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Atharva Pradhan

Dr. Aniruddha

Maggenome Technologies

22 May 2019

INTRODUCTION

This is an introductory report prepared by Atharva Pradhan on the topics of

Nanotechnology and Nanoparticles and their classifications, applications, synthesis etc. The

report will also focus on Magnetic materials and Magnetic Nano-Particles(MNP) that are

currently being used at Maggenome Technologies Pvt. Ltd. for the process of DNA Separation.

This Introductory report is being made before beginning the actual project of the

Automation of DNA Separation. This has been prepared with the intent to familiarize the trainee

with the different aspects of Nanoparticles and to be used as a reference in case of any doubts

that arise during the actual project.

Nanotechnology

Nanotechnology as an umbrella term refers to the designing, characterizing, production,

and application of structures, devices, and systems by a controlled manipulation of size and

shape at the nanometer scale(atomic, molecular, macromolecular scale). This is done in order to

produce the said structure, devices and systems with at least one superior characteristic. This

novel or superior characteristic of this system can then be used for specific purposes like binding,

separation, analysis or performing any particular activity. [1]

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We are working in the nanometer scale, so, what is the size of a nanometer? A nanometer

is one thousand millionth of a meter. Compared to other objects, a red blood cell is

approximately 7,000 nm wide and a water molecule is almost 0.3nm across. The nanoscale is

defined in terms of size from 100nm down to roughly the size of atoms(0.2nm). It has been

found that in this range the properties of materials are different as compared to the larger scale.

The reason for this difference in properties at the nano-scale can be attributed to the following:

Nanomaterials end up having more surface area, compared to the same mass in larger form. This

ends up making the surface more active to chemical reactions and/or affecting the electrical

properties. Nano-scale materials can be is nanoscale in one-dimension- Wires, tubes;

two-dimension- Nanocoating, Graphene etc; or three-dimension- Nanoparticles. [3]

In essence, Nanotechnology is the in-depth understanding and the control of various

materials at the nanometer scale, where unique properties of materials will enable novel

applications.

Nanoparticles

As we already know, Nanotechnology produces different types of materials at the

nanometer scale. We define Nanoparticles as a wide class of materials, which have a dimension

of 100nm atleast. These nanoparticles show characteristic properties with changes in shape, size

which can be used for various functions.

Nanoparticles are often composed of three separate layers:

1. The surface layer, which may be functionalized with a variety of small molecules,

metal ions, surfactants and polymers.

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2. The shell layer, which is chemically different material from the core in all aspects.

3. The core, which is essentially the central portion of the NP and usually refers the

NP itself. [4]

We tend to divide the Nanoparticles on the basis of their size, chemical properties and structure.

An overview of the few classes of Nanoparticles is as follows:

1) Carbon-based Nanoparticles:

Carbon-based nanoparticles include two main materials: carbon nanotubes (CNTs) and

fullerenes. Fullerenes are the allotropes of carbon having a structure of hollow cage of

sixty or more carbon atoms. The carbon units in these structures have a pentagonal and

hexagonal arrangement. The most popular is the C-60 Buckminsterfullerene, whose

structure is like that of a hollow football. CNTs are essentially Graphene sheets. These

sheets rolled into a tube give extra strength to the structure thus formed. ​CNTs are of two

types- single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes

(MWCNTs). CNTs are unique in a way as they are thermally conductive along the length

and non-conductive across the tube. [5]

Commercial applications such as fillers, efficient gas adsorbents for environmental

remediation and as support medium for different inorganic and organic catalysts.

2) Metal Nanoparticles:

These nanoparticles can be synthesized by chemical, electrochemical, or photochemical

methods. In chemical methods, the metal nanoparticles are obtained by reducing the metal-ion

precursors in solution by chemical reducing agents. Due to well-known localized surface

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plasmon resonance (LSPR) characteristics, these NPs are known to possess some unique

optoelectrical properties. Due to their advanced optical properties, metal NPs find applications in

many research areas. Gold NPs coating is widely used for the sampling of SEM, to enhance the

electronic stream, which helps in obtaining high quality SEM images.

