Chemical Authentication of Botanical Ingredients: A Review of Commercial Herbal Products
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MINI REVIEW
published: 15 April 2021
doi: 10.3389/fphar.2021.666850
Chemical Authentication of Botanical
Ingredients: A Review of Commercial
Herbal Products
Mihael Cristin Ichim 1* and Anthony Booker 2,3*
1
“Stejarul” Research Centre for Biological Sciences, National Institute of Research and Development for Biological Sciences,
Piatra Neamt, Romania, 2Research Centre for Optimal Health, School of Life Sciences, College of Liberal Arts and Sciences,
University of Westminster, London, United Kingdom, 3Pharmacognosy and Phytotherapy, UCL School of Pharmacy, London,
United Kingdom
Chemical methods are the most important and widely used traditional plant identification
techniques recommended by national and international pharmacopoeias. We have
reviewed the successful use of different chemical methods for the botanical
authentication of 2,386 commercial herbal products, sold in 37 countries spread over
six continents. The majority of the analyzed products were reported to be authentic (73%)
but more than a quarter proved to be adulterated (27%). At a national level, the number of
products and the adulteration proportions varied very widely. Yet, the adulteration reported
for the four countries, from which more than 100 commercial products were purchased
Edited by:
and their botanical ingredients chemically authenticated, was 37% (United Kingdom), 31%
Marcello Locatelli,
University of Studies G. d’Annunzio (Italy), 27% (United States), and 21% (China). Simple or hyphenated chemical analytical
Chieti and Pescara, Italy techniques have identified the total absence of labeled botanical ingredients, substitution
Reviewed by: with closely related or unrelated species, the use of biological filler material, and the hidden
Santhosh Kumar J. Urumarudappa,
Chulalongkorn University, Thailand
presence of regulated, forbidden or allergenic species. Additionally, affecting the safety
Subramanyam Ragupathy, and efficacy of the commercial herbal products, other low quality aspects were reported:
University of Guelph, Canada
considerable variability of the labeled metabolic profile and/or phytochemical content,
*Correspondence:
significant product-to-product variation of botanical ingredients or even between batches
Mihael Cristin Ichim
cichim@hotmail.com by the same manufacturer, and misleading quality and quantity label claims. Choosing an
Anthony Booker appropriate chemical technique can be the only possibility for assessing the botanical
a.booker@westminster.ac.uk
authenticity of samples which have lost their diagnostic microscopic characteristics or
Specialty section:
were processed so that DNA cannot be adequately recovered.
This article was submitted to
Keywords: chemical marker, natural product, herbal product, food supplement, herbal medicine, authentication,
Ethnopharmacology,
adulteration, contamination
a section of the journal
Frontiers in Pharmacology
Received: 11 February 2021
INTRODUCTION
Accepted: 09 March 2021
Published: 15 April 2021
Herbal products are being sold under many and diverse commercial descriptions in the international
Citation: marketplace, including herbal drugs, botanical drugs, botanicals, phytomedicines, traditional
Ichim MC and Booker A (2021)
medicines (TMs), herbal medicines (HMs), traditional herbal medicines products (THMPs),
Chemical Authentication of Botanical
Ingredients: A Review of Commercial
natural health products (NHPs), dietary supplements (DSs), plant food supplements (PFSs),
Herbal Products. nutraceuticals (NCs) and food supplements (FSs) (Ichim, 2019), the differences being mainly
Front. Pharmacol. 12:666850. due to the prevailing national legislation under which they are marketed (Simmler et al., 2018).
doi: 10.3389/fphar.2021.666850 Herbal products are commercialized as medicines or foods, according to their officially declared
Frontiers in Pharmacology | www.frontiersin.org 1 April 2021 | Volume 12 | Article 666850Ichim and Booker Chemical Authentication of Herbal Products
intended final use by their manufacturers operating under various identification, only recently adopted by the first two national
regulatory frameworks, and they are purchased, and subsequently Pharmacopoeias (Pharmacopoeia Committee of P. R. China,
used and consumed, for their medicinal claims (herbal 2015; British Pharmacopoeia Commission, 2018), facilitate
medicines) or their expected health benefits (food simultaneous multi-taxa identification by using the DNA of
supplements) (Thakkar et al., 2020). In the United Kingdom, different origins extracted from complex mixtures and
for example, plant products are regulated under two main criteria, matrices but false-negatives can be expected if the DNA has
the first being what is claimed, i.e. if a manufacturer claims a been degraded or lost during post-harvest processing or
medicinal effect, the product will automatically fall under manufacturing (Raclariu et al., 2018a; Ichim, 2019; Grazina
medicines legislation; the second consideration being the et al., 2020). In this respect, our review adds the much needed
activity of the plant in vivo, if it has shown to have a strong peer-reviewed, systematically searched information, about the
medicinal or pharmacological action then it is deemed a medicine successful use of chemical identification for the authentication of
regardless of the claims, the most notable plant in this category commercial herbal products. While doing so, our review also
being Hypericum perforatum L. (St John’s Wort). Whereas in the provides some missing pieces of the commercial herbal products’
United States most plant products are regulated as food authenticity puzzle.
supplements (botanicals) and in Germany the majority are
considered medicines. Unfortunately, these marketing
differences, due to significant differences between the METHODS
regulatory approaches across jurisdictions (Low et al., 2017),
are further contributing to their poor regulation on the Databases
international market. Search Strategy
Accidental contamination or the deliberate use of filler or Four databases were systematically searched for peer reviewed
substitute species (Shanmughanandhan et al., 2016) leads records following the PRISMA guidelines (Moher et al., 2009)
inherently to non-authentic, adulterated products (Simmler using combinations of relevant keywords, Boolean operators and
et al., 2018). The adulteration of commercial herbal products wildcards: [(“herbal product” OR “herbal medicine” OR
is an internationally widespread problem, as it has been reported “traditional medicine” OR “food supplement” OR “dietary
for many countries from all inhabited continents (Ichim, 2019; supplement” OR “herbal supplement” OR nutraceutical) AND
Ichim et al., 2020). Moreover, large percentages of adulterated (authentic* OR contaminat* OR substitut*)] for Web of Science,
products have been reviewed, irrespective of the formal category PubMed, Scopus, and [(“herbal product” OR “herbal medicine”
of herbal products, being affected food and dietary supplements OR “food supplement” OR “dietary supplement” OR “herbal
and medicines altogether (Ichim and de Boer, 2021), including supplement” OR nutraceutical) AND (authentication OR
products used in centuries or even millennia-old Ayurveda contamination OR substitution)] for ScienceDirect. The option
(Revathy et al., 2012; Seethapathy et al., 2019) and Asian “search alert” was activated for all four databases, to receive
traditional medicine systems (Masada, 2016; Xu et al., 2019). weekly updates after the literature search was performed.
