are two major neurotransmitters involved in various psychiatric disorders and neuronal growth in early neurodevelopmental processes, we investigated whether HF extract could modulate the molecular expression associated with DA and 5HT transmission as well as the structural formation of neurons. MATERIALS/METHODS: In vitro cell cultures were prepared from cerebral cortical neurons obtained from CD-1 mice on embryonic day 14. Cultured cells were treated with 0.1, 1.0, or 10.0 µg/mL of HT extract for 24 h, followed by fluorescence immunostaining for DA and 5HT-related receptors and transporters and some neuronal structural formation-associated molecules. RESULTS: HF extract dose-dependently upregulated the expression levels of selective DA and 5HT receptors, and downregulated the levels of DA and 5HT transporters. Moreover, HF extract increased the neurofilament light chain expression. CONCLUSION: These results suggest that HF may modulate DA and 5HT transmission, thereby affecting neurodevelopment.

Insight into systematic formation of hexafluorosilicate during crystallization via self-assembly in a glass vessel.

Formation of the unexpected hexafluorosilicate (SiF6 2-) anion during crystallization via self-assembly in glassware is scrutinized. Self-assembly of M(BF4)2 (M2+ = Cu2+ and Zn2+) with tridentate N-donors (L) in a mixture solvent including methanol in a glass vessel gives rise to an SiF6 2--encapsulated Cu3L4 double-decker cage and a Zn2L4 cage, respectively. Induced reaction of CuX2 (X- = PF6 - and SbF6 -) instead of Cu(BF4)2, with the tridentate ligands, produces the same species. The formation time of SiF6 2- is in the order of anions BF4 - < PF6 - < SbF6 - under the given reaction conditions. The SiF6 2- anion, acting as a cage template or cage-to-cage bridge, seems to be formed from the reaction of polyatomic anions containing fluoride with the SiO2 of the surface of the glass vessel.

Hygroscopic ramie fabrics for recovering highly viscous low sulfur fuel oil.

Low sulfur fuel oils (LSFOs) with less than 0.5% sulfur content have been mandated for marine vessels by the International Maritime Organization since 2020. However, owing to the low dispersibility and high viscosity of LSFOs, their oceanic spills are difficult to clean using conventional response systems. In this study, we propose a superhydrophilic and hygroscopic ramie to clean spilled LSFO. To this end, a raw ramie fiber, which is intrinsically hydrophobic, was treated using a mild alkali to remove its waxy, rough, and gummy veneer and reveal a smooth surface. This substantially improved its hygroscopic nature, superhydrophilicity, and water-retention, while preserving its mechanical durability in dry and wet environments. The hygroscopic ramie exhibited underwater superoleophobicity and self-cleaning abilities against highly adhesive LSFOs. Two proofs-of-concept are demonstrated in this study-an oil-proof glove for maximizing oil repellency and a direct oil-scooping device for simple and continuous recovery of spilled oil with high efficiency.

Pair of chiral 2D silver(I) enantiomers: chiral recognition of L- and D-histidine via differential pulse voltammetry.

Self-assembly of AgPF6 with a pair of chiral tridentate ligands (1S,1'S,1''S,2R,2'R,2''R) and (1R,1'R,1''R,2S,2'S,2''S)-(benzenetricarbonyltris(azanediyl))tris(2,3-dihydro-1H-indene-2,1-diyl)triisonicotinate (s,r-L) and (r,s-L) in a mixture of methanol and dioxane yields 2D sheets consisting of [Ag(s,r-L)](PF6)·3C4H8O2·0.5H2O and [Ag(r,s-L)](PF6)·3C4H8O2·0.5H2O, respectively. The differential pulse voltammetric (DPV) technique using the pair of chiral 2D-sheet enantiomers was employed for chiral discrimination of amino acid enantiomers, and was found to be an effective tool for enantio-recognition of L- and D-histidines. Both the size and the binding site of amino acids were strongly dependent on electrochemical enantio-recognition via the chiral 2D sheets.

Slippery, Water-Infused Membrane with Grooved Nanotrichomes for Lubricating-Induced Oil Repellency.

