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Smart Pharmaceutical Polymers Classification and Applications: A Review

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 Smart Pharmaceutical Polymers Classification and Applications: A Review

Nagham M. Zaki Dawood and Banan Borhan Saeed

Department of Pharmaceutical Chemistry, College of Pharmacy, University of Mosul, Mosul, Iraq

KEY WORDS Abstract: In recent years, smart polymers have been extensively studied
Polymer and many interesting properties and potential applications have been
Pharmaceutical polymer found and identified. The question of what makes smart polymers
Biopolymer, unique starts with this review post, and are there some features that
Biological activity differentiate them from other polymers. Because of their unique
structural and functional properties, smart polymers are well worth
researching further.

Corresponding Author:
Banan Borhan Saeed
Department of Pharmaceutical Chemistry, College of Pharmacy, University of Mosul, Mosul, Iraq

INTRODUCTION Hyatt utilizes camphor to plasticize nitrocellulose. L.

A polymer is a material composed of several
repeating subunits consisting of large molecules
(macromolecules). A two‐word notion, polymer means
numerous and mere is unity. The process of polymer
formation by combining structural units is referred to as
polymerization[1].
As a result of their diverse properties, both synthetic
and natural polymers play an important role in daily life.
Natural biopolymers such as DNA and bio‐structures,
include well‐known plastics produced by humans such as
polystyrene. A number of minute modules known as
monomers, natural and synthetic polymers are created
by polymerization. Its huge molecular mass hence
provides exceptional physical features such as hardness,
high elasticity and viscoelasticity in comparison to
composites of tiny molecules[2]. The tradition of human
polymer use has been long, since, 1839 C, when it
entered the chemical modification of natural polymers,
in the mid‐19th century. In research on rubber
vulcanization, Goodyear has found a crucial advance that
has turned natural rubber into a functional engineering
material[3]. In 1870, to produce nitrocellulose plastics, W.
1907 Baekeland announced the synthesis of the first
thermosetting phenolic resin, the first synthetic plastic
product to be industrialized in the 1920s[4]. The
researcher proposed in 1920 that polymers are
long‐chain molecules united by structural units by
conventional covalent connections. This was the
foundation for the formation of the contemporary
science of polymers. Carothers then classified the
synthetic polymers into two major categories, a
polycondensate an addition polymer produced by a
polyaddition reaction. other researchers created a
polymerization catalyst for coordination in the 1950s,
ushering in the era of stereoregular polymer synthesis.
The synthesis of high polymers has advanced rapidly
in the decades after the discovery of the
macromolecular principle and several critical polymers
have been industrialized one after the other. The
synthesis of high polymers has achieved rapid
development in the decades following the
establishment of the principle of macromolecules and
many essential polymers have been industrialized one
after another.

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 ACE J. Clin. Chem. Lab. Med., 1 (2): 7‐17, 2021

Fig. 1: Four strategies of polymers

Fig. 2: Parameters of copolymers

CLASSIFICATION OF POLYMERS Copolymers: The polymers formed by the addition of

In general, polymers can not be categorized into one various monomers such as ,Buna‐S (5), Buna‐N (6),
classification but are categorized into four strategies polyesters (7), alkyd resins (8) (Fig. 2).
including:
Condensation polymers: Formed by the repeated
Classification based upon the mode of condensation reaction of two different monomeric
polymerization [5] molecules, bi‐functional or tri‐functional. Small
Addition polymers: Polymers that are formed by molecules such as water, hydrogen chloride, are
repeated monomer addition which can be split into two removed in these reactions. Some common examples
types: include nylon 6,6 (9), terylene (10), Bakelite (11) etc.
(Fig. 3).
Homopolymers: Polymers which are formed by the
addition of the same monomers such as polyethene (1), Classification based upon source[5, 6]
poly propene (2), poly vinyl chloride (3), polyisoprene (4) Natural polymers: Animal and plant polymers such as
(Fig. 1). sugars, nucleotides, proteins, lipids (Fig. 4).

