INTRODUCTION: In science nano is a measurement and its value is equal to 10-
9
cm.
Drastic change is observed in the properties of certain materials when they acquire nano
dimensions. Nanotechnology refers to a field of applied science and technology whose theme
is the control of matter on the atomic and molecular scale, generally 100 nanometres or
smaller, and the fabrication of devices this technology materials that lie within that size
range.
CNTs are allotropes of carbon which possess nanostructure that can have a
length-to-diameter ratio of up to 28,000,000:1, which is larger in comparison to any other
material.
In the nanotechnology development, CNTs have attracted a great deal of attention due to their
properties. CNTs have unique structural, electrical and mechanical properties. Some of the
properties of CNTs are superior strength, flexibility,' electrical conductivity and easy
chemical fictionalization .These properties have been exploited for the biological application
both at the cellular and molecular level.
Amino acid -metal complex: Proteins are bio polymers comprising of amino acids as
monomer. Proteins when mixed when mixed with organic solvent like ethyl alcohol,
denaturation of protein takes place. The cause of denaturation is most proteins, including
albumen, are exposed to an aqueous environment. So amino acids on the surfaces of the
protein are compatible with the polar aqueous environment. But the interior regions of
proteins are often hydrophobic. Alcohol disrupts the hydrogen bonding between the water
and the surface polar residues, favouring exposure of the more hydrophobic residues buried
inside. This conformational change is referred to as denaturation ofprotein.
Amino acids are compounds containing -NH2 and -COOH groups within a single molecule.
-NH2 group possess one lone pair of electron on nitrogen atom. Even after denaturation
proteins retain their peptide structure. With the help of -NH2 and -COOH groups, amino
acids form complexes with metals. In these complexes different chains of amino. acids are
clubbed together. These compounds on decomposition give carbon -metal Nanotubes. When
aqueous solution of Nickel Salt is allowed to react with amino acids present in egg albumin
the lone pair present on nitrogen of -NH2 and oxygen of COO- of COOH group present in
amino acid form complex with Ni (ii). In this way nickel (ii) forms cross link between two
amino acid chains. .
The structure of amino acids present in denatured egg albumin is very complex and it is very
difficult to produce exact structure of amino acid-metal complex. Egg albumin contains a. I
number of different chemical compounds, which also form complex with metal. This metal -
amino acids complexes"are heated in muffle furnace till decomposition. Theses complexes on
decomposition give carbon Nanotubes.
Preparation of CNTs Using Egg and nickel Chloride in Organic medium
Preparation of EggNiCh (Ale)
CNTs are formed only when the concentration of carbon at a particular point is
high. So, to club various protein molecules together, alcoholic solution of Nickel Salt is
allowed to react with amino acids present in Egg. The lone pair present on nitrogen of -
NH2 and oxygen ofCOO- ofCOOH group present in amino acid form complex with Ni (ii).
In this way nickel (ii) forms cross link between two amino acid chains.
First of all Egg yolk is separated from egg serum and 2gms of it is kept in glass
beaker. Now 5ml of IN solution ofNiCh is prepared in ethyl alcohol and is mixed with egg
yolk for the reaction The complex is kept in desiccator for around fifteen days. After fifteen
days the complex is washed with water and dried again. The weight of dry complex is
2:327gms. The dry complex is now ready to decompose and for further studies.
Decomposition:
The complex formed is decomposed at 800°C in muffle furnace. For
decomposition 2gm of complex is weighed and kept in crucible. The complex is then kept in
muffle furnace for ten minutes at 800°C.The weight of decomposed complex is 0.161gms.
The same process is repeated at 900. The weight of complex was 0.155gms.
The complex of amino Acid and metal is expected to contain following groups:
(i) NH2 group
(ii) COOH group
(iIi) CH2 group
(iv) Amide group etc.
The presence of these groups is confirmed by using IR and NMR studies.
Characterization of Protein metal complex
IR Spectro'scopy
The results of IR spectra of Nickel salt and egg protein in alcoholic
medium are given below: I
1. .Functional group C-H (alkanes) is found at a absorption band of 1413 cm-
I
.
2. Functional group N-H stretching (symmetric and asymmetric) is found at an
absorption band of 3369 cm-I.
3. Functional group -0H stretching in -COOH is found at a absorption band of
2925.78 cm-
I
. It can be because ofC-H stretching in alkanes.
