Food Physical Chemistry and Biophysical Chemistry

• November 9, 20 11

Food Physical Chemistry and Biophysical Chemistry

I. C. Baianu

FSHN and NPRE Departments, University of Illinois at Urbana-Champaign,

AFC-NMR & FT-NIR Microspectroscopy Facility, Urbana IL 61801, USA

Email: ibaianu@illinois.edu

ABSTRACT

Food physical chemistry is considered to be a branch of Food chemistry [1] [2] concerned with the study of both
physical and chemical interactions in foods in terms of physical and chemical principles applied to food systems, as
well as the applications of physical/chemical techniques and instrumentation for the study of foods. [3] [4] [5] [6]
This field encompasses the "physiochemical principles of the reactions and conversions that occur during the
manufacture, handling, and storage offoods"[l]. Two rapidly growing, related areas are Food Biotechnology and
Food Biophysical Chemistry.

Keywords: Food chemistry, Physical Chemistry, Biophysical Chemistry applications to food systems; physical and
chemical principles applied to food systems, physical/chemical techniques and instrumentation utilized for the study
of foods; physical and chemical aspects of food processing; reactions in foods; chemical analysis and related
physical methods of analysis.

PACS: 82.70.-yxx; 82.80. -dxx ;44-XX; 47-XX; 47.50.+d; 47.55.-txx.; 47.70.-nxx;82.20.-wxx ; 82.56.-bxx; 82.60.-sxx.

1. INTRODUCTION

Food physical chemistry concepts are often drawn from rheology, theories of transport phenomena, physical and
chemical thermodynamics, chemical bonds and interaction forces, quantum mechanics and reaction kinetics,
biopolymer science, colloidal interactions, nucleation, glass transitions and freezing, [8] [9] disordered/ non-
crystalline solids. Techniques utilized range widely from dynamic rheometry, optical microscopy, electron
microscopy, AFM, light scattering, X-ray diffraction/neutron diffraction, [10] to MRI, spectroscopy (NMR,[11] FT-
NIR/IR, NIRS, Raman, ESR and EPR,[12] [13] CD/VCD,[14] Fluorescence, FCS [15] [16] [17] [18] [19] HPLC,
GC-MS,[20] [21] and other related analytical techniques. Understanding food processes and the properties of foods
requires a knowledge of physical chemistry and how it applies to specific foods and food processes. Food physical
chemistry is essential for improving the quality of foods, their stability and food product development. Because food
science is a multi-disciplinary field, food physical chemistry is being developed through interactions with other areas
of food chemistry and food science, such as: food analytical chemistry, food process engineering/food processing,
food and bioprocess technology, food extrusion, food quality control, food packaging, food biotechnology and food
microbiology.

2. TOPICS IN FOOD PHYSICAL CHEMISTRY

2.1. Topic Groups and Categories

The following are examples of topics in Food Physical Chemistry that are of interest to both Food Industry
and Food Science:

• Water in foods

• Local structure in liquid water

• Micro-crystallization in icecream emulsions

• Dispersion and surface-adsorption processes in foods; Food Dispersions

• Water and protein activities

• Food hydration and shelf-life

• Hydrophobic interactions in foods

• Hydrogen bonding and ionic interactions in foods

• Disulfide bond breaking and formation in foods

• Food dispersions

• Structure-functionality in foods

• Food micro- and nano- structure

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Baianu • Food Physical Chemistry & Biophysical Chemistry

Food gels and gelling mechanisms

Cross-linking in foods

Starch gelatinization and retrogradation

Physico-chemical modification of carbohydrates

Physico-chemical interactions in food formulations

Freezing effects on foods and freeze concentration of liquids

Glass transition in wheat gluten and wheat doughs

Drying of foods and crops

Rheology of wheat doughs, cheese and meat

Rheology of extrusion processes

Food enzyme kinetics

Immobilized enzymes and cells

Microencapsulation

Carbohydrates structure and interactions with water and proteins

Maillard browning reactions

Lipids structures and interactions with water and food proteins

Food proteins structure, hydration and functionality in foods

Food protein denaturation

Food enzymes and reaction mechanisms

Vitamin interactions and preservation during food processing

Interaction of salts and minerals with food proteins and water

Color determinations and food grade coloring

Flavors and sensorial perception of foods

Properties of food additives

tfll-VS. if \ \ 1

L JL

h

:e cream or gclato in Rome, Ita

iy

Origin

Alternative Eiame(s)

Gelato, sorbet, frozen custard

Dish details

Course served

Dessert

Main ingredient! s J

Milk/Cream, water ice, sugar

Figure 1.1. Examples of solid and glassy (non-crystalline) food dispersions that also includes ice microcrystals.

