Advances in Sample Preparation 5 (2023) 100051

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Advances in Sample Preparation

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

Paper-based sorptive phases for a sustainable sample preparation

Marisol González-Bermúdez, Ángela I. López-Lorente, Rafael Lucena, Soledad Cárdenas∗
Departamento de Química Analítica, Affordable and Sustainable Sample Preparation (AS2P) Research Group, Instituto Químico para la Energía y el Medioambiente
(IQUEMA), Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie (anexo), Córdoba, España

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

Keywords: In recent years, using natural materials to prepare sorbents has been a clear trend in the sample preparation
Natural sorbents context. This research line is supported by sustainable considerations, as it responds to the tenth principle of
Cellulose Green Analytical Chemistry. Also, the affordability and availability of natural materials open the door to de-
Paper-based sorptive phases
veloping global analytical solutions. Among all the available natural materials, cellulose paper presents unique
Synthesis
characteristics (porosity, mechanical resistance, and easy chemical/physical modification of the substrate) that
Microextraction
can be exploited in analytical extractions. This article reviews the role of paper-based sorptive phases in the
current sample preparation realm, putting more emphasis on their potential than on the description of specific
applications. The article covers the main synthetic routes described in the literature for preparing these phases
and the reported coatings. In contrast with the classical analytical workflow (based on the separated extraction,
elution, and analysis steps), the direct combination of sample preparation with instrumental techniques permits
further simplification of the analytical procedures. Cellulose paper can operate under both workflows, and the
main approaches based on spectroscopic and spectrometric analysis will be discussed. Finally, the combination
of both instrumental techniques (using the so-called dual substrates) will be outlined.

1. Introduction
The growing environmental awareness of contemporary society has
reached almost all fields of human activity. Chemistry has not been un-
connected to this trend, and this commitment was evidenced by the
definition of the Green Chemistry principles in 1998 [1]. The analytical
chemistry community has also adopted this objective, and the defini-
tion of Green Analytical Chemistry (GAC) principles [2] is an excellent
example of this environmental responsibility. These principles must be
applied keeping in mind the main objective of our discipline, which
is to provide useful chemical information with a satisfactory metrolog-
ical quality [3]. In this sense, although sample preparation can have
an inherent environmental impact, its use is entirely accepted in the
GAC realm when it is indispensable to solving a given analytical prob-
lem. Once the sample preparation is considered unavoidable, the green
aspects play a relevant role [4]. The recently reported Green Sample
Preparation (GSP) principles [5] emphasize how the greenness of these
procedures can be improved.
The environmental impact of sample preparation can be reduced
by using natural materials as precursors for the preparation of sorp-
tive phases. Although the materials can be used without [6] or with
minimal pretreatment [7,8], sometimes their sorption capacity or se-
lectivity needs to be improved by a chemical modification. The latter
aspect reduces the potential greenness of the procedure, but even un-
der these circumstances, the impact is lower compared to the synthesis
of a sorptive phase almost from scratch. Several natural materials have
been reported in sample preparation [9–11], although (ligno) cellulosic
materials have been extensively used in the last years due to their afford-
ability, low cost and valuable physicochemical properties. Among these
materials, paper [12], cotton [13,14], wood [15] and cork [16–18] can
be highlighted.
2. Paper as a substrate for preparing sorptive phases
Planar sorptive phases have found an application in sample prepara-
tion under the thin film microextraction (TFME) format [19–21]. These
planar phases present a high surface area that allows for an increase
in the active sorptive phase without increasing its thickness too much,
thus improving the extraction kinetics. Planar sorptive phases can be
synthesized by ad-hoc techniques [22] (e.g. electrospinning, spin coat-
ing) able to transform some precursors into a planar phase or using
an existing flat substrate that is afterward modified to include sorptive
groups on the surface. The second approach is simpler, as it reduces
the equipment needed, and it is the typical strategy followed to prepare
some sorbents like fabric phases [23] or paper-based sorptive phases
(PSP) [12].