3) Ceramic Nanoparticles:

Ceramics NPs are inorganic nonmetallic solids, synthesized via heat and successive

cooling. They can be found in amorphous, polycrystalline, dense, porous or hollow forms. They

have applications such as catalysis, photocatalysis, photodegradation of dyes, and imaging

applications. [7]

4) Semiconductor based Nanoparticles:

Semiconductor materials possess properties between metals and nonmetals, and thus

these kind of nanoparticles possess wide bandgaps and therefore showed significant alteration in

their properties with bandgap tuning. Some examples of semiconductor nanoparticles are GaN,

GaP, InP, InAs from group III-V, ZnO, ZnS, CdS, CdSe, CdTe are II-VI semiconductors and

silicon and germanium are from group IV from the periodic table.

5) Polymeric Nanoparticles:

These are normally organic based NPs. These have structures shaped like nanocapsular or

nanospheres. Nanospheres consist of an overall solid mass of core particles and the other

molecules are adsorbed at the outer boundary of the spherical surface. In the latter case the solid

mass is encapsulated within the particle completely.

6) Lipid based Nanoparticles:

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These kind of Nanoparticles contain lipids in them, and hence the name. A lipid NP is

spherical with diameter ranging from 10 to 1000 nm. Like polymeric NPs, lipid NPs possess a

solid core made of lipid and a matrix contains soluble lipophilic molecules.

Synthesis of Nanoparticles

For synthesis of nanoparticles, primarily two kinds of methods are used. These methods

can be further divided into various other categories based on our operation conditions and

desired results.

Top-Down Approach:

Destructive approach is employed in top-down approach. We begin with a large molecule

(micron-size), and then decompose this particle into smaller and smaller particles, till we reach

the desired Nanoparticle level. Various sub-methods of Top-Down synthesis are: Mechanical

milling, chemical milling, sputtering, laser ablation and electro-explosion.

Often, it is difficult to obtain uniformly shaped materials, and it is very difficult to realize very

small particles even with high energy consumption. Imperfections in the shape of the crystal

have a significant impact on physical properties and surface chemistry of nanostructures and

nanomaterials. [8]

Bottom-Up Approach:

In the Bottom-Up approach, we start with a very simple component, and we move up with a

building up approach. Common examples of such methods are sedimentation and reduction

techniques. We build up a material from bottom: atom-atom, molecule-by-molecule and then

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particle-to-particle. This method is most commonly used to prepare Nanoparticles as we can

control the shape and size of the desired particle and we can generate uniform size. [9]

Magnetic Nano-Particles

Before we begin to understand about Magnetic Nanoparticles, we should first cover the

basics of Magnetism and Magnetic Properties. Magnetic material in nature can be of one of the

following types: Diamagnetic, Paramagnetic, Ferromagnetic, Ferrimagnetic and

Antiferromagnetic.

1. Diamagnetism: Diamagnetism is a fundamental property of all matter, although it

is usually very weak. It is due to the non-cooperative behavior of orbiting

electrons when exposed to an applied magnetic field. Diamagnetic substances are

composed of atoms which have no net magnetic moments (ie., all the orbital

shells are filled and there are no unpaired electrons). However, when exposed to a

field, a negative magnetization is produced and thus the susceptibility is negative.

2. Paramagnetism: This class of materials, some of the atoms or ions in the material

have a net magnetic moment due to unpaired electrons in partially filled orbitals.

One of the most important atoms with unpaired electrons is iron. However, the

individual magnetic moments do not interact magnetically, and like

diamagnetism, the magnetization is zero when the field is removed. In the

presence of a field, there is now a partial alignment of the atomic magnetic

moments in the direction of the field, resulting in a net positive magnetization and

positive susceptibility.
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3. Ferromagnetic: Unlike paramagnetic materials, the atomic moments in iron,

nickel or magnetite exhibit very strong interactions. These interactions are

produced by electronic exchange forces and result in a parallel or antiparallel

alignment of atomic moments. Exchange forces are very large, equivalent to a

field on the order of 1000 Tesla, or approximately a 100 million times the strength

of the earth's field. Ferromagnetic materials exhibit parallel alignment of moments

resulting in large net magnetization even in the absence of a magnetic field. The

spontaneous magnetization is the net magnetization that exists inside a uniformly

magnetized microscopic volume in the absence of a field. The magnitude of this

magnetization, at 0 K, is dependent on the spin magnetic moments of electrons.

