Journal of Hazardous Materials 476 (2024) 135006

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journal homepage: [Link]/locate/jhazmat

Efficient extraction of textile dyes using reusable acrylic-based

smart polymers
Marta Guembe-García a , Gianluca Utzeri b , Artur J.M. Valente b , Saturnino Ibeas a ,
Miriam Trigo-López a , Jose Miguel García a , Saul Vallejos a, *
a
Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Plaza Misael Bañuelos s/n, 09001 Burgos, Spain
b
CQC-IMS, Department of Chemistry, University of Coimbra, 3004–535 Coimbra, Portugal

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Acrylic film with ion exchange behav­

iour for removing textile industry
pollutants.
• Removal percentages above 90 % for
anionic dyes from different families.
• Reusable, resistant and safer polymer DYE-POLLUTED
that can be used at least 5 times. WATER
• Suitable for both industrial and domes­
tic washing conditions.
• POC: study of indigo carmine removal
efficiency under domestic washing
conditions.

REUSABLE SMART POLYMER

REUSABLE
SMART POLYMER TRAPPING THE DYE

A R T I C L E I N F O A B S T R A C T

Keywords: Water pollution from industrial or household waste, containing dyes from the textile industry, poses a significant
Textile dyes environmental challenge requiring immediate attention. In this study, we have developed a crosslinked-smart-
Smart polymer polymer film based on 2-(dimethylamino)ethyl methacrylate copolymerized with other hydrophilic and hy­
Hydrogel
drophobic commercial monomers, and its efficacy in removing 21 different textile dyes was assessed. The smart
Acrylic polymers
polymer effectively interacts with and adsorbs dyes, inducing a noticeable colour change. UV-Vis spectroscopy
analysis confirmed a removal efficiency exceeding 90 % for anionic dyes, with external diffusion identified as the
primary influencing factor on process kinetics, consistent with both pseudo-first-order kinetics and the Crank-
Dual model. Isothermal studies revealed distinct adsorption behaviors, with indigo carmine adhering to a
Freundlich isotherm while others conformed to the Langmuir model. Permeation and fluorescence analyses
corroborated isotherm observations, verifying surface adsorption. Significantly, our proof-of-concept demon­
strated the resilience of the smart-film to common fabric softeners and detergents without compromising
adsorption capacity. Additionally, the material exhibited reusability (for at least 5 cycles), durability, and good
thermal and mechanical properties, with T5 and T10 values of 265 ◦ C and 342 ◦ C, respectively, a Tg of 168 ◦ C,
and a water swelling percentage of 54.3 %, thus confirming its stability and suitability for industrial application.

* Corresponding author.
E-mail address: svallejos@[Link] (S. Vallejos).

[Link]
Received 22 February 2024; Received in revised form 20 June 2024; Accepted 21 June 2024
Available online 24 June 2024
0304-3894/© 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license ([Link]
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Environmental implication: Dyes released during laundry processes should be classified as "hazardous materials"
owing to their significant toxicity towards aquatic organisms, with the potential to disrupt ecosystems and harm
aquatic biodiversity. This paper discusses the development of a novel acrylic material in film form, engineered to
extract toxic anionic dyes. This study directly contributes to mitigating the environmental impact associated with
the fashion industry and the domestic use of textiles. It can be implemented on both an industrial and personal
scale, thereby encouraging more sustainable practices and promoting collaborative citizen science efforts
towards

