Trends in Analytical Chemistry 156 (2022) 116711

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Trends in Analytical Chemistry

journal homepage: www.elsevier.com/locate/trac

Frontiers in ion imprinting of alkali- and alkaline-earth metal ions e

Recent advancements and application to environmental, food and
biomedical analysis

ski b, *
Monika Budnicka a, Monika Sobiech b, Joanna Kolmas a, Piotr Lulin
a
Department of Analytical Chemistry, Faculty of Pharmacy, Medical University of Warsaw, Banacha 1, 02-097, Warsaw, Poland
b
Department of Organic Chemistry, Faculty of Pharmacy, Medical University of Warsaw, Banacha 1, 02-097, Warsaw, Poland

a r t i c l e i n f o a b s t r a c t

Article history: Detection and determination of s-block metal ions are crucial for medical diagnosis, clinical toxicology,
Received 7 January 2022 environmental safety and energy generation/conversion, but complex matrices such as body fluids or
Received in revised form environmental samples and the presence of coexisting ions hamper analysis. Ion-imprinted polymers
17 May 2022
could be a good choice for selective materials in effective extraction of targeted ions. This review focuses
Accepted 7 June 2022
Available online 10 June 2022
on the description of ion-imprinting synthetic approaches that follow after a brief introduction to the
coordination polymers network. The application of s-block metal ion-imprinted materials for environ-
mental, food and biomedical purposes is discussed (with reference to recent papers) prior to identifi-
Keywords:
s-Block metal ions
cation of frontiers in the design of polymers imprinted by s-block metal ions. Finally, a summary and
Alkali- and alkaline-earth metal ions future perspectives are presented, indicating a research direction for further development of the field.
Ion-imprinted polymer © 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND
Coordination chemistry license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Environmental analysis

1. Introduction technology, but their extraction is problematic. Moreover, they can

Metal ion detection and determination are crucial in various
fields, such as medical diagnosis, clinical toxicology, environmental
safety and energy generation/conversion [1,2], and are connected
with a wide spectrum of metal applications and functions in or-
ganisms and the environment. Alkali- (lithium, sodium, potassium,
rubidium, caesium and francium) and alkaline-earth (beryllium,
magnesium, calcium, strontium, barium and radium) metal ions are
very diverse due to their biological role, incidence of occurrence,
impact on the environment and application. Lithium is attractive
especially in battery manufacturing. However, large doses can
cause serious health problems, and lithium levels in water should
be monitored. Appropriate levels of sodium, potassium, magne-
sium and calcium are very important for the proper functioning of
organisms, and they have to be monitored in intracorporeal fluids
in order to prevent health problems. Rubidium and caesium are
used in many fields, such as the electronics industry or space
* Corresponding author.
E-mail addresses: mbudnicka@wum.edu.pl (M. Budnicka), monika.sobiech@
wum.edu.pl (M. Sobiech), joanna.kolmas@wum.edu.pl (J. Kolmas), piotr.lulinski@

ski).
wum.edu.pl (P. Lulin
compete with Kþ ions, creating hazards for living organisms.
Francium and radium are extremely radioactive. Beryllium ions are
highly toxic, and their levels should be monitored in the environ-
ment. Strontium concentrations need to be controlled because of
the strontium-90 isotope, which is radioactive and can replace
calcium in the human body, leading to serious diseases. Barium ions
can also affect human health because they can change potassium
concentrations in blood. Levels of alkali- and alkaline-earth metals
need to be monitored in complex matrices such as body fluids, food
or environmental samples, and new sources of metal ions such as
salt brine need to be explored, with many coexisting ions requiring
selective materials for effective extraction of analysed ions. Ion-
imprinted polymers (IIPs) may be a good choice as a material that
selectively adsorbs defined ions. IIPs are prepared according to the
general rules of molecular/ion-imprinting technology and are
marked by good selectivity and specificity in relation to the chosen
chemical individuum.
Only a small number of reviews have been published recently,
summarizing various aspects of IIPs [3e6]. Available reviews are
focused mainly on IIPs dedicated to separation of heavy and tran-
sition metal ions. Some excellent critical reviews have been pub-
lished recently, emphasizing progress in ion-imprinting strategies

https://doi.org/10.1016/j.trac.2022.116711
0165-9936/© 2022 The Authors. Published 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/).
M. Budnicka, M. Sobiech, J. Kolmas et al. Trends in Analytical Chemistry 156 (2022) 116711

Abbreviations: ICP-MS inductively coupled plasma mass spectrometry

ICP-OES inductively coupled plasma optical emission
12C4 12-crown-4 spectrometry
18C6 18-crown-6 IIP ion imprinted polymer
2AM12C4 2-(allyloxy)methyl-12-crown-4 IPCA4A 4-carboxyphenylazocalix[4]arene
6OBA 4-((6-(Acryloyloxy)hexyl)oxy)benzoic acid ISE ion-selective electrode
6OBAM 4-{[6-(Acryloyloxy)hexyl]oxy}-2-methylbenzoic acid KH-560 2,3-epoxypropoxypropyltrimethoxysilicane
AAS atomic absorption spectrometry LOD limit of detection
AES atomic emission spectrometry LSC liquid scintillation counting
AFC aniline formaldehyde condensate MAA methacrylic acid
APTES (3-aminopropyl)triethoxysilane MBA N,N0 -methylenebisacrylamide
B12C4 benzo-12-crown-4 MD molecular dynamics
B15C5 benzo-15-crown-5 MGS methacrylate functionalized glass substrate
C222 cryptand 222 MIPs molecularly imprinted polymers
C4A calix[4]arene MMWCNTs magnetic multiwalled carbon nanotubes
CA cellulose acetate MOFs metal-organic frameworks
CE capillary electrophoresis MPS 3-(methacryloxyl)propyltrimethoxysilane
CM-CTS carboxymethyl chitosan MS mass spectrometer
CNCs cellulose nanocrystals N-CMS nitrogen-doped carbon microspheres
CPs coordination polymers NIP non-imprinted polymer
CQDs carbon quantum dots NIPAM N-isopropylacrylamide
CTS chitosan o-PD 1,2-phenylenediamine
DB21C7 dibenzo-21-crown-7 PAR 4-(2-pyridylazo)resorcinol
DB24C8 dibenzo-24-crown-8 PCPs porous coordination polymers
DC18C6 dicyclohexyl-18-crown-6 pDA polydopamine
DIMF dual-imprinted mesoporous film PDMS-COCl acylation-functionalized polydimethylsiloxane
DTC dithiocarbamate PEI polyetyleneimine
DVB divinylbenzene PIXE particle induced X-ray emission
DVPO N,N0 -dimethyl-N,N0 -bis(4-vinylphenyl)-3- PTWs potassium tetratitanate whiskers
oxapentanediamide PVC poly(vinyl chloride)
ECH epichlorhydrin PVDF poly(vinylidene fluoride)
EDTA ethylenediaminetetraacetic acid RAFT reversible addition-fragmentation chain transfer
EGDE ethylene glycol diglycidyl ether RM257 1,4-bis-[4-(3-acryloyloxypropyloxy)benzoyloxy]-2-
EGDMA ethylene glycol dimethacrylate methylbenzene
ESCA electron spectroscopy for chemical analysis RSD relative standard deviation
ETAAS electrothermal atomic absorption spectrometry SA sodium alginate
FAAS flame atomic absorption spectrometry SBA-15 Santa Barbara Amorphous-15
FAES flame atomic emission spectrometry SBA-15-TTCA SBA-15 modified with S-1-dodecyl-S-(a,a’-
FES flame emission spectrometry dimethyl-a’’-acetic acid)trithiocarbonate
GA graphene aerogel SEMA 2-sulfoethyl methacrylate
GO graphene oxide STWs sodium trititanate whiskers
GO-MPS graphene-oxide modified with 3-(methacryloxyl) TAC(S) (S)-indanyl substituted tetra-armed cyclen
propyltrimethoxysilane TEOS tetraethyl orthosilicate
GTA glutaraldehyde TGA thioglicolic acid
HM12C4 2-hydroxymethyl-12-crown-4 TMS-EDTA N-[(3-trimethoxysilyl)propyl]ethylendiamine
HMO hydrogen manganese oxide triacetic acid trisodium salt
HPLC high-performance liquid chromatography UV/Vis ultravioletevisible
IC ion chromatography XPS X-ray photoelectron spectroscopy
ICP inductively coupled plasma spectrometry XRF X-ray fluorescence spectroscopy

