Copper(II) complexes of tetrapeptides containing cysteinyl and histidinyl residues

It is becoming increasingly apparent that the coordination chemistry of oligopeptides with Cys-X-Y-Cys and His-X-Y-Cys sequences (X, Y = variable amino acid residues) is an important theme in transition metal and bioinorganic chemistry(1,2). The Cys-X-Y-Cys sequence is often encountered in the metal binding site of several metalloproteins, such as iron–sulfur proteins, e.g. rubredoxins(3) and ferrodoxins(4), high potential iron–sulfur proteins(5), metallothioneins(6), zinc proteins(7) etc. The amino acid sequence His-X-Y-Cys is also of bioinorganic importance since it has been found in the active site of copper(8), iron–sulfur(9) and zinc(10) proteins. We are currently seeking to develop the area of transition metal/Cys-X-Y-Cys and His-X-Y-Cys peptide interactions(11,12); our goals are: (i) to elucidate the role of these sequences in the biological activity and mechanism of action of the above metallobiomolecules, and (ii) to find possible new and more effective agents for the elimination of heavy metals from the human organism or from contaminated waste waters. Here we report the preparation and preliminary characterization of copper(II) complexes of tetrapeptide ligands containing the Cys-X-Y-Cys and His-X-Y-Cys sequences. This revised version was published online in June 2006 with corrections to the Cover Date.     

Investigation for the determination of ultra trace amounts of Co2+ complexed with 1,10-phenanthroline by adsorptive voltammetry

Summary The spontaneous adsorption of the Co²⁺ complex with 1,10-phenanthroline on HMDE was utilized for the development of a voltammetric analytical method employing phase selective alternating current, with first harmonic AC₁ in phase, =0°, voltammetry. The dependence of the analytical voltammetric response on physical and chemical parameters in various supporting electrolytes was investigated in detail. Optimum conditions for Co²⁺ determination were established. The method is very sensitive and selective. The determination limit is 205 ng/l Co²⁺ (adsorption time, t_ads=20 min). The precision and accuracy were evaluated: 1.84 g/l Co²⁺, RSD=3.24%, RE=–0.54%; for 205 ng/l Co²⁺, RSD=4.85%, RE=–3.90%. The results showed good reproducibility and reliabiality. The method was applied to natural waters, wines, mussel tissue and aquatic algae certified reference material.     

A remark on the negative activation volume for defects in solids

The evolution of the aging process of glassy materials quenched from temperatures above their glass transition temperature T_g, when plotting the relaxed enthalpy versus the decrease in volume, leads to a slope comparable to the isothermal compressibility close to T_g. This empirical result was explained in an earlier publication (V. Katsika-Tsigourakou, G. E. Zardas J. Non-Cryst. Solids 356 (2010) 179–180) by means of a thermodynamical model. Here, we show that the same model enables the explanation of the rare cases of negative defect activation in solids.     

Solid-Phase Synthesis of a Biotin Derivative and its Application to the Development of Anti-Biotin Antibodies

A biotin derivative, namely biotin–aminocaproic acid–lysine (BAL), was synthesized with solid-phase chemistry, conjugated to a carrier-protein, and used for rabbit immunization. The aminocaproic acid–lysine “long-arm” was used in order to project the biotin-hapten above the carrier-protein surface. Lysine was selected due to its N^ε-amino group, through which BAL was conjugated to the carrier-protein. BAL was synthesized on a commercially available resin with the Fmoc-solid-phase strategy; this has simplified the experimental procedure, overcome the need for intermediate purification steps, and led to a final product of high purity, with high yield. The anti-BAL antibodies recognized free biotin, as shown with an in-house-developed ELISA, in which biotin conjugated to a synthetic “lysine–dendrimer” was used to coat the ELISA microwells. In immunocytology and Western-blot experiments, the anti-BAL antibodies led to similar results with those obtained with streptavidin. Synthetic derivatives of hapten molecules that can be easily prepared with solid-phase chemistry, such as BAL, may be used for the development of specific antibodies for the corresponding hapten.     

Diastereocontrol in the intramolecular cycloadditions of 2-substituted-erythro-3,4-isopropylidenedioxyhex-5-enenitrile oxides

The influence of the 2-substituent on the diastereoselectivity of the intramolecular cycloadditions in a series of 2-substituted-erythro-3,4-isopropylidene-dioxyhex-5-enenitrile oxides, generated in situ from selected sugar derivatives, was examined.     

New Calix[4]arene‐Cored Peripherally Functionalized Dendrimers: Synthesis and Conformational Characteristics

New calixarene‐based dendrimers, containing calix[4]arene as the core and different generations of Fréchet‐type poly(benzyl ether) dendrons as building blocks, which possess either Br‐atoms or COO^tBu groups at their surface were synthesized and presented herein for the first time. The new calix[4]arene‐cored dendritic macromolecules were fully characterized and found to prefer strictly the cone conformation.     

The synthesis of 5-acyl-4-aryl(alkyl)-2-aryl-1,2,3-triazole 1-oxides by lead tetraacetate oxidation of mono- and bisarylhydrazones of α-hydroxyimino-β-diketones

The synthesis and lead tetraacetate oxidation of the title mono- and bis-arylhydrazones to the corresponding 5-acyl-4-aryl(alkyl)-2-aryl-1,2,3-triazole 1-oxides is described.     

A new strategy for the stereoselective synthesis of unnatural α-amino acids

A new method for the synthesis of racemic non-proteinogenic α-amino acids has been developed, which involves (i) hetero-Diels-Alder addition of ethyl 2-nitrosoacrylate to electron rich alkenes such as enol ethers, enamines and allylsilanes, (ii) NaCNBH₃ reduction of the CN bond in the oxazines thus generated, the stereochemistry of the products being controlled by epimerisation of the thermodynamically less stable isomer to the more stable one, (iii) protection of the N-H group as N-Boc and (iv) finally, N-O bond cleavage of both free and protected products to give proline or bis-homoserine derivatives, respectively. An example with concomitant reduction of the carboxylate group, resulting in the formation of the respective amino alcohol is reported. Applying this methodology to a homochiral enol ether, the protected parent d-proline was prepared in enantiomerically pure form, whereas the asymmetric synthesis of the respective bis-homoserine was unsuccessful.