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Magneticky modifikovan
aktivn uhl a biouhel a jejichvyuit
Ivo afak, Kateina Horsk,Kristna Pospkov, Zdenka Madrov,
Mirka afakov
Oddlen nanobiotechnologiestav nanobiologie a strukturn biologie CVGZ AVR
esk Budjovice
www.nh.cas.cz/people/safarik
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Types of magnetic nano- and
microparticles
Multi domain, single domain or
superparamagnetic
Magnetite (Fe3O4)
Ferrites (MeO . Fe2O3;Me = Ni, Co, Mg, Zn, Mn ...)
Maghemite (-Fe2O3)
Greigite (Fe3S4)
Iron, nickel
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Why magnetic materials are so
important in bioapplications?
They are smart materials!!!!
The following typical properties ofmagnetic materials form the basis
of their applications in biosciencesand biotechnology
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Important properties
Selective separation(removal) of magneticparticles from thesystem
Targeting (navigation)of magnetic particles
to desired area usingmagnetic field
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Important properties
keeping magneticparticles in
appropriate area
using magnetic field
Heat formation inalternated magnetic
field
http://images.google.com/imgres?imgurl=http://www.biomagres.com/content/figures/1477-044X-1-2-3.jpg&imgrefurl=http://www.biomagres.com/content/1/1/2/figure/F3&h=256&w=300&sz=30&hl=cs&start=1&um=1&tbnid=K7ADwlcaRzc7XM:&tbnh=115&tbnw=135&prev=/images%3Fq%3Dmagnetic%2Bdrug%2Btargeting%26svnum%3D10%26um%3D1%26hl%3Dcs%26newwindow%3D1%26sa%3DX -
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Important properties
Increasing of contrastduring MRI
Peroxidase-likeactivity
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Important properties
Hardening ofbiological structures
(chiton teeth)
Navigation inmagnetic field
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Important properties
Magnetic labeling ofbiologically activecompounds
Magnetization ofbiologicaldiamagnetic materials
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Examples of of magnetic nano- and
microparticlesapplications
From molecular biology to environmentaltechnologies
Manipulation of microliters as well asmillion of liters
Manipulation in suspension systems
Both separation and non-separationtechniques are important
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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 ironoxide nanoparticles: Synthesis, stabilization, vectorization, physicochemicalcharacterizations, and biological applications. Chem Rev 2008, 108(6):2064-2110.
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Postmagnetization
Chemical precipitation procedures
High temperature treatment
Ferrofluid treatment Microwave assisted procedures
Mechanochemistry
Encapsulation
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Review paper
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Conversion Of Activated Carbons (Charcoal) Into Their Magnetic
Derivatives Using Chemical Precipitation Procedures
Modification Procedure
Precipitation of magnetite from FeSO4 and Fe2(SO4)3 by NaOH in the presence of charcoal, followed by
aging for 24 h and heating at 473 K
Precipitation of iron oxides from FeSO4 and FeCl3 by NaOH in the presence of charcoal, followed by
drying at 100 C for 3 h
Precipitation of hydrated iron oxides from FeSO4
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(NO3)3
and Co(NO3)2 was quickly poured into the AC suspension and refluxed at 100 C for 2 h
Bamboo charcoal powder was suspended in Fe(NO3)3, Zn(NO3)2, Ni(NO3)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 CuCl2and FeCl3solution, followed by NaOH solution addition and
heating to 98-100 C for 2 h
FeCl3 and FeSO4solution 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
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Modification Procedure
Activated carbon was impregnated with an aqueous solution of sucrose and Ni(NO3)2, followed by heating at 600 Cunder N2for 3 hours. Ni nanoparticles were formed within the porous AC matrix
A solution of Ni(NO3)2was 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(NO3)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 HNO3 for 3 h at 80 C followed by suspending in Fe(NO3)3anddrying. Thermal treatment was conducted at 750 C for 3 h in the presence of N2to enable formation of magnetite
nanoparticles
Dried chitosan microspheres were immersed in (NH4)3[Fe(C2O4)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(NO3)3; after drying it was heated to 800 C in N2 atmosphere and after cooling
heated at 850 C in CO2 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(NO3)3 solution and then with ethylene glycol. The impregnated sample was
subjected to heat treatment under N2atmosphere at a temperature 250-450 C for 2 h
Activated carbon was filled with a Fe(NO3)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 N2 atmosphere at a temperature 350 or 450C for 2 h
Conversion Of Activated Carbons (Charcoal) Into Their Magnetic Derivatives By
High Temperature Treatment
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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 CaCl2 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(NO3)3and
Co(NO3)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 CaCl2 solution
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Application Of Magnetic Activated Carbons (Charcoal) For The Separation Of
Organic CompoundsType 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
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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
CommercialArsenic(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
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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
Fe2++ H2O Fe(OH)2
3 Fe(OH)2+ O2 Fe3O4+ 3 H2Omicrowave
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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
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Magnetic derivative of biochar
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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)
Qeq(mg/g)
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Sirofloc
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COST Action (do 25. 3. 2016)
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MC
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!!!!!
www.nh.cas.cz/people/safarik