[7,8]. However, there have not been any reviews focusing on IIPs of
alkali- and alkaline-earth metal ions. A comprehensive discussion
of IIPs destined for recognition of s-block metal ions (which are
important from a physiological, pathophysiological, disease diag-
nosis and industry development point of view) therefore consti-
tutes a novelty. In this review, covering papers published in recent
years, we focused on recent advances in the application of ion-
imprinting technology in alkali- and alkaline-earth metal anal-
ysis. As an introduction to the ion-imprinting process and synthetic
strategies, the coordination polymer networks with s-block metal
ions are briefly discussed, followed by an overview of recent ad-
vancements in IIPs application in analysis of s-block metal ions in
2
different complex samples. In the next part, current limitations in
the design of IIPs are outlined together with frontiers in the
determination of s-block metal ions in analytical methods sup-
ported by ion-imprinted polymers. Finally, future perspectives are
pointed out.
2. Coordination polymer networks with s-block metal ions
Coordination chemistry is the basis of research into the design
and synthesis of chemical compounds and macromolecules that
may imitate receptors in various applications such as sensors or
sorbents. Here, molecularly imprinted materials are a group of
M. Budnicka, M. Sobiech, J. Kolmas et al.
polymers that are considered to mimic natural receptors. The
receptor-analyte interactions are largely due to complex com-
pounds of metal ions with organic ligands, mainly macromolecular,
as well as supramolecular materials [9]. It is currently well known
that each metal ion is characterized by specific coordination
chemistry related to its electronic configuration, geometry and
charge density, defined as the ratio of electrical charge to volume.
This fact is very important, considering IIPs and their effective
fabrication. s-Block metal ions generally form weaker complexes
than transition metal ions and, having a subshell-closed electronic
configuration, form electrostatic interactions with ligands [10].
Stability of these interactions is primarily affected by the metal ion
charge-to-radius ratio (i.e., ionic potential) and increases with the
ion charge. Thus, the strongest complexes are formed by small ions
with a high charge, such as beryllium ions, and divergence is
explained by omitting the covalent contribution in metal-ligand
interactions.
A milestone in discovery of the coordination chemistry of s-
block metal ions was understanding their complexation during
biological processes, e.g., intracellular transport of potassium ions
or the mechanism of action of antibiotics. Among the first cyclic
compounds to show efficient complexation of potassium ions were
macrotetrolides and cyclodepsipeptides, followed by open-chain
carboxylic antibiotics, which revealed specificity towards sodium
ions. Subsequently, to facilitate interactions and to provide a proper
geometry for the ion, a plethora of synthetic complexing agents
was investigated, such as oligoethylene glycol dimethyl ethers
(glymes) [11]. However, the disadvantages of glymes related to low
stability constants and low specificity promoted further studies,
aimed at identifying alternative supramolecular compounds such
as coronands, cryptands and spherands (Fig. 1).
Among them, coronands, cyclic polyethers, are capable of
providing different cavity sites because of the number of oxygen
atoms located in the ring. The most effective interaction with a
cation has been found to occur when ethylene linker is employed in
the structure. Supramolecular compounds undergo a conforma-
tional rearrangement in order to reduce the size of the cavity,
improving the thermodynamic stability of crown complexes [12]. It
is worth noting that, in contrast to glymes, coronands limit the
impact of solvent molecules and reduce the endothermic des-
olvation process. The described macrocyclic effect explains the high
specificity of different structural coronands towards different alkali
metal ions.
The above-mentioned compounds have been used for analytical
purposes. However, a multiplicity of molecular and polymeric
structures can coordinate s-block metal ions, forming networks of
CPs, which extend the range of application of organic s-block metal
ligands. Thus, as the introduction to the topic of review, we have
discussed below briefly main aspects of the CPs networks with s-
block metal ion. It allows us to better understand the synthetic
approaches that were applied for effective synthesis of IIPs.
The chemistry of s-block metal ions is not limited to conven-
tional ionic behaviour observed in aqueous media, and their more
Fig. 1. In silico generated structures of potassium or lithium ions with macrocyclic
compounds: a) glyme, b) coronand, c) cryptand, d) spherand.
3
Trends in Analytical Chemistry 156 (2022) 116711
covalent character may emerge in polar organic solvents. X-ray
diffraction techniques have revealed a variety of molecules forming
networks of coordination polymers (CPs). The latter are mostly
constituted from neutral or anionic ligands (linkers), having at least
two donor sites, and metal ions or aggregates (nodes), having
instead at least two acceptor sites. The number and orientation of
donor atoms in the linker, as well as the metal coordination num-
ber, influence the possible dimension of the resulting construct.
Two- and three-dimensional assemblies, being porous coordina-
tion polymers (PCPs) (also known as metalorganic frameworks,
MOFs), possess remarkably high surface areas and are utilized in a
broad range of industries, such as energy, chemical sensing, catal-
ysis, transport, packaging and medicine (i.e., drug delivery and
respiratory systems) [13].
Alkali- and alkaline-earth metal ions possess a range of coor-
dination numbers, leading to less control over the final polymer
network structure, compared to transition metals. This is why most
results are likely to be discovered serendipitously, also triggering
less commercial utilization. Coordination polymer networks con-
structed with s-block metal ions are mainly linked with use of
anionic oxygen donor ligands. The latter correspond to the natural
biological environment of Naþ, Kþ, Mg2þ and Ca2þ ions. Never-
theless, a number of organic synthetic ligands of s-block metal ions
have been identified in the literature as being classical O-, N-, S- and
C-donors (i.e., aromatic rings) [10,14].
Amongst organic synthetic ligands of s-block metal ions, ethers
act as neutral oxygen donor ligands for alkali-metal compounds,
being ‘chemical scissors’ to alkali metal salts, hence stabilizing
structural fragments of these compounds. Apart from ordinary
solvents (such as tetrahydrofuran or diethyl ether, as well as pol-
ydentate ethers), various polyethers such as poly(ethylene oxide)
form coordination lattices with group 1 metal ions. Among these,
polyelectrolytes of lithium have gained much interest because of
use in rechargeable batteries [15]. Group 2 metal ions can be co-
ordinated by ethers as well. For example, a range of polyether
complexing agents was recently investigated for alkali- and
alkaline-earth metal catalysts in cyclic carbonate synthesis,
revealing the highest efficiency of poly(ethylene glycol) dimethyl
ether in combination with a CaI2 catalyst [16].
A lot of alkaline-earth metal compounds are hygroscopic in
nature. Thus, many of them include water molecules linked to the
metal ions or H-bonded to the assembled construct, affecting the
final structure [17]. It is also crucial to control the amount of water
present in the organic solvent system in view of ionic dissociation.
In order to improve the water stability of CPs, two successful
strategies were developed, viz. enhancing the hydrophobicity of
the surface through incorporating hydrophobic groups in the
bridged ligands and using high-oxidation-state metal ions as
inorganic nodes to strengthen coordination bonds with ligands
[18].
Anionic oxygen donor ligands are a large group of alkali- and
alkaline-earth metal coordination agents, consisting of alkoxides,
carboxylates and sulphonates. Aryloxides and amino acids have
also been widely reported as group 1 metal ions coordination
agents, whereas beta-diketonates and phosphonates have been
reported as group 2 metal ions ligands [14]. Furthermore, CPs
which are constructed with phosphonate linker molecules are
often characterized by high chemical and thermal stability and can
be successfully used in catalysis, gas storage, sensors or in proton
exchange membranes [19].
s-Block metal ions are considered to be rather hard cations and
thus interact preferably with oxygen donor atoms; pure nitrogen
donation is therefore scarce. Mixed oxygen and nitrogen donors are
more often used to satisfy coordination of the metal ions, especially
when single donors are not accessible in sufficient quantities [20].
M. Budnicka, M. Sobiech, J. Kolmas et al.
The structures of alkali- and alkaline-earth metal derivatives of
amino acids have also been gaining attention (when mixed with
transition metals) due to the enhanced chemical and physical
properties of their structures, for example, obtaining ligand-based
photoluminescence [21].
Cyclopentadienyl ligands and phenyl groups are the most
illustrative carbon donor ligands in formation of expanded struc-
tures. The interactions of s-block metal cations can have a signifi-
cant covalent nature. Larger and thus softer cations more readily
accept aromatic coordination, becoming visible in the zigzag
structures of heavier Kþ, Rbþ and Csþ ions, while Liþ and Naþ form
linear chains [22]. Recent investigations of alkaline-earth carbonyl
complexes have indicated that the bonding characteristics of
heavier elements (Ca, Sr and Ba) can mimic those of transition
metals, revealing a much more covalent character than previously
thought [23].
3. Principles of ion-imprinting technology
3.1. Concept of ion imprinting
Imprinting technology enables production of polymeric mate-
rials with specificity towards selected entities, either molecules or
ions, in template-tailored synthesis. The three-step process in-
volves formation of the pre-polymerization adduct, polymerization
(mostly in the presence of a cross-linker) and template removal.
The process is universal for fabrication of molecularly imprinted
polymers (MIPs) or IIPs, resulting in materials characterized by
specific regions on the surface of the polymer network, imprinted
either by molecules or ions [3,4,24e30]. Apart from their high
specificity, MIPs or IIPs are characterized by simple and low-cost
synthetic processes, good stability, and mechanical and chemical
resistance. These properties facilitate use in widespread applica-
tions in separation techniques, detection systems or catalysis. These
materials are also considered to be appropriate for use in cancer
and immunotherapy treatment and as potential drug-delivery ve-
hicles. The utility of imprinted materials has attracted the attention
of many research groups, stimulating rapid development of the
field of analytical chemistry and biomedical analysis [31e35].
In this section, we focus on the ion-imprinting process and
factors responsible for the effectiveness of the synthesis process.
Formation of a pre-polymerization adduct, a complex between
imprinted ion and components of the system before polymeriza-
tion (cross-linking), is crucial for successful preparation of IIPs.
Depending on the chemistry of ions and the strategy used for
fabrication of IIPs, non-covalent interactions or coordination bonds
can stabilize the complex. Three strategies based on a complex
composition can be distinguished (Fig. 2).
The first strategy involves polymer-ion interactions. Here, the
polymer chain acts as the chelator of ion because of intra-polymer
chelation and the flexibility of the chain, which enhance the sta-
bility of the complex. Such a strategy was first used by Nishide et al.
[36] in the process of cross-linking of poly(4-vinylpyridine), acting
as the polymer ligand for selected ions. It was found that the
polymer-ligand chain retained the most stable conformation for
templated ions, resulting in preferential adsorption of the imprin-
ted resin after the ion removal process. Subsequent studies allowed
extension of the applicability of various polymers, viz. poly(1-
vinylimidazole), for effective IIP fabrication [37e41]. Nowadays,
this strategy is mainly used to form complexes between ions and
natural polymeric chains such as cellulose or its modified forms,
viz. guanyl-cellulose, and it can be extended with the additional
support of chelating agents such as ethylene-1,2-diamine [42e44].
The second strategy involves monomer-ion interactions. Here,
the monomer acts as the ligand to form a complex with ion,
4
Trends in Analytical Chemistry 156 (2022) 116711
Fig. 2. A schematic overview of strategies involved in the formation of IIPs: polymer-
ion interactions (a), monomer-ion interactions (b), and chelator-ion interactions (c).
meaning that the ligand possesses polymerizable units capable of
being cross-linked in the following step. Mostly, commercially
available monomers are used to form complexes with ions such as
4-vinylpyridine and N-allylthiourea. Dual monomeric systems,
such as methacrylic acid and 1-vinylimidazole can also be consid-
ered effective for enhancing the stability of complexes [45e47].
This strategy is applied alternatively to form IIPs composed of an
inorganic silane network [48]. However, it should be underlined
that the IIPs obtained in such a way are characterized by low
selectivity. A few approaches have been proposed to enhance the
selectivity of resulting IIPs. One of these involves design and syn-
thesis of new chemical compounds that possess polymerizable
units and multiple structural regions, enabling interaction with
ions, for instance, 1-hydroxy-4-(prop-2-enyloxy)-9,10-
anthraquinone or 1-(pyridin-2-yl)-N-(3-vinylbenzyl)methan-
amine or use of polymerizable derivatives of supramolecular
compounds with specificity towards the selected ion, for instance,
benzo-15-crown-5-acrylamide [49e51].
The third strategy involves use of chelator agents as supporting
compounds for monomer-ion interaction (such as 2,20 -bipirydyl for
4-vinylpyridine functional monomer) or involves chelator-ion
interaction prior to monomer-chelator/ion complex formation.
This strategy could be classified as a hybrid molecular ion
imprinting strategy because the geometry of the cavity in the
polymer network of resultant material is affected by the ion-
supporting chelator or is a result of non-covalent interactions
that occur between monomer molecules acting as chelators in the
imprinting stage of fabrication. Different chelators have been
employed to form complexes with ions such as 1,5-
diphenylthiocarbazone or 3,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-
1,2-dihydro-1,2,4,5-tetrazine) [52e54] with these complexes
interacting with a functional monomer and cross-linker, viz.
methacrylic acid and ethylene glycol dimethacrylate, respectively,
to fabricate the IIPs. However, after the ion removal step, the
chelating agent remains in the polymer net, enabling specific
adsorption of ions.
M. Budnicka, M. Sobiech, J. Kolmas et al.
The above-mentioned strategies, with slight modifications, have
been employed for preparation of polymers imprinted by s-block
metal ions.
3.2. Outlook for synthetic strategies
In this part of the review, the outlook regarding synthetic stra-
tegies for preparation of polymers imprinted by ions of alkali- and