The substantial proportion of adulterated commercial herbal Furthermore, we used cross-referencing to identify additional
products described appears to be independent of the methods peer-reviewed publications.
used for their analysis, traditional pharmacopoeial methods being
employed, such as macroscopic inspection (van der Valk et al., Selection Process and Criteria
2017), microscopy (Ichim et al., 2020), chemical techniques (Li Identification: 10,497 records were identified through database
et al., 2008; Upton et al., 2020), or even the more recently searching (WoS 1,317, PubMed 3,253, Scopus 5,446, and
developed DNA-based ones, such as the rapidly ScienceDirect 481), and 196 additional records from cross-
technologically evolving DNA barcoding and metabarcoding referencing and the weekly updates from the four databases.
(Ichim, 2019; Grazina et al., 2020). Screening: after the duplicates had been removed, 2,326 records
On the global market, herbal products are sold in an extremely were collected and their abstracts screened. After screening, 1,745
diverse variety of forms, from single ingredient, unprocessed, raw, records were excluded for not reporting data relevant for the
whole plants to multi-species, highly processed extracts. chemical authentication of herbal products. Eligibility: 581 full-
Therefore, the successful authentication of commercial herbal text articles were assessed and screened based on the following
products reported by peer reviewed studies are a valuable and eligibility criteria: 1) The reported products had to be “herbal
useful source of information which provide the necessary products”; the full wide range of commercial names was searched
practicalities, including their strengths and the limitations, of for and accepted for being included in our analysis. 2) The
employing the right methods for a specific type of product along analyzed products had to be “commercial”; keywords such as
the length of its value chain (Booker et al., 2012). Such analyses of “purchased”, “bought”, were accepted. Our analysis excluded
peer-reviewed authentication reports focused exclusively on samples which were obtained “cost-free”, a “gift” or “donated”
commercial herbal products have concluded that, microscopy, by a person, institution or company. 3) The products had to be
a traditional pharmacopoeial identification method, is cost- clearly allocated to a “country” or “territory” (e.g., European
efficient and can cope with mixtures and impurities but it has Union). 4) The conclusion “authentic”/“adulterated” had to be
limited applicability for highly processed commercial samples e.g. drawn by the authors of the analyzed studies. 5) The products had
extracts (Ichim et al., 2020). On the other hand, DNA-based to be analyzed with a “chemical” method or techniques.
Frontiers in Pharmacology | www.frontiersin.org 2 April 2021 | Volume 12 | Article 666850Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
1 Australia grape seed extract 9 4 5 complete substitution or RP HPLC-UV-MS / not reported V. vinifera (seeds, seed Govindaraghavan (2019)
products (capsules) heavy adulteration, catechin, epicatechin, extracts), A. hypogaea,
from retail pharmacies, possibly with peanut skin procyanidin B2, procyanidin P. massoniana, P.
health stores / Vitis extract, Pinus massoniana A2, rape seed oligomeric pinaster, V.
vinifera (or other A-type proanthocyanidins macrocarpon, T. cacao
procyanidin-containing (extracts)
species)
New Zeeland 6 6 0 n/a
2 Australia gingko products 6 3 3 adulteration with flavonol RP HPLC, LC-MS / flavonol contained genistein, an authenticated samples Wohlmuth et al. (2014)
(capsule, tablets) from aglycones, likely with aglycones (quercetin, isoflavone that does not of dried Ginkgo biloba
retail stores / Ginkgo Styphnolobium japonicum kaempferol, isorhamnetin) occur in ginkgo leaf leaf from commercial
Denmark biloba 2 2 0 n/a suppliers
3 Belgium products (tablets and 69 48 21 adulteration/ FT-Mid-IR, HPLC-DAD, P. yohimbe or T. terrestris reference material of the Deconinck et al. (2019)
capsules) containing contamination with LC-MS not identified in some five plant species
regulated plants / unlabeled ingredients: A. products although (leaves, bark, fruits)
Aristolochia fangchi, Ilex fangchi (forbidden), I. claimed on the label
paraguariensis, paraguariensis,
Epimedium spp., Epimedium spp., T.
Pausinystalia johimbe, terrestris (all should be
3
Tribulus terrestris notified to authorities), P.
johimbe
4 Belgium herbal products 3 3 0 n/a HPLC-DAD, HPLC-MS not reported commercial P. edulis Deconinck et al. (2015)
(capsules, tablets) from (dry extract) (European
local pharmacy / Pharmacopoeia)
Passiflora edulis
5 Belgium products containing 3 3 0 n/a HPLC-DAD–ELSD, not reported commercial dry plant Deconinck et al. (2013)
three non-regulated HPLC-MS extracts of F. purshiana,
herbs (capsule, tablets) P. edulis, C. monogyna
from local pharmacy / (European
Frangula purshiana, Pharmacopoeia)
Passiflora edulis,
Crataegus monogyna
Chemical Authentication of Herbal Products
6 Belgium illegal products (tablets, 2 2 0 n/a HPLC-PDA. HPLC-MS adulteration with sildenafil self-made triturations in Custers et al. (2017)
April 2021 | Volume 12 | Article 666850
capsules) containing three different botanical
regulated plant species matrices from reference
/ Epimedium spp., standards of Epimedium
Tribulus terrestris spp. leaves, P. johimbe
bark, T. terrestris fruit
7 Brazil "carqueja" products 15 11 4 non-authentic GC-FID / essential oil intensity of the peaks in authenticated samples De Ferrante et al. (2007)
(bags with pulverized most of cases was of B. trimera (aerial
plant material or parts of different parts, leaves) / standard
the plant) from oil of B. trimera
commercial shops / (extracted)
Baccharis trimera
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
8 Brazil "sarsaparilla" products 15 0 15 different from the TLC / flavonoids, saponins, n/a authenticated reference Martins et al. (2014)
from drugstores / reference Smillax sp. terpenoids, steroids, material (roots) of S.