The difference between spontaneous magnetization and the saturation

magnetization has to do with magnetic domains. Saturation magnetization is an

intrinsic property, independent of particle size but dependent on temperature.

4. Ferrimagnetism: he magnetic structure is composed of two magnetic sublattices

(called A and B) separated by oxygens. The exchange interactions are mediated

by the oxygen anions. When this happens, the interactions are called indirect or

superexchange interactions. In ferrimagnets, the magnetic moments of the A and

B sublattices are not equal and result in a net magnetic moment. Ferrimagnetism

is therefore similar to ferromagnetism. It exhibits all the hallmarks of

ferromagnetic behavior- spontaneous magnetization, Curie temperatures,

hysteresis, and remanence. However, ferro- and ferrimagnets have very different

magnetic ordering. Magnetite is a well known ferrimagnetic material. Indeed,

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magnetite was considered a ferromagnet until Néel in the 1940's, provided the

theoretical framework for understanding ferrimagnetism.

5. Antiferromagnetism: Anti ferromagnetic materials exhibit a type of magnetism

known as anti ferromagnetism. In anti ferromagnetic materials the magnetic

moments of neighboring electrons point in opposite direction. This type of

magnetic ordering is called antiferromagnetism.

About Magnetic Nanoparticles

Nanoparticles posses different physical, chemical, electrical, and structural and magnetic

properties. Nanoparticles exerting magnetic properties with manipulation of magnetic field are

called as magnetic nanoparticles (MNP). The magnetic properties of nanoparticles are

determined by many factors, the key of these including the chemical composition, the type and

the degree of defectiveness of the crystal lattice, the particle size and shape the morphology (for

structurally inhomogeneous particles), the interaction of the particle with the surrounding matrix

and the neighboring particles. By changing the nanoparticle size, shape, composition, and

structure, one can control to an extent the magnetic characteristics of the material based on them.

Magnetic nanoparticle clusters that are composed of a number of individual magnetic

nanoparticles are known as magnetic nanobeads with a diameter of 50–200 nanometers. [10]

Magnetic nanoparticles are nanomaterials consist of magnetic elements, such as iron,

nickel, cobalt, chromium, manganese, gadolinium, and their chemical compounds. Magnetic

nanoparticles are superparamagnetic because of their nanoscale size, offering great potentials in

a variety of applications in their bare form or coated with a surface coating and functional groups
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chosen for specific uses. Especially, ferrite nanoparticles are the most explored magnetic

nanoparticles, which can be greatly increased by clustering of a number of individual

superparamagnetic nanoparticles into clusters to form magnetic beads.

Coating of Magnetic Nanoparticles

Uptil now, we have learned about the synthesis and various properties of the

Nanoparticles. But, most often these Nanoparticles are coated with various substances in order to

stabilize and to improve solubility of nanoparticles, increase their biocompatibility,

target-specificity, and to prevent from agglomeration, oxidation, corrosion, and toxicity. Streic

and electrostatic repulsion are the factors which are dealt in the process of stabilization

establishing an equilibrium between attractive and repulsive forces and to keep the nanoparticle

in suspended state. In order to prevent aggregation and minimize the interaction of the particles

with the system environment, surface coating may be required. The surface of ferrite

nanoparticles is often modified by surfactants, silica, silicones, or phosphoric acid derivatives to

increase their stability in solution. In general, coated magnetic nanoparticles have been widely

used in several medical applications, such as cell isolation, immunoassay, diagnostic testing and

drug delivery. [11]

Properties:

1) Magnetic Property: The properties of magnetic nanoparticles depend on the

synthesis method and chemical structure. In most cases, the magnetic

nanoparticles range from 1 to 100 nm in size and can display

superparamagnetism. Superparamagnetism is caused by thermal effects that the

thermal fluctuations are strong enough to spontaneously demagnetize a previously

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saturated assembly; therefore, these particles have zero coercivity and have no

hysteresis. In this state, an external magnetic field is able to magnetize the

nanoparticles with much larger magnetic susceptibility. When the field is

removed, magnetic nanoparticles exhibit no magnetization. This property can be

useful for controlled therapy and targeted drug delivery.