4. Functional group Carboxylic acid (hydrogen bonded) is found at a absorption
band of2966 cm-
I
.
5. Functional group C=O stretching in -COOH is found at an absorption band of
1630cm-
l
.'.
~--:""'t 5 9" DellI ""'t. .
\ l"J .. ' "', ·JOt.... tl ~ 10'~ . . ~1 ~~ .
6. Functional group Functional group C-N stretching in amines IS found at an
absorption ~and of 1147 cm-I.
7. Functional group C-O stretching is found at an absorption band of 1319 cm-I.
8. Functional group C-H deformed is found at an absorption band of 632 cm'l.
9. .Functional group N-H deformed is found at an absorption band of 1542 cm-
I
.
The IR spectra is shown in Fig.l.l
100
eo
70
60
g 50
..
I c:
40 e !-
#.
30
20
10
0
·10
4000 3500 3000
... G)
-.::
N
... ;:.
~ 0
'" '"
2500 2000
Wavenumbers {cm-1}
1500
...
'If
eli
...
(")
...
1000 500
Fig: 1.1 IR Spectra ofNickel salt and egg protein in alcoholic medium
~MR Spectroscopy
The results of NMR spectra of Nickel salt and egg protein in alcoholic medium
are given below: I1
-
59°EL\lJ
L For (CH3)3CH the chemical shift (0) value is 1.45 ppm.
2. For CH2- and NH2 the chemical shift (0) value is 4.4 ppm.
3. For-e~-the chemical shift (0) value is 5.5 ppm.
4. For-eH2-eOOH the chemical shift (0) value is 6 -7.8 ppm.
The NMR spectra is shown in Fig.l.2
• - • • • I II
t,Ht lUi ~ ~ ,Qq $0 fQlt.W l;)l:'~.
FIg: 1.2 NMR Spectra ofNickel salt and egg protein in alcoholic medium
From the results, ofNMR and IR it was found that the compound contain all the above
said groups. In other words, we can say that the desired chemical compound is formed.
Using IR and NMR data we can deduce the structure of amino acid. The structure
is drown in the Fig 1.3HO
-~
--1 fIIIl.. .5 9··· <; nv;,11 .• · ••, ... 1 W 1. ... '" r.'1 . .~ ~ . .
Fig!.3 Structure deduced by NMR &IR spectra
This structure resemble with Lucien protein, which is an essential constituent of
egg albumin and all the groups identified in IR and NMR spectra are present in the structure.
From the result of NMR and IR it is clear that +1 effect plays a vital role in the
preparation of protein nickel complex, the amino acid more no. of alkyl group form
compound with nickel.· Chemical and physical evidences suggest that alkyl group, relative to
hydrogen atoms release electrons to carbon. If an alkyl group is attached to an electron
deficient carbon it donates electrons through the carbon-carbon cr bonds.
2
The structure ofLucien Ni
2
+ complex is given in the Fig.l.4
Fig. 1.4 Structure ofLucien Ni
2
+ complex
Characterization of CNTs Using DLS
. CNTs were dissolved in ethylene glycol and analyzed.Result ofCNTs of Complex Egg NiCh (800Alc)
DLS Graph of CNTs prepared by using egg protein and nickel salt in alcoholic
medium and by decomposing the resultant compound in muffle furnace at 8000
C is shown in
Fig 1.5 and data is given in table 1.
~.
Malvern
s.-.~
......- tcIOlt..S)
IOP_ ...· .....
.............
................'11·· O.Ot
Olll ....~........__
~_tAa
.....,~ 16.t•
............O'......:......, .....01.1Otl) .2:...
~
., ,.n_rq;; B.. -.... ..
e-_~.1U '1 ~ ••
CIII~"'11 _ ~. ..11 "1,1
z"' .......... I~~ ;
N.- 1;
......11'. u., J:
......~; ....._....,~
...... ....
4e:t
••
..................
«u a=..
:u .nt
U 211""•
it .-••••••• >It ••• "If•••' iI:,. ""'.' ,. ""•• ll"- :. " ••• )Ii'••• ,.
• K • \0 :'
·
...............,
·
· ...,•., !
·
· ••• ' •••JJ •• !
·
·
, ,
...........•.'\- ........ ·········..r·······
............._ ' ...........••..••.........
