Applications of Polyhydroxamic acid for strategic and

environmental important metal ions

Content
•Synthesis of Polyhydroxamic acid

•PHA Bulk polymer

Application to Chromium Remediation

•PHA Sheet membrane

177
Lu-Radioactive Skin Patches

•PHA micro particles

Possible utility in Heptacellular carcinoma therapy
 Introduction

Polyhydroxamic acid

OH
=O

-
P -C-N-OH P - C= N - OH

H
P
P O
n+ C
M n+

=
HN M
N
n O
n
 Synthesis of PHA (polyhydroxamic acid)
Chem. Eng. J. 326 (2017) 318–32
Step:1 Synthesis of polyacrylamide
CH2 = CH CH2 CH CH2 CH CH2 CH
C=O C=O C=O C=O
NH NH2 NH2 NH
CH2= CH
CH2 AMP ( initiator) CH2
C=O
+ NH 70 ºC, 20 mins NH2 NH2 NH
NH2 C=O C=O C=O C=O
CH2 =CH CH2 CH CH2 CH CH2 CH
Acrylamide MBA Polyacrylamide

Step2: Conversion of polyacrylamide to polyhydroxamic acid

O O
O
P -C-NH2 + NH2OH OH
-
P C NH2 P -C-NHO Na+ + NH3
+
NH2OH H+

O
P -C-NH-OH
Polyhydroxamic acid
 Characterization
OH

=O
=O
P -C-NH 2 P -C-NH-OH P -C=N-OH

N-O stretching
of oxime group
-C=N-O

C-O stretching

Visual
Characterization of
PHA
PHA (a) Before (b) After uptake of Chromium
 Sources of Chromium

Chrome
Plating

Paints &
dyeing

Steel power
plant Chrome Plating Bath

Organic &
Inorganic
chemical
Leather
tanning

Leather tanning
 Effect of pH on chromium sorption

25 ml 5 mg L-1 Chromium solution (contact time=24 h; sorbent = 50 mg)

Charge on PHA surface

[Cr(H2O) 6]3+ pH < 3.5

HCrO 4
-
pH ~1- 6.5
[Cr(OH)(H2O) 5] 2+ pH > 3.5
CrO42-   pH > 6.5
[Cr(OH)2(H2O) 4] + pH ~ 7
 
[Cr(OH) 3(H2O) 3] 0 pH > 7
2HCrO4- Cr2O72- + H2O
(precipitate)
( pH 1-7 and concentration ≥1000 mg/L
 Kinetic Study

 Sorption kinetics of Cr (III) is more rapid as compared to Cr (VI) and

attained equilibrium in 20 min while that of Cr (VI) was within 8 h.
 Which implies different uptake mechanism
log(qe-qt) = log qe-(k1t/2.303) pseudo first order

t/qt = 1/k2qe2 + t/qe pseudo second order

qe = amount of metal ion sorbed (mg/g) at equilibrium
qt = amount of metal ion sorbed (mg/g) at time t
k1 = pseudo first order rate constant (min −1)
k2 = pseudo second order rate constant (g/mg/min)
t = time in min
 Effect of concentration

 Amount of chromium in solid

phase increases with increase in
initial chromium concentration
in solution

25 ml 5- 4000 mg L-1 Chromium solution (sorbent = 50 mg)

Ce ___
__ 1 C ___ 1
= e + Linear form
q e qm qm b

qm b C e
qe = _______ Non linear form
1 + b Ce
qe = amount of metal ion adsorbed (mg g -1)
qm = monolayer adsorption capacity (mg g -1)
Ce = equilibrium concentration (mg L-1) of bulk solution
b = related to free adsorption energy

Langmuir Adsorption Isotherm

 Freundlich Adsorption isotherm (a) Cr(VI) (b) Cr(III)

1/n
qe = KF Ce non linear form

lo g qe = log KF + 1/n log Ce linear form

qe = amount of metal ion sorbed (mg g -1)

Kf = constant indicative of the relative adsorption capacity
Ce = equilibrium concentration of metal ion in bulk solution (mg L -1)
1/n indicates intensity of adsorption
 Sorption mechanism

