Journal of Pharmaceutical Analysis 9 (2019) 20–24

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Journal of Pharmaceutical Analysis

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Original Article

Qualitative and semi-quantitative analysis of health-care

pharmaceutical products using laser-induced breakdown
spectroscopy
Sobia Nisar a,1, Ghulam Dastgeer b,n,1, Muhammad Shafiq c, Muhammad Usman d
a
Department of Industrial Engineering, University of Engineering and Technology, Taxila 47050, Pakistan
b
Department of Physics & Astronomy and Graphene Research Institute, Sejong University, Seoul 05006, Republic of Korea
c
Department of Engineering, University of Sannio, Piazza Roma 21, 82100 Benevento, Italy
d
Centre for Optical and Electromagnetic Research, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006,
PR China

art ic l e i nf o a b s t r a c t

Article history: Laser-induced breakdown spectroscopy (LIBS) is a sensitive optical technique that is capable of rapid
Received 25 June 2018 multi-elemental analysis. The development of this technique for elemental analysis of pharmaceutical
Received in revised form products may eventually revolutionize the field of human health. Under normal circumstances, the
11 October 2018
elemental analysis of pharmaceutical products based on chemical methods is time-consuming and
Accepted 12 October 2018
Available online 15 October 2018
complicated. In this investigation, the principal aim is to develop an LIBS-based methodology for ele-
mental analysis of pharmaceutical products. This LIBS technique was utilized for qualitative as well as
Keywords: quantitative analysis of the elements present in Ca-based tablets. All the elements present in the tablets
Laser-induced breakdown spectroscopy were detected and their percentage compositions were verified in a single shot, using the proposed
Elements identification
instrument. These elements (e.g., Ca, Mg, Fe, Zn, and others) were identified by the wavelengths of their
Health-care pharmaceutics
spectral lines, which were verified using the NIST database. The approximate amount of each element
Qualitative analysis
Quantitative analysis was determined based on their observed peaks and the result was in exact agreement with the content
specification. The determination of the composition of prescription drug for patients is highly important
in numerous circumstances. For example, the exploitation of LIBS may facilitate elemental decomposition
of medicines to determine the accuracy of the stated composition information. Moreover, the approach
can provide element-specific, meaningful, and accurate information related to pharmaceutical products.
& 2018 Xi'an Jiaotong University. Production and hosting by Elsevier B.V. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Laser-induced breakdown spectroscopy (LIBS) is a rapidly
evolving analytical technique based on optical emission spectro-
scopy of laser-produced plasma. In LIBS, a high-energy laser out-
put is focused on a small volume of sample (10 8 to 10 5 cm3) of
solid, liquid, or gas, which results in the generation of plasma due
to stimulation of the sample [1–3]. The process results in the
emission of an optical signal that is detected and analyzed using a
spectrometer. The resulting spectral lines are recorded by this
instrument, which is typically connected to a PC. When a typical
measurement is performed, the observed spectral lines are com-
pared with those in the database of the National Institute of
Standards and Technology (NIST) to facilitate the identification of
Peer review under responsibility of Xi'an Jiaotong University.
n been reported. Compared to available techniques for the analysis
Corresponding author.
E-mail address: G2016SFD004@sju.ac.kr (G. Dastgeer).
1
These authors contribute equally.
the elements [4,5]. LIBS is widely applied in numerous areas in-
cluding process monitoring due to its rapidity, ability to perform
noncontact optical measurement, minimal sample preparation
requirement, and potential to perform real-time in-situ measure-
ments for laboratory or industrial use. The application of LIBS for
quantitative elemental analysis has been demonstrated in me-
tallurgy, mining, environmental analysis and several other fields
[1,6,7].
In the pharmaceutical sector, there has been recent interest in
LIBS. To date, the application of this technique in the pharma-
ceutical field has been exclusively in the analysis of solid dosage
forms, such as quantitating active pharmaceutical ingredient (API).
The analysis is then based on an element specific to the API (e.g.,
chlorine, sulfur, fluorine, or bromine) [1,7,8]. The same analytical
scheme is applied in principle to liquid formulations. However, the
analysis of pharmaceutical products in solution by LIBS has not
of pharmaceutical liquids (colorimetric or potentiometric titration,
chromatography, and spectrometric methods), LIBS is a direct and