Water, abundant and ubiquitous in nature, is an easy yet powerful resource for the creatures to survive by putting together with their topologies interfacing their living environment. Here, a slippery, water-infusing surface (SWIS) that retains a thick and stable water layer on the membrane is presented, robustly maintaining the oil repellency against the pressure and friction of immiscible liquids. Inspired by the plant trichome structures and their function, grooved nanotrichome, formed on the fibrous membrane by the oxygen plasma etching, induces robust water lubrication on the SWIS. SWIS membrane repels and separates highly viscous and adhesive oils in air and underwater by preventing oils from adhering to the lubricating surface. Repeated tests both in air and underwater confirm the antiadhesion and self-cleaning properties of the SWIS. The SWIS oil scooper, fixed on a frame with a handle, successfully collects spilled oil on a pilot-scale oil spill site and a real ocean oil spill site by simply scooping and recovering the oil. In addition, SWIS membrane is expected to help protect environments with further applications such as oil-wastewater treatment and oil separation in food.

Assessing personal protective equipment needs for healthcare workers.

BACKGROUND: Personal protective equipment (PPE) is critical for healthcare workers (HCWs) since it acts as a barrier to infection transmission; however, current PPE is not ideally suited to their needs due to limitations in protection and comfort. Thus, the purpose of this study was to identify major issues of current PPE for body protection and assess its needs within health care. METHODS: An online survey was conducted with a convenience sample of 200 U.S. healthcare professionals who interact with patients. The survey was designed to identify the types of PPE that HCWs currently use, assess current PPE design features for body protection, examine the effect of PPE design features for body protection, and HCWs' years of work experiences on overall PPE acceptability, and explore current PPE maintenance practices. Both quantitative and qualitative data were used for analyses. RESULTS: This study showed the need for current PPE improvement in terms of fit, comfort, mobility, and donning and doffing for HCWs' safety and health. Donning and doffing plays an important role in HCWs' overall acceptance of PPE for body protection. This study revealed that most HCWs dispose of their PPE in a trashcan in a healthcare unit and non-disposed PPE is laundered at home, which may expose their family members to a health risk if a proper precaution is not followed. CONCLUSION: This study provides critical insights for the needs of (a) novel PPE design research and (b) proper donning and doffing training and its strict regulatory effort to ensure HCWs' safety and health.

The Habenula in the Link Between ADHD and Mood Disorder.

Attention-deficit/hyperactivity disorder (ADHD) is a childhood-onset, neurodevelopmental disorder, whereas major depressive disorder (MDD) is a mood disorder that typically emerges in adulthood. Accumulating evidence suggests that these seemingly unrelated psychiatric disorders, whose symptoms even appear antithetical [e.g., psychomotor retardation in depression vs. hyperactivity (psychomotor acceleration) in ADHD], are in fact associated with each other. Thus, individuals with ADHD exhibit high comorbidity with MDD later in life. Moreover, genetic studies have shown substantial overlaps of susceptibility genes between ADHD and MDD. Here, we propose a novel and testable hypothesis that the habenula, the epithalamic brain region important for the regulation of monoamine transmission, may be involved in both ADHD and MDD. The hypothesis suggests that an initially hypoactive habenula during childhood in individuals with ADHD may undergo compensatory changes during development, priming the habenula to be hyperactive in response to stress exposure and thereby increasing vulnerability to MDD in adulthood. Moreover, we propose a new perspective on habenular deficits in psychiatric disorders that consider the habenula a neural substrate that could explain multiple psychiatric disorders.

Cognitive and Affective Processes Associated with Social Biases.

BACKGROUND: Our social activities are quite often erroneous and irrational, based on biased judgements and decision-making, known as social biases. However, the cognitive and affective processes that produce such biases remain largely unknown. In this study, we investigated associations between social schemas, such as social judgment and conformity, entailing social biases and psychological measurements relevant to cognitive and affective functions. METHOD: This study recruited 42 healthy adult subjects. A psychological test and a questionnaire were administered to assess biased social judgements by superficial attributes and social conformity by adherence to social norms, respectively, along with additional questionnaires and psychological tests for cognitive and affective measurements, including negative affects, autistic traits, and Theory of Mind (ToM). Associations of social judgment and conformity with cognitive and affective functions were examined using a multiple regression analysis and structural equation modeling. RESULTS: Anxiety and the cognitive realm of ToM were mutually associated with both social judgments and conformity, although social judgements and conformity were still independent processes. Social judgements were also associated with autistic traits and the affective realm of ToM, whereas social conformity was associated with negative affects other than anxiety and an intuitive decision-making style. CONCLUSIONS: These results suggest that ToM and negative affects may play important roles in social judgements and conformity, and the social biases connoted in these social schemas.

