Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ³‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ³‐benziodoxolones are involved in these organocatalytic reactions.     

The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes

By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A₂L₃ complexes (A represents anion, here orthophosphate PO₄^3?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes.     

Logarithmic temperature dependence of the conductivity of the two-dimensional metal

We report on the first observation and studies of a weak delocalizing logarithmic temperature dependence of the conductivity, which causes the conductivity of the 2D metal to increase as T decreases down to 16 mK. The prefactor of the logarithmic dependence is found to decrease gradually with density, to vanish at a critical density n _c , 2∼2×10¹² cm⁻², and then to have the opposite sign at n>n _c ,2. The second critical density sets the upper limit on the existence region of the 2D metal, whereas the conductivity at the critical point, G _c ,2∼120e ²/h, sets an upper (low-temperature) limit on its conductivity. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 497–501 (25 September 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

The Hopf Algebra of Rooted Trees in Epstein-Glaser Renormalization

We show how the Hopf algebra of rooted trees encodes the combinatorics of Epstein-Glaser renormalization and coordinate space renormalization in general. In particular, we prove that the Epstein-Glaser time-ordered products can be obtained from the Hopf algebra by suitable Feynman rules, mapping trees to operator-valued distributions. Twisting the antipode with a renormalization map formally solves the Epstein-Glaser recursion and provides local counterterms due to the Hochschild 1-closedness of the grafting operator B₊.submitted 29/03/04, accepted 01/06/04     

Activity of microemulsion-based nanoparticles at the human bio-nano interface: concentration-dependent effects on thrombosis and hemolysis in whole blood

Background: Although microemulsion-based nanoparticles (MEs) may be useful for drug delivery or scavenging, these benefits must be balanced against potential nanotoxicological effects in biological tissue (bio-nano interface). We investigated the actions of assembled MEs and their individual components at the bio-nano interface of thrombosis and hemolysis in human blood. Methods: Oil-in-water MEs were synthesized using ethylbutyrate, sodium caprylate, and pluronic F-68 (ME4) or F-127 (ME6) in 0.9% NaCl_w/v. The effects of MEs or components on thrombosis were determined using thrombo-elastography, platelet contractile force, clot elastic modulus, and platelet counting. For hemolysis, ME or components were incubated with erythrocytes, centrifuged, and washed for measurement of free hemoglobin by spectroscopy. Results and conclusions: The mean particle diameters (polydispersity index) for ME6 and ME4 were 23.6 ± 2.5 nm (0.362) and 14.0 ± 1.0 nm (0.008), respectively. MEs (0, 0.03, 0.3, 3 mM) markedly reduced the thromboelastograph maximal amplitude in a concentration-dependent manner (49.0 ± 4.2, 39.0 ± 5.6, 15.0 ± 8.7, 3.8 ± 1.3 mm, respectively), an effect highly correlated (r2 = 0.94) with similar changes caused by pluronic surfactants (48.7 ± 10.9, 30.7 ± 15.8, 20.0 ± 11.3, 2.0 ± 0.5) alone. Neither oil nor sodium caprylate alone affected the thromboelastograph. The clot contractile force was reduced by ME (27.3 ± 11.1–6.7 ± 3.4 kdynes/cm², P = 0.02, n = 5) whereas the platelet population not affected (175 ± 28–182 ± 23 10⁶/ml, P = 0.12, n = 6). This data suggests that MEs reduced platelet activity due to associated pluronic surfactants, but caused minimal changes in protein function necessary for coagulation. Although pharmacological concentrations of sodium caprylate caused hemolysis (EC₅₀ = 213 mM), MEs and pluronic surfactants did not disrupt erythrocytes. Knowledge of nanoparticle activity and potential associated nanotoxicity at this bio-nano interface enables rational ME design for in vivo applications.     

Biopolymers for biocatalysis: Structure and catalytic mechanism of hydroxynitrile lyases

Hydroxynitrile lyases catalyze the reversible cleavage of α-cyanohydrins to yield hydrocyanic acid and the corresponding aldehyde or ketone. Besides its biological interest, this class of enzymes is also of relevance in industrial biocatalysis for the enantioselective condensation of HCN with a variety of aldehydes and ketones. Several distinctly different types of hydroxynitrile lyases (HNLs) are known, which must have originated through convergent evolution from different ancestral proteins. Three-dimensional structural data are known for three classes of hydroxynitrile lyases. Insights into the reaction mechanisms emerged from a combination of structural, enzyme kinetic, spectroscopic, and molecular modeling data. For all three types of HNLs, mechanisms involving acid–base catalysis were proposed. In members belonging to the α,β-hydrolase type, the amino acid residues of the catalytic triad presumably act as general acid/base, whereas for flavine adenine dinucleotide (FAD)-dependent HNLs a single histidine residue fulfills this function. In the third type of HNL—which is related to carboxypeptidase—acid–base catalysis involves the carboxylate of the C-terminal residue. The catalytic relevance of a positive electrostatic potential in the active site was suggested in some of the mechanistic proposals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 479–486, 2004     

Trovacenchemie. 13 [1] Weg und Irrweg zu Di([5]trovacenyl)keton

Trovacene Chemistry. 13 [1] On Being Lead and Mislead in the Synthesis of Di([5]trovacenyl)ketone Di([5]trovacenyl)ketone ( 3¨ ) has been prepared from lithio‐[5]trovacene and dimethylcarbamoyl chloride and studied by X‐ray diffraction, cyclic voltammetry, magnetic susceptometry and EPR spectroscopy. Slight variation of the synthetic protocol affords an unusual trinuclear complex 5 ? that is also fully characterized. Spin‐spin exchange interaction is smaller in 3¨ than in 1,1‐di([5]trovacenylethene ( 2¨ ), which differs from 3¨ by a replacement of O for CH₂. The novel trinuclear complex 5 ? , however, displays exchange coupling very similar to that observed in 1‐methoxy‐2,5,6‐tri([5]trovacenyl)benzene ( 7 ? ). In both cases, an unsymmetrical triangular arrangement of S = 1/2 centers is encountered. These findings are discussed in terms of the nature of the respective spacers.