Kinetic Investigation on Tetrakis(4-Sulfonatophenyl)Porphyrin J-Aggregates Formation Catalyzed by Cationic Metallo-Porphyrins

Under mild acidic conditions, various metal derivatives of tetrakis(4-N-methylpyridinium)porphyrin (gold(III), AuT4; cobalt(III), CoT4; manganese(III), MnT4 and zinc(II), ZnT4) catalytically promote the supramolecular assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into J-aggregates. The aggregation kinetics have been treated according to a well-established model that involves the initial formation of a critical nucleus containing m porphyrin units, followed by autocatalytic growth, in which the rate evolves as a power of time. An analysis of the extinction time traces allows to obtain the rate constants for the auto-catalyzed pathway, kc, and the number of porphyrins involved in the initial seeding. The aggregation kinetics have been investigated at fixed H2TPPS4 concentration as a function of the added metal derivatives MT4. The derived rate constants, kc, obey a rate law that is first order in [MT4] and depend on the specific nature of the catalyst in the order AuT4 > CoT4 > MnT4 > ZnT4. Both resonance light scattering (RLS) intensity and extinction in the aggregated samples increase on increasing [MT4]. With the exception of AuT4, the final aggregated samples obtained at the highest catalyst concentration exhibit a negative Cotton effect in the J-band region, evidencing the occurrence of spontaneous symmetry breaking. The role of the nature of the metal derivative in terms of overall charge and presence of axial groups will be discussed.

Synthesis of M-Toluidine-Aniline Chirality Copolymers Induced by D-Camphorsulfonic Acid

The copolymerization reaction of m-toluidine and aniline has been induced by D-camphorsulfonic acid. When the total concentrations of the acid, the oxidant and the monomer were maintained, the ratio of two types of monomers was varied to realize the structure and property control of m-toluidine-aniline copolymers. FTIR, UV-Vis, CD and SEM were utilized to characterize the products. The results showed that the synthesized copolymers were of fiber and tube structure with the diameter of approximately 70 nm. The introduction of methyl moiety in the molecular chain of benzene weakened the conjugation and blue shifts were observed in both FTIR and UV-Vis spectra. Besides, CD spectra verified the chirality of the copolymers. Negative cotton effect could be discerned at 400 nm and the chirality inversed when [m-An]/[An]=1:5.

Interaction of thiamin diphosphate with phosphorylated and dephosphorylated mammalian pyruvate dehydrogenase complex

Kinetic and binding studies were carried out on substrate and cofactor interaction with the pyruvate dehydrogenase complex from bovine heart. Fluoropyruvate and pyruvamide, previously described as irreversible and allosteric inhibitors, respectively, are strong competitive inhibitors with respect to pyruvate. Binding of thiamin diphosphate was used to study differences between the active dephosphorylated and inactive phosphorylated enzyme states by spectroscopic methods. The change in both the intrinsic tryptophan fluorescence and the fluorescence of the 6-bromoacetyl-2-dimethylaminonaphthalene-labelled enzyme complex produced on addition of the cofactor showed similar binding behaviour for both enzyme forms, with slightly higher affinity for the phosphorylated form. Changes in the CD spectrum, especially the negative Cotton effect at 330 nm as a function of cofactor concentration, both in the absence and presence of pyruvate, also revealed no drastic differences between the two enzyme forms. Thus, inactivation of the enzyme activity of the pyruvate dehydrogenase complex is not caused by impeding the binding of substrate or cofactor.

Outer-sphere interaction of (S)-asparagine and (S)-glutamine with [Co(NH3)6]3+ ion and its possible role in ligand substitution

Optical activity of the achiral cation [Co(NH3)6]3+ is induced both by (S)-AsnONa and (S)-GlnONa, as shown by a negative Cotton effect in the 1A1g → 1T1g transition region. An outer-sphere interaction by three-point attachment of the amides can explain the fact that substitution reaction of [Co(NH3)6]3+ with the mentioned amides in an alkaline medium is unusually slow as compared with other amino acids.

