Modification of mesoporous TiO2 electrodes with cross-linkable B12 derivatives

The modification of mesoporous TiO2 film electrodes with vitamin B12 derivatives (e.g., 1, 2, or 3) yields electrodes with interesting sensing and electrocatalytic properties. So far, only coordinative bonding between the B12 derivatives and the metal oxide surface was used, and B12 was lost under conditions of extended electrocatalysis [1. Schulthess, P.; Ammann, D.; Simon, W.; Caderas, C.; Stepanek, R.; Krautler, B. Helv. Chim. Acta 1984, 67 (4), 1026-1032. 2. Mayor, M.; Scheffold, R.; Walder, L. Helv. Chim. Acta 1997, 80 (4), 1183-1189. 3. Stepanek, R. Ph.D.; ETH: Zürich, 1987]. (1-3) We report here on a procedure that yields highly improved stabilities of the electrocatalysts toward reductive expulsion from the mesopores. It is based on cross-linking the B12 derivatives (4 or 5) equipped with multiple reaction sites in the TiO2 mesopores. The cross-linkers are multiple functionalized, one of them assisting the electron transfer from TiO2 to the Co centers via redox shuttling. The modified electrodes show high electrocatalytic reactivity toward organic halides and highly improved stability.     

Hydrophobic vitamin B12. Part 19: electroorganic reaction of DDT mediated by hydrophobic vitamin B12

The controlled-potential electrolysis of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) was carried out at -1.4 V vs. Ag-AgCl in the presence of a hydrophobic vitamin B12, heptamethyl cobyrinate perchlorate. DDT was dechlorinated to form 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene (DDE), 1-chloro-2,2-bis(4-chlorophenyl)ethylene (DDMU) and 1,1,4,4-tetrakis(4-chlorophenyl)-2,3-dichloro-2-butene (TTDB)(E/Z), and quantitative recovery of the catalyst after the electrolysis was confirmed by electronic spectroscopy. A photo-sensitive intermediate having a cobalt-carbon bond formed during the electrolysis was characterized by electronic spectroscopy. A mechanism for the formation of various dechlorinated products was investigated by using deuterium solvents and various spectroscopic measurements such as UV-VIS and the EPR spin-trapping technique.     

多壁碳纳米管修饰金电极测定维生素B12

抗贫血药物维生素B12(VB12)俗称(氰)钴胺素,维生素B12是DNA合成的必需物质,若体内缺乏它,就会引起巨幼细胞贫血,高同型半胱氨酸血症和神经系统损害。因此,检测维生素B12可为血液系统和神经系统一些疾病的诊治提供依据[1],建立快捷简便的检测方法,在药物分析和医学检验中有应用价值。测定VB12的方法有高效液相色谱法[2]、荧光法[3]、毛细管电泳法[4]、伏安法[5]等。作者研究了VB12在碳纳米管修饰金电极上的电化学行为,并用以测定了VB12样品的含量,结果令人满意。1实验部分1.1仪器与试剂CHI618B电化学工作站(上海辰华仪器公司);KQ?400…     

Cyanide-bridged vitamin B12-cisplatin conjugates

cis-[PtCl(OH2)(NH3)2]+, the monoactivated form of cisplatin, reacts with the cyano ligand of cobalt in vitamin B12 (cyanocobalamin) to form a Co-C[triple chemical bond]N-Pt conjugate (1). Compound 1 is prepared in good yield directly in aqueous solution. The remaining chloride ligand of Pt(II) is labile. It hydrolyzes slowly in aqueous solution and can be exchanged by stronger coordinating ligands, such as 9-methylguanine or 2'-deoxyguanosine, to yield vitamin B12-nucleobase conjugates. X-ray structures of the vitamin B12-cisplatin conjugate 1 as well as of the product with coordinated 9-methylguanine (2) are presented. The coordination geometry at Pt(II) is almost perfectly square-planar. The structure of the cobalamin compound remains essentially unchanged when compared with the original B(12) structure. The guanine moiety of compound 2 binds in a 45 degrees angle to the cisplatin molecule and interacts with neighboring molecules by means of pi stacking and hydrogen bonds.     

Radiometric microbiological estimation of vitamin B12

Estimation of vitamin B₁₂ in blood is very important to determine in decifiency and diagnosis of anemic patients. Vitamin B₁₂ in blood can be estimated by spectrochemical, enzymatic, radioisotopic and microbiological methods. In the present study vitamin B₁₂ was determined in 48 normal subjects of Rawalpindi/Islamabad by radiometric microbiological assay (RMA) technique using a very rapid, sensitive and automated instrument Bactec 460. In this procedure¹⁴C-glucose media and microorganismsLactobacillus leichmannii were used. The sensitivity of the method for vitamin B₁₂ is 1 pg/ml and the vitamin B₁₂ found in normal subjects was in the range of 105–535 pg/ml with a median value of 246±6 pg/ml.     

