Surface-Reconstructed Ru-Doped Nickel/Iron Oxyhydroxide Arrays for Efficient Oxygen Evolution.

The generation of an active phase through dynamic surface reconstruction is a promising strategy for improving the activity of electrocatalysts. However, studies investigating the reconstruction process and its impact on the intrinsic properties of the catalysts are scarce. Herein, the surface reconstruction of NiFe2 O4 interfaced with NiMoO4 (Ru-NFO/NMO) facilitated by Ru doping is reported. The electrochemical and material characterizations demonstrate that Ru doping can regulate the electronic structure of NFO/NMO and induce the high-valence state of Ni3.6+ δ , facilitating the surface reconstruction to highly active Ru-doped NiFeOOH/NiOOH (SR-Ru-NFO/NMO). The optimized SR-Ru-NFO/NMO exhibits promising performance in the oxygen evolution reaction, displaying a low overpotential of 229 mV at 10 mA cm-2 and good stability at varying current densities for 80 h. Density functional theory calculations indicate that Ru doping can increase the electron density and optimize intermediate adsorption by shifting the d-band center downward. This work provides valuable insights into the tuning of electrocatalysts by surface reconstruction and offers a rational design strategy for the development of highly active oxygen evolution reaction electrocatalysts.

Assessment of MMP-9 and clinical characteristics in dogs with tracheal collapse based on cough severity and fluoroscopic findings: a cross-sectional study.

BACKGROUND: Tracheal collapse (TC), a common disease in dogs, is characterized by cough; however, little is known about the serum biomarkers that can objectively evaluate the severity of cough in canine TC. Furthermore, studies elucidating the relationship of fluoroscopic characteristics with the severity of cough are lacking. Therefore, this study aimed to evaluate the relationship between cough severity and clinical characteristics, fluoroscopic images, and new serum biomarkers in canine TC. RESULTS: Fifty-one client-owned dogs diagnosed with TC based on fluoroscopic and clinical signs were enrolled in this study and divided into three groups according to the severity of cough (grade of cough: 0, 1, and 2). Signalments, comorbidities, and fluoroscopic characteristics were compared among the groups retrospectively. The serum matrix metalloproteinase-9 (MMP-9), interleukin-6 (IL-6), surfactant protein-A (SP-A), and syndecan-1 (SDC-1) levels were measured in all groups. No significant differences in age, breed, sex, or clinical history were observed among the groups. Concomitant pharyngeal collapse increased significantly with the severity of cough (p = .031). Based on the fluoroscopic characteristics, the TC grade of the carinal region increased significantly and consistently with the grade of cough (p = .03). The serum MMP-9 level was significantly higher in the grade 2 group than that in the grade 0 group (p = .014). The serum IL-6 level was significantly lower in the grade 1 group than that in the grade 0 group (p = .020). The serum SP-A and SDC-1 levels did not differ significantly among the groups. CONCLUSIONS: The severity of cough with the progression of TC can be predicted with the fluoroscopic TC grade at the carinal region. MMP-9 may be used as an objective serum biomarker that represents cough severity to understand the pathogenesis.

Pamidronate-induced irreversible symptomatic hypocalcemia in a dog with hypercalcemia after glucocorticoid withdrawal: a case report.

BACKGROUND: Pamidronate is used for the treatment of hypercalcemia. However, a rare but potential adverse event of pamidronate treatment is hypocalcemia. This report describes an unusual case of severe, irreversible hypocalcemia after a single injection of pamidronate for the treatment of hypercalcemia due to glucocorticoid withdrawal in a dog. CASE PRESENTATION: An 11-year-old castrated male Maltese dog presented with anorexia, vomiting, and diarrhea (day 0). The patient had calcinosis cutis throughout the body, calcification of intraabdominal organs, mild azotemia, and severe hypercalcemia. The severe calcification was attributed to long-term glucocorticoid administration, which was discontinued 1 month before presentation. Fluid therapy, diuretics, calcitonin, and a single intravenous injection of pamidronate were used for the treatment of hypercalcemia. On day 14, normocalcemia was achieved, but renal failure occurred. On day 20, severe and irreversible hypocalcemia occurred, and on day 42, the patient was euthanized at the owner's request because of worsened hypocalcemia and renal failure. CONCLUSIONS: Although hypocalcemia is an extremely rare adverse event of bisphosphonate treatment, bisphosphonates like pamidronate can result in potentially life-threatening conditions according to the patient's underlying conditions. Therefore, the patient's condition should be closely monitored and any underlying conditions should be carefully evaluated before initiating the treatment for hypercalcemia using pamidronate.

