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In this article, the basic principles of core–shell polymers (CSPs) such as definitions, classifications and
applications are critically investigated. Introduction of CSPs characterization techniques, such as
1 13
Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), H and C Nuclear
Magnetic Resonance Spectroscopy (NMR), Small Angle Neutron Scattering (SANS), Nonradioactive Direct
Energy Transfer (NRET), Photon Correlation Spectroscopy (PCS) and Dynamic Light Scattering (DLS), are
highlighted. In addition, preparation techniques and recent studies of CSPs are briefly discussed. The
factors that affect core-shell morphology and properties such as cross-linking radical penetration and
diffusion, processing techniques and monomers polarity are considered. Core-shell polymers are structured
Received 18th March 2013,
Accepted 31st May 2013
composite particles consisting of at least two different components, one at the center as a core and
surrounding by the second as a shell. Smart properties are considered to be the most desirable
DOI: 10.1039/c3ra41296b
characteristics that allow this class of polymer to be used in various applications, particularly in biomedicine
www.rsc.org/advances as drug delivery systems.
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divided into NIPAM-based and non-NIPAM-based materials MMA, St. The combination of hydrophilic and hydrophobic
and non-hydrogel CSPs can be divided into non-aqueous, monomers is useful in order to produce responsive CSPs. Babu
organic–inorganic hybrid and single-molecular particles. et al. developed novel core-shell microgels of poly(acrylamide-
Depending on size, spherical CSP can be divided into micro co-methyl methacrylate) (P(AAm-co-MMA)) for controlled
and nano as shown in Fig. 2. This section of the paper release (CR) applications.15 Xiao et al. developed positively
emphasizes CSP hydrogels and non-hydrogels. thermosensitive microgels of poly(acryamide-co-styrene)
(P(AAm-co-St)) core and interpenetrating polymer network
2.1 Core–shell polymer hydrogels (IPN) shell of poly(acrylamide)/poly(acrylic acid) (PAAm/
PAAc).14 Ramli et al. synthesized poly(styrene-co-methyl
CSP hydrogels are particles with a hydrogel shell surrounding
methacrylate) (P(St-co-MMA)) core and poly(acrylamide-co-
a non-hydrogel core or particles composed entirely of hydrogel
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on the surface of the particles.42 Silica is the most used tion of smaller cationic polymer particles onto larger anionic
inorganic material for core–shell NPs production. This is due polymer particles, followed by heat treatment has also been
to the ability of silica to prevent core aggregation and outsider reported (III). Block copolymers can also be used to produce
environmental attacks and the wide practical uses of silica in core–shell type polymer nanospheres via block copolymeriza-
separation, biotechnology, medicine, chemosensors and coat- tion (IV).
ing. The silica shells provide an additional benefit of
facilitating biocompatibility and biofunctionalization. In 3.1 Emulsion polymerization
addition, core materials in organic–inorganic core/shell NPs Emulsion polymerization synthesized process is commonly
can be a dye, fluorescent conjugated polymer and co- or used to produce water based resins with a variety of
terpolymer, etc.53 physicochemical and colloidal properties. The reaction system
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Single-molecular particles, also known as unimolecular is characterized by emulsified monomer droplets (ca. 1–10 mm
micelles, are non-crosslinked CSPs consisting of amphiphilic in diameter, 1012–1014 dm23) dispersed in a continuous
block or graft polymers in which hydrophobic and hydrophilic aqueous phase with the assistance of an oil-in-water surfactant
segments are covalently connected with the dendritic or at the very beginning of polymerization. Monomer swollen
hyperbranched core. Single-molecular particles demonstrate micelles (ca. 5–10 nm in diameter, 1019–1021 dm23 in number)
a micellar behavior as a single molecule54–57 and are usually may also exist in the reaction system, provided that the
prepared by a multi-step process, such as combination of concentration of surfactant in the aqueous phase is above its
alkyne polycyclotrimerization and alkyne-azide ‘‘click’’ chem- critical micelle concentration (CMC). Most of the monomer
istry,54 tandem coordination, ring-opening and hyperbranched
molecules dwell in giant monomer reservoirs (i.e. monomer
polymerization,58 self-condensation and ATRP.55,56,59 Single-
droplets). The polymerization is initiated by the addition of
molecular particles have attracted great attention from
initiator.69 The emulsion polymerization technique is a
scientists due to their potential in nanotechnology and
commercially and technologically important reaction system.
