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Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional

Medicines, 2012, 7(4)

Regular articles

Pharmaceutical - analytic study of the Ayurvedic


purification of Manahshila (realgar)
Naveena Kodlady a*, Doddamani MS b, Patgiri BJ c
a. Department of Rasashastra and Bhaishajya Kalpana including Drug Research, Institute
for Post Graduate Teaching & Research in Ayurveda, Gujarat Ayurved University,
Jamnagar 361008, Gujarat, India
b. Department of Rasashastra, Taranath Govt. Ayurvedic College, Bellary, Karnataka,
India
c. Department of Rasashastra and Bhaishajya Kalpana including Drug Research, Institute
for Post Graduate Teaching & Research in Ayurveda, Gujarat Ayurved University,
Jamnagar 361008, Gujarat, India

Abstract
Manahshila (realgar, arsenic disulphide) has been used in Ayurvedic medicine since ancient times for the treatment of conditions
such as skin diseases, cough, asthma, certain eye diseases, and psychological disorders etc. Shodhana (purification) is an integral
part of Ayurvedic processing especially for poisonous substances before they can be used for therapeutic purposes. In the case
of Manahshila, which contains the heavy metal arsenic, it is advised that it should be purified optionally by carrying out seven
levigations (Bhavana) of Zingiber officinalis Roscoe. (Ardraka) juice. A Shodhana of Manahshila was carried out and both
Ashodhita Manahshila (AM unpurified realgar) and Ardraka Shodhita Manahshila (ASM realgar purified with ginger juice)
were investigated by examination of the relevant physico chemical parameters, quantitative elemental analysis, including the
percentage of arsenic using atomic absorption spectrometry, particle size analysis using laser diffraction, and identification of
chemical moieties using X ray diffraction. A significant change was found in the particle size distribution where 50% of the AM
particles were found to be 54.18 m. while the figure for ASM was 15.55 m. There was no change in the chemical composition
and both AM and ASM remained as arsenic disulphide.

Key words: Manahshila; arsenic; shodhana; Ayurveda; XRD; laser diffraction

1 Introduction trioxide) in a number of Ayurvedic medicinal


formulations including those found in Brihattrayis
Manahshila is one of the three important (Three important ancient classics of Ayurveda viz.
arsenical compounds used in Ayurveda as a Caraka Samhita, Sushruta Samhita and Astanga
therapeutic agent (the other two being Haratala Sangraha/Astanga Hrudaya). The important
arsenic trisulphide, and Gouripashana arsenic therapeutic areas of Manahshila use include skin
diseases, respiratory diseases, certain ailments of
eyes and psychological disorders [1]. It is also used
* Author to whom correspondence should be addressed. Address: as an ingredient of various processing techniques
Department of Rasashastra and Bhaishajya Kalpana including
Drug Research, Institute for Post Graduate Teaching & Research in
involved in Rasashastra (a wing of Ayurveda
Ayurveda, Gujarat Ayurved University, Jamnagar 361008, Gujarat, dealing mainly with mercurial, metallic and mineral
India; Mobile No.: +919723844028; E-mail: naveenkodlady@gmail.
com
compounds along with herbal drugs) like Shodhana
(purification), Bhasmeekarana (incineration) and
Received: 2011-12-20 Accepted: 2012-06-25
Sattvapatana (metal extraction).