Imbalance between dopamine and serotonin caused by neonatal habenula lesion.

Alterations in dopamine (DA) and serotonin (5-HT) transmission have been implicated in the pathophysiology of attention deficit/hyperactivity disorder (ADHD). We have previously reported that juvenile rats with neonatal habenula lesion (NHL) exhibit an assortment of behavioral alterations resembling ADHD symptoms. In this study, we investigated the impacts of NHL on DA and 5-HT transmission in mesocorticolimbic regions of rats. Male Sprague-Dawley rats with microinjection of ibotenic acid into the habenula at postnatal day (PND) 7 were subjected for a battery of locomotion test, object exploration test and delay discounting test in the juvenile period (PND28-35), followed by DA and 5-HT brain tissue concentration measurements using high-performance liquid chromatography (HPLC). NHL rats exhibited hyperlocomotion, impulsivity, and attention deficits. NHL induced alterations of tissue DA and 5-HT concentrations only in some mesocorticolimbic regions. However, positive correlations, indicating the balance, between DA and 5-HT observed in control (CTR) rats, were more extensively disrupted across mesocorticolimbic regions in NHL rats. Pharmacological manipulations that modulated both DA and 5-HT systems simultaneously with Astragalus membranaceus (AM) and its active compound formononetin (FOR) normalized the NHL-induced DA and 5-HT imbalance in several brain areas, which consequently improved the behavioral alterations. These results suggest that behavioral alterations caused by NHL may be associated with mesocorticolimbic DA/5-HT imbalance. Drug treatments targeting multiple monoamine systems may be useful to improve the NHL-induced changes.

Alterations of amygdala-prefrontal cortical coupling and attention deficit/hyperactivity disorder-like behaviors induced by neonatal habenula lesion: normalization by Ecklonia stolonifera extract and its active compound fucosterol.

Alterations of monoamine transmission in mesocorticolimbic regions have been suggested in the pathophysiology of attention deficit/hyperactivity disorder (ADHD). The habenula is an important brain area in regulation of monoamine transmission. In this study, we investigated behavioral and electrophysiological alterations induced by neonatal habenula lesion (NHL) in rats. In NHL rats, age-dependent behavioral alterations relevant to the ADHD symptoms, such as hyperlocomotion, impulsivity, and attention deficit, were observed. Local field potentials (LFPs) in mesocorticolimbic regions of anesthetized rats were examined with in vivo electrophysiological recordings. Abnormally enhanced synchronization of slow (delta) and fast (gamma) LFP oscillations between the amygdala (AMY) and prefrontal cortex (PFC) was found in juvenile, but not in adult, NHL rats. We further examined the effects of an extract and the active compound from the perennial large brown algae Ecklonia stolonifera (ES), which have previously been demonstrated to modulate monoamine transmission, on these NHL-induced alterations. One week of ES extract treatments normalized the NHL-induced behavioral alterations, whereas the active compound fucosterol improved attention deficit and impulsivity, but not hyperlocomotion, in NHL rats. Consistent with the behavioral effects, ES extract treatments also normalized augmented AMY-PFC coupling. These results suggest that altered limbic-cortical information processing may be involved in ADHD-like behavioral alterations induced by NHL, which could be ameliorated by the natural substance, such as ES that affects monoamine transmission.

Direct recovery of spilled oil using hierarchically porous oil scoop with capillary-induced anti-oil-fouling.