Smilax goyazana, S. catechins brasiliensis, S.
rufescens, S. campestris, S.
brasiliensis, S. cissoides, S.
campestris, S. fluminensis, S.
cissoides, S. goyazana, S.
fluminensis, S. oblongifolia, S.
oblongifolia, S. rufescens, S. polyantha
polyantha
9 Brazil "copaiba" oil-resin 12 3 9 substitution and TLC not reported reference C. multijuga Barbosa et al. (2009)
products from local adulteration with oil-resins, prepared
markets / Copaifera soybean oil mixtures of soybean oil
multijuga and copaiba oil resin
10 Brazil "carqueja" products 12 12 0 n/a TLC / 3-o-methyl-quercetin large variations in the B. trimera reference Beltrame et al. (2009)
from herbal shops, percentage of flavonoids samples / Brazilian
pharmacies / Baccharis (quercetin) Pharmacopoeia (BP)
trimera
11 Brazil "janaguba" milk 10 4 6 complete substitution or TLC not reported authentic samples of Soares et al. (2016)
“janaguba” latex,
4
products from local adulteration with
market / Himatanthus Hancornia speciosa mango tree latex sample
drasticus
12 Brazil "Bauhinia spp." 9 2 7 not containing claimed B. HPLC-UV/PDA, MCR- not reported B. forficata, B. f. var. Ardila et al. (2015)
products (ground dry forficata ALS/PCA longifolia authenticated
leaves) from drugstores, leaves
local market / Bauhinia
forficata ssp.
13 Brazil “jatoba” sap products / 6 0 6 probably achieved by a HPLC-MS / flavonoids, n/a H. stigonocarpa, H. De Souza Farias et al.
Hymenaea decoction of the stem procyanidins martiana authenticated (2017)
stigonocarpa, bark or other sources sap and stem bark
Hymenaea martiana samples
14 Brazil herbal products from 3 1 2 possible substitution with FTIR, 1H NMR not reported M. ilicifolia control Preto et al. (2013)
Chemical Authentication of Herbal Products
commercial shops / plants from the same sample from the open
Maytenus ilicifolia family and/or market, in the selected
April 2021 | Volume 12 | Article 666850
contamination due to natural form, recognized
addition of similar other by ‘‘herbal trackers’’
plants parts to the
commercial one
15 Brazil herbal products (raw 3 3 0 n/a TLC / caffeic acid, isoorientin variable quantity of some Brazilian Dias et al. (2013)
material) from different and swertiajaponin, marker compounds Pharmacopoeia (BP)
suppliers / Echinodorus o-hydroxycinnamic acid 5th edition
grandiflorus derivatives
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
16 Canada Smilax ornata, organic 3 0 3 adulteration with 1H-NMR/HCA not reported reference samples of Kesanakurti et al. (2020)
Sarsaparilla root, Decalepis hamiltonii and known provenance of P.
Hemidesmus indicus Pteridium aquilinum aquilinum, Smilax
products from online aristolochiifolia, D.
store / Hemidesmus hamiltonii, H. indicus
indicus, Periploca
indicus
17 China "Tong-guanteng" 62 61 1 substitution with TLC, HPLC / TS-H contents (0.39- genuine M. tenacissima Yu et al. (2018)
products from medicine Tinospora sinensis tenacissoside H 1.09%) larger than that herb
markets, drug stores / regulated in the Chinese
Marsdenia tenacissima Pharmacopoeia (0.12%)
18 China ginseng products (pills, 40 38 2 P. ginseng products LC–MS / ginsenosides in few products markers authenticated ginseng Yang et al. (2016)
bag, injections, adulterated (weak for PG not detected, crude drug samples
capsules, tablets, chromatographic peaks, signals for PN
powders, dripping pills) and several marker (ginsenoside Rf) very
from drugstores / Panax compounds were not weak
ginseng, P. detected)
quinquefolius, P.
notoginseng
5
19 China Pinelliae rhizoma 39 12 27 substitution with Pinellia HPLC-DAD, HPLC-MS, LC- not reported authenticated batches Jing et al. (2019)
products from herbal pedatisecta MS / triglochinic acid of Pinelliae rhizoma and
medicine markets / Pinelliae pedatisectae
Pinellia ternata rhizoma / extracted and
purified triglochinic acid
20 China "Wuweizi" (Schisandrae 36 34 2 substitution with S. LC-DAD-MS, TLC, HPLC / not reported authenticated batches Jiang et al. (2016)
Chinensis Fructus) and aphenanthera schisandrin, anwulignan of batches of Wuweizi
"Nan-wuweizi" and Nan-wuweizi,
(Schisandrae reference crude drugs,
Sphenantherae Fructus) in-house prepared
products from mixtures
pharmaceutical
manufacturers,
Chemical Authentication of Herbal Products
pharmacies /
Schisandra chinensis,
April 2021 | Volume 12 | Article 666850
S. sphenanthera
21 China American or Asian 31 28 3 adulteration and 1H NMR-PCA / sucrose, not reported n/a Zhao et al. (2015)
ginseng root products substitution of wild with glucose, arginine, choline, 2-
from stores / Panax cultivated ginseng oxoglutarate, malate,
ginseng, P. ginsenosides
quinquefolius
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
22 China "Chaihu" (Bupleuri 31 20 11 substitution with B. HPLC-ELSD, HPTLC / great variation in the authenticated samples Tian et al. (2009)
Radix) products from longiradiatum, B. bicaule, saikosaponins content of the major of B. chinense, B.
major herbal distribution B. falcatum, B. saikosaponins scorzonerifolium, B.
centres / Bupleurum marginatum var. falcatum, B.
chinense, B. stenophyllum longiradiatum, B.
scorzonerifolium bicaule, B. marginatum
var. stenophyllum
23 China red yeast rice (RYR) 31 21 10 did not show the presence UHPLC–DAD–QToF-MS / n/a RYR authenticated Avula et al. (2014)
commercial raw of any monacolins monacolins, citrinin samples
materials from analyzed
supplement
manufacturers /
Monascus purpureus -
fermented rice
United States RYR-containing 14 14 0 n/a large variations (20-40
products from online fold) in quantity and
retailers / Monascus quality of monacolin K
purpureus - fermented
rice
6
24 China Asian and American 31 23 8 adulteration with P. UPLC/Q-TOF-MS / not reported self-prepared samples Li et al. (2010)
ginseng products from ginseng ginsenoside Rf, 24 (R)- with different contents
Canada herbal markets, local 5 5 0 n/a pseudoginsenoside F11 (spiking the Asian
United States drug stores / Panax 4 4 0 n/a ginseng powder into the
ginseng, P. American ginseng
quinquefolius powder)
25 China "Gou-Teng" batches of 20 16 4 substitution with other UPLC/Q-TOF MS / alkaloids not reported authenticated batches Pan et al. (2020)
(Uncariae Rammulus Uncaria sp. or unlabelled of five Uncaria sp.
