Thư viện tri thức trực tuyến
Kho tài liệu với 50,000+ tài liệu học thuật
© 2023 Siêu thị PDF - Kho tài liệu học thuật hàng đầu Việt Nam
Radiation Chemistry of Biopolymers
Nội dung xem thử
Mô tả chi tiết
Radiation Chemistry
of Biopolymers
This page intentionally left blank
Radiation Chemistry
of Biopolymers
V.A. Sharpatyi
1/NSP/11
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2006 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20120706
International Standard Book Number-13: 978-9-04-741867-2 (eBook - PDF)
This book contains information obtained from authentic and highly regarded sources. Reasonable
efforts have been made to publish reliable data and information, but the author and publisher cannot
assume responsibility for the validity of all materials or the consequences of their use. The authors and
publishers have attempted to trace the copyright holders of all material reproduced in this publication
and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any
future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced,
transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or
hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222
Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are
used only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Radiation chemistry ofbiopolymers
V.A. Sharpatyi
Edited by Prof. E.G. Zaikov
2006
ll V.A. Sharpatyi
TABLE OF CONTENTS
Page
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
Chapter 1. Radiation chemistry. Basic concepts of radiation
chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1. Types of radiation .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2. The effect of ionizing radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 2
1.3. Key terms of radiation chemistry.............................. 5
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. . . . .. . . . . . . . .. . .. . .. . 13
Chapter 2. Primary radiation-chemical processes..................... 14
2.1. Ions and ionic reactions .... .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. . .. .. 14
2.2. Excited states and conversions of excited molecules . . . . . ..17
2.3. Free radicals and their conversions .. .. .. .. .. .. .. . .. . .. .. .. . .. . 23
References . . .. . . . .. . .. . . . .. . .. . .. . . . .. . . . . . . . . . . .. . . . . . .. . . . . . . . .. . 25
Chapter 3. Detection methods for radiolytic products ... . .. . . .. . . . . . . 26
3 .1. Mass-spectroscopy method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.2. Luminescence methods.......................................... 28
3.3. The method of electron paramagnetic (spin) resonance . . .. 32
References . . . . . .. . . . . . . . .. . . . .. . . . . . . . . . . . . . . . . .. . . . . . . . .. . . . .. . . . ... 39
Chapter 4. Radiation chemistry ofwater and water solutions...... 40
4.1. Primary products ofwater radiolysis ........................... 40
4.2. Radiolysis of frozen-up aqueous solutions .. .... .... .... ...... 44
References . .. . . . . . . . . . . . . . . . . . .. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . ... 49
Chapter 5. Basic regularities of solution radiolysis 50
5.1. Substances- the radical acceptors............................. 50
5.2. Concentration dependence of dissolved substance
dissociation yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
References . ... . . . . . . . . . . . . . . . . .. . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . ... 63
Chapter 6. The regularities of radiolysis of aqueous biopolymers
and their components ... . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . ...... 64
Radiation Chemistry of Biopolymers iii
6.1. Biopolymers as radical acceptors .. .. .. .. .. .. .. .. .. .. .. .. .. .... 64
6.2. Concentration dependence of dissolved substance
conversion yield. Radiosensibilization effects . . . . . . . . . . . .... 68
6.3. Radiolysis of frozen-up aqueous solutions ofbiopolymers 73
References . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. . . . .. . . . . . . . . . . . . . ... .. . .. . 83
Chapter 7o The problems of radiation chemistry of protein
molecules oo o oo o oo o. oo. oo.......................................... 85
7 .1. Structure and composition of protein molecules . . . . . . . . . . . . 87
7.2. Basic radiolytic effects in proteins .. .. .. ...... .. ... ... ........ 88
7.3. Oxygen effect at protein radiolysis ..... ....................... 107
7.4. Reactions ofwater radicals with side branches of
polypeptide chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 09
7.5. Radiolysis features of aqueous solutions of proteid.......... 115
7.6. Conclusion . . .. . . . . . . . . . . . . . .. . . .. . . . . . . . . . . . . . . . . .. . . . .. . . . ... 117
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Chapter 8. Radiation chemistry of polysaccharides • • . . . • . . . . .. . . • . • . 124
8.1. Structure of carbohydrates, polysaccharides................. 125
8.2. The role of •OH and electron in carbohydrate degradation 128