1. Introduction Nevertheless, the most significant disadvantage of hydrogels is their

mechanical properties, notably their often-suboptimal manageability.
Currently, water pollution stemming from industrial waste repre­ These drawbacks may limit their practical deployment in everyday
sents a crucial environmental challenge [1]. A primary concern is rep­ users. Furthermore, the vast majority of the literature reviewed de­
resented by the 7 × 107 tons of synthetic dyes produced worldwide with scribes materials intended for single use, or for which reuse has not been
over 10,000 tons employed only in textile industry and 10 % of these evaluated [15]. In such scenario, possessing robust mechanical proper­
dyes end up in wastewater as waste.[2] However, their presence in ties is imperative.
aquatic environments can be also related to daily domestic activities. In response to this pressing issue, the present study embarks on the
These dyes are notorious for their high toxicity levels, which pose severe development and meticulous characterization of a smart polymer based
risks to human health and the integrity of aquatic ecosystems [3,4]. on 2-(dimethylamino)ethyl methacrylate, exhibiting behaviour akin to a
Their presence in water poses a risk to the environment and organisms. hydrogel membrane (with superior handling and mechanical proper­
The colour of the dyes impedes or hinders light penetration,[5] reducing ties). The enhancement in the mechanical properties and workability of
photosynthesis rates (damaging flora)[6] and consequently decreasing the polymer, compared to existing alternatives, is attributed to its
dissolved oxygen levels (harming fauna).[5] Additionally, many dyes composition, which results in a dense material. This material format has
are carcinogenic and/or mutagenic. They are persistent environmental previously yielded highly favourable outcomes in various applications
pollutants, spreading through the food chain (biomagnification), [36–39] This material is specifically engineered to capture textile dyes
meaning that the higher the trophic level, the greater the accumulated with a remarkably high efficiency, achieving a capture rate exceeding
contamination in organisms.[7]. 90 %. Herein, we can categorize the material reported in this work as a
In agriculture, dyes, especially azo dyes (with 15–50 % ending up in smart material based on the definition reported by García et al. [40],
wastewater), negatively affect soil microbiota, germination, and plant that is, a material capable of interacting with a target (dye) through a
growth. This poses a significant problem for emerging agricultural sec­ specific mechanism (ion exchange, electrostatic interaction) and
tors, such as in India, where the textile industry is prevalent (resulting in generating a precise response (extraction of the dye and consequent
large amounts of waste) and agriculture is developing[7,8]. coloration of the material). This ’material’s pivotal and innovative
Regarding human health risks, these dyes cause acute toxicity characteristic is its potential for reuse and sustained durability (Fig. 1)
through ingestion or inhalation,[9] and prolonged exposure can lead to since its adsorption properties are not affected by load-wash cycles.
short-term issues: skin and eye irritation;[10] medium-term: dermatitis, These features are crucial for two reasons. Firstly, it aims to minimize
allergic conjunctivitis, rhinitis, occupational asthma, and various al­ the generation of additional waste in the process of dye pollution
lergies;[11] and long-term: genotoxicity. Moreover, many dyes are remediation. Secondly, with robust mechanical properties, the material
carcinogenic, cytotoxic, mutagenic, and/or enzyme activity initiators. can be feasibly used by non-specialists, including everyday consumers,
[7]. allowing for potential application at a household level. Consequently,
Given the magnitude of the problem, driven by an ever-expanding this approach addresses the pollution issue comprehensively and fosters
industry, it is necessary to develop new materials or techniques for the sustainability in pollution management practices.
removal of these contaminants from the natural environment. The best While preceding research was predominantly concentrated on the
strategy for their removal from aqueous environments is adsorption utilization of hydrogel-type materials for the extraction of both cationic
rather than degradation, as degradation products of these compounds and anionic dyes from aqueous solutions [25], our research does not
are often more harmful than the original substances. Over the past de­ confine itself to the investigation of a singular dye family. Rather, it
cades, various techniques and materials have been proposed to address extends its exploration to evaluate the efficacy of the novel polymeric
this issue, involving different techniques, such as: ultrafiltration material across a diverse spectrum of dye families. This includes, but is
[12–18], coagulation/electrocoagulation [19,20], photocatalytic not limited to, families such as azo dyes, organometallic dyes,
degradation [21], adsorption [22–24], phytoremediation [2] and triarylmethane-derivatives, xhantene-derivatives, anthraquinone struc­
extraction using hydrogels [25,26] and aerogels [27]. The latter has tures, benzothiazolium salts, biindolinylidene-derivatives, quinone-i­
been one of the mostly reported in the literature, due to its ease of mine structures and carbocyanine based dyes.
preparation and application, and promising results documented for the The 21 dyes selected for this study, listed below, include both
detection and extraction of different pollutants [28]. Ibrahim et al. re­ cationic and anionic types and are predominantly used in the textile
ported 85–90 % extraction efficiencies for various dyes using polymers industry (Table 1): Mordant Blue 29, Mordant Blue 3, Rhodamine-B,
based on poly(2-acrylamido-2-methylpropane) sulphonic acid, sodium Alizarin Red S, Rose Bengal, Congo Red, Basic Yellow, Brilliant Green,
polyacrylate, and chitosan [25]. In a similar vein, Alsulami et al. pub­ Prussian Red, Indigo Carmine, Acid Yellow 36, Methylene Blue, Pina­
lished analogous results using polyurethane-based foams [29]. cyanol Chloride, Xylenol Orange, Crystal Violet, Direct Black 38, Orange
The extraction of ionic dyes with polymeric hydrogels is predicated GR, Black 5, Sunset Yellow, Navy Blue Erionyl R, and Reactive Orange 7.
on the electrostatic interactions between the material and the target This flexible and inclusive approach not only highlights the ’material’s
(dye) [30–32]. Indeed, polymeric hydrogels with positively charged adaptability but also enhances its potential for widespread use in
structure exhibit a high affinity and removal efficiency for anionic dyes. different industrial and household settings.
Analogous results have been obtained in the opposite conditions
[33–35].