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 ACE J. Clin. Chem. Lab. Med., 1 (2): 7‐17, 2021
Fig. 3: Condensation polymers
Fig. 4: Examples of natural polymers
Semisynthetic polymers: The majority of these polymers
are chemically modified naturally occurring polymers,
such as Cellulose and Vulcanized rubber.
Synthetic polymers: A large number of man‐made
polymers, including fibers and plastic rubbers are
commonly used in everyday life.
Classification based on structure[7]
Linear polymers: These polymers do not have branches
but have long and straight chains. High‐density polythene
(1), polyvinyl chloride (3) and polyester (7) are common
examples.
Branched‐chain polymer: In these polymers, the
monomer units not only combine to produce the linear
ACE Journal of Clinical Chemistry and Laboratory Medicine |ISSN: 2520‐3738 |Volume 1 |Number 2 |Page No. 7‐17 |2021
chain but also forms branches of different lengths with
the main chain. Some examples include low‐density
polythene (1), amylopectin (12) and glycogen (13)
(Fig. 5).
Cross‐linked polymers or network polymers: Polymers
that have a long straight chain but are linked by strong
covalent bonds by these chains. In these polymers, the
linear polymers originally formed are joined together to
create a three‐dimensional network structure. Bakelite
(11) and melamine (14) are examples (Fig. 6).
Classification based upon molecular forces[5]
Elastomer: The intermolecular attraction forces between
the polymer chains are weakest such as natural rubber
and Buna‐S‐S. (5).
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Fig. 5: Branched‐chain polymer
Fig. 6: Network polymers
Fibers: When the intermolecular forces of attraction are
the strongest, fibers are considered polymers. H‐bonding
and dipole‐dipole are consisting of these powers. As a
result of strong molecular force attractions, these
polymers have high tensile strength and low elasticity.
Terelyne, daction, polyacrylonitrile, for example (15).
Thermoplastics: Polymers are called thermoplastics,
where the attraction forces between elastomers and
fibers are inter‐molecular. They are linear or slightly
branched‐chain polymers that become challenging at
room temperature. It's possible to mold these into TV,
toys, buckets, telephones. For instance, polyethylene (1),
polyvinyl chloride (3), nylon 6,6 (9).
Thermosetting polymers: The semi‐solid substances that
undergo permanent changes in chemical composition
during heating to give hard and infusible solid mass are
called thermosetting polymers due to the extensive
cross‐linkage of molecules. Bakelite (11),
urea‐Formaldehyde (16), for example (Fig. 7).
Current practices are largely unsustainable in the
generation and disposal of synthetic polymers, causing
significant global polymer contamination and enormous
loss of value for materials. There are a number of
different research fronts that Produce polymers that
have closed‐loop life cycles. These serious
environmental and economic challenges must be
addressed (Fig. 8)[8].
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Fig. 7: Thermosetting polymers
Fig. 8: Illustrations of the economics of linear and new
economics frameworks in circular materials
The utilization and fabrication of biodegradable
polymer materials for life use have improved significantly
during the past few years. These materials have complex
physical, chemical, biological, biomechanical and
degrading properties and are therefore favorably prone
to degradable polymer implants. A wide range of
biopolymers is studied for different applications, both
natural and manufactured, which are capable of
hydrolytic or enzymatic deterioration[8].
APPLICATIONS OF POLYMERS
Polymers are one of the most interesting materials
of today's age in nearly every sphere of life. Polymers are
either available directly in nature or chemically produced
and employed according to specific uses. Advances in
polymer research and the use of new polymers have
helped create the special characteristics of polymers
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 ACE J. Clin. Chem. Lab. Med., 1 (2): 7‐17, 2021
Fig. 9: Biopolymers
extensively. Various kinds of polymers have been and will
be a core in numerous applications in several of the
advanced pharmaceutical research conducted
worldwide[9]. Some of them can be listed with various
polymer applications.
Biopolymers: More and more people are trying to
conserve our environment by using environmentally
sustainable natural green materials and using
decomposition‐friendly products which are fast gaining
in popularity. Biopolymers are made by living organisms
such as alginate and carrageenan which comprise
naturally occurring polysaccharides extracted from sea
algae[10]. It is found in insects and crustacean shells as
well as in numerous fungi, algae and yeast[11]. As
monomeric units, sugars, amino acids and nucleotides
make up biopolymers cellulose, starch and chitin are all
examples of biopolymers. There are a wide variety of
biopolymers and their derivatives and they are vital to
life. Depending on the application, they exhibit the
features of a beautiful and increasingly vital one. Proteins
and peptides can be separated from these biomaterials
as can polysaccharides and monosaccharides such as
cellulose and starch[12] (Fig. 9).
Smart polymers: They can undergo reversible and
considerable physical or chemical changes in response to
modest environmental factors, like temperature, pH,
light, magnetic or electric fields or ionic effects. In the
biomedical industry, smart polymers have very promising
applications, such as therapeutic agent delivery systems,
tissue engineering scaffolds, cell culture support,
bioseparation instruments, sensors[13]. Smart polymers
are attracting researchers to develop new delivery
mechanisms for drugs. In reaction to tiny changes in
