Solvent-Free Enantioselective Organocatalyzed Aldol Reactions

The use of proline as catalyst for the aldol process has given a boost to the development of organocatalysis as a research area. Since then, a plethora of organocatalysts of diverse structures have been developed for this and other organic transformations under different reaction conditions. The use of an organic molecule as catalyst to promote a reaction meets several principles of Green Chemistry. The implementation of solvent-free methodologies to carry out the aldol reaction was soon envisaged. These solvent-free processes can be performed using conventional magnetic stirring or applying ball milling techniques and are even compatible with the use of supported organocatalysts as promoters, which allows the recovery and reuse of the organocatalysts. In addition, other advantages such as the reduction of the required amount of nucleophile and the acceleration of the reaction are accomplished by using solvent-free conditions leading to a “greener” and more sustainable process.

Beyond the H2/CO2 upper bound: one-step crystallization and separation of nano-sized ZIF-11 by centrifugation and its application in mixed matrix membranes

The synthesis of nano-sized ZIF-11 with an average size of 36 ± 6 nm is reported. This material has been named nano-zeolitic imidazolate framework-11 (nZIF-11). It has the same chemical composition and thermal stability and analogous H2 and CO2 adsorption properties to the conventional microcrystalline ZIF-11 (i.e. 1.9 ± 0.9 μm). nZIF-11 has been obtained following the centrifugation route, typically used for solid separation, as a fast new technique (pioneering for MOFs) for obtaining nanomaterials where the temperature, time and rotation speed can easily be controlled. Compared to the traditional synthesis consisting of stirring + separation, the reaction time was lowered from several hours to a few minutes when using this centrifugation synthesis technique. Employing the same reaction time (2, 5 or 10 min), micro-sized ZIF-11 was obtained using the traditional synthesis while nano-scale ZIF-11 was achieved only by using centrifugation synthesis. The small particle size obtained for nZIF-11 allowed the use of the wet MOF sample as a colloidal suspension stable in chloroform. This helped to prepare mixed matrix membranes (MMMs) by direct addition of the membrane polymer (polyimide Matrimid®) to the colloidal suspension, avoiding particle agglomeration resulting from drying. The MMMs were tested for H2/CO2 separation, improving the pure polymer membrane performance, with permeation values of 95.9 Barrer of H2 and a H2/CO2 separation selectivity of 4.4 at 35 °C. When measured at 200 °C, these values increased to 535 Barrer and 9.1.

Ultrasound-assisted selective hydrogenation of C-5 acetylene alcohols with Lindlar catalysts

The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) was performed in the presence of Lindlar catalyst, comparing conventional stirring with sonication at different frequencies of 40, 380 and 850 kHz. Under conventional stirring, the reaction rates were limited by intrinsic kinetics, while in the case of sonication, the reaction rates were 50–90% slower. However, the apparent reaction rates were found to be significantly frequency dependent with the highest rate observed at 40 kHz. The original and the recovered catalysts after the hydrogenation reaction were compared using bulk elemental analysis, powder X-ray diffraction and scanning and transmission electron microscopy coupled with energy-dispersive X-ray analysis. The studies showed that sonication led to the frequency-dependent fracturing of polycrystalline support particles with the highest impact caused by 40 kHz sonication, while monocrystals were undamaged. In contrast, the leaching of Pd/Pb particles did not depend on the frequency, which suggests that sonication removed only loosely-bound catalyst particles.

Unity stronger than divisions. Ukraine's internal diversity. OSW Point of View Number 40, March 2014

Ukraine is deeply divided internally, although as a result of the changes that have taken place since its independence, the country’s internal divisions now have less and less to do with territorial divides, and the split into historical ‘sub-Ukraines’ has become less pronounced, especially for the younger generation. Ukraine is not a country of two competing regional identities, one in the west, the other in the east. The western identity, in which the unity of Ukraine is a key value, coexists with the multiple and diverse local patriotisms of the different regions in the east and the south of the country. The present protest movement has consolidated the country’s sense of unity. Its opponents have also been championing the indivisibility of Ukraine, even while they demanded a thorough decentralisation of the country, which was often mistaken for separatism. Russia has been stirring up separatist tendencies in Ukraine, but with little success. Crimea is an exception here, because in most respects it has remained unaffected by the dynamics of the social processes transforming mainland Ukraine – separatist tendencies are indeed deeply rooted in the peninsula.