2
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Fig. 1. Table of contents.

2. Experimental Field Emission Scanning electron microscopy (FESEM) was carried

out using a model GeminiSEM560, ZEISS. Parallelly, Energy Dispersive
2.1. Materials X-ray Spectrometry (EDXS) analysis was conducted using UltimMax
Extreme (Oxford). In both case, films were dried, freeze fractured, and
All materials and solvents were commercially available and used as gold coated in vacuum to ensure the electrical conductivity.
received unless otherwise indicated. The following materials and sol­ RAMAN spectra were recorded with a confocal AFM-RAMAN model
vents were used: methylmethacrylate (MMA) (Merck, 99 %), 1-vinyl-2- Alpha300R – Alpha300A AFM from WITec, using a laser radiation of
pyrrolidone (VP) (Acros Organic, 99 %), N,N-dimethylaminoethyl met­ 532 nm, at magnifications of 100 × . All spectra were taken at room
acrylate (NNDA) (Aldrich, 98 %), 2-hydroxyethyl acrylate (2HEA), temperature.
(Aldrich, 96 %), ethylene glycol dimethacrylate (E) (Aldrich, 98 %), The powder X-ray diffraction (PXRD) patterns were obtained using a
azo-bis-isobutyronitrile (AIBN, Aldrich, 98 %) was recrystallized twice diffractometer (D8 Discover Davinci design, Bruker Corporation, Bill­
from methanol, hydrochloric acid (VWR, 37 %), Mordant Blue 29 (MP, erica, Massachusetts, USA) operating at 40 kV, using Cu(Kα) as the ra­
100 %), Mordant Blue 3 (Acros Organic, 100 %), Thymol blue (Alfa diation source (1.54 Å), a scan step size of 0.05◦, and a scan step time of
Aesar, 100 %) Rhodamine-B (Alfa Aesar, 100 %), Alizarin red S (Alfa 2s
Aesar, 100 %), Rose Bengal (Thermo scientific, 100 %), Congo Red Tensile properties analysis was conducted using samples measuring
(Thermo scientific, 100 %), Basic yellow (Alfa Aesar, 75 %), Brilliant 5 × 9.44 × 0.122 mm, employing a Shimadzu EZ Test Compact Table-
green (Thermo scientific, 100 %), Prussian red (Thermo scientific, Top Universal Tester at a speed of 1 mm/min− 1 (EZ Test EZ-LX, Shi­
100 %), Indigo carmine (TCI, >95 %), Acid Yellow 36 (TCI, 100 %), madzu, Kyoto, Japan).
Methylene Blue (TCI, >70), Pinacyanol chloride (TCI, >90 %), Xylenol Samples for PXRD and ICP-MS tests were prepared by milling the
orange (TCI, 100 %), Crystal violet (TCI, 100 %), Direct Black 38 (TCI, polymeric materials using a ball mill machine (MM400, Retsch, Haan,
100 %), Orange GR (TCI, >97 %), Black 5 (Sigma Aldrich, ≥50 %), Germany). The equipment was operated at a frequency of 25 Hz for
Sunset yellow (Cayman Chemical Company, 100 %), Navy blue Erionyl 5 min, and the capsules were pre-immersed in liquid nitrogen for
R (Aldrich, 50 %), Reactive Orange 7 (Sigma Aldrich, ≥70 %), Eosin Y 20 min.
(Sigma Aldrich, ≈99 %), Fluorescein (Fluka, 100 %), Indigo (TCI, Total nitrogen (TN) was measured on an autoanalyzer TOC-V CSN
>97 %). (Shimadzu Corp., Kyoto, Japan).
For the proof of concept, commonly used laundry products such as For the calculation of the size of the dye molecules, the Avogadro
detergent and fabric softener were employed. Photographs of both software (Version 1.2.0) was utilized.
products and their respective ingredient lists can be found in the Elec­
tronic Supplementary Information (ESI-Section S1, Figure S1a and S1b).
2.3. Specific methods