Cum Uncis) from mixtures with the five (stems with hooks) /
markets / Uncaria officially accepted isolated and identified
macrophylla, U. hirsuta, Uncaria sp. alkaloids
U. sinensis, U.
sessilifructus
Chemical Authentication of Herbal Products
26 China Chaenomelis Fructus 20 19 1 the source plant is not C. HPLC–DAD / quinic acid, the relative contents of n/a Zhu et al. (2019)
(raw) products from speciosa malic acid, protocatechuic each component may
April 2021 | Volume 12 | Article 666850
manufacturers, herbal acid, shikimic acid, vary in some of the
markets / Chaenomeles chlorogenic acid samples
speciosa
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
27 China "Beimu" (Fritillariae 16 11 5 substitution or UPLC-QTOF-MS / steroidal loss of specific features, authenticated batches Liu et al. (2020)
Bulbus) products from adulteration with alkaloids possibly resulted from of Fritilaria sp.
drugstores / Fritillaria unlabeled F. ussuriensis different processes of
taipaiensis, F. different manufacturers
unibracteata var.
wabuensis, F. delavayi,
F. unibracteata, F.
przewalskii, F. cirrhosa,
F. ussuriensis, F.
thunbergii
28 China Menispermi Rhizoma 16 15 1 counterfeit (most of the UPLC-DAD-MS / alkaloids discrepancies among the authenticated MR Liu et al. (2013a)
products (dried important marker samples of different batches from various
rhizomes, pills, alkaloids could not be origins (the contents of drug stores / separated
capsules) from drug detected) the nine alkaloids varied and purified (from MR)
stores / Menispermum greatly) alkaloids
dauricum
29 China batches of "Shuxiong" 12 12 0 n/a UPLC/QDa-SIM / (saponins, low content of some crude drug reference Yao et al. (2016)
tablets from quinochalcone markers in a few materials Notoginseng
manufacturers, C-glycosides, products possibly Radix et Rhizoma,
7
drugstores / Panax 16 O-glycoside, phenolic caused by different Carthami Flos,
notoginseng, acid, pathalides preparation process or Chuanxiong Rhizoma
Carthamus tinctorius, use of poor-quality drug
Ligusticum striatum materials
30 China "Huangqi" (Radix 12 11 1 substitution with HPLC-UV / isoflavonoids total isoflavonoids n/a Wu et al. (2005)
Astragali) products from Astragalus tongonlensis content varies
wholesale TCM considerably
markets, city
pharmacies / Astragalus
prompiquus
31 China "ci-wu-jia" tea products 11 8 3 adulteration with green tea UHPLC-UV-MS/MS / not reported E. senticosus leaf Wang et al. (2019)
(leaf, leaf powder) from (Camellia sinensis) organic acid derivatives, samples collected from
local stores / flavonoids, triterpene China / in-house UNIFI
Chemical Authentication of Herbal Products
Eleutherococcus saponins library of
senticosus Eleutherococcus genus
April 2021 | Volume 12 | Article 666850
and green tea extracts
32 China Panax ginseng and P. 11 10 1 substitution or UHPLC-TOF/MS/ OPLS-DA n/a 34 white ginsengs, 23 Wu et al. (2020)
quinquefolius products adulteration with P. / ginsenosides red ginsengs, 30 P.
(bolus, tea, tablet, drink) ginseng notoginseng and 21 P.
from local pharmacies / quinquefolius collected
P. ginseng, P. samples
quinquefolius
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
33 China Panax notoginseng 10 9 1 adulteration, possibly with UPLC/Qtof MS/ PCA / not reported authenticated P. Liu et al. (2015)
powder products from flower material of P. notoginsenosides, notoginseng powder
drug stores, CHM notoginseng ginsenosides, 20S- samples
manufacturers / P. ginsenoside Rh1,
notoginseng gypenoside XVII
34 China "Xihuangcao" (Isodonis 9 7 2 substitution with I. HPTLC / 2α-O-β-D- not reported collected batches of I. Lin et al. (2019)
lophanthoidis herba) lophanthoides var. glucoside-12-en-28-ursolic lophanthoides
from herbal markets / gerardianus acid, 2α,19α-dihydroxy-12-
Isodon lophanthoides en-28-ursolic acid, 2α-
hydroxy-12-en-28-ursolic
acid, ursolic acid
35 China Panax ginseng 8 5 3 substitution with P. FT-NIR not reported authenticated P. Dong et al. (2020)
products from local quinquefolius, Platycodon ginseng samples
drug stores / P. ginseng grandiflorus, Physochlaina
infundibularis, Phytolacca
acinosa
36 China "Xihuangcao" products 8 0 8 no Isodon sp. material, UPLC-ESI-QTOF-MS n/a authenticated I. Wan et al. (2016)
(tea bags) from retail adulteration and lophanthoides and I.
stores / Isodon substitution with serra plant material /
8
lophanthoides, I. serra unlabeled plant species reference teas of many
plant species
37 China gingko leaf product and 6 5 1 adulteration (the rutin HPLC(EIS)/MS / flavonol not reported G. biloba leaves Song et al. (2010)
health foods (tea, content was glycosides, terpene collected from different
tablets, soft gels) from uncharacteristically high) trilactones, flavonol habitats
drug store, local stores / aglycones, biflavones
Gingko biloba
38 China St. John’s Worth 5 5 0 n/a HPTLC, 1H-NMR/PCA low content of typical authenticated Scotti et al. (2019)
Bulgaria products (loose 2 2 0 H.p. compounds Hypericum sp. samples
Greece material) from herbal 2 2 0 apparently due to higher
Chile markets, pharmacies 1 1 0 amount of woody
United Kingdom and producer’s 1 1 0 material
cultivation / Hypericum
Chemical Authentication of Herbal Products
perforatum
39 China Aquilariae Lignum 3 0 3 little or different resin FT-IR, SD-IR, 2D-IR not reported standard ALR (the resin- Qu et al. (2016)
April 2021 | Volume 12 | Article 666850
Resinatum (ALR) components rich wood of A. sinensis
products from market /
Aquilaria sinensis
40 China Aquilariae Lignum 3 0 3 Adulteration with other FT-IR, 2D–IR n/a reference A. sinensis Qu et al. (2017)
Resinatum (ALR) kind of wood (possibly samples, no-resin wood
products from market / Gonystylus spp.), and by of A. sinensis, authentic
Aquilaria sinensis adding cheap resin (e.g. ALR samples
rosin)
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
41 China Ophiocordyceps 2 1 1 substitution with HPLC / cordycepin, not reported authenticated O. Wen et al. (2016)
sinensis products from lepidopteran larvae adenosine and other sinensis specimens
TCM market / O. infected by nucleosides collected in Tibet
sinensis Metacordyceps taii.