Paper consists of cellulose fibers packed in a planar shape, where
the regularity of the packing depends on the type of paper (chromato-

∗
Corresponding author.
E-mail address: scardenas@uco.es (S. Cárdenas).

https://doi.org/10.1016/j.sampre.2023.100051
Received 15 November 2022; Received in revised form 30 December 2022; Accepted 3 January 2023
2772-5820/© 2023 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. González-Bermúdez, Á.I. López-Lorente, R. Lucena et al.
graphic, filter, etc.,). The cellulose structure gives the paper a high wet-
tability and the ability to interact with target compounds by H-bonding.
The surface is highly hydrophilic, although some hydrophobic com-
pounds can be retained by physical processes. Paper presents several
advantages, as indicated in Fig. 1, which make it a good support for
preparing sorptive phases. The easy modification of paper, covalently or
by physical deposition, increases the versatility of the sorptive phases.
This versatility is also improved using different analytical workflows
(extraction/elution or extraction/analysis). This flexibility permits to
adapt the strategy to the given analytical problem.
Paper is a readily available material. This aspect, together with the
easy fabrication of the phases, increases the idea transferability between
laboratories. Also, paper can be considered non-expensive, especially
if compared with other laboratory supplies. This aspect improves the
affordability of the resulting materials [24].
The use of paper as a sorptive phase was firstly reported by Hurtubise
and coworkers in the 1990–2000s [25–27]. In these pioneering works,
the authors described the use of commercial hydrophobic paper to ex-
tract polycyclic aromatic hydrocarbons (PAHs) from water samples. In-
terestingly, the researchers described the extraction/analysis workflow
for the first time since the analytes were fluorometrically analyzed on
the paper without needing their elution from the support. Since then,
paper has been successfully used to prepare paper-based analytical de-
vices, but its use in microextraction has been scarcely considered.
Although bare paper has demonstrated its suitability as sorbent [6],
functionalization of its surface with a plethora of materials broadens the
range of analytes that may be extracted by TFME, at the same that pro-
vides additional properties to the cellulose sorptive phase. This article
presents a general overview of the latest developments in the topic.
3. Paper-based sorptive phases prepared by the physical
deposition of the coating
The physical deposition of the coating over paper has been demon-
strated as an efficient and simple synthetic route. Several techniques
(dip-coating, drop-casting and filtration from a solution), which are de-
picted in Fig. 2, have been reported for this purpose.
Cellulose paper has been physically modified with a wide variety
of materials, such as polymers, also including polymeric ionic liquids
(PILs) and molecularly imprinted polymers (MIPs), nanomaterials, rang-
ing from metallic ones to carbon-based nanomaterials, in many cases
in combination with polymers in the so-called nanocomposites, metal-
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Advances in Sample Preparation 5 (2023) 100051
Fig. 1. The main advantages of paper for being used as the
substrate for preparing sorptive phases.
organic frameworks (MOFs) and covalent organic frameworks (COFs),
as well as other materials which are discussed below.
As commented above, Hurtubise and coworkers have employed com-
mercial hydrophobic paper, i.e., Whatman 1PS paper, for the extraction
of hydrophobic compounds, due to the presence of silicone on the pa-
per. Notwithstanding, to increase the hydrophobicity of cellulose paper,
they also developed coating methods using dichlorodimethylsilane and
poly(hydrogenmethylsiloxane) [27], which led to thermally stable pa-
per, whose hydrophobic coating layer did not leach from paper during
the extraction step. The modification was simply based on the immer-
sion of the paper in the coating solution using an appropriate solvent
namely, n-hexane and 1,1,1-trichloroethane for dichlorodimethylsilane
and poly(hydrogenmethylsiloxane), respectively, the solvent being left
to evaporate. PAHs were selected as the model analytes. More recently,
hydrophobic paper-based sorptive phases have also been reported by
paper modification with polyimides (PI) [28]. The procedure is based
on the synthesis of poly (amic acid) (PAA) solution in which the paper
is immersed, followed by thermal curing of the paper containing PAA
to induce imidization into water-insoluble PI over the cellulose paper.
