Characterizations of partially reduced polyoxometalate catalysts using ammonia adsorption microcalorimetry and methanol oxidation studies / by Suresh Babu Bommineni.

Phosphomolybdic acid (H3PMo12O40) along with niobium,pyridine and niobium exchanged phosphomolybdic acid catalysts were prepared. Ammonia adsorption microcalorimetry and methanol oxidation studies were carried out to investigate the acid sites strength acid/base/redox properties of each catalyst. The addition of niobium, pyridine or both increased the ammonia heat of adsorption and the total uptake. The catalyst with both niobium and pyridine demonstrated the largest number of strong sites. For the parent H3PMo12O40 catalyst, methanol oxidation favors the redox product. Incorporation of niobium results in similar selectivity to redox products but also results in no catalyst deactivation. Incorporation of pyridine instead changes to the selectivity to favor the acidic product. Finally, the inclusion of both niobium and pyridine results in strong selectivity to the acidic product while also showing no catalyst deactivation. Thus the presence of pyridine appears to enhance the acid property of the catalyst while niobium appears to stabilize the active site.

Performance evaluation of a novel asymmetric capacitor using a light-weight, carbon foam supported nickel electrode

Electrochemical capacitors have been an important development in recent years in the field of energy storage. Capacitors can be developed by utilizing either double layer capacitance at the electrode/solution interfaces alone or in combination with a battery electrode associated with a faradic redox process in one electrode. An asymmetric capacitor consisting of electrochemically deposited nickel hydroxide, supported on carbon foam as a positive electrode and carbon sheet as a negative electrode has been successfully assembled and cycled. One objective of this study has been to demonstrate the viability of the nickel carbon foam positive electrode, especially in terms of cycle life. Electrochemical characterization shows stable, high cycle performance in 26 wt. % KOH electrolyte with a maximum energy density of 4.1 Wh/Kg and a relaxation time constant of 6.24 s. This cell has demonstrated high cycle life, 14,500 cycles, with efficiency better than 98%. In addition, the cell failure mechanism and self-discharge behavior of the aforesaid capacitor are analyzed.

NICKEL-COBALT SOLID SOLUTION AND ITS APPLICATIONS AS CATALYSTS FOR CARBON DIOXIDE REFORMING OF METHANE

Global warming issue becomes more significant to human beings and other organisms on the earth. Among many greenhouse gases, carbon dioxide (CO2) has the largest contribution to global warming. To find an effective way to utilize the greenhouse gas is urgent. It is the best way to convert CO2 to useful compounds. CO2 reforming of methane is an attractive process to convert CO2 and methane into synthesis gas (CO/H2), which can be used as a feedstock for gasoline, methanol, and other hydrocarbons. Nickel and cobalt were found to have good activity for CO2 reforming. However, they have a poor stability due to carbon deposition. This research developed efficient Ni-Co solid solution catalysts with excellent activities and high stability for CO2 reforming of methane. First, the structure of binary oxide solid solution of nickel and cobalt was investigated. It was found that while the calcination of Ni(NO3)2 and Co(NO3)2 mixture with 1:1 molar ratio at a high temperature above 800 oC generated NiO-CoO solid solution, only Ni3O4-Co3O4 solid solution was observed after the calcination at a low temperature of 500 oC. Furthermore, if the calcination was carried out at a medium temperature arranged from 600 to 700 oC, both NiO-CoO and Ni3O4-Co3O4 solid solutions can be formed. This occurred because Co3O4 can induce the formation of Ni3O4, whereas NiO can stabilize CoO. In addition, the lattice parameter of Ni3O4, which was predicted by using Vegard’s Law, is 8.2054 Å. As a very important part of this dissertation, Ni-Co solid solution was evaluated as catalysts for CO2 reforming of methane. It was revealed that nickel-cobalt solid solution showed excellent catalytic performance and high stability for CO2 reforming of methane. However, the stability of Ni-Co solid solution catalysts is strongly dependent on their composition and preparation condition. The optimum composition is 50%Ni-50%Co. Furthermore, the structure of Ni-Co catalysts was characterized by XRD, Vvis, TPR, TPD, BET, AES, TEM, XANES and EXAFS. The relationship between the structure and the catalytic performance was established: (1) The reduced NiO-CoO solid solution possesses better catalytic performance and stability than the reduced Ni3O4-Co3O4 solid solution. (2) Ni is richer on surface in Ni-Co catalysts. And (3) the reduction of Ni-Co-O solid solution generated two types of particles, small and large particles. The small ones are dispersed on large ones as catalytic component.

