Research Article, Issue 1

Analytical Methods in Environmental Chemistry Journal

Journal home page: www.amecj.com/ir

AMECJ

------------------------

1. Introduction

Recently, more consideration has seen a flood of

enthusiasm for the shedding of graphene, other

layered mixes, particularly hexagonal boron nitride

(h-BN) [1-4]. The h-BNNs significantly higher

compound security and protection from oxidation

contrasted with that of graphene. Boron nitride

(BN) is the isoelectric and isostructural simple to

graphite with rotating boron and nitrogen iotas in the

structure [5,6]. Following these underlying reports,

a few different techniques, for example, mechanical

shedding by means of drawing, Lithium particle

intercalation and low vitality ball processing were

utilized to create little amounts of top-notch h-BN

nanosheets [7-11]. Substance shedding of h-BN

was later proceeded as an option in contrast to the

mechanical courses, driving a basic and practical

path for the mass peeling of h-BN nanosheets.

These were performed by treating the mass

h-BN powder in different natural solvents, N,N

Di-methylformamide (DMF), methane sulfonic

corrosive (MSA), and liquid metal hydroxides.

These methodologies yield low-convergence

* Corresponding Author: Rmesh K. Gupta

E-mail: r.gupta.k1983@gmail.com

DOI: https://doi.org/10.24200/amecj

Alisha Saanvi

, Ringo Krishnan

Amoli Hassan

, Rmesh K. Gupta

a,*

Department of Chemistry, Indian Institute for Advanced Materials, India

Fabrication of electrochemical sensor biosystems through

hexagonal boron nitride Nanosheets for extraction lead in

human serum

A R T I C L E I N F O:

Received 27 Nov 2019

Revised from 26 Jan 2020

Accepted 20 Feb 2020

Available online 29 Mar 2020

Keywords:

Boron nitride nanosheets,

Triazine azide,

Lead,

L-cysteine,

Electrochemical Sensor,

Solid phase extraction

A B S T R A C T

Lately a flood of expanded enthusiasm for the peeling of boron nitride (h-BN)

has seen because of its energizing electrical, warm, photonics mechanical

properties and detecting. A few ways to deal with have risen depicting the

peeling, functionalized and solubilization of h-BN. In this investigation,

we report on a direct way to deal with alter the surface and its application

as another sort of biomedical applications. The readied item is basically

described by FTIR spectroscopy, field outflow (FESEM), TGA strategy,

XPS range, and BET surface zone estimations. Nano-composites were

immobilized on terminals to distinguish the glucose, L-cysteine in cushion

medium by cyclic voltammetry (CV), square wave voltammetry (SWV),

and electrochemical impedance spectroscopic (EIS). Potential utilization

of the covalent functionalization, modest forerunners, biodegradability

and multifunctionality of superior composites boron nitride, they could be

utilized for a wide scope of things to come biomedical applications. Also,

the composites boron nitride was used for extraction lead (Pb

) ions in

human serum by micro solid phase extraction coupled with atom trap atomic

absorption spectrometry (AT-AAS) by researchers. The LOD and enrichment

factor was obtained 2.96 and 9.82, respectively for 10 mL of human serum

sample (RSD < 2%). The validation was confirmed by CRM, NIST solution.

Fabrication of electrochemical sensor by boron nitride Rmesh K. Gupta, et al

Anal. Method Environ. Chem. J. 3 (1) (2020) 49-54

of h-BN nanosheets significantly after broad

sonication [12-18]. With the expansion of practical

gatherings triazine azide an improved scattering

and strength of h-BN exists in an assortment of

solvents. In this, we report the covalent compound

functionalization of h-BN nanosheets utilizing

receptive nitrene radicals. Point by point portrayal

of the functionalized h-BN was performed to check

the covalent idea of the connection [6, 18-22].

