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Carbohydrate Chemistry for Food Scientists
This page intentionally left blank
Carbohydrate Chemistry
for Food Scientists

Third Edition

James N. BeMiller
Whistler Center for Carbohydrate Research,
Department of Food Science,
Purdue University,
West Lafayette, Indiana
Woodhead Publishing is an imprint of Elsevier
The Officers’ Mess Business Centre, Royston Road, Duxford, CB22 4QH, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
The Boulevard, Langford Lane, Kidlington, OX5 1GB, United Kingdom

Copyright © 2019 AACCI. Published by Elsevier Inc. in cooperation with

AACC International. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, recording, or any information storage and
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Licensing Agency, can be found at our website: www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by
the Publisher (other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices,
or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described
herein. In using such information or methods they should be mindful of their own safety and
the safety of others, including parties for whom they have a professional responsibility.
To the fullest extent of the law, neither AACCI nor the Publisher, nor the authors,
contributors, or editors, assume any liability for any injury and/or damage to persons or
property as a matter of products liability, negligence or otherwise, or from any use or
operation of any methods, products, instructions, or ideas contained in the material herein.
Library of Congress Cataloging-in-Publication Data
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A catalogue record for this book is available from the British Library

ISBN: 978-0-12-812069-9

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Contents

Carbohydrate Chemistry Preface xi

1 Monosaccharides 1
Introduction 2
Structures and nomenclature 4
Isomerization 11
Ring forms 11
Glycosides 18
Other types of monosaccharides 20
Additional resources 22

2 Carbohydrate Reactions 25
Introduction 26
Oxidation of the aldehydic group and the anomeric hydroxyl
group of aldopyranoses and aldofuranoses 26
Reduction of carbonyl groups 32
Cyclitols 38
Oxidation of nonanomeric hydroxyl groups 39
Esters 42
Ethers 45
Cyclic acetals 46
Additional resources 47

3 Oligosaccharides 49
Introduction 51
Origins of oligosaccharides 54
Shorthand designations 55
Maltose 56
Lactose 57
Sucrose 62
Oligosaccharides related to sucrose 70
Fructooligosaccharides 71
Trehalose 71
Oligosaccharides related to starch 73
Oligosaccharides from other sources 73
Additional resources 73
vi Contents

4 Polysaccharides: Occurrence, Structures, and Chemistry 75

Chemical structures and names of polysaccharides 76
Names of polysaccharides 85
Determination of structures 85
Average molecular weights 88
Structural modifications 91
Additional resources 101

5 Polysaccharides: Properties 103

Introduction 105
Water sorption by polysaccharides 107
Glass transitions of polysaccharides 108
Polysaccharide solubility 109
Properties of polysaccharide solutions 114
Random coils 117
Propertyeuse relationships 120
Molecular associations of polysaccharides 121
Characteristics of polysaccharide solutions 123
Viscosity grades of hydrocolloids 131
Characteristics of polysaccharide gels 137
Hydrocolloids as stabilizers 146
Choosing a hydrocolloid or starch product as a thickening,
gelling, or stabilizing agent 147
Additional resources 156

6 Starches: Molecular and Granular Structures and Properties 159

Introduction 160
Starch granules 161
Starch gelatinization, pasting, pastes, and gels 171
Retrogradation and staling 182
Complexes 184
Starch digestion and resistant starch 186
Manufacture of starches 187
Additional resources 188

7 Starches: Conversions, Modifications, and Uses 191

Products of hydrolysis (products of conversion) 193
Modified food starches 203
Pregelatinized and cold-water swelling starch products 212
Encapsulation 219
Additional resources 220
Contents vii

8 Cellulose and Cellulose-Based Hydrocolloids 223

Introduction 224
Powdered celluloses 225
Microcrystalline celluloses 226
Modified cellulose products 231
Regenerated cellulose 239
Additional resources 240

9 Guar, Locust Bean, Tara, and Cassia Gums 241

Sources, natures, and structures of guar and locust bean gums 242
Properties of guar and locust bean gums 244
Uses of guar and locust bean gums 248
Tara gum 251
Cassia gum 251
Additional resources 252

10 Inulin and Konjac Glucomannan 253

Introduction 253
Inulin 254
Konjac glucomannan 257
Additional resources 259

11 Xanthan 261
Introduction 261
Structure 262
Properties 262
Uses 265
Additional resources 268

12 Gellans, Curdlan, Dextrans, Levans, and Pullulan 271

Introduction 271
Gellan 272
Curdlan 274
Dextrans and levans 276
Pullulan 277
Additional resources 277

13 Carrageenans 279
Sources and manufacture of carrageenans 279
Structures 281
Properties 282
Uses 287
Agar: structure and uses 290
Additional resources 291
viii Contents

14 Algins/Alginates 293
Sources and manufacture 293
Structures 294
Properties 296
Uses 298
Additional resources 301

15 Pectins 303
Introduction 304
Structures 305
Properties and uses 307
Additional resources 311

16 Gum Arabic and Other Exudate Gums 313

Introduction 313
Gum arabic 314
Gum karaya 320
Gum ghatti 320
Gum tragacanth 320
Additional resources 321

17 Carbohydrate Nutrition, Dietary Fiber, Bulking Agents, and Fat

Mimetics 323
Introduction 325
Carbohydrate nutrition 325
Dietary fiber 329
Dietary fiber as an ingredient 343
Bulking agents 344
Fat mimetics 345
Additional resources 346

18 Nonenzymic Browning and Formation of Acrylamide and Caramel 351

Introduction 352
Maillard browning 352
Acrylamide 363
Caramel formation 366
Additional reading 369

19 Carbohydrate and Noncarbohydrate Sweeteners 371

Introduction 372
Nutritive/carbohydrate sweeteners 373
Reduced-calorie carbohydrate sweeteners 383
Other carbohydrate reducedecalorie sweeteners 388
Contents ix

“Natural sweeteners” 389

High-potency sweeteners 390
Future 396
Additional resources 396

20 Summary of Carbohydrate Functionalities 401

Additional reading 405

Index 407
This page intentionally left blank
Carbohydrate Chemistry Preface

The third edition of this textbookda textbook that grew out of my own experiences of
teaching in the classroomdhas been extensively rewritten. My goals were to update it
with new material, to explain concepts more clearly, to make it more straightforward,
readable, and easier to understand, to correct the mistakes that had crept into the sec-
ond edition, and to remove some materials unrelated to food science. The basic struc-
ture of the material remains the same as described in the prefaces to the first two
editions, but the material has been brought up to date. The book remains a beginning
textbook for learning about carbohydrates as food ingredients, but it is intended to be
thorough at that level.
It covers the portion of the vast field of carbohydrate chemistry that is important to
food science and helpful to food scientists. The chemistry of food carbohydrates is pre-
sented in the context of ingredient manufacture and properties. Ingredient properties
and structureefunction relationships are presented in the context of uses, which
include (1) the organic chemistry involved in the preparation of carbohydrate sub-
stances for use as ingredients, (2) the organic chemistry that could occur during prep-
aration of a product at a food processing facility or final preparation of it prior to
consumption, (3) the organic and physical chemistry that could be involved during
product storage, (4) the physical chemistry of such attributes as flow properties that
may be important during processing or use or to texture, and (5) fundamentals of
the relationships of carbohydrates and human health.
The book begins with the simplest carbohydrates (the monosaccharides) and builds
to oligosaccharides and then to polysaccharides (the most abundant and widely used
carbohydrates) over the first five chapters. Following this basic foundation of food car-
bohydrate chemistry are chapters on individual polysaccharides or groups of closely
related polysaccharides, beginning with starch (the most abundantly used carbohydrate
in foods), followed by chapters on cellulose and hydrocolloids with similar backbone
structures (the galactomannans and xanthan), the ionic and other hydrocolloids, dietary
fiber and other health-related topics, and sweeteners. Each chapter on a hydrocolloid,
or in some cases, sections of chapters, begins with the sources and the basic structure.
It then progresses to the chemistry used to modify structures of native polysaccharides
to expand their usefulness by altering their physicochemical properties and concludes
with uses, tying applications to structures and properties. The goal is to develop an un-
derstanding of how structures determine physical properties, how physical properties
determine functionalities, and how functionalities determine uses, so that knowing the
relationships, one can select a carbohydrate that will best provide the required
xii Carbohydrate Chemistry Preface

functionality (by knowing what physical properties are needed to provide the function-
ality needed and the structure needed to produce those properties) without memorizing
the properties and uses of each individual carbohydrate.
Food carbohydrate chemistry is the focus, but discussion of the health aspects of
carbohydrates (from a chemical standpoint) has been enlarged. Presentation of the
Maillard browning reaction and related topics, viz., acrylamide formation and caramel
color and flavor production, were made into a separate chapter. The very large chapter
on starch has been divided into two chapters.
Once again, I included what I thought were the most important things in the chapter,
that is, what I thought students should know and be able to do after study of each chap-
ter. Lists of “Additional Resources” that will provide students with options for
exploring topics more deeply have been updated and expanded. Overall, those who
have studied this book should have a good understanding of the number and variety
of carbohydrate ingredients available to the product developer and their attributes.
This edition is dedicated to Professor Roy Whistler, who originated the project and
coauthored the first edition (1996) with me.

