Quantum Mechanics Studies of Fuel Cell Catalysts and Proton Conducting Ceramics with Validation by Experiment

We carried out quantum mechanics (QM) studies aimed at improving the performance of hydrogen fuel cells. This led to predictions of improved materials, some of which were subsequently validated with experiments by our collaborators. In part I, the challenge was to find a replacement for the Pt cathode that would lead to improved performance for the Oxygen Reduction Reaction (ORR) while remaining stable under operational conditions and decreasing cost. Our design strategy was to find an alloy with composition Pt3M that would lead to surface segregation such that the top layer would be pure Pt, with the second and subsequent layers richer in M. Under operating conditions we expect the surface to have significant O and/or OH chemisorbed on the surface, and hence we searched for M that would remain segregated under these conditions. Using QM we examined surface segregation for 28 Pt3M alloys, where M is a transition metal. We found that only Pt3Os and Pt3Ir showed significant surface segregation when O and OH are chemisorbed on the catalyst surfaces. This result indicates that Pt3Os and Pt3Ir favor formation of a Pt-skin surface layer structure that would resist the acidic electrolyte corrosion during fuel cell operation environments. We chose to focus on Os because the phase diagram for Pt-Ir indicated that Pt-Ir could not form a homogeneous alloy at lower temperature. To determine the performance for ORR, we used QM to examine all intermediates, reaction pathways, and reaction barriers involved in the processes for which protons from the anode reactions react with O2 to form H2O. These QM calculations used our Poisson-Boltzmann implicit solvation model include the effects of the solvent (water with dielectric constant 78 with pH 7 at 298K). We found that the rate determination step (RDS) was the Oad hydration reaction (Oad + H2Oad -&#62; OHad + OHad) in both cases, but that the barrier for pure Pt of 0.50 eV is reduced to 0.48 eV for Pt3Os, which at 80 degrees C would increase the rate by 218%. We collaborated with the Pu-Wei Wu’s group to carry out experiments, where we found that the dealloying process-treated Pt2Os catalyst showed two-fold higher activity at 25 degrees C than pure Pt and that the alloy had 272% improved stability, validating our theoretical predictions. We also carried out similar QM studies followed by experimental validation for the Os/Pt core-shell catalyst fabricated by the underpotential deposition (UPD) method. The QM results indicated that the RDS for ORR is a compromise between the OOH formation step (0.37 eV for Pt, 0.23 eV for Pt2ML/Os core-shell) and H2O formation steps (0.32 eV for Pt, 0.22 eV for Pt2ML/Os core-shell). We found that Pt2ML/Os has the highest activity (compared to pure Pt and to the Pt3Os alloy) because the 0.37 eV barrier decreases to 0.23 eV. To understand what aspects of the core shell structure lead to this improved performance, we considered the effect on ORR of compressing the alloy slab to the dimensions of pure Pt. However this had little effect, with the same RDS barrier 0.37 eV. This shows that the ligand effect (the electronic structure modification resulting from the Os substrate) plays a more important role than the strain effect, and is responsible for the improved activity of the core- shell catalyst. Experimental materials characterization proves the core-shell feature of our catalyst. The electrochemical experiment for Pt2ML/Os/C showed 3.5 to 5 times better ORR activity at 0.9V (vs. NHE) in 0.1M HClO4 solution at 25 degrees C as compared to those of commercially available Pt/C. The excellent correlation between experimental half potential and the OH binding energies and RDS barriers validate the feasibility of predicting catalyst activity using QM calculation and a simple Langmuir–Hinshelwood model. In part II, we used QM calculations to study methane stream reforming on a Ni-alloy catalyst surfaces for solid oxide fuel cell (SOFC) application. SOFC has wide fuel adaptability but the coking and sulfur poisoning will reduce its stability. Experimental results suggested that the Ni4Fe alloy improves both its activity and stability compared to pure Ni. To understand the atomistic origin of this, we carried out QM calculations on surface segregation and found that the most stable configuration for Ni4Fe has a Fe atom distribution of (0%, 50%, 25%, 25%, 0%) starting at the bottom layer. We calculated that the binding of C atoms on the Ni4Fe surface is 142.9 Kcal/mol, which is about 10 Kcal/mol weaker compared to the pure Ni surface. This weaker C binding energy is expected to make coke formation less favorable, explaining why Ni4Fe has better coking resistance. This result confirms the experimental observation. The reaction energy barriers for CHx decomposition and C binding on various alloy surface, Ni4X (X=Fe, Co, Mn, and Mo), showed Ni4Fe, Ni4Co, and Fe4Mn all have better coking resistance than pure Ni, but that only Ni4Fe and Fe4Mn have (slightly) improved activity compared to pure Ni. In part III, we used QM to examine the proton transport in doped perovskite-ceramics. Here we used a 2x2x2 supercell of perovskite with composition Ba8X7M1(OH)1O23 where X=Ce or Zr and M=Y, Gd, or Dy. Thus in each case a 4+ X is replace by a 3+ M plus a proton on one O. Here we predicted the barriers for proton diffusion allowing both includes intra-octahedron and inter-octahedra proton transfer. Without any restriction, we only observed the inter-octahedra proton transfer with similar energy barrier as previous computational work but 0.2 eV higher than experimental result for Y doped zirconate. For one restriction in our calculations is that the Odonor-Oacceptor atoms were kept at fixed distances, we found that the barrier difference between cerates/zirconates with various dopants are only 0.02~0.03 eV. To fully address performance one would need to examine proton transfer at grain boundaries, which will require larger scale ReaxFF reactive dynamics for systems with millions of atoms. The QM calculations used here will be used to train the ReaxFF force field.</p