Marine fungi from the Northwest African upwelling areas and from the Atlantic off Portugal

Quantitative data on lower marine Phycomycetes (fungi) found in the upwelling waters off the West African coast during cruises No. 13 (1968), 19 (1970), 36 (1975) and 44 (1977) of R.V. "Meteor" are reported. The distribution of the total fungi numbers is presented and, as far as possible, the evaluation of the material up to species level is given. Several provisionally named forms and groups of morphologically related, undescribed fungi are included. A correlation between the number of fungi in sediments and the water depth and distance from the coast line is postulated. There are typical distributions of the lower marine fungi in water bodies and sediments. Different values within replicates of the stations in different years show that there is a sequence in development of fungal populations induced by changes in the water bodies. Surface water far from the coast has low numbers of fungi; numbers increase to a maximum nearer to the coast. In the vicinity of the coast the values decrease. The numbers of fungi in the deep sediments are low below 1,200 m. However, there are isolated areas of higher fungal activities, indicated by some deeper grab samples. During two cruises, the "overlying water" in the grab samples was investigated. It was evident that the numbers of fungi lost by stirring of the sediment when the grab was brought up to the surface were small, relatively and absolutely. The seamount "Josephine Bank" has been investigated for the first time with respect to lower marine fungi; the populations are low in the sediments, but one sample of the surface water had a higher number than the water in the surroundings. In some hydrographic series there was a peculiar depth distribution. An increase occurred at a depth greater than 1,000 m. The results are discussed and some correlations to the aging of the fungal populations in the water masses are constructed.

In defense of Harriet Shelley : and other essays /

In defense of Harriet Shelley.--Fenimore Cooper's literary offenses.--Traveling with a reformer.--Private history of the "Jumping frog" story.--Mental telegraphy.--Mental telegraphy again.--What Paul Bourget thinks of us.--A little note to M. Paul Bourget.--The invalid's story.--Stirring times in Austria.--The German Chicago.--Concerning the Jews.--About all kinds of ships.--From the "London times" of 1904.--A majestic literary fossil.--At the appetite cure.--Saint Joan of Arc.--In memoriam.--A biographical sketch.

Sir Francis Drake revived : who is or may be a pattern to stirre up all heroicke and active spirits of these times, to benefit their countrey and eternize their names by like noble attempts : Being a summary and true relation of foure severall voyages made by the said Sir Francis Drake to the West-Indies ... His voyage made with Chistopher Carleill, Martin Frobusher, Francis Knollis, and others, Their taking the townes of Saint Jago, Sancto Domingo, Carthagena and Saint Augustine : His last voyage (in which he dyed) being accompanied with Sir John Hawkins, Sir Thomas Baskerfield, Sir Nicholas Clifford, with others : His manner of buriall /

La primera obra relata el viaje de 1572-1573, la segunda el viaje de 1577-1580, la tercera el de 1585-1586 y la última del viaje de 1595-1596, en el que murió.

Literary essays /

How to tell a story.--In defence of Harriet Shelley.--Fenimore Cooper's literary offences.--Travelling with a reformer.--Private history of the "Jumping frog" story.-- Mental telegraphy again.--What Paul Bourget thinks of us.--A little note to M. Paul Bourget.--The invalid's story.--The captain's story.--Stirring times in Austria.--Concerning the Jews.--From the London times of 1904.--At the appetite cure.--In memorium.-- Mark Twain: a biographical sketch.

Alloying of pure magnesium with Mg-33.3 wt-%Zr master alloy

To capitalise on the strengthening potential of zirconium as a potent grain refiner for magnesium alloys, the mechanisms of adding zirconium to magnesium and its subsequent grain refining action need to be understood. Using a Mg-33.3Zr master alloy (Zirmax supplied by Magnesium Elektron Ltd) as a zirconium alloying additive, the influence of different alloying conditions on the dissolution of zirconium in magnesium was investigated. It was found that owing to the highly alloyable microstructure of Zirmax, the dissolution of zirconium was generally complete within a few minutes in the temperature range 730 to 780degreesC. Prolonging and/or intensifying stirring were found to have no conspicuous influence on further enhancing the dissolution of zirconium. In all cases studied, the average grain size increased with increasing holding time at temperature while the total zirconium content decreased. The finest grain structure and highest total zirconium content corresponded to sampling immediately after stirring. Pick up of iron by molten magnesium from the mild steel crucibles used for melting and holding, was significantly delayed or avoided in the temperature range 730 to 780degreesC by coating the crucibles with boron nitride. It is therefore feasible to conduct zirconium alloying at 730degreesC without the need of a considerable excess of Zirmax addition using a properly coated or lined steel crucible.