Anti-cancer effects of DHP107 on canine mammary gland cancer examined through in-vitro and in-vivo mouse xenograft models.

BACKGROUND: Canine mammary gland cancer (CMGC) is a common neoplasm in intact bitches. However, the benefit of adjuvant chemotherapy is unclear. The aim of this study was to investigate the anti-proliferative effects of paclitaxel on CMGC in in-vitro and in-vivo settings. RESULTS: Paclitaxel dose-dependently inhibited viability and induced G2/M phase cell cycle arrest and apoptosis in both primary and metastatic CMGC cell lines (CIPp and CIPm). In animal experiments, the average tumour volume decreased significantly in proportion to the administered oral paclitaxel dose. By examining tumour tissue using a TUNEL assay and immunohistochemical staining with anti-CD31 as a marker of endothelial differentiation, respectively, it was confirmed that oral paclitaxel induced apoptosis and exerted an anti-angiogenetic effect in tumour tissues. Further, downregulation of cyclin D1 in tumour tissues suggested that oral paclitaxel induced cell cycle arrest in tumour tissues in-vivo. CONCLUSIONS: Our results suggest that paclitaxel may have anti-cancer effects on CMGC through cell cycle arrest, induction of apoptosis, and anti-angiogenesis. This study could provide a novel approach to treat CMGC.

Rapid Synthesis of Oxygen-Enriched Porous Carbon through a Microwave Method and Its Application in Supercapacitors.

In this study, a strategy for the rapid and simple preparation of porous carbon (PC) using the microwave method was proposed. Oxygen-rich PC was synthesized by microwave irradiation in air, where potassium citrate and ZnCl2 served as the carbon source and microwave absorber, respectively. ZnCl2 achieves microwave absorption through dipole rotation, which uses ion conduction to convert heat energy in the reaction system. In addition, potassium salt etching improved the porosity of PCs. The PC prepared under optimal conditions had a large specific surface area (902 m2·g-1) and exhibited a significant specific capacitance (380 F·g-1) in the three-electrode system at 1 A·g-1. The energy and power densities of the assembled symmetrical supercapacitor device based on PC-375W-0.4 were 32.7 W·h·kg-1 and 0.65 kW·kg-1, respectively, at a current density of 1 A·g-1. Even after 5000 cycles at 5 A·g-1 current density, the excellent cycle life retained 94% of its initial capacitance.

Retrospective evaluation of prognosis and survival with various immunosuppressants in 82 dogs diagnosed with meningoencephalitis of unknown etiology (2010-2021).

BACKGROUND: Meningoencephalomyelitis of unknown etiology (MUE) is a comprehensive term for non-infectious inflammatory brain diseases of the central nervous system (CNS) caused by abnormal autoimmune responses. This study aims to compare the differences in survival and clinical response of MUE according to the adjuvant immunosuppressant use. Medical records of 82 dogs diagnosed with MUE were reviewed retrospectively. RESULTS: The overall survival time was 769 days (range 14-2687 days). The median survival time for each adjunctive was: leflunomide 1035 days (range 126-2163 days), mycophenolate mofetil 865 days (range 39-2191 days), cyclosporin 441 days (range 11-2176 days), cytosine arabinoside 754 days (range 6-1898 days) and a combination of mycophenolate mofetil and cytosine arabinoside 132 days (range 23-1227 days). There was no significant difference in the incidence rate of adverse events according to the immunosuppressants, but moderate to severe anemia was confirmed in 3 patients (18.7%) in the leflunomide group. CONCLUSIONS: The survival time and response rate of MUE dogs differed depending on which adjunctive immunosuppressants were used. Leflunomide showed a long survival time and a relatively good response rate in dogs with MUE. However, a large-scale further study with standardized doses of immunosuppressants and supportive treatment and constant monitoring interval is needed.