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Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
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Shodhana is the process by which the external powdering [8] in addition to modern analytical
and internal impurities of the drugs are removed. parameters.
Chemical purification is different from medicinal
2.1 Pharmaceutical
purification. Chemical purification involves only the
elimination of foreign matter, whereas medicinal Shodhana of Manahshila is recommended to
purification involves the removal of harmful be carried out by seven levigations with Zingeber
matter from the drug, modification of undesirable officinalis Roscoe. (Ardraka ginger) juice [9].
physical properties of the drug, alteration of some Raw realgar was powdered using a mortar and
of the characteristics of the drug and enhancement pestle and prepared with the sample name Ashodhita
of the therapeutic action [2]. There are various Manahshila (AM).
procedures involved in the Shodhana of different
Rasashastra drugs, like levigation (Bhavana), AM was placed in a mortar (Khalvayantra)
boiling (Swedana), sublimation (Patana), quenching and mixed with the juice of Zingeber officinalis
(Nirvapa), immersion (Sthapana), and dehydration Roscoe root and triturated with a pestle manually
(Nirjaleekarana) [3]. Arsenic is the most hazardous until the material in the mortar dried. In this way, a
substance among the top 20 listed by the Agency for total of seven impregnations of realgar with ginger
Toxic Substances and Disease Registry (ATSDR) [4]. juice were carried out. Later it was shade dried and
Since Manahshila containsit should be used only powdered by trituration in the mortar, and stored in
after proper purification. Shodhana of Manahshila air tight glass bottle and labeled as Ardraka Shodhita
involves a process called Bhavana (levigation) in Manahshila (ASM).
which powdered drug is triturated with certain liquid 2.2 Analysis
media till the contents are completely dried [5]. The
quantity of liquid medium should be sufficient to 2.2.1. Organoleptic characteristics
ensure that the powder is completely soaked [6]. The The colour, odour and texture of AM and ASM
test for proper Bhavana is described qualitatively were assessed.
and characterized by the softness, and flatness
(Chipitibhuya) when pressed between the fingers, 2.2.2 Physicochemical analysis
without any cracks at periphery [7]. Although The physicochemical analyses of both samples
purified Manahshila is used in several formulations included ash values, loss on drying, loss on ignition,
of Ayurveda, there are only few published reports pH as per the standard methods prescribed in
about the characterization of purified and unpurified Ayurvedic Pharmacopiea of India (API) [10]. The
Manahshila. Hence, an attempt was made to study particle size distribution was carried out usinglaser
the Ayurvedic purification of Manahshila through a diffraction [11] which relies on the fact that
study of scientific parameters. particles passing through a laser beam will scatter
light at an angle that is directly related to their
2 Materials and methods size. Determination of the chemical composition
and crystal structure was carried out using X-ray
Raw realgar was collected from a local market
diffraction (XRD) [12]. In the quantitative elemental
and its authenticity was confirmed byAyurvedic
analysis, the percentage of arsenic was estimated
descriptions of acceptable Manahshila such as its
using atomic absorption spectrometry (AAS)
reddish colour which changes to orange colour on
[13] while sulphur was determined by the Eschka

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Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
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gravimetric method [14]. The determination of after Shodhana. The weight of Manahshila before
the physicochemical characteristics and elemental Shodhana was 250 g while that of Manahshila after
analysis were conducted at the Ganesh consultancy Shodhana was 281 g.
and Analytical Services, Mysore, India. Xray
diffraction and particle size analysis were carried out The organoleptic characteristics are shown
at the Department of Materials Engineering, Indian in Table 1. The results of the physicochemical
Institute of Science, Bengaluru, India. analyses of AM and ASM are tabulated in Table
2. Regarding the particle size distribution, 50% of
the AM particles were 54.18 m (Fig. 1), while the
3 Results and discussion
corresponding figure for ASM was 15.55 m (Fig.
A total of 660 ml ginger juice was digested in 2). The results of the quantitative elemental analyses
250 g Manahshila by manual trituration for 27 hr are shown in Table 3.
and 5 min. An average of 94.28 ml ginger juice 3.1 XRD Analysis
and 3 hr 52 min of trituration were needed for each
levigation of Manahshila Shodhana. However, The XRD findings for AM (Fig. 3) are given in
for the initial levigations, slightly more juice and Table 4.
a longer period of trituration were needed while Note:
for the later levigations the opposite was the case.
The Shodhana process turned the orange powder A total of 60 peaks were identified in the AM
of Manahshila into a reddish yellow colour. There sample at different angels (2) ranging from 11.74
was an increase of 31 g in the weight of Manahshila (1st peak) to 70.88 (60th peak).

Table 1. Organoleptic characteristics of AM and ASM

Drug Colour Texture Odour


AM Orange Smooth, fine Odorless
ASM Reddish Yellow Smooth, fine Characteristic

20 100

90

80

70
Vollume (%)

60

10 50

40

30

20

10

0
0
0.1 1.0 10.0 100.0 1000.0
Particle diameter (m)
Fig. 1. Particle size report for Ashodhita Manahshila

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Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
Medicines, 2012, 7(4)

Table 2. Results of the physicochemical analysis of AM and The % intensity of standard arsenic disulphide
ASM (10, 10, 100 and 10) was approximately the same as
Parameters AM ASM the % intensity of 10, 14, 100 and 11, respectively.
Ash value 6.24% 7.72%
XRD findings for ASM (Fig. 4) are given in
Acid insoluble ash 0.84% 0.42%
Table 5.
Loss on drying at 105C 0.10% 0.18%
pH 8.15 7.39 Note:
Water Soluble Ash 0.04% 0.04%
Loss on ignition at 450C 91.24% 92.04% Totally 68 peaks were identified in ASM
sample at different angels (2) ranging from 11.68
Table 3. Percentage of arsenic and sulphur in AM and ASM (1st peak) to 86.66 (68th peak).