alkaline-earth metals will be presented. The discussion will take
into account pre-polymerization interactions in formed adducts,
viz. between the polymer and the ion, between the monomer and
the ion, and between the monomer and chelator-ion complex.
3.2.1. Polymer-ion imprinting
In an early approach to the ion-imprinting technique, Nishide
et al. [36] described formation of complexes between metal ions
and polymer chains. However, the first description of specific po-
tassium interactions with the polymer chain was based on obser-
vations provided by Skogseid [55]. It was indicated that nitrated
secondary aromatic amines selectively adsorbed Kþ, resulting in
insoluble macromolecular amines that possessed potassium (I)
selective ion-exchange properties, without any major structural
alteration of the polymer. A resin synthesized by substitution of
two nitro functional groups in 2- and 6-positions of the styrene
ring, and the (2,4,6-trinitrophenylamine) group in 4-position of the
styrene ring, allowed for selective adsorption of potassium ions.
Taking into account previous observations, Chough et al. [56]
conducted an investigation of ion-polymer interactions between
Ca2þ and poly(acrylic acid-co-methyl methacrylate). The polymer-
ization process was carried out in the presence of 4-ethylaniline, a
supporting reagent that interacts with carboxylic residues. The
spatial geometry that was created in the polymer network allowed
for selective adsorption of calcium (II) ions with the support of
negatively charged carboxylic residues.
The aromatic amine capacity to adsorb ions was also capitalized
upon in the study described by Sid Kalal et al. [57]. Aniline was
copolymerized by formaldehyde in the presence of strontium (II)
ions, providing specificity towards the resultant polymer. Amine
residues in the copolymer remained at a high ratio to methylene
units, indicating satisfactory adsorption capacity. However, it
should be underlined that the 2,6-methylene-substituted aniline
units in aniline-formaldehyde condensate were not as reactive as
an aniline monomer due to the strong steric effects of the methy-
lene linker. As a result, the polymerization yields were affected, and
the termination capability of aniline-formaldehyde condensate
increased, producing shorter polyaniline chain oligomers with a
branch-like structure. The adsorption process for obtained ion-
imprinted poly(aniline-formaldehyde) was characterized in detail,
employing Langmuir, Freundlich, Temkin and Redlich-Peterson
models. The analysis of adsorption thermodynamics indicated
that physical adsorption was an ascendant mechanism in the
sorption process.
Natural polymers can be used to overcome problems deriving
from the synthetic limits of polymers. Here, Wang et al. [58] pro-
posed a calcium ion-imprinted porous film, prepared from a
cellulose-alginate composite. Sodium alginate is a natural polymer
consisting of 1,4-linked D-mannuronic and L-guluronic acid resi-
dues, which features gelation behaviour in the presence of divalent
ions such as Ca2þ. It was supposed that only guluronate residues
were responsible for specific adsorption of calcium (II) ions, but the
cellulose component provided a porous network cross-linked by
epichlorohydrin to facilitate diffusion and adsorption of ion. It
should be emphasized that natural polymers are environmentally
benign, providing an additional advantage to the described
approach.
5
Trends in Analytical Chemistry 156 (2022) 116711
Chitosan is another example of a natural polymer used to form a
complex with s-block metal ions. Zhang and Li [59] have presented
a concept covering synthesis of potassium tetratitanate whiskers,
functionalized by chitosan imprinted by Sr2þ and cross-linked by 3-
(2,3-epoxypropoxy)propyltrimethoxysilane. The proposed mecha-
nism of adsorption is based on the assumption that amine residues
are the main reactive groups for metal ions, together with hydroxyl
groups (in the C-3 position), which might contribute to sorption as
well. The free electron doublet on the nitrogen atom in the amine
group can interact with metal cations, but high adsorption effi-
ciency can be obtained when the pH value is higher than 6. A
similar approach was used by Zhang et al. [60] to design IIPs for Csþ
ion adsorption.
3.2.2. Monomer-ion imprinting
Interactions between the compound possessing the polymer-
izable units (the monomer) and the ion can be considered as
adequate for monomer-template interactions in the MIP fabrication
process. Here, various commercially available functional monomers
have been applied to provide stable pre-polymerization complexes.
Alizadeh et al. [61] have presented an original approach for prep-
aration of selective calcium (II) ion separation material. The effec-
tiveness of the itaconic acid used as the monomer to form a
selective IIP was proved by comparison to IIPs synthesized from
other functional monomers, viz. methacrylic acid or acrylic acid.
Theoretical investigations were used to explain the stability of pre-
polymerization complexes. It was stated that the four molecules of
itaconic acid could interact with calcium ions, and the oxygen atom
from the carbonyl group was the main point of interaction. More-
over, because of the presence of carboxylic groups, hydrogen bonds
could exist between functional monomer molecules, which could
additionally stabilize the complex with ions.
The role of cross-linking agents has also been investigated. Liu
et al. [62] used methacrylic acid as the functional monomer to form
stable pre-polymerization complexes with strontium ions. Here,
N,N0 -methylenebisacrylamide (MBA) was applied as the cross-
linker to form a thermally responsive composite containing
magnetite nano-conjugates in the polyethyleneimine mesoporous
silica SBA-15 framework functionalized by 3-(trimethoxysilyl)pro-
pyl methacrylate. The material was used to remove Sr2þ ions from
aqueous solution with a maximum adsorption capacity close to
lower consolute temperature. In another excellent paper, Liu et al.
[63] revealed the applicability of a strontium IIP composed of
methacrylic acid (functional monomer) and ethylene glycol dime-
thacrylate (the cross-linker) conjugated to functionalized graphene
oxide sheets in order to enhance the hydrophilic nature of the
material. Addition-fragmentation chain transfer polymerization
was employed to control the thickness of the surface of the
imprinted layer. A functional monomer of methacrylic acid was also
used by Meng et al. [64] to form stable pre-polymerization com-
plexes with Csþ ions. Once again, addition-fragmentation chain
transfer polymerization was employed in order to control the
thickness of the surface of the imprinted layer of the functionalized
mesoporous silica SBA-15 framework.
In a more advanced approach, Moirangthem et al. [1] fabricated
an optical sensor based on photonic polymer film, for detection of
Ca2þ in serum samples. The sensor was constructed with specific
mesogenic functional monomers, such as 2-methyl-1,4-phenylene
4-(3-acryloyloxypropyloxy)benzoate and benzoic acid-derived
polymerizable compounds, which were applied to prevent crys-
tallization of chiral nematic liquid crystals in the presence of R-
(þ)-3-methyladipic acid, the chiral dopant. The polymer film
showed a high optical response for various ions, but selectivity in
relation to calcium ions was emphasized due to the preorganized
adsorption sites in the ordered liquid crystalline phase and
M. Budnicka, M. Sobiech, J. Kolmas et al.
interactions with carboxyl residues. This led to a blue reflecting
film, facilitating measurement of total calcium concentrations in
serum. The concentrations of calcium (II) ions in the samples,
mimicking hypocalcaemia and hypercalcemia, were also easy to
distinguish. It was concluded that the sensor could provide a cheap,
battery-free and easy-to-use alternative for calcium determination
in clinical diagnostics.
Application of specific functional monomers dedicated to
adsorption of calcium ions has also been proposed by Rosatzin et al.
[65]. Molecules of N,N0 -bis(4-vinylphenyl)-3-oxapentanediamide
or N,N0 -dimethyl-N,N0 -bis(4-vinylphenyl)-3-oxapentanediamide
were used as functionalized ligands in the presence of divinyl-
benzene (the cross-linker), and the resultant material was found to
exhibit high selectivity towards calcium ions, over other alkali- and
alkaline-earth metal ions. Interactions between oxygen atoms from
both carbonyl groups and oxygen linker heteroatom governed
specific adsorption of Ca2þ ions. In order to enhance the selectivity
of IIPs towards specified ions, functionalized supramolecular
compounds were used.
It is known that interactions between specific supramolecular
molecules and ions are highly selective due to the geometry and
diameter of crown ethers, calixarenes or cryptands. Sun et al. [66]
used (2-alloxy)methyl-12-crown-4-ether, a supramolecular mole-
cule functionalized with a polymerizable unit, to improve the
specificity of IIPs towards Liþ ions. The composite was cross-linked
by ethylene glycol dimethacrylate, consisting of a thin layer of
heterogeneous polydopamine-poly(vinylidene fluoride), which
was formed as a membrane. The selectivity tests revealed that the
proposed approach facilitated selective adsorption of Liþ ions in the
presence of Mg2þ. A similar strategy to improve the selectivity of
IIPs was presented by Wu et al. [51], who produced a poly (N-iso-
propylacrylamide-co-benzo-15-crown-5-acrylamide) network for
specific adsorption of Liþ ions.
Modern synthetic strategies focus on use of environmentally
benign components. For such purposes, Liu et al. [67] applied chi-
tosan functionalized with dithiocarbamate groups for specific
adsorption of Sr2þ ions. It is well known that dithiocarbamate an-
ions are one of the most effective metal-coordinating agents due to
the presence of two donor sulphur atoms. Similarly, Zheng et al.
[68] applied cellulose as the support for hydrogen manganese oxide
and N-[(3-trimethoxysilyl)propyl]ethylenediamine, acting as the
functional monomer for specific adsorption of Liþ and Rbþ ions. It
was underlined that cellulose provides excellent mechanical
strength, and hydrogen manganese oxide is responsible for the
ordered mesoporous structure, which together lead to a high de-
gree of specificity of the surface on the resultant material.
3.2.3. Chelator-ion imprinting
The chelator-ion imprinting strategy could be considered as a
hybrid strategy in formation of IIPs. This approach mostly involves
monomer-template non-covalent interactions between commer-
cially available functional monomers and organic template mole-
cules, acting as chelators for the specified ions as well as
interactions between the chelator and ion. In such an approach, the
critical stage of the fabrication involves the ion removal step, which
should proceed without extraction of the chelator compound. A
significant number of papers relating to IIPs for adsorption of s-
block metal ions have been devoted to use of various crown ethers
as the chelators. Shao et al. [69] employed benzo-15-crowm-5-
ether as a supramolecular chelator of Liþ. Interactions between
the methacrylic acid (functional monomer) and the chelator
molecule, mostly involving hydrogen bonds between the hydrogen
atom from the carboxyl group and oxygen heteroatom from crown
ether, allowed the pre-polymerization complex to stabilize effec-
tively. The ion removal step proceeded with 0.1 mol L1 aqueous
6
Trends in Analytical Chemistry 156 (2022) 116711
nitric acid treatment, avoiding chelator removal and polymer
hydrolysis.
Similar approaches were proposed by Hashemi et al. [70] who
used benzo-12-crown-4-ether as the chelator of Liþ ions and
methacrylic acid, which served as the functional monomer, by
Shamsipur and Rajabi [71] who applied dibenzo-24-crown-8-ether
as the chelator of caesium ions and methacrylic acid (the functional
monomer) and by Hashemi and Shamsipur [72] who used dibenzo-
21-crown-7-ether for rubidium ions and also methacrylic acid. Xu
et al. [73] used a mixture of 12-crown-4-ether and 18-crown-6-
ether for simultaneous adsorption of Liþ and Rbþ ions. The mate-
rial was composed of a siloxane functionalized imprinted polymer
layer, possessing residues of methacrylic acid and magnetite core,
which was introduced to facilitate the separation process. The in-
teractions between hydrogen atoms from methacrylic acid and
oxygen atoms from crown ethers stabilized the complexes with
specified ions. The crown ethers provided superior selectivity to-
wards specific ions because of their capacity to coordinate with
alkali metal ions to form stable complexes by virtue of the so-called
macrocyclic effect. However, effective adsorption only occurs with
alkali or neutral pH values due to the protonation of oxygen atoms
in acidic conditions, decreasing the selective ion-recognition
capability of supramolecular compounds. In order to overcome
this problem, Zhang et al. [74] proposed an electrochemically
switched ion-exchange technique to obtain an effective IIP for
adsorption of Liþ. The material was composed of polypyrrole (with
pyrrole serving as the monomer), graphene oxide (GO) and
nitrogen-doped carbon microspheres/graphene aerogel (GA), con-
taining benzo-12-crown-4-ether as a chelator of lithium ions. Here,
the complex was mainly stabilized by p-p interactions between the
benzene ring from the chelator and unsaturated bonds from the
graphene. The electrochemically switched ion-exchange process
was able to compensate for the weakened coordination ability of
benzo-12-crown-4-ether to Liþ, caused by protonation of oxygen
atoms in the acidic adsorption medium (Fig. 3).
Liu et al. [75] used pyrrole as the conductive reagent to form an
electrochemically imprinted membrane for separation of Liþ ions.
Pyrrole rings facilitated interaction with 2-hydroxymethyl-12-
crown-4-ether, a chelator for Liþ. Apart from crown ethers, other
macromolecular compounds have also been applied as chelators.
Hashemi et al. [76] employed cryptand-222 as the complexing
agent of Kþ, methacrylic acid as the functional monomer and
ethylene glycol dimethacrylate as the cross-linker. The proposed
mechanism of interactions between the monomer and chelator
involved hydrogen bonds between the hydrogen atom from the
carboxylic group and oxygen atoms from the supramolecular
molecule, but nitrogen as well as oxygen heteroatoms were
involved in interactions with the ion. The ion removal step pro-
ceeded using 3 mol L1 of aqueous nitric acid solution with no
eventual hydrolysis of the polymer being reported. In another
example, Kubo et al. [77] used 12-membered cyclen to obtain an IIP
for Naþ ions. Here, an ion-pair complex of sodium salt of (S)-indanyl
and 2-sulphoethyl methacrylate was formed in the pre-
polymerization mixture.
In another study, Wang et al. [78] prepared an IIP using various
calixarenes, viz. 4-t-butylcalix[4]arene, calix[4]arene or 4-
carboxyphenylazocalix[4]arene, serving as chelators in dual-
imprinted mesoporous material dedicated to separation of
lithium and rubidium ions. The tested compounds possessed four
hydroxy groups, each one substituted for each of the aromatic rings,
enabling interaction with functional groups of cellulose support.
Use of environmentally benign cellulose was an additional advan-
tage of the method. In conclusion, it was stated that the selectivity
of materials was high but comparable to other existing methods.
However, the high level of reusability of the proposed method was
M. Budnicka, M. Sobiech, J. Kolmas et al. Trends in Analytical Chemistry 156 (2022) 116711