2.2. Instrumentation and general methods 2.3.1. Preparation of the polymeric material
The procedure followed was that described by Vallejos et al., with
Thermal properties of the material were evaluated employing modifications.[41] The main material was synthesized through radical
different analytical methodologies. Thermogravimetric analysis (TGA) polymerization using four commercial copolymers: two hydrophilic
was conducted on 10 − 15 mg samples under synthetic air and a ni­ ones (vinylpyrrolidone, VP, and 2-hydroxyethyl acrylate, 2HEA), one
trogen atmosphere, utilizing a TA Instruments Q50 TGA analyser with a hydrophobic (methyl methacrylate, MMA), and a fourth one containing
heating rate of 10 ◦ C min− 1. Differential scanning calorimetry (DSC) a tertiary amine capable of protonation (N,N-dimethylaminoethyl
involved 10 − 15 mg samples under a nitrogen atmosphere, analysed methacrylate, NNDA), in molar proportions of 45/45/5/5
using a TA Instruments Q200 DSC analyser with a heating rate of (VP/MMA/NNDA/2HEA). Additionally, 1 % (w/w) of AIBN as a radical
20 ◦ C min− 1. thermal initiator, and 2 mol% of ethylene glycol dimethacrylate (E) as
The water-swelling percentage (WSP), at 20 ◦ C, was calculated using the cross-linking agent were added to the mixture. Bulk radical poly­
the formula: WSP = 100 × [(ωs− ωd)/ωd], where ωd represents the merization was conducted within a silanized glass mold of 100 µm
weight of a dry sample film, and ωs denotes its weight post-swelling. thickness, under an oxygen-depleted atmosphere at a temperature of
UV/Vis spectra were acquired employing a Hitachi U-3900 UV/Vis 60 ◦ C overnight. This procedure yielded the membrane denoted as F1,
spectrophotometer. The synthesized ’materials’ infrared spectra (FT-IR) which subsequently underwent a triple cleaning process with water,
were obtained using a JASCO FT-IR 4200 spectrometer in the acetone, and water again.
4000–400 cm− 1 range. Following this, the tertiary amine group within NNDA was proton­
Inductively coupled plasma mass spectrometry (ICP-MS) measure­ ated through the immersion of F1 in a 3.7 % aqueous HCl solution for
ments were recorded on a 7500 ICP-MS spectrometer (Agilent, Santa 1 h, resulting in the formation of membrane F2. The residual HCl was
Clara, CA. USA). removed by immersing membrane F2 three times in distilled water, with

