Electrochemical Formation of Divalent Samarium Cation and Its Characteristics in LiCl-KCl Melt.

The electrochemical reduction of trivalent samarium in a LiCl-KCl eutectic melt produced highly stable divalent samarium, whose electrochemical properties and electronic structure in the molten salt were investigated using cyclic voltammetry, UV-vis absorption spectroscopy, laser-induced emission spectroscopy, and density functional theory (DFT) calculations. Diffusion coefficients of Sm2+ and Sm3+ were electrochemically measured to be 0.92 × 10-5 and 1.10 × 10-5 cm2/s, respectively, and the standard apparent potential of the Sm2+/3+ couple was estimated to be -0.82 V vs Ag|Ag+ at 450 °C. The spectroelectrochemical study demonstrated that the redox behavior of the samarium cations obeys the Nernst equation ( E°' = -0.83 V, n = 1) and the trivalent samarium cation was successfully converted to the divalent cation having characteristic absorption bands at 380 and 530 nm with molar absorptivity values of 1470 and 810 M-1 cm-1, respectively. Density function theory calculations for the divalent samarium complex revealed that the absorption signals originated from the 4f6 to 4f55d1 transitions. Additionally, laser-induced emission measurements for the Sm cations in the LiCl-KCl matrix showed that the Sm3+ ion in the LiCl-KCl melt at 450 °C emitted an orange color of fluorescence, whereas a red colored emission was observed from the Sm2+ ion in the solidified LCl-KCl salt at room temperature.

Validation of the Korean Version of the Manchester-Oxford Foot Questionnaire in Patients With Hallux Valgus.

The Manchester-Oxford Foot Questionnaire (MOXFQ) is a practical, reliable, and valid questionnaire for hallux valgus surgery and has been translated into several languages. However, the MOXFQ has not been translated into Korean. In the present study, we aimed to translate and evaluate the validity and reliability of the Korean version of the MOXFQ for patients affected by hallux valgus. In accordance with the guidelines of cross-cultural adaptation, we translated the English version of MOXFQ into Korean and then backward translated it into English. We sent out letters that included the Korean version of the MOXFQ, a visual analog scale measure of pain, and a validated Korean version of the short-form 36-item Health Survey to 135 patients with hallux valgus. A retest was administered after 2 weeks. Of the 135 patients, 104 responded to the first questionnaire, and 82 of the first-time responders returned their second questionnaires. We evaluated the test-retest reliability, internal consistency, concurrent validity, and construct validity of the Korean version of the MOXFQ. The intraclass correlation coefficient for test-retest reliability was 0.82 for the total MOXFQ and ranged from 0.81 to 0.82 for the 3 subscales. Cronbach's alpha for the total MOXFQ was 0.85 and ranged from 0.8 to 0.92 for the 3 subscales. Concurrent and construct validity was supported by significant correlation with the visual analog scale and short-form 36-item Health Survey subscale scores. The Korean version of the MOXFQ was tested, and it was found to be a valid and reliable instrument for patients with hallux valgus.

Snail-like Particles from Compartmentalized Microfibers.

Electrohydrodynamic cojetting has been employed to synthesize compartmentalized microfibers from thermally responsive hydrogels. The synthesis of the hydrogels as well as their transformation into compartmentalized microcylinders is discussed. After programmable shape-shifting, snail-like particles are obtained that undergo functional and structural reconfiguration in response to a change in temperature.

Reliability and Validity of the Korean Version of the Foot Function Index.

Although translated versions of the Foot Function Index (FFI) in several languages are available, the absence of a Korean version has precluded comparing the data from Korea with the data from other countries using the FFI. We, therefore, evaluated the reliability and validity of the adapted Korean version of the FFI. We translated the English version of the FFI into Korean and back into English. We mailed the Korean version of the visual analog scale, FFI, and the previously validated Medical Outcomes Study Short-Form 36-item questionnaire (SF-36) to 121 patients with treated foot complaints. To evaluate the test-retest reliability and internal consistency, we used the intraclass correlation coefficient and Cronbach's α, respectively. We also evaluated the concurrent and construct validity of Korean version of the FFI by comparing the visual analog scale and SF-36. Cronbach's α was 0.91 and 0.95 for the pain and disability subscales, respectively. The reproducibility was good, and a strong correlation between the FFI and the SF-36 and visual analog scale with related content was observed, indicating good construct validity.The Korean version of the FFI is a reliable and valid questionnaire for the self-assessment of pain and disability in Korean patients with foot complaints.

Hapticity-dependent charge transport through carbodithioate-terminated [5,15-bis(phenylethynyl)porphinato]zinc(II) complexes in metal-molecule-metal junctions.