42 Croatia gingko products (GBEs, 10 8 2 substitution with Sophora HPLC / quercetin/ not reported n/a Budeč et al. (2019)
food supplements / japonica extracts kaempferol ratio, ginkgo
capsules, tablets, flavone glycosides
powder) / Ginkgo biloba (quercetin, kaempferol,
isorhamnetin)
43 Denmark St. John’s Worth 10 10 0 n/a 1H-NMR/PCA considerable differences n/a Rasmussen et al. (2006)
products (tablets, in the products
capsules) from composition (e.g.
commercial suppliers / flavonoids), inter-product
Hypericum perforatum and inter-batch variation
44 Egypt herbal products (teas) 3 0 3 adulterated with other GC-MS, HPLC / essential oil, some of the herbs used reference herbal teas Kamal et al. (2017)
from market / species, some labeled polyphenols, flavonoids are exhausted prepared from herbs
chamomile, marjoram, species missing those of purchased from the
licorice, fennel, dill, the formula market
caraway, basil, lemon
9
grass, anise, chicory,
achillea, verbascum,
hibiscus, vine
45 Egypt herbal products (tea) / 2 2 0 n/a HPLC, GC-MS / sennoside not reported prepared standard Abdel Kawy et al. (2012)
chicory, marjoram, A, esculetin, scopoletin. herbal mixtures
nettle and senna leaves, volatile oil
liquorices roots, celery
fruits, calendula flowers
and fennel, senna and
chicory
46 European Union Panax ginseng 12 6 6 P. ginseng leaf or other HPTLC, HPLC / not reported bulk crude P. ginseng Govindaraghavan (2017)
products (herb, root plant parts, P. ginsenosides dried root samples, P.
extracts, stem/leaf quinquefolius roots ginseng leaf and stem
Chemical Authentication of Herbal Products
Australia extract, berry extract) 4 1 3 P. ginseng leaf or other
(capsules, tablets) / P. plant parts
April 2021 | Volume 12 | Article 666850
China ginseng 1 0 1 leaf/stem
47 European Union food supplements 10 2 8 adulteration HPLC-UV, LC-MS/MS / n/a G. biloba herbal Czigle et al. (2018)
Greece containing ginkgo dry 1 0 1 flavonoids and terpenes medicinal product
extract or ginkgo leaf lactones (ginkgolides, (control)
(tablets, soft and hard bilobalide)
capsules) from local
community pharmacies
/ Ginkgo biloba
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
48 India "Asoka" raw herbal 25 3 22 substitution 1D/2D NMR/PCA not reported taxonomically Urumarudappa et al.
products from shops / authenticated samples (2016)
Saraca asoca of S. asoca (bark,
flower, stem)
49 India Garcinia products 5 5 0 n/a 1H NMR / (−)-hydroxycitric large variation in the authenticated BRM Seethapathy et al. (2018)
Norway (capsules, tablets) from 1 1 0 acid, (−)-hydroxycitric acid content of from eleven species of
Romania pharmacies, internet / 1 1 0 lactone (-)-hydroxycitric acid; only Garcinia L.
Sweden Garcinia gummi-gutta, 1 1 0 one product contained
United States G. indica 2 2 0 quantifiable amounts of
(−)-hydroxycitric acid
lactone
50 India licorice products (raw 2 2 0 n/a HPTLC, HPLC / 18β- not reported vouchered, botanically Frommenwiler et al.
material) from local glycyrrhizic acid confirmed sample, raw (2017)
shops / Glycyrrhiza materials (whole,
glabra, G. uralensis, G. chopped, or powdered)
inflata of licorice root /
United States
Pharmacopeia (USP)
51 Italy bilberry products 71 65 6 adulteration with HPLC-DAD, FT-NIR/PCA / the amount of refined and Gardana et al. (2018)
10
(extracts) from different anthocyanins extracted anthocyanins and the anthocyanins in the standardized dry extract
producers / Vaccinium from other berries (black respective aglycones bilberry extracts in the from the bilberry fruit
myrtillus mulberry, chokeberry, range 18–34%
blackberry)
52 Italy cranberry products 24 5 19 misidentification of the raw HPLC-UV/Vis, Orbitrap LC- only one product European Mannino et al. (2020)
(extracts) from herbal material MS / anthocyanins complied the criteria of Pharmacopeia
shops, local markets / good preparation,
Vaccinium respected their uniformity
macrocarpon of dosage, and contained
V. macrocarpon
53 Italy cranberry products 10 4 6 adulteration with Morus UPLC-DAD-Orbitrap-MS- only one product fruits and extract of Gardana et al. (2020)
(extracts) from herbal nigra extract PCA / anthocyanin, provided the daily dose possible adulterants
shops, local markets / epicatechin/catechin, deemed effective for
Chemical Authentication of Herbal Products
Vaccinium procyanidin A2/total treating a urinary tract
macrocarpon procyanidin, procyanidin/ infection
April 2021 | Volume 12 | Article 666850
anthocyanin ratios
54 Italy sweet fenel pre- 5 5 0 n/a GC–MS / constituents of possible presence of commercial reference Bilia et al. (2002)
packaged teabags and volatile oil bitter fennel or, for the samples of fruits of F.
instant tea products powdered material, the vulgare / European
(freeze-dried powders) presence of other parts of Pharmacopoeia (1997)
from local pharmacies, fennel monograph
grocery stores /
Foeniculum vulgare
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
55 Italy herbal product (liquid 2 0 2 adulteration with a root HPLC-DAD–MS, n/a purchased herbal Karioti et al. (2014)
preparations containing extract from a Rauvolfia HPLC–MS, NMR products and collected
four species) from sp. (indole alkaloids) plant material
herbalist shop / Olea
europaea, Crataegus
rhipidophylla, Fumaria
officinalis, Capsella
bursa-pastoris
56 Italy herbal product (liquid 1 0 1 adulteration with an HPLC-ESI-ITMS, NMR n/a n/a Gallo et al. (2012)
preparations containing extract from a Rauvolfia sp
five species) / Olea (indole alkaloids)
europaea, Crataegus
rhipidophylla, Fumaria
officinalis, Capsella
bursa-pastoris
57 Japan bilberry products 20 20 0 n/a LC-MS / anthocyanins marked composition V. myrtillus reference dry Cassinese et al. (2007)
United States (extracts) from the 15 7 8 substitution with berries differences extract
Italy marketplace (tablets, 4 2 2 different from V. myrtillus
Malaysia hard and soft gel caps) / 1 0 1
11
Vaccinium myrtillus
58 Japan herbal products (crude 14 1 13 mislabeling, adulteration HPLC-PDA / sennoside A, illegal adulteration with authenticated rhubarb Yoshida et al. (2015)
drug extracts) (soft aloe-emodin, emodin, rhein, sibutramine rhizome
capsules, hard chrysophanol
capsules, sugarcoated
tablets) from internet /
Poria sclerotium,
Ophiopogonis tuber,
Rheum emodi
59 Japan chasteberry extracts 11 8 3 adulteration, HPLC-PCA, quantitative poor formulation quality reference standard of V. Sogame et al. (2019)
(granules, tablets, soft contaminated with V. determination of chemical agnus-castus fruit dry
and hard capsules) negundo marker compounds / extract
purchased via internet / agnuside, casticin
Chemical Authentication of Herbal Products
Vitex agnus-castus
60 Japan herbal products (tea 8 5 3 adulteration with senna TLC, HPLC / sennoside A, the amount of reference raw senna Kojima et al. (2000)
April 2021 | Volume 12 | Article 666850
bags, granules, tablets) leaves and midribs sennoside B sennosides ranged from materials (stems, leaves)
containing senna stems 0.2-11 mg
/ Cassia alexandrina
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
61 Japan Siberian ginseng 4 3 1 substitution with Panax HPLC-DAD / eleutheroside not reported specimens of E. Zhu et al. (2011)
products (capsules, ginseng. B, eleutheroside E, senticosus, E.