3
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 1
List of dyes used in the preliminary study, indicating CAS number, common name, chemical formula, dye family to which they belong, obtained qe, and removal
percentage.
Dye Dye Family pKa qe, Dye
Nº mg/g removal %

1 Triarylmethane -2.2, 27.65 98.20

-1.2. 2.25, 4.88,
11.75[57]

Mordant Blue 29

CAS: 1667-99-8
Warnings: Toxic, eye damage and respiratory irritation[56]
2 Triarylmethane 0, 28.29 99.53
1.83, 5.74,
11.83[59]

Mordant Blue 3

CAS: 3564-18-9
Warnings: Toxic limit 2000 mg/Kg ([58])
3 Xhantene 2.9, 4.5[61] * *

Eosin Y

CAS: 15086-94-9
Warnings: Toxic and mutagenic[60]
4 Xhantene 2.2, 4.4, 6.7 * *
[61]

Fluorescein

CAS: 2321-07-5
Warnings: Low toxicity[62]
5 Triarylmethane 1.76, 9.05[64] * *

Thymol Blue

CAS: 76-61-9
Warnings: Damage to the digestive tract, respiratory tract and skin[63]
(continued on next page)

4
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 1 (continued )
Dye Dye Family pKa qe, Dye
Nº mg/g removal %

6 Xhantene 3.7[66] 6.25 22.00

Rhodamine-B

CAS: 81-88-9
Warnings: Toxic limit: 14 a 24 mg/L ([65])
7 Anthroquinone 4.5, 11[61] 27.87 98.63

Alizarin red S

CAS: 130-22-3
Warnings: Toxic limit: 70 mg/Kg ([67])
8 Xhantene 3.9, 4.7[68] 27.02 96.10

Rose Bengal

CAS: 632-69-9
Warnings: Eye damage and skin irritation[63]
9 AZO 4.1[61] 17.43 61.33

Congo

Red
CAS: 573-58-0
Warnings: Toxic limit: 3.11 mg/L ([69])
10 Benzothiazolium 1.8, 4.9[71]* * 1.83 6.44
salts

Basic yellow (Thioflavine T)

CAS: 2390-54-7
Warnings: Acute oral toxicity, eye damage and skin irritation.[70]
11 Triarylmethane 2.62, 4.93[73] 13.87 48.81

Brilliant green

CAS: 633-03-4
Warnings: Toxic limit: 50 mg/L ([72])
(continued on next page)

5
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 1 (continued )
Dye Dye Family pKa qe, Dye
Nº mg/g removal %

12 Organometallic * ** 28.49 99.61

Prussian red (Potassium hexacyanoferrate III)

CAS: 16746-66-2
Warnings:Toxic[74]
13 Biindolinylidene 10.1[71]* * * *

Indigo

CAS: 482-89-3
Warnings: Toxic limit: 5000 mg/Kg ([75])
14 Biindolinylidene 8.8[71]* * 29.28 98.58

Indigo carmine

CAS: 860-22-0
Warnings: Toxic limit: 500 mg/Kg ([76])
15 AZO 2.12[61] 27.39 96.36

Acid Yellow 36

CAS: 587-98-4
Warnings: Toxic and carcinogenic[77]
16 Quinone-imine 3.8[79] 3.25 11.44

Methylene Blue

CAS: 122965-43-9 (solution 61-73-4)

Warnings Toxic limit: 7 mg/Kg ([78])
17 Carbocyanine 3.5[81] 17.76 62.47

Pinacyanol chloride

CAS: 2768-90-3
Warnings: respiratory immunogenicity[80]
18 Triarylmethane 2.6, 6.4, 6.5, 27.45 96.62
10.5, 12.3[61]

Xylenol orange

CAS: 1202864-39-8
Warnings: Toxic[82]
(continued on next page)

6
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 1 (continued )
Dye Dye Family pKa qe, Dye
Nº mg/g removal %