James N. BeMiller
Monosaccharides
1
Chapter Outline

Introduction 2
Structures and nomenclature 4
Isomerization 11
Ring forms 11
Glycosides 18
Other types of monosaccharides 20
Some functions of monosaccharides in foods 21
Additional resources 22

Key information and skills that can be obtained from study of this chapter will enable
you to:
1. Define and/or identify

chiral carbon atom furanose ring

monosaccharide anomeric carbon atom
saccharose group anomers
dextrose axial positions
aldose equatorial positions
acyclic glycoside
D sugar glycosidic bond
L sugar aglycon
ketose deoxy sugar
pyranose ring hygroscopic
Haworth projection humectant

2. Identify and/or describe monosaccharides as to the kind of carbonyl group and number of
carbon atoms (for example, aldotetrose, octulose, etc.).
3. Give Fischer and specific anomeric furanose and pyranose ring structures (Haworth projec-
tions) for the following: L-arabinose, D-xylose, D-galactose, D-glucose, D-mannose, D-fructose.
4. Make interconversions between names, acyclic structures, Haworth ring structures, and/or
conformational ring structures of the sugars listed in objective 3.
5. Describe the chemical properties of hemiacetals and acetals.

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2 Carbohydrate Chemistry for Food Scientists

6. Show the interrelationships of D-glucose, D-mannose, and D-fructose via isomerization.

7. Describe the conditions under which isomerization occurs.
8. When given the name of a glycoside of a sugar listed in objective 3 (for example, ethyl b-D-
galactopyranoside), give its chemical structure and vice versa.
9. Describe the two general conditions under which hydrolysis of glycosides occurs.
10. Describe the relationship of carbohydrates to humectancy and water activity.

Introduction
Carbohydrates are present in all living cells. Energy reaching Earth in the form of
sunlight is transformed by land and marine plants into sugars, which are used partly
near the point of synthesis (that is, in a green growing shoot) for construction of
various plant components and structures, and in part they are transported to other
locations of the plant where they are used to make other components. These plant
components supply food and energy to all other forms of life. Some of the initial
photosynthetic carbohydrate material is converted into other organic compounds,
such as proteins, fats, and lignin. Most of the remaining carbohydrate is converted
into polymers of sugars (called polysaccharides, which constitute more than 90%
of the dry matter of plants and at least three-fourths of the dry weight of all living
organisms). It is estimated that as much as 1012 tons of biomass are produced each
year by photosynthesis.
Other than water, carbohydrates are the most common components of foods and
the human diet (both as natural components and as added ingredients). Because milk
contains carbohydrates (lactose and other oligosaccharides), carbohydrates are pre-
sent in the very first food consumed by all mammals, including humans, and because
they are constituents of all plant tissues, they are also present in the diets of almost all
adult humans. They provide at least three-fourths of the caloric intake of humans on a
worldwide basis. Starch, lactose, and sucrose are digested by normal humans, and
they, along with D-glucose and D-fructose, are human energy sources. (Digestible
carbohydrates, D-glucose, and D-fructose [along with proteins] contain about four
calories per gram [dry weight], whereas fats and oils provide about nine calories
per gram.)
Carbohydrates in foods are important, not only as energy sources but also as ingre-
dients that impart texture and as dietary fiber that contributes to human health. Their
use as food ingredients is large in terms of both quantities consumed and the variety
of applications and products. Carbohydrate ingredients are abundant. They are inex-
pensive. They can be obtained from a variety of replenishable sources. They occur
in diverse structures and degrees of polymerization. They are available in a large num-
ber of molecular sizes and shapes and in a variety of chemical and physical properties.
They are amenable to both chemical and biochemical modifications (and in some cases
physical and/or genetic modifications), and both modifications are employed to
improve their properties and extend their use as food ingredients. They are nontoxic
and, therefore, safe.
Monosaccharides 3

Naturally occurring and modified carbohydrates are used as ingredients in a wide

variety of food products because of the wide range of functionalities they can impart.
Therefore, much of the chemistry of carbohydrates is physical chemistry related to
such properties as crispness, crystallization, emulsion and suspension stabilization,
flow behavior, gel characteristics, gel formation, glass formation, glass transitions,
humectancy, mouthfeel, water-holding capacity, and viscosity.1 And carbohydrates
are often used as ingredients because of the effects they have on other components
of a formulation (the primary one being water, but including components such as pro-
teins and other carbohydrates). Some (those that are categorized as dietary fiber or pre-
biotics) are added as ingredients for their health benefits. A few (and only a few) impart
a sweet taste.
Enjoy your journey through the world of food carbohydrates. During your study,
you will learn that only a few carbohydrates are sweet and used to impart sweetness;
rather, most are not sweet and are used as ingredients to provide appearance, body,
convenience, flavor, stability, texture, and other attributes (for example, color and fla-
vor) to food products.1 For example, you will learn that the primary reason for using
sugar in a cake recipe is not to make the cake sweet but to provide the desired texture.
You will also learn the science behind the provision of such functionalities. You will
learn how chemical, enzyme-catalyzed, genetic, physical, and structural1 modifica-
tions of naturally occurring carbohydrates are employed to improve the properties
of the natural substances and to make new ingredients. And you will learn that carbo-
hydrates not only occur in different structural types but also have different physiolog-
ical effects (for example, digestible and nondigestible, metabolizable and
nonmetabolizable, caloric, reduced caloric and noncaloric, and prebiotic and nonpre-
biotic), although that is not the main focus of this text on the chemistry of carbohy-
drates (Box 1.1).

Box 1.1 Some Uses of Carbohydrates

In addition to making up a high percentage of the human diet, carbohydrates pro-
vide us with clothing (cotton, rayons) and shelter material (wood). They are
important in the manufacture of diverse products such as (in alphabetical order)
adhesives, concrete, cosmetics, detergents, paints, paper, pharmaceutical prod-
ucts, printing inks and pastes, processed food products, and toothpastes, in oil
and gas production, in ore recovery, and in many more applications. Carbohy-
drates are involved in many biological structures, including plant and bacterial
cell wall structures, and in many processes, including fertilization, immunolog-
ical responses, recognitions related to infections, and energy storage.

1
Throughout this book, various lists of attributes, properties, applications, etc. are given in alphabetical
order, rather than in order of importance.
4 Carbohydrate Chemistry for Food Scientists

Carbohydrates can be, and are, classified in several different ways. In the minds of
food scientists, they are sometimes classified according to functionality (for example,
as bulking agents, emulsion stabilizers, gel formers, suspending agents, viscosifiers,
etc.). In this book, the traditional approach is taken, classifying them according to mo-
lecular size, beginning in this chapter with the smallest molecules.

Structures and nomenclature

Carbohydrate (a term derived from the German kohlenhydrate and the similar French
hydrate de carbone) expresses the fact that most simple carbohydrates have the general
elemental composition Cx(H2O)y (that is, they are molecules that contain carbon atoms
plus hydrogen and oxygen atoms in the same ratio as they occur in water). Their
composition is related to the fact that they are produced by photosynthesis from carbon
dioxide and water as indicated by the following unbalanced equation:

CO2 þ H2O / a sugar þ O2

However, the great majority of natural carbohydrate compounds found in living or-
ganisms do not have the simple empirical formula Cx(H2O)y. Rather most naturally
occurring carbohydrates are oligomers (oligosaccharides [Chapter 3]) or polymers
(polysaccharides [Chapter 4]) made by joining sugars with the simple empirical for-
mula or sugars with modified structures related to the simple empirical formula. While
loweremolecular weight carbohydrates for food use are often obtained by depolymer-
ization of natural polymers, this book begins with a presentation of the simple sugars
and builds from there to larger and more complex structures.
A characteristic of carbohydrates (which are also called saccharides) is that they
contain chiral carbon atoms. A chiral carbon atom is a carbon atom that can exist
in two different spatial arrangements (configurations). Chiral carbon atoms can be
recognized easily because they are carbon atoms that have each of their four tetrahedral
bonds connected to different atoms or groups of atoms. The two different arrangements
of the four groups in space (configurations) are what are called nonsuperimposable
mirror images (Fig. 1.1). In other words, one is the reflection of the other that one
would see in a mirror, with everything on the right in one configuration on the left
in the other and vice versa (Box 1.2).
Monosaccharides are carbohydrate molecules that cannot be broken down by hy-
drolysis2 into simpler (smaller) carbohydrate molecules. Hence, monosaccharides are
at times referred to as “simple sugars” or just :sugars," which infers that they are the
simplest (smallest) of the carbohydrates. (The term saccharide is derived from saccha-
rose, which is an old term for cane sugar. Now, it refers to any carbohydrate, especially
a monosaccharide; but as subsequent chapters on oligo- and polysaccharides indicate,
it can be applied to any size carbohydrate. Mono is derived from the Greek word for

2
Hydrolysis refers to cleavage of a chemical bond with concurrent addition of the elements of water
(H- and eOH) to the ends of the two new molecules formed by the cleavage.
Monosaccharides 5

A A

E C B B C E

D D

Mirror
Figure 1.1 Chiral carbon atom. (A), (B), (D), and (E) represent different atoms or functional
groups2 attached to carbon atom (C). Wedges indicate chemical bonds projecting outward
from the plane of the page; dashes indicate chemical bonds projecting into or below the plane
of the page.

