M(II) effect on encapsulation of guests into a series of M3L2 chiral cages: enantio-recognition.

Self-assembly of M(ClO4)2 (M2+ = Ni2+, Cu2+, and Zn2+) with (1S,1'S,1''S,2R,2'R,2''R)-(benzenetricarbonyltris(azanediyl))tris(2,3-dihydro-1H-indene-2,1-diyl) trinicotinate (s,r-L) and the corresponding enantiomer (r,s-L) as a pair of chiral tridentate donors gives rise to the chiral cage pairs [M3(s,r- and r,s-L)2](ClO4)6. For the two pairs of [(Me2CO)(H2O)@M3(r,-s and s,r-L)2](ClO4)6 (M2+ = Ni2+ and Zn2+), the inner cavity is occupied by both an acetone and a single water molecule, whereas for the copper(II) pair of [Me2CO@Cu3(r,s- and s,r-L)2](ClO4)6 under the same conditions, the cavity is filled by only one acetone molecule. Thus, the encapsulation of guest molecules into the cages during self-assembly shows significant metal(II) ion effects. These chiral cages are effective for the enantio-recognition of chiral (S)-2-butanol and (R)-2-butanol via the shifts of the electrochemical oxidation potentials obtained by the linear sweep voltammetry (LSV) technique, density functional theory (DFT) calculations, and the chiral 2-butanol adsorption in the single-crystal-to-single-crystal (SCSC) mode.

Correlations in abnormal synergies between the upper and lower extremities across various phases of stroke.

BACKGROUND AND OBJECTIVES: The flexion synergy and extension synergy are a representative consequence of a stroke and appear in the upper extremity and lower extremity. Since the ipsilesional corticospinal tract (CST) is the most influential neural pathway for both extremities in motor execution, damage by a stroke to this tract could lead to similar motor pathological features (e.g., abnormal synergies) in both extremities. However, less attention has been paid to the inter-limb correlations in the flexion synergy and extension synergy across different recovery phases of a stroke. METHODS: We used results of the Fugl-Meyer assessment (FMA) to characterize those correlations in a total of 512 participants with hemiparesis post stroke from the acute phase to 1 year. The FMA provides indirect indicators of the degrees of the flexion synergy and extension synergy post stroke. RESULTS: We found that generally, strong inter-limb correlations (r>0.65 with all p-values<0.0001) between the flexion synergy and extension synergy appeared in the acute-to-subacute phase (<90 days). But correlations of lower-extremity extension synergy with upper-extremity flexion synergy and extension synergy decreased (down to r=0.38) around 360 days after stroke (p<0.05). DISCUSSION: These results suggest that preferential use of alternative neural pathways after damage by a stroke to the CST enhances inter-limb correlations between the flexion synergy and extension but a recovery of the CST functional and the fragmentation (remodeling) of the alternative neural substrates in the chronic phase contribute to diversity in neural pathways in motor execution, eventually leading to reduced inter-limb correlations.

Embryonic development through in vitro fertilization using high-quality bovine sperm separated in a biomimetic cervix environment.

This study is the first to identify bovine blastocysts through in vitro fertilization (IVF) of matured oocytes with a large quantity of high-quality sperm separated from a biomimetic cervix environment. We obtained high-quality sperm in large quantities using an IVF sperm sorting chip (SSC), which could mimic the viscous environment of the bovine cervix during ovulation and facilitates isolation of progressively motile sperm from semen. The viscous environment-on-a-chip was realized by formulating and implementing polyvinylpyrrolidone (PVP)-based solutions for the SSC medium. Sperm separated from the IVF-SSC containing PVP 1.5% showed high motility, normal morphology and high DNA integrity. As a result of IVF, a higher rate of hatching blastocysts, which is the pre-implantation stage, were observed, compared to the conventional swim-up method. Our results may significantly contribute to improving livestock with superior male and female genetic traits, thus overcoming the limitation of artificial insemination based on the superior genetic traits of existing males.

Coordinating nature of M6L12 double-stranded macrocycles: co-ligand competition of perchlorate, water, and acetonitrile depending on metal(II) ions.

Self-assembly of M(ClO4)2 (M(II) = Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)) with dicyclopentyldi(pyridine-3-yl)silane (L) as a donor in a mixture of acetonitrile and toluene produces crystals consisting of M6L12 double-stranded macrocycles. The geometry around the M(II) cations is a typical octahedral arrangement, but the metallamacrocycles' outer axial coordination environment is sensitive to the M(II) cations. The conformation of the unique metallamacrocycles is informatively dependent on the nature of the coordination around the M(II) cations via subtle co-ligand competition among perchlorate anions, water, and acetonitrile. Both the coordinated acetonitriles and the solvate molecules of the crystals are removed at 170 °C, thereby transforming the crystals into new crystals that return to their original form in the mixture of toluene and acetonitrile. Catalytic oxidation of 3,5-di-tert-butylcatechol using [Cu6(ClO4)8(CH3CN)4L12]4ClO4·5C7H8 is much faster than those using the transformed product, [Cu(ClO4)2L2], and a simple mixture of Cu(ClO4)2 + L.