Cijepni soj virusa zaraznog bronhitisa patogeniji je za pileće zametke od divljeg soja 2575/98.

An avian infectious bronchitis virus (IBV) strain 2575/98 was attenuated using serial chicken embryo passage to become a vaccine in Taiwan. The aim of this study was to investigate the replication ability, pathogenicity, and tissue tropism of the wild and vaccine strains in chicken embryos. The embryos were inoculated with different titers of wild and vaccine strains. Quantification of virus in allantoic fluid was evaluated using real time RT-PCR. The results showed that the vaccine strain replicated in higher titers than the wild strain, and caused embryo death so quickly that only a few dwarfisms occurred. The embryos inoculated with wild and vaccine strains had similar lesions that were confined primarily to the chorionallantoic membrane (CAM), liver, and kidneys. The immunohistochemical data showed that IBV was present predominantly in the lungs, kidneys, and CAM. Although both strains caused hepatic damage, very few virus antigens were detected in the hepatic tissue. The pathogenicity of the vaccine becomes higher in embryos although it is lower in chickens than its wild strain. The vaccine strain could be used as a possible new vaccine candidate for IBV control.Virus zaraznog bronhitisa peradi soj 2575/98 bio je oslabljen uzastopnim pasažama u pilećim zametcima da bi poslužio kao cijepni soj u Tajvanu. Cilj je ovog rada bio istražiti mogućnost umnožavanja, patogenost i tropizam terenskog i cijepnog soja u pilećim zametcima. Zametci su bili inokulirani cijepnim sojem različitog titra. Količina virusa u alantoisnoj tekućini bila je određena RT-PCR-om u stvarnom vremenu. Rezultati su pokazali da se cijepni soj umnažao u višem titru od divljeg soja i prouzročio uginuće zametaka tako brzo da se uspjelo razviti svega nekoliko kržljavih. U inokuliranih zametaka, bez obzira na divlji ili cijepni soj, razvile su se slične promjene pretežito na korioalantoisnoj opni, jetrima i bubrezima. Imunohistokemijski je dokazano da se virus zaraznog bronhitisa prvenstveno nalazio u plućima, bubrezima i korioalantoisnoj opni. Iako su oba soja prouzročila oštećenja jetara, neznatna količina virusnog antigena bila je dokazana u jetrenom tkivu. Patogenost cijepnog soja bila je u zametcima jača, a u pilićima slabija od divljeg soja. Cijepni soj bi se mogao rabiti kao mogući kandidat za proizvodnju novog cjepiva protiv zaraznog bronhitisa