biomedical applications, such as a signal-molecular template,
Currently, emulsion polymerization is the beginning of a
live-cell imaging, drug carrier and drug release.55,57,59–61
worldwide industry. This technique continues to grow through
its versatile reaction and its ability to tailor the properties of
the emulsion polymer produced.68
3. Preparation methods of core–shell Emulsion polymerization can be carried out using contin-
uous, batch and semi-batch process.68 Batch processes are of
polymers
limited versatility for producing emulsion and are mainly use
CSPs are typically prepared by a series of consecutive in academic research with simple reaction formulations.
emulsion, dispersion or precipitation polymerization Accordingly, novel polymerizations were developed to replace
sequences with different monomer type. Usually, CSP particles the batch process, such as semi-batch continuous process70
are prepared by multi-step procedures using seed particles as a and pre-emulsified semi-continuous seeded emulsion poly-
core material, where the second or third stage monomer is merization method.71 Semi-batch is a versatile process and
polymerized in the seed latex particles. These seed particles mainly use in industry. The process is widely used for all
may be prepared in a separate step, or form in situ during the emulsion polymerization due to the highly exothermic nature
polymerization.3,23,62 These techniques however have the of free radical polymerization and limited heat removal
significant limitations of being both expensive and time- capacity in big scale reactors.69 Moreover, semi-batch process
consuming, due to the multi step procedures. One-stage offers stringent quality control to produce emulsion products
reaction is a facile method to prepare polymer particles with with controlled particle morphology and polymer composition
and allows influence on the properties and applications of the
core–shell morphology.63
emulsion products.69 Any properties, such as composition,
Dispersion polymerization is a technique which produces
polymer architecture, particle size distribution, particle mor-
polymer particles in the range of 1–15 mm. The formed
phology and molecular weight distribution, can be tailored by
polymers are insoluble in continuous phase (e.g. ethanol,
this process.72,73
methanol, water).64 Dispersion polymerization is considered a
The most significant difference between batch and semi-
class of precipitation polymerization. However, larger particles batch emulsion polymerization is the polymerization ingre-
and irregular shape of polymer particles were produced in dients, such as surfactant, monomer, water and initiator, can
precipitation polymerization.65,66 Moreover, emulsion poly- be fed to the process reaction system during the polymeriza-
merization is the main process for the preparation of tion as depicted schematically in Fig. 5. Consequently, the
commercial emulsion, which involves a monomer that has residence time of particle nuclei distribution in semi-bath
limited solubility in water.67 The particle diameter is typically emulsion polymerization process is broader. These features
within the range of 1–10 mm.68 Fig. 4 illustrates common make semi-batch emulsion polymerization kinetics and
methods to prepare CSPs described by Li and Stover.5 Two- mechanisms more complicated in contrast with batch
stage emulsion polymerization (I) was the first general method process.69
developed to prepare CSP. CSP particles were also prepared by Semi-batch process allows two types of feed stream, M (neat
emulsion polymerization using reactive surfactants (II). The monomer) feed and E (emulsion) feed74,75 as shown in Table 1.
formation of core–shell particles by step-wise hetero-coagula- In M feed process, the reactor is initially charged with the
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monomer, water, emulsifier and initiator and polymerization (1) Good temperature control with extra cooling of poly-
is carried out by feeding the remaining monomer continu- merization process.
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ously. However, in E feed process, all of the monomers used (2) Easy to control polymerization rate by keeping process
are pre-emulsified.72 ‘starved’.
The beneficial effects of adding monomer and other (3) Flexible control of molecular weight.
ingredients continuously are: (4) Good polymer composition control.
Table 2 Monomer/materials that form CSP, preparation methods of CSP and their classification
Materials
Core Shell Preparation method Classification Ref.
