Inter- and Intra-Molecular Organocatalysis of SN2 Fluorination by Crown Ether: Kinetics and Quantum Chemical Analysis.

We present the intra- and inter-molecular organocatalysis of SN2 fluorination using CsF by crown ether to estimate the efficacy of the promoter and to elucidate the reaction mechanism. The yields of intramolecular SN2 fluorination of the veratrole substrates are measured to be very small (<1% in 12 h) in the absence of crown ether promoters, whereas the SN2 fluorination of the substrate possessing a crown ether unit proceeds to near completion (~99%) in 12 h. We also studied the efficacy of intermolecular rate acceleration by an independent promoter 18-crown-6 for comparison. We find that the fluorinating yield of a veratrole substrate (leaving group = -OMs) in the presence of 18-crown-6 follows the almost identical kinetic course as that of intramolecular SN2 fluorination, indicating the mechanistic similarity of intra- and inter-molecular organocatalysis of the crown ether for SN2 fluorination. The calculated relative Gibbs free energies of activation for these reactions, in which the crown ether units act as Lewis base promoters for SN2 fluorination, are in excellent agreement with the experimentally measured yields of fluorination. The role of the metal salt CsF is briefly discussed in terms of whether it reacts as a contact ion pair or as a "free" nucleophile F-.

A High Aspect Ratio Serpentine Structure for Use As a Strain-Insensitive, Stretchable Transparent Conductor.

The development of strain-insensitive stretchable transparent conductors (TCs) is essential for manufacturing stretchable electronics. Despite recent progress, achieving a high optoelectronic performance under applied strain of 50% continues to present a significant challenge in this research field. Herein, an ultratall and ultrathin high aspect ratio serpentine metal structure is described that exhibits a remarkable stretching ability (the resistance remains constant under applied strain of 100%) and simultaneously provides an excellent transparent conducting performance (with a sheet resistance of 7.6 Ω î¨-1 and a transmittance of 90.5%). It is demonstrated that the highly stretchable transparent conducting properties can be attributed to the high aspect ratio feature. A high aspect ratio (aspect ratio of 17-367) structure permits facile deformation of the serpentine structure with in-plane motion, leading to a high stretching ability. In addition, this structural feature avoids the classic tradeoff between optical transmittance and electrical conductance, providing a high electrical conductance without decreasing the optical transmittance. The practical utility of these devices is tested by using these TCs as stretchable interconnectors among LEDs or in wearable VOC gas sensors.

Recurrence Risk Evaluation in Patients with Papillary Thyroid Carcinoma: Multicenter Machine Learning Evaluation of Lymph Node Variables.

Background: Lymph node (LN)-related risk factors have been updated to predict long-term outcomes in patients with papillary thyroid carcinoma (PTC). However, those factors' analytic appropriateness and general applicability must be validated. This study aimed to assess LN-related risk factors, and suggest new LN-related risk categories. Methods: This multicenter observational cohort study included 1232 patients with PTC with N1 disease treated with a total thyroidectomy and neck dissection followed by radioactive iodine remnant ablation. Results: The median follow-up duration was 117 months. In the follow-up period, structural recurrence occurred in 225 patients (18.3%). Among LN-related variables, the presence of extranodal extension (p < 0.001), the maximal diameter of metastatic LN foci (p = 0.029), the number of retrieved LNs (p = 0.003), the number of metastatic LNs (p = 0.003), and the metastatic LN ratio (p < 0.001) were independent risk factors for structural recurrence. Since these factors showed a nonlinear association with the hazard ratio of recurrence-free survival (RFS) rates, we calculated their optimal cutoff values using the K-means clustering algorithm, selecting 0.2 cm and 1.1 cm for the maximal diameter of metastatic LN foci, 4 and 13 for the number of metastatic LN, and 0.28 and 0.58 for the metastatic LN ratio. The RFS curves of each subgroup classified by these newly determined cutoff values showed significant differences (p < 0.001). Each LN risk group also showed significantly different RFS rates from the others (p < 0.001). Conclusions: In PTC patients with an N1 classification, our novel LN-related risk estimates may help predict long-term outcomes and design postoperative management and follow-up strategies. After further validation studies based on independent datasets, these risk categories might be considered when redefining risk stratification or staging systems.

The Impact of the Coronavirus Disease - 19 Pandemic on the Clinical Characteristics and Treatment of Adult Patients with Acute Appendicitis.