Fig. 3. Electrochemical absorptionedesorption mechanism of lithium ions on the ion-imprinted surface of electrode. With permission of Elsevier [74].

exceptional. Lu et al. [79] described preparation of a multilayer ion-
imprinted membrane with selectivity towards lithium ions, using a
12-crown-4-ether chelator. The material was prepared as a multi-
layered structure, with polydopamine as the interfacial adhesion
layer, silane dioxide nanoparticles as the hydrophilic layer and IIPs
as the specific adsorption layer (Fig. 4). The membrane was char-
acterized by satisfactory hydrophilicity and stability, providing high
binding capacity and superior regeneration performance.
Finally, Cui et al. [80] have described a renewable and degrad-
able cellulose-chitosan composite IIP for separation of lithium ions,
with a 12-crown-4-ether chelator. Here, siloxane modification of
the composite with a functional monomer of (3-aminopropyl)
triethoxysilane allowed introduction of an amine group, which
interacted with oxygen atoms in the supramolecular compounds,
stabilizing the pre-polymerization complex. Similar approaches
have also been proposed in other papers [81,82].
4. Application of s-block metal ion-imprinted polymers in
environmental, food and biomedical analysis
4.1. s-Block ion-imprinted polymers as sorbents in separation/
enrichment techniques
4.1.1. Environmental samples
Environmental samples, including drinking, mineral, ground
and wastewater, have been analysed to determine potassium ions
with use of a Kþ-imprinted polymer as a sorbent material. Potas-
sium ions can be found in natural water, mainly from minerals or

Fig. 4. Schematic diagrams of the preparation route to obtain lithium-ion selective ion-imprinted membrane. With permission of Elsevier [79].

