Oxidative Alkene Cleavage by Chemical and Enzymatic Methods

The cleavage of alkenes to the corresponding carbonyl products is a widely employed method in organic synthesis, especially to introduce oxygen functionalities into molecules, remove protecting groups and tailor large molecules. Chemical methods available for alkene cleavage include, for instance, ozonolysis, several metal‐based variants (KMnO₄, OsO₄, RuO₄, etc.), electrochemical alternatives, singlet oxygen, hypervalent iodine and organic molecules in combination with oxygen. Furthermore, several enzymatic methods for alkene cleavage have been described to establish safe, mild and selective oxidation methods. Various heme and non‐heme iron‐dependent enzymes catalyse the alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing good chemo‐ and regioselectivities in selected cases. Quite recently some Cu‐, Mn‐ and Ni‐dependent enzymes have been identified for this reaction. This review gives an overview of the different chemical and enzymatic methods available for the cleavage of alkenes.

     

Microclimatic modeling of the urban thermal environment of Singapore to mitigate urban heat island

This study investigates the urban heat island effect in Singapore and examines the key factors causing this effect. The possibilities of improving heat extraction rate by optimizing air flow in selected hot spots were explored. The effect of building geometry, façade materials and the location of air-conditioning condensers on the outdoor air temperature was explored using computational fluid dynamics (CFD) simulations. It was found that at very low wind speeds, the effect of façade materials and their colours was very significant and the temperature at the middle of a narrow canyon increased up to 2.5 °C with the façade material having lower albedo. It was also found that strategically placing a few high-rise towers will enhance the air flow inside the canyon thereby reducing the air temperature. Adopting an optimum H/W ratio for the canyons increased the velocity by up to 35% and reduced the corresponding temperature by up to 0.7 °C.     

Room temperature amorphous to nanocrystalline transformation in ultra-thin films under tensile stress: an in situ TEM study

The amorphous to crystalline phase transformation process is typically known to take place at very high temperatures and facilitated by very high compressive stresses. In this study, we demonstrate crystallization of amorphous ultra-thin platinum films at room temperature under tensile stresses. Using a micro-electro-mechanical device, we applied up to 3% uniaxial tensile strain in 3-5 nm thick focused ion beam deposited platinum films supported by another 3-5 nm thick amorphous carbon film. The experiments were performed in situ inside a transmission electron microscope to acquire the bright field and selected area diffraction patterns. The platinum films were observed to crystallize irreversibly from an amorphous phase to face-centered cubic nanocrystals with average grain size of about 10 nm. Measurement of crystal spacing from electron diffraction patterns confirms large tensile residual stress in the platinum specimens. We propose that addition of the externally applied stress provides the activation energy needed to nucleate crystallization, while subsequent grain growth takes place through enhanced atomic and vacancy diffusion as an energetically favorable route towards stress relaxation at the nanoscale.     

IP over optical networks: architectural aspects

The Internet transport infrastructure is moving toward a model of high-speed routers interconnected by intelligent optical core networks. A consensus is emerging in the industry on utilizing an IP-centric control plane within optical networks to support dynamic provisioning and restoration of lightpaths. At the same time, there are divergent views on how IP routers must interact with optical core networks to achieve end-to-end connectivity. This article describes the architectural alternatives for interconnecting IP routers over optical networks, considering the routing and signaling issues. Also, the application of IP-based protocols for dynamic provisioning and restoration of lightpaths, as well as the interworking of multivendor optical networks is described     

Studies on Acid Leaching Methods for Fine Metal Powder Production

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Synthesis of boron/nitrogen substituted carbons for aqueous asymmetric capacitors

Boron/nitrogen substituted carbons were synthesized by co-pyrolysis of polyborazylene/coal tar pitch blends to yield a carbon with a boron and nitrogen content of 14 at% and 10 at%, respectively. The presence of heteroatoms in these carbons shifted the hydrogen evolution overpotential to −1.4 V vs Ag/AgCl in aqueous electrolytes, providing a large electrochemical potential window (∼2.4 V) as well as a specific capacitance of 0.6 F/m². An asymmetric capacitor was fabricated using the as-prepared low surface area carbon as the negative electrode along with a redox active manganese dioxide as the positive electrode. The energy density of the capacitor exceeded 10 Wh/kg at a power density of 1 kW/kg and had a cycle life greater than 1000 cycles.     

