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PL ISSN 0137- 5083

POLISH      
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Volume 71 Number 10 October 1997
Pages 1375- 1509

 
   


Polish Chemical Society 

   

CONTENTS


Page

REVIEW ARTICLE
1375 Generation and Reactions of Aza-ortho-xylylenes
— Wojciechowski K.
ORGANIC CHEMISTRY
1401 The Cyclolinopeptide A Analogues with D-Phe, D-Tyr, and L- and D-Trp Residues
— Cebrat M., Lisowski M., Siemion I.Z. and Wieczorek Z.
1413 Azoles. Part 41. An Improved Methodology for the Vicarious Nucleophilic Substitution in Some Nitroazoles
— Bernard M.K.
1421 Synthesis of Heteroaromatic Thioglycosides. I. Derivatives of Nitroimidazole
— Przybysz B., Szeja W., Walczak K. and Suwinski J.
PHYSICAL CHEMISTRY
1425 Radiolysis of CFCl3 in Methylcyclohexane and Binary Matrices at Low Temperature
— Suwalski J.P.
1436 One-component Adsorbate Association in a Mobile Adsorption Phase on Energetically
Homogeneous Solid Adsorbent — Garbacz J.K.
1445 Acid Properties of Dealuminated Mordenites Studied by IR Spectroscopy. 1. Accessibility of Acid Sites and Their Interaction with Adsorbed Molecules
— Guisnet M., Ayrault P. and Datka J.
1455 Acid Properties of Dealuminated Mordenites Studied by IR Spectroscopy. 2. Concentration, Acid Strength and Heterogeneity of OH Groups
— Guisnet M., Ayrault P. and Datka J.
1462 Anharmonic Vibrational Model in Ab Initio Full-Numerical Harmonic Analysis of p-Benzoquinone
— Pietrzycki W.
1471 Kinetics and Mechanism of Oxidation of L-Alanine by Alkaline Permanganate
— Chougale R.B., Hiremath G.A. and Nandibewoor S.T.
1479 Photoinitiated Degradation of PMMA in the Presence of Accelerating Additives
— Kaminska A., Swiatek M. and Kaczmarek H.
1487 On the Air Influence on the Surface Area of Clean Annealed Gold Film and Pyrex Glass
— Stobinski L. and Zommer L.
COMMUNICATIONS
1494 Extraction of Barium Picrate into Nitrobenzene in the Presence of Valinomycin
— Makrlik E. and Vanura P.
1499 Triterpenoids. Part XII. Oxidation Products of Methyl 11-Oxo-18Halpha- oleanolate by Sodium Dichromate
— Zaprutko L.
1502 Synthesis and Magnetism of Binuclear Cu(II)-Ni(II) Complexes with N,N'-bis(N-hydroxyethyl- - ethyleneamine)oxamido as Bridging Ligand
— Shi J.M., Liao D.Z., Cui J.Z., Jiang Z.H. and Wang G.L.
1506 A New Method of the Synthesis of Gly-Aaa Type Reduced Peptide Bond
— Wisniewski K., Joswig S., Falkiewicz B. and Kolodziejczyk A.


ABSTRACTS

1375-1400

Generation and Reactions of Aza-ortho-xylylenes

by K. Wojciechowski
Institute of Organic Chemistry Polish Academy of Sciences,
ul. Kasprzaka 44/52, PL 01-224 Warszawa 42, P.O.Box 58, Poland
e-mail: kris@ichf.edu.pl

(Received June 19th, 1997)

Methods of generation of aza-ortho-xylylenes (ortho-quinone methylene imines or 1-methylene- 6-imine-2,4-cyclohexadienes) and their reactions are described.