Cr(NO3)3 XRF of PHA XRF of Cr(VI)-PHA

(Cr in +3
O.S)

‘Cr’
sorbed
PHA

K2Cr2O7
(Cr in +6
O.S)

XPS of Cr(VI) loaded PHA XRF of Cr(III)-PHA

 Diphenylcarbazide method

Blank 0.4 0.6 0.8 1.0 1.0 0.7

Uptake of Cr(VI) 86.5%

Total Cr in equilibrium solution 13.5% (by AAS)
1 mg L -1 Cr(III)
Cr (VI) in equilibrium solution 1.4% (DPC method)

Reaction involve in Cr(VI) uptake mechanism

2Cr+6 + 6 R-CO-NH-OH → 2Cr+3 + 6 R-COOH + 3N2↑ + 6H+

4Cr+6 + 6 R-CO-NH-OH + 3H2O → 4Cr+3 + 6 R-COOH + 3N2O↑ + 12H+

 Interference study

% U p ta k e o f c h r o m iu m
100
Na
80 K

60 Mg
Ca
40
Cl
20 Sulphate

0 Mixed ions
0 100 500 1000
Concentration Interfering ions (mg L-1)

Effect of interfering ions on chromium uptake

Concentration (mg L-1) % Uptake of Cr (VI) (in the presence of )

Na K Mg Ca Sulphate Mixed ions

100 99 ±3 99 ±3 97 ±2 95 ±3 99 ±1 87 ±2
500 96 ±2 99 ±1 85 ±6 69 ±4 90 ±4 85 ±3
1000 93 ±5 93 ±3 80 ±4 49 ±5 86 ±6 83 ±5

Average (% uptake) ± SD, n=5

 Applicability to Ground Water Sample
 In order to evaluate the applicability of PHA to real sample, few groundwater samples were analyzed using
Atomic
absorption spectrometer (AAS) and Inductively Coupled Plasma mass spectrometer (ICP-MS).
 Two typical sample which contain maximum amount of ‘Cr’ (< 100ppb) and other elements are listed in the table
 Batch mode experiment was carried out to the ground water samples and Groundwater
spiked with a known amount of Cr(VI) at optimized condition.
Elements GW1 GW2
**
Na 908.96 511.68
**
K 7.50 17.4
**
Mg 25.2 51.5 % Uptake of ‘Cr’
**
Ca 5.0 14.9
**
Fe <0.2 <0.2 Sample Amount spiked % Uptake of Cr
*
Cr 64.7 95.4 GW1 0 55 ± 5
*
Cu 8.8 17.9 GW1 1 mg L-1Cr(VI) 72 ± 3
*
I 6 16
GW2 0 80 ± 4
*
Sr 510 1352
*
Zn 30 14 GW2 1 mg L-1Cr(VI) 90 ± 3
*
Al 61 29
*
Ni 0.7 1.6 Average (%Uptake) ± SD, n=5
*
Pb 3.8 10.1
*
B 767 1340
*
Li 25 51
*
Mn 4.7 17.6
*
Co 0.17 1.94

concentration in **
mg L-1 , * µg L-1
Instrumental RSD = 5%, n=5
 Application to real sample
Chromic acid bath contains larger amount of ‘Cr’
column mode experiment was carried out to the chromic acid bath at optimized condition

Recovery of chromium compound

XRD
∆
600 ˚C, 3h

Cr-PHA ‘Cr’ residue

XRD Plot of leftover residue after decomposition of
(a) Cr(VI)-PHA and (b)Cr(III)-PHA

Ref: 2003 JCPDS – International Centre for Diffraction data

 PHA Sheet membrane

Visual Characterization of PHA

Synthesis Scheme for PHA-cellulose sheet

S. No. Time (h) % Uptake of 177

Lu
1. 1 58.4±1.9
2. 1.5 61.5±2.1
3. 2 69.6±1.4
4. 3 79.8±1.1
5. 4 91.9±1.3
6. 5 98.1±1.5
7. 6 98.5±1.1