Mercury causes degradation of spatial cognition in a model songbird species.

Mercury is a widespread pollutant of increasing global concern that exhibits a broad range of deleterious effects on organisms, including birds. Because the developing brain is well-known to be particularly vulnerable to the neurotoxic insults of mercury, many studies have focused on developmental effects such as on the embryonic brain and resulting behavioral impairment in adults. It is not well understood how the timing of exposure, for example exclusively in ovo versus throughout life, influences the impact of mercury. Using dietary exposure to environmentally relevant methylmercury concentrations, we examined the role that timing and duration of exposure play on spatial learning and memory in a model songbird species, the domesticated zebra finch (Taeniopygia guttata castanotis). We hypothesized that developmental exposure was both necessary and sufficient to disrupt spatial memory in adult finches. We documented profound disruption of memory for locations of hidden food at two spatial scales, cage- and room-sized enclosures, but found that both developmental and ongoing adult exposure were required to exhibit this behavioral impairment. Methylmercury-exposed birds made more mistakes before mastering the spatial task, because they revisited unrewarded locations repeatedly even after discovering the rewarded location. Contrary to our prediction, hippocampal volume was not affected in birds exposed to methylmercury over their lifetimes. The disruption of spatial cognition that we detected is severe and would likely have implications for survival and reproduction in wild birds; however, it appears that individuals that disperse or migrate from a contaminated site might recover later in life if no longer exposed to the toxicant.

Fabrication and Performance Evaluation of Gelatin/Sodium Alginate Hydrogel-Based Macrophage and MSC Cell-Encapsulated Paracrine System with Potential Application in Wound Healing.

A gelatin/sodium alginate-based hydrogel microsphere has been fabricated after reaction condition optimization. Macrophages (RAW246.7) and adipose mesenchymal stem cells (ADSC) have been subsequently encapsulated in the microsphere in order to construct a 3D paracrine system for wound healing treatment. The synthesized microsphere displayed neglectable cytotoxicity toward both encapsulated cells until 10 days of incubation, indicating promising biocompatibility of the microsphere. A qRT-PCR and ELISA experiment revealed positive regulation of cytokines (Arg-1, IL-6, IL-8, IL-10, bFGF, HGF, VEGF, TLR-1, and CXCL13) expression regarding macrophage phenotype transformation and anti-inflammatory performance both inside the microsphere and in the microenvironment of established in vitro inflammatory model. Additionally, positive tendency of cytokine expression benefit wound healing was more pronounced in a fabricated 3D paracrine system than that of a 2D paracrine system. Furthermore, the 3D paracrine system exhibited more efficiently in the wound healing rate compared to the 2D paracrine system in an in vitro model. These results suggested the current paracrine system could be potentially used as a robust wound healing dressing.

Establishment of a piglet model for peritoneal metastasis of ovarian cancer.

BACKGROUND: A piglet model for peritoneal metastasis (PM) of ovarian cancer was developed. It will contribute to establishing innovative chemotherapeutical and surgical strategies without any limitation on rodent models. METHODS: A total of 12 four- to five-week-old piglets of 7 to 8 kg were used. Two phases of ovarian cancer cell injections were performed with laparoscopic surgery. In phase I trial, 5.0 × 106 SK-OV-3 cells in 0.1 ml suspension were inoculated into the omentum, peritoneum, and uterine horns of two piglets twice with a one-week interval. In the phase II trial, 5.0 × 106 SNU-008 cells in 0.1 ml suspension were injected only into uterine horns within the same time frame because tumor implantation after inoculation of SK-OV-3 cells was not observed at the omentum or peritoneum in the phase I trial. Modified peritoneal cancer index (PCI) score was used to monitor tumorigenesis up to 4 weeks after inoculation. Tumor tissues disseminated in the peritoneum 4 weeks after injection were used for histological examination with hematoxylin and eosin (H&E) and paired-box gene 8 (PAX-8) staining. RESULTS: In the phase I trial, two piglets showed PM with modified PCI scores of 5 and 4 at 3 weeks after the first inoculation, which increased to 14 and 15 after 4 weeks, respectively. In the phase II trial, PM was detected in eight of ten piglets, which showed modified PCI scores of 6 to 12 at 4 weeks after the first inoculation. The overall incidence of PM from the total of 12 piglets after inoculation was 75%. Immunohistochemical H&E and PAX-8 staining confirmed metastatic tumors. CONCLUSIONS: This study provides strong evidence that piglets can be employed as a model for PM by inoculating ovarian cancer cell lines from humans. Using two cell lines, the PM rate is 75%.

