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Here, we present the synthesis and characterization of a novel 2D crystalline framework, named C2O, which mainly consists of carbon and oxygen in a 2:1 molar ratio and features crown ether holes in its skeletal structure. The covalent-frameworked 2D crown ether can be synthesized on a gram-scale and exhibits fine chemical stability in various environments, including acid, base, and different organic solvents. The C2Oefficiently activates KI through the strong coordination of K+with crown ether holes in a rigid framework, which enhances the nucleophilicity of I–and significantly improves its catalytic activity for CO2fixation with epoxides. The presence of C2Owith KI results in remarkable increases in CO2conversion from 5.7% to 99.9% and from 2.9% to 74.2% for epichlorohydrin and allyl glycidyl ether, respectively. Moreover, C2Opossesses both electrophilic and nucleophilic sites at the edge of its framework, allowing for the customization of physicochemical properties by a diverse range of chemical modifications. Specifically, incorporating allyl glycidyl ether (AGE) as an electrophile or ethoxyethylamine (EEA) as a nucleophile into C2Oenables the synthesis of C2O-AGEor C2O-EEA, respectively. These modified frameworks exhibit improved conversions of 97.2% and 99.9% for CO2fixation with allyl glycidyl ether, outperforming unmodified C2Oshowing a conversion of 74.2%. This newly developed scalable, durable, and customizable covalent framework holds tremendous potential for the design and preparation of outstanding materials with versatile functionalities, rendering them highly attractive for a wide range of applications.

A nanographene-fused expanded carbaporphyrin (5) and its BF2complex (6) were synthesized. Single-crystal X-ray structures revealed that 5and 6are connected by two hexa-peri-hexabenzocoronene (HBC) units and two dipyrromethene or BODIPY units, respectively. As prepared, 5and 6both show nonaromatic character with figure-of-eight carbaoctaphyrin (1.1.1.0.1.1.1.0) cores and adopt tweezers-like conformations characterized by a partially confined space between the two constituent HBC units. The distance between the HBC centers is >10 Å, while the dihedral angles between the two HBC planes are 30.5 and 35.2° for 5and 6, respectively. The interactions between 5and 6and fullerene C60were studied both in organic media and in the solid state. Proton NMR spectral titrations of 5and 6with C60revealed a 1:1 binding mode for both macrocycles. In toluene-d8, the corresponding binding constants were determined to be 1141 ± 17 and 994 ± 10 M–1for 5and 6, respectively. Single-crystal X-ray diffraction structural analyses confirmed the formation of 1:1 fullerene inclusion complexes in the solid state. The C60guests in both complexes are found within triangular pockets composed of two HBC units from the tweezers-like receptor most closely associated with the bound fullerene, as well as an HBC unit from an adjacent host. Femtosecond transient absorption measurements revealed subpicosecond ultrafast charge separation between 5(and 6) and C60in the complexes. To the best of our knowledge, the present report provides the first example wherein a nanographene building block is incorporated into the core of a porphyrinic framework.

The peridynamic (PD) material parameters at boundaries where the neighborhood is incomplete exhibit a softer material response compared to bulk material points. This effect is called the surface or skin effect. This study presents a new surface correction method for bond-based peridynamics that calculates the PD material parameters discretely during numerical simulations. The discretely calculated material parameters can easily account for the effect of newly formed free surfaces, i.e., crack surfaces, that can occur during the simulation. Hence, the proposed surface correction technique provides a single context for a surface correction method that can be applied to static problems and dynamic problems. In numerical simulations, the meshfree discretization technique enhanced with the HHB algorithm is utilized for the spatial discretization to improve accuracy in the numerical integration over the spatial domain. In addition, a half-step time integration scheme is used in temporal discretization. The results obtained using the proposed surface correction method are compared with the surface correction methods available in the literature. It is shown that the proposed surface correction method is more accurate in the static and dynamic PD analyses by considering the missing neighbors along the problem boundaries and the newly emerging boundaries during the crack propagation. • Peridynamics constants are calculated in a discrete manner. • Newly formed free surfaces during crack propagation are considered. • The bond constant is degraded if there is damage at the material points. • The effect of horizon is predominent in crack tip instabilities. [ABSTRACT FROM AUTHOR]

Nucleotide excision repair removes DNA lesions caused by ultraviolet light, cisplatin-like compounds and bulky adducts1. After initial recognition by XPC in global genome repair or a stalled RNA polymerase in transcription-coupled repair, damaged DNA is transferred to the seven-subunit TFIIH core complex (Core7) for verification and dual incisions by the XPF and XPG nucleases2. Structures capturing lesion recognition by the yeast XPC homologue Rad4 and TFIIH in transcription initiation or DNA repair have been separately reported3–7. How two different lesion recognition pathways converge and how the XPB and XPD helicases of Core7 move the DNA lesion for verification are unclear. Here we report on structures revealing DNA lesion recognition by human XPC and DNA lesion hand-off from XPC to Core7 and XPA. XPA, which binds between XPB and XPD, kinks the DNA duplex and shifts XPC and the DNA lesion by nearly a helical turn relative to Core7. The DNA lesion is thus positioned outside of Core7, as would occur with RNA polymerase. XPB and XPD, which track the lesion-containing strand but translocate DNA in opposite directions, push and pull the lesion-containing strand into XPD for verification.

Stacked-ring aromaticity arising from the close stacking of antiaromatic π-systems has recently received considerable attention. Here, we realize stacked-ring aromaticity via a rational supramolecular approach. A nanocapsule composed of bent polyaromatic amphiphiles was employed to encapsulate several antiaromatic norcorrole Ni(II) complexes (NCs) in water. The resulting micellar capsules display high stability toward heating and concentration change. The encapsulation resulted in the appearance of a broad absorption band in the near-infrared region, which is characteristic of norcorroles with close face-to-face stacking. Importantly, a meso-isopropyl NC, which does not exhibit π-stacking even in a concentrated solution or the crystalline phase, adopted π-stacking with stacked-ring aromaticity in the supramolecular micellar capsule.