https://doi.org/10.1016/j.jpha.2018.10.003
2095-1779/& 2018 Xi'an Jiaotong University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
 S. Nisar et al. / Journal of Pharmaceutical Analysis 9 (2019) 20–24 21

rapid method that does not require sample preparation. The

technique also has several advantages such as high specificity
(analysis versus other preparation) and the possibility of avoiding
sample transfer. It is therefore an efficacious instrument in the
rapidly evolving field of process analytics [2,9]. LIBS is equally ef-
fective for liquids, solids, and gasses. It is a non- destructive
technique for the essential arrangement of a variety of gasses,
solids, and liquids. In the technique, a laser can be utilized in the
laboratory for element analysis and for quantitative assessment of
elements. LIBS is an extremely flexible technique and has several
important benefits. These benefits include rapid analysis, no
sample preparation for the majority of samples, responsiveness to
a large range of essentials as well as the option of immediate
multi-essential investigation [10–12].
Usually, standard samples are required prior to qualitative
analysis using LIBS to calibrate the system. However, several cali-
bration-free LIBS techniques have been developed [13–16].
In this investigation, we determined the elements present in
pharmaceutical tablets including metals and some non-metals
using LIBS. By utilizing a single incident pulse of LIBS on the tablet,
we identified the elemental compositions, which were further
confirmed by comparing the results with those in the NIST data-
base. In this case, we used calcium-based tablets for the analysis of
Ca (as an active agent) and other elements (as passive agents).
Moreover, the percentage of Ca and some other elements was also Fig. 1. (A) Schematic diagram demonstrating the analysis of tablet samples using
determined via quantitative analysis. an Nd: YAG laser where the wavelengths of the elements associated with the re-
In the pharmaceutical industry, tablets are composed of a pow- sulting plasma are detected by a spectrometer connected to a computer. (B) The
der mixture containing active and inactive agents. Some con- SEM image of tablet sample indicates the region where the laser is incident on the
sample to collect elemental analysis data.
stituents are also mixed to keep the tablets in a condensed form, but
these are present in very small amounts on the order of 0.5%–3%. The
substances which are used as active agents can constitute relative was used to investigate Ca and other elements present in different
amounts as low as 1%–2% and as high as 50%–60% of the mass of the samples of medicines. The Q-switched Nd: YAG laser with a pulse
tablet. Strict rules are often implemented for quality control in duration of 5 ns, a wavelength of 1064 nm and energy of 300 mJ,
pharmaceutics. By utilizing LIBS analysis, compliance will be very was used to irradiate the surface of the target sample (Ca-tablets)
simple and reliable. The purpose of this investigation was to identify using a 10 cm quartz lens [20]. The laser ablation region is shown
the elements present in pharmaceutical salts. This technique will be in the scanning electron microscope (SEM) image in Fig. 1B. In the
useful for pharmaceutical industry to differentiate the genuine and process of data acquisition, we optimized many experimental
counterfeit medicine [3,7,17]. parameters to improve the resolution and sensitivity of LIBS to
The tablet samples used in this research contained Ca as an minimize measurement fluctuation and problems due to the het-
active element and many other elements such as Fe, Mg, F, Zn, Cu, erogeneity of the sample [21]. The region of the laser spot on the
Ni, P, and Vitamin-D as passive agents. These medications are used sample was calculated using the Gaussian beam profile of the fo-
to prevent low blood pressure, bone loss (osteoporosis), weak cused beam. The target was mounted on the sample stage.
bones (Osteomalacia /Rickets), decreased activity of the para- Moreover, the region between the focusing lens and the target
thyroid gland, and a certain muscle disease. The samples may also sample was less than the central thickness of the lens in order to
be used by specific groups of patients to ensure that their dietary avoid signal acquisition from the ambient gas on the surface of the
needs in regard to Ca and vitamins are being met. This sample was sample [22]. Emission from the trail was registered using an
also purchased from a local market for the elemental analysis. HR4000 finding system in combination with a visual thread (high-
Prior to the investigation, the composition of the tablets was OH, center width: 600 mm) with a collimating lens (0–45 playing
carefully examined to ensure that elements would be accurately field of sight) located at 90° to the path of plasma development.
detected with little uncertainty. Output data was averaged for 10 laser shots. The data acquired by
In this study, the LIBS technique was utilized for the identifi- the spectrometer was stored on a PC for subsequent elemental
cation of the elements present in pharmaceutical tablets. A analysis [23]. The emission spectra were analyzed by comparing
Q-switched Nd: YAG pulsed laser (PULSED LASER / SOLID-STATE / the wavelengths in the spectra with NIST data to identify the op-
INFRARED / LPSS BRILLIANT, Quantel, France) was used as an ex- tical spectral signature of Ca and the other elements present.
citation source in this investigation [18]. The lasing medium of this
laser was an Nd: YAG (neodymium-doped yttrium aluminum
garnet; Nd: Y3Al5O12) crystal. A spectrometer with a wide spec- 3. Results and discussion
tral range and high sensitivity, fast response rate, with a time-
gated detector was also utilized. It was connected to a computer The acquired data was obtained using a pulsed laser with a
for rapid processing and interpretation of the acquired data [19] as spectrometer to investigate the spectral lines associated with dif-
shown in Fig. 1A. ferent elements on the basis of wavelength and energy. Specifi-
cally, the emissions produced by plasma were utilized to identify
2. Experimental procedure the constituent particle. The LIBS method involves a focused high-
energy laser beam which is used to produce plasma and to sti-
For the elemental analysis, medicine tablet-samples (OMC-D, mulate the sample. Generally, dual-pulse or high-power laser op-
Osnate-d, and Hectoral) were purchased from a local market. LIBS erations are used to produce the necessary plasma. Improved
22 S. Nisar et al. / Journal of Pharmaceutical Analysis 9 (2019) 20–24