7
M. Budnicka, M. Sobiech, J. Kolmas et al.
nitre depositions. Dietary sources of potassium include nuts and
chocolate, along with certain fruits and vegetables (such as to-
matoes, potatoes and bananas). Appropriate distribution of Kþ
across cell membranes is vitally important for normal cellular
function. However, a long-term high Kþ intake, where Kþ accu-
mulation in the renal interstitium exerts an inhibitory effect on Naþ
reabsorption, can result in increased delivery of Naþ and flow to the
aldosterone-sensitive distal nephron. Fluctuating potassium levels
can result in hyperkalaemia or hypokalaemia, disorders affecting
the nervous and cardiovascular systems, and they can affect mental
functions and physical processes [83].
Rajabi et al. [84] prepared imprinted nanobeads using the pre-
cipitation polymerization method and the following reagents: Kþ/
dicyclohexyl-18-crown-6-ether complex, methacrylic acid as the
functional monomer and ethylene glycol dimethacrylate as the
cross-linker, with a molar ratio equal to 1:10:100. The optimization
of synthetic process allowed to fabricate monodispersed particles
that contributed to faster sorption kinetics, increased surface area
and more favourable accessibility of functional groups of the ligand
in the cavities. Excellent reusability and the satisfactory stability
were recognised as the additional advantages of resultant Kþ-
imprinted polymer. The selectivity towards Kþ, when compared
with other ions (Liþ, Naþ, Rbþ, Csþ, Mg2þ, Ca2þ and Sr2þ) tested in
binary competitive studies, revealed a high specific-recognition
capability in relation to potassium ions. It has to be emphasized
that the selectivity of ordinary crown ethers for alkaline-earth
metal ions is much lower than that for alkali cations. After deter-
mination of the analytical parameters (Table 1), an analysis of real
samples was successfully conducted, showing high potassium ion
recovery levels. Similar synthetic approaches have also been pro-
posed to obtain Liþ-, Csþ- and Rbþ-imprinted polymers.
Lithium, as an electrochemically active element, has been
widely used in reactor control, the energy industry or for light alloy
fabrication. It can be sourced from salt like brines, but brines are
very complex matrices containing other ions, mainly magnesium,
making it difficult to solely extract Liþ. Moreover, the extraction
process increases lithium-ion levels in wastewater, causing serious
pollution and health problems because of lithium's impact on the
kidneys, liver and brain [85,86]. Caesium, on the other hand, is only
mildly toxic, but it has been shown that Csþ can compete with Kþ as
well as the chemically similar Rbþ in both active and passive
membrane transportation in living organisms, resulting in hyper-
irritability and spasms [87].
Rubidium's importance for the electronics industry and space
technology has been revealed recently, but problems with its
extraction from mineral and brine resources have been highlighted,
together with the impact of existing extraction methods on the
environment [88]. Liþ-, Csþ- and Rbþ-imprinted pre-polymer
mixtures have been created from a Liþ/benzo-12-crown-4-ether
complex (with LiClO4 dissolved in acetonitrile as the Liþ source)
[70]; Csþ/dibenzo-24-crown-8-ether complex (CsNO3 dissolved in
acetonitrile-dimethylsulphoxide solution as the Csþ source) [71];
and Rbþ/dibenzo-21-crown-7-ether complex (RbNO3 dissolved in
acetonitrile as the Rbþ source) [72]; along with other reagents used
in the previously mentioned study [83]. Utilization of specific su-
pramolecular compounds for each ion enhanced the selectivity of
respective IIPs, but once again, the stoichiometry required opti-
mization. Interestingly, the optimal molar ratios between the
template complex, monomer (methacrylic acid) and cross-linker
(ethylene glycol dimethacrylate) varied significantly from 1:5:20
for Liþ/benzo-12-crown-4-ether, to 1:8:30 for Rbþ/dibenzo-21-
crown-7-ether and 1:60:1200 for Csþ/dibenzo-24-crown-8-ether
template-monomer-cross-linker complexes, respectively. It has to
be underlined that the impact of cross-linking agents on adsorption
capacity was also found to be crucial. The reusability studies
8
Trends in Analytical Chemistry 156 (2022) 116711
showed satisfactory results even after a dozen cycles of use. The
selectivity studies confirmed high levels of distinctiveness among
the obtained polymers, which were selective towards the
following: Liþ, Csþ or Rbþ during analysis of binary mixtures of Liþ
and Naþ, Kþ, Rbþ and Csþ on Liþ-IIP, mixtures of Csþ and Liþ, Naþ,
Kþ, Rbþ, NHþ þ 2þ
4 , Ag , Mg , Ca
2þ
and Sr2þ on Csþ-IIP or mixtures of
Rbþ and Liþ, Naþ, Kþ and Csþ on Rbþ-IIP. Real sample analyses of tap
and well water, with application of synthesized Liþ-IIP material as
the sorbent, showed recovery of between 97.8 and 99.7%. Similar
high recovery rates were obtained during determination studies of
caesium(I) ions in ground and tap water samples and during
analysis of rubidium(I) ions in tap water (96.9e98.1% and
98.9e99.5%, respectively).
In another interesting example, Liu et al. [89] used sodium
alginate to form an IIP for selective recovery of Sr2þ from oilfield
water. Sodium alginate is characterized as a low-cost, environ-
mentally friendly, non-toxic and biodegradable material, rich in
carboxyl groups, which enable Sr2þ complexation. During the
preparation process, sodium alginate in the presence of Sr2þ
formed microspheres with a diameter of about 2e3 mm, which
were then modified by thioglycolic acid to improve their adsorption
performance (with introduction of mercapto groups). A pseudo-
second-order kinetic model described the adsorption on the ob-
tained IIP, indicating that the major Sr2þ adsorption mechanism
was chemisorption. Thermodynamic analysis showed that Sr2þ
adsorption on the analysed IIP was an exothermic, thermody-
namically feasible and spontaneous process. Interestingly, the
variation of adsorption capacity of Sr2þ with pH change was well
correlated to the surface charge of protonated material because of
the competitive adsorption of Hþ and the high priority of Hþ in the
ion-exchange process. The developed adsorbent presented a high
degree of stability and selectivity during analysis of oilfield water
samples, showing a change in adsorption capacity of only 0.42%
after five adsorption-desorption cycles.
IIPs obtained by traditional methods are characterized by high
specificity and selectivity, but the analytes’ ability to access recog-
nition sites is constricted due to the high degree of embedment.
Thus, surface-imprinting technology has been successfully applied
to produce imprinted materials with more accessible adsorption
sites, fast binding kinetics and good selectivity [84]. The synthetic
process used Csþ [60] and Sr2þ [59,90] ions (with CsCl or SrCl2
applied as templates) and potassium tetratitanate or trititanate
whiskers as supports; chitosan acted as the monomer, and (3-
glycidyloxypropyl)trimethoxysilane acted as the cross-linker. The
adsorption process was analysed, fitting well in the Langmuir
isotherm with kinetics fitted to a pseudo-second-order kinetic
equation. Respective IIPs were selective towards Csþ or Srþ in
competitive studies, where other ions such as Pb2þ, Zn2þ, Ce3þ,
Co2þ, Ni2þ, Ba2þ, Kþ and Mg2þ were present. Reusability studies
showed that even after six cycles of use, the adsorption capacities
did not drop below 83.7% of the virginal process. After detailed
analysis of different factors such as pH, sorbent mass, flow rate or
contact time in the IIP adsorption process, the optimized analytical
procedures were applied during analyses of environmental sam-
ples (river water, living sewage, pond water, industrial wastewater
and clay solutions), with recoveries of between 93.1 and 110.4%
(Table 1).
Aside from titanate whiskers, silica or chitosan beads have
become the most commonly used supports. However, the adsorp-
tion capacity of imprinted materials produced with application of
silica or chitosan can be insufficient. For this reason, supports with
a large surface area are promising for fabrication of surface-
imprinted polymers with a high adsorption capacity. One such
material is GO, which has an extremely large surface area, great
aqueous dispersibility, extraordinary mechanical stiffness and
 Table 1

M. Budnicka, M. Sobiech, J. Kolmas et al.

Representation of IIP composition (chelator, monomer and crosslinker) and form along with the corresponding analytical parameters (maximum sorbent capacity, limit of detection (LOD), linear range, recovery, relative standard
deviation (RSD) and adsorption/desorption time).

Ion Chelator Monomer Crosslinker Supporter/form Analytical method Maximum sorbent capacity LOD (mg/L) Linear range (mg/L) Recovery (%) RSD (%) Ads./des. Ref.
(mg/g) (min.)

Na+ TAC(S) SEMA EGDMA -/powder HPLC with UV-detector e e e e e / [77]
Li+ 12C4 APTES TEOS CA@CTS@pDA/ 20.1 e e e e 120/- [80]
composite
membrane
Li+ HM12C4 pyrrole Pt foil/membrane ICP-OES 16.4 e e <95.9 e 80/120 [75]
Li+ C4A triethylamine pDA@PDMS-COCl/ 50.9 e e e e -/90 [100]
membrane
Li+ B12C4 pyrrole, GO N-CMS@GA/film 41.1 e e <91.7 e 120/120 [74]
Li+ e EGDMA pDA@PVDF/ AAS 27.1 e e e e 60/- [66]
2AM12C4 macoporous
membrane
Li+ B15C5 MAA CQDs/ fluorometry e 1.11 3.47e347 102e111.6 4.5e12.2 10/- [69]
microparticles (n ¼ 3)
+
Li B12C4 7.07 3.29 10.0e300 97.8e99.7 2.1 (n ¼ 5) 15/15 [70]
FAES (imprinted ion), AAS (other
K+ C222 -/nanoparticles 4.69 4.62  103 10.0e500 92.7e100.3 1.61 (n ¼ 5) 10/12 [76]
ions)
K+ DC18C6 33.5 3.80  103 10.0e100 96.0e103.8 1.7 (n ¼ 3) 10/10 [84]
K+ B15C5 NIPAM MBA -/responsive e e e e e e / [51]
hydrogel
+
Rb DB21C7 MAA EGDMA -/nanoparticles FAAS 5.45 5.73 35.0e100  101 98.9e99.5 3.2 (n ¼ 5) 15/20 [72]
Li+/ IPCA4A/C4A e TEOS CNCs/DIMF ICP-MS 16.1(Li+) 10.6(Rb+) e e <85.0 e 120/- [78]
Rb+
Li+/ e HMO/TMS- TEOS CNCs/DIMF 6.30(Li+) e e <82.0 e 100/- [68]
Rb+ EDTA 6.21(Rb+)
Li+/ 12C4/18C6 MAA EGDE Fe3O4@SiO2/core- 0.125(Li+) e e <81.0 e 200/- [73]
Rb+ 0.0946(Rb+)
9

shell microspheres
ICP-OES
Cs+ e CTS KH-560 STWs/composite 32.9 0.180 50.0e100  10 2
98.6e101.2 0.98e2.21 120/360 [60]
(n ¼ 5)
+
Cs e MAA EGDMA SBA-15-TTCA/ 54.5 e e <92.0 e / [64]
particles
Cs+ e CM-CTS GTA Fe3O4@SiO2/core- FAAS 36.15 e e >88.0 e 360/360 [92]
shell microspheres
Cs+ DB24C8 MAA EGDMA -/nanoparticles AAS 50.0 0.700 10.0e800  101 96.9e98.1 0.9 (n ¼ 7) 20/7 [71]
Cs+ e CTS GTA MMWCNTs/ potentiometry e 5.32 13.3e133  102 94.8e105.8 0.6e0.8 (n ¼ 3) / [96]
composite
Be2+ Chrome Azurol APTES TEOS Fe3O4@SiO2/core- spectrophotometry 22.2 0.900 2.00e40.0 100.4e106.0 <4 (n ¼ 5) 20/25 [93]
S shell nanoparticles
Be2+ PAR o-PD Au electrode/ electrochemi-luminescence e 2.12  104 6.31  95.0e101.0 1.34e2.46 9/3 [97]
composite 104e7.21 (n ¼ 5)
 102