Excited-state aromatization dynamics in the photochemical ring opening of dihydroazulene (DHA) is investigated by nonadiabatic molecular dynamics simulations in connection with the mixed-reference spin-flip (MRSF)-TDDFT method. It is found that, in the main reaction channel, the ring opening occurs in the excited state in a sequence of steps with increasing aromaticity. The first stage lasting ca. 200 fs produces an 8π semiaromatic S1minimum (S1, min) through an ultrafast dampedbond length alternation (BLA) movement synchronized with a partial planarization of the cycloheptatriene ring. An additional ca. 200 fs are required to gain the vibrational energy needed to overcome a ring-opening transition state characterized by an enhanced Baird aromaticity. Unlike other BLA motions of ππ* state, it was shown that their dampingis a characteristic feature of aromatic bond-equalization process. In addition, some minor channels of the reaction have also been discovered, where noticeably higher barriers of the S1non/antiaromatictransition structures must be surmounted. These anti-Baird channels led to reformation of DHA or other closed-ring products. The observed competition between the Baird and anti-Baird channels suggests that the quantum yield of photochemical products can be controllable by tipping their balance. Hence, here we suggest including the concept of anti-Baird, which would expand the applicability of Baird rule to much broader situations.

Background: To develop an inflammation-related immunohistochemistry marker-based algorithm that confers higher diagnostic ability for idiopathic inflammatory myopathies (IIMs) than IIM-related histopathologic features. Methods: Muscle biopsy tissues from 129 IIM patients who met the 2017 EULAR/ACR criteria and 73 control tissues from patients with non-inflammatory myopathies or healthy muscle specimens were evaluated for histological features and immunostaining results of CD3, CD4, CD8, CD20, CD68, CD163, MX1, MHC class I, MHC class II, and HLA-DR. Diagnostic algorithms for IIM were developed based on the results of the classification and regression tree (CART) analysis, which used immunostaining results as predictor variables for classifying patients with IIMs. Results: In the analysis set (IIM, n= 129; control, n= 73), IIM-related histopathologic features had a diagnostic accuracy of 87.6% (sensitivity 80.6%; specificity 100.0%) for IIMs. Notably, muscular expression of CD163 (99.2% vs. 20.8%, p< 0.001) and MHC class I (87.6% vs. 23.1%, p< 0.001) was significantly higher in the IIM group than in controls. Based on the CART analysis results, we developed an algorithm combining CD163 and MHC class I expression that conferred a diagnostic accuracy of 95.5% (sensitivity 96.1%; specificity 94.5%). In addition, our algorithm was able to correctly diagnose IIM in 94.1% (16/17) of patients who did not meet the 2017 EUALR/ACR criteria but were diagnosed as having IIMs by an expert physician. Conclusions: Combination of CD163 and MHC class I muscular expression may be useful in diagnosing IIMs.

We investigated the effect of excited‐state antiaromaticity on the ligand‐to‐metal charge transfer (LMCT) process of metallohexaphyrins. According to Baird rule, the aromatic metallohexaphyrins in the S0state become antiaromatic in the S1state. Because of the metal–ligand redox‐like nature of LMCT process, the LMCT process can release the antiaromatic nature and its energetic destabilization. The metallohexaphyrins show a correlation between the S0‐state aromaticity and time constants for the LMCT process, which well demonstrates that the excited‐state antiaromaticity at the Franck–Condon state acts as a driving force for the LMCT process. These findings elucidate the effect of excited‐state antiaromaticity on the excited‐state behaviors and further provide an insight into the photochemistry of organic molecules. Here, the redox‐like LMCT process having the character of electron transfer between metal and ligand acts as a tool for alleviation of antiaromatic destabilization. The correlation between the S0‐state aromaticity and the time constants for the LMCT process well demonstrates that the LMCT process is driven by the excited‐state antiaromaticity and acts as a route for a relief of antiaromatic destabilization.

Environmental context The production and consumption of chlorofluorocarbons (CFCs) is regulated under the Montreal Protocol and its amendments, due to their role in stratospheric ozone depletion. Global atmospheric levels of CFC-11 did not decline as rapidly as expected during 2012–2018, in large part due to emissions from eastern China. In order to further clarify global CFC-11 emissions, this work provides a rare set CFC-11 measurements from understudied countries and sources throughout Asia (1998–2018). Abstract Trichlorofluoromethane (CFC-11) is an ozone-depleting substance whose production and consumption are regulated under the Montreal Protocol. Global atmospheric CFC-11 levels declined less quickly than expected during 2012–2018, largely because of ongoing emissions from eastern Asia. Satellite measurements suggest additional CFC-11 hotspots in the Arabian Peninsula and north India/Nepal. Here we present CFC-11 levels measured in dozens of Asian cities during 1998–2018, including China and Pakistan before the 2010 phaseout of CFC-11, and China, Nepal, Pakistan, Saudi Arabia and South Korea after the phaseout. Surface measurements of CFCs in Nepal, Pakistan and Saudi Arabia are very rare, and these surveys provide important observational constraints from understudied regions. During pre-phaseout campaigns, higher CFC-11 levels were measured in Beijing than Karachi, despite much higher overall volatile organic compound (VOC) levels in Karachi. During post-phaseout campaigns, average CFC-11 levels were higher in inland Shandong Province and Seoul (1.11–1.23× background) than in western Saudi Arabia, Lahore and Kathmandu (1.02–1.11× background), despite higher levels of other VOCs in the latter regions. While China is known to emit excess CFC-11, elevated CFC-11 levels in Seoul, especially during stagnant meteorological conditions, suggest local emissions in 2015–2016. Rough emission estimates suggest that South Korea is likely a relatively minor global source of excess CFC-11. Hotspot CFC-11 levels were measured from a landfill fire in Mecca (average of 1.8× background) and from garbage burning in Nepal (1.5× background). Because garbage burning and open burning in dumps are common practices, further investigation of CFC-11 emissions at dumps and landfills worldwide is encouraged to determine their global impact.