The hydrophobic character of the PI-modified paper has been used for
the extraction of methadone from oral fluid samples.
In 2017, Ríos-Gómez et al. described the preparation of polystyrene-
coated paper by the dip-coating technique [29], which has been the
most used approach for preparing PSPs. In this technique, a polymer
is dissolved in an appropriate solvent, and the paper is immersed in
and withdrawn from the resulting solution. After the cycle, the polymer
is precipitated over the paper by solvent evaporation or changeover.
The thickness of the coating can be varied by modifying the polymer
concentration on the precursor solution or by developing several dip-
coating cycles.
Although the polymeric coating is usually responsible for extract-
ing the target analytes, the cellulose substrate can also contribute to the
sorption capacity. Benedé et al. reported this synergetic effect by prepar-
ing a polyamide-coated paper [30]. The as-prepared PSP presented a
superior performance (ability to extract six analytes, i.e., penicillin-
derived antibiotics, in the logP interval 0.88 to 2.83) compared to com-
mercial nylon membranes (able to extract just four compounds) and raw
paper (capable of interacting only with the most polar compounds). The
same authors also reported a Janus paper containing two different po-
larities domains by simply combining a balanced hydrophilic-lipophilic
(polyamide) and a hydrophobic (polystyrene) polymer [31]. This Janus
material allowed to isolate compounds covering a wide range of polari-
M. González-Bermúdez, Á.I. López-Lorente, R. Lucena et al.
Fig. 2. Scheme of the main synthetic approaches for the preparation of paper-based sorptive phases by physical deposition.
ties (i.e., fourteen UV filters in the log P interval from −0.234 to 16.129)
in a single extraction.
In addition to aqueous samples, polymer-coated cellulose paper can
also be used to extract oil samples by modifying the paper with a suitable
coating. For example, polydopamine modified paper has been prepared
by incubating the paper strips on an alkaline dopamine solution under
shaking at 30 °C in an aerobic atmosphere, leading to the polymerization
of dopamine directly on the paper, which adheres to the paper surface
while the non-adhered polymer is removed by washing steps [32]. It was
applied to the TFME of phenolic compounds from cooking oil samples.
Within the different polymers that have been attached to cellulose
paper, PILs have also been incorporated via dip-coating and thermal
curing methods. In this sense, Ríos-Gómez and coworkers prepared an
imidazolium-based PIL based on the Radziszewski reaction, which was
immobilized on filter paper by dipping it on a 2% solution of the PIL
followed by thermal treatment [33]. Depending on the PIL counteran-
ion and the pH of the sample, different interactions with the target an-
alyte can be fostered, i.e., hydrophobic and mixed-mode interactions.
They demonstrated the extraction capacity towards non-steroidal anti-
inflammatory drugs by using the PIL coating with acetate as a counteran-
ion. More recently, Shahriman et al. have prepared a methyl methacry-
late (MMA) based PIL solution, i.e., (poly-(MMA-IL)), where the paper
was dipped, resulting in a PIL-coated paper which was applied to the
TFME of sulfonamides [34].
The versatility of the dip-coating technique allows to prepare func-
tional sorbents by simply adding a third component to the poly-
mer/solvent mixture. Díaz-Liñán and coworkers described the prepa-
ration of MIPs following this strategy [35,36]. In this case, the analyte
or a surrogate is incubated with the polymer. Once the dip-coating pro-
cedure is applied and the polymer precipitation induced, the polymeric
chains are arranged around the analyte creating selective cavities (in
size and chemical environment). Before being used, the paper must be
washed to release the cavities for molecular recognition. The integration
of MIPs as recognition elements in the so-called paper-based analytical
devices is attracting great attention [37]. They have been coupled to
several detection systems including spectroscopic and electrochemical
ones, in addition to the use of paper loaded with MIP particles prepared
ex-situ as sorbent material in disk-type solid-phase extraction [38,39].