Box 1.2 Mirror Images

Nonsuperimposable mirror images can be illustrated by pressing the palms of
your two hands together in front of you (fingers up). One is the reflection of
the other that you would see in a mirror with everything that is on the right in
one on the left in the other and vice versa, that is, your thumbs and each of
your four fingers oppose each other. Now if you orient your hands in the same
direction, for example, with the palms facing away from you, you will see that
the thumbs are on opposite sides and that your two hands are different, that is,
they are chiral and nonsuperimposable mirror images. You would soon find
this out if you tried to put a glove for the left hand on the right hand, for example.

one. In chemistry, it often means containing only one, so the term monosaccharide
means one saccharide or one sugar, indicating that it is a molecule composed of
only one sugar unit and not of two or more sugar units joined together). Monosaccha-
rides are the monomeric units of oligosaccharides (Chapter 3) and polysaccharides
(Chapter 4), both of which contain more than one saccharide (sugar) unit and can
be hydrolyzed to release their constituent monosaccharides. The common monosac-
charides used as building blocks for oligo- and polysaccharides found in foods contain
a group termed as the saccharose group.
R

C O

C(H)(OH)

R= H or CH2OH

The saccharose group, where R is a hydrogen atom (-H) (Aldoses) or a eCH2OH group
(Ketoses)
6 Carbohydrate Chemistry for Food Scientists

Discussion of specific carbohydrate structures begins with D-glucose, the most

common, most widely distributed, and most abundant carbohydrate (if all its com-
bined forms are considered). D-Glucose (known commercially as dextrose) is a
monosaccharide. D-Glucose is both a polyalcohol (polyhydroxy compound) and an
aldehyde. It and all sugars containing an aldehydic group are classified as aldoses
(Table 1.1). The prefix ald- indicates that they are aldehydes; the suffix -ose usually
(but not always as you will find out) signifies a nonpolymeric carbohydrate (that is, a
monosaccharide). D-Glucose contains six carbon atoms, making it a hexose (Ta-
ble 1.1); more specifically, it is an aldohexose. When the structure of D-glucose is
written in a vertical straight-chain fashion (termed an acyclic or open-chain structure)
with the aldehydic group (position 1 [C1]) at the top and the carbon atom with the
primary hydroxyl group attached to it at the bottom (at position 6 [that is, on C6]),
it can be seen that all secondary hydroxyl groups are on carbon atoms C2, C3, C4,
and C5. To make the determination/assignment of which side of the carbon chain
the hydroxyl groups are on, a convention for orientation of the carbon chain is
used. In this convention, the carbon chain is oriented so that each vertical (carbon-
to-carbon) bond projects into the plane of the page and each horizontal bond projects
outward from the plane of the page as in Fig. 1.1 (although in solution there is rota-
tion about the vertical bonds that allows a hydroxyl group to be in any position with
respect to the one above [or below] it, so that the molecules can actually assume a
large number of different conformations [shapes]). Each of the four carbon atoms
that have a secondary hydroxyl group attached to it (C2, C3, C4, C5) are chiral car-
bon atoms because each has four different substituents attached to it. Each chiral cen-
ter has a mirror image (Fig. 1.1), and mirror image chiral carbon atoms are not
superimposable on each other, just as a person’s two hands are mirror images and
are not superimposable.

Table 1.1 Classification of monosaccharides

Kind of carbonyl group
Number of
carbon atoms Aldehyde Ketone
3 triose triulose
4 tetrose tetrulose
5 pentose pentulose
6 hexose hexulose
7 heptose heptulose
8 octose octulose
9 nonose nonulose
Monosaccharides 7

H C O HC O C1

H C OH HCOH C2

HO C H HOCH C3

H C OH HCOH C4

H C OH HCOH C5

H C OH CH2OH C6

H
D-Glucose

Because each chiral carbon atom has a mirror image, there are 2n (where n is the
number of chiral carbon atoms) possible arrangements of these atoms. Thus, in a
six-carbon aldose (of which D-glucose is one), in which there are four chiral carbon
atoms, there are 24 or 16 different arrangements of the carbon atoms containing four
secondary hydroxyl groups (theoretically allowing formation of 16 different six-
carbon sugars with an aldehydic group). Eight of these sugars belong to what is
known as the D series; eight are their mirror images and belong to the L series. (All 16
of these aldohexoses have the empirical formula C6H12O6.) All sugars that have the
hydroxyl group on the highest-numbered chiral carbon atom (C5 in the case of D-
glucose) positioned on the right-hand side (using this projection and convention for the
chain conformation) are termed D sugars, and all with the highest-numbered chiral
atom having its hydroxyl group on the left are classified as L sugars. (Note that L-
glucose is the complete molecular mirror image of D-glucose and not the substance
with the opposite configuration of just C5. If only the configuration of C5 is changed,
the product is L-idose [see below].) The structure of D-glucose is shown in its open-
chain (acyclic) form (called the Fischer projection) with the carbon atoms numbered
in the conventional manner. As is customary, the horizontal lines indicating the co-
valent chemical bonds to the hydrogen atoms and hydroxyl groups are omitted in the
structure on the right. Because the lowermost carbon atom (C6 in the case of D-
glucose) is not chiral, the relative positions of the atoms and groups attached to it need
not be designated, and it is written as eCH2OH. The great majority of carbohydrates
found in foods are composed mostly of aldohexoses. Shown below is the aldopentose
arabinose in both the D and L forms, both of which occur in nature. Glucose is found
only in the form of D-glucose.

H C O
HC O C1
HO C H
HCOH C2
H C OH
HOCH C3
H C OH
HOCH C4
H C OH
CH2OH C5
H

D-Arabinose L-Arabinose
Mirror
8 Carbohydrate Chemistry for Food Scientists

An organic chemist say that D-glucose and all other carbohydrate molecules as
highly functionalized because there is a functional group3 on each carbon atom. The
complete functionalization of the backbone carbon atom structure with hydroxyl
groups, a carbonyl oxygen atom (in the case of the simple sugars), and a high percent-
age of chiral carbon atoms are distinguishing features of carbohydrates.
D-Glucose, as its O6 phosphate ester (D-glucose 6-phosphate), is the first sugar of
4

photosynthesis. D-Glucose 6-phosphate (Chapter 2) is present in only small amounts

because it is rapidly converted into sucrose (Chapter 3) for transport to various parts
of the plant where it is used for synthesis of other substances. Because D-glucose is
the monomeric building unit of cellulose (Chapter 8), it can be considered to be the
most abundantly available organic compound on Earth (if its combined forms are
considered). D-Glucose 6-phosphate is also used as an energy source in the plant’s
metabolism.
There are two aldoses containing three carbon atoms: D-glyceraldehyde and L-glyc-
eraldehyde (D- and L-glycerose according to formal carbohydrate nomenclature,
although these names are seldom used). Each possesses only one chiral carbon
atom. Aldoses with four carbon atoms (the tetroses) have two chiral carbon atoms. Al-
doses with five carbon atoms (the pentoses) have three chiral carbon atoms and
comprise the second most common group of aldoses. Extending the series above six
carbon atoms gives heptoses, octoses, and nonoses (seven, eight, and nine carbon
atoms, respectively). Nine carbon atoms is the size limit of naturally occurring sugars.
Only pentoses and hexoses are found in the common carbohydrates of food products.
Development of the eight D-hexoses from D-glyceraldehyde is shown below using the
Rosanoff shorthand projection (Fig. 1.2). In the Rosanoff projection, a circle represents
the aldehydic group; horizontal lines indicate the location of each hydroxyl group on
its chiral carbon atom, and the bottom of the vertical lines indicates the terminal, non-
chiral hydroxymethyl (-CH2OH) group (a primary hydroxyl group). Sugars whose
names are in italics in Fig. 1.2 are commonly found in plants, almost exclusively in

HC O

HCOH

HOCH

CH2OH

Figure 1.2 Relation of the Fischer projection to the Romanoff shorthand projection for
L-threose.

