Recycled-tire pyrolytic carbon made functional: A high-arsenite [As(III)] uptake material PyrC350®.

A novel material, PyrC350®, has been developed from pyrolytic-tire char (PyrC), as an efficient low-cost Arsenite [As(III)] adsorbent from water. PyrC350® achieves 31mgg-1 As(III) uptake, that remains unaltered at pH=4-8.5. A theoretical Surface Complexation Model has been developed that explains the adsorption mechanism, showing that in situ formed Fe3C, ZnS particles act cooperatively with the carbon matrix for As(III) adsorption. Addressing the key-issue of cost-effectiveness, we provide a comparison of As(III)-uptake effectiveness in conjunction with a cost analysis, showing that PyrC350® stands in the top of [effectiveness/cost] vs. existing carbon-based, low-cost materials.

New perspectives on thiamine catalysis: from enzymic to biomimetic catalysis.

This paper is a brief review of the detailed mechanism of action of thiamine enzymes, based on metal complexes of bivalent transition and post-transition metals of model compounds, thiamine derivatives, synthesized and characterized with spectroscopic techniques and X-ray crystal structure determinations. It is proposed that the enzymatic reaction is initiated with a V conformation of thiamine pyrophosphate, imposed by the enzymic environment. Thiamine pyrophosphate is linked with the proteinic substrate through its pyrophosphate oxygens. In the course of the reaction, the formation of the "active aldehyde" intermediate imposes the S conformation to thiamine, while a bivalent metal ion may be linked through the N1' site of the molecule, at this stage. Finally, the immobilization of thiamine and derivatives on silica has a dramatic effect on the decarboxylation of pyruvic acid, reducing the time of its conversion to acetaldehyde from 330 minutes for the homogeneous system to less than 5 minutes in the heterogenous system.

Practical tethering of vitamin B1 on a silica surface via its phosphate group and evaluation of its activity.

A convenient immobilization of thiamine pyrophosphate molecules on a silica surface through the phosphate group is developed, leading to a very active heterogenized biocatalyst for pyruvate decarboxylation.

Complexation of Cu(2+) by HETPP and the pentapeptide Asp-Asp-Asn-Lys-Ile: a structural model of the active site of thiamin-dependent enzymes in solution.

To obtain structural information on the active site of thiamin-dependent enzymes in solution, we have studied the interactions of Cu(2+) ions with 2-(alpha-hydroxyethyl)thiamin pyrophosphate (HETPP), the pentapeptide Asp-Asp-Asn-Lys-Ile surrounding the thiamin pyrophosphate moiety in the transketolase enzyme, and the tertiary Cu(2+)-pentapeptide-HETPP system in aqueous solutions at various pH values. In the binary Cu(2+)-pentapeptide system around physiological pH, the bonding sites were the terminal NH2 group, the aspartate beta-carboxylates, and a deprotonated peptide nitrogen, while, in the Cu(2+)-HETPP system at the same pH, the Cu(II) was coordinated to the pyrophosphate group and to the pyrimidine N(1') atom. It is found that, in the tertiary system at physiological pH, the peptide bone offers three coordination sites to the metal ion, and the coordination sphere is completed by two additional phosphate oxygens and the nitrogen N(1') of the thiamin coenzyme. The stability constants in the tertiary system are higher than those in the simpler Cu(2+)-HETPP and Cu(2+)-peptide systems. The present data show that the coenzyme adopts the so-called S conformation in solution. The importance of our findings concerning the N(1') coordination and the S conformation in the tertiary system is discussed in conjunction with the role of HETPP as an intermediate of thiamin catalysis.

On the mechanism of action of thiamin enzymes in the presence of bivalent metal ions.

Results on the interactions between the bivalent metal ions Zn2+, Cd2+, Hg2+, Co2+, Ni2+ and 'active aldehyde' thiamin derivatives are reviewed. The techniques used in these studies include spectroscopic methods, i.e., IR-Raman, UV-Vis, multidimensional and multinuclear NMR in solution and in solid state, and X-ray crystal structure determinations. More recently, potentiometric studies on thiamin pyrophosphate and 2-(alpha-hydroxyethyl)thiamin in combination with NMR and EPR techniques were also undertaken. All these studies lead to useful conclusions on the mechanism of action of thiamin enzymes in the presence of bivalent metal ions.

Design and synthesis of new biomimetic materials.

In this paper, it is reported that the histidine-silane derivative Boc-His(Boc)-CONH-(CH2)3Si(OEt)3 can be polymerized via the sol-gel method or can be grafted on a silica surface. The obtained organosilicas bear histidine molecules covalently bonded on the inorganic matrix. Their Cu(II) complexes have been evaluated as oxidation catalysts for the conversion of 3,5-di-tert-butylcatechol (DTBC) to 3,5-di-tert-butylquinone (DTBQ) in the presence of dioxygen.

Zinc(II) and cadmium(II) metal complexes of thiamine pyrophosphate and 2-(alpha-hydroxyethyl)thiamine pyrophosphate: models for activation of pyruvate decarboxylase.

Metal complexes of thiamine pyrophosphate (TPP) of the general formula [M2(TPPH)2Cl2]x4H2O (M = Zn2+, Cd2+) were isolated from methanolic solutions and characterized by elemental analysis, FT-IR, and multinuclear NMR spectroscopies. The data provide evidence for the bonding of the metals to the N(1') atom of the pyrimidine ring and to the pyrophosphate group. The stability constant measurements of TPP and 2-(alpha-hydroxyethyl)thiamine pyrophosphate (HETPP) metal complexes in aqueous solution imply the formation of dimeric complex species similar to the isolated solid products. They indicate also that HETPP forms more stable metal complexes than does TPP. To evaluate the coenzyme action of TPP and HETPP metal complexes, enzymic studies have been done using pyruvate decarboxylase apoenzyme. TPP metal complexes do not bind to the apoenzyme, unlike the Zn(II)-HETPP complex which can act as coenzyme. Considering these results, possible functional implications for thiamine involvement in catalysis are discussed.

Transition and group IIb metal complexes with "active aldehyde" derivatives of thiamine.

The Zn(2+), Cd(2+), Hg(2+), Co(2+) and Ni(2+) ions produce zwitterionic type complexes with the ligands (L), 2-(alpha-hydroxy-benzyl)thiamine=HBT and 2-(alpha-hydroxy-cyclohexyl-methyl)thiamine = HCMT, of the type MLCl(3). The ligands are in the S conformation, the metals are bound to N(1), of the pyrimidine moiety of thiamine and the complexes have a trigonally distorted tetrahedral structure, as the crystal structure of the complex Zn(HCMT)Cl(3) (orthorombic, a=14.4 b=14.1 c=17.4 beta=105.6(O) V=3392A(3) R=13.8%), the one and two dimensional (1)H nmr spectra of the Zn(2+), Cd(2+) and Hg(2+) complexes and the electronic spectra of the Co(2+) and Ni(2+) complexes show. A brief review of the previous techniques (structure of the Hg(HBT)Cl(3) complex, IR-Raman spectra, (13)C nmr in solution and solid state etc) used to characterize these complexes, is also given here and the proper conclusions drawn.