Anti-Metastatic Effects of Standardized Polysaccharide Fraction from Diospyros kaki Leaves via GSK3ß/ß-Catenin and JNK Inactivation in Human Colon Cancer Cells.

A polysaccharide fraction from Diospyros kaki (PLE0) leaves was previously reported to possess immunostimulatory, anti-osteoporotic, and TGF-ß1-induced epithelial-mesenchymal transition inhibitory activities. Although a few beneficial effects against colon cancer metastasis have been reported, we aimed to investigate the anti-metastatic activity of PLE0 and its underlying molecular mechanisms in HT-29 and HCT-116 human colon cancer cells. We conducted a wound-healing assay, invasion assay, qRT-PCR analysis, western blot analysis, gelatin zymography, luciferase assay, and small interfering RNA gene silencing in colon cancer cells. PLE0 concentration-dependently inhibited metastasis by suppressing cell migration and invasion. The suppression of N-cadherin and vimentin expression as well as upregulation of E-cadherin through the reduction of p-GSK3ß and ß-catenin levels resulted in the outcome of this effect. PLE0 also suppressed the expression and enzymatic activity of matrix metalloproteinases (MMP)-2 and MMP-9, while simultaneously increasing the protein and mRNA levels of the tissue inhibitor of metalloproteinases (TIMP-1). Furthermore, signaling data disclosed that PLE0 suppressed the transcriptional activity and phosphorylation of p65 (a subunit of NF-κB), as well as the phosphorylation of c-Jun and c-Fos (subunits of AP-1) pathway. PLE0 markedly suppressed JNK phosphorylation, and JNK knockdown significantly restored PLE0-regulated MMP-2/-9 and TIMP-1 expression. Collectively, our data indicate that PLE0 exerts an anti-metastatic effect in human colon cancer cells by inhibiting epithelial-mesenchymal transition and MMP-2/9 via downregulation of GSK3ß/ß-catenin and JNK signaling.

Extremely Stable Ag-Based Photonics, Plasmonic, Optical, and Electronic Materials and Devices Designed with Surface Chemistry Engineering for Anti-Tarnish.

Silver (Ag) metal-based structures are promising building blocks for next-generation photonics and electronics owing to their unique characteristics, such as high reflectivity, surface plasmonic resonance effects, high electrical conductivity, and tunable electron transport mechanisms. However, Ag structures exhibit poor sustainability in terms of device performance because harsh chemicals, particularly S2- ions present in the air, can damage their structures, lowering their optical and electrical properties. Here, the surface chemistry of Ag structures with (3-mercaptopropyl)trimethoxysilane (MPTS) ligands at room temperature and under ambient conditions is engineered to prevent deterioration of their optical and electrical properties owing to S2- exposure. Regardless of the dimensions of the Ag structures, the MPTS ligands can be applied to each dimension (0D, 1D, and 3D). Consequently, highly sustainable plasmonic effects (Δλ < 2 nm), Fabry-Perot cavity resonance structures (Δλ < 2 nm), reflectors (ΔRReflectance < 0.5%), flexible electrodes (ΔRelectrical < 0.1 Ω), and strain gauge sensors (ΔGF < 1), even in S2- exposing conditions is achieved. This strategy is believed to significantly contribute to environmental pollution reduction by decreasing the volume of electronic waste.

Discovery of enhanced lattice dynamics in a single-layered hybrid perovskite.

Layered hybrid perovskites exhibit emergent physical properties and exceptional functional performances, but the coexistence of lattice order and structural disorder severely hinders our understanding of these materials. One unsolved problem regards how the lattice dynamics are affected by the dimensional engineering of the inorganic frameworks and their interaction with the molecular moieties. Here, we address this question by using a combination of spontaneous Raman scattering, terahertz spectroscopy, and molecular dynamics simulations. This approach reveals the structural dynamics in and out of equilibrium and provides unexpected observables that differentiate single- and double-layered perovskites. While no distinct vibrational coherence is observed in double-layered perovskites, an off-resonant terahertz pulse can drive a long-lived coherent phonon mode in the single-layered system. This difference highlights the dramatic change in the lattice environment as the dimension is reduced, and the findings pave the way for ultrafast structural engineering and high-speed optical modulators based on layered perovskites.