3
A functional group is an atom (other than a hydrogen atom) or a collection of chemically bonded atoms
with a characteristic set of properties.
4
O6 indicates that the phosphate group of the ester is attached to the oxygen atom on carbon atom number 6
(C6).
Monosaccharides 9

combined forms. Thus, they are present in our diets in combined forms. Only a small
amount of D-glucose in the free monosaccharide form (section on Glycosides in this
chapter) is present in natural foods (except for honey), and it is generally the only
free aldose present.

D-Triose

D-Glycerose

D-Tetroses

D-Erythrose D-Threose

D-Pentoses

D-Ribose D-Arabinose D-Xylose D-Lyxose

D-Hexoses

D-Allose D-Altrose D-Glucose D-Mannose D-Gulose D-Idose D-Galactose D-Talose

D-Glyceraldehyde occurs naturally as its O3 phosphate ester. Most other natural

sugars, including the ubiquitous D-glucose, have the same configuration (D) of their
highest-numbered chiral carbon atom (C5 in the case of a hexose). L-Sugars are
much less numerous and abundant in nature than the D forms. The principal L-sugar
found in foods is L-arabinose, which occurs in a combined form in some
polysaccharides.
To make a molecular model of a sugar, two simple rules need to be followed. The first
is to consider only one carbon atom at a time in copying a projected structure such as a
Fischer projection or a Rosanoff structure. The second is to keep in mind that all horizon-
tal bonds in the projected structure are envisioned as protruding toward you from the car-
bon atom, whereas vertical bonds are envisioned as protruding away from you.
So far aldoses (in which the carbonyl unit of the saccharose group is that of an alde-
hyde) have been discussed. In another type of monosaccharide, the carbonyl unit in the
saccharose group is a ketone. These sugars are known as ketoses, with the prefix ket-
identifying them as having a ketone group. D-Fructose is the prime example of this
sugar group. D-Fructose is one of the two monosaccharide units of the disaccharide su-
crose (Chapter 3) (the other being D-glucose) and makes up ca. 55% of a common com-
mercial high-fructose syrup (Chapter 7) used in soft drinks. About 40% of the
carbohydrates of honey are D-fructose.
10 Carbohydrate Chemistry for Food Scientists

CH2OH C1

C O C2

HOCH C3

HCOH C4

HCOH C5

CH2OH C6

D-Fructose is the principal commercial ketose and the only one of importance in foods.
(In the past, D-fructose was called both levulose and fruit sugar, but these designations are
rarely used today.) D-Fructose has only three chiral carbon atoms (C3, C4, and C5). Thus,
there are only 23 or 8 ketohexoses. The various ketotetroses, -pentoses, and -hexoses are
related to nonchiral dihydroxyacetone. The suffix designating a ketose in systematic
carbohydrate nomenclature is eulose (Table 1.1). In systematic nomenclature, D-fruc-
tose is D-arabino-hexulose because its three chiral carbon atoms have the same config-
uration as those in D-arabinose. The Rosanoff projection of a ketopentose (pentulose)
with the D-threo configuration (that is the configuration of the two chiral carbon atoms
in D-threose) is given in Fig. 1.3 as another demonstration of the nomenclature principle.
CH2OH

C O Triulose

CH2OH

Dihydroxyacetone

O D-Erythrulose Tetruloses
(D-glycero-Tetrulose)

O D-Ribulose O D-Xylulose
Pentuloses
(D-erythro-Pentulose) (D-threo-Pentulose)

O O O O
Hexuloses

D-Psicose D-Fructose D-Sorbose D-Tagatose

(D-ribo-Hexulose) (D-arabino-Hexulose) (D-xylo-Hexulose) (D-lyxo-Hexulose)
Monosaccharides 11

CH2OH

C O
O
HOCH

HCOH

CH2OH

Figure 1.3 Rosanoff projection of a ketopentose (D-threo-pentulose, “D-xylulose”) showing the

configurations of the two chiral carbon atoms.

Isomerization
Simple aldoses and ketoses containing the same number of carbon atoms are isomers
of each other (that is, a hexose and a hexulose both have the empirical formula
C6H12O6). Isomerization5 of monosaccharides involves both the carbonyl group and
the adjacent hydroxyl group. By isomerization, an aldose is converted into another
aldose (with the opposite configuration of C2) and the corresponding ketose, and a
ketose is converted into the corresponding two aldoses (Fig. 1.4). Therefore, by isom-
erization, D-glucose, D-mannose, and D-fructose can be interconverted (Fig. 1.5). Isom-
erization can be catalyzed by either a base or an enzyme (Chapter 7).
D-Tagatose, which is the ketose formed by isomerization of D-galactose in the same
way as D-fructose is formed by isomerization of D-glucose (or D-mannose), is a
commercially available, reduced-calorie sweetener (Chapter 19). Another commer-
cially available, reduced-calorie ketose sweetener is called allulose by the company
that makes it, although it is better known as D-psicose (see the scheme showing the
four D hexuloses). Brown sugar, caramel, figs, maple syrup, molasses, and raisins
contain small amounts of D-psicose.

Ring forms
Carbonyl groups of aldehydes are reactive and readily undergo nucleophilic attack by
the unshared electrons of the oxygen atom of a hydroxyl group to produce a hemiac-
etal. By similar reactions, a carbonyl group of a ketone also produces a hemiacetal
(sometimes specifically designated a hemiketal).
RO H R OR
–HOH
H C O H C OH + H OR H C OR

R′ R′ R′

5
Isomerization is the process of converting one isomeric molecule into another.
12 Carbohydrate Chemistry for Food Scientists

H H O H

C O –H+ C O HC +H+ C O
H)÷ COH +H+ COH C OH –H+ HOCH

R R R R

+
+H+ –H

COH
COH

R
(cis or trans)

+
–H+ +H

H H H

C OH COH +H+ HCOH

R C C O –H+ C O
O R R
Figure 1.4 Monosaccharide isomerization.

HC O HOCH CH2OH HCOH HC O

HCOH COH C O HOC HOCH

HOCH HOCH HOCH HOCH HOCH

HCOH HCOH HCOH HCOH HCOH

HCOH HCOH HCOH HCOH HCOH

CH2OH CH2OH CH2OH CH2OH CH2OH

D-Glucose trans-enediol D-Fructose cis-enediol D-Mannose

Figure 1.5 Interrelationship of D-glucose, D-mannose, and D-fructose via isomerization.

Hemiacetal formation can occur intramolecularly (that is, within the same aldose or
ketose molecule) by reaction of the carbonyl group of a monosaccharide molecule with
one of its own hydroxyl groups, as illustrated in Fig. 1.6 with D-glucose laid coiled on
its side. The six-membered ring that results from reaction of an aldehydic group with
the hydroxyl group at C5 is called a pyranose ring. Notice that, for the oxygen atom of
the hydroxyl group at C5 to react to form the ring, C5 must rotate to bring its oxygen
Monosaccharides 13

HC1 O
H C6H2OH C6H2OH
HC2OH
C5 C6H2OH C5 O H 5
O
HOC3H H
OH
C4 HC1 O C4 HC1 O 4 1 OH
HC4OH HO
OH H
HO
OH
HO
OH
2
C3 C2 C3 C2 3
HC5OH
H OH OH OH
C6H2OH
D-Glucose D-Glucopyranose
(Fischer (Haworth projection)
projection)
Figure 1.6 Relationship of the acyclic and pyranose ring (Haworth projection) structures of D-
glucose.

atom upward. This rotation brings the hydroxymethyl group (C6) to a position above
the plane of the ring. The representation of the D-glucopyranose ring used in Fig. 1.6 is
called a Haworth projection.
To avoid clutter in writing ring structures, common conventions are adopted
wherein ring carbon atoms are indicated by angles in the ring, and hydrogen atoms
attached to carbon atoms are eliminated altogether (Fig. 1.7). A mixture of chiral forms
(anomeric forms [see below]) is indicated by a wavy line.
Monosaccharides can also occur in a five-membered ring called the furanose ring
(Fig. 1.8), but most free pentoses, hexoses, and heptoses occur in pyranose rings
because the six-membered pyranose ring is more stable than the furanose ring (see
below). Although the less stable furanose ring is less prevalent than the pyranose
ring, it is found in several oligo- and polysaccharides (and in nucleic acids). The fura-
nose ring is formed in the same way as the pyranose ring (Fig. 1.8).
When the carbon atom of the carbonyl group is involved in cyclic hemiacetal (py-
ranose or furanose ring) formation, it becomes chiral because four different groups
are now attached to it. With D sugars, the configuration that has the hydroxyl group
located below the ring is called the alpha form. For example, a-D-glucopyranose is
D-glucose in the pyranose (six-membered) ring form with the hydroxyl group of
the new chiral carbon atom (C1) in the alpha position (that is, below the plane
of the ring). When the newly formed hydroxyl group at C1 is above the ring, it is
in the beta position, and the structure is termed b-D-glucopyranose. This designation
holds for all D sugars. The new chiral carbon atom is called the anomeric carbon
atom, and the two anomeric forms (alpha [a] and beta [b]) are known as anomers
and form an anomeric pair. For sugars in the L series, the opposite is true (that is,
the anomeric hydroxyl group is up in the alpha anomer and down in the beta anomer),
so that a-D-glucopyranose and a-L-glucopyranose are mirror images of each other.
14 Carbohydrate Chemistry for Food Scientists

