Synthesis of macro molecules and polymer and application in diverse field

1. 1
Synthesis of macro molecules and polymer and
application in diverse field
Debdeep Maity
Ruđer Bošković Institute

2. 2
School of Chemical Science,
NISER, Bhubaneswar
Supervisor: Dr. Prasenjit Mal
March 2016- July 2018
Department of Supramolecule & organic
chemistry,
RBI, Croatia
Supervisor: Dr. Zoran Dzolic
Sept 2014- Feb 2016
CSIR-Central Salt and Marine Chemicals Research Institute, 2008 – 2014.
supervision of Dr. Parimal Paul.
Title of the Thesis : “Calixarene Based Molecular Sensors: Synthesis,
Characterisation and Application in Ion RecognitionStudy”.
Innocule Additive &
Materials, Bhubaneswar
Research scientist
Decembar 2018

3. 3
Industrial Experience:
Innocule Material and additive Pvt Ltd
Position: Research Scientist Department: Polymer
December 2018
 Activity
Development of polymer for dewatering of Mineral slurry during filtration.
Development of polymer using dust separation.
 Synthesis of high temperature polymer from cheap natural source to improve
coke quality from non coking coal.
New robust hydrophobic polymer for coating purpose.

4. 3
Post Doctoral Work :
National Institute of Science Education and Research,
Bhubaneswar. March, 2016 – March, 2018
Position: Postdoctoral Fellow Project: water soluble organic receptor
Ruder Boskovic Institute, Croatia, Europe. September 2014-
Feb 2016
Position: Postdoctoral Fellow Project:
Preparation of hybrid soft materials combining
supramolecular anthraquinone-based gel systems and gold
nanoparticles.

5. Synthesis of water soluble ligand for sensing Al3+ andP2O7
3-
4

6. Synthesis of Precursors for acence compound
5
• Schiff Base reaction conducted by ball milling

7. Oxalamide based chiral gel
Picoline based chiral gel
6
TEM Image of different chain length of gel and nanoparticles
presence prepared in situ
Gel-Sol conversionof prepared chiral gel treated withF-

8. Synthesis of Ruthenium(II) based hydro gelator
Synthesis of Stilbene based gelator
7

9. 8
Di-phenylether
Synthesis of Calix[4]arene
The term “calix” has
come from the Greek
word “calyx”. In Greek,
calyx means cup or
vase.
OH
OH
OH
OH

10. Synthesis of calix-crown hybrid ionophores
10
K+
Na+
Cs+

11. NMR Titration to Determine Binding Constant with Metal Ions
//
//
//
//
//
a
b
c
d
e
7.4 7.2 ppm 4.0 3.8 3.6 3.4 3.2 ppm
c
d
e
//
//
b
//
//
//
a
7.6 7.4 7.2 7.0 ppm 3.6 ppm
Relevant portion of the 1H NMR spectra of 2,
recorded with increasing concentration ofBa2+.
Relevant portion of the 1H NMR spectra of3
recorded with increasing concentration ofNa+
Binding constants (Ks) for the ionophores1-3
Ionophore Metal ion Binding constant
(Ks/M-1)
1 Na+ 3.10 x 103
K+ 4.17 x 103
2 Na+ 6.00 x 10
K+ 4.19 x 103
Rb+ 4.55 x 104
Ba2+ 3.35 x 102
3 Na+ 2.05 x 103
7.090
7.070
7.050
7.030
7.010
0.0 2.0 4.0 6.0 8.0 10.0
[M]/[Host]
Chemicalshift()
Obs.(yi)
Calcd(y0i)
The non-linear least square fit from 1HNMR
titration data for the binding of 2 withBa2+
New J. Chem., 2010, 34, 2796
11

12. Synthesis of calixarene derivatives for selective detection of different
anions
12
Colorimetric & NMR study
Reagents and conditions: i) AlCl3, Toluene, reflux; ii) BrCH2CH2CH3, K2CO3, acetonitrile, reflux; iii) BrCH2COOCH3, K2CO3, acetone,
reflux; iv) NH2(CH2CH2)NH2, MeOH-DCM, reflux; v) BrCH2COOCH3, K2CO3, acetone, reflux; vi) NH2(CH2CH2)NH2, MeOH-DCM, reflux;
vii) NH2(CH2CH2)NH-CH3, MeOH-DCM, reflux; ix) BrCOOC2H5, NaH, acetone, reflux; x) NH2(CH2CH2)NH2, MeOH-DCM, reflux.
Supramol.chem. 2017, 29,600

13. Synthesis of fluorescence sensitive calixerenes derivatives
 Monomer emission and excimer peak exhibit 408and 431, 515 nm.
Inorg.Chem.Commun., 2010, 13, 1522. 13

14. Recognition of anions in ACN-CHCl3 (9:1) and THF-Water (4:1)monitored
by Uv-Vis luminescence spectra
 Anions tested F-, Cl-, Br-, I-, H2PO4 , ClO4 , NO3 , BF4 , CH3COO , HSO4- - - - - -
450 600
F-
3 4
NO-
, ClO-
, Br-
,I-
,
BF-
,Cl-
, PO 3-
,AcO-
,14 4
Wavelegth(nm)
UV-Vis spectral change for 1 (1.83×10-5M) recorded in acetonitrile-
chloroform in presence of various anions (100 equiv).
Luminescence spectra of 1 (1 x 10-6M) recorded in acetonitrile-chloroform
inpresence of various cations (100 equiv)
Colour change for 1 upon addition of various anionsin
acetonitrile -chloroform
14
-6
-1.2
0.0
1.2
-5 -4 -3
Log[M]
Log(Fo-F)/(F-F)
400 500 600 700
Emission spectral changes for 1
(1 x 10-6 M) in ACN-CHCl3
(9:1) upon addition of
increasing amount of TBAF(0
to 100 equivalent).