,,_ ••_ + ~ ~'••••••••••(- '" .
, . .
Fig1.5 DLS Graph ofCNTs prepared by complex ofEggNich (800Alc)Table 1: DLS Data
S.No Typ Sample Tern . z- Pdl Pkl Pk2 Pk3 Pkl Pk2 Pk3 Meao Multimod Cumulaot. Numbe Volum e Name Ave Mea Mea Mea Are Are Area Couo al Fir error s . Fit rMeao eMeao
o lot o lot o lot a lot a lot Ioteosit t Error
y Rate
°C d.om d.om d.om d.mn % % % kcps d.om d.om 1. Size 800c S 25 572. 0.46 867. 19.9 0.00 92.5 7.5 0.0 200.4 0.00835 0.0238 19.15 388.3
1 2 I 5 3 0
2. Size 800c S 25 206. 1.00 2342 37.7 0.00 77.8 22.2 0.0 186.1 0.00697 0.00857 35.63 1006
2 7 0 9 0
3. Size 800c S 25 153. 1.00 3264 43.0 228. 62.1 29.6 8.2 171.7 0.00505 0.00705 40.61 1417
3 5 0 2 4•
Discussion ofDLS Results
DLS gives us idea about the particle size. It is based on the fact larger the particle
size more light will be scattered by it. It is clear from the graph that when the metal protein
complex were decomposed at SOO°C, the number of particles having nanodimensions (from
10 to 100nm) is more, as the from the graphs it is clear that the peaks corresponding to
particle size 10 to1OOnm are smaller than the peaks corresponding to 900 to 10000nm. This
shows high concentration of smaller particles as small particles scatter less amount of light.
O.TruspikeVych et ae characterized Carbon Nanotubes Thermo Tropic
pneumatic Liquid Crystal Composites, using DLS and reported similar findings. Therefore,
DLS result conform the formation ofnanosized particles
Characterization Using SEM
SEM results give us idea about surface topography ofCNTs. It also gives us idea
about their surface morphology. The CNTs were analyzed at Nano centre of Allahabad
University.
SEM Images of CNTs of Complex Egg NiCh( 800Alc)
SEM images of CNTs formed by the reaction of egg protein and nickel salt in alcoholic
medium and decomposed at SOO°C in muffle furnace. This image is shown in Fig 1.6
SEM image show formation ofCNTs
4
•
5
,6
Fig: 1.6 SEM Images ofCNTs of complex Egg NiCh (900AIc.)
O.Truspike Vych etae characterized Carbon Nanotubes Thermo Tropic
pneumatic Liquid Crystal Composites using ESEM the SEM figure resembles with the figure
ofmy CNT samples And conforms the formation ofCNT
K.Atre eta!? of Nanomaterial and nanoresearch laboratory, USA synthesized
vertically aligned carbon nanotubes and characterized using SEM. Some oftheir SEM images
showed resemblance with our SEM images. This conform the formation ofCNTs.
Characterization Using XRD
XRD analysis gives idea about internal structure and crystal spacing within the
crystal.,Results of Sample Analyzed by Using XRD
Different samples ofCNTs were analyzed using XRD. The analyses were carried
out at lIT Roorkee.
XRD Graph ofComplex Egg NiCh (900Alc)
The CNTs were prepared by using egg protein and nickel salt in alcoholic
medium and decomposed in muffle furnace at 9000
C.The results ofXRD are shown in table
2 and graph is shown in fig 1.7
Table 2: XRD Data
2 eAn2le Intensity d-Value
5.621 753 d=15.70903
15.188 411 d=5.82885
16.308 440 d=5.43114
17.49 455 d=5.06666,
18.078 501 d=4.90308
18.495 462 d=4.79340
21.38 868 d=4.37208
21.621 543 d=4.10685
22.16 708 d=4.00821
23.888 470 d=3.72199
25.047 508 d=3.55239
25.837 441 d=3.44553
26.603 441 d=3.J4798
28.107 435 . d=3.17220
29.64 496 d=3.01154
29.871 490 d=2.98875
30.836 597 d=2.89743
32.35 447 d=2.76515
33.385 441 d=2.68178
34.756 436 d=2.57906
36.319 422 d=2.47155
39.669 456 d=2.27025
45.423 451 d=1.99511
48.087 435 d=1.89062
49.104 474 d=1.85384
83.637 360 d=1.15526
100.l9 351 d=1:00416XRDGraph
1.000
900
800
700
600
~ W 500
- c:
400
300
200
100
o .--..- ..---..------- --- - ..- --- -- --------................ . - ..-.- - -----..