Dipole-Dependent Waveguiding in an Anisotropic Metal-Organic Framework.

The interaction between excitons and photons underlies a range of emergent technologies, such as directional light emission, molecular lasers, photonic circuits, and polaritonic devices. Two of the key parameters that impact exciton-photon coupling are the binding energy of excitons and the relative orientations between the exciton dipole and photon field. Tightly bound excitons are typically found in molecular crystals, where nevertheless the angular relationship of excitons with photon fields is difficult to control. Here, we demonstrate directional exciton dipoles and photon fields, anchored by metal-ligand coordination. In a pyrene-porphyrin bichromophoric metal-organic framework (MOF), we observe that the perpendicular arrangement of the pyrene- and porphyrin-based exciton dipoles engenders orthogonal polarizations of their respective emissions. The alignment of the directional exciton and photon fields gives rise to an anisotropic waveguide effect, where the pyrene- and the porphyrin-based emissions show distinct spatial distribution within microplate-shaped MOF crystals. This capability to simultaneously host heterogenous excitonic states and anisotropic photon fields points toward MOFs' yet-to-be-realized potential as a platform for advancing the frontier in the field of exciton-photonics, which centers around engineering emergent properties from the interplay between excitons and photons.

1D Hybrid Semiconductor Silver 2,6-Difluorophenylselenolate.

Organic-inorganic hybrid materials present new opportunities for creating low-dimensional structures with unique light-matter interaction. In this work, we report a chemically robust yellow emissive one-dimensional (1D) semiconductor, silver 2,6-difluorophenylselenolate─AgSePhF2(2,6), a new member of the broader class of hybrid low-dimensional semiconductors, metal-organic chalcogenolates. While silver phenylselenolate (AgSePh) crystallizes as a two-dimensional (2D) van der Waals semiconductor, introduction of fluorine atoms at the (2,6) position of the phenyl ring induces a structural transition from 2D sheets to 1D chains. Density functional theory calculations reveal that AgSePhF2 (2,6) has strongly dispersive conduction and valence bands along the 1D crystal axis. Visible photoluminescence centered around λp ≈ 570 nm at room temperature exhibits both prompt (110 ps) and delayed (36 ns) components. The absorption spectrum exhibits excitonic resonances characteristic of low-dimensional hybrid semiconductors, with an exciton binding energy of approximately 170 meV as determined by temperature-dependent photoluminescence. The discovery of an emissive 1D silver organoselenolate highlights the structural and compositional richness of the chalcogenolate material family and provides new insights for molecular engineering of low-dimensional hybrid organic-inorganic semiconductors.

Dipole-mediated exciton management strategy enabled by reticular chemistry.

Selectively blocking undesirable exciton transfer pathways is crucial for utilizing exciton conversion processes that involve participation of multiple chromophores. This is particularly challenging for solid-state systems, where the chromophores are fixed in close proximity. For instance, the low efficiency of solid-state triplet-triplet upconversion calls for inhibiting the parasitic singlet back-transfer without blocking the flow of triplet excitons. Here, we present a reticular chemistry strategy that inhibits the resonance energy transfer of singlet excitons. Within a pillared layer metal-organic framework (MOF), pyrene-based singlet donors are situated perpendicular to porphyrin-based acceptors. High resolution transmission electron microscopy and electron diffraction enable direct visualization of the structural relationship between donor and acceptor (D-A) chromophores within the MOF. Time-resolved photoluminescence measurements reveal that the structural and symmetry features of the MOF reduce the donor-to-acceptor singlet transfer efficiency to less than 36% compared to around 96% in the control sample, where the relative orientation of the donor and acceptor chromophores cannot be controlled.

Light Emission in 2D Silver Phenylchalcogenolates.