In addition, molecularly imprinted-interpenetrating polymers networks
prepared by combining polystyrene and silica gel polymers by radical
polymerization process have been deposited on Whatman Grade 1 filter
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Advances in Sample Preparation 5 (2023) 100051
paper discs, which are then washed to remove the template and unre-
acted monomers and to condition the paper [40].
The use of nanoparticles (NPs) as the third component allows the
synthesis of nanocomposite coatings. In this case, the NPs are dispersed
into the polymeric solution. During the dip-coating process, the poly-
mer precipitates entrapping the nanoparticles in the network. The NPs
may play several roles in the coatings. They interfere with the normal
stacking of the polymeric chains creating imperfections, thus increasing
the porosity of the coating. The NPs can provide primary or secondary
interaction chemistries with the target analytes, or they can provide the
final nanocomposite with special properties (e.g., magnetism, photocat-
alytic properties, among others). On the other hand, the polymer can
provide a primary interaction chemistry and mechanically stabilizes the
NPs during the extraction.
For example, Casado-Carmona and coworkers modified via dip coat-
ing a filter paper by its immersion in a solution of nylon 6 in formic
acid, which contained magnetic nanoparticles [41]. The nanocompos-
ite paper depicts extraction features due to the polymer coating at the
same time that the silica-shielded Fe3 O4 nanoparticles provide magnetic
properties to facilitate the extraction procedure and improve mass trans-
ference. The modified paper was coupled with a drill-based sampler to
extract parabens and triclosan in swimming pool water samples.
A similar approach was followed by Ayazi et al. for the incorpora-
tion of ex-situ synthesized ZnO nanoparticles, which are dispersed in
a polyamide solution in formic acid [42]. A thin nanocomposite coat-
ing is deposited on the cellulose paper via a solvent exchange. The
nanocomposite paper was used to extract organophosphorus pesticides
via ultrasound-assisted TFME. The presence of ZnO improves the sur-
face area for extraction while polyamide allows interactions with polar
analytes. Furthermore, other semiconductor materials, e.g., TiO2 , have
also been incorporated on cellulose modified with polymeric nanocom-
posites via dip coating and solvent exchange. In this case, TiO2 nano-
materials may provide additional photocatalytic properties [43,44].
Carbon nanomaterials have been widely employed as sorbent materi-
als [45] and for the preparation of membranes for filtration [46]. These
nanomaterials have also been incorporated into cellulose nanocompos-
ites. For example, graphene oxide embedded in a polyamide coating
has been attached to paper by the previously described solvent exchange
method [47]. In this case, the modified papers were applied as a layered
sorbent for microextraction by packed sorbent (MEPS) of organophos-
phorus pesticides. Moreover, paper modified with polystyrene contain-
M. González-Bermúdez, Á.I. López-Lorente, R. Lucena et al.
Fig. 3. Scanning electron microscopy pictures of (A) raw paper where the cellulose fibers are easily visible; and (B) paper coated with carbon nanohorns suprastruc-
tures. Reproduced under creative commons attribution (CC BY) license from reference [49].
ing montmorillonite (MMT) via solvent exchange from a tetrahydrofu-
ran dispersion of MMT/PS into water, have been also applied as layered
MEPS sorbent. The presence of MMT increased the specific surface area
and thus enhanced the extraction capacity of the sorbent, toward fluox-
etine [48].