Microelectrodes are widely used for neural signal analysis because they can record high-resolution signals. In general, the smaller the size of the microelectrode for obtaining a high-resolution signal, the higher the impedance and noise value of the electrodes. Therefore, to improve the signal-to-noise ratio (SNR) of neural signals, it is important to develop microelectrodes with low impedance and noise. In this research, an Au hierarchical nanostructure (AHN) was deposited to improve the electrochemical surface area (ECSA) of a microelectrode. Au nanostructures on different scales were deposited on the electrode surface in a hierarchical structure using an electrochemical deposition method. The AHN-modified microelectrode exhibited an average of 80% improvement in impedance compared to a bare microelectrode. Through electrochemical impedance spectroscopy analysis and impedance equivalent circuit modeling, the increase in the ECSA due to the AHN was confirmed. After evaluating the cell cytotoxicity of the AHN-modified microelectrode through an in vitrotest, neural signals from rats were obtained in in vivoexperiments. The AHN-modified microelectrode exhibited an approximate 9.79 dB improvement in SNR compared to the bare microelectrode. This surface modification technology is a post-treatment strategy used for existing fabricated electrodes, so it can be applied to microelectrode arrays and nerve electrodes made from various structures and materials.

The corrole derivative meso-oxoisocorrole has been theoretically predicted to be antiaromatic, despite its formally cross conjugated electronic system. In this study, this prediction has been experimentally proven by the facile preparation of meso-oxoisocorrole via the oxidation of a mesofree corrole with MnO2and its comprehensive characterization using NMR, UV/vis absorption, FT-IR, and transient-absorption spectroscopy, cyclic voltammetry, and X-ray diffraction analysis. Furthermore, the free base meso-oxoisocorrole was metalated by treatment with Ni(acac)2, PdCl2(PhCN)2, and Zn(OAc)2to give the corresponding metal complexes. These complexes are more strongly antiaromatic, and their degree of paratropicity depends on their planarity. Thus, fine tuning of their antiaromaticity was achieved with concomitant modulation of their HOMO–LUMO gaps. In the presence of tris(pentafluorophenyl)borane, their antiaromaticity is significantly enhanced due to the elongation of the C═O bond, which promotes the polarized C+–O–resonance state. Furthermore, a distinct frequency shift of the C═O vibrational mode in the triplet state was observed in the time-resolved IR spectra in accordance with the Baird rule, which indicates aromaticity reversal in the excited state.

ABSTRACTIntroduction: Treatment of rheumatoid arthritis (RA) has been revolutionized by the introduction of biologic disease-modifying antirheumatic drugs, such as tumor necrosis factor (TNF) inhibitors. With patent expiry approaching for many expensive biologic molecules, such as etanercept, more affordable biosimilar drugs are being developed. LBEC0101 is an etanercept biosimilar approved in Japan and South Korea for all etanercept indications including RA.Areas covered: We discuss the pharmacological characteristics, pharmacokinetics, efficacy, and safety of LBEC0101 compared with the etanercept reference product (ETN-RP). Preclinical studies showed that the binding affinity to TNFα and biological activity of LBEC0101 were similar to those of the ETN-RP. The pharmacokinetic profile of LBEC0101 was also similar to that of the ETN-RP. A Phase III, randomized, double-blind, 54-week study showed that the efficacy of LBEC0101 was equivalent to that of the ETN-RP in RA patients. An extension study showed that efficacy was sustained long-term in patients receiving LBEC0101 and in those switching from the ETN-RP to LBEC0101. The safety profile of LBEC0101 was also confirmed to be comparable with the ETN-RP.Expert opinion: LBEC0101 has shown equivalent pharmacokinetics and efficacy and comparable safety to the ETN-RP, and the lower cost of LBEC0101 provides a good cost–benefit ratio.

To evaluate the long-term efficacy, safety and immunogenicity of continuing LBEC0101; the etanercept (ETN) biosimilar; or switching from the ETN reference product (RP) to LBEC0101 in patients with rheumatoid arthritis (RA). This multicentre, single-arm, open-label extension study enrolled patients who had completed a 52-week randomised, double-blind, parallel phase III trial of LBEC0101 vs ETN-RP. Patients treated with ETN-RP during the randomised controlled trial switched to LBEC0101; those treated with LBEC0101 continued to receive LBEC0101 in this study. LBEC0101 (50 mg) was administered subcutaneously once per week for 48 weeks with a stable dose of methotrexate. Efficacy, safety and immunogenicity of LBEC0101 were assessed up to week 100. A total of 148 patients entered this extension study (70 in the maintenance group and 78 in the switch group). The 28-joint disease activity scores (DAS28)-erythrocyte sedimentation rate (ESR) were maintained in both groups from week 52 to week 100 (from 3.068 to 3.103 in the maintenance group vs. from 3.161 to 3.079 in the switch group). ACR response rates at week 100 for the maintenance vs. switch groups were 79.7% vs. 83.3% for ACR20, 65.2% vs. 66.7% for ACR50 and 44.9% vs. 42.3% for ACR70. The incidence of adverse events and the proportion of patients with newly developed antidrug antibodies were similar in the maintenance and switch groups (70.0% and 70.5%, 1.4% and 1.3%, respectively). Administration of LBEC0101 showed sustained efficacy and acceptable safety in patients with RA after continued therapy or after switching from ETN-RP to LBEC0101. ClinicalTrials.gov, NCT02715908. Registered 22 March 2016.

Figure-eight-shaped nonplanar π-systems adopt distinctive chiral D2-symmetric structures, which are ideal for realizing efficient circularly polarized luminescence (CPL). However, the short-step and enantioselective synthesis of figure-eight π-systems represents a considerable challenge for the conventional bottom-up synthetic strategy. Herein, we report that the oxidative cleavage of the internal double bond of a commercially available polycyclic aromatic hydrocarbon, i.e., dibenzo[g,p]chrysene (DBC), catalytically affords a figure-eight electron-accepting macrocycle, i.e., cyclobisbiphenylenecarbonyl (CBBC), with high scalability (up to 3.3 g) and excellent enantioselectivity (94% ee). This inner-bond-cleavage approach also applies to larger PAHs, affording highly distorted molecular frameworks that comprise two figure-eight subunits. Furthermore, we demonstrate that the peripheral functionalization of CBBC with carbazole afforded donor–acceptor-type emitter, which shows thermally activated delayed fluorescence and emits CPL with a gvalue of 1.0 × 10–2. This gvalue is ten times higher than those of previously reported chiral TADF-active emitters for circularly polarized organic light-emitting diodes. These results demonstrate that oxidative inner-bond cleavage is a powerful synthetic strategy for creating innovative materials that incorporate molecules with figure-eight structures.