Evidence of the existence of multiple modules for the stroke-caused flexion synergy from Fugl-Meyer assessment scores.

Stroke-caused synergies may result from preferential use of the reticulospinal tract (RST) due to damage to the corticospinal tract. The RST branches multiple motoneuron pools across the arm together resulting in gross motor control or muscle synergies, and accordingly the controllability of individual muscles is reduced. It is not clear whether the muscles involuntarily activated by abnormal synergy vary with the muscles voluntarily activated when motor commands descend through the RST. Studies showed that abnormal synergies may originate from merging and re-weighting of synergies individuals without neurological deficit. This leads to a hypothesis that those abnormal synergies are still selectively excited depending on the context. In this study, we test this hypothesis, leveraging the Fugl-Meyer assessment (FMA) that could characterize the neuroanatomical architecture in individuals with a wide range of impairment. We examine the ability to perform an out-of-synergy movement with the flexion synergy caused by either shoulder or elbow loading. The results reveal that about 14% (8/57, 95%CI: [5.0%, 23.1%]) of the participants with severe impairment (total FM score <29) in the chronic phase (6 months after stroke) are able to keep the elbow extended during shoulder loading and keep the shoulder at neutral during elbow loading. Those participants undergo a different course of neural reorganization which enhanced abnormal synergies in comparison with individuals with mild impairment (p<0.05). These results evidence that separate routes and synergy modules to motoneuron pools across the arm might exist even if the motor command is mediated possibly via the RST.

Non-flammable Gel Polymer Electrolyte for Enhancing the Safety and High-Temperature Performance of Lithium-Ion Batteries.

As the applications of lithium-ion batteries (LIBs) have expanded, battery safety has emerged as a major concern because of the thermal runaway of LIBs arising from the use of flammable liquid electrolytes (LEs). Gel polymer electrolytes (GPEs) have been considered as potential candidates to replace LEs and improve the thermal safety of LIBs. In our study, a chemically cross-linked nonflammable GPE was synthesized and used in an LIB. A cross-linking agent, spirocyclic pentaerythritol diphosphate perfluorinated ether acrylate, comprising a phosphorus moiety and a fluoroether chain, was designed and synthesized to prepare a nonflammable cross-linked GPE. The obtained GPE effectively suppressed the deleterious reactions of the LE and imparted nonflammable characteristics. The pouch-type graphite/LiNi0.6Co0.2Mn0.2O2 cell with a nonflammable GPE delivered an initial discharge capacity of 146.7 mAh g-1 with a capacity retention of 71.1% after 300 cycles at 0.5 C and 55 °C. Moreover, the chemically cross-linked GPE exhibited excellent dimensional and thermal stability, which allowed for the safer operation of LIBs even under harsh conditions. This work provides guidelines for designing nonflammable electrolyte systems for advanced LIBs with high safety, enhanced thermal stability, and good cycling characteristics at elevated temperatures.

Interactions in abnormal synergies between the upper and lower extremities in various phases of stroke: A cohort study.

Objective: The flexion synergy and extension synergy are a representative consequence of a stroke and appear in the upper extremity and lower extremity. Since the ipsilesional corticospinal tract (CST) is the most influential neural pathway for both extremities in motor execution, damage by a stroke to this tract could lead to similar motor pathological features (e.g., abnormal synergies) in both extremities. However less attention has been paid to the inter-limb correlations in the flexion synergy and extension synergy across different recovery phases of a stroke. Methods: In this study, we used results of the Fugl-Meyer assessment (FMA) to characterize those correlations in a total of 512 participants with hemiparesis post stroke from the acute phase to 1 year. The FMA provides indirect indicators of the degrees of the flexion synergy and extension synergy post stroke. Results: We found that generally, strong inter-limb correlations (r>0.65 with all p-values<0.0001) between the flexion synergy and extension synergy appeared in the acute-to-subacute phase (<90 days). But correlations of lower-extremity extension synergy with upper-extremity flexion synergy and extension synergy decreased (down to r=0.38) around 360 days after stroke (p<0.05). Interpretation: These results suggest that the preferential use of alternative neural pathways after damage by a stroke to the CST enhances inter-limb correlations between the flexion synergy and extension, however a recovery of the CST or/and the functional fragmentation (remodeling) of the alternative neural substrates in the chronic phase contribute to diversity in neural pathways in motor execution, eventually leading to reduced inter-limb correlations.

