A One‐Pot Synthesis of N‐Aryl‐2‐Oxazolidinones and Cyclic Urethanes by the Lewis Base Catalyzed Fixation of Carbon Dioxide into Anilines and Bromoalkanes

The multicomponent assembly of pharmaceutically relevant N‐aryl‐oxazolidinones through the direct insertion of carbon dioxide into readily available anilines and dibromoalkanes is described. The addition of catalytic amounts of an organosuperbase such as Barton's base enables this transformation to proceed with high yields and exquisite substrate functional‐group tolerance under ambient CO₂ pressure and mild temperature. This report also provides the first proof‐of‐principle for the single‐operation synthesis of elusive seven‐membered ring cyclic urethanes.     

Stochastic programs without duality gaps

This paper studies dynamic stochastic optimization problems parameterized by a random variable. Such problems arise in many applications in operations research and mathematical finance. We give sufficient conditions for the existence of solutions and the absence of a duality gap. Our proof uses extended dynamic programming equations, whose validity is established under new relaxed conditions that generalize certain no-arbitrage conditions from mathematical finance.     

Preparation of 4-Vinyl-2(5H)-Furanoid Structural Unit via Organosilicon and - Selenium Intermediates

Two syntheses of the 2(5H)-furanoid structural unit (especially the 3-methyl derivative 1) have been reported from this laboratory.^1,2 The unit 1 is found in many naturally occurring compounds (especially sesqui terpenes). The 4-substi tuted d erivatives of 1 also occur frequently i n natural products, e.g. furospongolide³ 2.     

The effect of palladium dispersion and promoters on lactose oxidation kinetics

Lactose oxidation was investigated at 70 °C and at pH 8 using oxygen as an oxidant over a comprehensive set of commercially available mono- and multi-metallic as well as promoted Pd catalysts with active carbon, alumina and calcium carbonate as catalyst supports. An optimum cluster size of 6–10 nm resulted in the highest initial turnover frequencies. High conversion levels above 90% were achieved on Pd/C catalyst, as well as over Pd/Al₂O₃ and (Pd–Pb)/CaCO₃, whereas (Pd–V)/C catalyst gave only 30% conversion after 200 min. The latter catalyst was relatively inactive due to its high support acidity and profound deactivation during oxidation. Besides the main oxidation product, lactobionic acid, also, lactulose was generated as a result of lactose isomerisation under alkaline conditions. The electrochemical potentials of the catalysts were measured during lactose oxidation. The main result of these measurements was that, when the electrochemical potential of the catalyst increased very quickly, its oxidation activity was low due to metal over-oxidation. The selectivities to the desired product, lactobionic acid, were relatively high, above 80% for most of the catalysts, except for (Pd–V)/C. Furthermore, the selectivity to the lactobionic acid decreased with increasing metal dispersion, thus, indicating that the optimum metal particle sizes for producing high amounts of lactobionic acid is above 3 nm.     

Electrical manipulation and measurement of spin properties of quantum spin Hall edge states

We study the effects of a gate-controlled Rashba spin-orbit coupling to quantum spin Hall edge states in HgTe quantum wells. A uniform Rashba coupling can be employed in tuning the spin orientation of the edge states while preserving the time-reversal symmetry. We introduce a sample geometry where the Rashba coupling can be used in probing helicity by purely electrical means without requiring spin detection, application of magnetic materials or magnetic fields. In the considered setup a tilt of the spin orientation with respect to the normal of the sample leads to a reduction in the two-terminal conductance with current-voltage characteristics and temperature dependence typical of Luttinger liquid constrictions.     

Graph-distance convergence and uniform local boundedness of monotone mappings

In this article we study graph-distance convergence of monotone operators. First, we prove a property that has been an open problem up to now: the limit of a sequence of graph-distance convergent maximal monotone operators in a Hilbert space is a maximal monotone operator. Next, we show that a sequence of maximal monotone operators converging in the same sense in a reflexive Banach space is uniformly locally bounded around any point from the interior of the domain of the limit mapping. The result is an extension of a similar one from finite dimensions. As an application we give a simplified condition for the stability (under graph-distance convergence) of the sum of maximal monotone mappings in Hilbert spaces.