teas) from internet / isofraxidin sessiliflorus and
Eleutherococcus congeneric species,
senticosus crude drugs from
markets / chemical
standards isolated from
an authenticated
commercial SG sample
62 Malaysia "Tongkat Ali" products 46 20 26 substitution HPLC, 2DE / protein marker the amount of the purified E. longifolia Vejayan et al. (2018)
from pharmacies, night (A), eurycomanone markers detected varies crude extract
markets, jamu shops, among the products
food courts, on-line
stores / Eurycoma
longifolia
63 Malaysia ‘Tongkat Ali’ products 29 18 11 substitution 2DE / protein markers (A, B) not reported standardized E. Vejayan et al. (2013)
(capsules, spherical (∼14kDa) longifolia root extracts
tablets) from
pharmacies, drug
12
stores / Eurycoma
longifolia
64 Malaysia "Tongkat Ali" products 7 3 4 substitution HPLC-DAD / eurycomanone none of the products met authenticated E. Abubakar et al. (2018)
(capsules, tea, tablet) the officially required longifolia plant and five-
from retail shops / minimum concentration year-old root sample
Eurycoma longifolia of eurycomanone
65 Mexic "Damiana" botanical 6 3 3 substitution, adulteration 1H-NMR/PCA / differences in the authenticated T. diffusa Lucio-Gutiérrez et al.
products (extracts) from hepatodamianol chemical components specimens / purified (2019)
local markets / Turnera chemical reference
diffusa standard
(hepatodamianol)
66 Pakistan crude drugs from local 6 6 0 n/a TLC, spectrophotometry, all the samples of n/a Fatima et al. (2020)
market / Foeniculum FTIR / anethole, barbaloin, Plantago ovata do not
Chemical Authentication of Herbal Products
vulgarae, Curcuma xylose, galactose, gingerol- comply with the
longa, Aloe vera, 1, gingerol-2, 6-gingerol, pharmacopoeial
April 2021 | Volume 12 | Article 666850
Plantago ovata, Zingiber glycerrihitic acid, curcumin standard
officinale, Glycyrrhiza
glabra
67 Pakistan "guggul" gum resin 1 0 1 adulteration with NMR n/a authenticated gum resin Ahmed et al. (2011)
product from herbal Mangifera indica gum samples of C. wightii
market / Commiphora and M. indica
wightii
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
68 Poland chamomile samples 19 19 0 n/a HPLC / phenolic acids not reported n/a Viapiana et al. (2016)
(fragmented, (gallic, caffeic, syringic,
granulated) from p-coumaric, ferulic),
different manufacturers / flavonoids (rutin, myricetin,
Matricaria chamomilla quercetin, kaempferol)
69 Poland ginkgo products (leaf 16 9 7 adulteration probably with ATR-FTIR, iPLS-DA / rutin, large amounts of standardized (24/6) Walkowiak et al. (2019)
extracts) (capsules, Sophora japonica (fruit or quercetin, kaempferol quercetin and kaempferol ginkgo extracts
tablets) from local flower extracts)
pharmacies, markets,
online pharmacies /
Ginkgo biloba
70 Poland herbal products 6 5 1 substitution TLC / rosmarinic acid not reported S. officinalis Cieśla and
containing sage authenticated botanical Waksmundzka-Hajnos
ethanolic extract extracts (2010)
(capsules, tablets,
ointments, tincture,
finished product) /
Salvia officinalis
71 Romania St. John’s Wort 50 34 16 substitution with other TLC, HPLC-MS / rutin, not reported authenticated reference Raclariu et al. (2017)
13
Slovakia products (herbal teas, 3 1 2 Hypericum sp. or did not hyperoside, hyperforin, plant material of H.
Turkey capsules, tablets, 2 1 1 contain Hypericum hypericin elegans, H. maculatum,
extracts) from species in detectable H. olympicum, H.
pharmacies, herbal amounts patulum, H. perforatum,
Austria shops, supermarkets, 2 2 0 n/a H. polyphyllum
Czech Republic internet / Hypericum 1 1 0
France perforatum 1 1 0
Germany 4 4 0
Italy 1 1 0
Netherlands 1 1 0
Poland 4 4 0
Spain 2 2 0
Sweden 1 1 0
Chemical Authentication of Herbal Products
United Kingdom 2 2 0
72 Romania Echinacea products 34 30 4 substitution or HPTLC / echinacoside, products totally devoided reference botanical Raclariu et al. (2018b)
April 2021 | Volume 12 | Article 666850
Czech Republic (teas, capsules, tablets, 2 0 2 adulteration with cynarin, cichoric acid, of any Echinacea sp. standards: E. purpurea,
Germany extracts) from retail 3 0 3 unlabeled Echinacea sp. chlorogenic acid, caffeic material E. angustifolia, E.
Italy stores, e-commerce / 1 0 1 acid, caftaric acid pallida (UPS)
Poland Echinacea purpurea, E. 2 1 1
Spain angustifolia, E. pallida 2 0 2
Austria 1 1 0 n/a
France 1 1 0
Norway 4 4 0
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
73 South Korea Panax ginseng 81 81 0 n/a HPLC, UPLC–DAD–ESI-IT- not reported raw plant material of P. Choi et al. (2018)
(decoctions, beverages, TOF-MS / lobetyolin, ononin ginseng, P.
capsules, tablets), grandiflorum, C.