The pitcher plant has evolved its hierarchically grooved peristome to enhance a water-based slippery system for capturing insects with oil-covered footpads. Based on this, we proposed a hierarchically porous oil scoop (HPOS) with capillary-induced oil peel-off ability for repeatable spilled oil recovery. As the HPOS scoops oil-water mixture, water passes through the hole while the oil is confined within a curved geometry. The filter in HPOS has three levels of porous structures; (1) 3D-printed mesh structure with sub-millimeter scale hole to filter out oil from an oil-water mixture, (2) internal micropore in fibers enhancing capillarity and water transport, (3) O2 plasma-induced high-aspect-ratio nanopillar structures imposing anti-oil-fouling property with capillary-induced oil peeling. As the oil-contaminated HPOS makes contact with water, water meniscus rises and peels off the oil immediately at the air-water interface. The oil-peel-off ability of the HPOS would prevent pores from clogging by oils for reuse. The study demonstrated that the HPOS recovers highly viscous oil (up to 5000 mm2·s-1) with a high recovery rate (>95%), leaving the filtered water with low oil content (<10 ppm), which satisfies the discharge criterion of 15 ppm.

Flexibility and anion exchange of [(X)@Pd2L4] cages for recognition of size and charge of polyatomic anions.

The self-assembly of Pd(NO3)2 with L (L = 1,2-bis(dimethyl(pyridin-3-yl)silyl)ethane) gives rise to [PdL2](NO3)2 in high yields. Anion exchange of [PdL2](NO3)2 with X- (X- = BF4-, ClO4-, and PF6-) changes the skeleton into a cage of [(X)@Pd2L4](X)3. Successive anion exchange of [(X)@Pd2L4](X)3 (X- = BF4-, ClO4-, and PF6-) with X- (X- = ReO4- and SiF62-) produces [(ReO4)@Pd2L4](ReO4)3 and [(SiF6)@Pd2L4](SiF6), respectively, irrespective of anion charge. The flexible nature and conformation of cages are significantly dependent on the nestled polyatomic anions. Thus, this system can be used as a molecular recognizer of the size and charge of ubiquitous polyatomic anions.

Beneficial effect of black rice ( Oryza sativa L. var. japonica ) extract on amyloid ß-induced cognitive dysfunction in a mouse model.

Alzheimer's disease (AD) is an age-dependent progressive neurodegenerative disease, resulting in memory loss and cognitive dysfunction. The accumulation of amyloid ß (Aß) has been identified as the most important risk factor for AD. Black rice (BR; Oryza sativa L. var. japonica), which is widely consumed in Asia, is a good source of bioactive compounds including anthocyanins. Therefore, the aim of the present study was to evaluate the protective effect of BR extracts against Aß25-35-induced memory impairment in an in vivo AD mouse model. After intracerebroventricular injection of Aß25-35, mice were treated with BR extract supplementation for 14 days. Memory and cognition function were evaluated over this period in both treated and untreated animals using T-maze, novel object recognition and Morris water maze tests. After behavioral tests, malondialdehyde (MDA) and nitric oxide (NO) concentrations in brain, liver and kidney tissues were analyzed. Mice treated with Aß25-35 had impaired memory and cognitive function; however, mice administered BR extract (100 mg/kg/day) demonstrated an improvement in cognition and memory function compared with the Aß25-35-injected control group. Furthermore, injection of Aß25-35 significantly increased MDA and NO generation in the brain, liver and kidney of mice. However, the group administered with BR extract had significantly inhibited lipid peroxidation and NO generation in the brain, liver and kidney. In addition, the protective effect of BR on lipid peroxidation and NO production by Aß25-35 was stronger in the brain compared with other tissues. Collectively, these findings suggested that BR supplementation may prevent memory and cognition deficits caused by Aß25-35-induced oxidative stress.

Monoamine and genome-wide DNA methylation investigation in behavioral addiction.