(A) (B)
CH2OH CH2OH
C O O
H H H H
H H
C C
OH H OH H
HO OH HO OH
C C
H OH H OH

(C) CH OH (D) CH OH
2 2
O O

OH OH
HO OH HO OH

OH OH

(E)
O

Figure 1.7 Five representations of the structure of a-D-glucopyranose. These two-dimensional

representations of the pyranose ring are Haworth projections. Actually, the ring is not flat but
puckered. (A) All C, H, and O atoms are shown. (B) C2, C3, C4, C5, and O5 are represented by
a hexagon. (C) Hydrogen atoms attached to C1, C2, C3, C4, and C5 are indicated but not
shown. (D) Hydrogen atoms attached to C1, C2, C3, C4, and C5 are omitted. (E) A skeletal
structure in which the hydroxyl groups are also omitted, although their positions are indicated.
Form D is the preferred form for ease of recognition and is used in this book.

HC1 O
HOC5H2
HC2OH C5H2OH O
H
HC3OH C4 HC1 O 4 1 OH
H H
HC4OH HO 3 3 2
C C2
C5H2OH OH OH OH OH

D-Ribose D-Ribofuranose

Figure 1.8 Formation of the furanose ring form of D-ribose.

Monosaccharides 15

CH2OH
O

OH
OH
HO

OH
D-Glucopyranose

CH2OH CH2OH
O O
OH

OH OH
HO OH HO

OH OH
α-D-Glucopyranose β-D-Glucopyranose

However, pyranose rings are not flat with the attached groups sticking straight up
and straight down as the Haworth representation suggests. Rather, they occur in a va-
riety of shapes (conformations)dmost commonly in one of two chair conformations
(so-called because they are shaped somewhat like a chair). In a chair conformation,
one bond on each carbon atom projects either up or down from the ring; these are
called axial bonds and the attached atom or group is said to be in an axial position. The
other bonds not involved in ring formation project out around the perimeter of the ring
in what are called equatorial positions (Fig. 1.9), so they are called equatorial bonds.
Equatorial bonds are either up or down with respect to the axial bonds, but not straight
up or straight down with respect to the ring as are axial bonds.
The pyranose ring in a chair conformation can be pictured as a disk with about one-
third of the disk bent slightly up and the one-third directly opposite the bent-up part
bent slightly down. The equatorial positions are those that project outward around
the perimeter (equator) of the structure, and the axial positions are those that project
above and below the disk. The six-membered pyranose ring distorts the normal carbon
and oxygen atom bond angles less than rings of other sizes do, so it is the predominate
ring form. Strain is further lessened when the larger hydroxyl groups (that is, larger

CH2OH
=

Figure 1.9 A pyranose ring showing the equatorial (solid line) and axial (dashed line) bond
positions.
16 Carbohydrate Chemistry for Food Scientists

H
CH2OH O
HO H
H
HO OH
HO
H H
Figure 1.10 b-D-Glucopyranose in the C1 conformation as drawn in structural formulas. All
4

bulky groups are in equatorial positions, all hydrogen atoms in axial positions.