Moreover, nanomaterials can also be incorporated into paper with-
out needing a polymer to entrap them. One example is the modifica-
tion of cellulose paper with carbon nanohorns suprastructures. The pro-
cedure simply consisted of immersing a paper in a dispersion of the
nanomaterial in chloroform [49]. Evaporation of the solvent led to the
coating of the paper with dahlia aggregates suprastructures (Fig. 3),
which can be used to extract antidepressants by allocating the paper
on a pipette tip.
Furthermore, paper modified with metal nanoparticles, i.e., AgNPs,
via in situ chemical reduction of AgNPs on filter paper, have been used
for the preconcentration by filtration through the AgNP-modified paper
of aqueous solution for Hg(II) followed by detection with a direct mer-
cury analyzer based on atomic absorption of the pyrolyzed paper [50].
More recently, the same authors have also developed AgNP-modified
cellulose substrates for the preconcentration of volatile hydride-forming
elements (i.e., As, Bi, Sb, Se and Te) by using sodium tetrahydroborate
to continuously generate the hydrides, which are trapped on the AgNP-
paper via dynamic TFME and subsequently determined upon elution
from the paper by inductively coupled plasma mass spectrometry [51].
In addition to nanomaterials, other compounds such as MOFs have
also been embedded into paper, e.g., by using chitosan as the adhesive
agent. The aqueous dispersion of the MOF in chitosan was vacuum fil-
tered on the cellulose paper for its use in TFME [52]. The incorporation
of the chitosan/MOF, i.e., MIL-101(Cr), on cellulose paper provided ad-
sorption capacity toward triazine herbicides, via hydrophobic interac-
tion between the analytes and terephthalic moieties of the MOF. More-
over, COFs have also been deposited on paper by filtration of a starch so-
lution of a hydrophobic COF through the paper [53]. On the other hand,
it has also been described the preparation of thin-film nanocomposites
composed of 1,5-diamino naphthalene-covalent organic polymer (COP)
and cellulose nanocrystalline (CNC) for the extraction of imipramine
from biological fluids [54].
4. Paper-based sorptive phases prepared by covalent
modification of the cellulosic substrate
Modification of cellulose paper via deposition of the sorbent phase
is the simplest and greenest approach. However, their use in combina-
tion with some instrumental analytical techniques such as ambient mass
spectrometry, may entail some risk related to the partial detachment of
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Advances in Sample Preparation 5 (2023) 100051
the material during the elution step that could reach the instrument
blocking, for example, the interface.
Saraji and Farajmand modified cellulose paper with different
reagents (octadeciltrichlorosilane, diphenyldichlorosilane, cyclohexyl
isocyanate and phenyl isocianate) to determine some synthetic and natu-
ral estrogenic hormones in environmental waters and human urine [55].
In addition to the potential extractant ability of the coating, it also pre-
serves cellulose from degradation in aqueous media by increasing its
hydrophobicity. Among the coatings tested, the isolation of the target
compounds was favoured by using phenyl groups thanks to the addi-
tional polar interactions they establish with the selected analytes. In
fact, nice results were obtained when phenyl carbamate modified cellu-
lose paper was selected for the analytical problem chose. The wettability
of the material was studied by means of the contact angle of a water drop
in contact with the different coatings. According to the results, phenyl
carbamate was more hydrophobic than the bare cellulose paper but less
than the octadecylsilane material. As a result, it allows a reasonable pen-
etration of the aqueous phase thus increasing the extraction efficiency.
Analysis of biofluids can also be afforded by using highly selective
(specific) units during the extraction process. In this way, the interaction
with the target analyte is promoted, reducing to the minimum the coex-
traction of potential interferents from the matrix. The use of aptamers
is specifically remarkable in this context as they are more stable against
experimental conditions than, for example, antibodies or enzymes. Their
potential under the TFME format was demonstrated via covalent modi-
fication of a Whatman paper (ashless filter paper 44 grade) with amino-
modified anticodeine aptamer [56]. The selective papers were prepared
generating aldehyde groups on the surface by oxidation with NaIO4 .