Advanced Nanostructured Electro-Catalysts for Electricity Generation and Biorenewable Alcohol Conversion

In my Ph.D research, a wet chemistry-based organic solution phase reduction method was developed, and was successfully applied in the preparation of a series of advanced electro-catalysts, including 0-dimensional (0-D) Pt, Pd, Au, and Pd-Ni nanoparticles (NPs), 1-D Pt-Fe nanowires (NWs) and 2-D Pd-Fe nanoleaves (NLs), with controlled size, shape, and morphology. These nanostructured catalysts have demonstrated unique electro-catalytic functions towards electricity production and biorenewable alcohol conversion. The molecular oxygen reduction reaction (ORR) is a long-standing scientific issue for fuel cells due to its sluggish kinetics and the poor catalyst durability. The activity and durability of an electro-catalyst is strongly related with its composition and structure. Based on this point, Pt-Fe NWs with a diameter of 2 - 3 nm were accurately prepared. They have demonstrated a high durability in sulfuric acid due to its 1-D structure, as well as a high ORR activity attributed to its tuned electronic structure. By substituting Pt with Pd using a similar synthesis route, Pd-Fe NLs were prepared and demonstrated a higher ORR activity than Pt and Pd NPs catalysts in the alkaline electrolyte. Recently, biomass-derived alcohols have attracted enormous attention as promising fuels (to replace H2) for low-temperature fuel cells. From this point of view, Pd-Ni NPs were prepared and demonstrated a high electro-catalytic activity towards ethanol oxidation. Comparing to ethanol, the biodiesel waste glycerol is more promising due to its low price and high reactivity. Glycerol (and crude glycerol) was successfully applied as the fuel in an Au-anode anion-exchange membrane fuel cell (AEMFC). By replacing Au with a more active Pt catalyst, simultaneous generation of both high power-density electricity and value-added chemicals (glycerate, tartronate, and mesoxalate) from glycerol was achieved in an AEMFC. To investigate the production of valuable chemicals from glycerol electro-oxidation, two anion-exchange membrane electro-catalytic reactors were designed. The research shows that the electro-oxidation product distribution is strongly dependent on the anode applied potential. Reaction pathways for the electro-oxidation of glycerol on Au/C catalyst have been elucidated: continuous oxidation of OH groups (to produce tartronate and mesoxalate) is predominant at lower potentials, while C-C cleavage (to produce glycolate) is the dominant reaction path at higher potentials.

Implant-supported distal extensions in severely resorbed posterior alveolar ridges

The application of implant-borne rehabilitations in residual alveolar ridges may be restricted by various anatomic conditions, as available bone height and characteristics. Here we report the clinical outcome of implants placed in severely resorbed posterior ridges, in addition to various implant-supported treatment modalities. Extra Oral implants (Straumann, Basel, Switzerland) with the intraosseous length of 2.5–5mm were installed in the posterior alveolar ridges. Following the healing period of 4–6 months, implants were exposed and included in the distal extensions of fixed and removable prosthesis. At recall appointments were collected surgical, clinical and radiological variables, including the evidence of adverse effects. An 8-years life table analysis was calculated. The treatment protocol was applied in thirty-five patients, presenting 31 removable and 4 fixed complete implant-supported dentures. A total of 61 Extra Oral implants were placed posterior to the distal implants, at the mean distance of 29.8mm (range 15.6–62.7mm). Three implants failed during the osteointegration phase, yielding an 8-year cumulative success rate of 92.24%. Following the osteointegration period, no major bone loss or other adverse events were found. The clinical results indicated that the Extra Oral implants may be successfully used in addition to the other, longer implants. Thus, a relatively long extension in the posterior region may be employed. With careful preoperative planning, this technique offers a simple and beneficial complementary treatment option for removable and fixed complete dentures.