83
St St, MPS Emulsion NPs
132
2VP NIPAM Dispersion Microgel
4,115
NIPAM, AAc NIPAM Precipitation Microgel
9
NIPAM, AAc/AFA NIPAM, APMA Precipitation Nanogel
NIPMAM, AAc/AFA NIPMAM, APMA
32,79
NIPAM AAc Emulsion Nanogel
10
NIPMAM NIPAM Precipitation Microgel
133
St, CdS/ZnS MMA Miniemulsion Nanoscale
134
TBA St Emulsion Microgel
135
MMA St Emulsion Microparticle
7
(PBA/MMA/MAA) PSt/AN, PBA/MMA Emulsion Microparticle
136
PI AAc/AAm Self-assembly Nanogel
36
NIPMAM NNPAM Dispersion Microgel
15
MMA AAm Emulsion Microgel
14,90
AAM, St AAm, AAc Emulsion Microgel
137
MMA St Emulsion Microparticle
138
NIPAM CMCS Emulsion Microgel
139
NIPAM NIPAM, APBA Precipitation Microgel
52
Silica PSt Emulsion NPs
11
NIPAM 4VP Dispersion Nanogels
89
NIPAM NIPAM/NIPAM, BMA Precipitation Nanogels
1
St PFA Emulsion Microparticle
80
PDVB, St VAc Emulsion Microparticle
62
BMA, PheMMA NIPAM, AnMA Precipitation NPs
82
AN NIPAM Emulsion Nanogel
81
NIPAM 2MBA Emulsion Nano/Microgel
53
SAM Silica Emulsion NPs
5
DVB CMS Precipitation Microgels
25,119
NIPAM NIPMAM Emulsion Microgels
110
NIPAM SA Emulsion Microgels
63
St Py Emulsion Nanoparticle
30
NIPAM, St NIPAM Emulsion Microgel
24
St NIPAM Emulsion Microgel
122
NIPAM PEI/Chitosan Dispersion Microgel
107
BMA, An/Phe PBBT, An/Phe Emulsion NPs
92
St NIPAM Photoemulsion Microgel
140
MMA St Dispersion Microparticles
141
NIPMAM NIPAM, AAc Precipitation Microgel
126
NIPAM St Emulsion Microgel
91
BA BA, St Emulsion Nanogels
125
AL CH L-b-L NPs
33
St, MMA AAm, AAc Emulsion Microgel
44
CMONS Silica Spray-drying NPs
46
ClO4, BF4, PF6 PEDOT Electro-polymerization NPs
47
DTH-Fe3O4 Silica Silanol hydrolysis NPs
54
PF PEG Polycyclotrimerization, ‘‘click’’-chemistry
142
NIPAM, HFMA PEGMEMA Emulsion Microgels
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Fig. 7 Schematic representation of the formation of the core–shell NPs by semi-batch emulsion polymerization. Reproduced from ref. 83 by permission of American
Chemical Society.
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Fig. 9 Schematic illustration of the synthesis route of single-molecular CSP multi-HPBPEA-g-PNIPAM. Reproduced from ref. 56 by permission of Wiley.
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Fig. 10 Schematic illustration of preparation of MMLCS emulsion and nanostructured polymer film. Reproduced from ref. 91 by permission of Elsevier.
polymerization, cross-linker is used to control the particle forces which compete with the interfacial forces to control the
morphologies and enhance the mechanical properties of the particle structure, which is very sensitive to the level of cross-
product.95 Cross-linking of the seed polymer creates elastic linking.96,97
Fig. 11 Schematic representation of the preparation of PSt–NIPAM core-shell particles by photoemulsion polymerization. Reproduced from ref. 12 and 92 by
permission of Elsevier and Wiley.
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Fig. 13 Free energy pathway for transforming a core–shell particle into an Fig. 15 Possible particle morphologies produced from differing radical pene-
occluded structure (OCC). Reproduced from ref. 96 by permission of American tration depth. Reproduced from ref. 100 and 104 by permission of Elsevier and
Chemical Society. Taylor & Francis.