Platycodon grandiflorus lanceolata, P. montana
(decoctions, var. lobata
beverages),
Codonopsis lanceolata
(decoctions,
beverages), Pueraria
montana var. lobata
(beverages) from local
markets / P. ginseng, P.
grandiflorum, C.
lanceolata, P. montana
var. lobata
74 South Korea "Malabar tamarind" 11 11 0 n/a HPLC / cyanidin-3-O- not reported collected fruit rinds of G. Jamila et al. (2016)
products from local sambubioside, cyanidin-3- gummi-gutta,
market / Garcinia O-glucoside purchased G. indica fruit
gummi-gutta samples
14
75 Taiwan "myrobalan" (Fructus 28 20 8 substitution with T. HPLC / tannin-related not reported reference standards, Juang and Sheu (2005)
Chebulae) products chebula var. parviflora constituents including some isolated
from local herbal previously from T.
markets / Terminalia chebula
chebula, Terminalia
chebula var. tomentella
76 Taiwan herbal materials of 12 12 0 n/a HPLC-UV / peimine, product with low total n/a (Lin et al., 2015)
Fritillariae Thunbergii peiminine content of peimine (not to
Bulbus from local be used clinically)
markets / Fritillaria
thunbergii
77 Taiwan white ginseng products 8 7 1 not composed of 6 years 1H-NMR/PCA/CA not reported authenticated, one to six Lin et al. (2010)
(radix sliced material, old ginseng radix only year-old, fresh white
Chemical Authentication of Herbal Products
powder, capsules) / ginseng radix (P.
Panax ginseng ginseng)
April 2021 | Volume 12 | Article 666850
78 Taiwan 5:1 concentrated 6 6 0 n/a HPLC / baicalin, baicalein significant product-to- n/a Ye et al. (2004)
China extract products 4 4 0 product and batch-to-
(prepared from dried batch variation of the
roots) from different marker compounds
companies / Scutellaria
baicalensis
79 Thailand white "Kwao Krua" 7 7 0 n/a HPLC / isoflavone not reported authenticated P. Intharuksa et al. (2020)
products from Thai local glycosides (puerarin, candollei, Mucuna
markets, drugstores / daidzin, genistin), macrocarpa, Butea
Pueraria candollei isoflavones (daidzein, superba plant material,
genistein) Kwao Krua crude drugs
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
80 Thailand Garcinia atroviridis 5 4 1 substitution CZE / hydroxycitric acid and not reported n/a Muensritharam et al.
products (capsules) hydroxycitric acid lactone (2008)
from market / G.
atroviridis
81 Thailand "Ya dok khao" smoking 1 1 0 n/a HPTLC / triterpenoid not reported C. cinereum, E. Thongkhao et al. (2020)
cessation tea product compounds (ß-amyrin, sonchifolia collected
from local market / taraxasterol, lupeol, betulin) samples, raw C.
Cyanthillium cinereum cinereum materials
82 Turkey chamomile products 16 5 11 adulteration (possibly with HPLC, HPTLC - PCA, HCA / A7G content in different wild and cultivated Guzelmeric et al. (2017)
(tea bags, bulk or Anthemis spp., apigenin 7-O-glucoside tea brands ranged from varieties of chamomiles,
packaged crude Tanacetum sp. and 0.43-0.80 mg/g chamomile-like flowers
flowers) from food Chrysanthemum sp.) (Anthemis L., Bellis L.,
stores, bazaar / Tanacetum L.,
Matricaria chamomilla Chrysanthemum L.)
83 Turkey Ginkgo products 13 13 0 n/a LC-MS, HPLC-DAD / total flavonoids and chemical reference Demirezer et al. (2014)
(extracts) from local ginkgolides, flavonoid ginkgolides higher in standards (ginkgolides
pharmacy, local aglycones medicinal products, no or A, B, C, J), quercetin,
markets / Ginkgo biloba very little flavonoids in kaempferol, rutin
food supplements (isolated), isorhamnetin
15
(prepared by acidic
hydrolysis)
84 Turkey "okaliptus" products 13 0 13 substitution with E. TLC / essential oils n/a E. camaldulensis, E. Tombul et al. (2012)
(leaves, essential oils) camaldulensis globulus, E. grandis
from herbal shops / reference plant material
Eucalyptus globulus / essential oils extracted
from the reference plant
material
85 United Kingdom turmeric products 50 48 2 absence of C. longa 1H-NMR/ PCA, HPTLC / significant quality n/a Chatzinasiou et al.
Germany (capsules, tablets, soft curcumin , piperine, (S)-ar- variation between (2019)
United States gels, powder, extracts) Turmerone samples
from stores, internet /
Curcuma longa
Chemical Authentication of Herbal Products
86 United Kingdom St John’s Wort 22 14 8 adulteration (possibly with HPTLC, 1H-NMR/ PCA significant compositional SJW registered and Booker et al. (2018)
United States products (tablets, 17 8 9 other Hypericum sp. variation among quantified products,
April 2021 | Volume 12 | Article 666850
Germany capsules, powder) from 8 7 1 obtained from China or commercial finished SJW EP Reference
internet, pharmacies, use of chemically distinct products, adulteration Standard
stores / Hypericum H. perforatum cultivars or with food dyes
perforatum chemotypes)
87 United Kingdom Sedum roseum 39 32 7 substitution, adulteration HPTLC, MS, 1H NMR / lower rosavin content, S. roseum crude drug Booker et al. (2016b)
products (root and with other Rhodiola sp. rosavin, salidroside substitution with 5- material, R. crenulata
rhizome powders) (hard (e.g. R. crenulata) hydroxytryptophan aqueous extracts
capsules, soft gel
capsules, tables) from
retail outlets, internet /
S. roseum
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
88 United Kingdom Ginkgo food 33 5 28 adulteration (not in 1H NMR/ PCA, HPTLC / variable quality (different quantified and licensed Booker et al. (2016a)
supplements (tablets, compliance with their label flavonoids, terpene lactones from that described in Ginkgo extracts, G.
hard capsules, caplets) specification) pharmacopoeias) biloba leaf samples
from health food stores,
supermarkets,
pharmacies, internet/
Ginkgo biloba
89 United Kingdom American ginseng, 8 8 0 n/a LC/MS/MS / malonyl- not reported authentic root samples Kite et al. (2003)
white Asian ginseng, ginsenosides of P. ginseng, P.
sanchi ginseng samples quinquefolius, P.
from importing notoginseng
companies / Panax
ginseng, P.
quinquefolius, P.
notoginseng
90 United Kingdom herbal tinctures from 4 4 0 n/a 1H-NMR, MS / hyperforin, not reported n/a Politi et al. (2009)
health shop / Echinacea hypericin, ginkgolic acids,
purpurea, Hypericum terpene lactones ginkgolides
perforatum, Ginkgo A, B, and C
16
biloba, Valeriana
officinalis
91 United Kingdom herbal product 3 1 2 no Equisetum sp. material TLC / kaempferol glucosides not reported material deposited in Saslis-Lagoudakis et al.