o 20 40 60 80
2-Theta-Scale
100 120
Fig: 1.7 XRD Graph of complex Egg NiCh (900Alc)
The results were found to be almost similar to the results reported by for multi walled CNTs
prepared by C.R.Bharadwalby pyrolysis of turpentine oil (28=25.6) and with loan Stalin
etal
9
who prepared CNTs by catalytic pyrolysis ofphenol formaldehyde resin(28 =26.2).
Characterization using TEM
TEM image of CNTs is shown in fig 1.8. The image of CNT is on magnification
scale of IOOnm.
These images shows resemblance with the results ofChang Xin Chen, Wenzhe Chen
Yafei ZhangI3
·and LI Wei-xue, HAO Yuan, , CUI Yorig-fu, OAI Jian-feng, , CHEN
Ti-jun, WANG Qing" WU Zhong-li , LI Yang
14
•
Fig.I.8 TEM image ofCNTsStudy of Properties of CNTs
. With syntl\esis and characterization of CNTs the study of properties is also
equally important. So some major properties ofCNTs are studied, they are as under:
TGA, DTA, DTG Thermogram ofCNTs ofComplex Egg NiCh (900Alc)
TGA, DTA, DTG thermo gram ofCNTs prepared by the reaction of egg protein
and Nickel salt in alcoholic medium and decomposing the compound at 900°C.The analyses
was carried out by adjusting the furnace temperature at 1550°C, which is the maximum limit
ofthe instrument. The thermogram is shown in Fig 1.9.
-0,600
-0,800
-1.000
-0,80
1530 eel
22.4% i
40.0 -100
799 eel
1000 eel 1201 eel
25.3 % 24.0% 23.8 %
-1.20 i
120.0
I I I I
200 400 600 800 1000 1200 1400
Temp eel
Fig: 1.9 TGA, DTA, DTG Thermo Gram ofCNTs of complex Egg NiCh (950AIc)
Their thermo grams showed similarities with the thermo grams ofmy sample but
there CNTs decomposed at about 800 to 850°C.They carried out the test in air but my
samples were decomposed in the atmosphere of Nitrogen. That might be the reason of such
difference.
VSM Graph of CNTs ofComplex Egg NiCh (900Alc)Graph ofMagnetic properties ofCNTs prepared by using Nickel salt and egg protein
in alcoholic medium and by decomposing the compound at 900°C. The graph of blank is also
given for reference. The graph is shown in Fig·1.10 and graph of blank reference is given in
Fig 1.11
Table 3:VSM Data(Sample)
Meg. Meg.
Field Moment
9560 0.0408
9425 0.0402
8833 0.0396
8584 0.0393
4097 0.0383
3893 0.0343
3376 0.0334
2747 0.0328
1393 0.033
982 0.0308
772 0.0308
572 0.022
517 0.0068
368 0.0223
-4 -0.0009
-9389 -0.0122
0.05
0.04
J
...
c
CII
E o
~ u
+:
CII
c
till
RI
~
-15000
D.03 ,r
0.02
0.01
-10000 -5000~ ________ -0.01
r(JQl1e ic Field
5000 10000 15000
Fig: 1.10 VSM Graph ofCNTs of complex EggNiCh( 900Alc)Table4:VSM Data(Blank)
mag. Mag.
Field Moment
7499 0.00294
7665 0.00286
8746 0.00281
8871 0.00275
6254 0.00259
1362 0.00247
520 0.00231
-10371 0.00023
-10039 0.00073
-7431 0.00041
0.0035 I
0.003
....
c:
CII
E o
:E u
.. CII
c:
tlO
III
:E
-15000 -10000 -5000 o
Magnetic Field
5000 10000 15000
Fig: 1.11 VSM Graph of blank for reference
LI Wei-Xue etal
12
studied the magnetic properties of multi-walled carbon nanotubes
encapsulated Fe/Co particles. There graph shows resemblance with the graph ofmy sample.
IIi both the graphs CNTs are paramagnetic in nature. Graphs show increase in magnetic
moment with increase in magnetic field strength.K.Atre etal
7
of Nanomaterial and nano research laboratory, USA synthesized
vertically aligned carbon nanotubes. They also studied magnetic properties using VSM.