Fig. 2. The LIBS data obtained for OMC-D tablet is plotted in the range of 300–700 nm wavelength. (A) The elements observed in the range of 300–700 nm wavelength.
(B) The elements observed in the range of 385–425 nm wavelength. (C) The elements observed in the range of 580–600 nm wavelength. (D) The elements observed in the
range of 600–630 nm wavelength. (E) The elements observed in the range of 635–675 nm wavelength.

plasma radiation can be created by dual-pulse operations
where the interval between the first and second pulse, and the
laser beam geometry play a key role in optimizing the produced
signal [24].
The first investigated sample was OMC-D which contained Ca
as an active agent and additional elements as passive agents. The
spectra obtained by LIBS was used to identify the elements present
in these pharmaceuticals tablets. A laser operating at 1064 nm
with 61 mJ per pulse was focused on the Crafilm tablet. The
Q-switched Nd:YAG (Quantel Brilliant) laser beam with an FL-Q-
switch delay of 280 μs in a spectral range of 300–700 nm was used
to ablate the sample. The emission spectrum was recorded using
an Avantas Spectrometer placed at an angle of 90° with respect to
the surface of the sample, regardless of the direction of the laser
beam. The spectrum was recorded using a continuous beam of the
Nd:YAG laser with a first harmonic of 1064 nm. The spectrum data
for each sample was recorded two to three times to minimize the
uncertainty or the errors. The emission spectrum consists of singly
or doubly ionized spectral lines of Ca, Fe, Mg and other elements
such as Ni, Zn, P and Cu as shown in Fig. 2. The specified results of
OMC-D tablet described in Table 1 accurately match the NIST
database results. The transition from the upper level to the lower
level was expressed in each table for each sample individually.
The intensity (I) of the spectral lines was calculated by using
the following equation [24].
 S. Nisar et al. / Journal of Pharmaceutical Analysis 9 (2019) 20–24 23

Table 1 Table 3
The elements traced by their spectral lines present in each sample of OMC-D tablets The elements traced by their spectral lines present in each sample of Hectoral ta-
using 1064 nm Nd:YAG laser. blets using 1064 nm Nd:YAG laser.