     

Application of enriched stable 196Hg isotope for monitoring the stability of total mercury in water samples

A novel tool for the investigation of stability of total mercury in water samples is presented. The study focuses on the application of enriched ¹⁹⁶Hg stable isotopic reagent for the stability studies. Natural abundance of ¹⁹⁶Hg in water samples is only 0.15%. Thus, the use of the ¹⁹⁶Hg isotope spike represents a major advantage, when it can be assumed that all the measured isotope is the same as is accurately added by the analyst, and the change in its mass concentration can be followed simply and reliably. Tests were carried out with industrial waste water and two type of the natural water. Cold vapour (CV) inductively coupled plasma mass spectrometer (ICP-MS) technique was applied for the mercury measurements. Monitoring was continued for approximately 100 days. It is commonly advised that the measurement for total mercury in water samples should be carried out within 14 days. In this study the samples were observed to be stable for more than three months, if they were stored at a temperature of 4–6°C. The results of this stability study were in line with the guidance presented in EPA standard 1631. However, the samples were noticed to be stable for a much longer time than is presented in the standard method ISO 17852.     

Hydrophobicity within the three-dimensional Mercedes-Benz model: potential of mean force

We use the three-dimensional Mercedes-Benz model for water and Monte Carlo simulations to study the structure and thermodynamics of the hydrophobic interaction. Radial distribution functions are used to classify different cases of the interaction, namely, contact configurations, solvent separated configurations, and desolvation configurations. The temperature dependence of these cases is shown to be in qualitative agreement with atomistic models of water. In particular, while the energy for the formation of contact configurations is favored by entropy, its strengthening with increasing temperature is accounted for by enthalpy. This is consistent with our simulated heat capacity. An important feature of the model is that it can be used to account for well-converged thermodynamics quantities, e.g., the heat capacity of transfer. Microscopic mechanisms for the temperature dependence of the hydrophobic interaction are discussed at the molecular level based on the conceptual simplicity of the model.     

Feasibility of using atmospheric pressure matrix-assisted laser desorption/ionization with ion trap mass spectrometry in the analysis of acetylated xylooligosaccharides derived from hardwoods and Arabidopsis thaliana

The atmospheric pressure matrix-assisted laser desorption/ionization with ion trap mass spectrometry (AP-MALDI-ITMS) was investigated for its ability to analyse plant-derived oligosaccharides. The AP-MALDI-ITMS was able to detect xylooligosaccharides (XOS) with chain length of up to ten xylopyranosyl residues. Though the conventional MALDI–time-of-flight/mass spectrometry (TOF/MS) showed better sensitivity at higher mass range (>m/z 2,000), the AP-MALDI-ITMS seems to be more suitable for detection of acetylated XOS, and the measurement also corresponded better than the MALDI-TOF/MS analysis to the actual compositions of the pentose- and hexose-derived oligosaccharides in a complex sample. The structures of two isomeric aldotetrauronic acids and a mixture of acidic XOS were elucidated by AP-MALDI-ITMS using multi-stages mass fragmentation up to MS³. Thus, the AP-MALDI-ITMS demonstrated an advantage in determining both mass and structures of plant-derived oligosaccharides. In addition, the method of combining the direct endo-1,4-β-d-xylanase hydrolysis of plant material, and then followed by AP-MALDI-ITMS detection, was shown to recognize the substitution variations of glucuronoxylans in hardwood species and in Arabidopsis thaliana. To our knowledge, this is the first report to demonstrate the acetylation of glucuronoxylan in A. thaliana. The method, which requires only a small amount of plant material, such as 1 to 5 mg for the A. thaliana stem material, can be applied as a high throughput fingerprinting tool for the fast comparison of glucuronoxylan structures among plant species or transformants that result from in vivo cell wall modification.     

Kinetics of lactose and rhamnose oxidation over supported metal catalysts

Several mono- and bimetallic Pd, Pt, Rh and Ru supported on alumina and active carbon catalysts were characterized by CO chemisorption, nitrogen adsorption, XPS and XRD and acidity titrations were performed for active carbon supported catalysts. These catalysts were tested in oxidation of two sugars, namely lactose and rhamnose, at 60 °C and at 70 °C under slightly alkaline conditions (pH 8) with molecular oxygen. The results revealed that there is an optimum metal particle size in a range of 3-10 nm giving the highest initial TOFs for both oxidations. Furthermore, the catalytic activities and conversions were related to other catalyst properties, such as the type and amount of promoters and the presence of different phases. In situ catalyst potential measurements revealed that there is an inverse correlation between the increase of catalyst potential as a function of sugar conversion and the catalyst activity after prolonged reaction times. This method is a valuable tool for in situ characterization of catalysts correlating well with their activities.