Silver phenylselenolate (AgSePh, also known as "mithrene") and silver phenyltellurolate (AgTePh, also known as "tethrene") are two-dimensional (2D) van der Waals semiconductors belonging to an emerging class of hybrid organic-inorganic materials called metal-organic chalcogenolates. Despite having the same crystal structure, AgSePh and AgTePh exhibit a strikingly different excitonic behavior. Whereas AgSePh exhibits narrow, fast luminescence with a minimal Stokes shift, AgTePh exhibits comparatively slow luminescence that is significantly broadened and red-shifted from its absorption minimum. Using time-resolved and temperature-dependent absorption and emission microspectroscopy, combined with subgap photoexcitation studies, we show that exciton dynamics in AgTePh films are dominated by an intrinsic self-trapping behavior, whereas dynamics in AgSePh films are dominated by the interaction of band-edge excitons with a finite number of extrinsic defect/trap states. Density functional theory calculations reveal that AgSePh has simple parabolic band edges with a direct gap at Γ, whereas AgTePh has a saddle point at Γ with a horizontal splitting along the Γ-N1 direction. The correlation between the unique band structure of AgTePh and exciton self-trapping behavior is unclear, prompting further exploration of excitonic phenomena in this emerging class of hybrid 2D semiconductors.

Anterior Thigh Pain Following Minimally Invasive Oblique Lateral Interbody Fusion: Multivariate Analysis from a Prospective Case Series.

Background: Oblique lateral interbody fusion (OLIF) involves the antepsoas approach and psoas major muscle (PMM) retraction to insert the interbody cage orthogonally. Therefore, OLIF is often associated with postoperative anterior thigh pain (ATP) on the approach side. However, there is limited evidence on the nature and risk factors of ATP following OLIF. Methods: Consecutive patients who planned to undergo minimally invasive OLIF and percutaneous pedicle screw instrumentation for lumbar degenerative diseases were prospectively enrolled. The visual analog scale (VAS) for ATP was recorded, and a pain map was drawn daily from the operation day to postoperative day 7 in all patients. We also prospectively collected the preoperative and intraoperative data to identify the risk factors associated with ATP. Radiologically, the total cross-sectional area (CSA), retraction length, and retraction CSA of PMM were measured from the preoperative T2-weighted axial magnetic resonance imaging scans at the L4-5 intervertebral disc level. The patients were stratified into two groups based on the experience of ATP with a VAS score of ≥ 7 at any time point. Additionally, a binary logistic regression analysis was performed to identify the associated factors. Results: The current prospective study included 92 patients (31 men, 61 women) with a mean age of 70.4 years (range, 56-86 years), who underwent OLIF at our institution. The left-side approach was used in 73 patients (79.3%), while 19 (20.7%) underwent a right-side approach. Sixty-five of the total patients (70.6%) experienced approach-side ATP to any extent during postoperative 0-7 days following OLIF. The mean pain VAS (4.4 ± 2.1) and the prevalence (57.6%) were highest at postoperative 2 days. On postoperative day 7, there were 19 patients (20.7%) who complained of residual ATP with a mean VAS of 2.6 ± 1.8. In the multivariate analysis, the PMM retraction length was significantly associated with ATP of VAS ≥ 7 (adjusted odds ratio, 2.316; p = 0.044). Conclusions: In this study, we prospectively collected and analyzed the ATP and associated factors following OLIF and identified the PMM retraction length as a potential independent risk factor for severe ATP in the immediate postoperative period following OLIF. Keywords: Anterior thigh pain, Psoas major muscle, Antepsoas, Oblique lateral interbody fusion, Genitofemoral nerve.

Uniaxial Strain Engineering via Core Position Control in CdSe/CdS Core/Shell Nanorods and Their Optical Response.

Anisotropic strain engineering has emerged as a powerful strategy for enhancing the optoelectronic performance of semiconductor nanocrystals. Here, we show that CdSe/CdS dot-in-rod structures offer a platform for fine-tuning the optical response of CdSe quantum dots through anisotropic strain. By controlling the spatial position of the CdSe core within a growing CdS nanorod shell, varying degrees of uniaxial strain can be introduced. Placing CdSe cores at the end of the CdS nanorod induces strong asymmetric compression along the c-axis of the wurtzite CdSe core, dramatically altering its absorption and emission characteristics, whereas CdSe cores located near the middle of the nanorod experience a comparatively weak uniaxial strain field. The change in absorption and emission spectra and dynamics for highly strained end-position CdSe/CdS nanorods is explained by (1) relative shifting of the valence band light hole and heavy hole levels and (2) introduction of a strong piezoelectric potential, which spatially separates the electron and hole wave functions. The ability to tune the degree of uniaxial strain through core position control in a nanorod structure creates opportunities for precisely modulating the electronic properties of CdSe nanocrystals while simultaneously taking advantage of dielectric and optical anisotropies intrinsic to 1D nanostructures.