Sr. No Wavelength (nm) Traced Transitions Sr. No Wavelength (nm) Traced Transitions
elements elements
Lower energy Upper energy Lower energy Upper energy

6 2 1 6 2 3 6 2
1 393.33 Ca II 3p 4s S /2 3p 4p P° /2 1 305.56 Fe I 3d 4s 3d6(3G)4s4p(3P°)
2 396.80 Ca II 3p64s 2S 1/2 3p64p 2P° 1/2 2 319.63 Zn II – –
3 422.88 Fe II 3d6(3P1)4p 3d6(3G)4d 3 334.89 Ni II 5p5 (2P°) 6s 5p64p 2P° 3/2
4 585.69 Cu I 3d9(2D)4s4p(3P°) 3d94s(3D)5s 4 370.39 Mg III 2s22p5(2P°3/2)4p 2s22p5(2P°3/2)5s
6 588.97 Fe I 3p64s4f 3d7(4F)4d 6 393.33 Ca II 3p64s2S1/2 3p64p 2P° 3/2
7 589.18 Fe I 3d72f4s 3d6(3D)4s4p(3P°) 7 396.80 Ca II 3p64s 2S 1/2 3p64p 2P° 1/2
8 610.27 Ca I 3p64s4p 3p64s5s 8 430.77 Ca I 3p64s4p 3p64p2
9 612.73 Mg III 2s22p5(2P°3/2)4s 2s22p5(2P°3/2)4p 9 453.07 Cu I 2s22p5(2P°1/2)3d 2s22p5(2P°1/2)4f
10 616.21 Ca I 3p64s4p 3P° 3p64s5s3S 10 498.16 Fe I 3d7(4F)4p 3d7(4F)4d
11 617.68 Ni I 3d8(3F)4s4p(3P°) 3d9(2D5/2)4d 11 500.73 Mg III 2s22p5(2P°1/2)4p 2s22p5(2P°1/2)4d
8 643.63 PI – – 8 502.14 Ca II 3p65p 3p66d
9 644.76 Cu II 3d8(1G)4s4p(3P°) 3d9(2D5/2)8d 9 518.88 Ca I 3p64s4p 3p64s5d
10 646.25 Ca I 3p63d4s 3p63d4p 10 551.72 PI 3d6(5D)4s 3d5(6S)4s4p(1P°)
14 647.91 Zn I – – 14 558.92 Ca I 3p64s2S1/2 3p63d4p3D°
15 649.44 Ca I 3p63d4s 3p64s4f 15 588.97 Fe I 3p64s4f 3d7(4F)4d
16 649.96 Fe I 3d7(4F)4p 3d6(5D)4s (6D)4d 16 625.72 Ca I 2s24p2P° 2s25d
17 671.83 Ni I 3s23p2(3P)4p 3s23p2(3P)5d 17 671.83 Ni I 3s23p2(3P)4p 3s23p2(3P)5d

