Heptakis-6-(5-methylene-thioureido-5′-methyl-2,2′-bipyridyl)-β-cyclodextrin: synthesis and metal complexation study

A new heptapode heptakis-6-(5-methylene-thioureido-5′-methyl-2,2′-bipyridyl)-β-cyclodextrin was prepared and its complexation properties towards metal cations were investigated. Substituting the urea functions by the corresponding thioureas promoted the inversion of the metal coordination selectivity. Preliminary results showed the heptapode unable to complex lanthanides but authorise selective complexation of ‘soft’ and ‘borderline’ metal cations.     

A general approach toward the synthesis of 8-acylamidopyrazolo[1,5-a]-1,3,5-triazines

An expedient synthesis of 8-acylamidopyrazolo[1,5-a]-1,3,5-triazines was developed by treating 8-amino-4-[N-(4-aminophenyl)-N-(methyl)amino]pyrazolo[1,5-a]-1,3,5-triazine with various acyl chlorides following by the displacement of the so-formed N-(methyl)-N-[4-(acylamido)phenyl]amino leaving group with various amines. Applications to high-throughput synthesis are suggested.     

Efficient indirect electrochemical in-situ regeneration of nadh:electrochemically driven enzymatic reduction of pyruvate catalyzed by d-ldh

Using [Cp(Me)₅Rh(bipy)C1]C1 (1) as redox catalyst for the continous NADH regeneration it was possible to perform an electrochemically driven enzymatic reduction of pyruvate to D-lactate catalyzed by D-LDH at a rate of 5 turnovers per hour. This is by a factor of 20 faster than the best results obtained until now. Current yields of 50 to 70 % may be obtained.     

Palladium-Catalyzed Hydroaminocarbonylation of Olefins with Aliphatic Amines without Additives

Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct-1-ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N-nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo-, regio- and enantioselectivities was also studied. Plausible explanation was given for the additive-free hydroaminocarbonylation reaction.     

Improved quantitation of 13-cis- and all-trans-acitretin in human plasma by normal-phase high-performance liquid chromatography.

A reliable analytical method has been developed for measurement of 13-cis- and all-trans-acitretin (Neotigason) in human plasma by normal-phase high-performance liquid chromatography, with ultraviolet detection. Human plasma was obtained after centrifugation of whole blood samples and deproteinized by ethanolic denaturation. After liquid-liquid extraction with water-n-hexane, and aliquot ws chromatographed on a silica column using isocratic elution with n-hexane-methylsalicylate-acetic acid (200:18:0.6, v/v). The wavelength was set at 360 nm, and for plasma samples a limit of quantification of 3-4 ng/ml was obtained. All manipulations were carried out under dim light conditions to prevent photoisomerization.     

The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline‐Catalyzed Oxidation of Alkyl Halides to Aldehydes

An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis.     

Glycosyl‐Substituted Dicarboxylates as Detergents for the Extraction,Overstabilization, and Crystallization of Membrane Proteins

To tackle the problems associated with membrane protein (MP) instability in detergent solutions, we designed a series of glycosyl‐substituted dicarboxylate detergents (DCODs) in which we optimized the polar head to clamp the membrane domain by including, on one side, two carboxyl groups that form salt bridges with basic residues abundant at the membrane–cytoplasm interface of MPs and, on the other side, a sugar to form hydrogen bonds. Upon extraction, the DCODs 8 b , 8 c , and 9 b preserved the ATPase function of BmrA, an ATP‐binding cassette pump, much more efficiently than reference or recently designed detergents. The DCODs 8 a , 8 b , 8 f , 9 a , and 9 b induced thermal shifts of 20 to 29 °C for BmrA and of 13 to 21 °C for the native version of the G‐protein‐coupled adenosine receptor A_2AR. Compounds 8 f and 8 g improved the diffraction resolution of BmrA crystals from 6 to 4 Å. DCODs are therefore considered to be promising and powerful tools for the structural biology of MPs.     

The protonated 4,4'-diaminotriphenylmethyl cation as a reagent and cyclohexanone as an absorbant for sulphur dioxide determination

Protonated 4,4'-diaminotriphenylmethyl cation, DATM, has been investigated as a colorimetric reagent for the determination of sulphur dioxide. The bisulphite addition compound with formaldehyde alkylates a primary arylamine group in the protonated reagent to re-establish resonance, and hence produces a colour that is proportional in intensity to the concentration of either bisulphite or formaldehyde (the other being in excess). The large bathochromic spectral shift results in a negligible blank correction. Cyclohexanone in aqueous solution has been found to stabilize bisulphite solutions for up to 6 hr. The stabilization by cyclohexanone has been compared with stabilization by tetrachloromercurate(II). The Beer-Lambert law is obeyed with good precision for both sulphite and formaldehyde determination.