Many method was used for triazine determination

in liquid phases. The functionalization technique

was reached out to covalently unite triazine azide

to the outside of h-BN nanosheets by nitrene

addition and utilize these nano composites-

functionalized BN nanosheets for cooperations

with biosystems and improve detecting properties

[22-26]. Electrochemical impedance spectroscopy

(EIS) has as of late developed as a device to analyze

forms that happen at various timescales. The idea

of “impedance” is comparable to opposition yet

takes into account depiction of complex circuits

which have nonlinear current–voltage connections,

for example, those which show capacitance,

inductance, or mass dispersion. EIS exploits this

idea by relating hypothetical circuit components

to real electrochemical procedures happening in a

material and permitting fitting of current, voltage,

and recurrence information to equal circuit models.

EIS information is produced by applying an AC

potential to an electronic gadget, estimating the

AC current reaction, and recording stage move

and adequacy changes over a scope of applied

frequencies. By analyzing the present reaction

over a scope of frequencies permits partition of

procedures which happen on various timescales,

making it perfect for isolating electronic and ionic

procedures in blended conductors [27-30]. This is

a key favorable position of EIS making it a well-

suited instrument to consider particle dispersion

in HOIPs and resolve the substance personality of

the particle [3]. In addition h-BN nanosheets was

used for separation Pb ions in human biological

samples by covalence bonding of BN to Pb (BN:---

-Pb) by μ-SPE coupled to AT-AAS. The absorption

capacity was achieved 141.4 mg g-1 at pH=8.2.

2. Experimental

2.1. Materials and Instruments

All general materials such as KCl, Fe(CN)

, triazine

azide, and azine were provided by Merck. h-BNN

were purchased from Sigma-Aldrich company.

The graphene was provided by Indian Institute for

Technology. Other chemicals with analytical grad

such as HNO

, HCl and NaOH were purchased

from Merck, Germany. The pH was adjusted based

on 0.32 mol L

-1

of buffer solution (HPO

)

from pH of 5.0 to 8.4. The polyoxyethylene octyl

phenyl ether as the anti-sticking material was used

in human samples (Merck). GBC906 Flame atomic

absorption spectrophotometer based on atom trap

(AT-FAAS, AUS) measured Pb in serum samples.

The air-acetylene based on background correction

(LD

) tuned by the software of AVANTA of AT-

FAAS. The AT-FAAS can be determined Pb with

micro liter of the sample with LOD of 0.04 mg L

-1

2.2 Preparation of h-BNNs

h-BNNs were modified with triazine azide at

room temperature with a ratio of 1:2 weight from

h-BN nanosheets: triazine azide for giving TN

functionalized BNNSs (TN

-h-BNNs). After

stirring for 24 h, the final product was centrifuged

at 5500 rpm per minute. The obtained Tr-h-BNNs

sediment was purified by dialysis against DMF for

2 days and dried at 100˚C. So., a white powder was

obtained for characterization.

2.3 Electrochemical characterization of BN-TrAz

modied electrode

The electrochemical properties of BN-TrAz/

GCE were examined using EIS and CV. The EIS

method can be used to study the kinetics of electron

transfer between electrolyte and electrode surface.

According to Fig. 1, the effect of the modified

electrode on the electrochemical response, the EIS

spectrum (A) and the cyclic voltammonogram (B)

of the 7 mM [Fe(CN)

]

solution containing 0.1 M

KCl for bare glass carbon electrodes (a) BN/GCE

Fabrication of electrochemical sensor by boron nitride Rmesh K. Gupta, et al

2.4. SPE procedure

By μ-SPE method, 10 mL of serum were used for

speciation and determination of lead ions at pH

8.2. First, 20 mg of h-BNNs added to 1-octyl-3-

methylimidazolium hexafluorophosphate [OMIM]

[PF

] in ethanol and the suspension of h-BNNs in IL

were injected to serum sample with concentration

of 100 µg L

−1

at pH=8.2. After shaking with an

ultrasound bath for 6.0 min, the Pb (II) ions were

efficiently extracted with the nitrate of h-BNNs

(N:---Pb) as dative bond in pH=8.2. The h-BNNs

trapped in [OMIM][PF

] and separated from the

liquid phase in the bottom of the conical tube after

centrifuging (3500 rpm). Then, the pb

ions back-

extracted from h-BNNs by 0.5 mL of nitric acidic

(0.2M, up to 1mL) and after diluted determined by

AT-FAAS.