Overweight and Obesity-related Metabolic Disorders in Hospital Employees

BackgroundObesity is associated with metabolic disorders and cardiovascular diseases. This study investigated the relationship between overweight and obese status and the incidence of type 2 diabetes, hypertension, hyperlipidemia and hyperuricemia.MethodsThis prospective cohort study comprised 1749 hospital employees who received baseline health check-ups in 1993. Data from the 1027 participants (832 women, 195 men; mean age, 36 ± 7 years) who repeated check-ups in 2003 were used in the analysis. Relative risks (RRs) for development of metabolic disorders during follow-up associated with different body mass index (BMI) categories at baseline as defined by Asia-Pacific recommendations and the Department of Health in Taiwan were calculated after adjustment for covariates.ResultsThe prevalence of overweight and obesity at baseline check-up were 17.6% and 14.5%, respectively. Obese subjects with baseline BMI ≥ 25 kg/m2 had a significant multivariate-adjusted RR of 2.7 for hypertension, 14.8 for type 2 diabetes, 3.2 for hypertriglyceridemia, and 2.8 for hyperuricemia, compared to subjects with baseline BMI < 23.0 kg/m2. RR for diabetes was higher in women than in men, but RR for hypertriglyceridemia was higher in men. The risks of hypertension and hyperuricemia significantly increased for subjects with baseline BMI ≥ 23 kg/m2, while RRs for type 2 diabetes increased significantly for baseline BMI ≥ 24 kg/m2 and hypertriglyceridemia increased for baseline BMI ≥ 25 kg/m2. The risks attributable to obesity (baseline BMI ≥ 25 kg/m2) were 23.0% for hypertension, 70.8% for diabetes, 27.9% for hypertriglyceridemia, and 24.1% for hyperuricemia.ConclusionThis study revealed that a high prevalence of overweight and obesity was associated with significantly increased risk of development of type 2 diabetes, hypertension, hypertriglyceridemia and hyperuricemia in hospital employees, suggesting the need for programs to improve weight management

Factors Associated With Leisure Participation Among the Elderly Living in Long-term Care Facilities

SummaryBackgroundA lack of participation in leisure activities often leads to depression in the elderly. This study investigated the factors impacting leisure participation among the elderly living in long-term care facilities.MethodsThis cross-sectional study recruited 309 individuals older than 65 years from six long-term care facilities located in the Taipei area. Structured in-person questionnaires were administered to assess their demographic characteristics, general self-rated health status, leisure constraints, and leisure participation.ResultsThe average frequency of leisure participation was 27.20 ± 12.48 points. The top five most popular leisure activities were watching television, walking, chatting, reading, and participating in religious activities. Elderly subjects who tended to be female, have religious beliefs, have a high school education level, be married, perceive themselves in better health, demonstrate better cognitive function and have higher scores on activities of daily living and instrumental activities of daily living scales were more likely to participate in leisure activities (p < 0.05). In contrast, those who were older, had stayed in the facility for a longer time period and had more leisure constraints were less likely to participate in leisure activities (p < 0.05). Overall, the predictive factors for leisure participation included religious beliefs, educational level, cognitive skill, instrumental activities of daily living score, depression, personal inner constraints, and structural constraints. The entire model was significant (F = 11.03, p < 0.001).ConclusionBased on the self-reported interests, health status and level of cognitive skill of elderly residents, long-term care facilities should arrange appropriate leisure activities to prevent depression and to improve quality of life

The flow and turbulence structure at a rectangular bridge pier with a low angle of attack

River hydrodynamicsInteraction with structure

Topographic Study of Extracted Molars with Advanced Furcation Involvement: Furcation Entrance Dimension and Molar Type

This study investigated the topography of the furcation entrance dimension (FED) on molars with advanced furcation involvement (FI). The sample pool consisted of 169 maxillary and mandibular molars from a group of 165 individuals with severely advanced periodontal destruction. The subjects included men and women aged 24 to 84 years (mean, 47.8 ± 7.2 years). The FEDs of the maxillary buccal, mesial, and distal surfaces as well as the mandibular buccal and lingual surfaces were measured under a stereomicroscope and clarified into grades I (FED < 0.55 mm), II (0.55-0.75 mm), and III (> 0.75 mm) using automatic grading system software designed by our research associates. The differences and relationships among molar location, furcation site, and FED grade were analyzed using the chi-square test. There was a significant difference among buccal (BFED), mesial (MFED), and distal (DFED) FEDs in both the maxillary first (χ24 = 58.915, p < 0.001) and second (χ24 = 66.839, p < 0.001) molars. The relationship between molar type and FED grade was statistically significant for both the BFED (p < 0.001) and the DFED (p < 0.001) of maxillary molars, as well as for both the BFED (p < 0.0001) and LFED (p < 0.0001). The difference in FED grade between the first and second molars was statistically significant in both maxillary (p < 0.001) and mandibular (p < 0.0001) molars. There was a significant relationship between FED grade and tooth location at molars with advanced FI

Thrombolysis in Myocardial Infarction Frame Count in Single-Vessel Disease After Angioplasty