• November 2011

Baianu • Food Physical Chemistry & Biophysical Chemistry

Figure 1.2. Corn starch - an example of an important and major, but common, food ingredient that includes
paracrystals — in this case a mixture of crystalline and non-crystalline structures.

2.2. Paracrystal Theory and Convolution Algebra

A detailed example of physical chemistry applications to heterogeneous systems such as solid foods and food
dispersions is the paracrystal theory application to X-ray and neutron scattering data from such complex systems.

Figure 2.1. An example of a non- crystalline and non-Newtonian, but textured food system; this is usually classified
as a gel that has a complex, hydrated network structure.

As reported in a recent publication [21], the general theory of scattering by partially ordered, atomic or molecular,

• November 201 1 Baianu • Food Physical Chemistry & Biophysical Chemistry

structures in terms of paracrystals and lattice convolutions was formulated by Hosemann and Bagchi in [145] using
basic techniques of Fourier analysis and convolution products. A natural generalization of such molecular, partial
symmetries and their corresponding analytical versions involves convolution algebras - a functional/distribution
[247, 248] based theory that we will discuss in the context of a more general and original concept of a
convolution-algebroid of an extended symmetry groupoid of a paracrystal, of any molecular or nuclear system, or
indeed, any quantum system, in general. Such applications also include quantum fields theories, and local quantum
net configurations that are endowed with either partially disordered or "completely' ordered structures, as well as in
the graded, or super-algelbroid extension of these concepts for very massive structures such as stars and black holes
treated by quantum gravity theories.

A statistical analysis linked to structural symmetry and scattering theory considerations shows that a real paracrystal
can be defined by a three dimensional convolution polynomial with a semi-empirically derived composition law, *,
[146]. As was shown in [13, 14] - supported with computed specific examples - several systems of convolution can
be expressed analytically, thus allowing the numerical computation of X-ray, or neutron, scattering by partially
disordered layer lattices via complex Fourier transforms of one -dimensional structural models using fast digital
computers. The range of paracrystal theory applications is however much wider than the one-dimensional lattices
with disorder, thus spanning very diverse non-crystalline systems, from metallic glasses and spin glasses to
superfluids, high-temperature superconductors, and extremely hot anisotropic plasmas such as those encountered in
controlled nuclear fusion (for example, JET) experiments. Other applications - as previously suggested in [12] - may
also include novel designs of "fuzzy' quantum machines and quantum computers with extended symmetries of
quantum state spaces.

2.2.1. Convolution product of groupoids and the convolution algebra of functions

From a purely mathematical perspective, Alain Connes introduced the concept of a C -algebra of a (discrete) group
(see, e.g., [91]). The underlying vector space is that of complex valued functions with finite support, and the
multiplication of the algebra is the fundamental convolution product which it is convenient for our purposes to write
slightly differently from the common formula as

(/*g)(z) =£/(*)*(?),

xy=z

and * -operation

f(x) = f(x- 1 ).
The more usual expression of these formulas has a sum over the elements of a selected group. For topological
groups, where the underlying vector space consists of continuous complex valued functions, this product requires
the availability of some structure of measure and of measurable functions, with the sum replaced by an integral.

