Bifunctional Catalysts Stabilized on Nanocrystalline Magnesium Oxide for One‐Pot Synthesis of Chiral Diols

New bifunctional catalysts composed of PdCl₄²⁻, OsO₄²⁻ and OsO₄²⁻, WO₄²⁻ designed and prepared by a counterionic stabilization technique involving the reactions of Na₂PdCl₄‐K₂OsO₄ and K₂OsO₄‐Na₂WO₄ with nanocrystalline MgO are well characterized. These bifunctional catalysts, NAP‐Mg‐PdOs and NAP‐Mg‐OsW perform tandem Heck asymmetric dihydroxylation and asymmetric dihydroxylation‐N‐oxidation reactions, respectively, in the presence of the chiral ligand 1,4‐bis(9‐o‐dihydroquinidinyl)phthalazine [(DHQD)₂PHAL] in a single pot. It is quite impressive to note that H₂O₂ is used as a terminal oxidant to provide N‐methylmorpholine N‐oxide (NMO) in situ by the oxidation of N‐methylmorpholine (NMM) in the asymmetric dihydroxylation‐N‐oxidation catalyzed by NAP‐Mg‐OsW.     

Achiral Dihydroxylation of Olefins by Osmate (OsO42−) Stabilised on Nanocrystalline Magnesium Oxide

A recoverable and reusable new heterogeneous AP‐Mg‐OsO₄ catalyst was designed and developed for the first time via a counterionic stabilisation of OsO₄²⁻ with Mg²⁺ present on the corner or edge of nanocrystalline MgO. AP‐Mg‐OsO₄ catalysed the dihydroxylation of olefins to afford diols with excellent yields in the presence of N‐methylmorpholine N‐oxide for the first time. The absence of osmium and no progress of the dihydroxylation reaction with the filtrate samples withdrawn periodically during the reaction rule out the leaching of osmium unambiguously and provide evidence for the heterogeneity of the reaction. Identification of surface intermediate species by XPS and TGA‐DTA‐mass thermography gives an insight into the mechanism of the dihydroxylation reaction.     

Voltammetric study of the cyanide complexes of osmium—I. The reduction of the cyanide complex of Os(VI) on a platinum rde

Two forms of cyanide complexes of hexavalent osmium were found in alkaline KCN solutions. The initially formed complex, OsO₂(OH)₂(CN)^2?₂, is stable only in solutions with at least a ten-fold excess of OH^? ions over CN^? ions. At higher cyanide concentrations it is converted into the OsO₂(CN)^2?₄ complex. Both these complexes are reduced to tervalent osmium. A more detailed study of complex OsO₂(OH)₂(CN)^2?₂ has shown that it is reduced electrochemically according to the scheme of a consecutive electrochemical reaction.OsO₂(OH)₂(CN)^2?₂ + 2e(k₁,α₁) → Os(IV) + e(k₂,α₂) → Os(OH)₄(CN)^3?₂The values α₁ = 0.65 and α₂ = 0.40 and the potential dependences of constants k₁ and k₂ were determined.     

Catalytic Asymmetric Dihydroxylation of Aliphatic Olefins with Reusable Resin‐Osmium Tetroxide

Asymmetric dihydroxylation of aliphatic olefins to chiral diols with good yields and ees by a heterogeneous Resin‐OsO₄ catalyst using ferricyanide as cooxidant is disclosed for the first time. The catalyst was recovered quantitatively by simple filtration and reused for several times without significant loss of activity.     

Microencapsulated Osmium Tetroxide‐Catalyzed Asymmetric Dihydroxylation of Olefins in Water without Using Organic Cosolvents

The asymmetric dihydroxylation of olefin using phenoxyethoxymethyl‐polystyrene (PEM)‐based microencapsulated osmium tetroxide (PEM‐MC OsO₄) proceeded smoothly in water as the sole solvent. The catalyst was recovered quantitatively by simple filtration and reused several times without loss of activity.     