Trends in Analytical Chemistry 156 (2022) 116711

Ca2+ e cellulose, ECH -/film spectrophotometry 2.92 e e e e 40/- [58]
SA
2+ 4
Ca e itaconic acid EGDMA PVC/membrane potentiometry e 30.1 40.0e400  10 e e / [61]
(nanoparticles)
Ca2+ e DVPO, styrene DVB -/bulk FAAS e e e e e / [65]
Ca2+ e 6OBA, 6OBAM RM257 MGS/film optical detection e e 400  101 e e / [1]
e400  103
Sr2+ e AFC aniline -/powder ICP-OES 24.6 e e 68.9e88.4 1.64e3.41 300/180 [57]
(n ¼ 3)
2+
Sr e MAA EGDMA GO-MPS/composite 146 1.06 e 99.8e100.4 1.85 (n ¼ 11) 60/720 [63]
particles
Sr2+ e CTS KH-560 PTWs/composite 27.6 0.210 30.0e300 93.1e104.0 6e9 (n ¼ 5) 180/1440 [90]
ICP-OES
Sr2+ e CTS KH-560 PTWs/composite 32.6 0.300 50.0e100  102 101.7e110.4 1.18e2.18 150/360 [59]
(n ¼ 5)
Sr2+ e SA-TGA -/microspheres 177 e e <99.6 e 180/- [89]
(continued on next page)
 M. Budnicka, M. Sobiech, J. Kolmas et al. Trends in Analytical Chemistry 156 (2022) 116711

[67]
[94]
[62]
strength [63,91]. Liu et al. [63] prepared a surface IIP based on GO
Ref.

for removal of Sr2þ from aqueous solution. The preparation process

50/- employed Sr(NO3)2 as the template, methacrylic acid as the hy-
/
/

drophilic monomer and ethylene glycol dimethacrylate as the

Ads./des.
(min.)

cross-linker in a molar ratio of 1:4:20. In order to control the

thickness of the imprinted surface layer, the reversible addition-
fragmentation chain transfer (RAFT) method was applied, with
use of 2,20 -azobisisobutyronitrile (the initiator) and 2,2'-[carbon-
e
e
e

othioylbis(thio)]bis[2-methylpropanoic acid] (the chain transfer

LOD (mg/L) Linear range (mg/L) Recovery (%) RSD (%)

agent). The GO was modified by 3-(methacryloxyl)propyl-

trimethoxysilane, facilitating an effectively imprinted layer. The
structure and composition of the resultant material was confirmed
<93.3

by different instrumental methods (such as infra-red spectrometry,

e
e

scanning and transmission electron microscopies, atomic force

microscopy, X-ray diffraction, water contact-angle measurements
and thermogravimetric analysis), revealing the highly ordered ho-
mogenous structure of the imprinted layer on the GO surface. The
adsorption study revealed that the saturated adsorption capacity of
e
e
e

an IIP synthesized using RAFT methodology was higher than the

saturated adsorption capacity of IIPs obtained by the traditional
method or an NIP. Characterization of Sr2þ adsorptions on IIPs and
NIPs were well fitted by the Langmuir model. It could therefore be
e
e
e

supposed that adsorption sites on the adsorbent surface were ho-

mogenous, leading to monolayer binding. The kinetics study
proved that a pseudo-second-order model could explain the
adsorption mechanism, and the chemical adsorption was an
Maximum sorbent capacity

ascendant mechanism in the Sr2þ sorption process on the IIP. The

material possessed a high degree of selectivity towards Sr2þ ions,
confirmed by competitive and binary studies involving use of
86.7

89.1
e

various ions, such as Zn2þ, Ce3þ, Co2þ, Cu2þ and Ca2þ. Reusability
studies confirmed that after five cycles of use, the adsorption ca-
pacity of the sorbent was not significantly lower. Optimized
(mg/g)

adsorption and desorption conditions were applied to analyse Sr2þ

content in river water samples, showing excellent recovery rates
(more than 99%) and good analytical performance (Table 1).
In order to facilitate the process of separation, the sorption
material can be enriched by additional properties. This excellent
FAAS, ICP-OES

strategy involves use of magnetic cores during the surface

LSC, AES
FAAS

imprinting procedure, to fabricate the material, which enables

Analytical method

easier separation due to the response to the external magnetic field.

Yang et al. [92] fabricated a surface magnetic IIP for selective
adsorption and separation of Csþ formed in salt-lake brine. The
magnetic core (Fe3O4) was prepared by the hydrothermal method
from FeCl3 in the presence of sodium acetate, ethylene glycol and
15@MPS/core-shell

poly(ethylene glycol) of average molecular weight

Fe3O4@PEI-SBA-
-/nanoparticles

nanoparticles

(10,000 g mol1), in autoclaves, followed by covering of the

Crosslinker Supporter/form

magnetite with a siloxane layer of tetraethoxysilane and modifi-

cation by amino or aldehyde groups, with use of 3-
aminopropyltriethoxysilane or glutaraldehyde, respectively. The
IIP layer was formulated from CsCl (as the template), carbox-
ymethyl chitosan (the monomer) and glutaraldehyde (the cross-
EGDMA
MBA
GTA

linker). In addition to various instrumental techniques, which

confirmed composition of the material, vibrating sample magne-
tometer analysis was carried out to prove the presence of a
MAA, NIPAM

magnetite core in the IIP. Freundlich isotherm and pseudo-first-

CTS-DTC
MAA
Monomer

order kinetic models were also applied to predict the sorption

process. Competitive selectivity studies of binary mixtures con-
sisting of Csþ and Liþ, Naþ, Kþ, Rb þ or Sr2þ ions revealed that the
designed IIP could selectively recognize the target ion. Reusability
tests showed a good adsorption rate (exceeding 88%) after five
DC18C6
Table 1 (continued )

Chelator

cycles of use. Finally, the IIP was successfully applied for separation
of Csþ ions from salt such as brine samples, with a recovery rate
equal to 71.6%.
Sr2+
Sr2+
Sr2+