Nitrogen and Sulfur Codoped Porous Carbon Directly Derived from Potassium Citrate and Thiourea for High-Performance Supercapacitors.

By introducing a heteroatom into carbon material, an effective improvement in capacitance can be realized owing to surface oxidation and reduction reactions of pseudocapacitors. Herein, a simple one-pot carbonization activation method was proposed to convert potassium citrate into three-dimensional interconnected porous carbon (PC). Then, an effective double heteroatom doping method by thiourea was used to prepare nitrogen-sulfur-doped PC (N,S-PC). This porous structure facilitates the storage of a large number of ions and reduces their diffusion path. The synthesized N,S-PC nanomaterial has a capacitance of 674 F/g at 1 A/g in a 1 M H2SO4 electrolyte, can retain 94.41% of the initial capacitance after 10 000 cycles at 5 A/g, and has a long cycle life. More importantly, a symmetric supercapacitor assembled with this material can exhibit an energy density of up to 32.6 (W·h)/kg at a high-power density of 750 W/kg. This is due to the high performance of N,S-PC in supercapacitor electrode materials.

Early-stage breast cancer menopausal symptom experience and management: exploring medical oncology clinic visit conversations through qualitative analysis.

PURPOSE: Women being treated with chemotherapy for breast cancer experience menopausal symptoms that vary in presentation and impact on quality of life. The clinical visit before each chemotherapy cycle provides an important opportunity to allow patients to dialogue with their medical oncology healthcare providers about these symptoms and identify strategies for self-management. The objective of this study was to characterize patient and provider interactions regarding the menopausal symptom experience and management in the context of breast cancer treatment. METHODS: Thematic analysis was employed to analyze 61 transcripts from clinical encounters of women receiving chemotherapy treatment for breast cancer. Transcripts were chosen based on their inclusion of menopausal symptom discussion. RESULTS: Themes were separated into three distinct categories: patient, clinician, and dyadic themes. The overarching theme was goal discordance in the clinical visit, which was reflected in the following themes: unexpected and unprepared; distressed, disrupted and disturbed; clinical insensitivity; missed opportunity for management and empathy; and use of humor and colloquial language. Overall, women were unprepared for the menopausal symptom experience, and clinicians did not often provide management, interventions, or empathetic responses. CONCLUSION: There is a need to develop more astute assessment and communication regarding menopausal symptoms during the clinical visit. Possible interventions include a more holistic assessment, algorithms to facilitate the clinician's attention and response to menopausal symptoms, and treatment of symptoms.

Evaluation of endothelial cell-specific molecule-1 as a biomarker of glycocalyx damage in canine myxomatous mitral valve disease.

BACKGROUND: Endothelial cell-specific molecule-1 (ESM-1) has emerged as a potential biomarker for cardiovascular disease in humans. Myxomatous mitral valve disease (MMVD) is the most common heart disease in dogs, and we hypothesized that MMVD causes chronic inflammation that increases susceptibility to endothelial glycocalyx (eGCX) damage. In this study, we measured the concentration of ESM-1 in a group of dogs with MMVD and evaluated factors affecting eGCX damage. RESULTS: Sixty-four dogs (control, n = 6; MMVD, n = 58) were enrolled in this study. There was no significant difference in serum ESM-1 concentrations among the MMVD stages. The serum ESM-1 concentration was significantly higher in the death group than in the alive group in MMVD dogs. (p = 0.006). In five dogs with MMVD, serum ESM-1 concentrations tended to decrease when the cardiac drug (pimobendan, furosemide, and digoxin) dose was increased. CONCLUSIONS: In cases where MMVD progressed to decompensated heart failure with clinical symptoms and resulted in death, the concentration of serum ESM-1 increased significantly. Therefore, ESM-1 could be utilized as a new potential negative prognostic factor in patients with MMVD.