Influence of contact time on Lu uptake

Influence of pH on Lu uptake
a b

Autoradiograph of 177Lu-PHA-cellulose
SEM images of (a) cellulose (b) PHA-cellulose
Position Optical Density at various exposure times
10 Sec 20 Sec 40 Sec 80 Sec
1. 0.71 0.98 1.70 3.03
2. 0.69 0.98 1.62 2.90
3. 0.70 1.01 1.68 2.81
4. 0.73 0.95 1.72 2.93
5. 0.66 1.01 1.78 3.02
Mean±SD 0.69±0.03 0.99±0.03 1.70±0.06 2.94± 0.09

EDS of (a)PHA-cellulose (b) PHA-cellulose loaded with Lu

 PHA micro-particles

SEM image of PHA micro-particles

Influence of pH of reaction on the yield of

177Lu–PHA microparticles XRF of PHA and Lu-PHA
 Inorganic sorbent

Inorganic sorbents possesses certain properties such as enhanced surface area

and morphologies that make it a great candidate as an adsorbent for removing
heavy metals from contaminated waters

The larger surface area per mass allows more sites for surface chemistry.

They also have the ability to be tuned with different chemical species to
increase their functionality toward specific targets

TiO2

TiO2 is well known inorganic metal oxide widely investigated for its huge
application

TiO2 has great potential for the removal of environmental pollutants due its high
surface area, mechanical strength and photo catalytic ability
 Sorption studies with TiO2

pH study Kinetic study

25 ml 5 mg L-1 Chromium solution (contact time=24 h; sorbent = 50

mg)
 Cr(VI) sorption process in presence of light

Cr(VI)
e- e- e- e- e- e- e-

Recombination
hv
Cr(III)

Excitation
h+ h+ h+ h+ h+ h+ h+
TiO2

Photo catalytic reduction of Cr(VI) to Cr(III) by TiO 2

 Presence of Cr(III) on TiO2 surface confirmed by XPS analysis

Disadvantage
The photo reduction process is very slow, work up to 10 mg L -1 solution.
It is not always possible to have sunlight.

To overcome this problem, Ascorbic acid, hydroxylamine hydrochloride and

hydrazine hydrochloride were explored as alternatives of sun light.
 Rate of Cr(VI) reduction

 The reduction rate of Cr(VI) was found to be quite rapid in case

of ascorbic and hydroxylamine hydrochloride

 Complete reduction of Cr(VI) occurred within 15 min (ascorbic acid) and

45 min (hydroxylamine hydrochloride)

Cr(VI) solution = 50ml 50 mg L-1 Reducing agent = 5.0 ml 0.1M

Theoretically the reaction,

4CrO4 2− + 3N2H4 + 4H2 O 4Cr3+ + 3N2 + 20 OH−
Journal of Hazardous Materials B123 (2005) 176–180

Cr2O72- + 3 Ascorbic acid + 8H+ 2Cr3+ + 3 Dehydroascorbic acid +7 H2 O

Chemosphere 57 (2004) 609–613

2Cr6+ + 6NH3OH+ 2Cr3+ + 6H2O + 3N2 + 12H+

4Cr6+ + 6NH3OH+ 4Cr3+ + 3H2O + 3N2O + 18H+

Radiochim. Acta 96, 333–343 (2008) / DOI 10.1524/ract.2008.1502

 The sorption capacity of TiO 2 for Cr(VI) (after reduction) was similar as that Cr(III) and followed Langmuir adsorption isotherm
 Incorporation of hydrazine to TiO2
Journal of the American Chemical Society, 133(2011) 9516

Aqueous 1 hour TiO2-hydrazine

Hydrazine
K2TiF6 composite
hydrate microwave oven
solution (LHT)
Layered hydrazine
titanate

Characterization

IR spectra X-ray diffraction Charge on sorbent surface

 Sorption studies chromium using LHT

pH study
Kinetic study of (a) Cr(VI) (b) Cr(III)