Lagerstroemia macrocarpa extract inhibits Th2-mediated STAT6 signaling pathway in human keratinocytes.

In this study, we examined physiological functions as a key material to develop cosmeceuticals using extracts of Lagerstroemia macrocarpa Wall. Ex Kurz (L. macrocarpa). Initially, the L. macrocarpa extract was treated by different concentration and antioxidant assay (DPPH and ABTS) were performed to measure free radical scavenging ability. In the cytotoxicity experiment, the extract was treated into human epidermal keratinocytes with different concentrations to measure cytotoxicity. We found that the extract induces differentiation markers such as keratin (KRT)1, KRT2, KRT9, KRT10 in keratinocytes. Furthermore, the extract significantly induces involucrin (IVL), loricrin (LOR), claudin1 (CLDN1), and filaggrin (FLG) expression, suggesting that it may enhance skin barrier functions. Especially, the extract restored FLG expression inhibited by interleukin (IL)-4/IL-13 in in vitro atopic dermatitis-like model. Therefore, we expect L. macrocarpa extract will be an effective material to develop the therapeutic and cosmeceutical of atopic dermatitis.

Exploring the Cathode Active Materials for Sulfide-Based All-Solid-State Lithium Batteries with High Energy Density.

All-solid-state lithium batteries (ASSLBs) are considered promising alternatives to current lithium-ion batteries that employ liquid electrolytes due to their high energy density and enhanced safety. Among various types of solid electrolytes, sulfide-based electrolytes are being actively studied, because they exhibit high ionic conductivity and high ductility, which enable good interfacial contacts in solid electrolytes without sintering at high temperatures. To improve the energy density of the sulfide-based ASSLBs, it is essential to increase the loading of active material in the composite cathode. In this study, the Ni-rich LiNix Coy Mn1-x-y O2 (NCM) materials are explored with different Ni content, particle size, and crystalline form to probe suitable cathode active materials for high-performance ASSLBs with high energy density. The results reveal that single-crystalline LiNi0.82 Co0.10 Mn0.08 O2 material with a small particle size exhibits the best cycling performance in the ASSLB assembled with a high mass loaded cathode (active mass loading: 26 mg cm-2 , areal capacity: 5.0 mAh cm-2 ) in terms of discharge capacity, capacity retention, and rate capability.

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.

Crystals of Ni6L12 Ellipsoidal Tubes as Single-Crystal-to-Single-Crystal Adsorption Matrix: Penetrative Study of Self-Assembled Crystals vs Guest-Exchanged Crystals.

Informative similarities/differences between self-assembled and single-crystal-to-single-crystal (SCSC) guest-exchanged crystals based on both the molecular structure and adsorption nature are observed. The self-assembly of Ni(ClO4)2 with a dicyclopentyldi(pyridine-3-yl)silane bidentate ligand (L) in a mixture of toluene and acetonitrile gives rise to purple crystals consisting of double-stranded ellipsoidal tubes, [Ni6(ClO4)4(CH3CN)8L12]·8ClO4·4CH3CN·5C7H8. The coordinated acetonitriles as well as the solvates are removed at 170 °C to transform the purple crystals into blue crystals of [Ni(ClO4)2L2]n that return to the original crystals in the mixture of toluene and acetonitrile. Further, the toluene and acetonitrile solvates of the original crystals are replaced by o-, m-, and p-xylene isomers within 5 min in a SCSC manner. In the present study, SCSC xylene-exchanged crystals were compared with crystals obtained from direct self-assembly in a mixture of each xylene isomer and acetonitrile.

Clinical Significance of Radical Prostatectomy in Clinical Lymph Node Metastasis in Prostate Cancer.