Notice also that this algebra has an identity, the distribution function S 1 , which has value one on the identity 1 of

the group, and has zero value elsewhere. Given this convolution/distribution representation that combines crystalline
("perfect' or global-group, and/or group-like symmetries) with partial symmetries of paracrystals and glassy solids
on the one hand, and also with non-commutative harmonic analysis [182] on the other hand, we propose that several
extended quantum symmetries can be represented algebraically in terms of certain structured groupoids, their

C -convolution quantum algebroids, paragroup/ 'quantized groups and/or other more general mathematical
structures that will be introduced in this report. It is already known that such extensions to groupoid and
algebroid/coalgebroid symmetries require also a generalization of non-commutative harmonic analysis which
involves certain Haar measures, generalized Fourier - Stieltjes transforms and certain categorical duality
relationships representing very general mathematical symmetries as well. A very promising approach to nonlinear
(anharmonic) analysis of aperiodic quantum systems represented by rigged Hilbert space bundles may involve the
computation of representation coefficients of Fourier - Stieltjes groupoid transforms.

Currently, however, there are several important aspects of quantum dynamics left out of the invariant, simplified
picture provided by group symmetries and their corresponding representations of quantum operator algebras [126].
An alternative approach proposed in [140] employs differential forms to find such symmetries. Physicists deal often
with such problems in terms of either spontaneous symmetry breaking or approximate symmetries that require
underlying assumptions or ad-hoc dynamic restrictions that have a phenomenological basisl. A well-studied example
of this kind is that of the dynamic Jahn -Teller effect and the corresponding "theorem' (Chapter 21 on pp. 807 - 831,
as well as p. 735 of [1]) which in its simplest form stipulates that a quantum state with electronic non-Kramers
degeneracy may be unstable against small distortions of the surroundings, that would lower the symmetry of the
crystal field and thus lift the degeneracy (i.e., cause an observable splitting of the corresponding energy levels). This
effect occurs in certain paramagnetic ion systems via dynamic distortions of the crystal field symmetries around

• November 201 1 Baianu • Food Physical Chemistry & Biophysical Chemistry

paramagnetic or high-spin centers by moving ligands that are diamagnetic. The established physical explanation is
that the Jahn - Teller coupling replaces a purely electronic degeneracy by a vibronic degeneracy (of exactly the
same symmetry!). The dynamic, or spontaneous breaking of crystal field symmetry (for example, distortions of the

octahedral or cubic symmetry) results in certain systems in the appearance of doublets of symmetry y 3 or singlets

of symmetry y l or y 2 . Such dynamic systems could be locally expressed in terms of symmetry representations of a
Lie algebroid, or globally in terms of a special Lie (or Lie - Weinstein) symmetry groupoid representations that can
also take into account the spin exchange interactions between the Jahn - Teller centers exhibiting such quantum
dynamic effects. Unlike the simple symmetries expressed by group representations, the latter can accommodate a
much wider range of possible or approximate symmetries that are indeed characteristic of real, molecular systems
with varying crystal field symmetry, as for example around certain transition ions dynamically bound to ligands in
liquids where motional narrowing becomes very important. This well known example illustrates the importance of
the interplay between symmetry and dynamics in quantum processes. Therefore, the various interactions and
interplay between the symmetries of quantum operator state space geometry and quantum dynamics at various levels
leads to both algebraic and topological structures that are variable and complex, well beyond symmetry groups and
well-studied group algebras (such as Lie algebras, see for example [126]).

This important example is drawn from the general theory of scattering by partially ordered, atomic or molecular,
structures in terms of paracrystals and lattice convolutions that was formulated in [145] using basic techniques of
Fourier analysis and convolution products. Further specific applications of the paracrystal theory to X -ray
scattering, based on computer algorithms, programs and explicit numerical computations, were subsequently
developed by the first author [13] for one-dimensional paracrystals, partially ordered membrane lattices [14] and
other biological structures with partial structural disorder [16]. Such biological structures, "quasi-crystals 1 , and the
paracrystals, in general, provide rather interesting physical examples of extended symmetries (cf. [144], [new
IJRRAS]).