Novel and advanced analytical methods should allow for

Ion

simultaneous determination of two or more analytes in the

10
M. Budnicka, M. Sobiech, J. Kolmas et al.
complex sample. Taheri et al. [93] prepared two magnetic IIPs to
develop an analytical method, using UVeVis spectroscopy and
mean-centring of the ratio method, for simultaneous quantification
of Al3þ and Be2þ ions in water samples. The magnetic core was
prepared from the same reagents as described earlier [92] and was
covered by a silica layer. Magnetic IIPs were synthesized using the
sol-gel method, with fabrication of a ligand-metal complex from
Al(NO3)3 or Be(NO3)2 and Chrome Azurol S (trisodium 5-[(E)-(3-
carboxy-5-methyl-4-oxocyclohexa-2,5-dien-1-ylidene) (2,6-
dichloro-3-sulfonatophenyl)methyl]-3-methyl-2-oxidobenzoate, a
functional ligand). After optimization of the adsorption conditions,
the equilibrium isotherm and adsorption capacity of the imprinted
and control materials were studied. The Sips model (a combination
of the Freundlich and Langmuir models) was the isotherm with the
best fit for adsorption of Al3þand Be2þ ions, suggesting that the
monolayer of ions was adsorbed on the sorbent with a non-uniform
surface. The effect of coexisting ions was studied, revealing no
significant interference from most of the studied ions in the
adsorption process of the target analytes. However, the addition of
20 times the concentration of some two-valent cations caused
interference in the adsorption of Al3þ and Be2þ because of the
similar size and geometry of ions. The IIPs presented a change in
recovery rates: less than 7% after three or four cycles for Al3þ-IIP
and Be2þ-IIP, respectively. After determining the analytical pa-
rameters (Table 1), an analysis of tap and well-water samples was
performed, showing recovery rates of between 92.0 and 108.0%.
4.1.2. Food samples
Application of IIPs for analysis of real samples is mainly
described for different types of water samples, involving an envi-
ronmental matrix, which is probably the simplest matrix for study.
Analysis of more complex samples such as food is more difficult and
laborious. However, a few examples of IIPs used as a sorbent during
analysis of food samples have been described. Hashemi et al. [76]
prepared Kþ-IIP nanoparticles using cryptand-222 as the com-
plexing agent, KNO3 as the template, methacrylic acid as the
monomer and ethylene glycol dimethacrylate as the cross-linker,
with a molar ratio between the template, monomer and cross-
linker equal to 1:6:22.5. Optimization of the adsorption process
was carried out. It was found that the pH value of the sorption
solution affected the adsorption capacity of Kþ which was highest
at the pH value between 8.0 and 10.0. The phenomenon was
explained by the presence of oxygen and nitrogen donating atoms
in the cryptand-222 structure which can be protonated and,
therefore, negligible amounts of potassium ions were adsorbed to
the sorbent. Competitive selectivity batch studies of binary mix-
tures consisting of Kþ and Liþ, Naþ, Rbþ or Csþ revealed that the
designed IIP could selectively recognize the target ions. However,
the selectivity was lower than in Kþ-IIP prepared with use of
dicyclohexyl-18-crown-6-ether [84]. Reusability tests showed good
adsorption rates after six cycles of use. Finally, the IIP was suc-
cessfully applied for extraction of Kþ ions from tap water and food
samples: apple vinegar, various vegetables, tomatoes and bananas,
with recovery values of between 92.7 and 100.3%.
4.1.3. Biomedical samples
Another example of complicated samples that can be analysed
using IIPs is that of biomedical matrices, but there are few reports
showing application of IIPs in analyses of real samples. Bahraini
et al. [94] synthesized a Sr2þ selective sorbent for urine bioassay
purposes, using dicyclohexyl-18-crown-6-ether (as the template),
methacrylic acid (the monomer) and ethylene glycol dimethacry-
late (the cross-linker), with a molar ratio equal to 1:8:4. The con-
ditions for extraction of the 90Sr2þ strontium isotope from urine
samples were optimized, and the imprinted material attained 98%
11
Trends in Analytical Chemistry 156 (2022) 116711
of the Sr2þ. The sorption properties were strongly related to the
radius and charge of the cation; thus, it was necessary to remove
the 90Y3þ ions from the analysed sample.
4.2. s-Block ion-imprinted polymers in sensing devices
4.2.1. Environmental samples
Surface molecular imprinting is often used to produce ion
sorption material. Moreover, application of an appropriate core in
the synthetic process can facilitate fabrication of a sensor designed
to identify target ions. In an excellent example, Shao et al. [69]
employed carbon quantum dots (CQDs) to create a fluorescent IIP
for selective determination of Liþ ions in water samples. CQDs
possess stable photoluminescence, with the potential for applica-
tion in fluorescence recognition. Additionally, CQDs have beneficial
properties such as being easy to manufacture, biocompatibility and
non-toxicity [95]. The preparation process for CQD-IIP materials
used by Shao et al. was based on the hydrothermal synthesis
method, with cores obtained through carbonization of citric acid
with ethylenediamine, fabrication of a protective shell on the CQDs
by a modified version of the Sto €ber method, and finally synthesis of
the imprinted layer by copolymerization of methacrylic acid and
ethylene glycol dimethacrylate in the presence of a complex of Liþ-
benzo-15-crown-5-ether (prepared from LiNO3 as a source of
lithium ions). The synthesized product was characterized by
various techniques, including photoelectron spectroscopy and X-
ray diffraction, revealing spherical particles 30e80 nm in size,
validating the success of the preparation process.
Fluorescence quenching of the CQDs was observed (covering of
the core by shells during polymerization). The template washing
process from the IIP matrix, after synthesis, facilitated an increase
in the fluorescence intensity, proving that Liþ adsorbed onto the IIP
quenched the fluorescence. To analyse the specificity, Stern-Volmer
fluorescence quenching constants were assigned, enabling calcu-
lation of the imprinting factor, which was equal to 4.5. The prepared
sensor showed a high degree of selectivity (compared to the
adsorption of 21 different cations), satisfactory recovery rates of
between 102.0 and 111.6% during analysis of lake water samples
and good analytical performance (Table 1).
In recent work, Wang et al. [96] described preparation, charac-
terization and application of a potentiometric sensor constructed
from a glassy carbon electrode modified with a magnetic multi-
walled carbon nanotubes (MMWCNTs)/Csþ-IIP composite. Two
materials were applied as supports to prepare the surface of the IIP,
viz. MMWCNTs, creating a large surface area and resulting in a
higher adsorption capacity, good stability and Fe3O4, which facili-
tated the separation process. Firstly, MMWCNTs were carboxyl-
functionalized by being treated with nitrifying mixture. Magnetic
nanocomposite was then prepared from carboxyl-functionalized
MMWCNTs and iron salts. The IIP layer was deposited on the core
with use of CsCl (as the template), chitosan (the monomer) and
glutaraldehyde (the cross-linker) in the presence of sorbitol oleate
(Span-80 as the surfactant), ammonium persulphate and sodium
bisulphate (the initiators) in aqueous acetic acid solution. Finally,
the membrane prepared from the MMWCNTs/Csþ-IIP composite
(ionophore as the modifier), polyvinylchloride (PVC as the neutral
carrier), 2-nitrophenyloctyl ether (the plasticizer) and sodium tet-
raphenylborate (lipophilic salt) was coated on the surface of the
glassy carbon electrode. Analysis of the reproducibility and lifetime
of the sensor showed a highly reproducible response, functioning
for 6 weeks without significant potential deviation and a short
response time of less than 5 s. Good electrochemical performance
of the sensor (Table 1) (in comparison to reports of other analytical
methods for Csþ analysis) revealed indications of Csþ ions in real
water samples, with recovery rates of between 94.8 and 105.8%.
M. Budnicka, M. Sobiech, J. Kolmas et al.
4.2.2. Food samples
Analysis of more complicated samples than water is difficult,
and there are relatively few reports of the use of s-block IIPs in
sensing devices during analytical and quantification procedures
involving food samples. In one interesting example, Li et al. [97]
constructed a molecularly imprinted electrochemiluminescence
sensor for sensitive and selective determination of Be2þ in rain,
bottle and well water, as well as in rice samples. A Be2þ complex
with 4-(2-pyridylazo)resorcinol was applied as a template during
electropolymerization of o-phenylenediamine (the monomer) on
the surface of the Au electrode. After characterization of the sensor
and optimization of the detection conditions, analytical parameters
were determined (Table 1), and selectivity, stability and repro-
ducibility studies were performed. The results demonstrated that
other tested ions had no impact on Be2þ detection when their
concentrations were less than 500e5000 times (depending on the
ion type) that of Be2þ. The sensor was found to have good repro-
ducibility during electrochemiluminescence intensity tests in five
cycles and good stability for 15 days. Recovery rates ranged from
95.0% to 101.0% in the analysis of real samples.
4.2.3. Biomedical samples
s-Block IIP application in sensing devices for analysis of
biomedical samples has been demonstrated by Moirangthem et al.
[1] who fabricated an optical sensor for detection of Ca2þ in serum
samples. Polymer binding efficacy tests of different ions (viz. Naþ,
Mg2þ, Ca2þ, Zn2þ, Cd2þ and Pb2þ) showed that the reflection band
underwent a blue shift to different extents. Ca2þ shifted the most
and the blue reflective film, whose colour change could be seen
with the naked eye. The photonic sensor produced was selective
towards Ca2þ ions in the competitive study, and it was related to
preorganized adsorption sites in the ordered liquid crystalline
structure. The obtained film was sensitive to changes in Ca2þ levels
in serum samples and could be a promising battery-free metal-ion
sensor for clinical applications.
At this point, as a critical comment, it should be stated that the IIPs
have found broad application in environmental analysis. However,
the area of biomedical and food analyses still can be explore more
effectively, mainly because of the role of selected s-block metal ions in
the physiological or pathological processes as well as because of the
increasing necessity of food control. As it can be identify, only a few
papers are devoted to analytical methods supported by IIPs for
determination of s-block metal ions in clinical or food samples. The
complexity of the samples and the presence of interfering compo-
nents could be here a reason that limits application of IIPs based
sorbents and sensors. It has to be underlined that factors such as in-
dividual composition variations from person to person and from re-
gion to region, feeding habits and physical activities makes clinical
samples very difficult for analysis. Considering food samples, the di-
versity of components and diverge physicochemical properties of
aliment, making the food analysis very challenging. Thus, the fabri-
cation of effective IIP still requires time-consuming and laborious
optimizations of the synthetic procedures and sorption protocols.
Further frontiers in the designing of IIPs and in the determination of s-
block metal ions in analytical methods supported by ion-imprinted
polymers are discussed below.
5. Frontiers in the design of polymers imprinted by s-block
metal ions
The design of IIPs can be affected by various factors, producing
materials with low levels of selectivity and heterogeneous distri-
bution of sorption sites; with the sorption medium's limited
accessibility and high ratio of leaching ion; and last but not least,
with low eco-friendliness of the material, resulting in analytical
12
Trends in Analytical Chemistry 156 (2022) 116711
methods that are less ‘green’.
In order to overcome ion-cavity site-construction limitations,
the surface imprinting process was proposed [98]. The surface ion-
imprinting process can be considered to be an ion-templated
polymerization reaction that occurs on the interface of solid sub-
strates. This process results in formation of the layer, for instance, a
thin film or a shell with a modified surface, possessing geometrical
regions capable of adsorbing specific ions. This approach allows us
to obtain material with increased separation efficiency and a faster
adsorption ratio. Moreover, the material is characterized by a more
homogeneous population of adsorption regions, and the leaching of
embedded template-ions is significantly reduced. Fabrication
methods for obtaining surface-imprinted materials are as follows:
sacrificial carrier, solid-phase synthesis and chemical grafting (such
as pre-grafting polymerization and post-cross-linking ion
imprinting; grafting synchronized with cross-linking and ion
imprinting; and ion imprinting synchronized with cross-linking).
These methods have been used for fabrication of ion-imprinted
materials for analysis of various ions, mainly p-block metals [99].
However, s-block metal ions have also been investigated, with
application of the surface ion-imprinting technique.
Liu et al. [63] synthesized a hydrophilic polymer using GO-based
composite material for removal of strontium ions from aqueous
solutions. The polymerization process was carried out using the
RAFT polymerization technique, which facilitates formation of a
homogeneous, thin layer. The advantages of surface ion imprinting,
merged with those of controlled polymerization, resulted in ma-
terial characterized by excellent imprinting efficacy and high
adsorption capacity. Li et al. [90] prepared a surface ion-imprinted
layer on potassium tetratitanate whiskers for adsorption of stron-
tium. Finally, Yu et al. [100] fabricated a hydrophilic membrane
composed of a polydopamine-imprinted layer conjugated with a
polydimethoxysiloxane support, producing a highly effective sor-
bent capable of recovering lithium ions from seawater.
Electrochemical polymerization is another approach that can be
used for forming surface-imprinted material. This involves use of
electrochemical methods to polymerize monomers directly on the
surface of the electrode via potentiostatic, galvanostatic or cyclic
voltammetry. These approaches have been applied to synthesize
IIPs that can recognize various ions [101], also involving s-block
metal ions. Li et al. [97] applied an electropolymerization process to
obtain an electrochemiluminescence sensor for analysis of beryl-
lium ions using 4-(2-pyridylazo)resorcinol as the complexing
agent, with an LOD equal to 2.35  1011 mol L1.
The eco-friendliness and sustainability of IIPs cannot be ignored
either. To produce an ion-imprinted material in an analytical,
environmentally benign manner, it must be designed in a way that
meets rigorous evaluation criteria relating to environmental
contamination. It should also be emphasized that application of
analytical procedures can involve use of or can generate hazardous
chemicals that increase environmental pollution, causing detri-
mental changes in water resources, air purity and soil quality, and
as a consequence, a deterioration in human health. In order to
prevent the negative impact of analytical methods on the envi-
ronment, the ‘green analytical chemistry’ philosophy was intro-
duced. This emphasizes development of environmentally benign
analytical methodologies, which improve the ‘green’ character of
analytical protocols, such as eliminating use of hazardous sub-
stances during production of sorbents, minimizing the amount of
hazardous waste generated and guaranteeing safer procedures
aimed at accident prevention during the fabrication of sorbents. For
example, due to the greenness of the starting materials used (which
are non-toxic and neither corrosive nor explosive), there is no
major risk for users; the materials used will degrade easily after
use, and efforts are made to use renewable raw materials wherever
M. Budnicka, M. Sobiech, J. Kolmas et al. Trends in Analytical Chemistry 156 (2022) 116711