Solid–liquid extraction of terbium from phosphoric acid solutions using solvent‐impregnated resin containing TOPS 99

BACKGROUND: In this work, the solid‐liquid extraction of terbium from phosphoric acid solutions using solvent‐impregnated resin containing TOPS 99, an equivalent of di‐2‐ethylhexyl phosphoric acid, has been investigated. The parameters studied include equilibration time, acid concentration, amount of resin, metal concentration, kinetics, temperature, loading, elution, regeneration and recycling. RESULTS: FT‐IR results confirm the physical interaction of the extractant with the resin. The extraction of terbium with TOPS 99 impregnated Amberlite XAD 4 resin was acid dependent and transfer of metal follows a cation exchange mechanism. The loading capacity of TOPS 99‐impregnated resin for terbium was calculated to be 23.8 mg g^?1 resin. Controlling mechanism of the adsorption was found to be a chemical reaction following pseudo‐second‐order kinetics. The endothermic nature of extraction was confirmed by temperature studies. Among the various eluants studied, H₂SO₄ was the best. Regeneration and recycling of the resin indicated the resin can be used for continuous cycles. CONCLUSIONS: Terbium was successfully extracted from phosphoric acid using TOPS 99 extractant impregnated into Amberlite XAD4 with a maximum loading of 23.8 mg g^?1 resin and fully recovered with 1 mol L^?1sulfuric acid. The resin was subjected to seven cycles of extraction and elution without any loss of performance. Further studies showed that terbium could be separated from lutetium. Copyright © 2010 Society of Chemical Industry     

Synthesis of Amino Acid Conjugates and Further Derivatives of 3α‐Hydroxylup‐20(;29)ene‐23,28‐dioic acid

Triterpenes of betulinic acid type exhibit many interesting biological activities. Therefore a series of new 3α‐hydroxy‐lup‐20(29)‐ene‐23,28‐dioic acid derivatives 2a—22 with putative pharmacological activities were synthesized. As starting compounds 3α‐hydroxy‐lup‐20(29)‐ene‐23,28‐dioic acid ( 1a ), isolated from Schefflera octophylla, or its 3‐O‐acetyl derivative 1b were used. Mono‐ and diesters ( 2a—b from 1a , and 4d from 4c ) were prepared with CH₂N₂. Oxidation of the isopropenyl side chain with OsO₄ yielded the 20,29‐diols ( 4a—b from 1b , and 19 from 17 ), which were in the case of 4b further transformed to the 29‐norketones 8a/mdash;b . Oxidation of the isopropenyl side chain with m‐chloroperbenzoic acid afforded the 20,29‐epoxide 12 (from 1b ) and the 29‐aldehydes and a‐hydroxy aldehydes ( 13a—c from 2a, 14a—c from 2b , and 16a—c from 15a ). Ring A was modified by a tosylation—elimination sequence using p‐TsCl/NaOAc, which afforded diolefin 15a (from 2a ) with Δ^2,20(29) double bonds or 23‐nor‐Δ^3,20(29)diolefin 17 (from 1a ). Compounds 4b, 4c , and 8a were coupled with L ‐methionin, L ‐phenylalanin, L ‐alanin, L ‐serin, and L ‐glutaminic acid via amide bonds at positions 23 and 28 to afford the amino acid conjugates 5a—7b and 9a—11 .     

Strategies to optimize phosphate removal from industrial anaerobic effluents by magnesium ammonium phosphate (MAP) production

BACKGROUND: Owing to more stringent phosphate discharge requirements and the increasing prices of fertilizers, beneficial recovery and reuse of phosphate from industrial anaerobic effluents is becoming an important issue. Phosphate recovery by struvite or magnesium ammonium phosphate (MAP) permits its recycling in the fertilizer industry because struvite is a valuable slow release fertilizer. Two different approaches to MAP crystallization depending on initial levels of phosphate in the wastewaters were tested and compared. RESULTS: For low‐phosphate‐containing anaerobic effluents (<30 mg PO₄^3?‐P L^?1), a novel approach using ureolytic induced MAP formation with MgO addition appeared to be suitable. The residual phosphate concentrations in the effluent ranged from 5 to 7 mg PO₄^3?‐P L^?1 and the separated matter contained residual amounts of Mg(OH)₂. High‐phosphate‐containing anaerobic effluents (100 to 120 mg PO₄^3?‐P L^?1) were treated efficiently using air stripping combined with MgCl₂ and NaOH reagents, yielding residual phosphate levels of 8 to 15 mg PO₄^3?‐P L^?1 and spherical pure MAP crystals of 0.5 to 2 mm. CONCLUSION: Results show that depending on the initial phosphate concentrations in the wastewaters and the ammonium and magnesium levels, the strategy selected for struvite crystallization is a determinative factor in achieving a cost effective technology. Copyright © 2008 Society of Chemical Industry     