Quantitative analysis AM ASM 6 peaks were chosen with their relative


As 61.39% 62.22% intensity and compared to standard Xray powder
S 27.94% 27.24% diffraction file (JCPDS).

6 peaks were chosen with their relative 6th peak with relative intensity of 100% was
intensity and compared with standard Xray powder considered as significant at 16.253, having a 5.453
diffraction data (JCPDS). d space value.

6th peak with a relative intensity of 100% was The d values of standard arsenic disulphide
considered as significant at 16.28, having a 5.445 (3.06, 4.67 and 5.75) are almost similar to the ASM
d- space value. values found (3.065, 4.548 and 5.453).

The d values of standard arsenic disulphide The % intensity of standard arsenic disulphide
(2.102, 4.67, 5.75 and 6.76) were almost identical to (50, 10 and 100) was close to the % intensity found
the AM sample values (1.935, 4.65, 5.445 and 6.82, (50, 11 and 100, respectively).
respectively).

20 100

90

80

70
Vollume (%)

60

10 50

40

30

20

10

0 0
0.1 1.0 10.0 100.0 1000.0

Particle diameter (m)


Fig. 2. Particle size report for Ardraka Shodhita Manahshila

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Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
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Table 4. XRD findings for AM


Standard Identified
d space Intensity D space Intensity Peak No Angle 2
6.76 10% 6.82 11% 2 12.98
5.75 100% 5.445 100% 6 16.28
4.67 10% 4.65 14% 8 19.08
4.110 30% 4.093 24% 10 21.71
3.06 50% 3.063 45% 17 29.15
2.102 10% 1.935 10% 41 46.96
Name of standard: arsenic disulphide (As2 S2), JCPDS No: 21- 0805, Crystal structure: Monoclinic crystals

Table 5. XRD findings for ASM


Standard Identified
d space Intensity D space Intensity Peak No Angle 2
6.76 10% 6.862 14% 2 12.90
5.75 100% 5.453 100% 6 16.25
4.67 10% 4.548 11% 8 19.08
4.110 30% 4.095 24% 10 21.70
3.06 50% 3.065 50% 16 29.13
2.102 10% 2.015 13% 41 44.98
Name of standard: arsenic disulphide (As2 S2), JCPDS No:73-1593, Crystal structure: Monoclinic crystals

A comparison of the values of AM and ASM the Manashila after Shodhana due to the addition of
obtained is shown in Table 6. the ginger juice. Similarly, the levigation with ginger
changed the orange colour of the Manahshila powder
In the pharmaceutical study of the purification to reddish yellow. In the physico-chemical analysis,
of Manahshila, there was an increase in the weight of the AM had a total ash value of 6.24% while the value
Counts

Degrees 2-Theta
Fig. 3. XRD of Ashodhita Manahshila (shows that the sample is similar to standard arsenic disulphide)

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Pharmaceutical - analytic study of the Ayurvedic purification of Manahshila (realgar) / Asian Journal of Traditional
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Counts

Degrees 2-Theta
Fig. 4. XRD of Ardraka Shodhita Manahshila (shows that the sample is similar to standard arsenic disulphide)