possible. From this point of view, the greenness of the material, its
non-toxicity, degradability and renewability should be considered
to be just as important as the capability of the analytical method to
produce accurate measurements [102,103]. Although various pa-
pers [104] have suggested green and feasible strategies for the
separation and determination of s-block metal ions by IIPs, it has
yet to be proved whether or not the methods described fully accord
with the principles of ‘green analytical chemistry’. Thus, further
investigations should be conducted which consider environmental
issues when proposing new analytical methods for determination
of s-block metal ions using IIPs.
6. Frontiers in determination of s-block metal ions in
analytical methods supported by ion-imprinted polymers
To date, numerous analytical methods have been used to
determine s-block ions content, aiming to overcome a major
challenge e the elemental analysis of samples with complex
heterogenous matrices, especially biological (plants and food),
biomedical (blood, urine and human tissue) and environmental
(geology, soil and atmospheric deposits) [105,106].
A brief summary of analytical methods used for determination
of s-block metal ions together with their advantages and disad-
vantages are presented in Table 2. The choice of method depends on
many factors, including the physical state of the sample, the
amount of the determined ion, the complexity of the matrix and the
availability of equipment. Among them, spectrometric and spec-
troscopic methods (i.e., inductively coupled plasma mass spec-
trometry (ICP-MS), atomic absorption spectrometry (AAS), flame
emission spectrometry (FES), and electrochemical methods such as
potentiometry have been used for analysis in analytical methods
supported by IIPs.
In the group of spectroscopic and spectrometric methods,
inductively coupled plasma optical emission spectrometry and

Table 2
Advantages and disadvantages of analytical methods used for alkali- and alkaline-earth metal ions determination.

Methods Advantages Disadvantages

Classical methods Titration Gravimetry Low cost Time consuming

Low sensitivity
Low selectivity
Lack of specific reactions
Long time of analysis
Spectrometry and Atomic absorption spectrometry (AAS) Fast Destructive for the sample
spectroscopy Inexpensive Relatively large sample quantities required
Easy to use
High sensitivity
High accuracy
High selectivity
Atomic emission spectrometry (AES) Sensitivity Spectral interferences
Fast measurements Limited to alkali and alkali earth metals
Low risk of ionization
Low matrix effects
Relatively stable
Inductively coupled plasma spectrometry Low chemical interference High cost of instrument and maintenance
(ICP) Stable, reproducible signal
High sensitivity
Simultaneous analysis of multiple components
X-ray photoelectron spectroscopy (XPS) Non-destructive for surface measurement Expensive
Simple and fast preparation of sample Large analysis area
High vacuum requirements
Low resolution
Slow
Auger electron spectroscopy Sensitivity Analysis performed under ultra-high vacuum
Analysis of very small regions Destructivity of the sample
Expensive
X-ray fluorescence spectroscopy (XRF) Simple and fast preparation of sample Limitation in measuring lighter elements
Fast analysis
Used both in the analysis of solid and liquid
samples
Non-destructive
Particle induced X-ray emission (PIXE) non-destructive Expensive instrument
accuracy above sodium
suitable for trace analysis
Electrochemistry ISE potentiometry Low cost and simplicity to use Interference with other ions in solution
Short analysis time Narrow working concentration rate
Requires high volume of sample
Capillary electrophoresis Simplicity Low reproducibility
Short analysis time
High separation efficiency
Low waste generation
Requires low volume of sample
Chromatography Ion chromatography High selectivity Requires high volume of sample
Simultaneous analysis of multiple components Expensive instrument and chemicals (buffers)
used
Analysis of complex matrices Limited to charged ions
Low maintenance cost
Short time of separation
Specific detection
Environmental friendly

13
M. Budnicka, M. Sobiech, J. Kolmas et al.
mass spectrometry (ICP-OES and ICP-MS) methods both deserve
special attention as they are very fast methods for the determina-
tion of many elements (including alkali- and alkaline-earth metals)
at trace and ultra-trace levels [107e109]. Regarding ICP-MS, ions
produced in the argon plasma are fed into the mass spectrometer,
where they are separated by a mass-to-charge ratio. For this reason,
this method is characterized by high sensitivity and precision, the
possibility of simultaneous determination of many elements and
selectivity, allowing determination of individual isotopes of the
element in complex matrices. Moreover, ICP-MS is a method that
can accommodate low detection limits (for solutions at levels of pg
L-1) because of high ionization efficiency in plasma and a broad
range of straightness of the calibration curves. In the ICP-MS
technique, it is possible to determine both trace elements and
macro-components in one measurement. This is an excellent
method for analysing metal ions in concentrations below levels of
ng L-1 [105]. However, ICP-MS requires experienced specialists to
manage the analysis. It should be noted that during measurements,
many interferences, both spectroscopic (when non-analyte ions
have the same m/z ratio as the analyte) and non-spectroscopic
(resulting from the samples matrix and instrument drift), will
appear, affecting the analytical process. Economic aspects of anal-
ysis, such as the high cost of both the ICP-MS instrument and its use
(argon supply), cannot be ignored.
Nevertheless, new methods are being developed to improve
selectivity, precision, sensitivity and measurement times and to
reduce analysis costs. However, it have to be underlined that not all
known to date novel and advanced instrumental techniques were
employed for the determination of s-block metal ions in the
analytical methods supported by IIPs. An excellent example is a
PIXE method. It is not a universal quantitative method that can be
used for determination of elements heavier than sodium [110]. An
interesting exemplary of application of the PIXE method was pre-
sented by Terakawa et al. [111] who investigated Lentinula edodes
mushrooms contaminated with radioactive caesium. The content
and spatial distribution of potassium and rubidium were studied,
and the mechanism of accumulation of these elements was
suggested.
Other methods for determination of alkali- and alkaline-earth
metal ions have also been reported in the literature. These
include electrochemiluminescence, which has been used for Liþ,
Mg2þ, Ca2þ, Ba2þ and Be2þ ions. In the work of Li et al. [97] a new
sensor based on the Be2þ complex, with 4-(2-pyridylazo)resorcinol
(PAR) in a molecule-imprinted polymer, was used for determina-
tion of trace amounts of Be. Another method involves detection of
ionizing radiation for 90Sr, a fission product that may accumulate in
human tissues, especially bones, and thus pose a significant health
risk [112].
To sum up, it has to be stated that new synthetic strategies that
allow to produce effective IIPs together with advanced instru-
mental techniques could guarantee broad applicability in the field
of analytical chemistry for the determination of s-block metal ions.
7. Summary and future perspectives
s-Block metal IIPs are effective sorbents that have been applied
in various analytical methods for complex sample pre-treatment.
Due to recent synthetic approaches and advances in the chemis-
try of materials, magnetic or quantum dot nanoparticles have been
conjugated to these sorbents, providing additional physicochemical
properties that significantly facilitate the analytical process. Thus,
future applications should gain from recent progress in surface
imprinting strategies, using advanced core-shell materials with
cores, such as gold nanoparticles and nanoclusters or carbon
nanomaterials such as carbon dots. Future development should
14
Trends in Analytical Chemistry 156 (2022) 116711
include new detection devices that possess IIP receptors, allowing
for fast and reliable analysis of s-block metal ions, not only in
environmental samples but also in a vast array of clinical and food
analyses. Novel IIPs should be constructed, considering the prin-
ciples of ‘green chemistry’, to provide new analytical methods that
will be more environmentally benign. Thus, future studies should
consider naturally occurring components such as chitosan and al-
ginates and biocompatible materials such as polyvinyl alcohol, or
they should be based on biodegradable materials. Combination of
novel IIPs with advanced instrumental techniques such as PIXE
could also be expected to improve the analytical performance of
different methods.
Funding
This work was supported by the National Science Centre Poland
grant number DEC-2021/05/X/ST4/00858 and by the Medical Uni-
versity of Warsaw grant number FW232/1/F/MBM/N/21.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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