Silica Gel‐Supported Cinchona Alkaloid‐OsO4 Complex for Catalytic Heterogeneous Asymmetric Dihydroxylation of Olefins by H2O2 using a Titanium Silicalite‐Based Coupled Catalytic System

A triple catalytic system designed for asymmetric dihydroxylation of olefins, composed of NMM and two divergent heterogeneous catalysts, titanium silicalite and silica gel‐supported 1,4‐bis(9‐O‐dihydroquinidinyl)phthalazine [SGS‐(DHQD)₂PHAL)]‐OsO₄ complex relays the transport of two electrons from olefin to H₂O₂ used as a terminal oxidant to provide chiral diols with good yields and high enantiomeric excesses in a single pot.     

Controlled Reversible Anchoring of η6‐Arene/TsDPEN‐ Ruthenium(II) Complex onto Magnetic Nanoparticles: A New Strategy for Catalyst Separation and Recycling

A new catalyst separation and recycling protocol combining magnetic nanoparticles and host‐guest assembly was developed. The catalyst, (η⁶‐arene)[N‐(para‐toluenesulfonyl)‐1,2‐diphenylethylenediamine]ruthenium trifluoromethanesulfonate [Ru(OTf)(TsDPEN)(η⁶‐arene)] bearing a dialkylammonium salt tag, was easily separated from the reaction mixtures by magnet‐assisted decantation, on basis of the formation of a pseudorotaxane complex by using dibenzo[24]crown‐8‐modified Fe₃O₄ nanoparticles. The ruthenium catalyst has been successfully reused at least 5 times with the retention of enantioselectivity but at the expense of relatively low catalytic activities in the asymmetric hydrogenation of 2‐methylquinoline.     

Rückgewinnung Seltener Erden aus FeNdB‐Dauermagneten mittels Feststoffchlorierung

Solid state chlorination with NH₄Cl as chlorinating agent represents a new way for rare earth recovery from end‐of‐life‐magnets. Compared to hydrometallurgical recycling approaches this process provides a number of economic advantages. As a first step, solid state chlorination was adjusted with disused FeNdB magnets from a wind power plant. The SE yield of the chlorination step was optimized according to a 3³‐Box‐Behnken design with varying temperature, time, and NH₄Cl/magnet ratio. Likewise, the process profits from leaching with a sodium acetate/acetic acid buffer following the chlorination step.     

Recycling Chiral Imidazolidin‐4‐one Catalyst for Asymmetric Diels–Alder Reactions: Screening of Various Ionic Liquids

Various imidazolium ionic liquids such as [Bmim]PF₆, [Bmim]SbF₆, [Bmim]OTf and [Bmim]BF₄ were screened for recycling an organic catalyst [(5S)‐5‐benzyl‐2,2,3‐trimethylimidazolidin‐4‐one ( 1 )] for asymmetric Diels–Alder reactions. Good yields and enantioselectivies (up to 85% yield and 93% ee) were obtained from reactions in [Bmim]PF₆ or [Bmim]SbF₆. However, reactions in [Bmim]OTf or [Bmim]BF₄ gave racemic products in low yields. Isolation of the products by simple extraction using diethyl ether allowed recycling of the ionic liquid containing the immobilized catalyst in subsequent reactions without significant decrease of yields and enantioselectivities.     

Voltammetric study of the cyanide complexes of osmium—II. The behaviour of lower oxidation state cyanide complexes of osmium on a platinum rde