Negative marital interaction, purpose in life, and depressive symptoms among middle-aged and older couples: evidence from the Health and Retirement Study.

OBJECTIVE: Negative marital interaction and purpose in life have been associated with depressive symptoms. Yet, these associations have not been fully explored in a dyadic context. This study examines the actor (intra-individual) and partner (cross-spousal) effects of negative marital interaction on depressive symptoms in couples and the potential mediating role of purpose in life. METHODS: Data came from 1186 heterosexual married couples who participated in the 2016 (T1) and 2018 (T2) waves of the Health and Retirement Study and completed the psychosocial questionnaire in 2016. Structural equation modeling was used to estimate the direct and indirect associations among T1 negative marital interaction, T1 purpose in life, and T2 depressive symptoms at the actor and partner levels. Models controlled for age, race, educational level, self-rated health, and length of marriage. RESULTS: At the actor level, a greater negative marital interaction was associated with significantly lower levels of purpose in life for husbands and wives. Negative marital interaction was also associated with depressive symptoms for wives. Purpose in life mediated the relationship between negative marital interaction and depressive symptoms. At the partner level, wives' negative marital interaction was negatively associated with husbands' purpose in life, independent of husbands' own effects. CONCLUSION: The findings support the dominant marital discord model of depression and highlight gender differences in the cross-spousal effects of negative marital interaction on purpose in life. Positive psychology interventions can be beneficial to promote purpose in life and subsequently improve mental health outcomes among couples.

Effect of crank length on biomechanical parameters and muscle activity during standing cycling.

This study investigated the effect of crank length on biomechanical parameters and muscle activity during standing cycling. Ten participants performed submaximal cycling trials on a stand-up bicycle using four crank lengths. Joint angles, moments, powers, and works of the lower limbs were calculated from motion data and pedal reaction forces. Electromyographic (EMG) data were recorded from gluteus maximus (GM), vastus medialis, rectus femoris, biceps femoris (BF), gastrocnemius medialis, soleus, and tibialis anterior, and used to obtain the integrated EMG. Statistical parametric mapping was employed to analyse the biomechanical parameters throughout the pedalling cycle. Knee and hip flexion angles and hip power increased at the initiation (0-20%) of pedalling with increasing crank length, while the BF and GM muscle activities increased during propulsion (20-40%). Additionally, increasing the crank length resulted in increased knee power absorption during upstroke phase (70-100%). Peak knee extension moment increased with decreasing crank length during propulsion, but the moment at a short crank length during propulsion was comparable to fast walking. Consequently, longer crank lengths require increased propulsion power by the lower limb muscles during standing cycling compared to shorter crank lengths. Therefore, shorter crank lengths are recommended for stand-up bicycles to avoid fatigue.

Design and Micro-Fabrication of Focused High-Frequency Needle Transducers for Medical Imaging.

In this study, we report an advanced fabrication technique to develop a miniature focused needle transducer. Two different types of high-frequency (100 MHz) transducers were fabricated using the lead magnesium niobate-lead titanate (PMN-0.3PT) and lithium niobate (LiNbO3) single crystals. In order to enhance the transducer's performance, a unique mass-spring matching layer technique was adopted, in which gold and parylene play the roles of the mass layer and spring layer, respectively. The PMN-0.3PT transducer had a 103 MHz center frequency with a -6 dB bandwidth of 52%, and a signal-to-noise ratio (SNR) of 42 dB. The center frequency, -6 dB bandwidth, and SNR of the LiNbO3 transducer were 105 MHz, 66%, and 44 dB, respectively. In order to compare and evaluate the transducers' performances, an ultrasonic biomicroscopy (UBM) imaging on the fish eye was performed. The results showed that the LiNbO3 transducer had a better contrast resolution compared to the PMN-0.3PT transducer. The fabricated transducer showed an excellent performance with high-resolution corneal epithelium imaging of the experimental fish eye. These interesting findings are useful for the future biomedical implementation of the fabricated transducers in the field of high-resolution ultrasound imaging and diagnosis purpose.