8.3. The origin of carbohydrate radicals ... . .. .. . .. . .. . .. . .. .. .. . .. 131
8.4. Primary macroradical transformations........................ 138
8.5. Oxygen effect..................................................... 153
8.6. Formation mechanisms for low-molecular products ........ 160
8.7. The role of adsorbed water in formation and conversions
of macroradicals; radio lysis of the structured starch-water
system............................................................. 191
8.8. Post-radiation effects in polysaccharides..................... 206
References . .. . . .. . .. . .. . .. . . . . . .. . . . . . . ... . . .. . .. . . .. . . .. . . .. . .. .. . . ... 213
Chapter 9. The radiolysis method for glycoproteids ................... 219
9.1. Structure and properties of glycoproteids. .............. ..... 219
9 .2. Radiolytic properties of glycoproteid components . .. . . . . . . . 222
9.3. Formation and conversions of radicals in glycoproteid
components . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
9.4. Radiolysis of glycoproteid and radical conversions . ... . .... 243
References.............................................................. 255
iv V .A. Sharpatyi
Chapter 10. Radiation chemistry of DNA aqueousolutions......... 257
10.1. DNA structure................................................... 257
1 0.2. Radiological effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . ... 258
10.3. Macroradical conversions..................................... 264
1 0.4. Oxygen effect . . .. . . . .. . . .. . . . . . .. . . .. .. .. . .. .. . . .. .. . .. . .. . .. .. . 271
+0.5. Abcmt molecular mechanisms of radiation mutagenic
action............................................................ 280
References . .. . . . . . ... . . . . . . . . . .. . . . . . . . . . . . . . . . . . .. . .. . . . . . . . . . . .. .. 284
Chapter 11. Chromatin DNP radiolysis .................................. 287
11.1. Composition and structure of DNP complex .. . . . . . . . . . . . . . 287
11.2. Basic radio lytic effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 289
11.3. On the origin ofDNP radicals .. .. .. .. ... .. .. .. .. .. .. .. .. .... 293
11.4. DNA fragment degradation .. .. .. .. .. . .. . .. . . .. .. .. .. .. .. .. . .. 298
11.5. On the mechanism of radical conversions.................. 303
11.6. DNA-protein crosslink formation .. .. .. .. .. .. .. . .. .. . .. . .. . .. 306
References .. . .. .. . .. .. . .. .. .. .. .. .. .. .. .. .. . .. .. .. .. .. . .. .. .. . .. .. .. . .. 311
Chapter 12 •. Radiolysis in-the cell. Primary stages·ofradiolysis ..... 313
12.1. Problems in describing radiation-chemical processes
proceeding in the cell .. .. .. .. .. . .. .. .. .. .. .. .. .. . .. .. .. .. .. .. .. 313
12.2. Low-temperature radio lysis of chlorella cells . . . . . . . . . . . .. 314
12.3. Electron spin resonance (ESR) of irradiated chlorella
cells............................................................... 318
12.4. Low-temperature radiolysis of animal tissues.............. 321
12.5. On the origin of free radicals in irradiated plant tissues ... 324
References . .. . . . . . . . . . . . . . . .. . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. . ... 329
Chapter 13. The effects of radioprotection and sensibilization of
radiation degradation of biopolymers in aqueous
solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 330
13.1. General principles of organics radioprotection in the
condensed phase ... .. .. .. .. .. .. ... .. .. .. .. .. .. .. . .. .. . .. .. .. ... 330
13.2. On radioprotection ofbiopolymers at primary physical
stages of radio lysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
13.3. The effects of radioprotection.and.radio ... sensibilization
.of biopolymer degradation at the -stages of radical
formation and conversion . .. . .. .. .. .. .. .. .. . .. .. .. .. .. .. . .. .. . 336
Radiation Chemistry of Biopolymers v
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 353
VI V.A. Sharpatyi
INTRODUCTION
In recent 20 - 25 years, the interest to investigations of the
transformation mechanisms of biological macromolecules induced by ionizing
radiation was continuously increased. This problem is touched upon in
monographs and reviews on radiation chemistry of various systems, including
biological systems, published in Russia and abroad. This is assignable, because
the practice of ionizing radiation energy use poses the problem of effective
control over radiation processes, for example, associated with processing and
modification of natural raw stock, agriculture waste utilization - in industry
and cattle breeding, and protection ofthe living cell and human organism from
radiation-in radiobiology and medicine.
The resolution of these problems significantly depends the
understanding of primary mechanisms of the radiation-chemical degradation of
biopolymers, which are the basic components of natural raw stock and a cell, at
their radiation in the composition of complex heterogeneous system as, for
example, raw stock and industrial and agricultural wastes, and the more so the
cell.