The circular dichroism of a,b-unsaturated ketones. I. Circular dichroism in the singlet-singlet and singlet-triplet n «p* transitions of steroidal 4-en-3-ones

The circular dichroism from 22 steroidal 4-en-3-ones in cyclohexane solution has been recorded through the wavelength range 400-265 nm. It is shown that both the singlet-triplet and the singlet-singlet n → π* electronic transitions contribute. Through examination of evidence from c.d. and X-ray structure analysis, it is concluded that the conformation of the chromophore and its immediate environment remains constant under the conditions of measurement. In three of the 6β- substituted compounds the normal, highly structured, negative Cotton effect from the singlet-singlet n → π* transition is modified by positive c.d. with the same vibrational structuring. The origin of the positive contribution is discussed.

Cobalt(III) Complexes of a Stereospecific Ligand Derived from (S)-Proline

The quadridentate ligand, (2S,2'S)-1,1'-(ethane-1,2-diyl)bis(pyrrolidine-2-carboxylic acid) dihydrochloride (H2pren,2HCl), has been derived from (S)-proline. The preparations of the cobalt(III) complexes Na [Co(pren)(CO3)],3H2O, [CO(pren)(H2O)2] ClO4,- 2H2O and [Co(pren)(H2O)Cl],1�5H2O are described. All exist as cis-α geometrical isomers. 13C N.M.R. and absorption spectral measurements confirm the cis-α arrangement. The complex cis-α- [Co(pren)(H2O)Cl],1�5H2O rapidly aquates with retention of configuration. The compounds having actual or near C2 symmetry exhibit a strong negative c.d. band under the 1A1g → 1T1g cubic absorption band which is due to the 1A1 →1E tetragonal component, consistent with the Δ absolute configuration imposed by the (S) configuration of the asymmetric carbon atom in the (S)-proline moiety. The o.r.d. spectrum of cis-α-Na [Co(pren)CO3],3H2O in aqueous solution has a negative Cotton effect at low energy as expected for the Δ absolute configuration.

CHANGE IN THE STRUCTURE OF SHOPE PAPILLOMA VIRUS-INDUCED ARGINASE ASSOCIATED WITH MUTATION OF THE VIRUS

The change in the state of the virus-induced enzyme associated with a mutation in the virus provides additional evidence that the enzyme is synthesized from virus rather than rabbit genetic information. This change in structure results in differences in stability of polymerization, degree of optical rotary dispersion (ORD) specific rotation, change in elution characteristics from carboxymethyl cellulose, and a reduction in specific activity of the arginase. Liver arginase differs markedly in ORD characteristics from the virus-induced enzyme. In contrast to the virus-induced enzyme, it showed no negative Cotton effect at 233 nm until it was activated with manganese. Manganese had no influence on the ORD spectrum of virus-induced arginase. In addition, liver arginase is denatured by 4 M urea, while the virus-induced enzyme requires 10 M urea for denaturation.

The Effect of Ligand Binding on the Optical Rotatory Dispersion of Lactoperoxidase

The optical rotatory dispersion of lactoperoxidase and its cyanide and fluoride complexes was studied over the spectral region 210–500 nm, and that of the azide complex from 350–450 nm. Results of the measurements of the reduced mean rotation at 233 nm lead to the conclusion that there are no significant changes in gross protein conformation upon the binding of these ligands to lactoperoxidase. Lactoperoxidase was estimated to have 17% α-helical character at pH 7.0. Results of studies in the Soret region indicate that lactoperoxidase, unlike horseradish peroxidase, hemoglobin, and myoglobin, exhibits a negative Cotton effect as do its cyanide, azide, and fluoride complexes. The binding of these ligands apparently causes an alteration of the geometry of the heme group with respect to the protein moiety.

Diterpenoids. XXI. 8-Oxo-14-norlabdanes

Structure and optical rotation are correlated for some 8-oxo-14- norlabdanes which all have a negative rotation at the sodium D line and a negative Cotton effect. A correlation of communic acid with agathic acid is shown to be correct in spite of some erroneous rotations in the original publication.