The immobilization is completed under mild conditions (room tempera-
ture, overnight in the dark). For the extraction, the aptamer immobilized
paper was attached to a stainless-steel cuter pin. It was applied to the
determination of codeine in urine. Analogs of the analye were evaluated
as potential interferents, namely: morphine, oxycodone and papaverine.
All exhibited weaker binding ability towards the aptamer and, therefore,
the performance of the material was not affected by their presence in
the sample matrix. Finally, a reusability of up to 20 times was fixed by
the authors without observing leaks of fine fibers to the liquid phase
(standards or samples).
Ionic liquids (ILs) have been extensively used in microextraction
thanks to their higher efficiency as compared to conventional solvents as
well as their tunability according to the specific requirements of selected
application. In TFME format, they have been chemically fabricated on
the surface of a filter paper [57]. 1-Dodecylimidazolium chloride with
amphiphilic structure was identified as the best option to isolate and
preconcentrate bisphenol-A from plant oil samples (sunflower, maize,
soyabean and peanuts oils). Although the synthetic pathway proposed
M. González-Bermúdez, Á.I. López-Lorente, R. Lucena et al.
by the authors required the implementation of several steps, the extrac-
tion takes place under mild conditions (30 °C, 150 rpm, 80 min). The
scanning electron microscopy (SEM) images of the coated paper showed
the thin layer of the IL that hinders the identification of the cellulose
fibers and therefore, the extraction can be entirely attributed to the IL.
Nanostructured materials have also been covalently bounded to cel-
lulose paper. In addition to the specific interactions that can be estab-
lished with the analytes and the inherent increase of the porosity, in
general, the synthetic procedures described are simple, cost-effective
and environmentally friendly than other alternatives. In the first exam-
ple, cellulose filter paper was coated with zinc oxide nanorods via a low
temperature hydrothermal method followed by a chemical modification
of the hydroxyl groups with phenyl isocyanate [58]. The phenyl carba-
mate functionalized zinc oxide nanorods (ZnO/PHIC) were capable of
isolating phenyl urea herbicides from waters. Although ZnO and PHIC
can separately improve the extraction of the model compounds in com-
parison with the raw paper, their combination provides the best results
thanks to the synergic combination of the nanostructured material and
the functional groups (phenyl, -OCO- and –NH-). The enhanced sensitiv-
Fig. 4. SEM images of (a), the bare cellulose paper, (b) MMT-cellulose paper prepared in aqueous media, (c) and (d) MMT-cellulose paper prepared in acetone with
different magnification (1500, 1000, 1000 and 2500 fold, respectively). Reproduced with permission of Elsevier from Ref. [9].
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Advances in Sample Preparation 5 (2023) 100051
ity it provides is also a consequence of the flexibility of the final paper
that can be rolled in a small vial thus needing very low volumes of sol-
vent for quantitative elution. Although the material can be reused up to
15 times, its low cost and easy preparation suggest a single use.
The surface of the cellulose paper can also be modified via sol-gel
process. In this case, an ultrathin zirconia gel film was nanocoated
(layer-by-layer) over the paper [59]. This approach combines the sta-
bility of the ZrO2 under extreme extraction environment with the high
porosity, reduced cost and sustainability of the cellulose. The selected
analytical problem, determination of ribonucleosides in human urine
takes advantage of the affinity of ZrO2 to selective capture cis-diol com-
pounds. The overall analytical process is fast (ca. 10 min) as it uses
direct nESI-MS/MS avoiding chromatographic separation. The coating
contributes to enhance the sensitivity up to 459 folds compared with
the use of unmodified cellulose paper.
To conclude this section, a final example of the covalent modifica-
tion of the cellulose paper surface with nanomaterials will be discussed.