It was found that the product of the reduction of the cyanide complex of hexavalent osmium, OsO₂(OH)₂(CN)^2?₂ is the Os(OH)₄(CN)^3?₄ complex and the product of the reduction of the OsO₂(CN)^2?₄ complex is the Os(OH)₂(CN)^2?₂ complex. Further reduction of the Os(OH)₄(CN)^3?₄ complex of trivalent osmium is complicated by a follow-up chemical reaction and the stable reduction product is a complex of divalent osmium, Os(OH)₂(CN)^4?₄ which forms a reversible redox system with the Os(OH)₂(CN)^3?₂ complex with a formal redox protential (1 M KOH, 0.1 M KCN) of ?760 mV/sce. The Os(OH)₄(CN)^3?₂ and Os(OH)₂(CN)^4?₄ complexes are stable only in solutions with at least a ten-fold excess of OH^? ions over the concentration of CN^t- ions. At greater cyanide concentrations, the chemical reactioins, Os(OH)₄(CN)^3?₂ → Os(OH)₂(CN)^3?₄ and Os(OH)₂(CN)^4?₄ → Os(CN)^4?₆, occur. The reaction rate for the latter reaction was found to be ?₄ = 1.87 × 10^t-4 l mol^?1 s^?1 in solutions with pH = 11.8. The characteristics of the individual forms of the cyanide complexes of osmium are also discussed.     

A diamino based resin modified silica composite for the selective recovery of tungsten from wastewater

A new adsorbent was developed by synthesizing 1,8‐diaminonaphthalene formaldehyde resin (DANFR) and coating it over the surface of silica gels. The silica composite was then treated with HCl for the activation of binding sites (?NH₃⁺Cl^?) on its surface. The structure of DANFR and its coating over the silanols were thoroughly characterized. Further, the adsorbent was applied to remove tungsten (W) from printed circuit board recycling unit wastewater that contained various co‐metal ions such as Na⁺, K⁺, Ca²⁺, Mg²⁺, Pb²⁺, NH₄⁺, Zn²⁺, Cu²⁺ and Mn²⁺. The selective removal was achieved due to the anion exchange mechanism of Cl^? with W(VI) while other cations get repelled from the surface (?NH₃⁺) of the DANFR‐silica composite. X‐ray photoelectron spectroscopy studies, Raman spectra and overlay chromatograms of ion chromatography demonstrated selective separation of WO₄^2? species from the wastewater. A removal capacity of 55.32 mg g^?1 for W(VI) was achieved from the wastewater within 45 min of reaction (pH ca 6.0). Simultaneous treatment with neat aqueous solution of W brings out 63.27 mg g^?1 of W(VI) removal. Finally, recovery of WO₄^2? ions and regeneration of the adsorbent were carried out by using alkaline solution which demonstrated successful desorption, as investigated by using ion chromatography. © 2016 Society of Chemical Industry     

Struktur und Eigenschaften von ABS-Polymeren. XII. Oxydativer Abbau von Polybutadien-Pfropfpolymeren aus ABS; Vergleich verschiedener Abbaumethoden

Polybutadiene graft polymers are characterized by first degrading polybutadiene under mild oxidation conditions with tert-butylhydroperoxide and OsO₄ at 110°C for 30 min is p-dichlorbenzene and then degrading it in a second step with periodic acid at room temperature. This degradation method is compared with a degradation procedure with KMnO₄ and a degradation with tert-butylhydroperoxide and OsO₄ in toluene and benzene at different temperatures and for different degradation times. It could be shown, that the described degradation method fully degrades polybutadiene without changing the chain length of the grafted styrene-acrylonitrile-copolymer chains.     

Preparation and characterization of natural rubber dispersed in nano-matrix

Preparation of a model nano-matrix-dispersed polymer was investigated in terms of graft-copolymerization of deproteinized natural rubber latex with styrene, using tert-butyl hydroperoxide/tetraethylenepentamine as an initiator. The products were characterized by ¹H-NMR spectroscopy and size-exclusion-chromatography after ozonolysis. The grafting efficiency of styrene was found to be more than 90% under the best condition of the graft-copolymerization. The morphology of the film specimens, prepared from graft-copolymers, was observed by transmission electron microscopy after staining the films with OsO₄. Natural rubber particle of about 0.5 μm in diameter was dispersed in polystyrene matrix of about 15 nm in thickness.     

Infrared Photochemistry with Shaped Laser Pulses

A relatively simple design for a hybrid CO₂ laser and electrooptic crystal switch is described, which can be used to produce pulses with fast (< 10 ns) rise and fall times with constant power over their duration (50–1000 ns). Gaussian beam profiles allow separate and quantitative determination of both fluence (J cm⁻²) and intensity (W cm⁻²) dependences of processes induced by IR multiple photon absorption (MPA). Visible luminescence accompanying MPA of OsO₄ is shown to depend on intensity, and the dependences of MPA cross sections in SF₆ on fluence and intensity are derived from optoacoustic and long path absorption measurements.     

