Magneticky modifikovan

aktivn uhl a biouhel a jejich

vyuit

Ivo afak, Kateina Horsk,
Kristna Pospkov, Zdenka Madrov,
Mirka afakov

Oddlen nanobiotechnologie
stav nanobiologie a strukturn biologie CVGZ AVR
esk Budjovice

ivosaf@yahoo.com

www.nh.cas.cz/people/safarik

Types of magnetic nano- and
microparticles
Multi domain, single domain or
superparamagnetic

Magnetite (Fe
3
O
4
)
Ferrites (MeO . Fe
2
O
3;
Me = Ni, Co, Mg, Zn, Mn ...)
Maghemite (-Fe
2
O
3
)
Greigite (Fe
3
S
4
)
Iron, nickel

Why magnetic materials are so
important in bioapplications?

They are smart materials!!!!

The following typical properties of
magnetic materials form the basis
of their applications in biosciences
and biotechnology

Important properties
Selective separation
(removal) of magnetic
particles from the
system


Targeting (navigation)
of magnetic particles
to desired area using
magnetic field


Important properties
keeping magnetic
particles in
appropriate area
using magnetic field

Heat formation in
alternated magnetic
field
Important properties
Increasing of contrast
during MRI




Peroxidase-like
activity






Important properties
Hardening of
biological structures
(chiton teeth)




Navigation in
magnetic field




Important properties
Magnetic labeling of
biologically active
compounds



Magnetization of
biological
diamagnetic materials






Examples of of magnetic nano- and
microparticles applications
From molecular biology to environmental
technologies
Manipulation of microliters as well as
million of liters
Manipulation in suspension systems
Both separation and non-separation
techniques are important
Preparation of magnetic particles
for bioapplications
Precipitation
High-temperature reactions
Reactions in steric environments
Sol-gel reactions
Decomposition of organometallic precursors
Polyol methods
Biosynthesis


Laurent S, Forge D, Port M, Roch A, Robic C, Elst LV, Muller RN: Magnetic iron
oxide nanoparticles: Synthesis, stabilization, vectorization, physicochemical
characterizations, and biological applications. Chem Rev 2008, 108(6):2064-2110.


Postmagnetization
Chemical precipitation procedures
High temperature treatment
Ferrofluid treatment
Microwave assisted procedures
Mechanochemistry
Encapsulation


Review paper
Conversion Of Activated Carbons (Charcoal) Into Their Magnetic
Derivatives Using Chemical Precipitation Procedures

Modification Procedure
Precipitation of magnetite from FeSO
4
and Fe
2
(SO
4
)
3
by NaOH in the presence of charcoal, followed by
aging for 24 h and heating at 473 K
Precipitation of iron oxides from FeSO
4
and FeCl
3
by NaOH in the presence of charcoal, followed by
drying at 100 C for 3 h
Precipitation of hydrated iron oxides from FeSO
4
by NaOH in the presence of charcoal, followed by
heating to 100 C for 1 h
Activated carbon was suspended in NaOH solution and heated to 100 C; then a solution of Fe(NO
3
)
3

and Co(NO
3
)
2
was quickly poured into the AC suspension and refluxed at 100 C for 2 h
Bamboo charcoal powder was suspended in Fe(NO
3
)
3
, Zn(NO
3
)
2
, Ni(NO
3
)
2
and aqueous ammonia
solution and then heated in an autoclave at 180 C for 2 h and air cooled to room temperature
Activated carbon was suspended in CuCl
2
and FeCl
3
solution, followed by NaOH solution addition and
heating to 98-100 C for 2 h
FeCl
3
and FeSO
4
solution was mixed with NaOH solution to keep pH value of 9.5, then activated carbon
was added and the obtained material was dried in an oven at 100 C for 3 h