MMT grafted onto this support results very convenient for the isolation
and preconcentration of carvedilol from urine and plasma samples un-
M. González-Bermúdez, Á.I. López-Lorente, R. Lucena et al.
der the MEPS format [9]. MMT exhibits higher surface area and poros-
ity, which results in excellent sorption capacity. The thin film was pre-
pared by using glutaraldehyde (GA) as crosslinker. In fact, the GA acts as
bridge between the free OH groups of cellulose and those of MMT. Once
obtained, the modified cellulose paper was cut into 6 mm diameter cir-
cles, incubated in acidic media and dried at 60 °C for 1 h. The influence
of the conditions governing the binding of MMT to the GA as binding
agent was deeply studied. These covalent boundaries are favoured in
acetone rather than in water as the presence of MMT nanoclays onto the
surface was higher and more homogeneous (Fig. 4). This fact increases
the surface area and introduces additional ion exchange interactions
when the analyte is preconcetrated under pH conditions that promotes
the protonation of the amine groups of the carvedilol. The flexibility and
porosity of the MMT-cellulose paper was higher enough to facilitate the
packaging of up to 4 layers on the syringe barrel.
5. Analysis workflows
The classical procedure of sorbent-based microextraction techniques
includes the elution of the analytes as the latter step prior to their in-
strumental analysis. This workflow has been applied in many methods
with high success. The manifolds required for this approach are well
established, and the eluates can be easily analyzed, especially if an au-
tosampler is employed, providing a high sample throughput. In fact,
most of the works described above rely on this consolidated approach.
However, elution involves dilution, and the potential sensitivity is
not fully reached in many applications as a fraction of the eluates, and
not the full extract, is introduced in the instrument. Different alterna-
tives have been proposed to overcome this shortcoming (see Fig. 5), and
they can be classified into two different groups: (i) those that permit the
analysis of the whole extract by eluting the analytes in-line or on-line
with the instrument; (ii) those that avoid the elution by determining the
analytes on the surface of the sorbent.
In fiber solid phase microextraction is a clear example of the first
group of approaches since the fiber can be thermally or chemically
eluted in the injector of a chromatograph [60]. The application of this
approach when PSP are employed is challenging. Thermal desorption
is not recommended as the cellulosic substrate can be easily degraded
at intermediate temperatures generating a high signal background, thus
limiting the sensitivity and reducing the lifespan of the equipment. How-
ever, the in-line elution of the analytes and their almost complete trans-
ference to the instrument has given rise to special techniques like paper-
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Advances in Sample Preparation 5 (2023) 100051
spray mass spectrometry (PS-MS) [61]. In most reported applications,
even those based on modified papers, the cellulosic material acts as the
mere electrospray substrate [62]. This role is also played when combin-
ing liquid phase microextraction (LPME) and PS-MS. In these applica-
tions, the extractant phase obtained in the extraction is deposited over
the paper for its final PS-MS analysis [63–65]. Although scarce, some ap-
plications are based on using the modified paper as both sorptive phase
and electrospray substrate. Following this strategy, Zhang et al. used
COF-based paper to extract tetrabromobisphenol A and its final PS-MS
analysis [53]. In the same way, Zargar and coworkers designed a paper
subsequently modified with carbon nanoparticles and an aptamer for
the selective extraction of methamphetamine. After the extraction, the
paper was analyzed by PS-MS [66].