Vicinal Diol-Tethered Nucleobases as Targets for DNA Redox Labeling with Osmate Complexes

Six-valent osmium (osmate) complexes with nitrogenous ligands have previously been used for the modification and redox labeling of biomolecules involving vicinal diol moieties (typically, saccharides or RNA). In this work, aliphatic (3,4-dihydroxybutyl and 3,4-dihydroxybut-1-ynyl) or cyclic (6-oxo-6-(cis-3,4-dihydroxypyrrolidin-1-yl)hex-2-yn-1-yl, PDI) vicinal diols are attached to nucleobases to functionalize DNA for subsequent redox labeling with osmium(VI) complexes. The diol-linked 2′-deoxyribonucleoside triphosphates were used for the polymerase synthesis of diol-linked DNA, which, upon treatment with K₂OsO₃ and bidentate nitrogen ligands, gave the desired Os-labeled DNA, which were characterized by means of the gel-shift assay and ESI-MS. Through ex situ square-wave voltammetry at a basal plane pyrolytic graphite electrode, the efficiency of modification/labeling of individual diols was evaluated. The results show that the cyclic cis-diol (PDI) was a better target for osmylation than that of the flexible aliphatic ones (alkyl- or alkynyl-linked). The osmate adduct-specific voltammetric signal obtained for Os^VI-treated DNA decorated with PDI showed good proportionality to the number of PDI per DNA molecule. The Os^VI reagents (unlike OsO₄) do not attack nucleobases; thus offering specificity of modification on the introduced glycol targets.     

Nitrification by immobilized cells in a micro‐ecological life support system using packed‐bed bioreactors: an engineering study

The nitrifying component of a micro‐ecological life support system alternative (MELISSA) based on microorganisms and higher plants was studied. The MELISSA system consists of an interconnected loop of bioreactors to allow the recycling of the organic wastes generated in a closed environment. Conversion of ammonia into nitrates in such a system was improved by selection of microorganisms, immobilization techniques, reactor type and operation conditions. An axenic mixed culture of Nitrosomonas europaea and Nitrobacter winogradskyi, immobilized by surface attachment on polystyrene beads, was used for nitrification in packed‐bed reactors at both bench and pilot scale. Hydrodynamics, mass transfer and nitrification capacity of the reactors were analysed. Mixing and mass transfer rate were enhanced by recirculation of the liquid phase and aeration flow‐rate, achieving a liquid flow distribution close to a well‐mixed tank and without oxygen limitation for standard operational conditions of the nitrifying unit. Ammonium conversion ranged from 95 to 100% when the oxygen concentration was maintained above 80% of saturation. The maximum surface removal rates were measured as 1.91 gN‐NH₄⁺ m^?2 day^?1 at pilot scale and 1.77 gN‐NH₄⁺ m^?2 day^?1 at bench scale. Successful scale‐up of a packed‐bed bioreactor has been carried out. Good stability and reproducibility were observed for more than 400 days. Copyright © 2004 Society of Chemical Industry     

Struktur und Eigenschaften von ABS-Polymeren. IV. Teilchengrößenbestimmungen an Butadien-Homo- und Pfropfpolymerisat-latices mit dem Elektronenmikroskop

A summary of the different electron-microscopic preparation methods for latices (hardening and contrasting by addition of OsO₄, Br₂, uranyl acetate etc.; addition of monomeric styrene, followed by γ-ray or X-ray radiation; electron curing, taking of surface replicas after low temperature shock etc.) is followed by a discussion of the customary methods for interpretation of electron micrographs of latices. Particular attention is drawn to the possibilities for errors in measurement of the particle size distribution of polybutadiene latices after fixation with OsO₄. Series of measurements corresponding to increasing fixation times and/or rising concentrations of the fixation solution show that low fixation results in flattening, while high fixation (owing to incorporation of OsO₄) rasults in swelling of the spherical particles; in both cases excessive particle diameters are obtained. Determinations of mass with an integration photometer are used as controls. In connection with measurements to find the particle sizes of butadiene homopolymer and graft polymer latices the ratio between the volume of the grafting stock and that of the graft polymer is determined and satisfactory agreement with the starting ratio is found.