BACKGROUND: This study aimed to investigate the role of radical prostatectomy (RP) among clinical nodal metastasis prostate cancer and whether histological confirmation of lymph node metastasis through surgery can help with treatment. PATIENTS AND METHODS: After excluding patients with distant metastatic prostate cancer or neoadjuvant androgen deprivation therapy, 42 patients with clinical nodal metastasis who underwent RP at our institution were included in the study. We classified them as having or not having pathological lymph node metastasis. Clinicopathologic data were analyzed in this retrospective chart review. Kaplan-Meier analysis was used to calculate the estimated castration-resistant prostate cancer (CRPC)-free survival, biochemical recurrence (BCR)-free survival, and cancer-specific survival (CSS). RESULTS: There is no significant difference in age, presence of diabetes mellitus, hypertension, BCR time, CRPC time, overall survival, salvage RT rate, and initial prostate-specific antigen level between the two groups. However, there is a significant difference in the pathology N1 group in terms of pathological T stage, pathologic Gleason score, BCR rate, CRPC rate, and CSS. A multivariate Cox proportional hazard regression analysis was used to identify predictors of CRPC-free survival. Patients with pathological lymph node metastasis had a shorter CRPC-free survival [hazard ratio (HR) 4.87; 95% confidence interval (CI) 1.25-19.00, p = 0.02]. CONCLUSION: Radical prostatectomy can confirm lymph node metastasis. Although pathologic diagnosis has no effect on time to BCR and CPRC, because it affects BCR rate, CRPC rate, and CSS, an accurate pathological diagnosis obtained through surgery is beneficial in the treatment of clinical lymph node metastasis prostate cancer.

Novel Quinazoline Derivative Induces Differentiation of Keratinocytes and Enhances Skin Barrier Functions against Th2 Cytokine-Mediated Signaling.

Atopic dermatitis (AD) is a common inflammatory skin disease characterized by pruritic lesions and skin barrier dysfunction. In this study, we evaluated the effect of a quinazoline derivative, SH-340, on TSLP expression and signaling in human primary keratinocytes. Our results demonstrated that SH-340 significantly increased factors for differentiation and skin barrier function including KRT1, KRT2, KRT10, IVL, LOR, CLDN1, OVOL1, and FLG, whereas it inhibited TSLP expression in a dose-dependent manner, both at the mRNA and protein levels. Furthermore, SH-340 was found to inhibit the phosphorylation of STAT6, a downstream signaling molecule of IL-4 and IL-13, in keratinocytes. These findings suggest that SH-340 may suppress TSLP expression by inhibiting the IL-4/IL-13-STAT6 signaling pathway. Finally, SH-340 may potentially contribute to both the alleviation of inflammation and the restoration of skin barrier function.

Solid Hybrid Electrolyte Featuring a Vertically Aligned Li6.4La3.0Zr1.4Ta0.6O12 Membrane for All-Solid-State Lithium Batteries.

All-solid-state lithium batteries (ASSLBs) with enhanced safety are considered one of the most promising substitutes for liquid electrolyte-based Li-ion batteries. However, many properties of solid electrolytes, such as ionic conductivity, film formability, and electrochemical, mechanical, thermal, and interfacial stability need to be improved for their practical application. In this study, a vertically aligned Li6.4La3.0Zr1.4Ta0.6O12 (LLZO) membrane with finger-like microvoids was prepared using processes involving phase inversion and sintering. A hybrid electrolyte was then obtained by infusing the LLZO membrane with a solid polymer electrolyte based on poly(ε-caprolactone). The solid hybrid electrolyte (SHE) was a flexible thin film with high ionic conductivity, superior electrochemical stability, high Li+ transference number, enhanced thermal stability, and improved Li metal electrode-solid electrolyte interfacial stability. A solid-state Li/LiNi0.78Co0.10Mn0.12O2 cell assembled with the hybrid electrolyte exhibited good cycling performance, in terms of discharge capacity, cycling stability, and rate capability. Accordingly, the SHE using a vertically aligned LLZO membrane is a promising solid electrolyte for realizing safe, high-performance ASSLBs.

Honey Bee Colonies (Apis mellifera L.) Perform Orientation Defensiveness That Varies among Bred Lines.

Honey bees (Apis mellifera L.) express complex behavioral patterns (aggressiveness) in defensive mechanisms for their survival. Their phenotypic expression of defensive behavior is influenced by internal and external stimuli. Knowledge of this behavior has recently become increasingly important, though beekeepers are still faced with the challenges of selecting defensive and less-defensive bred lines. Field evaluation of defensive behavior among bred lines of honey bees is required to overcome the challenges. Chemical cues (alarm pheromone and isopentyl acetate mixed with paraffin oil) and physical and visual stimuli (dark leather suede, colony marbling, and suede jiggling) were used to evaluate defensiveness and orientation among five bred lines of honeybee colonies. Our results showed that both chemical assays recruited bees, but the time of recruitment was significantly faster for alarm pheromone. Honeybees' response to both assays culminated in stings that differed among bred lines for alarm pheromone and paraffin when colonies were marbled. Honeybee orientation defensiveness varied among bred lines and was higher in more defensive bred lines compared to less-defensive bred lines. Our findings suggest that it is crucial to repeatedly evaluate orientation defensiveness at the colony level and among bred lines when selecting breeding colonies.