Single molecule break junction experiments and nonequilibrium Green's function calculations using density functional theory (NEGF-DFT) of carbodithioate- and thiol-terminated [5,15-bis(phenylethynyl)-10,20-diarylporphinato]zinc(II) complexes reveal the impact of the electrode-linker coordination mode on charge transport at the single-molecule level. Replacement of thiolate (-S(-)) by the carbodithioate (-CS2(-)) anchoring motif leads to an order of magnitude increase of single molecule conductance. In contrast to thiolate-terminated structures, metal-molecule-metal junctions that exploit the carbodithioate linker manifest three distinct conductance values. We hypothesize that the magnitudes of these conductances depend upon carbodithoate linker hapticity with measured conductances across Au-[5,15-bis(4'-(dithiocarboxylate)phenylethynyl)-10,20-diarylporphinato]zinc(II)-Au junctions the greatest when both anchoring groups attach to the metal surface in a bidentate fashion. We support this hypothesis with NEGF-DFT calculations, which consider the electron transport properties for specific binding geometries. These results provide new insights into the origin of molecule-to-molecule conductance heterogeneity in molecular charge transport measurements and the factors that optimize electrode-molecule-electrode electronic coupling and maximize the conductance for charge transport.

Photoswitchable particles for on-demand degradation and triggered release.

On-demand degradable polymer particles are fabricated via electrospraying of a solution of acetal-protected dextran that further includes 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine as a photoacid generator. The illumination of UV light gives rise to photoacid and activates the catalytic deprotection of hydroxyl groups of dextran, leading to controlled dissolution of the microparticles in water.

Janus-core and shell microfibers.

Janus microcylinders composed of different polymers were prepared through coaxial co-jetting with dual-core flows, followed by cross-linking, microsectioning, and shell removal. Uniquely shaped building blocks can be fabricated by photo-patterning of one hemisphere of the microcylinders.

Quasi-ohmic single molecule charge transport through highly conjugated meso-to-meso ethyne-bridged porphyrin wires.

Understanding and controlling electron transport through functional molecules are of primary importance to the development of molecular scale devices. In this work, the single molecule resistances of meso-to-meso ethyne-bridged (porphinato)zinc(II) structures (PZn(n) compounds), connected to gold electrodes via (4'-thiophenyl)ethynyl termini, are determined using scanning tunneling microscopy-based break junction methods. These experiments show that each α,ω-di[(4'-thiophenyl)ethynyl]-terminated PZn(n) compound (dithiol-PZn(n)) manifests a dual molecular conductance. In both the high and low conductance regimes, the measured resistance across these metal-dithiol-PZn(n)-metal junctions increases in a near linear fashion with molecule length. These results signal that meso-to-meso ethyne-bridged porphyrin wires afford the lowest ß value (ß = 0.034 Å(-1)) yet determined for thiol-terminated single molecules that manifest a quasi-ohmic resistance dependence across metal-dithiol-PZn(n)-metal junctions.

Electronic transport in porphyrin supermolecule-gold nanoparticle assemblies.

Temperature-dependent transport of hybrid structures consisting of gold nanoparticle arrays functionalized by conjugated organic molecules [(4'-thiophenyl)ethynyl-terminated meso-to-meso ethyne-bridged (porphinato)zinc(II) complexes] that possess exceptional optical and electronic properties was characterized. Differential conductance analysis distinguished the functional forms of the temperature and voltage dependences for a range of sample particles and molecular attachments. Thermally assisted tunneling describes transport for all cases and the associated mechanistic parameters can be used to determine the relative roles of activation energy, work function, and so forth. These results provide the basis on which to examine plasmon-influenced conduction in hybrid systems.

Six-Year Survival Outcomes for Patients with HER2-Positive Early Breast Cancer Treated with CT-P6 or Reference Trastuzumab: Observational Follow-Up Study of a Phase 3 Randomised Controlled Trial.

BACKGROUND: The Phase 3 CT-P6 3.2 study demonstrated equivalent efficacy and comparable safety between CT-P6 and reference trastuzumab in patients with human epidermal growth factor receptor-2 (HER2)-positive early breast cancer after up to 3 years' follow-up. OBJECTIVE: To investigate long-term survival with CT-P6 and reference trastuzumab. METHODS: In the CT-P6 3.2 study, patients with HER2-positive early breast cancer were randomised to neoadjuvant chemotherapy with CT-P6 or reference trastuzumab, surgery, and adjuvant CT-P6 or reference trastuzumab before a 3-year post-treatment follow-up. Patients who completed the study could enter a 3-year extension (CT-P6 4.2 study). Data were collected every 6 months to assess overall survival (OS), disease-free survival (DFS), and progression-free survival (PFS). RESULTS: Of 549 patients enrolled in the CT-P6 3.2 study, 216 (39.3%) patients continued in the CT-P6 4.2 study (CT-P6, 107; reference trastuzumab, 109) (intention-to-treat extension set). Median follow-up was 76.4 months for both groups. Medians were not reached for time-to-event parameters; estimated hazard ratios (95% confidence intervals) for CT-P6 versus reference trastuzumab were 0.59 (0.17-2.02) for OS, 1.07 (0.50-2.32) for DFS, and 1.08 (0.50-2.34) for PFS. Corresponding 6-year survival rates in the CT-P6 and reference trastuzumab groups, respectively, were 0.96 (0.90-0.99) and 0.94 (0.87-0.97), 0.87 (0.78-0.92) and 0.89 (0.81-0.94), and 0.87 (0.78-0.92) and 0.89 (0.82-0.94). CONCLUSIONS: Data from this extended follow-up of the CT-P6 3.2 study demonstrate the comparable long-term efficacy of CT-P6 and reference trastuzumab up to 6 years. EUDRACT NUMBER: 2019-003518-15 (retrospectively registered 10 March 2020).