19 Triarylmethane 9.4[61] 2.17 7.62

Crystal violet

CAS: 548-62-9
Warnings: Toxic, Genotoxic and Carcinogenic[83]
20 AZO 4.2, 5.1, 5.2, 8.71 30.64
9.8, 12. 12.4
[71]* *

Direct Black 38

CAS: 1937-37-7
Warnings: Toxic limit: 1500 mg/L ([84])
21 AZO 8.26, 11.4[61] 27.44 96.55

Orange GR

CAS: 633-96-5
Warnings: Carcinogens[85]
22 AZO 3.5, 4.7, 9.4 27.30 96.04
[71]* *

Black 5

CAS: 17095-24-8
Warnings: Toxic limit: 28 mg/L ([8])
23 AZO 6.1, 11.8[87] 25.63 90.16

Sunset yellow

CAS: 2783-94-0
Warnings: Toxic limit: 2.5 mg/Kg ([86])
(continued on next page)

7
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 1 (continued )
Dye Dye Family pKa qe, Dye
Nº mg/g removal %

24 AZO 4.3, 11.5 27.47 96.63

[71]* *

Navy blue Erionyl R (Acid Blue 113)

CAS: 3351-05-1
Warnings: Acute toxic[88]
25 AZO 5.4, 13.2[71] 27.65 98.20
**

Reactive Orange 7

CAS: 12225-83-1
Warnings: Toxic limit: 2.5 mg/Kg ([89])

* The experiments were not conducted due to the low or negligible water solubility of the dye.
* * Theoretically calculated pKa values.
* ** Without theoretical or experimental values.

each immersion lasting for 5 min. The chemical structure and a photo­ 2.3.3. Isotherm study by UV-Vis spectroscopy
graph of the material are illustrated in Figs. 2a and 2b, respectively. The isotherm study was conducted through two experimental pro­
cedures, A and B. In the case of procedure A, the concentration of the dye
2.3.2. Removal and kinetic study by UV-Vis spectroscopy solution was kept constant at 50 mg L − 1, and the size of the smart
A prior calibration was performed using solutions of 2.5 to 60 mg L polymer disc was varied (3 to 14 mm in diameter). For procedure B, the
− 1
for each dye. disc size was kept at 10 mm, and different concentrations of dye (2.5 to
For these studies, F2 was punched into 10 mm diameter discs and 60 mg/L) were used. In both cases, each solution was measured prior to
then immersed in 3.5 mL of solutions with a concentration of 50 mg L − 1 introducing the F2 disk, and approximately 24 h elapsed after intro­
of each dye. The UV-Vis absorption spectrum (200–900 nm) was ducing the F2 disk. The obtained results were analysed using Freundlich
measured every 15 min for 24 h. To calculate the percentage of dye and Langmuir isothermal models. When adsorption equilibrium is
removal, the following formula was employed: reached, the solute is distributed between the solution and the solid,
where qe can be computed by the following equation:
C0 − CF
Dye removal% = × 100 (1)
C0 Co − Ce
qe = V (5)
w
where C0 and CF are the initial and the final concentrations of the dye
in the solution. where V (L) is the volume of the solution used, and w is the mass in
Consistent with previous studies about adsorption processes in grams of the absorbent.
acrylic polymers [42], the analysis of the obtained results assumed a Langmuir was the first proposing an adsorption theory on a flat
pseudo-first-order kinetic: surface from a kinetic perspective [43,44]. The model suggests adsorp­
( ) tion in a single layer on the surface, considering a finite number of active
qt = qe 1 − e− k1 t (2) sites at identical energy. Adsorption takes place on these centres with
where, qt (mg g− 1) is the milligrams of adsorbate per gram of only one molecule per site. The following equation describes this model:
adsorbent at a time t, qe (mg g− 1) is the amount of dye adsorbed at qmax KL Ce
equilibrium and k1 is the first-order kinetic constant. For the diffusion qe = (6)
1 + KL Ce
study, the Crank-Dual model was employed:
where qmax (mg/g) is a constant indicating the maximum adsorption
( / )
qt ∑ ∞
2B2i exp − β2n Ds t l2 capacity in the monolayer, and KL (L/mg) defines the affinity of the
= 1− ( 2 ) (3)
qe 2 2
βn βn + Bi + Bi adsorbate for the adsorbent. These two constants allow calculating the
n=1
thermodynamic equilibrium constant, Kc, from their product:
βn tanβn = Bi (4) Kc = KL qmax (7)
Bi is Biot number, i.e., ratio of external film diffusivity to intra­ On the other hand, Freundlich isotherm model is an empirical
particle diffusivity, Ds (cm2 min− 1) is the diffusion coefficient of sorbate equation, assuming that the adsorbent surface is energetically hetero­
within the sorbent and kf (cm min− 1) are external or film mass transfer geneous, formed by different adsorption sites with characteristic en­
coefficient. ergies [45]. Differently to the Langmuir model, the Freundlich isotherm
considers the formation of adsorbate-adsorbate interactions with