1401-1412

The Cyclolinopeptide A Analogues with D-Phe, D-Tyr, and L- and D-Trp Residues

by M. Cebrat1, M. Lisowski1, I.Z. Siemion1 and Z. Wieczorek2
1Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wroclaw, Poland
2Institute of Immunology and Experimental Therapy, Polish Academy of Sciences,
Weigla 12, 53-114 Wroclaw, Poland

(Received May 26th, 1997; revised manuscript July 10th, 1997)

A series of nine linear and nine cyclic analogues of cyclolinopeptide A (CLA), in which the Phe residues were substituted by the aromatic D-residues (D-Phe, D-Tyr, D-Trp) or by the L-Trp residue, was synthesized by SPPS method. The peptides were tested for their influence on humoral and cellular immune response in mice. Most of the analogues show some immunosuppressive activity similar to that of CLA. High biological activity was observed for the cyclic peptides modified in position 9, especially [D-Phe9]CLA. This corresponds well with the peptide CD spectrum, which shows that the backbone conformation of this analogue resembles most the conformation of CLA.

1413-1420

Azoles. Part 41 [1]. An Improved Methodology
for the Vicarious Nucleophilic Substitution
in Some Nitroazoles

by M.K. Bernard
Department of Organic Chemistry, University of Medical Sciences,
ul. Grunwaldzka 6, 60-780 Poznan, Poland

(Received May 23rd, 1997; revised manuscript July 11th, 1997)

Improved procedures, including either specific reaction conditions or the use of protecting groups, were described for the vicarious nucleophilic substitution of hydrogen in some unreactive or weakly reactive nitroazoles.

1421-1424

Synthesis of Heteroaromatic Thioglycosides. I.
Derivatives of Nitroimidazole

by B. Przybysz, W. Szeja, K. Walczak and J. Suwinski
Silesian Technical University, Department of Chemistry, 44-100 Gliwice, Poland

(Received May 12th, 1997; revised manuscript June 25th, 1987) Nitroimidazoyl 1-thioglycosides were obtained in good yields from per-O-acetyl 1-thiosugar and bromo- nitroimidazole derivatives.

1425-1435

Radiolysis of CFCl3 in Methylcyclohexane
and Binary Matrices at Low Temperature

by J.P. Suwalski
Institute of Radiation Chemistry, Technical University of Lodz,
93-590 Lodz, Wroblewskiego 15, Poland

(Received January 9th, 1997; revised manuscript May 19th, 1997)

Results of pulse and gamma-radiolysis of CFCl3 in methylcyclohexane and binary matrices methylcyclohexane/iso-pentane at 6-77 K are presented and discussed. The model of the radical cation scavenging at low temperature is proposed and discussed and the influence of the ionization energy of the matrix on the electron transfer reaction between radical cation and scavenger at low temperature is presented.

1436-1444

One-component Adsorbate Association
in a Mobile Adsorption Phase on Energetically
Homogeneous Solid Adsorbent

by J.K. Garbacz
Department of Physicochemistry of Surface, University of Technology and Agriculture,
85-326 Bydgoszcz, Poland and
Department of Physical Chemistry, L. Rydygier Medicine University,
85-094 Bydgoszcz, Poland

(Received May 21st, 1997)

The new description of adsorbate-adsorbate association on energetically homogeneous adsorbents surface has been presented. The suitable relations have been formulated for a mobile adsorption of a single gas. Adsorption experimental data have been described theoretically by the equations derived. The calculation results proved a good applicability of the idea proposed.

1445-1454

Acid Properties of Dealuminated Mordenites Studied by IR Spectroscopy. 1. Accessibility of Acid Sites and Their Interaction with Adsorbed Molecules

by M. Guisnet1, P. Ayrault1 and J. Datka2
1URA CNRS, 350, Universite de Poitiers, 40 avenue du Recteur Pineau, 86022 Poitiers, cedex France
2Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Cracow, Poland

(Received March 28th, 1997; revised manuscript May 28th, 1997)

The series of dealuminated H-Mordenites (Si/Al = 6.6-120) was studied. Dealumination created mesopores, the volume of which increased with the degree of dealumination. IR studies evidenced that in the non-dealuminated H-Mordenite, only HF hydroxyls in large channels (3610 cm-1) were accessible to benzene, and could protonate pyridine. In dealuminated mordenites some LF hydroxyls in narrow channels (3585 cm- 1) were accessible to benzene, their contribution increased with the degree of dealumination. Some other LF hydroxyls remained inaccessible to benzene, but all of them were able to protonate pyridine. Thus the protonation of pyridine by LF hydroxyls inaccessible to benzene most likely occurred by the migration of protons from narrow channels to pyridine molecules inside large channels. The experiments of coadsorption of pyridine and ammonia suggested that ammonium ions inside narrow channels were stabilized by interaction with the oxygens of the channel walls. Ammonium ions (dia. = 0.29 nm) fitted well the side pockets of the size (0.39-0.47 nm). Pyridine desorption suggested a higher acid strength of HF hydroxyls in large channels than of LF ones in narrow channels.

