Characterization of Pt?CAu and Ni?CAu Clusters on TiO2(110)

The surface composition and properties of Pt?CAu and Ni?CAu clusters on TiO₂(110) have been studied by scanning tunneling microscopy (STM), low energy ion scattering (LEIS) and soft X-ray photoelectron spectroscopy (sXPS). STM studies show that bimetallic clusters are formed during sequential deposition of the two metals, regardless of the order of deposition. At the 2?ML of Au/2?ML of Pt or Ni coverages studied here, the second metal contributes to the growth of existing clusters rather than forming new pure metal clusters. LEIS experiments demonstrate that the surfaces of the bimetallic clusters are almost 100% Au when 2?ML of Au is deposited on top of 2?ML of Pt or Ni. However, a much larger fraction of Pt or Ni (50 and 20%, respectively) remains at the surface when 2?ML of Pt or Ni is deposited on 2?ML of Au, most likely due to limited diffusion of atoms within the clusters at room temperature. According to sXPS investigations, the binding energies of the metals in the bimetallic clusters are shifted from those observed for pure metal clusters; the Pt(4f_7/2) and Ni(3p_3/2) peaks are shifted to lower binding energies while the position of the Au(4f_7/2) peak is dominated by surface core level shifts. Pure Pt clusters as well as 0.4?ML of Au on 2 ML of Pt clusters reduce the titania support upon encapsulation after annealing to 800?K, whereas 2?ML of Au on 2?ML of Pt clusters do not reduce titania, presumably because there is no Pt at the surface of the clusters. Pure Ni clusters are also known to become encapsulated upon heating, but the reduction of titania is much less extensive compared to that of pure Pt clusters.     

A proprietary alpha-amylase inhibitor from white bean (Phaseolus vulgaris): A review of clinical studies on weight loss and glycemic control

Obesity, and resultant health hazards which include diabetes, cardiovascular disease and metabolic syndrome, are worldwide medical problems. Control of diet and exercise are cornerstones of the management of excess weight. Foods with a low glycemic index may reduce the risk of diabetes and heart disease as well as their complications. As an alternative to a low glycemic index diet, there is a growing body of research into products that slow the absorption of carbohydrates through the inhibition of enzymes responsible for their digestion. These products include alpha-amylase and glucosidase inhibitors. The common white bean (Phaseolus vulgaris) produces an alpha-amylase inhibitor, which has been characterized and tested in numerous clinical studies. A specific and proprietary product named Phase 2^® Carb Controller (Pharmachem Laboratories, Kearny, NJ) has demonstrated the ability to cause weight loss with doses of 500 to 3000 mg per day, in either a single dose or in divided doses. Clinical studies also show that Phase 2 has the ability to reduce the post-prandial spike in blood glucose levels. Experiments conducted incorporating Phase 2 into food and beverage products have found that it can be integrated into various products without losing activity or altering the appearance, texture or taste of the food. There have been no serious side effects reported following consumption of Phase 2. Gastro-intestinal side effects are rare and diminish upon extended use of the product. In summary, Phase 2 has the potential to induce weight loss and reduce spikes in blood sugar caused by carbohydrates through its alpha-amylase inhibiting activity.     

Development of new device for measuring thermal stresses

In recent years, numerous analytical and experimental researches have been performed on the prediction of thermal stresses in mass concrete structures. However, due to the difficulty of the problem, limitations still exist for both analytical and experimental methods of measuring thermal stresses in mass concrete. In this research, a new experimental device measuring thermal stresses directly in a laboratory setting is developed. The equipment is located in a temperature chamber that follows the temperature history, which has been previously obtained from temperature distribution analyses. Thermal forces are measured continuously by two load cells in the device. The results show that the thermal stresses estimated by the newly developed device agree well with general stress variations in actual structures.     

Development of refinery scheduling system using mixed integer programming and expert system

This paper presents a hybrid refinery scheduling system combining mathematical programming model and expert system. Mixed-integer linear programming models for crude oil movement between units are merged into the expert system that is for qualitative issues concerning crude vessel unloading operations. The target problem ranging from the crude unloading to the crude charging to distillation towers is decomposed into several module problems for efficiency. Compared with existing scheduling approaches for oil movement, the proposed hybrid refinery scheduling system is very effective in dealing with timing decisions involving vessel unloading operations due to the advantages of an expert system. Since the proposed scheduling system can generate solutions so fast, it is expected to play a key role in the real processes. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Complete Elastic Tensor for Mullite (∼2.5Al2O3·SiO2) to High Temperatures Measured from Textured Fibers

Directionally solidified mullite fibers have been grown by the laser-heated, float-zone method from starting materials with a nominal composition of 3Al₂O₃·2SiO₂. The fibers used in this study have large single-crystal regions with composition 2.5Al₂O₃·SiO₂ and (001) fiber axis orientation. The complete elastic tensor of these samples has been determined by Brillouin spectroscopy at room temperature and elevated temperatures up to 1200°C. Isotropic moduli (bulk, shear, and Young's) have been calculated using the Voigt–Reuss–Hill averaging scheme. The room-temperature values obtained are K _VRH= 173.5 ± 6.9 GPa, G _VRH= 88.0 ± 3.5 GPa, E _VRH= 225.9 ± 9.0 GPa. All moduli show gradual, linear decreases with temperature. The temperature derivatives obtained for the equivalent, isotropic moduli are d K _VRH/d T =−17.5 ± 2.5 MPa/°C, d G _VRH/d T =−8.8 ± 1.4 MPa/°C, d E _VRH/d T =−22.6 ± 2.8 MPa/°C. Substantial differences between bulk properties calculated from the single–crystal measurements in this study and the properties reported in the literature for polycrystalline sintered mullite are identified, indicating the importance of factors such as microstructure, intergranular phases, and composition to the elasticity of mullite ceramics.     

