Stochastic global optimization methods part I: Clustering methods

In this stochastic approach to global optimization, clustering techniques are applied to identify local minima of a real valued objective function that are potentially global. Three different methods of this type are described; their accuracy and efficiency are analyzed in detail.     

Rapid synthesis of 1-deoxygalactonojirimycin using a carbamate annulation

A remarkably efficient synthesis of the biologically important iminosugar 1-deoxygalactonojirimycin (DGJ) is presented. Key to this strategy is the development of a novel carbamate annulation reaction that favours formation of a six-membered carbamate-containing piperidine skeleton over its five-membered counterpart.     

Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source

The use of water as an oxygen and hydrogen source for the paired oxygenation and hydrogenation of organic substrates to produce valuable chemicals is of utmost importance as a means of establishing green chemical syntheses. Inspired by the active Ni³⁺ intermediates involved in electrocatalytic water oxidation by nickel‐based materials, we prepared NiB_x as a catalyst and used water as the oxygen source for the oxygenation of various organic compounds. NiB_x was further employed as both an anode and a cathode in a paired electrosynthesis cell for the respective oxygenation and hydrogenation of organic compounds, with water as both the oxygen and hydrogen source. Conversion efficiency and selectivity of ≥99 % were observed during the oxygenation of 5‐hydroxymethylfurfural to 2,5‐furandicarboxylic acid and the simultaneous hydrogenation of p‐nitrophenol to p‐aminophenol. This paired electrosynthesis cell has also been coupled to a solar cell as a stand‐alone reactor in response to sunlight.     

Solvent sorption measurements in polymeric membranes with ATR-IR spectroscopy

Long-term stability and performance of polymeric membranes in solvent and mixed solvent media can be reduced due to sorption and swelling of the membrane matrix. For this reason quantification of sorption and swelling is of major importance for the development of future applications of membrane processes in solvent and mixed solvent media. In this work a method is discussed, based on attenuated total reflectance infrared spectroscopy (ATR-IR), to establish sorption and sorption selectivity of a cellulose acetate (CA) membrane in water/methanol and water/ethanol mixtures. By analysis of specific peaks from the ATR-IR spectra of the solvents, the preferential sorption of water in CA membranes can be quantified. In the presence of methanol, the selectivity for water ranges from 2.5 to 3.5 between 52 and 90% of methanol. For ethanol, the selectivity for water ranges from about 1 (30% ethanol) to 2 (90% ethanol). From the work it follows that ATR-IR provides an easy and non-destructive method to study the sorption behavior of the polymeric membrane separation layer.     

Acid-Assisted Direct Olefin Metathesis of Unprotected Carbohydrates in Water

The ability to use unprotected carbohydrates in olefin metathesis reactions in aqueous media is demonstrated. By using water-soluble, amine-functionalized Hoveyda–Grubbs catalysts under mildly acidic aqueous conditions, the self-metathesis of unprotected alkene-functionalized α-d -manno- and α-d -galactopyranosides could be achieved through minimization of nonproductive chelation and isomerization. Cross-metathesis with allyl alcohol could also be achieved with reasonable selectivity. The presence of small quantities (2.5 vol %) of acetic acid increased the formation of the self-metathesis product while significantly reducing the alkene isomerization process. The catalytic activity was furthermore retained in the presence of large amounts (0.01 mm ) of protein, underlining the potential of this carbon–carbon bond-forming reaction under biological conditions. These results demonstrate the potential of directly using unprotected carbohydrate structures in olefin metathesis reactions under mild conditions compatible with biological systems, and thereby enabling their use in, for example, drug discovery and protein derivatization.     

FUROCOUMARIN-PHOTOSENSITIZEDHYDROXYLATION OF GUANOSINE IN RNA AND DNA

Abstract— Guanosine hydroxylation was used as a marker for assessing photooxidation of DNA and RNA sensitized by monofunctional and bifunctional furocoumarins. DNA or RNA, treated with sensitizer and UVA light, was enzymatically hydrolyzed, dephosphorylated and then analyzed by reversed-phase HPLC with electrochemical detection. Hydroxylated guanosine, i.e. 8-hydroxy-2'-deoxyguanosine (8-OHdG) or 8-hydroxyguanosine (8-OHG), was quantitated. 3-Carbethoxypsoralen (3-CP) was found to be an efficient photosensitizer for oxidation of guanosine in DNA, resulting in conversion of up to 0.4% of guanosine residues to 8-OHdG. In contrast, dramatically lower levels of guanosine hydroxylation were observed in 3-CP-photosensitized RNA. Psoralen was found to be a more efficient photosensitizer than angelicin in both DNA and RNA. Additional studies of oxidation of 3-CP-photosensitized DNA indicated that double-stranded DNA is 10 times more susceptible to photooxidation than single-stranded DNA, implicating 3-CP binding to DNA as an important mechanistic step in photooxidation of guanosine. The effects of D₂O and degassing with argon on photooxidation of guanosine in DNA sensitized by 3-CP were inconsistent with a mechanism involving ¹O₂. In addition, chelation of adventitious metal ions present in preparations of DNA photosensitized by 3-CP had no effect on hydroxylation of guanosine.     

Miniaturized measurement system for ammonia in air

The development of a miniaturized ammonia sensor made using microsystem technology is described. Gas is sampled in a sampler comprising two opposite channels separated by a gas permeable, water repellent polypropylene membrane. Subsequently, the acid sample solution is pumped into a selector where an alkaline solution is added to ionize all sampled ambient acid gasses, resulting in an enhanced selectivity. In the selector, the ammonia can diffuse through a second membrane into a purified water stream where an electrolyte conductivity sensor quantifies the resulting ammonium concentration. The realized system is shown to be selective enough not to be influenced by normal ambient carbon dioxide concentrations. Experiments with a gas flow of 3 ml/min, containing ammonia concentrations ranging from 9.8 to 0.3 ppm in a nitrogen carrier flow, into a 15 μl/min sample solution flow and finally into a 5 μl/min purified water stream have been carried out and show that the system is sensitive to ammonia concentration below 1 ppm.     

Cooperation and game-theoretic cost allocation in stochastic inventory models with continuous review

We study cooperation strategies for companies that continuously review their inventories and face Poisson demand. Our main goal is to analyze stable cost allocations of the joint costs. These are such that any group of companies has lower costs than the individual companies. If such allocations exist they provide an incentive for the companies to cooperate.     

Cost sharing of cooperating queues in a Jackson network

We consider networks of queues in which the independent operators of individual queues may cooperate to reduce the amount of waiting. More specifically, we focus on Jackson networks in which the total capacity of the servers can be redistributed over all queues in any desired way. If we associate a cost to waiting that is linear in the queue lengths, it is known from the literature how the operators should share the available service capacity to minimize the long run total cost. This paper deals with the question whether or not (the operators of) the individual queues will indeed cooperate in this way, and if so, how they could share the cost in the new situation such that each operator never pays more than his own cost without cooperation. For the particular case of a tandem network with two or three nodes it is known from previous work that cooperation is indeed beneficial, but for larger tandem networks and for general Jackson networks this question was still open. The main result of this paper gives for any Jackson network an explicit cost allocation that is beneficial for all operators. The approach we use also works for other cost functions, such as the server utilization.