environmental parameters such as pH, dual stimuli, light,
temperature and phase transition, smart polymers
undergo reversible physical or chemical changes that
boost their value. As a result, smart polymers provide
intriguing solutions for medication administration, gene
therapy, actuator stimulation, and protein folders[14].
Advantages of smart polymers: Patients comply
better with smart polymers because they are
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Fig. 10: Poly (methacrylic acid‐g‐ethylene glycol)
P(MAA‐g‐EG)
non‐thrombogenic, biocompatible, flexible, solid and
strong. They also maintain drug stability and maintain
drug levels within the therapeutic window[15].
Classification of smart polymers
PH sensitive smart polymer: Changes in pH cause
polyelectrolytes to accept or discharge protons[16]. Poly
(methacrylic acid‐g‐ethylene glycol) P(MAA‐g‐EG)
prepared microparticles (Fig. 10) loaded with Glucose
sensors exhibited Acidic media generate interpolymer
complexes that dissociate in neutral and basic
environments which is a unique pH‐responsive feature.As
a result of the development of interpolymer complexes
between protonated pendant acid groups and etheric
groups on the graft chains, methacrylic acid copolymer
networks grafted with polyethylene glycol show
reversible swelling activities. The decomposition of
P(MAA‐g‐EG) gels containing PEG grafts resulted in
significant insulin release in vitro[17, 18].
When the net charge of the polymer molecule is
decreased, the polymer transitions from a soluble to an
insoluble state. In order to lower the macromolecule's
hydrophilicity, the pH is changed to neutralize the
charges on it. The copolymer of methylmethacrylate and
methacrylic acid (18) precipitates from aqueous solutions
when acidified to roughly a pH of 5, however, it is
soluble at low pH but occurs in an alkalin. pH‐sensitive
smart polymers with reversible transitions have
been produced as a result of monomer
copolymerizations[19, 20] (Fig. 11).
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Fig. 11: The copolymer of methylmethacrylate and
methacrylic acid
The mixing ratio of the copolymer's components can
be adjusted to manage the medication release site.
Example: The methacrylic acid copolymer A‐NF and B‐NF
copolymers (1:1), also known as methacrylic acid
copolymers of type A‐NF. As an excipient, it is used in
pharmaceutical manufacture. Pharmaceutical
compounds are granulated into powder form to control
release and site‐specific medication administration is
performed with it. A frequent route for its release in the
gastrointestinal tract is through the jejunum.
Temperature sensitive smart polymers: Some polymeric
systems are temperature sensitive. When heated,
these polymers undergo a gel‐to‐gel change that can be
exploited to deliver medicinal compounds in vivo. In this
type of system, water typically has a critical solution
temperature at which the polymer and solution process
is adjusted according to its composition. As a function of
ambient temperature, many polymers demonstrate
sudden changes in their solubility. This property has been
used to produce aqueous solutions of these polymers
that, in response to temperature changes, undergo
sol‐gel transition. Heat‐sensitive polymers include Poly
(N‐alkyl substituted acrylamide), Poly (N‐isopropyl
acrylamide)(20) and Poly (N‐vinyl isobutyramide)(21)[21]
(Fig. 12).
Phase sensitive smart polymers: According to
researchers, using phase‐sensitive smart polymers,
biocompatible formulations for regulated protein
distribution in a conformationally stable and
physiologically active state can be developed. Comprising
several advantages over other systems such as easy
manufacturing, lower conditions of production for
vulnerable medicinal molecules, and high load capacity,
these smart polymeric systems offer many[22].
Some applications of pharmaceutical polymers:
Eudragit® is a commercial polymer derived from poly
(methacrylate) that is used for many purposes in the
pharmaceutical field. It is available in two varieties‐
Eudragit® E 100 and Eudragit® E PO(22). Both are used as
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Fig. 12: Temperature sensitive smart polymers
Fig. 13: The pharmaceutical polymers:
coating materials to avoid hydrolysis effects or to
improve the organoleptic aspects of pharmaceutical
tablets[23]. These materials are usually co‐polymers in a
ratio of 2: 1: 1 from the dimethyl aminoethyl
methacrylate groups, butyl methacrylate and methyl
methacrylate[24] (Fig. 13).
The Eudragit® E 100 and Eudragit® PO commercial
copolymers come from amino methacrylate groups,
under acidic circumstances. The groups are ionizable or
degradable via hydrolyte polymer structure. These two
recycled polymer materials have been chemically,
physically and surface‐modified according to Eudragit® E
100 & Eudragit® E‐PO. Acidic conditions have been used
to solubilize and dry polymers in commercial
products.The polymeric materials were found to be
highly ionized even without hydrolysis of the esterified
groups. In outre, the material's flow properties and
solubility in aqueous solutions at pH>5 have been
improved while its hydrophobicity has been preserved.
(Fig. 14, 15)[25].
BMP‐2 has received much attention for its bone
mobility but due to its instability and harmful effects, its
use is limited. The complication with heparin is a
promising way to reduce the BMP‐2 dose, as heparin
improves the bone conductivity of BMP‐2. However,
heparin's anticoagulant property has limited therapeutic
use. Four compounds having polycarboxylate groups
(PAA, PMAA, PAsp and PGlu) (Fig. 16) were selected
utilizing alternate polymers by Terauchi and his team.
BMP‐2 was examined for heparin‐like activity and
its ability to alter bone conductivity. When these
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Fig. 14: Protonated of Eudragit® E 100 and PO