than hydrogen atoms) are separated maximally from each other by a ring conformation
(shape) that arranges the greatest number of them in equatorial rather than axial posi-
tions, so rotation of carbon atoms takes place on their connecting bonds to swivel the
hydroxyl groups to equatorial positions in so far as is possible.
Using b-D-glucopyranose as an example, C2, C3, C5, and the ring oxygen atom
remain in a plane, but C4 is raised slightly above the plane and C1 is positioned
slightly below the plane as in Figs. 1.9 and 1.10, giving the ring somewhat the shape
of a chair. This conformation is designated the 4C1 conformation. The notation C in-
dicates that the ring is chair shaped; the superscript and subscript numbers indicate that
C4 is above the plane of the ring formed by C2, C3, C5, and the ring oxygen atom and
C1 is below the plane. There are two chair forms. The second (1C4) has all the axial and
equatorial groups reversed, and therefore, has the hydroxyl groups of D-glucopyranose
axial, causing nonbonding steric hindrance (interference). Because the 1C4 conforma-
tion is a higher energy form, little, if any, D-glucopyranose ever exists in that
conformation.
As noted, b-D-glucopyranose has all of its hydroxyl groups in the equatorial
arrangement. Each is located either slightly above or slightly below the true equatorial
position. In b-D-glucopyranose, the hydroxyl groups (all of which are in equatorial po-
sitions) alternate in an up-and-down arrangement, with that on C1 positioned slightly
up and that on C2 positioned slightly down, and continuing around the ring. The bulky
hydroxymethyl group (CH2OH; C6 in hexoses) is essentially always in a sterically
free equatorial position.
In addition to the two chair forms, other conformations can exist, depending on the
configuration of the sugar and any groups that may be attached to it. Thus, there are six
boat conformations and six skew (twisted boat) shapes possible for the pyranose ring.
Few molecules assume these higher energy forms, though in solution, they may occur
momentarily.
C
C C
C C
C C
C O C
C O
Boat Skew
Other documents randomly have
different content
address you briefly, and to take, in your presence, the oath
prescribed by the Constitution of the United States to be taken
by the President before he enters on the execution of his office.
“I do not consider it necessary, at present, for me to discuss
those matters of administration about which there is no special
anxiety or excitement. Apprehension seems to exist among the
people of the Southern States, that, by the accession of a
Republican Administration, their property and their peace and
personal security are to be endangered. There has never been
any reasonable cause for such apprehension. Indeed, the most
ample evidence to the contrary has all the while existed, and
been open to their inspection. It is found in nearly all the
published speeches of him who now addresses you. I do but
quote from one of those speeches, when I declare that ‘I have
no purpose, directly or indirectly, to interfere with the institution
of slavery in the States where it exists.’ I believe I have no
lawful right to do so; and I have no inclination to do so. Those
who nominated and elected me, did so with the full knowledge
that I had made this, and made many similar declarations, and
had never recanted them. And, more than this, they placed in
the platform, for my acceptance, and as a law to themselves
and to me, the clear and emphatic resolution which I now read:
“‘Resolved, That the maintenance inviolate of the rights of
the States, and especially the right of each State to order and
control its own domestic institutions according to its own
judgment exclusively, is essential to that balance of power on
which the perfection and endurance of our political fabric
depend; and we denounce the lawless invasion, by armed force,
of the soil of any State or Territory, no matter under what
pretext, as among the gravest of crimes.’
“I now reiterate these sentiments; and in doing so I only
press upon the public attention the most conclusive evidence of
which the case is susceptible, that the property, peace and
security of no section are to be in anywise endangered by the
now incoming administration.
“I add, too, that all the protection which, consistently with
the Constitution and the laws, can be given, will be cheerfully
given to all the States when lawfully demanded, for whatever
cause, as cheerfully to one section as to another.
“There is much controversy about the delivering up of
fugitives from service or labor. The clause I now read is as
plainly written in the Constitution as any other of its provisions:
“‘No person held to service or labor in one State under the
laws thereof, escaping into another, shall, in consequence of any
law or regulation therein, be discharged from such service or
labor, but shall be delivered up on claim of the party to whom
such service or labor may be due.’
“It is scarcely questioned that this provision was intended by
those who made it for the reclaiming of what we call fugitive
slaves; and the intention of the lawgiver is the law.
“All members of Congress swear their support to the whole
Constitution​—​to this provision as well as any other. To the
proposition, then, that slaves whose cases come within the
terms of this clause ‘shall be delivered up,’ their oaths are
unanimous. Now, if they would make the effort in good temper,
could they not, with nearly equal unanimity, frame and pass a
law by means of which to keep good that unanimous oath?
“There is some difference of opinion whether this clause
should be enforced by National or by State authority; but surely
that difference is not a very material one. If the slave is to be
surrendered, it can be of but little consequence to him or to
others by which authority it is done; and should any one, in any
case, be content that this oath shall go unkept on a merely
unsubstantial controversy as to how it shall be kept?
“Again, in any law upon this subject, ought not all the
safeguards of liberty known in civilized and humane
jurisprudence to be introduced, so that a free man be not, in
any case, surrendered as a slave? And might it not be well at
the same time to provide by law for the enforcement of that
clause in the Constitution which guarantees that ‘the citizens of
each State shall be entitled to all the privileges and immunities
of citizens in the several States?’
“I take the official oath to-day with no mental reservations,
and with no purpose to construe the Constitution or laws by any
hypercritical rules; and while I do not choose now to specify
particular acts of Congress as proper to be enforced, I do
suggest that it will be much safer for all, both in official and
private stations, to conform to and abide by all those acts which
stand unrepealed, than to violate any of them, trusting to find
impunity in having them held to be unconstitutional.
“It is seventy-two years since the first inauguration of a
President under our National Constitution. During that period,
fifteen different and very distinguished citizens have in
succession administered the executive branch of the
Government. They have conducted it through many perils, and
generally with great success. Yet, with all this scope for
precedent, I now enter upon the same task, for the brief
constitutional term of four years, under great and peculiar
difficulties.
“A disruption of the Federal Union, heretofore only
menaced, is now formidably attempted. I hold that in the
contemplation of universal law and of the Constitution, the
Union of these States is perpetual. Perpetuity is implied, if not
expressed, in the fundamental law of all national governments.
It is safe to assert that no government proper ever had a
provision in its organic law for its own termination. Continue to
execute all the express provisions of our National Constitution,
and the Union will endure forever, it being impossible to destroy
it, except by some action not provided for in the instrument
itself.
 “Again, if the United States be not a government proper, but
an association of States in the nature of a contract merely, can
it, as a contract, be peaceably unmade by less than all the
parties who made it? One party to a contract may violate it​—​
break it, so to speak; but does it not require all to lawfully
rescind it? Descending from these general principles, we find
the proposition that in legal contemplation the Union is
perpetual, confirmed by the history of the Union itself.
“The Union is much older than the Constitution. It was
formed, in fact, by the Articles of Association in 1774. It was
matured and continued in the Declaration of Independence in
1776. It was further matured, and the faith of all the then
thirteen States expressly plighted and engaged that it should be
perpetual, by the Articles of the Confederation, in 1778; and,
finally, in 1787, one of the declared objects for ordaining and
establishing the Constitution was to form a more perfect Union.
But if the destruction of the Union by one or by a part only of
the States be lawfully possible, the Union is less than before,
the Constitution having lost the vital element of perpetuity.
“It follows from these views that no State, upon its own
mere motion, can lawfully get out of the Union; that resolves
and ordinances to that effect, are legally void; and that acts of
violence within any State or States against the authority of the
United States, are insurrectionary or revolutionary, according to
circumstances.
“I therefore consider that, in view of the Constitution and
the laws, the Union is unbroken, and, to the extent of my ability,
I shall take care, as the Constitution itself expressly enjoins
upon me, that the laws of the Union shall be faithfully executed
in all the States. Doing this, which I deem to be only a simple
duty on my part, I shall perfectly perform it, so far as is
practicable, unless my rightful masters, the American people,
shall withhold the requisition, or in some authoritative manner
direct the contrary.
 “I trust this will not be regarded as a menace, but only as
the declared purpose of the Union that it will constitutionally
defend and maintain itself.
“In doing this there need be no bloodshed or violence, and
there shall be none unless it is forced upon the National
authority.
“The power confided to me will be used to hold, occupy,
and possess the property and plants belonging to the
Government, and collect the duties and imposts; but beyond
what may be necessary for these objects there will be no
invasion, no using of force against or among the people
anywhere.
“Where hostility to the United States shall be so great and
so universal as to prevent competent resident citizens from
holding Federal offices, there will be no attempt to force
obnoxious strangers among the people that object. While the
strict legal right may exist of the Government to enforce the
exercise of these offices, the attempt to do so would be so
irritating, and so nearly impracticable withal, that I deem it best
to forego, for the time, the uses of such offices.
“The mails, unless repelled, will continue to be furnished in
all parts of the Union.
“So far as possible, the people everywhere shall have that
sense of perfect security which is most favorable to calm
thought and reflection.
“The course here indicated will be followed, unless current
events and experience shall show a modification or change to
be proper; and in every case and exigency my best discretion
will be exercised according to the circumstances actually
existing, and with a view and hope of a peaceful solution of the
National troubles and the restoration of fraternal sympathies
and affections.
 “That there are persons, in one section or another, who
seek to destroy the Union at all events, and are glad of any
pretext to do it, I will neither affirm nor deny. But if there be
such, I need address no word to them.
“To those, however, who really love the Union, may I not
speak, before entering upon so grave a matter as the
destruction of our National fabric, with all its benefits, its
memories, and its hopes? Would it not be well to ascertain why
we do it? Will you hazard so desperate a step, while any portion
of the ills you fly from have no real existence? Will you, while
the certain ills you fly to are greater than all the real ones you
fly from? Will you risk the commission of so fearful a mistake?
All profess to be content in the Union if all constitutional rights
can be maintained. Is it true, then, that any right, plainly written
in the Constitution, has been denied? I think not. Happily the
human mind is so constituted, that no party can reach to the
audacity of doing this.
“Think, if you can, of a single instance in which a plainly-
written provision of the Constitution has ever been denied. If, by
the mere force of numbers, a majority should deprive a minority
of any clearly-written constitutional right, it might, in a moral
point of view, justify revolution; it certainly would, if such right
were a vital one. But such is not our case.
“All the vital rights of minorities and of individuals are so
plainly assured to them by affirmations and negations,
guaranties and prohibitions in the Constitution, that
controversies never arise concerning them. But no organic law
can ever be framed with a provision specifically applicable to
every question which may occur in practical administration. No
foresight can anticipate, nor any document of reasonable length
contain, express provisions for all possible questions. Shall
fugitives from labor be surrendered by National or by State
authorities? The Constitution does not expressly say. Must
Congress protect slavery in the Territories? The Constitution
does not expressly say. From questions of this class, spring all
our constitutional controversies, and we divide upon them into
majorities and minorities.
“If the minority will not acquiesce, the majority must, or the
Government must cease. There is no alternative for continuing
the Government but acquiescence on the one side or the other.
If a minority in such a case will secede rather than acquiesce,
they make a precedent which, in turn, will ruin and divide them,
for a minority of their own will secede from them whenever a
majority refuses to be controlled by such a minority. For
instance, why not any portion of a new Confederacy, a year or
two hence, arbitrarily secede again, precisely as portions of the
present Union now claim to secede from it? All who cherish
disunion sentiments are now being educated to the exact
temper of doing this. Is there such perfect identity of interests
among the States to compose a new Union as to produce
harmony only, and prevent renewed secession? Plainly, the
central idea of secession is the essence of anarchy.
“A majority held in restraint by constitutional check and
limitation, and always changing easily with deliberate changes
of popular opinions and sentiments, is the only true sovereign of
a free people. Whoever rejects it, does, of necessity, fly to
anarchy or to despotism. Unanimity is impossible; the rule of a
majority, as a permanent arrangement, is wholly inadmissible.
So that, rejecting the majority principle, anarchy or despotism,
in some form, is all that is left.
“I do not forget the position assumed by some that
constitutional questions are to be decided by the Supreme
Court, nor do I deny that such decisions must be binding in any
case upon the parties to a suit, as to the object of that suit,
while they are also entitled to a very high respect and
consideration in all parallel cases by all other departments of the
Government; and while it is obviously possible that such
decision may be erroneous in any given case, still the evil effect
following it, being limited to that particular case, with the
chance that it may be overruled and never become a precedent
for other cases, can better be borne than could the evils of a
different practice.
“At the same time the candid citizen must confess that if the
policy of the Government upon the vital question affecting the
whole people is to be irrevocably fixed by the decisions of the
Supreme Court, the instant they are made, as in ordinary
litigation between parties in personal actions, the people will
have ceased to be their own masters, unless having to that
extent practically resigned their Government into the hands of
that eminent tribunal.
“Nor is there in this view any assault upon the Court or the
Judges. It is a duty from which they may not shrink, to decide
cases properly brought before them; and it is no fault of theirs if
others seek to turn their decisions to political purposes. One
section of our country believes slavery is right and ought to be
extended, while the other believes it is wrong and ought not to
be extended; and this is the only substantial dispute; and the
fugitive slave clause of the Constitution, and the law for the
suppression of the foreign slave-trade, are each as well
enforced, perhaps, as any law can ever be in a community
where the moral sense of the people imperfectly supports the
law itself. The great body of the people abide by the dry legal
obligation in both cases, and a few break over in each. This, I
think, can not be perfectly cured, and it would be worse in both
cases after the separation of the sections than before. The
foreign slave-trade, now imperfectly suppressed, would be
ultimately revived, without restriction, in one section; while
fugitive slaves, now only partially surrendered, would not be
surrendered at all by the other.
“Physically speaking we can not separate; we can not
remove our respective sections from each other, nor build an
impassable wall between them. A husband and wife may be
divorced, and go out of the presence and beyond the reach of
each other, but the different parts of our country can not do
this. They can not but remain face to face; and intercourse,
either amicable or hostile, must continue between them. Is it
possible, then, to make that intercourse more advantageous or
more satisfactory after separation than before? Can aliens make
treaties easier than friends can make laws? Can treaties be
more faithfully enforced between aliens than laws can among
friends? Suppose you go to war, you can not fight always; and
when, after much loss on both sides, and no gain on either, you
cease fighting, the identical questions as to terms of intercourse
are again upon you.
“This country, with its institutions, belongs to the people
who inhabit it. Whenever they shall grow weary of the existing
government, they can exercise their constitutional right of
amending, or their revolutionary right to dismember or
overthrow it. I can not be ignorant of the fact that many worthy
and patriotic citizens are desirous of having the National
Constitution amended. While I make no recommendation of
amendment, I fully recognize the full authority of the people
over the whole subject, to be exercised in either of the modes
prescribed in the instrument itself, and I should, under existing
circumstances, favor rather than oppose, a fair opportunity
being afforded the people to act upon it.
“I will venture to add, that to me the Convention mode
seems preferable, in that it allows amendments to originate with
the people themselves, instead of only permitting them to take
or reject propositions originated by others not especially chosen
for the purpose, and which might not be precisely such as they
would wish either to accept or refuse. I understand that a
proposed amendment to the Constitution (which amendment,
however, I have not seen) has passed Congress, to the effect
that the Federal Government shall never interfere with the
domestic institutions of States, including that of persons held to
service. To avoid misconstruction of what I have said, I depart
from my purpose not to speak of particular amendments, so far
as to say that, holding such a provision to now be implied
constitutional law, I have no objection to its being made express
and irrevocable.
“The Chief Magistrate derives all his authority from the
people, and they have conferred none upon him to fix the terms
for the separation of the States. The people themselves, also,
can do this if they choose, but the Executive, as such, has
nothing to do with it. His duty is to administer the present
government as it came to his hands, and to transmit it
unimpaired by him to his successor. Why should there not be a
patient confidence in the ultimate justice of the people? Is there
any better or equal hope in the world? In our present
differences is either party without faith of being in the right? If
the Almighty Ruler of nations, with his eternal truth and justice,
be on your side of the North, or on yours of the South, that
truth and that justice will surely prevail by the judgment of this
great tribunal, the American people. By the frame of the
government under which we live, this same people have wisely
given their public servants but little power for mischief, and
have with equal wisdom provided for the return of that little to
their own hands at very short intervals. While the people retain
their virtue and vigilance, no administration, by any extreme
wickedness or folly, can very seriously injure the government in
the short space of four years.
“My countrymen, one and all, think calmly and well upon
this whole subject. Nothing valuable can be lost by taking time.
“If there be an object to hurry any of you, in hot haste, to a
step which you would never take deliberately, that object will be
frustrated by taking time: but no good object can be frustrated
by it.
“Such of you as are now dissatisfied, still have the old
Constitution unimpaired, and on the sensitive point, the laws of
 your own framing under it; while the new administration will
have no immediate power, if it would, to change either.
“If it were admitted that you who are dissatisfied hold the
right side in the dispute, there is still no single reason for
precipitate action. Intelligence, patriotism, Christianity, and a
firm reliance on Him who has never yet forsaken this favored
land, are still competent to adjust, in the best way, all our
present difficulties.
“In your hands, my dissatisfied fellow-countrymen, and not
in mine, is the momentous issue of civil war. The Government
will not assail you.
“You can have no conflict without being yourselves the
aggressors. You have no oath registered in Heaven to destroy
the Government; while I shall have the most solemn one to
‘preserve, protect, and defend’ it.
“I am loath to close. We are not enemies, but friends. We
must not be enemies. Though passion may have strained, it
must not break our bonds of affection.
“The mystic cords of memory, stretching from every battle-
field and patriot grave to every living heart and hearthstone all
over this broad land, will yet swell the chorus of the Union,
when again touched, as surely they will be, by the better angels
of our nature.”