Fine-mapping and candidate gene analysis for the foxglove aphid resistance gene Raso2 from wild soybean PI 366121.

KEY MESSAGE: The foxglove aphid resistance gene Raso2 from PI 366121 was fine-mapped to 77 Kb region, and one candidate gene was identified. The foxglove aphid (FA: Aulacorthum solani Kaltenbach) is an important insect pest that causes serious yield losses in soybean. The FA resistance gene Raso2 from wild soybean PI 366121 was previously mapped to a 13 cM interval on soybean chromosome 7. However, fine-mapping of Raso2 was needed to improve the effectiveness of marker-assisted selection (MAS) and to eventually clone it. The objectives of this study were to fine-map Raso2 from PI 366121 using Axiom® 180 K SoyaSNP array, to confirm the resistance and inheritance of Raso2 in a different background, and to identify candidate gene(s). The 105 F4:8 recombinant inbred lines were used to fine-map the gene and to test antibiosis and antixenosis of Raso2 to FA. These efforts resulted in the mapping of Raso2 on 1 cM interval which corresponds to 77 Kb containing eight annotated genes based on the Williams 82 reference genome assembly (Wm82.a2.v1). Interestingly, all nonsynonymous substitutions were in Glyma.07g077700 which encodes the disease resistance protein containing LRR domain and expression of the gene in PI 366121 was significantly higher than that in Williams 82. In addition, distinct SNPs within Glyma.07g077700 that can distinguish PI 366121 and diverse FA-susceptible soybeans were identified. We also confirmed that Raso2 presented the resistance to FA and the Mendelian inheritance for single dominant gene in a different background. The results of this study would provide fundamental information on MAS for development of FA-resistant cultivars as well as functional study and cloning of the candidate gene in soybean.

Factors associated with symptom distress in women with breast cancer prior to initiation of chemotherapy.

BACKGROUND: Symptom distress in women with breast cancer is associated with early discontinuation of chemotherapy and may influence treatment outcomes. Describing racial differences in prechemotherapy symptom distress and examining contextual variables of the symptom experience may inform our understanding of the complex problem of racial disparities in breast cancer. AIM: To determine if perceived social support, healthcare system distrust, and economic hardship predict symptom distress in women with breast cancer prior to their first chemotherapy treatment. DESIGN: Descriptive, correlational, cross-sectional. METHODS: Baseline data (N = 119) was used from a multisite, longitudinal study comparing the symptom experience and ability to receive chemotherapy of Black and White women with breast cancer (R01MD012245; Rosenzweig, PI). Measures included the Symptom Distress Scale, Interpersonal Support Evaluation List, Health Care System Distrust Scale, and Psychological Sense of Economic Hardship scale. The analysis consisted of multiple regression and a t-test. RESULTS: On average, participants reported five symptoms prior to chemotherapy. Black women reported higher symptoms distress than White women; t(68.34) = 2.15, p = 0.035. The model explained 26% of variance in symptom distress; F(5, 112) = 9.01, p < 0.001. While controlling for age and race, greater perceived economic hardship contributed to higher symptom distress (ß = 0.36, p = 0.001, 95% CI: 0.34 to 1.34). Race, health care system distrust and social support did not significantly predict symptom distress. CONCLUSION: Assessment of perceived financial hardship prior to beginning chemotherapy is critical to identify those patients at risk for greater symptom distress.

Psychometric properties of a single-item visual analog scale measuring goals of care in patients with advanced cancer.