8πhc Nkgi
I=α
λ 3 Nigk
∫ ( 1−e−k( v)l)dv
Here α is a constant, λ is known as a transition wavelength, h is
Plank's constant, Nk and Ni are number densities and gk and gi are
statistical weights. Finally, k is the absorption coefficient at frequency.
The width of the spectral line is estimated by the equation [24] given
below:
⎛ Ne ⎞
Δλ1/2 = 2ω ⎜ 16 ⎟
⎝ 10 ⎠

where Ne denotes the electron number density and ω denotes the

electron-impact broadening parameter.
Calcium carbonate is the most commonly used form of Ca
supplement and it is available as capsules, tablets, oral suspension,
and chewable tablets. Moreover, the elements identified in Os-
nate-d and Hectoral tablets are expressed with their transition
states shown in Table 2 and Table 3, respectively. In the Osnate-d
tablets, Ca, Mg, Fe, and other elements were traced and their peaks
were obtained by utilizing the LIBS technique as presented in Fig. 3. The LIBS data obtained for Osnate-d tablet is plotted in the range of 300–
700 nm wavelength. The small arrows indicate the identified peaks of the elements.

Table 2
The elements traced by their spectral lines present in each sample of Osnate-d Fig. 3, and verified by comparison with the NIST database results
tablets using 1064 nm Nd:YAG laser.
[24,25]. The elements traced in the Hectoral tablets are expressed
Sr. No Wavelength (nm) Traced Transitions in Fig. 4 using LIBS. Further, a quantitative-based analysis of each
elements tablet was performed and the results were compared with the
Lower energy Upper energy prescription provided by each medical company. The estimated
amount for Ca, Fe, Mg, and other elements are 29%, 20%, 10%, and
1 317.22 Zn II – –
2 319.63 Zn II 41%, respectively, which is precisely comparable to the prescrip-
3 393.33 Ca II 6 2 1
3p 4s S /2 3p64p 2P° 3/2 tions provided by medical companies. It is observed from Figs. 2–4
4 396.80 Ca II 3p64s 2S 1/2 3p64p 2P° 1/2 that Ca is relatively abundant in all samples as compared to other
6 422.88 Fe II 3d6(3P1)4p 3d6(3G)4d
elements. The approximate quantity of Ca, Fe, and Mg with some
7 430.77 Ca I 3p64s4p 3p64p2
8 440.62 Ca III 3s23p5(2P°1/2)4d 3s23p5(2P°1/2)4f other constituents is determined by their observed peaks [26],
9 442.31 Mg III 2s22p5(2P°3/2)4p 2s22p5(2P°1/2)4d which are in accordance with the indicated prescription of the
10 453.07 Cu I 2s22p5(2P°1/2)3d 2s22p5(2P°1/2)4f tablets.
11 487.80 Ca I 3p63d4s 3p64s4f
8 516.71 Mg I 3s3p 3s4s
9 519.13 P II 3s23p4s 3s23p4p
10 527.09 Ca I 3p63d4s 3p64s4f 4. Conclusion
14 551.72 PI 3d6(5D)4s 3d5(6S)4s4p(1P°)
15 588.97 Fe I 3p64s4f 3d7(4F)4d We concluded that LIBS is an important technique that can be
16 625.72 Ca I 2s24p2P° 2s25d
17 671.83 Ni I 3s23p2(3P)4p 3s23p2(3P)5d
used to characterize samples in liquid, solid, and gaseous forms. A
portable version of an LIBS device has been designed and used in
24 S. Nisar et al. / Journal of Pharmaceutical Analysis 9 (2019) 20–24
Fig. 4. The LIBS data obtained for Hectoral tablet is plotted in the range of 300–700
nm wavelength. The small arrows indicate the identified peaks of the elements.
this investigation. In this research, LIBS was used to detect the
elements present in pharmaceutical products (Calcium tablets)
which contain Ca and numerous other elements. The LIBS ap-
proach yielded accurate and precise results which were obtained
in a short time from a small sample volume. All the elements (Ca,
Mg, Fe, Zn, and others) were determined by the wavelengths of
their spectral lines, which were verified using the NIST database.
The approximate amount of element was determined by their
observed peaks, which are in exact agreement with the prescrip-
tion. We believe that in the future LIBS may revolutionize the
pharmaceutical industry because of its rapid and accurate analysis.
Conflicts of interest
All authors declare that there are no conflicts of interest.
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