Bionic Prototyping of Honeycomb Patterned Polymer Composite and Its Engineering Application

Polymeric honeycombs have always enticed researchers due to their lightweight, high stiffness-to-weight ratio, and well developed energy absorption characteristics, owing which they find themselves extensively used in automotive and aerospace engineering. Simultaneously, additive manufacturing methodologies offers enticing pathway for prototyping of functional materials starring complex heterogeneous structural designs with varying wall thickness inspired from biological systems, paving way for augmenting the mechanical and physical properties for specifically tailored applications. We have portrayed potential and possible challenges for 3D printing for prototyping of polymeric honeycomb composites, not constrained by existing engineering principles, offering designer proficiency to build resilient architectures.     

Chiral mercaptoacetamides display enantioselective inhibition of histone deacetylase 6 and exhibit neuroprotection in cortical neuron models of oxidative stress

Mercaptoacetamide-based ligands have been designed as a new class of histone deacetylase (HDAC) inhibitors for possible use in the treatment of neurodegenerative diseases. The thiol group of these compounds provides a key binding element for interaction with the catalytic zinc ion, and thus differs from the more typically employed hydroxamic acid based zinc binding groups. Herein we disclose the chemistry and biology of some substituted mercaptoacetamides with the intention of increasing HDAC6 isoform selectivity while maintaining potency similar to their hydroxamic acid analogues. The introduction of a stereocenter α to the thiol group was found to have a considerable impact on HDAC inhibitor potency. These new compounds were also profiled for their therapeutic potential in an in?vitro model of stress-induced neuronal injury and were found to act as nontoxic neuroprotective agents.     

Selective homogeneous and heterogeneous catalytic conversion of methanol/dimethyl ether to triptane

The demand for specific fuels and chemical feed-stocks fluctuates, and as a result, logistical mismatches can occur in the supply of their precursor raw materials such as coal, biomass, crude oil, and methane. To overcome these challenges, industry requires a versatile and robust suite of conversion technologies, many of which are mediated by synthesis gas (CO + H(2)) or methanol/dimethyl ether (DME) intermediates. One such transformation, the conversion of methanol/DME to triptane (2,2,3-trimethylbutane) has spurred particular research interest. Practically, triptane is a high-octane, high-value fuel component, but this transformation also raises fundamental questions: how can such a complex molecule be generated from such a simple precursor with high selectivity? In this Account, we present studies of this reaction carried out in two modes: homogeneously with soluble metal halide catalysts and heterogeneously over solid microporous acid catalysts. Despite their very different compositions, reaction conditions, provenance, and historical scientific context, both processes lead to remarkably similar products and mechanistic interpretations. In both cases, hydrocarbon chains grow by successive methylation in a carbocation-based mechanism. The relative rates of competitive processes-chain growth by methylation, chain termination by hydrogen transfer, isomerization, and cracking-systematically depend upon the structure of the various hydrocarbons produced, strongly favoring the formation of the maximally branched C(7) alkane, triptane. The two catalysts also show parallels in their dependence on acid strength. Stronger acids exhibit higher methanol/DME conversion but also tend to favor chain termination, isomerization, and cracking relative to chain growth, decreasing the preference for triptane. Hence, in both modes, there will be an optimal range: if the acid strength is too low, activity will be poor, but if it is too high, selectivity will be poor. A related reaction, the methylative homologation of alkanes, offers the possibility of upgrading low-value refinery byproducts such as isobutane and isopentane to more valuable gasoline components. With the addition of adamantane, a hydride transfer catalyst that promotes activation of alkanes, both systems effectively catalyze the reaction of methanol/DME with lighter alkanes to produce heavier ones. This transformation has the further advantage of providing stoichiometric balance, whereas the stoichiometry for conversion of methanol/DME to alkanes is deficient in hydrogen and requires rejection of excess carbon in the form of carbon-rich arenes, which lowers the overall yield of desired products. Alternatively, other molecules can serve as sacrificial sources of hydrogen atoms: H(2) on heterogeneous catalysts modified by cations that activate it, and H(3)PO(2) or H(3)PO(3) on homogeneous catalysts. We have interpreted most of the features of these potentially useful reactions at a highly detailed level of mechanistic understanding, and we show that this interpretation applies equally to these two widely disparate types of catalysts. Such approaches can play a key role in developing and optimizing the catalysts that are needed to solve our energy problems.