One point was established, at least, by this inaugural, whatever

uncertainties might cluster about it​—w​ e had, at last, a Government.
No Buchanan ruled the hour. Loyal men of every shade breathed
more freely. At the same time, the whole drift was toward securing,
if possible, an honorable reconciliation. If, after this lucid, temperate
statement of the plans and purposes of the new Administration, the
blow must fall, which all wished to avoid, it was encouraging to feel​
—​as every one who heard Mr. Lincoln on that eventful day must
have felt​—​that a man was at the helm who had firm faith that the
organic law, so far from providing for the dissolution of the Union,
had vitality and force within itself sufficient to defend the nation
against dangers from within as well as from without.
The announcement of the President’s cabinet, likewise​—​
composed, as it was, of the ablest men in his own party, the
majority of whom had been deemed worthy of presentation as
candidates for the high office which he held​—​imparted confidence to
all who wished well to the country. The able pen of the Secretary of
State was at once called into requisition to communicate, through
the newly appointed ministers abroad, the true state of affairs to the
European powers. As speedily as possible the Departments were
purged of disloyal officials, although the deceptions and subterfuges
which constituted a goodly portion of the stock in trade of the
rebellion rendered this a work of more time than was satisfactory to
many.
The Davis dynasty, at Montgomery, having, on the 9th of March,
passed an act to organize a Confederate army, two persons​—​one
from Alabama and the other from Georgia​—a ​ nnounced themselves,
three days later, as “Confederate Commissioners,” accredited for the
purpose of negotiating a treaty. The President declined to recognize
these “Commissioners,” who were referred to a copy of his inaugural
enclosed for a full statement of his views.
On the 21st of March, Alexander H. Stephens, of Georgia, Vice-
President of the Montgomery traitors, up to that time regarded as
one of the most moderate​—a ​ s he certainly was one of the ablest​—​of
the conspirators, in a speech at Savannah, silenced all questionings
as to the intent of himself and co-workers.
He said on that occasion:

“The new Constitution (that adopted at Montgomery) has

put at rest forever all the agitating questions relating to our
peculiar institutions​—A
​ frican slavery as it exists among us​—​the
proper status of the negro in our form of civilization. This was
 the immediate cause of the late rupture and present revolution.
Jefferson, in his forecast, had anticipated this as the rock upon
which the old Union would split. He was right. What was
conjecture with him, is now a realized fact. But whether he fully
comprehended the great truth upon which that rock stood and
stands, may be doubted. The prevailing ideas, entertained by
him and most of the leading statesmen, at the time of the
formation of the old Constitution, were, that the enslavement of
the African was in violation of the laws of nature; that it was
wrong in principle, socially, morally, and politically. It was an evil
they knew not well how to deal with; but the general opinion of
the men of that day was, that, somehow or other, in the order
of Providence, the institution would be evanescent and pass
away. * * *
“Our new Government is founded upon exactly the opposite
ideas. Its foundations are laid, its corner-stone rests upon the
great truth that the negro is not equal to the white man; that
slavery, subordination to the superior race, is his natural and
normal condition. This, our new Government, is the first in the
history of the world based upon this great physical,
philosophical, and moral truth. * * * It is upon this, as I have
stated, our social fabric is firmly planted; and I can not permit
myself to doubt the ultimate success of a full recognition of this
principle throughout the civilized and enlightened world. * * *
This stone, which was rejected by the first builders, ‘is become
the chief stone of the corner’ in our new edifice.”