Purpose: This study aimed to investigate the characteristics, severity, and treatment of adult patients with acute appendicitis in Korea over a 2-year period during the coronavirus disease (COVID-19) pandemic compared to those before the pandemic. We also investigated whether there were any changes in clinical characteristics of acute appendicitis before and after vaccination against the coronavirus. Methods: We retrospectively reviewed the medical records of patients who were diagnosed with acute appendicitis at our institution between March 1, 2019, and August 31, 2021. We divided the patients into three groups (pre-pandemic, before vaccination, and after vaccination) and analyzed the clinical outcomes. Results: The time from symptom onset to hospital arrival and the time from symptom onset to operation increased during the COVID-19 pandemic period compared to the pre-pandemic period. The rate of complicated appendicitis during the pandemic was higher than that before the pandemic. In addition, the number of new daily cases showed a positive correlation with the time from symptom onset to hospital arrival (OR, 0.03; 95% CI, 0.02 to 0.04; P < 0.001) and complicated appendicitis (OR, 1.002; 95% CI, 1.001-1.002; P = 0.0017). The vaccination rate showed a negative correlation with the time from symptom onset to hospital arrival (OR, -2.26; 95% CI, -3.42 to -1.11; P < 0.001) and complicated appendicitis (OR, 0.915; 95% CI, 0.84 to 0.996; P = 0.0404). Conclusions: Employing hospital-wide efforts, such as screening by rapid PCR testing, to avoid further time delays, and nationwide efforts, such as vaccination, to shorten the time from symptom onset to hospital arrival, are necessary to maintain the quality of treatment of acute appendicitis during an infectious disease pandemic.

Recent Progress in Simple and Cost-Effective Top-Down Lithography for ≈10 nm Scale Nanopatterns: From Edge Lithography to Secondary Sputtering Lithography.

The development of a simple and cost-effective method for fabricating ≈10 nm scale nanopatterns over large areas is an important issue, owing to the performance enhancement such patterning brings to various applications including sensors, semiconductors, and flexible transparent electrodes. Although nanoimprinting, extreme ultraviolet, electron beams, and scanning probe litho-graphy are candidates for developing such nanopatterns, they are limited to complicated procedures with low throughput and high startup cost, which are difficult to use in various academic and industry fields. Recently, several easy and cost-effective lithographic approaches have been reported to produce ≈10 nm scale patterns without defects over large areas. This includes a method of reducing the size using the narrow edge of a pattern, which has been attracting attention for the past several decades. More recently, secondary sputtering lithography using an ion-bombardment technique was reported as a new method to create high-resolution and high-aspect-ratio structures. Recent progress in simple and cost-effective top-down lithography for ≈10 nm scale nanopatterns via edge and secondary sputtering techniques is reviewed. The principles, technical advances, and applications are demonstrated. Finally, the future direction of edge and secondary sputtering lithography research toward issues to be resolved to broaden applications is discussed.

A mechanistic study of S(N)2 reaction in a diol solvent.

We present calculations for the mechanism of S(N)2 reactions in ethylene glycol, focusing on the role of two protic functional groups (-OH) in the solvent molecule. We find that some hydroxyl groups act as Lewis base to interact with the cation, whereas others affect the reaction as Lewis acid to the nucleophile. We predict that the nucleophile (F-) reacts as an ion pair rather than as a solvent-separated ion when metal cation (Cs+) is used as a counterion. The overall influence of ethylene glycol manifests itself as the reaction barrier (E(double dagger) = 20.0, G(353K)(double dagger) = 21.5 kcal/mol) that is a bit smaller than that in tert-butyl alcohol, which proved to be a very efficient solvent for S(N)2 reactions [Kim, D. W., et al. J. Am. Chem. Soc. 2006, 128, 16394]. We therefore show that a small protic solvent such as ethylene glycol may be as efficient as a bulky alcohol for S(N)2 reactions.

Arginine zwitterion is more stable than the canonical form when solvated by a water molecule.

We present calculations for the Arg-H2O system and predict that the zwitterionic Arg is thermodynamically more stable than the canonical form in the gas phase under the influence of a single water molecule because of the strongly basic guanidine side chain. Canonical conformers of Arg-H2O are found to isomerize to the zwitterionic forms via a small barrier (approximately 6 kcal/mol).

Correction: A three-dimensional metal grid mesh as a practical alternative to ITO.