2) Magnetocaloric Effect: Some magnetic materials heat up when they are placed in

a magnetic field and cool down when they are removed from a magnetic field,

which is defined as the magnetocaloric effect (MCE). Magnetic nanoparticles

provide a promising alternative to conventional bulk materials because of their

particle size-dependent superparamagnetic features. In addition, the large surface

area in magnetic nanoparticles has the potential to provide better heat exchange

with the surrounding environment. By careful design of core-shell structures, it

would be possible to control the heat exchange between the magnetic

nanoparticles and the surrounding matrix, which provide a possible way for

improving therapy technologies, such as hyperthermia.[12]

Magnetic Nanoparticle Types:

1. Iron-Based Magnetic Nanoparticles: Magnetic iron oxide nanoparticles represent

materials with required magnetic properties mostly used for biomedical

applications. Significant advantages include primarily price, stability, and

compatibility—magnetic iron oxide nanoparticles are inexpensive to produce,

exhibit sufficient physical and chemical stability, as well as biocompatibility and

are environmentally safe.

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2. Cobalt Based Magnetic Nanoparticles: Examples of synthesis and bioapplications

of magnetic nanoparticles of cobalt are much less common than iron due to cobalt

toxicity.

3. Other Magnetic Nanoparticles: In typical applications ultrafine superparamagnetic

particles based on Fe3O4 and γ-Fe2O3 are commonly used. Meanwhile other

magnetic particles are studied and used exceptionally, e.g. Y3Fe5O12,

SrFe12O19 or SmCo5. [13]

Magnetic Nanoparticle Synthesis:

1. Physical synthesis: Physical synthesis of np is done by ball milling,

thermal evapouration, lithography, vapour phase etc. The typical

'top-down' approach is high energy ball milling, which can yield sub-10nm

particles. But the major drawbacks are surface contamination and

introduction of structural defects. The 'bottom-up' variety of physical

techniques can be classsified into the following two categories- Using

Spray techniques such as spray dry, freeze dry, plasma spray and hot

spray. And PVD-based techniques are particularly suitable for obtaining

nanocrystalline thin films.

2. Biological synthesis: Biological methods of nanoparticle preparation using

microorganisms have been recommended as possible eco-friendly

substitutes to chemical and physical methods. Sometimes, the nanoparticle

preparation using plants or parts of plants can prove advantageous over

other biological processes, by eliminating the elaborate work involved in

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maintaining microbial cultures. Green synthesis of NPs makes use of

environmentally friendly, non-toxic and safe Artificial Cells,

Nanomedicine, and Biotechnology. The development of reliable, nontoxic,

and eco-friendly methods for the synthesis of NPs is of extreme

importance to develop their biomedical applications.

3. Chemical synthesis: One of the oldest techniques for the preparation of

NPs is the precipitation of products from solutions. In precipitation

reactions, the metal precursors are dissolved in an ordinary solvent, such

as water, and a precipitating agent is added to generate an insoluble solid.

The main advantage of precipitation reactions is its high yield.

Co-precipitation is the most widely used and most proper method for the

synthesis of MNPs of controlled sizes and magnetic properties. It is

extensively used for biomedical applications, because of the ease of

application. In this method, MNPs are prepared from aqueous salt

solutions, by the addition of a base under an inert atmosphere at room

temperatures or at high temperature. Co-precipitation is the most widely

used and most proper method for the synthesis of MNPs of controlled

sizes and magnetic properties. In this method, MNPs are prepared from

aqueous salt solutions, by the addition of a base under an inert atmosphere

at room temperatures or at high temperature. In this method Iron oxides

(either Fe3O4 or γ-Fe2O3) are prepared by an adding a stoichiometric

mixture of ferrous and ferric salts in aqueous medium. The sol-gel process
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includes hydrolysis and condensation of metal alkoxides. Metal alkoxides

are good precursors, due to their endurance in the face of hydrolysis.

Factors that need to be considered in a sol-gel method are the solvent type,

temperature, precursors, catalysts, pH, additives and mechanical agitation.

These factors can affect the kinetics, growth, and hydrolysis and

condensation reactions. The laser pyrolysis method includes heating a

flowing mixture of gases with a continuous wave CO 2 laser, which

initiates and sustains a chemical reaction.

Magnetite (Fe3O4)

Iron oxide nanoparticles such as magnetite (Fe3O4) or its oxidized form maghemite

(γ-Fe2O3) are by far the most commonly employed nanoparticles for biomedical applications.