•ANDez consolidates multiple ML techniques for disambiguation.•Built using Python and popular ML libraries.•Provides a unified platform to evaluate and refine ML methods.•Assists scholars with limited ML expertise in bibliographic data analysis.

Using updated emission inventories can enhance the accuracy of air quality forecast models. Given China’s rapid economic growth and Korea’s geographical and meteorological position on the windward side of China, updating China’s emission inventory has become particularly crucial for Korea’s air quality modeling. This study aimed to develop an updated version of China’s Emission Inventory in Comprehensive Regional Emissions for Atmospheric Transport Experiments version 3 for the base year of 2019 (CREATEv3 (YR 2019)). To achieve this goal, we utilized the Chinese emission inventory of CREATEv3 for the base year of 2015 (CREATEv3 (YR 2015)) as a framework to incorporate the latest Chinese emission data from the Multi-resolution Emission Inventory Model for Climate and Air Pollution Research for the base year of 2019 (MEIC COVID-19 (YR 2019)) and update the inventory. The updated China’s annual emissions are now reflected in CREATEv3 (YR 2019), and the amounts are as follows: 132 Tg for CO, 21 Tg for NOx, 8 Tg for SO2, 7 Tg for PM2.5, 9 Tg for NH3, and 28 Tg for volatile organic compound (VOC). By comparing previous Chinese emission inventories with the updated inventory developed in this study, it was found that SO2, NOx, VOC, and NH3emissions were decreased. Therefore, using the updated inventory seemingly reduces the impact of China’s fine dust on Korea. By comparing emissions by pollutant and region in China using CREATEv3 (YR 2019), it was found that regions with high emissions of targeted pollutants strongly correlated with major industries operating in those areas. This study is expected to provide insights into China’s emission changes in 2019 and support air quality forecasting.

This study aims to understand the impact of previous air quality improvement policies on historical emission changes by examining long-term emission trends in Korea. Annual emissions from 2000 to 2018 were estimated using Korea’s official emissions inventory, the Clean Air Policy Support System (CAPSS). To ensure a consistent comparison, standardization of the method for calculating emissions and unification of the reported emission sectors were conducted each year. Furthermore, Korea’s emissions history was compared with that of neighboring countries, such as China and Japan. The annual emissions of these countries were acquired from the HTAPv3 emissions inventory, an international long-term emission trend study. For comparison, the emission source classification of Korea was matched with that of HTAPv3. As a result of the analysis, NOxand SOxemissions in Korea have shown decreasing trends, whereas VOCs (volatile organic compounds) have indicated a gradual increasing trend since 2000. Compared to the previous period of implementing South Korea’s air quality improvement policy, changes in NOx and SOx emissions, which are combustion-related pollutants, showed a relationship with the policy’s timeline. However, non-combustion-related pollutants such as VOCs did not exhibit such a relationship. It was concluded that the related policies were not as effective in reducing VOCs as planned in the policy. By comparing the emission trends of Japan, Korea, and China, it was confirmed that Japan was the first country to experience a decrease in combustion-related pollutants emissions, followed by Korea and China. Additionally, combustion-related pollutants decreased in all three countries, whereas VOCs decreased only in Japan. VOC is a precursor material generating secondary PM2.5and Ozone; considering that, if relevant policies are additionally implemented to control future PM2.5concentrations, and to reduce emissions efficiently and effectively, Japan’s VOC reduction policies can be applied to Korea’s emission reduction policies. These results are expected to serve as important references when establishing future air quality improvement policies in Korea.

Hybrid nanorings composed of 2,5‐pyrrolylene, 2,5‐thienylene, and bridging ortho‐phenylene were synthesized by strategic cross‐coupling reactions, and their structures were unambiguously revealed by X‐ray diffraction analysis. These nanorings showed highly twisted structures in the solid‐state, while exhibiting symmetric 1H NMR spectra, indicating their conformational flexibilities in solution. The photophysical and electrochemical properties of these nanorings were studied in detail by UV/Vis and fluorescence spectroscopy, femto‐second laser‐based spectroscopy, and cyclic voltammetry with the aid of DFT calculations. It is shown that hybridization of nanorings with 2,5‐thienylene and 2,5‐pyrrolylene is an effective means to tune their electronic properties. Twisted rings: Conjugated nanorings composed of 2,5‐pyrrolylene and 2,5‐thienylene bridged by ortho‐phenylenes were synthesized. The solid‐state structures proved to be highly twisted, depending on the ratio of thienylene and pyrrolylene units. The optical and electrochemical properties were also studied, demonstrating the tunability of these properties by hybridization.

Both self-healable conductors and stretchable conductors have been previously reported. However, it is still difficult to simultaneously achieve high stretchability, high conductivity, and self-healability. Here, we observed an intriguing phenomenon, termed “electrical self-boosting”, which enables reconstructing of electrically percolative pathways in an ultrastretchable and self-healable nanocomposite conductor (over 1700% strain). The autonomously reconstructed percolative pathways were directly verified by using microcomputed tomography and in situscanning electron microscopy. The encapsulated nanocomposite conductor shows exceptional conductivity (average value: 2578 S cm–1; highest value: 3086 S cm–1) at 3500% tensile strain by virtue of efficient strain energy dissipation of the self-healing polymer and self-alignment and rearrangement of silver flakes surrounded by spontaneously formed silver nanoparticles and their self-assembly in the strained self-healing polymer matrix. In addition, the conductor maintains high conductivity and stretchability even after recovered from a complete cut. Besides, a design of double-layered conductor enabled by the self-bonding assembly allowed a conducting interface to be located on the neutral mechanical plane, showing extremely durable operations in a cyclic stretching test. Finally, we successfully demonstrated that electromyogram signals can be monitored by our self-healable interconnects. Such information was transmitted to a prosthetic robot to control various hand motions for robust interactive human-robot interfaces.