There VSM graph also showed similar findings and resembled with the graph ofmy sample.
Conclusion
CNTs can be prepared by the reaction of Amino Acid with Nickel salt and by
decomposing the compound formed. Chemical ~ompound can be formed in both aq~eous and
organic medium. This shows that even after denaturation protein formed desired compound
with Nickel salt. This indicates that primary peptide structure is involved in compound
formation.
Decomposition temperature also plays a vital rok in the formation of CNTs.
DLS and SEM results reveals that 800 and 900 are the optimum temperatures for the
formation ofCNTs. SEM and DLS results also confirm the formation ofCNTs.
The formation ofCNTs is again confirmed by XRD and TEM results. XRD and
TEM results reveal that MWNT are formed.
Some properties of CNTs were also studied TGA, DTG, and DTA results give
idea about thermal properties of CNTs. These studies tell us that the CNTs possess high
thermal stability and high melting point.
VSM studies confirm the paramagnetic nature ofCNTs.
Reference:
1. B.DMistry, A Handbook of Spectroscopic Data Chemistry ,2009 pp27-
53&101-127
2. Organic Chemistry ,Alans, Wingrove, Robert.L.Carot pp63
3. O. Truspike Vych, N Callings, T. Hasan, V. Scardaci, and AC Ferrari and co-
workers ,Characterization of Carbon Nanotubes Thermo Tropic Pneumatic
Liquid Crystal Composites, Journal ofPhysics Vol. 41 ,2008.
4. B. Tiwari, J.P. Tripathi, Sanjay Saxena, Synthesis and Characterization of
CNTs by Prepared by Denatured Protein, Inventi International Journal, Vol. J ,
2011.
5. B. Tiwari, J.P.Tripathi, Sanjay Saxena, Synthesis and Characterization of
Carbon metal Nanotubes, Conference Proceedings American Institute of
Physics, 2010.
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Using Spinach, Characterization and Study ofMagnetic Properties. Journal of
Indian Chemical Society, Vo1.89, ppI143-1148, 2012.
7. K.Aatre et ai, Synthesis of Vertically Aligned Carbon Nanotube and Magnetic
CNTs For Cellular Growth and Detection, Proc ofSPIC, Vo16931, 2008.
8. C.R. Bhattacharji, A.Nath and coworker ,Synthesis and Characterization of
Carbon Nanotubes using a national precursor turpentine oil ,Science Journal
UBU vol.2, pp36-42,2011
9. loan Stalin Etal, Synthesis and Characterization of Carbon Nanotubes by
Catalytic Pyrolysis of Phenol formal resigns, Physics vol.37, pp44-48,2007
10. X.Chang et ai, Characterization of Multiwalled Carbon Nanotubes Dispersing
in Water and Associate With Biological Effects, Journal of Nanomaterials
vol.20 11 ,201111. Sumio Iijima et ai, Thermo gravimetric analysis of single wall carbon
nanotubes ultrasonicated in mono chloro benzene, Chemical Physics
letters,vo1364 pp420-426,2004
12..LI Wei-xue, HAO Yuan, , CUI Yong-fu, DAI Jian-feng, , CHEN Ti-jun,
WANG Qing, , WU Zhong-Ii, , LI Yang, Magnetic Properties of Multi-
Walled Carbon Nanotubes Encapsulated Fe/Co Particles, Journal of Trans Non
Ferrous Matal Society of china Volume 17 pp. 696-699 , 2007.
13. Chang Xin Chen, Wenzhe Chen Yafei Zhang, Synthesis of Carbon Nanotubes
by Pulsed Laser Ablation at Normal Pressure in Metal Nano-Sol., Material
Synthesis Papers, Vol. 28 Issue 2, pp. 121-127,2005.
14..LI Wei-xue, HAO Yuan, , CUI Yong-fu, DAI Jian-feng, , CHEN Ti-jun,
WANG Qing" WU Zhong-Ii, LI Yang, Magnetic properties ofmulti-walled
carbon nanotubes encapsulated with Fe/Co, Journal of Trans Non Ferrous
Metal Society of China Vol. 17 pp. 696-699, 2007.

We want to get a process patent on preparation of cnts. using amino acids and transition metal in organic medium (a