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acid (MAA).104 Fig. 16 (A) SEM image of poly(DVB-55) microspheres (PP112-02) with porous
Karlsson et al. reported the results of adding MAA into shells prepared in a toluene : acetonitrile(40 : 60) mixture. (B) TEM micrograph
styrene seeds latex and second-stage polymers of isoprene– of PP112-02 microspheres having dense poly(DVB-55) cores and porous
styrene. The result showed that adding 10% MAA to the poly(DVB-55) shells. Reproduced from ref. 5 by permission of American
Chemical Society.
second-stage monomers resulting in the poly(isoprene-co-
styrene) moving to the outside of the particle, forming a
‘sandwich’ structure. When the acid was added to the seed
polymer instead of the second-stage, the structures resembled Lin et al. applied the staining technique with uranyl acetate
hemispheres.105 Fukuhara and Sundberg reported the results (UAc) to observe the distribution of the anionic (carboxylic
of adding MAA varing from 0–10% into poly(butyl acrylate-co- acid) functional group in the PNIPAM-based copolymers
styrene) (P(BA-co-St)) seeds lattices. Second-stage polymers microgels. Acrylic acid distribution was imaged in TEM
were either PMMA or less polar poly (butyl methacrylate) photograph as shown in Fig. 18. The anionic sites were
(PBMA). In the case of the poly(methyl methacrylate) (PMMA), selectively stained with UAc acetate to appear darker in these
the structure changed from a well defined core–shell (at 0% images.110
MAA) to an apparent homogeneous particle at 10% MAA. In
contrast, using PBMA led to changing the particle morphology 5.2 1H and 13
C nuclear magnetic resonance spectroscopy
from hemispherical (at 0% MAA) to an inverted core–shell at (NMR)
10% MAA.104,106 Solid-state NMR 1H spin-diffusion method (TEM) is used to
clarify the complex structures in the current latex system. This
characterization allows quantitative determination of the
5. Characterizations extent of coverage of the core by the shell polymer and the
interphase thickness. Mellinger et al. applied spin-diffusion
CSP properties mainly depend on the internal structure of the techniques, exploiting demagnetization and remagnetization
particles, therefore it is necessary to find the right method and effects in three-component system consisting of a PBA/PSt/
technique that are able to deliver information on the PAAc latex film containing residual water, as shown in Fig. 19
distribution of the polymers which form the core and the which showsa three-dimensional representation of the remag-
shell of the particles.107 netization process.111
Ishida et al. examined the structure of core–shell type
5.1 TEM and SEM polymer particles composed of PBA and PMMA using a magic
SEM and TEM are usually used to investigate the polymer angle spinning (MAS) system of solid-state 13C NMR as shown
morphology as these techniques can provide valuable detail on in Fig. 20. They found that the polymer particles of PBA/PMMA
the internal structure of core–shell particles.107 SEM and TEM (BM) do not have a typical core–shell type phase-separated
were used by Li and Stover to study the particle morphology of structure, but rather an incompletely phase-separated struc-
cross-linked core–shell polymer microspheres in terms of
diameter and homogeneities. The findings indicated that both
the core particles and the final core–shell particles have
spherical shape and smooth surface as shown in Fig. 16(A) and
16(B).5,108
Kirsch et al. investigated the particle morphology of poly(n-
butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) compo-
site latex particles using TEM and different staining techni-
ques. Preferential staining with ruthenium tetraoxide (RuO4)
and a Pt-shadowing technique was used to distinguish
between soft and hard phases. Fig. 17(A) shows that the PBA
rich phase appears darker than a PMMA phase which is not
stainable with RuO4 and Fig. 17(B) indicated that PBA particles Fig. 17 TEM pictures of samples with different soft to hard phase ratio
are almost completely covered by the PMMA phase and no contrasted by (a) preferential staining with RuO4 and, (b) Pt-shadowing
shadow is detectable.109 technique. Reproduced from ref. 109 by permission of Wiley.
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Fig. 18 Observation of ultrathin cross sections of copolymer particles stained with a 1% uranyl acetate (UAc) solution. Reproduced from ref. 110 by permission of
Wiley.
ture in which small PMMA domains are dispersed in the hydrogenated (50/50) P(St-co-MMA) seed. The resulting poly-
continuous PBA phase.112 mers possess a core–shell structure as determined by SANS
where the radius of the core is approximately 50 nm and the
5.3 Small angle neutron scattering (SANS)
shell radius 14 ¡ 6 nm.113
This technique can provide more detailed information of
internal structure of the entire CSP, such as the relationship
between temperature and the hydrodynamic radius depending
on scattering intensity. In addition, scattering data is used to
organize the density profile and the distance between the
center and the outer of the particles. SANS data obtained with
a core–shell microgel are shown in Fig. 21.25 SANS machine
allows us to cover a large q-interval (q is the magnitude of
scattering vector) ranging down to q-values usually probed in
light scattering experiments. Therefore, the machine is well
suited to characterize colloidal particles with rather large
diameters and crystals formed by these particles.24 Wai et al.
reported the SANS study of polymer particle morphology
formed by polymerization of trideuteromethyl (methyl-d3)
methacrylate in the presence of a well characterized core of
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(1)
Fig. 22 Comparison of the donor concentration profiles obtained for CS3 and
CS8 from the best fit of eqn (1) to the fluorescence decay data. Reproduced
from ref. 107 by permission of American Chemical Society.