Properties of Magnetite:

1. Structure: Magnetite has an inverse spinel structure with oxygen forming a

face-centered cubic crystal system. In magnetite, all tetrahedral sites are occupied

by Fe3+ and octahedral sites are occupied by both Fe3+ and Fe2+. [14] It has

diameter between about 1 and 100 nanometers. Maghemite differs from

magnetite in that all or most of the iron is in the trivalent state (Fe3+) and by the

presence of cation vacancies in the octahedral sites. Maghemite has a cubic unit

cell in which each cell contains 32 O ions, 21​1⁄3 Fe3+ ions and 2​2⁄3 vacancies.

The cations are distributed randomly over the 8 tetrahedral and 16 octahedral

sites.
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2. Physical Properties: The surface area of the bulk magnetite is less as compared to

the nano magnetite per unit area. Whereas, in terms of colour both these have the

same black colour.

3. Magnetic Properties: Due to its 4 unpaired electrons in 3d shell, an iron atom has

a strong magnetic moment. Ions Fe2+ have also 4 unpaired electrons in 3d shell

and Fe3+ have 5 unpaired electrons in 3d shell. Therefore, when crystals are

formed from iron atoms or ions Fe2+ and Fe3+ they can be in ferromagnetic,

antiferromagnetic or ferrimagnetic states. Magnetite’s Curie temperature is

observed at 850 K. Below the Curie temperature, magnetic moments on

tetrahedral sites, occupied by ferric species, are ferromagnetically aligned while

magnetic moments on octahedral sites, occupied by ferrous and ferric species, are

antiferromagnetic and cancel each other; such combined behavior is termed

ferrimagnetic. Therefore, at room temperature, magnetite is ferrimagnetic. [15] As

temperatures increase to the Curie temperature, thermal fluctuations destroy the

ferromagnetic alignment of magnetic moments on tetrahedral sites; hence,

ferrimagnetic strength is diminished. When the Curie temperature is attained, net

magnetization becomes zero and superparamagnetic behavior is observed.

Coercivity, the magnitude of applied magnetic field required for zero

magnetization after magnetic saturation. [16]

Applications of Magnetite:

1. Industrial Applications: Hematite and magnetite have been applied as catalysts for

a number of important reactions, such as the preparation of NH3, the

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desulfurization of natural gas, and the high-temperature water-gas shift reaction.

Other reactions include the Fishere-Tropsch synthesis for hydrocarbons, the

dehydrogenation of ethylbenzene to styrene, the oxidation of alcohols, and the

large-scale synthesis of butadiene. [17]

2. Biomedical Applications: Biomedical applications of magnetic nanoparticles can

be classified according to their application inside or outside the body (in vivo, in

vitro). For in vitro applications, the main use is in diagnostic separation, selection,

and magnetorelaxometry, while for in vivo applications, it could be further

separated in therapeutic (hyperthermia and drug-targeting) and diagnostic

applications (nuclear magnetic resonance [NMR] imaging). [18]

a) In-Vivo: Two major factors play an important role for the in vivo uses of these particles:

size and surface functionality. Even without targeting surface ligands, superparamagnetic

iron oxide NP [SPIOs] diameters greatly affect in vivo biodistribution. Particles with

diameters of 10 to 40 nm including ultra-small SPIOs are important for prolonged blood

circulation; they can cross capillary walls and are often phagocytosed by macrophages

which traffic to the lymph nodes and bone marrow. [19]

b) In-Vitro: In- Vitro applications primarily includes Diagnostic applications like Separation

and Selection, Magnetorelaxometry.It was introduced as a method for the evaluation of

immunoassays. Magnetorelaxometry measures the magnetic viscosity, i.e., the relaxation

of the net magnetic moment of a system of magnetic nanoparticles after removal of a

magnetic field. [20] Other Applications include Magnetic resonance imaging,

Bioseparation and for Catalysis applications.

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3. Environmental applications: Modified iron nanoparticles, such as catalyzed and

supported nanoparticles, have been synthesized to further enhance their speed and

efficiency of remediation. In spite of some still unresolved uncertainties associated with

the application of iron nanoparticles, this material is being accepted as a versatile tool for

the remediation of different types of contaminants in groundwater, soil, and air on both

the experimental and field scales.

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