3. RELATED FIELDS TO FOOD PHYSICAL CHEMISTRY:

Food chemistry

Food physics and Rheology

Food technology, Food engineering, Food safety and Food biotechnology

Agricultural biotechnology

Biophysical chemistry

Physical chemistry

Chemical physics

Chemical engineering

Spectroscopy-applied

Intermolecular forces

Nanotechnology and nanostructures

Molecular dynamics

Surface chemistry and Van der Waals forces

Chemical reactions and Reaction chemistry

Quantum chemistry

Quantum genetics

Bioorganic chemistry

Polymer chemistry

Biochemistry and Biological chemistry

Molecular models of DNA and Molecular modelling of proteins and viruses

Enzymology

Protein-protein interactions

Biomembranes

Complex system biology

Systems biology

Integrative biology

Mathematical biophysics

Genomics, Proteomics, Interactomics, Structural bioinformatics and Cheminformatics

Immobilized cells and enzymes

Microencapsulation of food additives and vitamins, etc.

• November 2011

Baianu • Food Physical Chemistry & Biophysical Chemistry

• Plant biology and Crop sciences

• Animal sciences

Visualisation of the human interaetome network

topology with the blue lines between proteins

(represented as points) showing protein-protein

interactions.

Figure 3.1. Visualisation of the human interactome network topology with the blue lines between proteins
(represented as points) showing protein-protein interactions.

• November 2011

Baianu • Food Physical Chemistry & Biophysical Chemistry

4. TECHNIQUES GALLERY: High-Field NMR, CARS / Raman Spectroscopy, Fluorescence Confocal

Microscopy and Hyperspectral Imaging

YeusL mcmhraii: pculfiii
imaging

Dividing cell
niKirew^nce

QfetaHTWWg

• November 201 1 Baianu • Food Physical Chemistry & Biophysical Chemistry

5. JOURNALS SPECIALIZED IN FOOD PHYSICAL CHEMISTRY AND RELATED FIELDS

• Journal of Agricultural and Food Chemistry

• AOCS Journal

• Biophysical Chemistry journal: http://www.elsevier.com/wps/find/iournaldescription.cws home/52499

• Magnetic Resonance in Chemistry

• Starke/ Starch Journal

• Journal of Dairy Science® (JDS): http://www.iournalofdairvscience.org/

• Chemical Physics Letters

• International Journal of Research and Reviews in Applied Sciences http://www.arpapress.com/

• Zeitschrift fur Physikalische Chemie (1887)

• Biopolymers

• Journal of Food Science (IFT, USA)

• International Journal of Food Science & Technology http://www.wiley.com/bw/iournal. asp?ref=0950-5423

• Macromolecular Chemistry and Physics (1947)

• Journal of the Science of Food and Agriculture ( http://www.onlinelibrarv.wiley.eom/ioumal/1 0.1 002/
(ISSN)1 097-0010)

• Polymer Preprints http://www.polyacs.Org/1 1 .html (ACS)

• Integrative Biology- Journal of the Royal Society of Chemistry http://pubs.rsc.org/en/iournals/iournalissues/ib

• Organic & Biomolecular Chemistry http://pubs.rsc.org/en/iournals/iournalissues/ob
(An RSC Journal)

• Nature

• Journal of Biological Chemistry

• Proceedings of the National Academy of Sciences of the United States of America

6. EXTERNAL LINKS

• ACS Division of Agricultural and Food Chemistry (AGFD) (http:// agfd. sites, acs. org/ )

• American Chemical Society (ACS) (http:// portal, acs. org/ portal/ acs/ corg/ content)

• Institute of Food Science and Technology (IFST), (formerly IFT) (http:/ / www. ifst. org/ )

• Dairy Science and Food Technology (http:/ / www. dairyscience. info/ index, php)

• Physical Chemistry. (Keith J. Laidler, John H. Meiser and Bryan C. Sanctuary
http://www.mchmultimedia.com/store/Phvsical-Chemistry-ebooks.html

• The World of Physical Chemistry http://books.google.co. uk/books?id=01LRIPbH80cC
(Keith J. Laidler,1993)

• Physical Chemistry from Ostwald to Pauling h ttp://books. google. co.uk/books?id=1UZiU2Wfl_AoC
(John W. Servos, 1996)

• 100 Years of Physical Chemistry http://www.amazon.com/ Years-Physical-Chemistrv-Roval-
Society/dp/0854049878/ (Royal Society of Chemistry, 2004)

• The Cambridge History of Science: The modern physical and mathematical sciences
http://books.qoogle.co. uk/?id=B3WvWhJTTX8C (Mary Jo Nye, 2003).

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