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Fig. 26 (a) Schematic illustration of the mechanism for the preparation of core-shell poly (St/Py) particles. (b) Detailed reaction mechanism of pyrrole monomers via
Fe3+-catalyzed oxidative polymerization. Reproduced from ref. 63 by permission of American Chemical Society.
poly(N-n-propylacrylamide) (PNNPAM) and a core consisting of responsive behavior might be advantageous for new actuator
poly(N-isopropylmethacrylamide) (PNIPMAM). In the region designs and responsive coatings.36
between 25 uC and 41 uC, the response of the particles is Peng et al. studied a novel approach for preparing hollow
directly proportional to the temperature as shown in Fig. 29. PSt particles by seed emulsion polymerization. The particles
This material is of particular interest because its unique are composed of PNIPAM cores and PSt shells and became
hollow upon dehydration of the PNIPAM microgels. Hollow
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Fig. 28 (a) SEM images and (b) illustration of the ‘‘raspberry’’-shape of the structure of the core particle. Reproduced from ref. 33 by permission of Elsevier.
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Fig. 29 Linear temperature response. (a) Schematic illustration of a core-shell microgel which undergoes three regions of different swelling behavior (completely
reversible process). b, corresponding classification of previously mentioned regions in an exemplary Rh(T)-diagram of a core-shell microgel system with 10 mol% cross-
linked cores. In region I we find a restricted shell collapse, while region II covers the linear swelling behavior. Region III indicates the occurrence of an active core
collapse. Reproduced from ref. 36 by permission of Elsevier.
semiconductor quantum dots (QDs) have been incorporated The use of CSP microgels for controlled uptake and release
into the voids of colloidal crystals by in situ growth method. of active species has a great potential. Microgel particles are
However, the incorporation of QDs does not protect the QDs attractive for controlled uptake and release because they
from oxidation and the method does not allow the formation respond much more rapidly to external stimuli in comparison
of high quality QDs, known for low PDI and strong to macrogels, and they are highly stable to aggregation, at least
photoluminescence (PL). Accordingly, Fleischhaker and in their swollen state.132 The thickness of the gel layer offers
Zentel prepared composites PCs from CSP, which incorporated control over the size of the final shell formed. The responsive
highly fluorescent CdSe quantum dots (QDs) in the core by nature of the gel layer to external triggers, such as tempera-
modified miniemulsion polymerization. CSP of different ture, can be used to control their catalytic activity.149 Microgel
diameters have been self-assembled to colloidal photonic particles with temperature-responsive PNIPAM cores and pH
crystals (PCs) with photonic stop bands located in the visible responsive poly(4-vinylpyridine) (P4VP) shells prepared by Li
range of the electromagnetic spectrum. The controlled et al. showed that the shell does not significantly perturb the
combination of electronic confinement, originating from the temperature-induced volume phase transition of the core.11
QDs, and photon confinement, due to the periodic dielectric Accordingly, Bradley and Vincent improve the CSP properties
structure of the colloidal crystal, as it has been realized in this by introducing pH-responsive poly(2-vinylpyridine) (P2VP) as a
work presents a huge platform for the design and construction core and temperature-responsive PNIPAM as a shell. The
of novel optoelectronic devices based on PCs.133 uptake and release of an anionic surfactant from the microgels
has been investigated as a function of solution pH and
temperature. The results indicate that the surfactant mainly
interacts with the PVP core. The results indicate that
electrostatic attraction between the anionic surfactant and
the cationically charged core of the microgel particles is the
dominant mechanism for absorption of the surfactant into the
core–shell microgel particles.132