Morphological Control of 2D Hybrid Organic-Inorganic Semiconductor AgSePh.

Silver phenylselenolate (AgSePh) is a hybrid organic-inorganic two-dimensional (2D) semiconductor exhibiting narrow blue emission, in-plane anisotropy, and large exciton binding energy. Here, we show that the addition of carefully chosen solvent vapors during the chemical transformation of metallic silver to AgSePh allows for control over the size and orientation of AgSePh crystals. By testing 28 solvent vapors (with different polarities, boiling points, and functional groups), we controlled the resulting crystal size from <200 nm up to a few µm. Furthermore, choice of solvent vapor can substantially improve the orientational homogeneity of 2D crystals with respect to the substrate. In particular, solvents known to form complexes with silver ions, such as dimethyl sulfoxide (DMSO), led to the largest lateral crystal dimensions and parallel crystal orientation. We perform systematic optical and electrical characterizations on DMSO vapor-grown AgSePh films demonstrating improved crystalline quality, lower defect densities, higher photoconductivity, lower dark conductivity, suppression of ionic migration, and reduced midgap photoluminescence at low temperature. Overall, this work provides a strategy for realizing AgSePh films with improved optical properties and reveals the roles of solvent vapors on the chemical transformation of metallic silver.

Size and Quality Enhancement of 2D Semiconducting Metal-Organic Chalcogenolates by Amine Addition.

The use of two-dimensional (2D) materials in next-generation technologies is often limited by small lateral size and/or crystal defects. Here, we introduce a simple chemical strategy to improve the size and overall quality of 2D metal-organic chalcogenolates (MOCs), a new class of hybrid organic-inorganic 2D semiconductors that can exhibit in-plane anisotropy and blue luminescence. By inducing the formation of silver-amine complexes during a solution growth method, we increase the average size of silver phenylselenolate (AgSePh) microcrystals from <5 µm to >1 mm, while simultaneously extending the photoluminescence lifetime and suppressing mid-gap emission. Mechanistic studies using 77Se NMR suggest dual roles for the amine in promoting the formation of a key reactive intermediate and slowing down the final conversion to AgSePh. Finally, we show that amine addition is generalizable to the synthesis of other 2D MOCs, as demonstrated by the growth of single crystals of silver 4-methylphenylselenolate (AgSePhMe), a novel member of the 2D MOC family.

Ink-Lithography for Property Engineering and Patterning of Nanocrystal Thin Films.

Next-generation devices and systems require the development and integration of advanced materials, the realization of which inevitably requires two separate processes: property engineering and patterning. Here, we report a one-step, ink-lithography technique to pattern and engineer the properties of thin films of colloidal nanocrystals that exploits their chemically addressable surface. Colloidal nanocrystals are deposited by solution-based methods to form thin films and a local chemical treatment is applied using an ink-printing technique to simultaneously modify (i) the chemical nature of the nanocrystal surface to allow thin-film patterning and (ii) the physical electronic, optical, thermal, and mechanical properties of the nanocrystal thin films. The ink-lithography technique is applied to the library of colloidal nanocrystals to engineer thin films of metals, semiconductors, and insulators on both rigid and flexible substrates and demonstrate their application in high-resolution image replications, anticounterfeit devices, multicolor filters, thin-film transistors and circuits, photoconductors, and wearable multisensors.

Machine learning assisted network classification from symbolic time-series.

Machine learning techniques have been witnessing perpetual success in predicting and understanding behaviors of a diverse range of complex systems. By employing a deep learning method on limited time-series information of a handful of nodes from large-size complex systems, we label the underlying network structures assigned in different classes. We consider two popular models, namely, coupled Kuramoto oscillators and susceptible-infectious-susceptible to demonstrate our results. Importantly, we elucidate that even binary information of the time evolution behavior of a few coupled units (nodes) yields as accurate classification of the underlying network structure as achieved by the actual time-series data. The key of the entire process reckons on feeding the time-series information of the nodes when the system evolves in a partially synchronized state, i.e., neither completely incoherent nor completely synchronized. The two biggest advantages of our method over previous existing methods are its simplicity and the requirement of the time evolution of one largest degree node or a handful of the nodes to predict the classification of large-size networks with remarkable accuracy.