PURPOSE: The purpose of this study was to examine the psychometric properties of a single-item visual analog scale (VAS) to measure goals of care in patients with advanced cancer. METHODS: Data were obtained from 378 patients with diagnoses of advanced lung, gastrointestinal, or pancreatic cancer. Goal of care was measured at baseline and every 3 months until patient death or completion of the 15-month study period. A single-item VAS ranging from 0 (quality of life is all that matters) to 100 (length of life is all that matters) was used to measure patients' goals of care for all study subjects; a subsample of subjects also completed the Quality of Life-Length of Life scale which asked patients to select categories of preferences. Test-retest reliability (intra-class correlation) and construct validity (known-groups, convergent, divergent) were evaluated. RESULTS: At 9 and 12 months, the test-retest reliability for patients with stable symptoms (n = 107) was established with the ICC(1,3) = 0.81, p < .001. Known-groups (r = 0.99, p < .001), convergent (r = 0.78, p < .001), and divergent (r = .06, p = 0.24) validity all demonstrated evidence of good construct validity. CONCLUSIONS: Preliminary psychometric testing for a single-item VAS that measures goals of care in a sample of patients with advanced cancer met standard requirements for reliability and validity. While further testing with a larger sample size is recommended, the tool's use in the clinical area to assess cancer patients' goals of care is appropriate. Such a tool could facilitate goals of care discussions in the clinical area.

Alignment Strategy for Constricted Maxillary Dental Arch in Patients With Unilateral Cleft Lip and Palate Using Fixed Orthodontic Appliance.

The purpose of this study was to compare the alignment pattern of the constricted maxillary dental arch by fixed orthodontic treatment (FOT) in the well-aligned and constricted arches of unilateral cleft lip and palate (UCLP) patients. 19 UCLP patients were divided into Group 1 (well-aligned arch, n = 9) and Group 2 (constricted arch, n = 10). After the cephalometric and maxillary dental arch variables before (T1) and after FOT (T2) were measured, statistical analysis was performed. There were no significant differences in the surgical timing of cheiloplasty, palatoplasty, and secondary alveolar bone grafting and in the surgical method of cheiloplasty between the 2 groups. However, Group 2 had a higher percentage of palatoplasty method, which could leave the denuded bone for secondary healing than Group 1 (P < 0.05). Although Group 2 showed more constriction and asymmetry in the maxillary dental arch compared to Group 1 at the T1 stage (inter-second premolar width, greater segment angle [GSA], and lesser segment angle [LSA], all P < 0.05), these problems could be effectively resolved by FOT. As a result, at the stage T2, there was no significant difference in all the variables between the 2 groups. During T1-T2, there was a different pattern in change of variables between Groups 1 and 2 (anterior segment angle in the greater segment [P < 0.05] in Group 1 and U1-SN [P < 0.01], inter-molar width [P < 0.05], GSA [P < 0.05[, and LSA [P < 0.01] in Group 2). Therefore, according to the maxillary dental arch shape, different strategy is necessary to obtain proper alignment by FOT.

VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu2(µ-O2)], [Fe2(µ-O2)] and Fe(IV)-O cores based on DFT potential energy surfaces.

High-valent Cu and Fe species, which are generated from dioxygen activation in metalloenzymes, carry out the functionalization of strong C-H bonds. Understanding the atomic details of the catalytic mechanism has long been one of the main objectives of bioinorganic chemistry. Large H/D kinetic isotope effects (KIEs) were observed in the C-H activation by high-valent non-heme Cu or Fe complexes in enzymes and their synthetic models. The H/D KIE depends significantly on the transition state properties, such as structure, energies, frequencies, and shape of the potential energy surface, when the tunneling effect is large. Therefore, theoretical predictions of kinetic parameters such as rate constants and KIEs can provide a reliable link between atomic-level quantum mechanical mechanisms and experiments. The accurate prediction of the tunneling effect is essential to reproduce the kinetic parameters. The rate constants and HD/KIE have been calculated using the variational transition-state theory including multidimensional tunneling based on DFT potential energy surfaces along the reaction coordinate. Excellent agreement was observed between the predicted and experimental results, which assures the validity of the DFT potential energy surfaces and, therefore, the proposed atomic-level mechanisms. The [Cu2(µ-O)2], [Fe2(µ-O)2], and Fe(IV)-oxo species were employed for C-H activation, and their role as catalysts was discussed at an atomic level.