The use of polymeric systems particularly provides a clear
optimization to develop controlled release (CR)142,150 formula-
tions to achieve the desired therapeutic results at the target
site. Solubility of drug in the polymer matrix is an important
factor in controlling the delivery. One important step in the
development of CR drug delivery systems is the loading of the
Fig. 30 Preparation of hollow particles with PNIPAM microgels as the cores. drug into the polymeric matrix. Drug loading within the
Reproduced from ref. 126 by permission of Elsevier. polymer matrix depends upon the release, which involves
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outer shell–inner core combinations, the drug action would APBA Acrylamidophenylboronic acid
offer important new information to design improved core– APMA N-(3-aminopropyl) methacrylamide hydro-
shell microparticles for fine-tuning of drug release, as well as chloride
for a deeper understanding of the drug action mechanisms APS Ammonium persulfate
through the core–shell structures.15 ATRP Atom transfer radical polymerization
CSPs in paints and coating applications are used to BA Butyl acrylate
improve the hiding power of coatings and as pigments. The BAP Hyperbranched polymer
chief ingredients of shell in this CSP are styrene–acrylonitrile/ BF4 Boron
butyl acrylate/methyl methacrylate copolymer. These air voids BIBB 2-Bromoisobutyryl bromide
and non-pigmented emulsions are transparent to light, but BM PBA/PMMA
they have different refractive indices (RI; air – 1.0 and binder – BMA Butyl methacrylate
1.58, in general any binder has a RI in this range), causing BPEA 2-((2-bromopropionyl)oxy)ethyl acrylate)
opacity in the dried film of the emulsion paint. Incorporation 2BMA 2-Butyl methacrylate
of such a core–shell polymer in water based paints, together CC Cross polarization
with well dispersed titanium dioxide, will enhance the opacity CH Chitosan
of the paint. The optimum composition of shell in the CSP of ClO4 Chlorine
poly(butyl acrylate-co-methyl methacrylate-co-methacrylic acid) CMC Critical micelle concentration
(PBA/MMA/MAA) core and a poly(styrene-co-acrylonitrile) (PSt/ CMCS Carboxymethyl chitosan
AN), poly(butyl acrylate-co-methyl methacrylate) (PBA/MMA) CMS Chloromethylstyrene
shell was investigated by Khan et al. and was applied in CMONS a-[(4-Methoxyphenyl)methylene]-4-nitro-
emulsion paint as a paint binder.7 benzeneacetonitrile
3CMS 3-Chloromethylstyrene
CR Controlled release
9. Conclusion CS Core-shell
CSP Core-shell polymer
This paper presents a general overview of core–shell polymers CSPs Core-shell polymers
(CSPs). The combination of a core in the center surrounded by CuBr Cuprous bromide
the shell seems to have unique properties of both the raw CuCl Cuprous chloride
materials of the core and the shell. However, applications of DD Dipolar decoupling
CSPs are expanding in various areas such as impact modifiers, DDS Drug delivery systems
surface coatings, printing, catalysis, pollution control, sensing, DLS Dynamic light scattering
and drug delivery in biomedical applications. Morphological DOX Doxorubin
analysis of CSPs is the most important data that can provide DSB Diphenyl ether disulfonate
detailed information about internal structure which leads to DTH 3;5-di-tert-butyl-2-hydroxybenzaldehyde
an estimation of their properties. The environmental DVB Divinylbenzene
responses of CSPs, such as thermoresponse and pH sensitivity, EGDMA Ethyleneglycol dimethacrylate
are the most important characteristic for drug delivery
Fe3O4 Ferum Oxide
applications. TEM, SEM, NMR, SANS, NRET, PCS and DLS
5-FU 5-Fluorouracil
were used to provide important data in terms of the final
GMA Glycidyl methacrylate
structure of CSPs. According to the literature, emulsion
HCPE Hyperbranched conjugated polyelectrolyte
polymerization seems to be the most used technique to
HFMA 2,2,3,4,4,4-hexafluorobutyl methacrylate
prepare CSPs in different size. NIPAM is the most commonly
HMEM 2-[P(2-hydroxy-2-methylpropiophenone)]-
used monomer to prepare CSPs, due to its high response to the
ethyleneglycol methacrylate
environmental change.
HMTETA 1,1,4,7,10,10-
Hexamethyltriethylenetetramine
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