15. Synthesis of calixarene-Ru(II) polypyridyl complex
RSC Adv. 2015, 5, 6151. 15

16. Binding Study of NaCN
600 700 800
0.2
-4.3 -4.2 -4.1 -4.0 -3.9
0.4
0.6
0.8
0xx
Log(F-F)/(F-F)
Log[CN]
1
Emission spectral changes of
-61 (3.3 x 10 M) upon
addition of increasing
of CN- ofconcentration
sodium salt.
0.1
0
0.4
0.3
0.2
-6.35 -4.72 -4.25 -4.05
Log [CN-]
Intensity(Fx–F0)/F0
LOD
Plot of relative Intensity vs.
[CN-] with LOD = 70 ppb for
detection of the lowest
detection limit
Bar diagram showing amount of quenching
of emission intensity for complex 1 at 642
nm upon addition of CN- and mixture of
anions containing 10% of CN- and 90% of
other anions recorded in H2O-CH3CN
(95:5) solvent
Bar diagram of reversible study of
complex 1 with addition of NaCN and
Cu(ClO4)2.
Bar diagram showing emission
intensity before after addition of CN- in
different pH values.
-2.0E+06
-1.2E+06
-4.0E+05
4.0E+05
ΔI(CPS)
Change in intensity in Emission
spectra for 1 (2 x 10-6 M) in presence
of anions of sodium salts (2 x 10-4 M)
2 3in H O: CH CN (95:5) solvent
16

17. Route followed for the synthesis of calixarene functionalized gold
nanoparticles
Reagent and condition (i) NaH, BrCH2COOEt, THF; (ii) NH2-NH2, MeOH, 12h reflux; (iii) CS2, Et3N, THF, 24h rt; (iv) HAuCl4,
NaBH4, toluene.
SENSOR ACTUAT B-CHEM, 2014, 191, 757. Colloids Surf. A 2014, 455,122. 17
Calixarene anchor gold nanoparticles
Mechanistic pathway for sensingmetal
ion
Uv-Vis spectral change and nanoparticles aggregation inpresence
of metal ion

18. Route followed for the synthesis of calixarene functionalized gold nanoparticles
Microchimica Acta. 2015, 182,377. J.Chem.Sci. 2014, 126, 627. 18

19. Future Research Plan
Carbon/Quantum dot hybridised new supramolecular chiral gel involving FRET ON-OFF system and
application in biosensing
A schematic diagram of quantum or carbon dots composite
proposed hydrogel.
A schematic diagram of mechanism of FRET based fluorescent
probe during recognition of guest

20. A. Synthetic route a) SOCl2, MeoH b) mono Boc diamine c) TFA, 4'-methyl-[2,2'-bipyridine]-4-carboxylic acid d) 7-methyl-1,10-phenanthroline-
4-carboxylic acid B) List of the metallogelators will be used for the proposed study
Synthetic path for the preparation of chiral gel
Excitation
CB
VB
Decreasing size
CB
VB
Quantum/car
bon dot PL
A)
B)
A)
B)
 A) A schematic diagram of “quantum size effect” on shifting of band gap. B) Schematic diagram of photoluminescence
quenching effect of quantum/carbon dot in presence of product of various oxidative catalytically enzymatic reaction
Guest molecule

21.  Research Highlights
 Designing, synthesis and characterization of organic macro molecules involving multi-step reaction like
condensation, substitution, amide coupling, oxidation, reduction, protection, D-protection.
 For the purpose of organic synthesis different type reagent even air sensitive also for example n-Butyl lithium,
DIBAL, TEMPO, NaH, NaBH4, LiALH4,, Cr-salt, LiClO4, Pd-based catalyst , DMAP , Na-metal, Mg-Metal etc.
and also carried out different name reaction Suzuki coupling, Heck , Sonogashira coupling.
 Synthesis and performing air, moisture and light sensitive reactions, reactions involving very low temperature to
high temperature (-107 °C to 280 °C).
 Purification of conformation isomer mixture with Column- Chromatography and structural Analysis of the
complicated organic structure using IR, HRMS, and1D spectral data.
 Exposure to the synthesis of complicated systems and their detailed microscopic, photo physical studies and
electrochemical studies.
 Computational knowledge
 Well versed MS Office programs and with various chemistry related computer packages viz Chem
Draw, Chem-3D, Origin SciFinder, Reaxyes and Scopus etc.

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T h a n k You