Age Hardening of Silver-Platinum Alloys

The alloy system selected for study was the binary alloy of platinum and silver. An examination of the various silver alloy diagrams revealed that of several possible alloys, the silver platinum was the most suit­able with regard to solubility.

A systematic review of the survival and complication rates of implant supported fixed dental prostheses with cantilever extensions after an observation period of at least 5 years

OBJECTIVE: The aim of this systematic review was to assess the survival rates of short-span implant-supported cantilever fixed dental prostheses (ICFDPs) and the incidence of technical and biological complications after an observation period of at least 5 years. MATERIAL AND METHODS: An electronic MEDLINE search supplemented by manual searching was conducted to identify prospective or retrospective cohort studies reporting data of at least 5 years on ICFDPs. Five- and 10-year estimates for failure and complication rates were calculated using standard or random-effect Poisson regression analysis. RESULTS: The five studies eligible for the meta-analysis yielded an estimated 5- and 10-year ICFDP cumulative survival rate of 94.3% [95 percent confidence interval (95% CI): 84.1-98%] and 88.9% (95% CI: 70.8-96.1%), respectively. Five-year estimates for peri-implantitis were 5.4% (95% CI: 2-14.2%) and 9.4% (95% CI: 3.3-25.4%) at implant and prosthesis levels, respectively. Veneer fracture (5-year estimate: 10.3%; 95% CI: 3.9-26.6%) and screw loosening (5-year estimate: 8.2%; 95% CI: 3.9-17%) represented the most common complications, followed by loss of retention (5-year estimate: 5.7%; 95% CI: 1.9-16.5%) and abutment/screw fracture (5-year estimate: 2.1%; 95% CI: 0.9-5.1%). Implant fracture was rare (5-year estimate: 1.3%; 95% CI: 0.2-8.3%); no framework fracture was reported. Radiographic bone level changes did not yield statistically significant differences either at the prosthesis or at the implant levels when comparing ICFDPs with short-span implant-supported end-abutment fixed dental prostheses. CONCLUSIONS: ICFDPs represent a valid treatment modality; no detrimental effects can be expected on bone levels due to the presence of a cantilever extension per se.

Comparative study of four retentive anchor systems for implant supported overdentures--retention force changes

OBJECTIVES: Wear of attachments leads to a loss of retention and potentially reduces the function of complete dentures. This study evaluated the retention force changes of different prefabricated attachment systems for implant-supported overdentures to estimate the wear constancy and applicability in clinical practice. METHODS: Four prefabricated attachment systems were tested [Group SG: retentive ball attachment (Straumann, Switzerland) with gold matrix, Group ST: retentive ball attachment (Straumann, Switzerland) with titanium spring matrix, Group IB: UNOR i-Ball with Ecco matrix (UNOR, Switzerland) and Group IMZ: IMZ-TwinPlus ball attachment with gold matrix (DENTSPLY Friadent, Germany)]. Ten samples of each system were subjected to 10,000 insertion-separation cycles. RESULTS: Results showed that all types of attachments showed wear, which led to a loss of retention force after an initial increase at the beginning of the wear simulation. Attachments with a plastic retention insert or gold matrices underwent the smallest changes in retention force. The titanium spring system showed the largest changes in retention force and a greater variation between the different cycles and specimen. This behaviour is probably caused by a large fitting tolerance of the titanium spring. CONCLUSIONS: Attachment systems which possess a male and female component of different material composition are preferable. They show smaller changes in the retention force. For retention force increase and wear compensation, an attachment system should be adjustable.