Correction for 'A three-dimensional metal grid mesh as a practical alternative to ITO' by Sungwoo Jang et al., Nanoscale, 2016, 8, 14257-14263.

An Ultrastable Ionic Chemiresistor Skin with an Intrinsically Stretchable Polymer Electrolyte.

Ultrastable sensing characteristics of the ionic chemiresistor skin (ICS) that is designed by using an intrinsically stretchable thermoplastic polyurethane electrolyte as a volatile organic compound (VOC) sensing channel are described. The hierarchically assembled polymer electrolyte film is observed to be very uniform, transparent, and intrinsically stretchable. Systematic experimental and theoretical studies also reveal that artificial ions are evenly distributed in polyurethane matrix without microscale phase separation, which is essential for implementing high reliability of the ICS devices. The ICS displays highly sensitive and stable sensing of representative VOCs (including toluene, hexane, propanal, ethanol, and acetone) that are found in the exhaled breath of lung cancer patients. In particular, the sensor is found to be fully operational even after being subjected to long-term storage or harsh environmental conditions (relative humidity of 85% or temperature of 100 °C) or severe mechanical deformation (bending to a radius of curvature of 1 mm, or stretching strain of 100%), which can be an effective method to realize a human-adaptive and skin-attachable biosensor platform for daily use and early diagnosis.

A three-dimensional metal grid mesh as a practical alternative to ITO.

The development of a practical alternative to indium tin oxide (ITO) is one of the most important issues in flexible optoelectronics. In spite of recent progress in this field, existing approaches to prepare transparent electrodes do not satisfy all of their essential requirements. Here, we present a new substrate-embedded tall (∼350 nm) and thin (∼30 nm) three-dimensional (3D) metal grid mesh structure with a large area, which is prepared via secondary sputtering. This structure satisfies most of the essential requirements of transparent electrodes for practical applications in future opto-electronics: excellent optoelectronic performance (a sheet resistance of 9.8 Ω□(-1) with a transmittance of 85.2%), high stretchability (no significant change in resistance for applied strains <15%), a sub-micrometer mesh period, a flat surface (a root mean square roughness of approximately 5 nm), no haze (approximately 0.5%), and strong adhesion to polymer substrates (it survives attempted detachment with 3M Scotch tape). Such outstanding properties are attributed to the unique substrate-embedded 3D structure of the electrode, which can be obtained with a high aspect ratio and in high resolution over large areas with a simple process. As a demonstration of its suitability for practical applications, our transparent electrode was successfully tested in a flexible touch screen panel. We believe that our approach opens up new practical applications in wearable electronics.

Microsolvation of lysine by water: computational study of stabilized zwitterion.

We present calculations for Lys-(H(2)O)(n) (n = 2, 3) to examine the effects of microsolvating water on the relative stability of the zwitterionic vs canonical forms of Lys. We calculate the structures, energies, and Gibbs free energies of the conformers at the B3LYP/6-311++G(d,p), wB97XD/6-311++G(d,p), and MP2/aug-cc-pvdz levels of theory, finding that three water molecules are required to stabilize the Lys zwitterion. By calculating the barriers of the canonical ↔ zwitterionic pathways of Lys-(H(2)O)(3) conformers, we suggest that both forms of Lys-(H(2)O)(3) may be observed in low temperature gas phase.

Effects of bioconjugation on the structures and electronic spectra of CdSe: density functional theory study of CdSe-adenine complexes.

We present density functional theory (DFT) and time-dependent DFT (TD-DFT) study of the structures and electronic spectra of small CdSe nanocluster-adenine complexes Cd(n)Se(n)-adenine (n = 3, 6, 10, 13). We examine the changes in the geometries and excitation spectra of the nanoclusters induced by DNA base-binding. By comparing the results calculated for the bare (Cd(n)Se(n)), hydrogen-passivated (Cd(n)Se(n)H(2n)), as well as the corresponding adenine (Ade)-bound clusters (Cd(n)Se(n)-Ade, Cd(n)Se(n)H(2n)-Ade, Cd(n)Se(n)H(2n-2)-Ade), we find that binding with Ade slightly blue-shifts (up to 0.18 eV) the electronic excitations of bare nanoclusters but strongly red-shifts (<1.2 eV) those of hydrogen-passivated nanoclusters. Natural bond orbital analysis shows that the LUMO of Cd(n)Se(n)H(2n)-Ade is a pi* orbital located on the purine ring.