for ASM was 7.72%, indicating a slight increase Shodhana offers the possibility of absorption. The
in the total ash of Manahshila after Shodhana, loss on drying at 110C is a physical test to determine
which might be due to the inorganic components of the percentage moisture content and, hence, the shelf-
the Shodhana medium. In a study of thechemical life of the sample. In the present study, Shodhita
composition of ginger root, it was reported that 100 g Manahshila was found to exhibit a loss on drying
of sample contained 3.85 g ash along with a number of only 0.18% (ASM). Because of the presence of
of minerals, namely, iron (8 mg), calcium (88.4 mg), organic material there was an increase in the loss on
phosphorous (174 mg), zinc (0.92 mg), copper (0.545 drying of ASM compared with that of AM (0.10%).
mg), chromium (70 g) and manganese (9.13 mg) Hence, this shows that it has a very low moisture
as well as vitamin C (9.33 mg) [15]. There was only content and so a very low probability of allowing
a very low amount of raw and purified Manahshila bacterial and fungal growth. Ginger juice with a
which was acid insoluble, indicating that both AM pH of 3.6 is acidic nature reduces the alkalinity of
and ASM are absorbed in the stomach with the gastric AM. Overall, ASM is weakly alkalineand will be
juice. The acid-insoluble ash content of AM was less chemically active on administration. There was
0.84% while that of ASM was 0.42% suggesting that no change in the water soluble ash content between
AM and ASM although there was a slight increase in
Table 6. Comparison of identified d values of AM and ASM the loss on ignition after Shodhana of Manahshila,
AM ASM probably due to the increased organic content. There
D space Intensity (%) D space Intensity (%) was a small change in the concentrations of arsenic
6.820 11 6.862 14 and sulphur. i.e. a slight increase in the quantity
5.445 100 5.453 100 of arsenic and slight decrease in the quantity of
4.650 14 4.548 11 sulphur, although this difference was negligible in
4.093 24 4.095 24 quantitative terms and may be due to the relative
3.063 45 3.065 50 changes in the weight of arsenic, sulphur and other
1.935 10 2.015 13 minerals after levigation with ginger juice.

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The surface area of the drug particles is one Cysteine, which is a methyl donor peptide in ginger,
of the parameters that influence drug dissolution helps in the process of methylation. c) Preservation
and, in turn, drug absorption. Smaller particles with of Glutathione: Glutathione, a natural antioxidant
a greater surface area dissolve more rapidly than recycling enzyme is an important detoxifying
larger particles. There was a significant decrease compound present in the blood, which combines
in the 50% particle size distribution of AM after with arsenic and excretes it via the bile. Arsenic
undergoing Shodhana. The particle size of AM poisoning reduces the level of glutathione in the
was 54.18 m while that of ASM was 15.55 m, blood. It has been shown that, following ingestion
indicating possibly better absorption of the drug ginger reduces the fall in the amount of glutathione
after purification. The powder Xray diffraction in the blood [17]. Hence, it supports detoxification
studies help in determining the composition of the as well as combatting its possible depletion due to
compound. On comparing the d values of both the arsenic. d) Neutralization of alkalinity: Ginger is
samples with their respective d standard showed acidic with a pH value of 3.6 and Manahshila has a
that the samples were similar to standard arsenic pH value of 8.15. Because of its acid-base reaction,
disulphide (As2S2). There were changes in the total the alkalinity of Manahshila is reduced and is
number of peaks; AM produced a total of 60 peaks at safer to use. In a previous research study, Ardraka
different angles ranging from 11.7470.88 whereas Shodhita Manahshila was found to be nontoxic in
ASM produced 68 peaks at angles ranging from experimental animals [18].
11.6886.66. At 100% intensity, there was a small
increase in the d space in the ASM compared with In-depth analysis of the organic and inorganic
AM. The d space of AM at 100% was 5.445 while components of ginger juice acquired by Manahshila
that of ASM was 5.453 where the standard peak was after Shodhana will throw more light on the
5.75. This indicates that ASM is more close to the purification which was not the part of the present
standard As2S2. This also supports the fact that the study. Thin layer chromatograpy of AM and ASM
medicinal purification can also involve chemical would be helpful in standardization of the Shodhana
purification. process of Manahshila which could provide a useful
drug fingerprint.
There are several positive factors associated with
ginger in the mode of Shodhana of Manahshila by 4 Conclusion
Ardraka Swarasa. a) Phytochelation: Phytochelatins
are heavy metal-binding peptides that play an There are only minor changes in the preliminary
important role in detoxification of heavy metals physico-chemical parameters of Manahshila
by chelation [16]. Ginger contains two important after being subjected to Shodhana by levigation
sulphur-based amino acids called cysteine and with ginger juice. Shodhana does not change the
methionine which can act as phytochelatins and chemical composition of Manahshila. However,
can render arsenic nontoxic in the Manahshila. b) there is a marked change in the particle size due to
Methylation: Methylation is a process of detoxifying Shodhana and about a 12.4% increase in the weight
arsenic in the body through accelerated excretion. of Manahshila after Shodhana.
This process takes place in the liver by the addition
of a methyl group to the arsenic and transforms Acknowledgements
it into a nontoxic form which is then excreted.