Among the broad literary data on radiation chemistry of various organic
compounds, there are scanty works devoted to the study of primary
mechanisms of biopolymer radiolysis. In this monograph, we classify the ideas
about primary stages of radiation-chemical transformation of the main
biopolymers, paying special attention to radio lysis of their aqueous solutions,
formation and conversion mechanisms of macroradicals, synthesized in acts of
solvent radical interaction with biopolymer molecules and in their natural
complexes. In this connection in initial Chapters (1 - 6) the ideas about water
radio lysis mechanism and the basic regularities of aqueous solution radio lysis
of biologically valuable substances are discussed. The subsequent Chapters (7
- 12) are devoted to radiolytic properties of biopolymers - protein,
polysaccharides, DNA, and their natural complexes - showing extending
charts of their radiolysis mechanisms. The conclusive Chapter 13 presents data
on the mechanisms and abilities of radioprotection and sensitizing of the
radiation degradation of biomacromolecules.
This monograph includes, first of all, the data of Soviet (Russian)
investigators, who have decisively contributed inthe development of this field
of knowledge (the schools headed by Academicians N.N. Semenov, N.M.
Emanuel, N.K. Kochetkov, and many others).
Radiation Chemistry of Biopolymers vii
The monograph is based on the course of lectures on radiation
chemistry of biopolymers, read by the author to students specializing in
physics, radiation biophysics and radiobiology.
Prof. G.E. Zaikov
viii V.A. Sharpatyi
Acknowledgement
The author is greatly thankful to Professor Gennady E. Zaikov for
reviewing and editing the manuscript and Alex Yu. Borissevitch for translation
and preparation of the book CRC.
Chapter 1. Radiation chemistry. Basic concepts of radiation
chemistry
1.1. TYPES OF RADIATION
In physics, the term "irradiation" defines emission of electromagnetic
waves (the field theory) or photons (the corpuscular theory), as well as other
corpuscular emissions: ex.- and ~-particles, neutrons, protons and nuclei. The
class of electromagnetic radiation includes:
1) X-rays and "(-irradiation-electromagnetic emissions at the wavelength
between 1 o-Il and 1 o-7 em, which represent the short-wave region of
the spectrum;
2) charged particles having kinetic energy enough for ionization act as
they pass through the medium: electrons, protons, deuterons, a.-
particles, polyvalent ions, nuclear fission products of heavy elements.
Being electrically neutral particles, neutrons themselves passing
through the medium may not induce ionization acts. As they interact with
atoms of the medium, neutrons may produce the above-mentioned ionizing
particles or photons, and electromagnetic emissions. The type of neutron
interaction with the substance is defined by the energy of neutrons and the type
of nuclei. The specific energy of ionizing radiation is electron-Volt ( e V) equal
energy obtained by electron (charged 1.602x 1o-19 C) as it passes the potential
drop equal 1 Volt.
Sometimes, X-ray radiation is characterized by the wavelength. The
quantum energy expressed in electron-Volts i related to the wavelength (A., A)
by the following ratio:
E= 12,400.
A.
2 V.A. Sharpatyi
1.2. THE EFFECT OF IONIZING RADIATION
As ionizing radiation hits the substance, itionizes and excites atoms
and molecules in the substance. The ionization act (electron removal from
electron shell of an atom or molecule) is accompanied by occurrence of two
oppositely charged ions: positively charged ions (an atom or a molecule which
lost an electron) and negatively charged ion (an atom or a molecule obtaining
electron).
Excited states of atoms of molecules are formed under the impact of
ionizing radiation on them, which induces electron transition from basic to
excited orbital. At the reverse transition from excited to basic orbital, the
energy is emitted as photons of visible, ultraviolet light or X-rays.
Charged particle interaction with the matter
As passing through the matter, charged particles lose energy due to
various processes. For heavy particles, the energy losses are generally caused
by elastic occlusions with electrons of atoms from the medium and, the more
so, by losses for irradiation and scattering. The energy scattering rate depends
on the charged particle origin. For heavy charged particles, the average energy
loss per specific path or the so-called stopping power of the matter (Erg/em) is
expressed by the Bethe formula:
where Ze is the charge of moving particle, electrostatic units; e is the electron
charge; m is the rest mass of electron, g; vis the particle speed, cm/s; NA is the
Avogadro number; p is the medium density; A and Z are atomic weight and the
number of atom; f3 = v, where cis the light speed; I is the average potential of
c
the medium atom excitation; o is a correction factor for polarization of the
matter atoms in electrical field of moving particle; E is the kinetic energy of
electron.