A cyclodecapeptide ligand to vitamin B12

Libraries of cyclic decapeptides were screened with vitamin B(12) derivatives to give cyclic peptide ligands incorporating histidine and cysteine as coordinating residues and negatively charged amino acids. Two hits, cyclo-(HisAspGluProGlyIleAlaThrProdGln) and cyclo-(ValAspGluProGlyGluAspCysProdGln) were resynthesized in good yields for solution experiments. The peptides bind aquocobalamin with coordination of His or Cys to the cobalt with high affinities (K(a) approximately 10(5) M(-1)). Additional interactions between the peptide side chains and the vitamin B(12) corrin moiety were determined by studying the (1)H NMR solution structure. The cyclopeptide-cobalamin complex with the histidine residue showed enhanced stability towards cyanide exchange, demonstrating the shielding effect of the ligand on the metal center.     

Determination of vitamin B12 via pH-dependent quenching of the fluorescence of nitrogen doped carbon quantum dots

Microchimica Acta - Highly stable, hydrophilic carbon quantum dots (CQDs) with a fluorescence quantum yield of 43% were prepared by dehydration/condensation and aromatization/carbonization of a...     

A solid-phase enzyme-linked assay for vitamin B12

A new solid-phase enzyme-linked competitive binding assay for vitamin B₁₂ (cyanocobalamin) is described. The assay is based on the competition between analyte B₁₂ molecules and a glucose-6-phosphate dehydrogenase-vitamin B₁₂ conjugate for a limited number of R-protein binding sites immobilized on sepharose particles. After appropriate incubation and washing steps, the enzyme activity bound to the solid-phase is inversely related to the concentration of B₁₂ in the sample. Under optimized conditions, the method can detect B₁₂ in the range of 3×10^–10–1×10^–8 M (using 100l sample) with high selectivity over other biological molecules.     

Determination of vitamin B12 in multivitamin tablets by multimode high-performance liquid chromatography

Quantitative determination of vitamin B₁₂ in B-complex tablets was performed by using multimode high-performance liquid chromatography. The multivitamin tablets (B₁, B₆ and B₁₂) were sonicated for 30 min in methanol–water (50:50, v/v) and diluted to appropriated volume with the same solvent. The resulting solution was filtered and the filtrate was analysed on a phenylpropanolamine bonded silica column (15 cm×4.6 mm I.D., 5 μm). The optimized mobile phase was 30 mM phosphate buffer (pH 3.00) containing 6% (v/v) acetonitrile at a flow-rate of 1 ml min⁻¹ and the detection was measured at 361 nm. The calibration graph prepared using standards was linear from 0.05 to 0.25 μg. The determination limit was 25 ng, the relative standard deviation was 0.47% and recovery from tablet solution was 100%. An analysis was completed in 5 min. The new method is simple, rapid and precise.     

Mild olefin formation via bio-inspired vitamin B12 photocatalysis

Dehydrohalogenation, or elimination of hydrogen-halide equivalents, remains one of the simplest methods for the installation of the biologically-important olefin functionality. However, this transformation often requires harsh, strongly-basic conditions, rare noble metals, or both, limiting its applicability in the synthesis of complex molecules. Nature has pursued a complementary approach in the novel vitamin B₁₂-dependent photoreceptor CarH, where photolysis of a cobalt–carbon bond leads to selective olefin formation under mild, physiologically-relevant conditions. Herein we report a light-driven B₁₂-based catalytic system that leverages this reactivity to convert alkyl electrophiles to olefins under incredibly mild conditions using only earth abundant elements. Further, this process exhibits a high level of regioselectivity, producing terminal olefins in moderate to excellent yield and exceptional selectivity. Finally, we are able to access a hitherto-unknown transformation, remote elimination, using two cobalt catalysts in tandem to produce subterminal olefins with excellent regioselectivity. Together, we show vitamin B₁₂ to be a powerful platform for developing mild olefin-forming reactions.

Terminal or subterminal olefins can be selectively formed from alkyl electrophiles via bio-inspired vitamin B₁₂ photocatalysis.     

Quantum-chemical simulation of the active center of vitamin B12

The electronic structure of porphin and corrin complexes of cobalt differing with respect to the oxidation state of the central ion has been investigated by the MO-LCAO-SCF-CNDO method with the Kai-Nishimoto parameters for transition metals. On the basis of an analysis of the distribution of the electron density and the structure of the energy spectrum, it has been shown that the oxidation-reduction processes of the complexes are accompanied by restructuring of the energy spectrum, and the differences between the electronic structures of porphin and corrin complexes have been discussed. It has been established that cobalt(I) porphin has stronger nucleophilic properties than does cobalt(I) corrin. The electronic structure of hexacoordinate complexes in which an imidazole molecule and a molecule of L (L = H₂O, CH₃ ⁺, CN^–) are axially coordinated has been calculated. The mechanisms of the dissociation of cobalt alkyl complexes and the differences between the processes of the heterolytic dissociation of porphin and corrin complexes have been discussed. It has been shown that the elimination of a CH₃ ⁺ cation, which plays an important role in biomethylation reactions, is more favorable in corrin complexes.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 4, pp. 400–409. July–August, 1986.