SUMMARYBackgroundWe compared the thrombolysis in myocardial infarction (TIMI) frame count and examined the impact of angioplasty on the count between patients with normal coronary angiograms and those with single-vessel disease (SVD).MethodsIn 780 consecutive patients referred for coronary angiography, TIMI frame count was measured for 149 patients who had SVD and 32 patients with normal angiograms who underwent the procedure for electro-physiologic study or valvular heart disease survey.ResultsComparison of each of the three vessels in the normal vessel group with the corresponding non-stenotic vessels in the SVD group showed similar counts in each of the left anterior descending artery (LAD), left circumflex artery (LCX), and right coronary artery (RCA). For the stenotic vessels, after successful angioplasty, the counts were all reduced (LAD, 54.5 ±28.8 vs. 34.0 ±19.3; LCX, 67.3 ±31.1 vs. 34.1 ±19.0; RCA, 33.2 ±28.1 vs. 19.3 ±7.9; all p <0.05). In addition, the count in the RCA after angioplasty was lower, compared with the RCA of the normal group (19.3 ±7.9 vs. 29.1 ±14.6, p = 0.001). Multivariate analysis showed that the use of oral calcium channel blockers was the only independent predictor for the reduction in RCA after angioplasty.ConclusionIn patients with SVD, the data of TIMI frame count in the nonstenotic vessels were similar to those without the disease, suggesting that the count in the normal artery is not affected by the adjacent stenotic artery. For the stenotic vessels, angioplasty had differential effects on each of the three arteries, indicating the existence of distinct properties, which is affected by calcium channel blockers, for individual coronary arteries in response to atherosclerosis and/or angioplasty

Automatic Cephalometric Landmark Detection on X-Ray Images Using Object Detection

We propose a new deep convolutional cephalometric landmark detection framework for orthodontic treatment. Our proposed method consists of two major steps: landmark detection using a deep neural network for object detection, and landmark repair to ensure one instance per landmark class. For landmark detection, we modify the loss function of the backbone network YOLOv3 to eliminate the constrains on the bounding box and incorporate attention mechanism to improve the detection accuracy. For landmark repair, a triangle mesh is generated from the average face to eliminate superfluous instances, followed by estimation of missing landmarks from the detected ones using Laplacian Mesh. Trained and evaluated on a public benchmark dataset from IEEE ISBI 2015 grand challenge, our proposed framework obtains comparable results compared to the state-of-the-art methods for cephalometric landmark detection, and demonstrates the efficacy of using a deep CNN model for accurate object detection of landmarks defined by only a single pixel location

TGF-β inhibits IL-1β-activated PAR-2 expression through multiple pathways in human primary synovial cells

To investigate the mechanism how Transforming growth factor-β(TGF-β) represses Interleukin-1β (IL-1β)-induced Proteinase-Activated Receptor-2 (PAR-2) expression in human primary synovial cells (hPSCs). Human chondrocytes and hPSCs isolated from cartilages and synovium of Osteoarthritis (OA) patients were cultured with 10% fetal bovine serum media or serum free media before treatment with IL-1β, TGF-β1, or Connective tissue growth factor (CTGF). The expression of PAR-2 was detected using reverse transcriptase-polymerase chain reaction (RT-PCR) and western blotting. Collagen zymography was performed to assess the activity of Matrix metalloproteinases-13 (MMP-13). It was demonstrated that IL-1β induces PAR-2 expression via p38 pathway in hPSCs. This induction can be repressed by TGF-β and was observed to persist for at least 48 hrs, suggesting that TGF-β inhibits PAR-2 expression through multiple pathways. First of all, TGF-β was able to inhibit PAR-2 activity by inhibiting IL-1β-induced p38 signal transduction and secondly the inhibition was also indirectly due to MMP-13 inactivation. Finally, TGF-β was able to induce CTGF, and in turn CTGF represses PAR-2 expression by inhibiting IL-1β-induced phospho-p38 level. TGF-β could prevent OA from progression with the anabolic ability to induce CTGF production to maintain extracellular matrix (ECM) integrity and to down regulate PAR-2 expression, and the anti-catabolic ability to induce Tissue inhibitors of metalloproteinase-3 (TIMP-3) production to inhibit MMPs leading to avoid PAR-2 over-expression. Because IL-1β-induced PAR-2 expressed in hPSCs might play a significantly important role in early phase of OA, PAR-2 repression by exogenous TGF-β or other agents might be an ideal therapeutic target to prevent OA from progression