Expanded porphyrins have been attracting increasing attention owing to their unique optical and electrochemical properties as well as switchable aromaticity. Toward material applications, regioselective functionalization of the expanded porphyrins at their periphery is indeed challenging due to the presence of multiple reactive sites. Herein, a set of regioselective halogenated isomers (L5-Br-A/B/C) of neo-confused isosmaragdyrin (L5) are synthesized by a combination of the halogenation reaction of L5and sequential macrocycle-to-macrocycle transformation reactions of its halogenated isomers. On this basis, the regioselectively functionalized isosmaragdyrins are utilized as building blocks for constructing multichromophoric porphyrinoids, specifically, heterodyads L5-ZnP-A/B/C, in which a common zinc porphyrin is linked at three different pyrrolic positions of isosmaragdyrins, respectively, by Sonogashira coupling reactions. The highly efficient energy cascade from porphyrin to isosmaragdyrin is elucidated using steady-state/time-resolved spectroscopies and theoretical calculations. Notably, the energy transfer processes from the porphyrin to the isosmaragdyrin moieties as well as the excitation energy transfer rates in L5-ZnP-A/B/Care highly dependent on the linking sites by through-bond and Förster-type resonance energy transfer mechanisms. The site-selective functionalization and subsequent construction of a set of heterodyads of the expanded porphyrinoid would provide opportunities for developing new materials for optoelectronic applications.

One of the ultimate wearable heath-monitoring gears, smart contact lens, requires miniaturized devices compounded and interconnected with each other on the lens for a successful system functioning. Because of the different device thickness, the interconnect patterns need to be three-dimensional (3D) conforming the steps given by the diversified on-lens devices. Also, the patterns should be low-temperature processed and flexible considering the mechanical and thermal property of the lens material. We demonstrate the 3D interconnects electrosprayed on a contact lens platform with Ag–Ag nanowire (NWs) composite ink conforming the steps. Quantitative and informative analysis on the interconnects is presented. Thick polyimide film (12.5 μm) in C-shape is employed as a primary substrate to form the 3D patterns that is to be transferred onto the contact lens. The AgNWs act as frames to support the Ag ion inks printed across the steps. The resultant interconnects realized with the Ag/AgNW composite ink with 0.3 wt % AgNW have the sheet resistance (Rs) of 0.396 Ω/□ spanning the height difference of 300 μm. AgNWs also provide durability to the patterns against crack formation and propagation under significant device deformation. Unlike pure Ag pattern which shows the Rschanges of 86.1% in the bending condition, the optimally formulated composite pattern shows the suppressed Rschange of only 15.2% with a bending radius of 3 mm.

We report a micromachined H2sensor that is composed of a Pt micro-heater, low-stress insulating layer (SiO2/SiNx/SiO2), Pt-interdigitated electrodes, and gas sensing materials. Three types of Pt micro-heater are designed as function of electrode width, and their thermal properties are systematically analyzed by finite element modeling FEM with infrared camera. The power consumptions when the surface temperature reached 150, 200, 250, and 300 °C are calculated to approximately 33, 48, 67 and 85 mW, respectively. The response of the PdO nanoparticles-decorated TiO2thin films to H2is much higher than those of other gases such as CH4and CO at 200 °C (48 mW). Further, the response time is reduced to approximately 3 s. The enhancement of gas sensing properties is related to well-designed micro-heater and catalytic effects of PdO nanoparticles such as electronic and chemical sensitization. These results suggest that the PdO nanoparticles-decorated TiO2thin film, namely MEMS-based H2sensors are very promising for use in IoT application to improve the quality of human’s life.

Applying the concept of triadic closure to coauthorship networks means that scholars are likely to publish a joint paper if they have previously coauthored with the same people. Prior research has identified moderate to high (20 to 40%) closure rates; suggesting this mechanism is a reasonable explanation for tie formation between future coauthors. We show how calculating triadic closure based on prior operationalizations of closure, namely Newman’s measure for one-mode networks (NCC) and Opsahl’s measure for two-mode networks (OCC) may lead to higher amounts of closure compared to measuring closure over time via a metric that we introduce and test in this paper. Based on empirical experiments using four large-scale, longitudinal datasets, we find a lower bound of 1–3% closure rates and an upper bound of 4–7%. These results motivate research on new explanatory factors for the formation of coauthorship links.

5,10,23-Trimesityl-substituted [24]hexaphyrin(1.1.0.0.1.0) was synthesized as a stable antiaromatic molecule by base-catalyzed twofold SNAr reaction and was reduced to the corresponding [26]hexaphyrin, which was an unstable aromatic molecule because it easily oxidized to the [24]hexaphyrin. The [24]hexaphyrin served as a ligand to give the bis-PdIIcomplex and tris-RhIcomplex with unique structures. The former complex has two square-planar-coordinated PdIIions bridged by an acetate anion and shows a strong paratropic ring current, while the latter complex has three RhIions coordinated with two pyrrolic nitrogen atoms and two carbonyl groups, but one carbonyl group is shared with two RhIions in a unique manner.

Background: There is limited information regarding disease-modifying antirheumatic drug (DMARD)-dependent risks of overall, incident, and recurrent herpes zoster (HZ) during first-line biologic DMARD (bDMARD) or targeted synthetic DMARD (tsDMARD) treatment among patients with seropositive rheumatoid arthritis (RA) in terms of HZ risk. Methods: A total of 11,720 patients with seropositive RA who were prescribed bDMARD or tofacitinib between January 2011 and January 2019 from the Korean Health Insurance Review & Assessment Service database were studied. A multivariate Cox proportional hazards regression model was adopted to evaluate the adjusted hazard ratio (aHR) with 95% confidence interval (CI) for the risk of HZ dependent on the choice of first-line bDMARDs or tsDMARD, including etanercept, infliximab, adalimumab, golimumab, tocilizumab, rituximab, tofacitinib, and abatacept. Results: During the 34,702 person-years of follow-up, 1686 cases (14.4%) of HZ were identified, including 1372 (11.7%) incident and 314 (2.7%) recurrent HZs. Compared with that of the abatacept group, tofacitinib increased the overall risk (aHR, 2.46; 95% CI, 1.61–3.76; P<0.001), incidence (aHR, 1.99; 95% CI, 1.18–3.37; P=0.011), and recurrence (aHR, 3.69; 95% CI, 1.77–7.69; P<0.001) of HZ. Infliximab (aHR, 1.36; 95% CI, 1.06–1.74; P=0.017) and adalimumab (aHR, 1.29; 95% CI, 1.02–1.64; P=0.032) also increased the overall HZ risk. Moreover, a history of HZ was found to be an independent risk factor for HZ (aHR, 1.54; 95% CI, 1.33–1.78; P<0.001). Conclusions: HZ risk is significantly increased in RA patients with a history of HZ after the initiation of bDMARDs or tsDMARD. The risk of incident and recurrent HZ was higher after tofacitinib treatment in patients with RA than that after treatment with bDMARDs. Individualized characteristics and history of HZ should be considered when selecting bDMARDs or tsDMARD for RA patients considering HZ risks.