Monitoring parameter change for bivariate time series models of counts.

In this study, we consider an online monitoring procedure to detect a parameter change for bivariate time series of counts, following bivariate integer-valued generalized autoregressive heteroscedastic (BIGARCH) and autoregressive (BINAR) models. To handle this problem, we employ the cumulative sum (CUSUM) process constructed from the (standardized) residuals obtained from those models. To attain control limits, we develop limit theorems for the proposed monitoring process. A simulation study and real data analysis are conducted to affirm the validity of the proposed method.

Pair of (Hg2II)3L2 Chiral Cages and Successive Transformation into (HgII)3L2 Chiral Cages: Chiral DOPA Recognition via Chiral Cages.

Self-assembly of Hg(ClO4)2 with a pair of C3-symmetric chiral ligands, (1S,1'S,1″S,2R,2'R,2″R)-(benzenetricarbonyltris(azanediyl))tris(2,3-dihydro-1H-indene-2,1-diyl)trinicotinate (s,r-L) and (1R,1'R,1″R,2S,2'S,2″S)-(benzenetricarbonyltris(azanediyl))tris(2,3-dihydro-1H-indene-2,1-diyl)trinicotinate (r,s-L), produces a pair of chiral cages C4H8O2@[(Hg2II)3(ClO4)6(s,r-L)2(H2O)7](C4H8O2)7 and C4H8O2@[(Hg2II)3(ClO4)6(r,s-L)2(H2O)7](C4H8O2)7, respectively, via straightforward formation of the reduced Hg2II species with an inner cavity in which a single dioxane molecule is nestled. The pair of chiral cages are transformed into their downsized pair of cages, [Hg3II(ClO4)6(s,r-L)2] and [Hg3II(ClO4)6(r,s-L)2], respectively, in the presence of hydrochloric acid. The original chiral cages are more effective than the corresponding downsized cages for enantiorecognition of chiral 3,4-dihydroxyphenylalanine (DOPA) via the shifts of electrochemical oxidation potentials observed by linear sweep voltammetry (LSV) technique. Furthermore, the photoluminescence (PL) spectral shifts show that the downsized chiral cages significantly recognize chiral DOPA.

MCP extensors respond faster than flexors in individuals with severe-to-moderate stroke-caused impairment: Evidence of uncoupled neural pathways.

Damage in the corticospinal system following stroke produces imbalance between flexors and extensors in the upper extremity, eventually leading to flexion-favored postures. The substitution of alternative tracts for the damaged corticospinal tract is known to excessively activate flexors of the fingers while the fingers are voluntarily being extended. Here, we questioned whether the cortical source or/and neural pathways of the flexors and extensors of the fingers are coupled and what factor of impairment influences finger movement. In this study, a total of seven male participants with severe-to-moderate impairment by a hemiplegic stroke conducted flexion and extension at the metacarpophalangeal (MCP) joints in response to auditory tones. We measured activation and de-activation delays of the flexor and extensor of the MCP joints on the paretic side, and force generation. All participants generated greater torque in the direction of flexion (p = 0.017). Regarding co-contraction, coupled activation of the extensor is also made during flexion in the similar way to coupled activation of the flexor made during extension. As opposite to our expectation, we observed that during extension, the extensor showed marginally significantly faster activation (p = 0.66) while it showed faster de-activation (p = 0.038), in comparison to activation and de-activation of the flexor during flexion. But movement smoothness was not affected by those factors. Our results imply that the cortical source and neural pathway for the extensors of the MCP joints are not coupled with those for the flexors of the MCP joints.

Ultrasensitive Ionic Liquid Polymer Composites with a Convex and Wrinkled Microstructure and Their Application as Wearable Pressure Sensors.

The development of pressure sensors with high sensitivity and effectiveness that exhibit linearity over a wide pressure range is crucial for wearable devices. In this study, we fabricated a novel ionic liquid (IL)/polymer composite with a convex and randomly wrinkled microstructure in a cost-effective and facile manner using an opaque glass and stretched polydimethylsiloxane template. The fabricated IL/polymer composite was used as the dielectric layer in a capacitive pressure sensor. The sensor exhibited a high linear sensitivity of 56.91 kPa-1 owing to the high interfacial capacitance formed by the electrical double layer of the IL/polymer composite over a relatively wide range (0-80 kPa). We also demonstrated the sensor performance for various applications such as a glove-attached sensor, sensor array, respiration monitoring mask, human pulse, blood pressure measurement, human motion detection, and a wide range of pressure sensing. It would be expected that the proposed pressure sensor has sufficient potential for use in wearable devices.