3. Results and Discussion

3.1. Characterization

As appeared in Figure 1, the IR range of perfect

h-BN uncovers a deviated bond at 1384 cm-1

which compares to B-N stretch and the bond at 818

cm-1 doled out to B-N-B extending vibration. The

IR range of Triazine shows groups at 1701 cm−1

which were appointed to C=N extending vibration.

The morphology and structure of h-BNNs and

Tr h-BNNs was explored by SEM. The shedding

procedure brings about not many layer h-BNNs

sheets with smooth surfaces and edges and

sidelong size in the scope of 1-2 µm (Fig. 1). The

Tr -h-BNNs sample showed a morphology different

from that for h-BNNs. Due to the grafted Triazine-

azide groups, surface of Nitrene -h-BNNs become

relatively smooth and compact with porous features

with the structure of h-BNNPs crystalline produced

is preserved [9-11].

According to Figure 2, the effect of the modified

electrode on the electrochemical response, the EIS

spectrum (A) and the cyclic voltammonogram (B)

of the 7 mM [Fe(CN)6]

3−/4-

solution containing 0.1

M KCl for bare glass carbon electrodes (a) BN/GCE

behavior of the electrode was investigated after

interaction with 200 μM L-cysteine by DPV method

was investigated and the results were shown in

(Fig.3).

3.2. Optimization and Validation

All parameters such as pH, sample volume, mass

of sorbent, shaking time for extraction Pb from

serum samples was optimized, Based on procedure

sample volume from 5-15 mL have good efficiency

for lead extraction so 10 mL of sample was used

for further study. Also, pH of sample was evaluated

between 2-10 and results showed us the pH 7.5-8.2

have high recovery for lead extraction, So, pH of 8

was used as optimum pH (Fig. 4). The amount of

Fig. 1. A) FTIR spectra of (a) h-BNNs, (b) Triazine, (c) Triazine-azide, (d) Tr- BN. B) Different magnification of SEM

images of the a) h-BNNs and b) Tr-BN.

Anal. Method Environ. Chem. J. 3 (1) (2020) 49-54

Fig. 2. The impedance spectra (A) and CV voltammograms (B) of for bare glass carbon electrodes (a) BN/GCE (c)

and TriAz/BN/GCE (b) in 7 mM [Fe(CN)6]

3−/4-

solution containing 0.1 M KCl

Fig. 3. Difference pulse voltammogram of 200 μML- cysteine for different electrodes at pH =7. DPV Voltammograms

at the bare glass carbon (b), BN/GCE (a) and TriAz/BN/GCE (c).

Fig. 4. The effect of pH on lead extraction by BNNs

Fabrication of electrochemical sensor by boron nitride Rmesh K. Gupta, et al

h-BNNs for extraction was optimized and 20 mg of

sorbent was selected as optimum mass. The CRM

was used for validation samples as Table 1.

4. Conclusions

In present study, nitrene molecules were successfully

grafted on the surface of h-BNNs and the resulted

compound was used as an L-cysteine sensor of

two sulfur of L-cysteine through the formation of

Substitution reaction to Chlorine triazine azide.

The most important achievement of this study is

that L-cysteine is diagnosed in a straightforward

manner. In summary, this synthesized modified

electrode, could be used as a biosensing interface in

the fields of biomedical and clinical diagnostics of

Sulfur Protein Amino Acid such as L-cysteine. The

modified electrochemical sensor was characterized

by SWV, CV, and EIS. Based on results lead (Pb)

can be extracted by h-BNNs in pH=8 by μ-SPE

method at optimized conditions

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CRM

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-----271.5 ± 14.4-----277.6 ± 1.6

CRM

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