We aimed to investigate the prevalence of osteoporosis and low lean mass, either together or in isolation, and their association with physical function, pain, and quality of life (QOL) in patients with end-stage knee osteoarthritis (OA).This retrospective cross-sectional observational study included 578 patients (77 males and 501 females) diagnosed with end-stage knee OA. Patients were divided into 4 groups based on body composition parameters: control, osteoporosis, low lean mass, and osteoporosis + low lean mass. All participants underwent performance-based physical function tests, including a stair climbing test (SCT), a 6-minute walk test, a timed up and go test, and instrumental gait analysis, to examine spatiotemporal parameters. Self-reported physical function and pain levels were measured using the Western Ontario McMaster Universities Osteoarthritis Index and visual analog scale, respectively. Self-reported QOL was measured using the EuroQOL 5 dimensions (EQ-5D) questionnaire.Of 578 patients, 268 (46.4%) were included in the control group, 148 (25.6%) in the osteoporosis group, 106 (18.3%) in the low lean mass group, and 56 (9.7%) in the osteoporosis + low lean mass group. Analysis of variance revealed that the scores for the osteoporosis + low lean mass group in the SCT-ascent, SCT-descent, and timed up and go test were significantly higher, whereas those for the 6-minute walk test, gait speed, and cadence were significantly lower than those for the other groups (P< .05). After adjusting for age, sex, and body mass index, multiple linear regression analysis identified SCT-ascent (β = 0.140, P= .001, R2= 0.126), SCT-descent (β = 0.182, P <.001, R2= 0.124), gait speed (β = –0.116, P= .005, R2= 0.079), and cadence (β = –0.093, P= .026, R2= 0.031) as being significantly associated with osteoporosis + low lean mass.Thus, osteoporosis + low lean mass correlates with poor physical function, but not pain and QOL, in patients with end-stage knee OA.

Empirical studies of the relationship between depression and cardiovascular disease (CVD) tend to be limited to examination of one-way relationships. This study assessed both cross-sectional association and longitudinal reciprocal relationships between late-life depressive symptoms and CVD.

Manipulating neural stem cell (NSC) fate is of great importance for improving the therapeutic efficacy of NSCs to treat neurodegenerative disorders. Biophysical cues, in addition to biochemical factors, regulate NSC phenotype and function. In this study, we assessed the extent to which surface nanotopography of culture substrates modulates human NSC (hNSC) differentiation. Fibronectin-coated polymer substrates with diverse nanoscale shapes (groove and pillar) and dimensions (ranging from 300 to 1500 nm groove width and pillar gap) were used to investigate the effects of topographical cues on hNSC morphology, alignment, focal adhesion, and differentiation. The majority of nanopatterned substrates induced substantial changes in cellular morphology and alignment along the patterned shapes, leading to alterations in focal adhesion and F-actin reorganization. Certain types of nanopatterned substrates, in particular the ones with small nanostructures (e.g., 300–300 nm groove ridges and 300–300 nm pillar diameter gaps), were found to effectively enhance focal adhesion complex development. Consequently, these substrates enhanced hNSC differentiation toward neurons and astrocytes. Nanotopographical-induced formation of focal adhesions in hNSCs activates integrin-mediated mechanotransduction and intracellular signaling pathways such as MEK-ERK, which may ultimately promote gene expression related to NSC differentiation. This strategy of manipulating matrix surface topography could be applied to develop culture substrates and tissue engineered scaffolds that improve the efficacy of NSC therapeutics.

A micro-fabricated bridge sensor for determining minute magnetic field variation is proposed. A micro-bridge with $100\times 400$ μm2dimensions (width $\times$ length) comprises a multi-layered structure of Tb0.3Dy0.7Fe1.9/SiO2/Pt/PbZr0.52Ti0.48O3/Pt/Ta on a SiNxsupporting layer. We observed the limit of detection under small DC magnetic field as $1\times 10^{-11}$ T which was converted electrically to 77 μV with a 5 μV noise floor via elastic coupling between magnetostrictive and piezoelectric thin film. The magnetoelectric (ME) voltage was linearly proportional to small magnetic field variance, and the experimental ME coefficient was measured as 9.9 V/(cm$\cdot$Oe).

The aim of this study was to compare the diagnostic performances of two hand perfusion scintigraphy protocols for diagnosing Raynaud’s phenomenon (RP).

Nanoscale voiding in electrolytic was studied by varying Au strike deposition conditions. Two kinds of voids were observed in electrolytic when electric current was not applied during strike plating. One was located along the interface between Ni and Au, which could deteriorate the adhesion between Ni and Au. The other was nanoscale bubbles coated with Ni inside Au film, which could result in porous Au layer. Our results suggest that Ni could grow on the surface of hydrogen bubbles and then the bubbles trapped in the Au film. Needlelike Au or Au whiskers were also observed on the Au surface and a line of nanoscale voids was found beneath Au whiskers when electric current was not applied during Au strike process. We propose a model that the nanoscale voiding and Au whisker formation could be related to a galvanic displacement reaction and hydrogen evolution at the early stage of Au electrodeposition.