Fig. 15: Processed polymers EuCl‐E‐100 and EuCl‐E‐PO

Fig. 16: Chemical structures of polycarboxylates where n indicates the degree of polymerization

polycarboxylates were combined with BMP‐2, they
generated multi electrolyte complexes. Comparing
polycarboxylate/BMP‐2 complexes to heparin/BMP‐2
complexes, bone differentiation performance was
investigated. Consequently, the PGlu/BMP‐2 complex
displayed the highest alkaline phosphatase activity,
which is a hallmark of bone differentiation and fast
mineralization at the initial stages This suggests that PGlu
could replace heparin in BMP‐2‐induced bone
regeneration[26].
Pectin (23) has very strong gel‐forming properties
and is a polysaccharide that has historically seen major
applications in the food and pharmaceutical industries.
A novel tablet formulation has been developed targeting
the colon with pectin as the carrier and diltiazem
hydrochloride and indomethacin as the model drug[27].
In vitro research has shown that the prepared dosage
forms have the ability to release the drug mainly into the
colon and not into the stomach and small intestine.
Pectin can be used efficiently to target both
water‐soluble and insoluble drugs[28, 29] (Fig. 17).
In pharmaceutical research and production,
synthetic and natural polymers play a vital role.From
inert bulk excipients to sophisticated drug delivery
methods, polymers have a wide range of pharmaceutical
applications. Pharmacologically inert polymers, such as
those utilized in drug delivery, are currently the most
often employed polymers. When it comes to drug