1455-1461

Acid Properties of Dealuminated Mordenites
Studied by IR Spectroscopy.
2. Concentration, Acid Strength and Heterogeneity
of OH Groups

by M. Guisnet1, P. Ayrault1 and J. Datka2
1URA CNRS, 350, Universite de Poitiers, 40 avenue du Recteur Pineau, 86022 Poitiers, cedex France
2Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Cracow, Poland

(Received March 28th, 1997; revised Manuscript May 28th, 1997)

The concentration of OH groups was determined with two probe molecules: ammonia and pyridine. With all the mordenites, the concentration determined with ammonia was close to calculated values (amount of framework Al minus amount of Na). Quantitative IR studies of pyridine sorption evidenced that in a non-dealuminated mordenite about a half of all the hydroxyls was situated inside large (HF), and a half inside narrow channels (LF). With dealuminated mordenites, the concentration of hydroxyls determined with pyridine and ammonia was close to calculated values. The comparison of the values of OH extinction coefficients both determined with ammonia and pyridine suggested that the acid strength of OH groups increased with the degree of dealumination. The experiments of ammonia desorption evidenced that OH groups in H-Mordenites were heterogeneous. The dealumination removed the less acidic hydroxyls and hydroxyls became more acidic and more homogeneous. In mordenite of Si/Al = 120 the OH groups were practically homogeneous.

1462-1470

Anharmonic Vibrational Model in Ab Initio
Full-Numerical Harmonic Analysis of p- Benzoquinone

by W. Pietrzycki
Department of Chemistry, University of Agriculture,
A. Mickiewicz Av. 21, 31-120 Krakow, Poland
E-mail: rrpietrz@cyf-kr.edu.pl

(Received May 6th, 1997; revised manuscript June 12th, 1997)

Optimized geometry of the p-benzoquinone molecule was found with Polak-Ribiere conjugate gradient self-consistent procedure using independently the STO-6G, 3-21G, 6-31G, 6-31G** and D95 bases. Harmonic vibrational analysis of the p-benzoquinone molecule is carried out. The mass-weight Cartesian displacements (qk) were taken as the internal coordinates. Field force constants, Fkl, were calculated by the numeric differentation of the analytically calculated first derivatives, dU/dqk. The {xi0} set of the anharmonic initial coefficients in the Morse potential theory of i-th normal vibration were correlated with the 1- Timin experimental data in the IR absorption spectra, as well with 1/Ti min and ln(1/Timin). The linear regression analysis of (nui - nuiexpl) = [1 - 2a(1/Timin] + b equation estimated a, b and q constants for every basis, yielding significant agreement between calculated anharmonic (nuianh) and experimental frequencies (nuiexpl).

1471-1478

Kinetics and Mechanism of Oxidation
of L-Alanine by Alkaline Permanganate

by R.B. Chougale, G.A. Hiremath and S.T. Nandibewoor
P.G. Department of Studies in Chemistry, Karnatak University, Dharwad 580 003, India

(Received January 29th, 1997; revised manuscript June 16th, 1997)

The kinetics of oxidation of L-Alanine by permanganate in aqueous alkaline medium at constant ionic strength of 1.0 mol dm-3 has been studied spectrophotometrically. The reaction is of first order in [permanganate ion] and of fractional order in both [L-Alanine] and [alkali]. Addition of products have no significant effect on the reaction rate. Increase in ionic strength and dielectric constant of the medium increases the rate. The oxidation process in alkaline medium has been shown to proceed via two paths: one involving the interaction of L-Alanine with permanganate ion in a slow step to yield products. The other path involves the interaction of alkali with permanganate ion to give manganate. The rate constants are in excellent agreement with observed rate constants. The activation parameters have been computed with respect to the slow step.

