Hydrothermal extraction of potassium,sodium, rubidium and cesium from rocks by lithium hydroxide and determination at very low natural levels

The selective extraction of Na, K, Rb and Cs from rocks is described. The method is particularly designed for low levels of rubidium and cesium in basic and ultrabasic rocks. The rocks are decomposed with lithium hydroxide solution at 180°C. Only part of the aluminium and chromium accompany the alkali metals into solution; all other rock constitutents are left behind as insoluble lithium silicate, hydroxides of divalent metals, etc. Concentration of rubidium and cesium too low to be determined directly by flame emission spectrometry are pre-concentrated up to 25-fold by liquid-liquid extraction. Quantitative recovery (>99.5%) of the two metals is achieved by coprecipitation with potassium tetraphenylboron within the organic phase (di-isobutyl ketone) for subsequent back-extraction and dissolution in an acidic aqueous phase. Detection limits are 1 mg kg^?1 Na or K, 0.1 mg kg^?1 Rb and 0.05 mg kg^?1 Cs in the rock for the direct determination and 0.003 mg kg^?1 Rb and 0.001 mg kg^?1 Cs after preconcentration. Methods are described for the purification of lithium hydroxide and the potassium nitrate used as carrier. Results are presented for the Na₂ O, K₂O, Rb and Cs contents and the K/Rb values for 23 geochemical references samples (basic and ultrabasic rocks, and iron formation samples).     

Methyl methacrylate polymerization at samarium(II)-grafted MCM-41

Sm(II)-modified periodic mesoporous silica (PMS), Sm[N(SiHMe₂)₂]₂(THF)_x@MCM-41, was used for the synthesis of Sm(II) alkyl, alkoxide, and indenyl surface species via secondary ligand exchange. The performance of the novel Sm(II)-based organometallic–inorganic hybrid materials as initiators for the graft polymerization of methyl methacrylate (MMA) is reported. All of the Sm(II) hybrid materials including the new PMMA–PMS composites were characterized via N₂ physisorption, elemental analysis, FTIR spectroscopy, and scanning electron microscopy (SEM). The organic–inorganic composites revealed complete pore blockage as well as enrichment and strong adhesion of the polymer at the exterior of the porous silica material.     

Novel UDP-glycal derivatives as transition state analogue inhibitors of UDP-GlcNAc 2-epimerase

The "epimerisation" of UDP-GlcNAc to ManNAc, the first step in the biosynthesis of sialic acids, is catalyzed by UDP-GlcNAc 2-epimerase. In this paper we report the synthesis of transition state based inhibitors of this enzyme. To mimic the assumed first transition state of this reaction (TS 1), we designed and synthesized the novel UDP-exo-glycal derivatives 1-4. We also report herein the synthesis of 5 and 6, the first C-glycosidic derivatives of 2-acetamidoglucal, and the synthesis of the ketosides 7 and 8, which were designed as bis-substrate analogue and bis- product analogue, respectively, to mimic the second step of the reaction via the assumed second transition state TS 2.     

Crystal engineering: Supramolecular structures by cocrystallization ofMeso-1,2-diphenyl-1,2-ethanediol and bisimines,simple cases of molecular recognition

The crystal structures of molecular complexes betweenmeso- 1,2-diphenyl-1,2-ethanediol and two bisimines (N,N-(dibenzylidene)-ethylenediamine and glyoxylidene-bis(2,4-dimethyl-3-pentyl-amine) are reported at different temperatures. The structure-determining motif of the cocrystalline arrangement is one single O-H . N hydrogen bond resulting in infinite ladderlike polymers. The supramolecular structure is formed by recognition of fitting species: Thed- orl-isomers do not arrange in such structures.¹H NMR experiments show that no prearrangements take place by forming complexes in solution.     

Synthesis and characterization of dinuclear ruthenium complexes covalently linked to Ru(II) tris-bipyridine: an approach to mimics of the donor side of photosystem II

To mimic the electron-donor side of photosystem II (PSII), three trinuclear ruthenium complexes (2, 2a, 2b) were synthesized. In these complexes, a mixed-valent dinuclear Ru2(II,III) moiety with one phenoxy and two acetato bridges is covalently linked to a Ru(II) tris-bipyridine photosensitizer. The properties and photoinduced electron/energy transfer of these complexes were studied. The results show that the Ru2(II,III) moieties in the complexes readily undergo reversible one-electron reduction and one-electron oxidation to give the Ru2(II,III) and Ru2(III,III) states, respectively. This could allow for photooxidation of the sensitizer part with an external acceptor and subsequent electron transfer from the dinuclear ruthenium moiety to regenerate the sensitizer. However, all trinuclear ruthenium complexes have a very short excited-state lifetime, in the range of a few nanoseconds to less than 100 ps. Studies by femtosecond time-resolved techniques suggest that a mixture of intramolecular energy and electron transfer between the dinuclear ruthenium moiety and the excited [Ru(bpy)3]2+ photosensitizer is responsible for the short lifetimes. This problem is overcome by anchoring the complexes with ester- or carboxyl-substituted bipyridine ligands (2a, 2b) to nanocrystalline TiO2, and the desired electron transfer from the excited state of the [Ru(bpy)3]2+ moiety to the conduction band of TiO2 followed by intramolecular electron transfer from the dinuclear Ru2(II,III) moiety to photogenerated Ru(III) was observed. The resulting long-lived Ru2(III,III) state decays on the millisecond timescale.     

Linear extension sums as valuations on cones

The geometric and algebraic theory of valuations on cones is applied to understand identities involving summing certain rational functions over the set of linear extensions of a poset.     

Weyl Group $${\varvec{q}}$$ q -Kreweras Numbers and Cyclic Sieving

Catalan numbers are known to count noncrossing set partitions, while Narayana and Kreweras numbers refine this count according to the number of blocks in the set partition, and by its collection of block sizes. Motivated by reflection group generalizations of Catalan numbers and their q-analogues, this paper concerns a definition of q-Kreweras numbers for finite Weyl groups W, refining the q-Catalan numbers for W, and arising from work of the second author. We give explicit formulas in all types for the q-Kreweras numbers. In the classical types A, B, C, we also record formulas for the q-Narayana numbers and in the process show that the formulas depend only on the Weyl group (that is, they coincide in types B and C). In addition, we verify that in the classical types A, B, C, D the q-Kreweras numbers obey the expected cyclic sieving phenomena when evaluated at appropriate roots of unity.

     

One Facile Preparation of N‐Aroyl‐N′‐arylsulfonylhydrazines by Oxidation of Aromatic Aldehyde N‐Arylsulfonylhydrazones with bis(Trifluoroacetoxy)iodobenzene

N‐aroyl‐N′‐arylsulfonylhydrazines can be obtained by oxidation of aromatic aldehyde N‐arylsulfonylhydrazones with bis(trifluoroacetoxy)iodobenzene in acetone at room temperature in mild to good yields.     

Enantioselective Total Synthesis of (−)‐Blennolide A

Blennolide A can be synthesized through an enantioselective domino‐Wacker/carbonylation/methoxylation reaction of 7 a with 96 % ee and an enantioselective Wacker oxidation of 7 b with 89 % ee. Further transformations led to the α,β‐unsaturated ester (E)‐ 17 , which was subjected to a highly selective Michael addition, introducing a methyl group to give 18 a . After a threefold oxidation and an intramolecular acylation, the tetrahydroxanthenone 4 was obtained, which could be transformed into (?)‐blennolide A (ent‐ 1 ) in a few steps.