On the 13th of April, the President was waited upon by a

committee from a Convention of the State of Virginia, which
Convention was discussing the question whether to go with the
States already in rebellion, or to remain in the Union, for the sake of
furthering the ends of the rebels. The object of the visit, and its
result, may be determined from Mr. Lincoln’s response:
 “Gentlemen:​—A
​ s a committee of the Virginia Convention, now
in session, you present me a preamble and resolution, in these
words:
“‘Whereas, In the opinion of this Convention, the uncertainty
which prevails in the public mind as to the policy which the
Federal Executive intends to pursue towards the seceded States
is extremely injurious to the industrial and commercial interests
of the country, tends to keep up an excitement which is
unfavorable to the adjustment of the pending difficulties, and
threatens a disturbance of the public peace; therefore,
“Resolved, That a committee of three delegates be
appointed to wait on the President of the United States, present
to him this preamble, and respectfully ask him to communicate
to this Convention the policy which the Federal Executive
intends to pursue in regard to the Confederate States.’
“In answer, I have to say, that having, at the beginning of
my official term, expressed my intended policy as plainly as I
was able, it is with deep regret and mortification I now learn
there is great and injurious uncertainty in the public mind as to
what that policy is, and what course I intend to pursue. Not
having as yet seen occasion to change, it is now my purpose to
pursue the course marked out in the inaugural address. I
commend a careful consideration of the whole document as the
best expression I can give to my purposes. As I then and
therein said, I now repeat, ‘The power confided in me, will be
used to hold, occupy, and possess property and places
belonging to the Government, and to collect the duties and
imposts; but beyond what is necessary for these objects, there
will be no invasion, no using of force against or among the
people anywhere.’ By the words ‘property and places belonging
to the Government,’ I chiefly allude to the military posts and
property which were in possession of the government when it
came into my hands. But if, as now appears to be true, in
pursuit of a purpose to drive the United States authority from
 these places, an unprovoked assault has been made upon Fort
Sumter, I shall hold myself at liberty to repossess it, if I can, like
places which had been seized before the Government was
devolved upon me, and in any event I shall, to the best of my
ability, repel force by force. In case it proves true that Fort
Sumter has been assaulted, as is reported, I shall, perhaps,
cause the United States mails to be withdrawn from all the
States which claim to have seceded, believing that the
commencement of actual war against the Government justifies
and possibly demands it. I scarcely need to say that I consider
the military forts and property, situated within the States which
claim to have seceded, as yet belonging to the Government of
the United States, as much as they did before the supposed
secession. Whatever else I may do for the purpose, I shall not
attempt to collect the duties and imposts by any armed invasion
of any part of the country​—​not meaning by this, however, that I
may not land a force deemed necessary to relieve a fort upon
the border of the country. From the fact that I have quoted a
part of the inaugural address, it must not be inferred that I
repudiate any other part, the whole of which I reaffirm, except
so far as what I now say of the mails may be regarded as a
modification.”

Fort Sumter fell on the day following the reception of these

commissioners, after every effort, consistent with the means at the
disposal of the government, had been made to prevent what then
seemed a catastrophe. This action could bear but one interpretation.
A reconciliation of difficulties was utterly impracticable. An appeal
had been made to the sword. The power and authority of the United
States had been defied and insulted. No loyal man could now
hesitate. If, however, there were any who, even then, clung to the
fallacy that compromise could save us, Abraham Lincoln was not of
the number.
 CHAPTER VII.
PREPARING FOR WAR.

Effects of Sumter’s Fall​—​President’s Call for Troops​—​

Response in the Loyal States​—I​ n the Border States​—​
Baltimore Riot​—​Maryland’s Position​—​President’s Letter
to Maryland Authorities​—​Blockade Proclamation​—​
Additional Proclamation​—​Comments Abroad​—S ​ econd
Call for Troops​—S​ pecial Order for Florida​—​Military
Movements.

Sumter fell, but the nation arose. With one mind the Free States
determined that the rebellion must be put down. All were ablaze
with patriotic fire. The traitors at heart, who lurked in the loyal
States, found it a wise precaution to float with the current. The
shrewder ones among them saw well how such a course would give
them vantage-ground when the reaction, which they hoped, and for
which in secret they labored, should come. But the great mass of the
people would not have admitted the possibility of any reaction​—​
action was to continue the order of the day until the business in
hand was finished.
* * * * *

On the 15th of April, 1861, the President issued his first

proclamation:
 “Whereas, The laws of the United States have been for some
time past, and now are opposed, and the execution thereof
obstructed, in the States of South Carolina, Georgia, Alabama,
Florida, Mississippi, Louisiana, and Texas, by combinations too
powerful to be suppressed by the ordinary course of judicial
proceedings, or by the powers vested in the marshals by law;
now, therefore, I, Abraham Lincoln, President of the United
States, in virtue of the power in me vested by the Constitution
and the laws, have thought fit to call forth, and hereby do call
forth, the militia of the several States of the Union to the
aggregate number of seventy-five thousand, in order to
suppress said combinations and to cause the laws to be duly
executed.
“The details for this object will be immediately
communicated to the State authorities through the War
Department. I appeal to all loyal citizens to favor, facilitate, and
aid this effort to maintain the honor, the integrity, and existence
of our national Union, and the perpetuity of popular
government, and to redress wrongs already long enough
endured. I deem it proper to say that the first service assigned
to the forces hereby called forth, will probably be to repossess
the forts, places, and property which have been seized from the
Union; and in every event the utmost care will be observed,
consistently with the objects aforesaid, to avoid any
devastation, any destruction of, or interference with property, or
any disturbance of peaceful citizens of any part of the country;
and I hereby command the persons composing the
combinations aforesaid, to disperse and retire peaceably to their
respective abodes, within twenty days from this date.
“Deeming that the present condition of public affairs
presents an extraordinary occasion, I do hereby, in virtue of the
power in me vested by the Constitution, convene both Houses
of Congress. The Senators and Representatives are, therefore,
summoned to assemble at their respective chambers at twelve
o’clock, noon, on Thursday, the fourth day of July next, then
 and there to consider and determine such measures as in their
wisdom, the public safety and interest may seem to demand.
“In witness whereof, I have hereunto set my hand, and
caused the seal of the United States to be affixed.
“Done at the City of Washington, this fifteenth day of April,
in the year of our Lord, one thousand eight hundred and sixty-
one, and of the independence of the United States the eighty-
fifth.
“By the President: Abraham Lincoln
“William H. Seward, Secretary of State.”

In response to this proclamation enthusiastic public meetings

were held throughout the loyal States; all party lines seemed
obliterated; enlistments were almost universal; Washington, which
was at one time in imminent danger, was soon considered amply
defended. The majority entertained no doubt that with the force
summoned the rebellion would be nipped in the bud; the more
sagacious minority shook their heads, and wished that a million of
men had been asked.
An excellent opportunity was afforded to the border slave States
for pronouncing their election​—w ​ hether to stand by the
Government, or, practically, to furnish aid and comfort to the rebels.
Magoffin, Governor of Kentucky, was soon heard from: “Kentucky
will furnish no troops,” said he, “for the wicked purpose of subduing
her sister Southern States.” Letcher, of Virginia: “The militia of
Virginia will not be furnished to the powers at Washington for any
such case or purpose as they have in view;” and on the 17th, the
State was dragooned into passing, in secret, an ordinance of
secession, and immediately commenced those warlike preparations,
whose evil fruits she was destined so soon and in so much sorrow to
reap. The Executives of Tennessee and North Carolina refused
compliance; and those States, together with Arkansas, went over to
the “Confederacy.”
 How was the call for troops received by the rebel conclave at
Montgomery? They laughed.
The first blood shed in the war was in the streets of Baltimore,
on the 19th of April. Massachusetts troops, passing through that city
for the defence of the common capitol, were attacked by a mob,
instigated and encouraged by men of property and social standing.
The State hung trembling in the balance between loyalty and
treason. Had its geographical position been other than it was, it
would have undeniably embraced the fortune of the South. Its
Governor was, however, strongly inclined to support the
Government, although the peculiar circumstances in which he was
placed called for peculiar tact and dexterity in management. It was
seriously proposed that no more troops should be sent through
Baltimore.
* * * * *

The day following this attack, the President sent the following
letter in reply to a communication broaching this modest proposition:

“Washington, April 20th, 1861.

“Governor Hicks and Mayor Brown:
“Gentlemen:​—Y​ our letter by Messrs. Bond, Dobbin, and
Brune, is received. I tender you both my sincere thanks for your
efforts to keep the peace in the trying situation in which you are
placed. For the future, troops must be brought here, but I make
no point of bringing them through Baltimore.
“Without any military knowledge myself, of course I must
leave details to General Scott. He hastily said this morning in
presence of those gentlemen, ‘March them around Baltimore,
and not through it.’
“I sincerely hope the General, on fuller reflection, will
consider this practical and proper, and that you will not object to
 it. By this a collision of the people of Baltimore with the troops
will be avoided, unless they go out of the way to seek it. I hope
you will exert your influence to prevent this. Now and ever, I
shall do all in my power for peace, consistently with the
maintenance of government.
“Your obedient servant,
“A. Lincoln.”

To a delegation of rebel sympathizers from the same State, who

demanded a cessation of hostilities until Congress should assemble,
and accompanied their demand with the statement that seventy-five
thousand Marylanders would dispute the passage of any more
United States troops over the soil of that State, he quietly remarked
that he presumed there was room enough in the State to bury that
number, and declined to accede to their proposal. The Maryland
imbroglio was, after no great time, adjusted, and ample precautions
taken to guard against any future trouble in that quarter.
* * * * *

On the 19th of April, every port of the States in rebellion was

declared blockaded by the following proclamation:

“Whereas, An insurrection against the Government of the

United States has broken out in the States of South Carolina,
Georgia, Alabama, Florida, Mississippi, Louisiana, and Texas,
and the laws of the United States for the collection of the
revenue can not be efficiently executed therein conformably to
that provision of the Constitution which requires duties to be
uniform throughout the United States:
“And Whereas, A combination of persons, engaged in such
insurrection, have threatened to grant pretended letters of
marque to authorize the bearers thereof to commit assaults on
the lives, vessels, and property of good citizens of the country
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