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 ACE J. Clin. Chem. Lab. Med., 1 (2): 7‐17, 2021
23
Fig. 17: Polymers_based therapeutic
Polymeric drug Poly drug
Poly plex
Polymer‐drug Polymer‐protein
Polymeric
conjugate conjugate micelle
Fig. 18: Polymer’s advantages in drug delivery
applications
delivery, polymers provide a lot of advantages including
controlled drug release, a customizable pharmacokinetic
and biodistribution profile, as well as enhanced drug
protection (Fig. 18)[30].
These can be inert bulk excipients, or they can be
complex drug delivery systems used in pharmaceuticals.
Currently, polymers are generally used in applications
where they are meant to be pharmacologically inactive
and actually supply small molecules or the
macromolecule. The benefits of polymers in
drug‐delivery applications including management of drug
release, the customizable profile of drugs
pharmacokinetics and biodistribution as well as the
better protection against drugs, are surely varying
(Fig. 18)[30].
Polymeric drugs with conventional small molecule
drugs will add many possible benefits to the
development of drugs that are not readily available.
Macromolecular targets are the most often investigated
biological targets for therapeutic treatments. Multiple
interactions dictate whether signaling pathways are
activated or inhibited as well as whether targets are
bound. Like protein macromolecules, polymers have
multivalent properties that are difficult to combine into
small molecules[31].
Immediate‐release dosage forms: Microcrystalline
cellulose is commonly used in tablet formulations of
extremely active low‐dose drugs as an alternative to
carbohydrates as diluents. The addition of polymers such
as polyvinylpyrrolidone (24) and hydroxypropyl
methylcellulose (25) in tablet formulations before tablet
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24
25
Fig. 19: The addition of polymers
manufacturing improves flow and compaction
qualities[32]. Many of the polymeric excipients used are
often the same as those used in immediate‐release
tablets to bulk out capsule fills. Gelatine has been used
for hard (two‐piece) and soft (one‐piece) capsules almost
exclusively as a shell material[33]. HPMC has recently been
produced and approved for the development of hard
(two‐piece) capsules as an alternative material[32]
(Fig. 19).
Modified release dosage form: Polymers have been
tested for their ability to extend drug stay in the stomach
by binding to the mucous lining of the stomach and
floating overthe stomach contents to achieve mucosal
adhesive low‐density gastric retention[33].
Extended‐release dosage forms: In order to retain a
therapeutic impact, prolonged and continuous release
dosage forms prolong the time that systemic medication
levels are within the therapeutic range and thereby
decrease the amount of doses that the patient must
receive, thus improving compliance. Water‐insoluble
polymers, such as cellulose derivatives, cellulose acetate,
and polyvinyl derivative polyvinyl acetate (Fig. 20) are
most commonly used in extended‐release
applications[33].
Polymeric drugs with anti‐cancer activity: Except for
hematological cancers, cancer is characterized by
uncontrolled cell growth and the absence of cell death,
resulting in an irregular cell mass or tumor. It appears
that cancer is the world's second‐largest cause of death,
after cardiovascular disease, despite substantial
advancements in cancer treatment[34]. Particularly when
triggered by endogenous or exogenous stimuli, smart
polymeric nanocarriers can improve therapy efficiency by
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 ACE J. Clin. Chem. Lab. Med., 1 (2): 7‐17, 2021
Drug
Slowly dissolving
polymer
Water influx
Fig. 20: Diagrammatic representation of coating
dissolution sustained system
delivering anticancer drugs locally, briefly and at
controlled doses. To take it a step further, by molecularly
imprinting chemotherapy into the polymer matrix, it is
feasible to not only significantly boost the loading power
of polymeric carriers but also to improve their drug
release kinetics and stimulus response[35].
A sequence of structurally related copolymers of the