The planar shape of paper allows it direct measurement by spectro-
scopic techniques. MIP-coated paper has been reported for the determi-
nation of quinine in soft drinks by fluorescence spectroscopy [35]. Cel-
lulose paper impregnated with a solution of Fe(III), 1,10-phenanthroline
and acetate buffer was employed for the HS-TFME of sulfite, which
is subsequently detected via colorimetric measurements with a smart-
phone, based on the conversion of sulfite to SO2 , which reduces Fe(III)
to Fe(II) on the paper, forming a red complex upon reaction with 1,10-
phenanthroline [67]. Similarly, paper impregnated with silver nitrate
can act as recognition element for volatile arsine, which is generated
for arsenic speciation [68]. Bromine speciation has been also reported
by using Whatman No.1 paper in which hydrophobic barriers had been
created by wax printing, while in the hydrophilic detection area a citric
acid/cysteamine derived fluorescent probe had been deposited, the for-
mation of a dibrominated derivative leading to fluorescence quenching
of the probe, which could be detected with a smartphone [69]. More-
over, waterproof cellulose substrates, e.g., Whatman 1PS paper, can hold
large drop volumes of metallic NPs, which are employed to carry out in-
drop enrichment of in situ generated volatiles (e.g., acid-labile sulfide),
while colorimetric detection can be performed directly on the modified
paper [70]. On the other hand, core-shell gold nanorods-quantum dots
embedded on a MOF (i.e., GNRs-QDs@NU-901) have been deposited on
paper by vacuum filtration [71]. The modified paper has been employed
in the vapor generation-TFME determination of benzaldehyde, where
the presence of the MOF favors diffusion, and the nanoparticles enable
the subsequent detection via both fluorescence and surface-enhanced
Raman spectroscopy (SERS).
Dual substrates, able to be measured by spectrometric and spectro-
scopic techniques, are interesting material as they provide orthogonal
Fig. 5. Schematic representation of the main
workflows that can be used to include paper-
based sorptive phases in the analytical proce-
dure.
M. González-Bermúdez, Á.I. López-Lorente, R. Lucena et al.
information. Diaz-Liñán et al. reported a dual paper for the determina-
tion of drugs by SERS and PS-MS [72].
6. Conclusions and perspectives
This article reviews the state of the art of paper-based sorptive phases
in microextraction. The main characteristics of paper are initially de-
scribed as a necessary preamble to understand the approaches reported
in the literature for its modification. They are intentionally described
from a general perspective to show the versatility of these sorptive
phases, which can be easily adapted to a given analytical problem. This
flexibility is even expanded if the different analytical workflows are also
considered.
Simplification, sustainability, and affordability are underlying con-
cepts in the evolution of paper-based sorptive phases. On the one hand,
the use of an existing planar material simplifies in a large extent the
preparation of planar sorptive phases. On the other hand, the natural
origin of cellulose contributes to the greenness of the sorptive phases.
However, this aspect can be negatively counterbalanced if the synthe-
sis of the sorbent phase or its incorporation into the paper does not
meet sustainability criteria. Therefore, when selecting these coatings,
their environmental impact and their sorptive potential must also be
balanced to minimize the environmental impact as much as possible.
Finally, paper is a cheap and available material that can make easy the
development of global analytical solutions.
A growth of paper-based sorptive phases is envisaged for the next
decade. The development of new modification strategies, the coupling
of these phases with different instrumental techniques, and their appli-
cation in other microextraction formats (in liquid-based and solid-based
techniques) are predicted.
Another interesting research line is the in-situ preparation of the cel-
lulose network instead of using laboratory cellulose paper. There are
several sustainable procedures for this purpose, such as ball-milling
or focused microwaves. The main advantage is the inclusion of all
the reagents during the synthesis. This strategy minimizes the use of
reagents and chemicals while optimizing the time and energy resources
needed to obtain the paper-based sorptive phases.
Most of the applications described up to date use solid coatings of
polymeric or composite nature. However, the advances in developing
sustainable liquid phases (ionic liquids, switchable solvents or natural
deep eutectic solvents) envisage their immediate transference to the pa-
per substrate. In most situations, the liquid phase can be tailored to the
given analytical problem, which would help to spread their application
in different analytical fields.
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 article.
Data availability
No data was used for the research described in the article.
Acknowledgments
The project PID2020-112862RB-I00 funded by MCIN/AEI/10.
13039/501100011033 (Feder "Una manera de hacer Europa) is grate-
fully acknowledged. This article is based upon work from the Sample
Preparation Study Group and Network supported by the Division of An-
alytical Chemistry of the European Chemical Society.
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