Modification Procedure
Activated carbon was impregnated with an aqueous solution of sucrose and Ni(NO
3
)
2
, followed by heating at 600 C
under N
2
for 3 hours. Ni nanoparticles were formed within the porous AC matrix
A solution of Ni(NO
3
)
2
was dropped into NaOH solution, then ethanol solution of phenolic resin was added followed by
solvent evaporation at 333 K and carbonization under argon atmosphere at 873 K
Impregnation of activated carbon with Fe(NO
3
)
3
solution followed by drying at 90 C and heated to 700 C under
argon; then benzene vapor was introduced
Activated carbon from rice husk was modified with HNO
3
for 3 h at 80 C followed by suspending in Fe(NO
3
)
3
and
drying. Thermal treatment was conducted at 750 C for 3 h in the presence of N
2
to enable formation of magnetite
nanoparticles
Dried chitosan microspheres were immersed in (NH
4
)
3
[Fe(C
2
O
4
)
3
] solution followed by washing and drying, then the
sample was carbonized under Ar atmosphere at 700-1000 C for 4 h
Activated carbon was suspended in Fe(NO
3
)
3
; after drying it was heated to 800 C in N
2
atmosphere and after cooling
heated at 850 C in CO
2
atmosphere for 1.5 h
A mixture of the anthracite powder, coal tar, Ni(NO3)2 and water was mixed and extruded in the form of 1 cm
cylinders. After drying the material was carbonized under a flow of N2 at 600 C and then activated at 880 C
under a flow of N2
Activated carbon was impregnated with Fe(NO
3
)
3
solution and then with ethylene glycol. The impregnated sample was
subjected to heat treatment under N
2
atmosphere at a temperature 250-450 C for 2 h
Activated carbon was filled with a Fe(NO
3
)
3
solution in ethanol and then dried at 90 C for 2 h. Then the sample was
impregnated with ethylene glycol followed by heat treatment under N
2
atmosphere at a temperature 350 or 450
C for 2 h
Conversion Of Activated Carbons (Charcoal) Into Their Magnetic Derivatives By
High Temperature Treatment
Conversion Of Activated Carbons (Charcoal) Into Their
Magnetic Derivatives By Encapsulation
Modification Procedure
Activated carbon was mixed with alginate solution and citrate stabilized ferrofluid and then the suspension was
added dropwise into a CaCl
2
solution
Cellulose was dissolved in a cooled NaOH/urea solution followed by the addition of maghemite nanoparticles
and activated carbon; the suspension was added dropwise into a NaCl solution. The formed beads were cross-
linked with epichlorohydrin
Charcoal and magnetisable ferric oxide were entrapped in a polyacrylamide gel followed by lyophilisation and
micronisation
Charcoal and barium ferrite microparticles were mixed with bovine serum albumin solution followed by
emulsification in n-butanol castor oil glutaraldehyde continuous phase
Charcoal and magnetisable ferric oxide were entrapped in a polyacrylamide gel followed by drying at 80 C
overnight and milling to obtain particles of less then 50 m in diameter
Activated carbon was suspended in NaOH solution and heated to 100 C; then a solution of Fe(NO
3
)
3
and
Co(NO
3
)
2
was quickly poured into the AC suspension and refluxed at 100 C for 2 h. This material was added
to Na alginate solution followed by pouring dropwise into CaCl
2
solution
Application Of Magnetic Activated Carbons (Charcoal) For The Separation Of
Organic Compounds
Type of MAC Separated organic compound
Almond shells 2,4,6-Trinitrophenol from water; 97% desorption achieved by methanol and hot water
Orange peel Naphthalene and p-nitrotoluene
Commercial Methylene blue from river water; maximum adsorption capacity was 47.62 mg g
-1

Hydro-thermal process Methyl orange from water; maximum adsorption capacity was 44.65 mg g
-1

Coconut shell Humic substances
Bitumine Methylene blue; maximum adsorption capacity was 229.5 mg g
-1

Commercial Adsorption of methylene blue by activated carbon/cobalt ferrite/alginate composite beads
Chezacarb B Water soluble organic dyes from aqueous solutions
Chezacarb B Crystal violet and safranin O; magnetic solid-phase extraction used for preconcentration
Palm shells Oil from palm oil mill effluent
Commercial (Norit) Imidacloprid from water
Phenolic resin Methylene orange from water; maximum adsorption capacity was 0.16 mg m
-2

Coconut shell Methyl orange from water; regeneration by hydrogen peroxide performed
Rice husk Methylene blue from water, maximum adsorption capacity was 321 mg g
-1

Commercial Malachite green from water; maximum adsorption capacity was 89.29 mg g
-1

Application Of Magnetic Activated Carbons (Charcoal) For
The Separation Of Inorganic Compounds
Type of MAC Separated inorganic compound
Coconut shell
Mercury; maximum adsorption capacity was 38.3 mg g
-1
. Hg desorption can be
performed by heating
Bituminous coal Mercury(II) from water
Commercial
Arsenic(V) removal from contaminated water with MAC coated with bacteria or
biopolymers
Coconut or fruit pit Gold from cyanide leach liquor or cyanide pulp
Orange peel Phosphate from wastewater
Microwave assisted synthesis of
magnetically responsive biochar


Biochar
Ferrous sulfate
Microwave oven
high pH

Magnetic properties are caused by the deposition of magnetic iron oxides nano-
and microparticles on the biochar surface using the developed procedure
Magnetic biochar

Fe
2+
+ H
2
O Fe(OH)
2

3 Fe(OH)
2
+ O
2
Fe
3
O
4
+ 3 H
2
O
microwave



Safarik,I., Horska,K., Pospiskova,K., Maderova,Z., Safarikova,M.:
Microwave Assisted Synthesis of Magnetically Responsive Composite
Materials. IEEE Trans. Magn. 49 (1) (2013) 213-218

Magnetic derivative of biochar
Adsorption of acridine orange

Akridinov oran 50mg mag.biochar
0
5
10
15
20
25
30
0 10 20 30 40 50 60
Ceq ( mg/l)
Q
e
q

(
m
g
/
g
)
Sirofloc

COST Action (do 25. 3. 2016)
MC
!!!!!
ivosaf@yahoo.com

www.nh.cas.cz/people/safarik