1:2 alternating divinyl ether and maleic anhydride
(DIVEMA) cyclocopolymer Antitumor characteristics were
identified. The synthesis and structures of these
copolymers and their efficacy as antitumor agents are
discussed[36]. Polyacrylic acid, polyvinyl sulfate and
polyamido amines are examples of synthetic polymers
that were influenced by (DIVEMA's) early production.
Many of these polymers have shown antitumor activity
in animal models[37, 38].
Polymeric drugs with antiviral activity: The coordinated
action of several surface epitopes helps viruses dock to
host cells and enhance a cellular entrance, replication of
their own genetic material, and assembly of new virus
particles, all of which are necessary to complete the
usual viral replication cycle. Contrary to small molecule
antivirals which can intervene at multiple stages of viral
replication, fusion inhibitors, reverse transcriptase
inhibitors, or integrase inhibitors, antiviral polymers are
primarily designed to interfere with viral host cell
interactions[39]. The antiviral action of polymers can be
attributed to either steric viral surface shielding or
competitive suppression by a large molecular weight and
a multivalent binding. Either the virus is connected to a
polymer or the host cell is connected to receptors
necessary for viral docking and entry, resulting in a
decreased viral entrance (Fig. 21)[40].
Influenza treatments derived from polymer materials:
Due to multivalent interactions between SA and its
hemagglutinin HA receptor, the Whiteside laboratory
found that linear polyacrylamides with pendent sialic
acid groups strongly inhibited influenza virus‐induced
erythrocyte adhesion[41]. Polymeric inhibitors with
ACE Journal of Clinical Chemistry and Laboratory Medicine |ISSN: 2520‐3738 |Volume 1 |Number 2 |Page No. 7‐17 |2021
Virus Masking viral
epitopes
Blocking host
cell receptors
Fig. 21: By inhibiting connections between the virus and
the host cell, antiviral polymeric medicines
prevent viral entrance into the body
(a)
(b)
(c)
Fig. 22: Polymeric drugs with antimicrobial activity
varying molecular weights have a 1,000‐to‐a‐million‐fold
better binding affinity with the viral surface than the
monomer. Hydrophobic linkers greatly boost
multitalented binding and antiviral activity[42]. Further
research revealed that H1N1 was resistant to the
antiviral drug[43].
Polymeric drugs with antimicrobial activity: For the
treatment of infections caused by rapidly evolving
multidrug‐resistant bacterial strains, new therapeutic
approaches are urgently needed. Bacterial surfaces are
usually targeted by polymeric antimicrobials, either by
direct membrane damage, limiting interactions with host
cells or by decoration with identifiable moieties to
combat phagocytosis (Fig. 22). In addition to directly
damaging the bacterial membrane, polymeric
medications also inhibit the bacteria from interacting
with host cells and they enhance the cell's ability to
phagocytose germs[44].
CONCLUSION
Progress in the field of polymer research and the
introduction of novel polymers have helped to achieve
the extensive development of specialized polymers. In
drug delivery, polymers offer a variety of advantages,
including the regulated release of medicines, a
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 ACE J. Clin. Chem. Lab. Med., 1 (2): 7‐17, 2021
customizable pharmacokinetic and biodistribution
profile. Smart polymers, therefore, encourage scientists
to create new medication delivery strategies. Smart
polymers are a promising medium to improve the
delivery of targeted drugs and gene therapy. Polymeric
medicine provides prospective advantages as therapies
resulting from the ability to link the advantages of small
molecules medicine’s development processes readily to
the advantages of protein therapies commonly linked to
large molecules. A lot of research has been carried out
that confirms the efficacy of polymeric medicines as
anti‐cancer agents, anti‐microbials and antiviral agents as
they have been effective. Much research has been
undertaken to confirm that polymeric medicinal products
are effective as anti‐carcinogenic agents, anti‐microbials
and antiviral agents.
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