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The shifts caused by nickel and hydrogen isotopic substitutions indicate that three bands at 342, 297 and 222 cm −1 are Ni-ligand stretching vibrations complicatedly coupled with Ni-O and Ni-N stretching vibrations. The conformational differences between gauche-anti and anti-gauche serinates in metallo-serinate complexes are characterized by the COO deformation vibrations. A normal coordinate analysis on the basis of a complete molecular conformation of Ni(L-ser) 2 •2H 2 O and an intermolecular force field reproduced well the observed frequencies and isotope shifts

The infrared spectra of bis (L-and DL-phenylalaninato) copper (II) and their N-deuterated analogues have been recorded in the region between 4000 and 200cm-1. The vibrational assignments of the Cu-ligand stretching vibrations have been made by means of the metal isotope technique, 63Cu and 65Cu substitution. Three bands of trans-bis (L-phenylalaninato) copper at 400, 380, and 339cm-1 shift appreciably on 63Cu-65Cu substitution. The blue isomer of bis (DL-phenylalaninato) copper also shows three copper isotope-sensitive bands at 380, 340, and 328cm-1, analogous to those of trans-bis (D-alaninato)-and (L-phenylalaninato) copper. However, the blue-violet isomer of the DL complex shows only two sensitive bands at 370 and 322cm-1, as in the case of cis-bis (D-alaninato) copper. Frequency shifts on N-deuteration suggest that one of the Cu-N stretching vibrations is at higher frequency than the Cu-O stretching vibrations for bis (L-phenylalaninato) copper, but this frequency order is reversed for the two isomers of bis (DL-phenylalaninato) copper, but this frequency order is reversed for the two isomers of bis (DL-phenylalaninato) copper.

Etude des spectres IR des composes cites et de leurs derives isotopiques pour le metal et les hydrogenes

A new indirect spectrophotometric method for the determination of phosphate ion by the use of solid ferric salt of tetraphenylporphine-trisulfonic acid (TPPSFe) was developed. The method is based on the measurement of the absorbance of TPPS liberated from TPPSFe at its Q band (procedure A) or its Soret band (procedure B). Phosphate ion ranging from 10 to 50μg and from 4 to 20μg could be determined based on the absorption coefficients of 8.2×103 at 512nm (procedure A) and 2.2×105 at 434nm (procedure B). The advantages of this method are its simple procedure and mild conditions. Procedure A was successfully applied to the determination of phosphate ion liberated from glucose-1-phosphate by acid phosphatase.

The infrared (IR) spectra of bisbenzenesulfonimide, bistoluenesulfonimide and benzenetoluenesulfonimide are reported together with the spectra of the corresponding N-deuterated samples. The isotopic shifts of the bands near 3180 cm-1 and 1400cm-1 of bisarylsulfonimide derivatives give the evidence of the assignment of these bands to the N-H group. The dichroic properties of these bands in bisbenzenesulfonimide suggest that the molecule has the C2 symmetry. On this ground, the symmetric and antisymmetric S-N-S stretching bands are clearly distinguished from each other in the polarized spectra. The IR spectrum of bispentadeuterobenzenesulfonimide has been measured. The effects of the N-deuteration and the ring deuteration on the characteristic frequencies are discussed. The IR spectra of the corresponding N-alkyl-bisarylsulfonimide derivatives are also discussed.

In an attempt to develop a practically useful mimesis of peroxidase, the peroxidase-like catalytic activity of anion exchange resins (Amberlite IRA 900) modified with manganese, cobalt, iron, copper and zinc complexes of some porphyrins was examined in terms of the accelerating effect on dye formation in the following reaction. The evaluation of the activity was carried out by comparison of the effect obtained by using the resins with that obtained by using peroxidase.4-aminoantipyrine +N, N-diethylaniline + 2H2O2peroxidase→quinoid dye + 4H2OAmberlite IRA 900 modified with manganese-tetrakis (sulfophenyl) porphine was found to be the best among the resins tested.

Etude de l'influence de l'isomerie cis-trans sur les vibrations de valence Cu-coordinat par spectrometrie IR du complexe [bis-(D-alaninato) Cu(II)] n a l'etat normal et deuterie, cis et trans, completee par une analyse en coordonnees normales

The infrared spectra of [bis-(L-asparaginato) copper (II)] n and its isotopic complexes containing copper and hydrogen isotopes have been measured in the region between 4000 and 200 cm-1. By referring to the isotope shifts on 63Cu and 65Cu substitution, two bands at 359 and 318 cm-1 have been assigned to metal-ligand stretching vibrations. The frequency shifts on N, N'-deuteration revealed that the Cu-N stretching frequency is larger than the Cu-O stretching frequency.

The infrared spectra of [bis (L-asparaginato) zinc (II)]n and its isotopic complexes containing 64Zn, 68Zn and deuterium have been measured in the region between 4000 and 200 cm-1. By referring to the isotope frequency shifts, three bands at 301, 265 and 244 cm have been assigned to Zn-ligand stretching vibrations caused from coupling among Zn-O and Zn-N stretching vibrations. The frequency range of the Zn-O stretching vibrations suggests that the Zn-O binding force of zinc-amino acids is probably larger than has been considered.

The infrared spectra of [Cu (glutamate)·(H2O)]n·(H2O)n, [Zn (glutamate)·(H2O)]n·(H2O)n and their isotopic complexes containing metal and hydrogen isotopes have been measured in the region between 4000 and 200 cm-1. The isotope shifts on 63Cu and 65Cu substitution have been observed for bands at 404, 352 and 279 cm-1 of the Cu complex. Bands at 300, 245 and 227 cm-1 of the Zn complex are apparently sensitive to 64Zn and 68Zn substitution. The frequency shifts on N, O-deuteration indicated that a Cu-OOC stretching vibration is localized for the Cu complex whereas Zn-OOC stretching vibrations couple with Zn-NH2 and/or Zn-OH2 stretching vibrations.

The infrared spectra of 25 kinds of benzenesulfinamide and p-toluenesulfinamide derivatives were measured. The S-N bands were observed between 928 cm-1 and 872 cm-1 as in benzenesulfonamide and methanesulfonamide derivatives. Moreover, the bands near 1090 cm-1 were found in all of the sulfinamide derivatives. The spectral change on deuteration were examined. In the compounds having -S-NH-and-S-NH2 form, the bands near 900 cm-1 region shifted to the lower wave number (about 110∼18 cm-1). But no such shift has been observed in the bands near 1090 cm-1 and in the range 1075∼1035 cm-1.