Fast frequency discrimination and phoneme recognition using a biomimetic membrane coupled to a neural network.

In the human ear, the basilar membrane plays a central role in sound recognition. When excited by sound, this membrane responds with a frequency-dependent displacement pattern that is detected and identified by the auditory hair cells combined with the human neural system. Inspired by this structure, we designed and fabricated an artificial membrane that produces a spatial displacement pattern in response to an audible signal, which we used to train a convolutional neural network. When trained with single frequency tones, this system can unambiguously distinguish tones closely spaced in frequency. When instead trained to recognize spoken vowels, this system outperforms existing methods for phoneme recognition, including the discrete Fourier transform, zoom FFT and chirp z-transform, especially when tested in short time windows. This sound recognition scheme therefore promises significant benefits in fast and accurate sound identification compared to existing methods.

Associations between surrounding residential greenness and intelligence quotient in 6-year-old children.

BACKGROUND: Residential greenness has been reported to be positively associated with health benefits for children, including improved cognitive function. We investigated the association between the intelligence quotient (IQ) of 6-year-old children in Seoul, South Korea and surrounding greenness currently and during the mothers' pregnancy. We also analyzed whether these effects differed by the type of greenness, such as natural or built greenness. METHODS: This study considered 189 mother-child dyads from the Environment and Development of Children Cohort study, who lived in Seoul during the prenatal period and when the child was 6 years old. We defined surrounding greenness using Landsat image data from Korean Arirang satellite images with buffers within 100 m - 2000 m of the radius of each participant's residential address. We separately analyzed two types of greenness, namely natural and built greenness. The children's IQ (total, verbal, and performance IQ) was measured using the Korean Educational Developmental Institute's Wechsler Intelligence Scale for Children. RESULTS: Prenatal exposure to built greenness in 500 m and 1000 m buffers was associated with children's total IQ in a full model [difference in IQ (95% CI): 3.46(0.68, 6.24) and 3.42 (0.53, 6.31) per interquartile increase in proportion of greenness]. However, postnatal exposure to built greenness in all buffers was associated in children's total IQ. We found a stronger association between children's total IQ and built greenness rather than natural greenness. CONCLUSIONS: We found that 6-year-old children tended to score higher on total IQ if they lived in greener neighborhoods. The results provide further evidence of the health benefits of greenness and provide support for urban planning and public health to build healthy urban cities for children and pregnant women.

Residential pyrethroid insecticide use, urinary 3-phenoxybenzoic acid levels, and attention-deficit/hyperactivity disorder-like symptoms in preschool-age children: The Environment and Development of Children study.

Previous animal studies have reported that pyrethroids can cause dopamine system abnormalities and attention-deficit/hyperactivity disorder (ADHD) phenotypes. However, epidemiological studies investigating the associations between pyrethroid exposure and ADHD are limited. We aimed to investigate the association between pyrethroid exposure and ADHD-like symptoms among preschool-age children. We used data from 385 children at 4 years of age participating in the Environment and Development of Children (EDC) study. We evaluated pyrethroid exposure through questionnaires and urinary 3-phenoxybenzoic acid (3-PBA) concentrations. We assessed ADHD-like symptoms using the Korean ADHD rating scale (K-ARS). We conducted negative binomial regressions to evaluate the associations between pyrethroid exposure and ADHD-like symptoms. Residential use of insecticide adhesive (ß = 0.42, 95% CI: 0.11, 0.74) and insecticide spray (ß = 0.33, 95% CI: 0.08, 0.59) was associated with an increase in log-transformed creatinine-adjusted urinary 3-PBA concentrations. Residential insecticide adhesive use was associated with a 51.6% increase in K-ARS scores (95% confidence interval [CI]: 6.3, 116.1) among boys, when compared with non-users. When compared with creatinine-adjusted 3-PBA levels <0.50 µg/g creatinine, creatinine-adjusted 3-PBA levels ≥3.80 µg/g creatinine were associated with a 58% increase in K-ARS scores (95% CI: 0.1, 150.5) among boys. We found associations of residential pyrethroid insecticide use and urinary 3-PBA concentrations with K-ARS scores among preschool-age boys. Since the present study explored cross-sectional associations in preschool-age children, the possibility of reverse causality cannot be dismissed. Further studies implementing a cohort study design are warranted.