(capsules) / Equisetum (no TLC chromatogram) herbarium / characters (2015)
arvense used in the European
Bulgaria herbal product (tea) / E. 1 0 1 adulterated with E. Pharmacopoeia to
arvense palustre identify Equisetum sp.
Germany herbal product (tea) / E. 1 1 0 n/a
arvense
92 United States bitter orange products 59 59 0 n/a LC–MS/MS / very few appear to meet n/a Pawar et al. (2020)
(tablets, capsules, gel- phenethylamines claims for their label
containing capsules, (synephrine, octopamine, concentration
drink powders) from tyramine, N-methyltyramine, declarations
Chemical Authentication of Herbal Products
online / Citrus aurantium hordenine)
93 United States Echinacea preparations 49 31 18 adulteration, substitution TLC / cichoric acid, variability in chemical n/a Gilroy et al. (2003)
April 2021 | Volume 12 | Article 666850
(tablet, caplet, capsule, with unlabeled Echinacea echinacoside composition
liquid, powder, granule) sp., no measurable
from health food, drug, Echinacea
and grocery stores / E.
purpurea, E.
angustifolia, E. pallida
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
94 United States herbal supplements 41 27 14 adulteration and HPLC/DAD / anthocyanins wide variation of the verified authentic fruit Lee (2016)
(loose powders, substitution with (cyanidin-3-glucoside) anthocyanin content with known anthocyanin
capsules, tablets, liquid Vaccinium sp. profiles, anthocyanin
extracts, dried fruit profiles of small
forms) to contain authenticated fruit
cranberry, lingonberry, samples
bilberry, or blueberry
from local stores or
internet / Vaccinium
macrocarpon, V. vitis-
idaea, V. myrtillus, V.
corymbosum
95 United States goldenseal products 35 32 3 adulteration with Berberis. LC-MS/PCA / berberine, not reported reference materials (H. Wallace et al. (2018)
(dried material, extract, vulgaris, B. aquifolium, hydrastine, canadine canadensis, C.
freeze-dried material) Coptis. chinensis chinensis, B. aquifolium,
(capsules, tinctures, B. vulgaris) / canadine
powdered bulk reference (isolated and
materials, tea bags) purified from H.
from online / Hydrastis canadensis)
17
canadensis
96 United States black cohosh products 33 19 14 not containing A. UPLC-PDA, UPLC-MRM / not containing the full authenticated rhizome/ Geng et al. (2019)
(powder, dried extract, racemosa material V9c and V9a markers, spectrum of plant root materials from
liquid extract) (capsules, caffeic acid, ferulic acid, chemicals after different Actaea sp.
tablets, soft gels, drops) isoferulic acid preparation process
from local stores or
Internet / Actaea
racemosa
97 United States ginkgo products 27 27 0 n/a HPLC / flavone glycosides, relevant compositional EGb 761 extract Kressmann et al. (2002)
(tablets, capsules, terpene lactones, ginkgolic differences, particularly
caplet) from health food acids with regard to the content
stores, supermarkets / of ginkgolic acids
Ginkgo biloba
Chemical Authentication of Herbal Products
98 United States "‘buchu" products 27 16 11 not containing labeled A. HPTLC / rutin, chlorogenic not reported A. betulina, A. crenulata Raman et al. (2015)
(whole leaves, powders, betulina or A. crenulata acid, kaempferol plant reference material
April 2021 | Volume 12 | Article 666850
capsules, tea bag) /
Agathosma betulina
99 United States yohimbe products 26 17 9 not containing yohimbe GC/MS / yohimbine HCl, containing only trace authenticated johimbe Betz et al. (1995)
(powder, caplet, material ajmaline, corynanthine amounts of yohimbine, bark
capsules, liquid, largely devoid of the other
powdered drink mix) alkaloids, possible
from retail health food presence of undeclared
outlets / Pausinystalia diluents
johimbe
(Continued on following page)Frontiers in Pharmacology | www.frontiersin.org
Ichim and Booker
TABLE 1 | (Continued) The authenticity of the chemically authenticated commercial herbal products at global level.
No. Country / Products Products Adulteration Authentication Additional Botanical/ Bibliographic
crt. territory (details) / reported method / quality chemical reference
total authentic/
authenticated marker issues reference
adulterated
species (if reported) detected materials/
no. no. no. standards
100 United States ginseng preparations 25 25 0 n/a LC-MS, HPLC / ginsenoside product-to-product n/a Harkey et al. (2001)
from the genera Panax (Rb1, Rb2, Rc, Rd, Re, Rf, variability in the amount of
or Eleutherococcus Rg1), eleutheroside (B ginsenosides or
from local health food and E) eleutherosides present
store / P. ginseng, P.
quinquefolius, P.
notoginseng, E.
senticosus
101 United States German chamomile, 24 20 4 substitution (not GC/MS, PLS-DA / volatile not reported authenticated C. nobile, Wang et al. (2014a)
Roman chamomile and containing the labeled compounds (b-Farnesene, M. chamomilla, C.
Juhua products (crude chamomille species) did a-bisabolol oxide A, B) morifolium samples /
drugs, capsules, tea not contain any detectable essential oil samples
bags, crude drugs volatile components obtained from the
China mixed with other plant 11 11 0 n/a authenticated plant
materials, powder, materials
extracts) from
supermarkets, local
retail pharmacies, online
/ Matricaria chamomilla,
18
Chamaemelum nobile,
Chrysanthemum
morifolium
102 United States grape seed powder 21 12 9 adulteration with peanut HPLC/UV/MS, LC–MS, TLC wide degree of variability authenticated grape Villani et al. (2015)
products (capsules) skin extract / proanthocyanidin B-type in chemical composition seed extract, peanut
from vitamin dimers skin extract, pine bark
supplement retailers, extract
supermarkets, online /
Vitis vinifera
103 United States gingko products (leaf 21 21 0 n/a GC/MS, LC/MS, UHPLC/ not reported G. biloba authenticated Wang et al. (2014b)
extracts) from food MS / ginkgolic acids, and commercial plant
supermarkets, local terpene trilactones, flavonol samples (leaves, seeds,
retail pharmacies, online / glycosides leaf extracts, sarcotesta)
Chemical Authentication of Herbal Products
Ginkgo biloba
104 United States American and Korean 20 18 2 devoid of ginseng material RP-HPLC / ginsenosides not reported n/a Mihalov et al. (2000)
April 2021 | Volume 12 | Article 666850
ginseng products (fresh (Rf, Rb1, Rc)
or dried roots)
(powders, capsules,
tablets) from local and
national herbal health
care stores / Panax
ginseng, P.
quinquefolius
China 2 2 0 n/a
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