1479-1486

Photoinitiated Degradation of PMMA
in the Presence of Accelerating Additives

by A. Kaminska, M. Swiatek and H. Kaczmarek
Nicolaus Copernicus University, Faculty of Chemistry, Gagarina 7, 87-100 Torun, Poland

(Received March 24th, 1997; revised manuscript June 30th, 1997)

The influence of low molecular compounds as naphthalene, ß-carotene and methylene blue on the photooxidative degradation of poly(methyl methacrylate) has been investigated. The viscosimetry measurements, gel permeation chromatography, thermal analysis and infrared spectroscopy has been used in these studies. The results indicate that the additives accelerate and increase the efficiency of the photodestruction and the photooxidation procceses in PMMA. Moreover, a lower thermal stability of photodegradated PMMA in the presence of additives has been observed.

1487-1493

On the Air Influence on the Surface Area
of Clean Annealed Gold Film and Pyrex Glass

by L. Stobinski and L. Zommer
Institute of Physical Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warszawa, Poland
E-mail: LSTOB@ichf.edu.pl; E-mail: ZOM@ichf.edu.pl

(Received May 26th, 1997; revised manuscript July 4th, 1997)

The influence of air on the surface area of thin gold films deposited onto Pyrex glass under ultra-high vacuum (UHV) conditions and on Pyrex glass has been investigated. The samples' surface area was determined in situ by the BET (Brunauer-Emmett-Teller) adsorption isotherm method and ex situ by Atomic Force Microscopy (AFM) in air. The surface area of clean, annealed, continuous and non-continuous gold film, measured in situ under UHV conditions by the BET adsorption method, is several times greater than its geometric area, whereas calculated from their air AFM images is equal to their geometric area. The surface area of clean, annealed gold film, prepared under UHV conditions but then exposed to air and again determined by the BET isotherm method is several times smaller than that not exposed to air. The Pyrex glass surface area, calculated from its air AFM image and measured by the BET isotherm method is equal to its geometric area.

1494-1498

Extraction of Barium Picrate into Nitrobenzene
in the Presence of Valinomycin

by E. Makrlik1 and P. Vanura2
1Department of Chemistry, Charles University, Faculty of Education,
M.D. Rettigove 4, 116 39 Prague 1, Czech Republic
2Department of Analytical Chemistry, Prague Institute of Chemical Technology,
Technicka 5, 166 28 Prague 6, Czech Republic

(Received April 28th, 1997; revised manuscript June 19th, 1997)

1499-1501

Triterpenoids. Part XII. [1].
Oxidation Products of Methyl
11-Oxo-18Halpha-oleanolate by Sodium Dichromate

by L. Zaprutko
Department of Organic Chemistry, K. Marcinkowski University of Medical Sciences, Grunwaldzka 6, 60-780 Poznan, Poland

(Received March 17th, 1997; revised manuscript July 9th, 1997)

1502-1505

Synthesis and Magnetism of Binuclear Cu(II)-Ni(II) Complexes with N,N'-bis(N-hydroxyethyl-ethylene-
amine)oxamido as Bridging Ligand

by J.M. Shi, D.Z. Liao, J.Z. Cui, Z.H. Jiang and G.L. Wang
Department of Chemistry, Nankai University, Tianjin 300071, P. R. China

(Received March 27th, 1997; revised manuscript July 14th, 1997)

1506-1509

A New Method of the Synthesis
of Gly-Aaa Type Reduced Peptide Bond

by K. Wisniewski1, S. Joswig1, B. Falkiewicz1,2 and A. Kolodziejczyk1
1Faculty of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk, Poland
2Faculty of Biotechnology, University of Gdansk & Medical University of Gdansk,
Kladki 24, 80-822 Gdansk, Poland

(Received June 24th, 1997; revised manuscript July 23rd, 1997)


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© 1997 Polish Journal of Chemistry
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