Using different structure types of microemulsions for the preparation of poly(alkylcyanoacrylate) nanoparticles by interfacial polymerization

A phase diagram of the pseudoternary system ethyloleate, polyoxyethylene 20 sorbitan mono-oleate/sorbitan monolaurate and water with butanol as a cosurfactant was prepared. Areas containing optically isotropic, low viscosity one-phase systems were identified and systems therein designated as w/o droplet-, bicontinuous- or solution-type microemulsions using conductivity, viscosity, cryo-field emission scanning electron microscopy and self-diffusion NMR. Nanoparticles were prepared by interfacial polymerization of selected w/o droplet, bicontinuous- or solution-type microemulsions with ethyl-2-cyanoacrylate. Morphology of the particles and entrapment of the water-soluble model protein ovalbumin were investigated. Addition of monomer to the different types of microemulsions (w/o droplet, bicontinuous, solution) led to the formation of nanoparticles, which were similar in size (similar to 250 nm), polydispersity index (similar to 0.13), zeta-potential (similar to-17 mV) and morphology. The entrapment of the protein within these particles was up to 95%, depending on the amount of monomer used for polymerization and the type of microemulsion used as a polymerization template. The formation of particles with similar characteristics from templates having different microstructure is surprising, particularly considering that polymerization is expected to occur at the water-oil interface by base-catalysed polymerization. Dynamics within the template (stirring, viscosity) or indeed interfacial phenomena relating to the solid-liquid interface appear to be more important for the determination of nanoparticle morphology and characteristics than the microstructure of the template system. (c) 2005 Elsevier B.V. All rights reserved.

In-vitro study of the spontaneous calcification of PHEMA-based hydrogels in simulated body fluid

In-vitro calcification of poly(2-hydroxyethyl methacrylate) (PHEMA)-based hydrogels in simulated body fluid (SBF) under a steady/batch system without agitation or stirring the solutions has been investigated. It was noted that the formation of calcium phosphate (CaP) deposits primarily proceeded through spontaneous precipitation. The CaP deposits were found both on the surface and inside the hydrogels. It appears that the effect of chemical structure or reducing the relative number of oxygen atoms in the copolymers on the degree of calcification was only important at the early stage of calcification. The morphology of the CaP deposits was observed to be spherical aggregates with a thickness of the CaP layer less than 0.5 mu m. Additionally, the CaP deposits were found to be poorly crystalline or to have nano-size crystals, or to exist mostly as an amorphous phase. Characterization of the CaP phases in the deposits revealed that the deposits were comprised mainly of whitlockite [Ca9MgH(PO4)(7)] type apatite and DCPD (CaHPO4 center dot 2H(2)O) as the precursors of hydroxyapatite [Ca-10(PO4)(6)(OH)(2)]. The presence of carbonate in the deposits was also detected during the calcification of PHEMA based hydrogels in SBF solution.

Zirconium alloying and grain refinement of magnesium alloys

Factors that influence alloying zirconium to magnesium with a Mg-33.3Zr master alloy and the subsequent grain refinement are discussed based on a large number of experiments conducted at the laboratory scale (up to 30 kg of melt). It is shown that the zirconium particles released from the Zirmax(R) master alloy must be brought into thorough contact with the melt by an appropriate stirring process in order to attain a good dissolution of zirconium. The influence of alloying temperature on the recovery of zirconium was found to be negligible in the range from 680 to 780 degreesC. An ideal zirconium alloying process should end up with both high soluble and high total zirconium in the melt in order to achieve the best grain refinement in the final alloy. The distribution of zirconium in the final alloy microstructure is inhomogeneous and almost all of the zirconium in solution is concentrated in zirconium-rich cores in the microstructure.

A new zirconium-rich master alloy for the grain refinement of magnesium alloys

A new zirconium-rich magnesium-zirconium master alloy (designated AM-cast) has been developed by the CRC for Cast Metals Manufacturing in collaboration with Australian Magnesium Corporation for use as a grain refiner for magnesium alloys that do not contain aluminium. This work describes the microstructural characteristics of this new grain refiner and its grain refining ability when added to different magnesium alloys under various conditions (alloying temperature from 680 °C to 750 °C; weight of melt from 1 kg to 150 kg and sample thickness from 7 mm to 62 mm). Owing to its highly alloyable microstructure, AM-cast can be readily introduced into molten magnesium at any temperature when assisted by a few minutes of stirring or puddling. Little sludge has been found at the bottom of the alloying vessel in these trials due to the fine zirconium particles contained in the master alloy. The recovery of zirconium is normally in the range from 40% to 60% with respect to 1% zirconium addition as the master alloy. It is shown that this new master alloy is an excellent grain refiner for aluminium-free magnesium alloys.

Hypervalent iodine in synthesis 93. A facile synthesis of 2-substituted imidazo[1,2-a]pyrimidines by cyclocondensation of alkynyl(phenyl)iodonium salts and 2-aminopyrimidine

Simple stirring of a mixture of the alkynyl(phenyl)iodonium salts 1 with 2-aminopyrimidine 2 in chloroform under reflux for two hours in the presence of K2CO3 gave, after workup, the 2-substituted imidazo[1,2-]pyrimidines 3 in moderate to good yields. A possible mechanism for the formation of 3 involves the intramolecular cyclization of the intermediate alkylidenecarbene 6.

NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf