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Preface
Smart polymers are becoming increasingly more popular as scientists learn about the
chemistry and stimuli that increate changes in polymer structures and devise ways to
take advantage of and control them. Smart polymers have a lot of special characteristics
like pH sensitive, thermo-responsive, light sensitive and magnetic sensitive. New
polymeric materials are being chemically formulated that sense specific environmental
changes in drug delivery, wastewater treatment, oil recovery, texitle, catalysis in the
reaction and some biotechnology. Then this report will present and discuss for the
synthesis and applications of smart polymers.
Contents
Chapter I: OVERVIEW OF THE SMART POLYMERS ................................................................ 3
1. Introduction ............................................................................................................................... 3
2. Classification .................................................................................................................................. 3
a. Coacervation/Precipitation ................................................................................8
A B
Figure 1: Structure and states depending on the ionization of the ionic chain
groups of pH - responsive polyelectrolytes (A) poly(acrylic acid) and (B)
poly (N,N-dimethylaminoethylmethacrylate)
The polyacids or polyanion are pH sensitive polymers in their structure contain the
acidic groups. The acidic groups accept protons at low pH values and release protons at
high pH values [36]. The pH increases the polymers lead to the structure of polymer
reduce for negatively charged in acidic group. At low pH, smart polymers are able to
create a chemical connection with the heavy metal ions in wastewater. For example,
Weak polyacids accept protons at low pH and release protons at neutral and high pH.
Poly acrylic acids (PAAc) and poly methacrylic acids (PMAAc) are commonly used
pH-responsive polyacids. As the environmental pH changes, the acidic group undergoes
ionisation at specific pH called as pKa. Therefore, polyanion can apply in wastewater
treatment such as adsorption.
hydrophobic and hydrophilic interactions between the polymer chains and the aqueous Commented [A1]: file:///C:/Users/ADMIN/Downloads/Re
sponsive_Polymers_in_Controlled_Drug_Delivery.pdf
medium. Temperature-sensitive polymers include low critical solution temperature
(LCST) and upper critical solution temperature (UCST). The polymers that become Commented [pp2R1]:
insoluble above a critical temperature called the lower critical solution temperature Commented [pp3R1]:
(LCST) and the polymers that precipitate and undergo phase change below a critical Commented [pp4R1]:
temperature called as the upper critical solution temperature (UCST). The first class of
polymers, when polymers exhibiting LCST are dissolved in an aqueous system, they are
completely dissolve at normal temperature, but they become insoluble when we increase
in temperature to above a critical value and then they show phase separation. The most
common of these is poly(N-isopropylacrylamide) (PNIPAAm). PNIPAAm has a lower
critical solution temperature, LCST of around 32°C, a very useful temperature for
biomedical applications since it is close to the body temperature (37°C). The second
class of polymers are UCST, the temperature above which these polymers remainsoluble
in solution and as temperature of the solution falls below critical value, phase separation
occurs, for example, poly(acrylic acid) (PAA), polyacrylamide (PAAm), and
poly(acrylamide-co-butyl methacrylate).
2.3 Light sensitive smart polymers
Photosensitive polymers is a polymer that changes its properties when exposed to light.
The molecular change by light is expressed in a change of material properties such as
shape, humidity, solubility, optical properties, conductivity, adhesion, etc. Light-control
has a lot advantages that allows remote control without physical contact or a mechanical
apparatus. Light is a external stimulus for drug delivery systems because it is
inexpensive and easily controlled.
2.4 Magnetic sensitive smart polymers
Some polymers can associate with nano or microsized solid materials and apply for the
new technology. In recent years, many scientists have studied for the application of
magnetic field-responsive smart polymer composites especially drug delivery. The
properties of magnetic sensitive smart polymer usually apply in drug delivery. Some
metals like cobalt, ferrite and carbonyl iron are magnetic. Therefore, these metals are
usually used to create the magnetic drug carries and they are biocompatible, non-toxic
and non-immunogenic [38]. Moreover, the popular polymers like as Poly(3,4-
ethylenedioxythiophene) (PEDOT) and its derivatives PEDOT poly(styrene sulfate)
(PEDOT:PSS), PEDOT:biopolyme and poly(3,4-Propylenedioxythiophene) (ProDOT)
and which are most successful in bioelectronics and have been used as electrode for
electro-physiolgy, organic chemical transistors (OECTS), organic electronic ion-pump
(OEIP), electronic textiles and electronic skin.
The
structure of a molecular chitosan had a lot of special properties of amino group (-NH)
and hydroxyl (-OH). We were capable of bonding with many metals to create the
compound called chelate. Amino groups in Chitosan were the higher free energy.
Therefore, chitosan can dissolve in the organic acid and some inorganic acid. Moreover,
chitosan can be hydrolyzed because the molecule contained many glucoside bonds and
peptide bonds. Chitosan were strongly in base solution but we can be hydrolyzed in acid
solution. When Chitosan were completely hydrolyzed in acid solution, we transformed
from monosaccharide-D-glucosamine or oligosaccharide. Chitosan was synthesized
from many raw materials as crust, crab shells, cuttlefish and some types of crustacean
shells. Chitosan has the characterization of smart polymer by properties of pH
sensitive.Thus, Chitosan is applied for drug delivery.
There are mainly three methods to synthesis of nanochitosan in drug delivery:
- Coacervation/Precipitation
- Emulsion-droplet coalescence
- Ionic gelation
a. Coacervation/Precipitation
b. Emulsion-droplet coalescence
Nano particle
Extraction particle
c. Ionic gelation
Valve
Chitosan solution
Nano – Chitosan particles
Step 1: Initiation
Step 2: Propagation
Step 3: Tetramination
Combination of radical species
Figure 9: The polymetric mechanism of acrylamide by Chemistry Libretexts
Figure 10: The diffuse polymerization of acrylamide [40] Commented [P5]: Wuxiangmei et al, Studies on the
absorption of Amino Metylene phosphonic
acid resin for Homium (III), Journal of rare earth, 2003,
21(6), 613
Zn(NO3)2
NaOH
Neutralizing to pH values of
12
Mixing and heating to 70 °C
on magnetic stirrer
Separating the solids by
centrifugation
Powder
NiPAM, ZnO
nanoparticles, BIS, SDS
and deionised water
Drying
Powder
The ZnO nanoparticles and deionised water were mixed well and added to PNIPAAm.
NH4OH was then quickly added to the solution, which immediately produced a
precipitate. The suspension was then stirred for 30 min at 70 °C. Then the ZnO-
PNIPAAm was separated out by centrifugation (12,000 rpm for 30 min) and washed
with deionised water. The ZnO-PNIPAAm dried using a rotary evaporator (25 mbar at
40 °C). The resultant powder was stored in the dark at room temperature [42].
ZnO nanoparticles,
deionised water and
PNIPAAm
Powder
ZnO nanoparticles,
deionised water and
PNIPAAm
Powder
In human melanoma A375 cells, DOX is located of different particle and controll
formulations in melanoma. Moreover, the oral drug delivery is a important process
because pH (high acidic stomach), the presence of enzymes impact to the oral drug
delivery, chitosan nanoparticle have a lot of benefit such as small particle size, large
surface and potentially a modifiable surface. According to particle size is the precent of
dissolution rate of drugs increasingly. Thus, chitosan nanoparticle can increase the
stability of acid labile drugs than other delivey system such as liposomes and lipid.
Figure 16 shows the adsorption of chitosan NP is better than other drug delivery system
in stomach.
2. Application of smart polymers in thermo- responsive .
Figure 17: The flowchart shows in the adsorption drug by using chitosan NP
Thermo- responsive and mechanic of smart polymers apply for oil recovery. Crude oil
is an important fuel in the industry to use for many different purposes. Biofuels like as
ethanol and biodiesel are aslo used as petroleum products, mainly in mixture with
gasoline and diesel fuel. However, crube oil is a non-renewable fuel.Thus, the amounts
of crude oil has gradually decreased by the exploited excess to serve for many different
purposes. Therefore, oil recovery is very necessary to maintain the sources of crude oil
in the world. With the development of science, smart polymers are applied in oil
recovery by them have a lot of sensitve such as polymer addition increase the viscosity
of aqueous phase and modifies the ratio of water to oil [44] and increase amount of oil
recovery [45]. There are a lot of way to improve the efficiency of oil crube by changing
their chemical structure. The common polymer like as polyacryamide usually apply in
oil recovery. However, polyacrylamide has some limitations, such as high surface
absorption, undersiable plugging, polymer concentration limitation, thermal,
mechanical and bacterial degradation. Therefore, polyacryamide mix with other
polymers to increase viscocity of aqueous phase. Some smart polymers of polymers like
as Acrylamide- Styrene Copolymer presented as Figure 17
When water is injected into a reservoir, it seeks the path of least resistance (usually the
layers of highest permeability) to the lower pressure region of the reservoir. If the oil in
place has a higher viscosity than the injected water, the water will finger through this oil
and result in a low sweep efficiency. Addition of polymer into reservoir increases the
viscosity of water and reduces relative permeability of water in the reservoir then
increases oil recovery due to increase of fractional flow. If the mobility ratio is one or
slightly less, the displacement of the oil by the water will be efficient. If the mobility
ratio is greater than one, the more mobile water will finger through the oil and leave
behind regions of unswept oil.
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