Behavioral addiction (BA) is characterized by repeated, impulsive and compulsive seeking of specific behaviors, even with consequent negative outcomes. In drug addiction, alterations in biological mechanisms, such as monoamines and epigenetic processes, have been suggested, whereas whether such mechanisms are also altered in BA remains unknown. In this preliminary study with a small sample size, we investigated monoamine concentrations and genome-wide DNA methylation in blood samples from BA patients and control (CT) subjects. Higher dopamine (DA) metabolites and the ratio between DA and its metabolites were observed in the BA group than in the CT group, suggesting increased DA turnover in BA. In the methylation assay, 186 hyper- or hypomethylated CpGs were identified in the BA group compared to the CT group, of which 64 CpGs were further identified to correlate with methylation status in brain tissues with database search. Genes identified with hyper- or hypomethylation were not directly associated with DA transmission, but with cell membrane trafficking and the immune system. Some of the genes were also associated with psychiatric disorders, such as drug addiction, schizophrenia, and autism spectrum disorder. These results suggest that BA may involve alterations in epigenetic regulation of the genes associated with synaptic transmission, including that of monoamines, and neurodevelopment.

Concurrent and Delayed Behavioral and Monoamine Alterations by Excessive Sucrose Intake in Juvenile Mice.

Our daily diet in the modern society has substantially changed from that in the ancient past. Consequently, new disorders associated with such dietary changes have emerged. For instance, excessive intake of compounds, such as sucrose (SUC), has recently been reported to induce pathological neuronal changes in adults, such as food addiction. It is still largely unclear whether and how excessive intake of such nutrients affects neurodevelopment. We investigated changes in behavior and monoamine signaling caused by excessive, semi-chronic intake of SUC and the non-caloric sweetener saccharin (SAC) in juvenile mice, using a battery of behavioral tests and high-performance liquid chromatography. Both SUC and SAC intake induced behavioral alterations such as altered amphetamine responses, sucrose preference, stress response, and anxiety, but did not affect social behavior and cognitive function such as attention in juvenile and adult mice. Moreover, SUC and SAC also altered dopamine and serotonin transmission in mesocorticolimbic regions. Some of these behavioral and neural alterations were triggered by SAC and SUC but others were distinct between the treatments. Moreover, alterations induced in juvenile mice were also different from those observed in adult mice. These results suggest that excessive SUC and SAC intake during the juvenile period may cause concurrent and delayed behavioral and monoamine signaling alterations in juvenile and adult mice, respectively.

Subwavelength Hollow-Nanopillared Glass with Gradient Refractive Index for Ultralow Diffuse Reflectance and Antifogging.

Nanostructured glass with subwavelength hollow nanopillars of diameters of sub-65 nm was fabricated, showing high optical transmittance and ultralow diffuse reflectance. A simple process involving single-step plasma etching was used on a glass slide coated with a SiO2 sacrificial film. First, SiO2 nanodot structures were formed using plasma-induced anisotropic etching with CF4 plasma. The SiO2 nanodot array then became a secondary etching mask to form hollow nanopillars on the glass. The hollow structures formed at the upper part reaching up to the apex of the nanopillar had a lower solid fraction, while the lower part had a higher fraction. The refractive index (RI) gradually increased from 1.09 (near the value for air) to 1.42 (near the value for glass). Geometry-induced RI gradient enhanced light transmi, while it significantly reduced diffuse reflectance, particularly in the shorter wavelengths, thus suppressing the haziness or milky appearance of the nanostructured glass. Superhydrophilic and antifogging properties of nanostructured glasses and dental mirrored glasses were also demonstrated with water spraying and exhaled breath tests. Results showed that the wettability was enhanced in hydrophilicity and antifogging property by both the hydrophilic nature of the glass and the newly formed nanostructures. The nanostructured, superhydrophilic glass was also found to have easy cleaning nature against fine sand dust adhesion by simply blowing air or spraying water. Results of this study showed that such a hollow-pillared glass surface with gradient RI and special wettability could be applied in a variety of optical and optoelectronic applications requiring superwetting, such as optical windows for solar cell panels, display panels, light-emitting diodes, and medical devices even with curved surfaces.

Atypical Social Rank Recognition in Autism Spectrum Disorder.

Social animals, including humans, structure social groups where social hierarchy exists. Recognizing social rank of other group members is a crucial ability to subsist in such environments. Here we show preliminary evidence with a relatively small number of samples that children with autism spectrum disorder, a neurodevelopmental disorder involving social dysfunction, exhibit atypical, and more robust recognition of social rank than normal children, which may be developed to compensate deficits of the neural systems processing social information.