Qm = 75 mg g-1
Qm = 89 mg g-1

Langmuir adsorption isotherm (a) Cr(VI) (b) Cr(III) using LHT

 Interference study

% Uptake of Cr(III) % Uptake of Cr(VI)

Interfering ions Concentration of Interfering ions

Concentration of Interfering ions
100 500 1000
100 500 1000
( µg mL )
-1
( µg mL )
-1

Na+ 100 ± 4 100 ± 1 100 ± 4 100 ± 2 100 ± 2 100 ± 5

K+ 100 ± 3 100 ± 2 100 ± 3 100 ± 5 100 ± 5 100 ± 3

Mg2+ 100 ± 2 100 ± 5 100 ± 1 100 ± 1 100 ± 2 100 ± 2

Ca2+ 99 ± 5 98 ± 2 97 ± 3 96 ± 3 92 ± 3 90 ± 3

Cl- 100 ± 3 100 ± 3 98 ± 2 100 ± 4 100 ± 4 99 ± 4

NO3- 100 ± 1 100 ± 2 98 ± 5 100 ± 2 100 ± 1 98 ± 2

SO42- 100 ± 2 100 ± 5 98 ± 5 100 ± 5 100 ± 2 96 ± 2

Combined ions 100 ± 2 99 ± 3 98 ± 2 99 ± 2 93 ± 5 82 ± 4

Average(%Uptake) ± SD, n=5

 Comparative Study
Parameters / Sorbent Polyhydroxamic acid TiO2 TiO2-hydrazine
composite
Capacity(mg/g)
Cr(III) 322 69 87
C(VI) 178 **65 75
Concentration range
Cr(III) 5 - 1500 mg L-1 5 – 2000 mg L-1 5 – 2000 mg L-1
Cr(VI) 5 -4000 mg L-1 * 0.1- 10 mg L-1 5 – 2000 mg L-1

pH
Cr(III) 4-7 4-7 3- 7
Cr(VI) 4 < *6 3-10

Equilibrium time

Cr(III) 30 min 2 hr 30 min

Cr(VI) 8h *6 hr 3 hr

* in presence of light
** external reducing agent added (1ml 0.1 M Ascorbic acid for 10 m l 100 mg L -1 Cr(VI) solution)
 Conclusion
 Among the three sorbents (PHA, TiO2 and TiO2-hydrazine composite) PHA has
maximum sorption capacity and applicable to variety of industrial waste which
contain larger amount of chromium

 TiO2 can be applied as promising sorbent for remediation of Cr(VI) in presence of

light from groundwater

TiO2-hydrazine composite has wide pH (3-10) applicability for Cr(VI) uptake

 Uptake rate of chromium significantly improved after incorporation of hydrazine on

TiO2
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 Publications
• Samina H. Shaikh, Sanjukta A. Kumar, Polyhydroxamic acid functionalized sorbent for effect removal
of chromium from ground water and chromic acid cleaning bath, Chem. Eng. J. 326 (2017) 318–32.

• Sanjay Kumar Saxena, Yogendra Kumar, Samina H. Shaikh, Usha Pandey, Sanjukta A. Kumar, and
Ashutosh Dash, Preparation of radioactive skin patches using polyhydroxamic acid grafted cellulose
film towards applications in treatment of superficial tumors, Cancer biother. & radiopharm., 32 (2017)
364-370.

• Usha Pandey, Suresh Subramanian, Samina Shaikh, Naresh Gamre, Sanjukta Kumar, and Ashutosh
Dash, Synthesis and Preliminary Biological Evaluation of 177Lu-Labeled Polyhydroxamic Acid
Microparticles Toward Therapy of Hepatocellular Carcinoma, CANCER BIOTHERAPY AND
RADIOPHARMACEUTICALS, Volume 34, Number 5, 2019

Symposium
Samina H. Shaikh, Shailaja P. Pandey, Harshala J. Parab and Sanjukta A. Kumar*, Evaluation of
Polyhydroxamic acid as a potential sorbent for Cr (III) and Cr(VI), DAE-BRN 6 th Interdisciplinary
Symposium on material Chemistry (ISMC), held at multipurpose Hall during 6th-10th December
2016.