Abstract: This paper reports a novel approach for improving the nanotribological properties of silicon (Si) surfaces by topographically and chemically modifying the surfaces. In the first step, Si (100) wafers were topographically modified into nano-pillars by using the photolithography and reactive ion etching (RIE) techniques. Various patterns, including nano-pillars of varying diameters and pitches (distance between pillars), were fabricated. Then, the patterns were coated with a Z-DOL (perfluoropolyether (PFPE)) lubricating film using a dipcoating technique, and this process was followed by thermal treatment. These modified surfaces were tested for their nanotribological properties, namely adhesion and friction forces, using an atomic force microscope (AFM). The results showed that the topographical modification and Z-DOL coating each independently reduced the adhesion and friction forces on the Si surfaces. However, the combination of the two surface treatments was most effective in reducing these forces. This is attributed to the combined effects of the reduction in the real area of contact due to patterning and the low surface energy of the Z-DOL lubricant. Further, it was found that adhesion and friction forces of the surfaces with combined modification varied significantly depending on the diameter of the pillars and the pitch. It is proposed that such a combination of surface modifications promises to be an effective method to improve the nanotribological performance of miniaturized devices, such as MEMS, in which Si is a typical material.

Abstract: In this paper, we report on the replication of surface topographies of natural leaves of water-repellent plants of Lotus and Colocasia onto thin polymeric films using a capillarity-directed soft lithographic technique. The replication was carried out on poly(methyl methacrylate) (PMMA) film spin coated on silicon wafer using poly(dimethyl siloxane) (PDMS) molds. The friction properties of the replicated surfaces were investigated at micro-scale in comparison with those of PMMA thin film and silicon wafer. The replicated surfaces exhibited superior friction property when compared to those of PMMA thin film and silicon wafer. The superior friction behaviour of the replicated surfaces was attributed to the reduced real area of contact projected by them.

OBJECTIVE: To determine the expression of vascular endothelial growth factor-C (VEGF-C) in the synovial fluid of patients with rheumatoid arthritis (RA) and to investigate the regulation of VEGF-C production by major proinflammatory cytokines in fibroblast-like synoviocytes (FLS). METHODS: The concentrations of VEGF-C, tumor necrosis factor-a (TNF-a), and interleukin 1ß (IL-1ß) were measured using an ELISA method in synovial fluids obtained from 20 patients with RA and 20 with osteoarthritis (OA). Primary cultured RA FLS were stimulated with TNF-a or IL-1ß, and the expression levels of VEGF-C mRNA and protein were assessed by quantitative real-time polymerase chain reaction and ELISA. RESULTS: Significantly higher levels of VEGF-C were found in RA synovial fluids compared to OA synovial fluids. VEGF-C levels showed a highly significant correlation with the levels of both TNF-a and IL-1ß in the synovial fluid of patients with RA. TNF-a stimulation significantly increased VEGF-C mRNA and protein expression in RA FLS in a dose-dependent manner. A tendency to increased expression of VEGF-C was also observed after IL-1ß stimulation in FLS. CONCLUSION: Overexpression of VEGF-C in FLS by stimulation with TNF-a may play an important role in the progression of synovial inflammation and hyperplasia in RA by contributing to local lymphangiogenesis and angiogenesis.

This paper presents a novel highly efficient passive micromixer that employs diffusion for micromixing. Since conventional fabrication methods cannot form precise aligned microchannels, the realization of a complex 3D micromixer has been difficult. Here, we report a novel micromixer, named a chessboard mixer. In addition, a new polydimethylsiloxane (PDMS) bonding method was developed to produce the proposed mixer. The new PDMS bonding technique requires PDMS-to-PDMS bonding and the moldable flexibility of partially cured PDMS to form the structure. Accordingly, a two-step curing process was used to solve these problems. Adhesion control was also considered when forming the PDMS membranes. Complex 3D microchannels in the micromixer were aligned within 1 m using the proposed new bonding method. The presented micromixer could increase the mixing effect by expanding interfaces between mixing fluids. Thus, this mixer makes it possible to mix within a shorter distance than other pre-existing micromixers do. A simulation using computational fluid dynamics (CFD)-ACE software showed a highly efficient performance, and an experiment involving the mixing of NaOH and phenolphthalein confirmed the rapid mixing performance (<1400 µm).

This paper presents a new technique to fabricate three-dimensional thin polymer structures with different geometries on each side for cell-polymer microstructures. To make complex 3D polymer structures, we manufacture a 3D-micromolding aligner, which can make two molding masters be aligned within 2 µm and allows for applying high pressure to construct thin membranes of less than 20 µm. Using this system, wafer-level fabrication of thin polymer structures with complex 3D geometries is realized successfully. Generally, 3D polymer microstructures are used in microfluidic systems, such as micromixers, valves and pumps. In this study we demonstrate some applications for these 3D structures as versatile cell-based microsensors for understanding structural and functional changes of cells and as hybrid organic-inorganic actuators that can be operated independently without external power sources.

In organometallic complexes containing π-conjugated macrocyclic chelate ligands, conformational change significantly affects metal–ligand electronic interactions, hence tuning properties of the complexes. In this regard, we investigated the metal–ligand interactions in hexaphyrin mono-Pd(II) complexes Pd[28]Mand Pd[26]H, which exhibit a redox-induced switching of Hückel–Möbius aromaticity and subsequent molecular conformation, and their effect on the electronic structure and photophysical behaviors. In Möbius aromatic Pd[28]M, the weak metal–ligand interaction leads to the π electronic structure of the hexaphyrin ligand remaining almost intact, which undergoes efficient intersystem crossing (ISC) assisted by the heavy-atom effect of the Pd metal. In Hückel aromatic Pd[26]H, the significant metal–ligand interaction results in ligand-to-metal charge-transfer (LMCT) in the excited-state dynamics. These contrasting metal–ligand electronic interactions have been revealed by time-resolved electronic and vibrational spectroscopies and time-dependent DFT calculations. This work indicates that the conspicuous modulation of metal–ligand interaction by Hückel–Möbius aromaticity switching is an appealing approach to manipulate molecular properties of metal complexes, further enabling the fine-tuning of metal–ligand interactions and the novel design of functional organometallic materials.