[Rehabilitation of a periodontally compromised dentition with implant-supported zirconia bridges. Case report]

Clinical aspects of reconstruction with fix prosthesis and dental implants in a patient with a history of periodontitis is shown. A successful stabilization and rehabilitation of the periodontally involved dentition can be achieved with tooth-worn crown and bridge reconstructions. From a functional and aesthetic point of view the result may not be satisfying due to mobility and overlength of the teeth and open approximal spaces. Today, dentist and patient have often to weigh if teeth shall be maintained or replaced by dental implants. Thereby, both must be aware of the fact that in complex cases long-term success and aesthetic outcome may be difficult to predict. An intense discussion with the patient on his expectations, invasive treatment, risks with regard to biologic and prosthetic aspects is mandatory and must be based on the best scientific evidence available. The present case report shows different considerations and describes a radical solution which meets the patient's needs and is based on modern CAD-CAM technology.

Endothelial cell activation leads to neutrophil transmigration as supported by the sequential roles of ICAM-2, JAM-A, and PECAM-1

Leukocyte transmigration is mediated by endothelial cell (EC) junctional molecules, but the associated mechanisms remain unclear. Here we investigate how intercellular adhesion molecule-2 (ICAM-2), junctional adhesion molecule-A (JAM-A), and platelet endothelial cell adhesion molecule (PECAM-1) mediate neutrophil transmigration in a stimulus-dependent manner (eg, as induced by interleukin-1beta [IL-1beta] but not tumor necrosis factor-alpha [TNF-alpha]), and demonstrate their ability to act in sequence. Using a cell-transfer technique, transmigration responses of wild-type and TNF-alpha p55/p75 receptor-deficient leukocytes (TNFR(-/-)) through mouse cremasteric venules were quantified by fluorescence intravital microscopy. Whereas wild-type leukocytes showed a normal transmigration response to TNF-alpha in ICAM-2(-/-), JAM-A(-/-), and PECAM-1(-/-) recipient mice, TNFR(-/-) leukocytes exhibited a reduced transmigration response. Hence, when the ability of TNF-alpha to directly stimulate neutrophils is blocked, TNF-alpha-induced neutrophil transmigration is rendered dependent on ICAM-2, JAM-A, and PECAM-1, suggesting that the stimulus-dependent role of these molecules is governed by the target cell being activated. Furthermore, analysis of the site of arrest of neutrophils in inflamed tissues from ICAM-2(-/-), JAM-A(-/-), and PECAM-1(-/-) mice demonstrated that these molecules act sequentially to mediate transmigration. Collectively, the findings provide novel insights into the mechanisms of action of key molecules implicated in leukocyte transmigration.

Aza-Michael addition of amines to activated alkenes catalyzed by Silica supported perchloric acid under a solvent-free condition

An efficient aza-Michael addition of amines to a series of ,-unsaturated ketones, carboxylic esters, nitriles and chalcones has been carried out using perchloric acid supported over silica gel (HClO4-SiO2) at room temperature in high yields under solvent-free reaction conditions.

A user supported object tracking framework for interactive video production

We present a user supported tracking framework that combines automatic tracking with extended user input to create error free tracking results that are suitable for interactive video production. The goal of our approach is to keep the necessary user input as small as possible. In our framework, the user can select between different tracking algorithms - existing ones and new ones that are described in this paper. Furthermore, the user can automatically fuse the results of different tracking algorithms with our robust fusion approach. The tracked object can be marked in more than one frame, which can significantly improve the tracking result. After tracking, the user can validate the results in an easy way, thanks to the support of a powerful interpolation technique. The tracking results are iteratively improved until the complete track has been found. After the iterative editing process the tracking result of each object is stored in an interactive video file that can be loaded by our player for interactive videos.