Graph theory augmented math programming approach to identify minimal reaction sets in metabolic networks

Bioprocesses are of growing importance as an avenue to produce chemicals. Microorganisms containing only desired catalytic and replication capabilities in their metabolic pathways are expected to offer efficient processes for chemical production. Realizing such minimal cells is the holy grail of metabolic engineering. In this paper, we propose a new method that combines graph-theoretic approaches with mixed-integer liner programming (MILP) to design metabolic networks with minimal reactions. Existing MILP based computational approaches are computationally complex especially for large networks. The proposed graph-theoretic approach offers an efficient divide-and-conquer strategy using the MILP formulation on sub-networks rather than considering the whole network monolithically. In addition to the resulting improvement in computational complexity, the proposed method also aids in identifying the key reactions to be knocked-out in order to achieve the minimal cell. The efficacy of the proposed approach is demonstrated using three case studies from two organisms, Escherichia coli and Saccharomyces cerevisiae.     

Studies on spinel cobaltites,MCo2O4 (M = Mn,Zn, Fe,Ni and Co) and their functional properties

Optimization of electrodes for charge storage with appropriate processing conditions places significant challenges in the developments for high performance charge storage devices. In this article, metal cobaltite spinels of formula MCo₂O₄ (where M = Mn, Zn, Fe, Ni and Co) are synthesized by oxalate decomposition method followed by calcination at three typical temperatures, viz. 350, 550, and 750 °C and examined their performance variation when used as anodes in lithium ion batteries. Phase and structure of the materials are studied by powder x-ray diffraction (XRD) technique. Single phase MnCo2O4,ZnCo2O4 and Co3O4 are obtained for all different temperatures 350 °C, 550 °C and 750 °C; whereas FeCo₂O₄ and NiCo₂O₄ contained their constituent binary phases even after repeated calcination. Morphologies of the materials are studied via scanning electron microscopy (SEM): needle-shaped particles of MnCo₂O₄ and ZnCo₂O₄, submicron sized particles of FeCo₂O₄ and agglomerated submicron particle of NiCo₂O₄ are observed. Galvanostatic cycling has been conducted in the voltage range 0.005–3.0 V vs. Li at a current density of 60 mA g^?1 up to 50 cycles to study their Li storage capabilities. Highest observed charge capacities are: MnCo₂O₄ – 365 mA h g^?1 (750 °C); ZnCo₂O₄ – 516 mA h g^?1 (550 °C); FeCo₂O₄ – 480 mA h g^?1 (550 °C); NiCo₂O₄ – 384 mA h g^?1 (750 °C); and Co₃O₄ – 675 mA h g^?1 (350 °C). The Co₃O₄ showed the highest reversible capacity of 675 mA h g^?1; the NiO present in NiCo₂O₄ acts as a buffer layer that results in improved cycling stability; the ZnCo₂O₄ with long needle-like shows good cycling stability.     

THE FLOW BEHAVIOR OF SUBMICRON α-Al2O3 AQUEOUS SUSPENSIONS

The viscosity of aqueous, charged a-Al₂O₃ suspensions with and without added polyelectrolytes (polyacrylic acid (PAA 1800)) is investigated over a wide range of volume fractions and shear rates. The Carreau-Yasuda model is used for both cases for examining the shear-rate dependence; for the electrostatically-stabilized suspensions the Krieger-Dougherty and Quemada models are used to determine the maximum packing fraction. The latter analysis shows that the suspension behavior changes from liquid-like to solid-like at a volume fraction of 0.71 in the low-shear limit and at 0.89 at the high-shear limit (because of the polydispersity of the suspension). The results with polyelectrolytes indicate that the dosage of the polymer plays an important role in the viscosity of suspensions and that there is an optimum dosage of polyelectrolyte that must be added to reduce the viscosity at high volume fractions of solids.