Colloidal-annealing of ZnO nanoparticles to passivate traps and improve charge extraction in colloidal quantum dot solar cells.

The popularity of colloidal quantum dot (CQD) solar cells has increased owing to their tunable bandgap, multiple exciton generation, and low-cost solution processes. ZnO nanoparticle (NP) layers are generally employed as electron transport layers in CQD solar cells to efficiently extract the electrons. However, trap sites and the unfavorable band structure of the as-synthesized ZnO NPs have hindered their potential performance. Herein, we introduce a facile method of ZnO NP annealing in the colloidal state. Electrical, structural, and optical analyses demonstrated that the colloidal-annealing of ZnO NPs effectively passivated the defects and simultaneously shifted their band diagram; therefore, colloidal-annealing is a more favorable method as compared to conventional film-annealing. These CQD solar cells based on colloidal-annealed ZnO NPs exhibited efficient charge extraction, reduced recombination and achieved an enhanced power conversion efficiency (PCE) of 9.29%, whereas the CQD solar cells based on ZnO NPs without annealing had a PCE of 8.05%. Moreover, the CQD solar cells using colloidal-annealed ZnO NPs exhibited an improved air stability with 98% retention after 120 days, as compared to that of CQD solar cells using non-annealed ZnO NPs with 84% retention.

Risk Factor Analysis of Extended Opioid Use after Coronary Artery Bypass Grafting: A Clinical Data Warehouse-Based Study.

OBJECTIVES: A clinical data warehouse (CDW) is part of our hospital information system, and it provides user-friendly 'data search and extraction' interfaces for query composition. We carried out a risk factor analysis for the extended use of opioids after coronary artery bypass grafting (CABG), taking advantage of the CDW system. METHODS: From 2015 to 2017, clinical data from 461 patients who had undergone either isolated or concomitant CABG were extracted using the CDW; the extracted data included baseline patient characteristics, various examination results, and opioid prescription information. Supplementary data that could not be extracted with the CDW were collected via manual review of the electronic medical records. RESULTS: Data from a total of 447 patients were analyzed finally. The mean patient age was 66.8 ± 10.9 years, 332 patients (74%) were male, and 235 patients (53%) had diabetes. Among the 447 patients, 90 patients (20.1%) took some type of opioid at the 15th postoperative day. An oral rapid-acting agent was the most frequently used opioid (83%). In the risk factor analysis for extended opioid use, duration of operation was the only significant risk factor (odds ratio = 1.004; 95% confidence interval, 1.001-1.007; p = 0.008). CONCLUSIONS: Longer operation time was associated with the risk of extended opioid use after CABG. CDW was a helpful tool for extracting mass clinical data rapidly, but to maximize its utility, the data should be checked carefully as they are entered in the system so that post-processing can be minimized. Further refinement of the clinical data input and output interface is warranted.

Wearable sensors based on colloidal nanocrystals.

In recent times, wearable sensors have attracted significant attention in various research fields and industries. The rapid growth of the wearable sensor related research and industry has led to the development of new devices and advanced applications such as bio-integrated devices, wearable health care systems, soft robotics, and electronic skins, among others. Nanocrystals (NCs) are promising building blocks for the design of novel wearable sensors, due to their solution processability and tunable properties. In this paper, an overview of NC synthesis, NC thin film fabrication, and the functionalization of NCs for wearable applications (strain sensors, pressure sensors, and temperature sensors) are provided. The recent development of NC-based strain, pressure, and temperature sensors is reviewed, and a discussion on their strategies and operating principles is presented. Finally, the current limitations of NC-based wearable sensors are discussed, in addition to methods to overcome these limitations.