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The authors express their sincere gratitude 11th ed. New Delhi: Motilala Banarasidas, 1979, 2/51,
to Prof. M.S. Baghel, Director, IPGT&RA; Prof. 22.
[8] Jha CB. Ayurvediya Rasashastra. Varanasi: Chowkambha
P.K.Prajapati, Head and Dr. Galib, Assistant Surabharati Prakashna, 2000, 263-264
professor, Dept. of Rasashastra and Bhaishajya [9] Kulkarni DA. Vagbhatacharyas Rasa Ratna Samucchaya.
Kalpana, IPGT&RA, Gujarat Ayurved University, New Delhi: Meharachand Lachhmandas Publications,
Jamanagar for their technical input and constant 2006, 3/93, 57.
[10] Anonymous. The Ayurvedic Pharmacopoeia of India.
encouragement. Thanks are also due to the Part 1, Vol. IV, 1st ed. New Delhi: Gov. of India, 2004.
Department of Materials Engineering, Indian [11] Merkus HG. Particle Size Measurements: Fundamentals,
Institute of Science, Bengaluru, India, and Ganesh Practice, Quality. New York: Springer, 2008, 259.
consultancy and Analytical Services, Mysore, India [12] Cullity BD. Elements of X ray diffraction. 2nd ed.
London: Addison Wesley Publishing Company. Palo.
for providing the analytical facilities. Alto, 1978.
[13] Butcher DJ, Sneddon J. A practical guide to graphite
References furnace atomic absorption spectrometry. New York:
Wiley-IEEE, 1998.
[1] Kodlady N, Doddamani MS, Vishwanath Y, Patgiri BJ, [14] Wilfred W. Scott. Standard methods of chemical
Vishwanath Y, Patgiri BJ. Sedative hypnotic activity analysis, 2nd ed. New York: D.VanNostrand Company;
of Manahshila (realgar) An experimental evaluation. 1917, 393-395.
Ancient Sci Life, 2011, 30: 78 -83.
[15] Adel PRS, Prakash J. Chemical composition and
[2] Raisuddin S, Bhasmas A. In Scientific basis for antioxidant properties of ginger root (Zingiberofficinale).
Ayurvedic Therapies. Lakshmi Chandra Mishra, editor. J Med Plants Res, 2010, 4: 2674-2679.
Washington: CRC PRESS, 2004. 88. [16] Raab A, Ferreira K, Andrew A, Meharg, Feldmann J.
[3] Jha CB. Ayurvediya Rasashastra. Varanasi: Chowkambha Can arsenicphytochelatin complex formation be used
Surabharati Prakashna, 2000. as an indicator for toxicity in Helianthus annuus? J Exp
[4] Cruz GC, Din Z, Feri CD, Balaoing AM, Gonzales EM, Bot, 2007, 58: 1333-1338.
Navidad HM, Schlaaff MF, Willter J. Analysis of toxic [17] Jagetia GC, Baliga MS, Venkatesh P, Ulloor JN. Ulloor
heavy metals (arsenic, lead, and mercury) in selected Influence of Ginger Rhizome (ZingiberofficinaleRosc.)
infant formula milk commercially available in the on Survival, Glutathione and Lipid Peroxidation in
philippines by AAS. E-ISRJ, 2009, 1: 40-51. Mice after Whole-Body Exposure to Gamma Radiation.
[5] Kashinathashastri. Sadananda Sharmas Rasa Tarangini. Radiat Res, 2003, 160: 584-592.
11th ed. New Delhi: Motilala Banarasidas, 1979, 2/49,
[18] Krithiga M, Sarashetti RS, Karigaudar M, Sattar
21.
A. Physico chemical analysis and toxicity study of
[6] Kashinathashastri. Sadananda Sharmas Rasa Tarangini.
shuddha manashila prepared with various swarasa. Post
11th ed. New Delhi: Motilala Banarasidas, 1979, 2/50,
graduation thesis. Rajeev Gandhi University of Health
21.
Sciences, Bangalore, 2008.
[7] Kashinathashastri. Sadananda Sharmas Rasa Tarangini.

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