An amendment to this paper has been published and can be accessed via the original article.

Background: Interleukin-6 (IL-6) is involved in fibroblast-like synoviocyte (FLS) activation and promotes pannus formation and bone and cartilage destruction in rheumatoid arthritis (RA). Cysteine-rich 61 (Cyr61) protein regulates cell proliferation, migration, and differentiation. The aim of this study was to investigate the role of Cyr61 in RA-FLS migration and invasion after IL-6 stimulation. Methods: Western blotting, immunohistochemistry, reverse transcription-polymerase chain reaction, and real time-polymerase chain reaction were used to examine protein and mRNA levels of Cyr61, matrix metalloproteinases (MMPs), and other signalling proteins. Knockdown of gene expression was performed with siRNA, and RNA sequencing was performed for differential gene analysis. Migration and invasion were assessed by wound healing and Boyden chamber assays. Results: Cyr61 levels were elevated in FLSs from RA patients compared to those in osteoarthritis patients. Control and IL-6-treated FLSs showed differential gene expression. IL-6 stimulated protein synthesis of Cyr61, which was attenuated by the extracellular signal-related kinase 1/2 (ERK 1/2) inhibitor, PD98059, and knockdown of early growth response 3 (EGR3), but not of JUN. IL-6-induced Cyr61 protein synthesis increased expression of MMP2. Cyr61 promoted FLS migration and invasion in an autocrine manner. Knockdown of CYR61and a neutralising antibody attenuated Cyr61 synthesis and IL-6-induced FLS migration. Conclusions: By modulating the ERK/EGR3 pathway, IL-6 stimulated Cyr61 production and in turn increased invasiveness of FLS. Our data suggest that Cyr61 might be a potential target to prevent the progression of joint damage in RA.

AbstractAimsTo evaluate the bidirectional relationship between blood pressure (BP) and depressive symptoms using a large prospective cohort study.MethodsProspective cohort study was performed in 276 244 adults who participated in a regular health check-up and were followed annually or biennially for up to 5.9 years. BP levels were categorised according to the 2017 American College of Cardiology and American Heart Association hypertension guidelines. Depressive symptoms were assessed using Centre for Epidemiologic Studies-Depression (CESD) questionnaire and a cut-off score of ≥25 was regarded as case-level depressive symptoms.ResultsDuring 672 603.3 person-years of follow-up, 5222 participants developed case-level depressive symptoms. The multivariable-adjusted hazard ratios (HRs) [95% confidence interval (CI)] for incident case-level depressive symptoms comparing hypotension, elevated BP, hypertension stage 1 and hypertension stage 2 to normal BP were 1.07 (0.99–1.16), 0.93 (0.82–1.05), 0.89 (0.81–0.97) and 0.81 (0.62–1.06), respectively (pfor trend <0.001). During 583 615.3 person-years of follow-up, 27 787 participants developed hypertension. The multivariable-adjusted HRs (95% CI) for incident hypertension comparing CESD 16–24 and ⩾25 to CESD < 16 were 1.05 (1.01–1.11) and 1.12 (1.03–1.20), respectively (pfor trend <0.001) and in the time-dependent models, corresponding HRs (95% CI) were 1.12 (1.02–1.24) and 1.29 (1.10–1.50), respectively (pfor trend <0.001).ConclusionsIn this large cohort study of young and middle-aged individuals, higher BP levels were independently associated with a decreased risk for developing case-level depressive symptoms and depressive symptoms were also associated with incident hypertension. Further studies are required to elucidate the mechanisms underlying the bidirectional association between BP levels and incident depression.

Objective:To examine both cross-sectional and longitudinal relationships between older adults’ perceptions of social cohesion in their community and depressive symptoms and the potential mediating effect of the frequency of going outside one’s home/building. Method:Using two waves (T1 and T2) of the National Health and Aging Trend Study (n= 5,326), gender-stratified structural equation models were estimated to determine direct and indirect effects of perceived social cohesion on depressive symptoms. Results:At T1, both perceived cohesion and frequency of going out were directly associated with depressive symptoms; however, perceived cohesion predicted frequency of going out only for women. At T2, only frequency of going out was directly associated with depressive symptoms, although perceived cohesion predicted frequency of going out for both genders. T1 perceived cohesion did not predict T2 depressive symptoms. T1 depressive symptoms were the strongest predictor of T2 depressive symptoms. Conclusion:The findings underscore the importance of enhancing the social environment in promoting mental health in late life through active aging.

• Establishment of a new size-dependent theory within a stationary variational framework. • A consistent unification of the classical elasticity and the stress gradient theory. • Rigorous analysis of a FG bar via the mixture stress gradient theory of elasticity. • Exact analytical solution of elastostatic axial displacement field of FG nano-bar. • Proposing an effective meshless approach based on stationary variational principle. The mixture stress gradient theory of elasticity is conceived via consistent unification of the classical elasticity theory and the stress gradient theory within a stationary variational framework. The boundary-value problem associated with a functionally graded nano-bar is rigorously formulated. The constitutive law of the axial force field is determined and equipped with proper non-standard boundary conditions. Evidences of well-posedness of the mixture stress gradient problems, defined on finite structural domains, are demonstrated by analytical analysis of the axial displacement field of structural schemes of practical interest in nano-mechanics. An effective meshless numerical approach is, moreover, introduced based on the proposed stationary variational principle while employing autonomous series solution of the kinematic and kinetic field variables. Suitable mathematical forms of the coordinate functions are set forth in terms of the modified Chebyshev polynomials, satisfying the required classical and non-standard boundary conditions. An excellent agreement between the numerical results of the axial displacement field of the functionally graded nano-bar and the analytical solution counterpart is confirmed on the entire span of the nano-sized bar, in terms of the mixture parameter and the stress gradient characteristic parameter. The effectiveness of the established meshless numerical approach, demonstrating a fast convergence rate and an admissible convergence region, is hence ensured. The established mixture stress gradient theory can effectively characterize the peculiar size-dependent response of functionally graded structural elements of advanced ultra-small systems. [ABSTRACT FROM AUTHOR]