8
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Fig. 2. a) Selected formulation for the manufacture of the smart polymer. b) Photograph of the prepared membrane. c) Solutions of 3.5 mL dyes at an initial
concentration of 50 ppm (above) and once the adsorption process is completed (below).

multilayer formation: 2.3.5. Fluorescence study

Besides the visible absorbance of dyes, most dye molecules also show
qe = KF C1/n
e (8) photoluminescence. This property has been employed in several fields
where KF (mg/g (mgL ) − 1 − 1/n
) and n represents the capacity and in­ [47–51].
tensity of adsorption, respectively. In this study, we exploit this property to obtain complementary
qualitative information that allows for a better understanding of the
2.3.4. Permeation analysis by UV-Vis spectroscopy adsorption process in terms of the adsorbent-adsorbate interaction. F2
The permeation study was conducted by time-lag analysis using a membranes used in permeation experiments were characterized by
system consisting of horizontal communicating vessels, as described in fluorescence. Measurements were performed using Horiba-Jobin-Ivon
reference [46]. In this setup, the material under investigation (F2) serves SPEX Fluorolog 3.22 spectrofluorometer and all fluorescence spectra
as a barrier between the channel connecting the two vessels. Cutting the were corrected for the wavelength response of the system. In general,
membrane in circular shape of a defined diameter permits obtaining a depending on the dye analysed three different wavelength (nm) of
defined permeation area of 2 cm2. Vessel "A" contains Milli-Q ultrapure excitation was employed (e.g. λ1 = 420 nm, λ2 = 520 nm and λ3 =
water, while vessel “B” holds an aqueous dye solution of 50 mg/L. The 600 nm).
permeation process was monitored by measuring the absorbance at the
λmax of the solution in the vessel "A" over time, using a UV–visible 2.3.6. Reusability study
spectrophotometer (UV-2600i, Shimadzu, Germany). Calibration curves The evaluation of material reusability was conducted using adsorp­
were generated for each dye within the analytical range of 0–60 mg/L. tion and desorption cycles, following published strategies with modifi­
The F2 membrane has a thickness (L = 100 µm) and permeation area (A cations [52]. An F2 disc of 10 mm diameter was immersed in 3.5 mL of
= 2 cm2), the cell volume (V = 200 mL), and the concentration of dye in dye 14 (10 mg/L) overnight. Subsequently, the disc was removed from
the donor cell (Cdye = 50 mg L⁻1). The diffusion coefficient (D) and the solution, and the absorbance of the solution was measured.
permeation coefficient (P) are computed using the following equations: Desorption of dye 14 was achieved by immersing the disc in 5 mL of
1 mol L − 1 NaOH. To obtain complete desorption, the disc was immersed
L2 in the basic solution overnight, preceded by a wash in 5 mL of distilled
D= (9)
θ water for 5 min. Once the dye was removed, the disc was immersed in
10 mL of a 4 % HCl solution for 1 h and washed three times with 5 mL of
(V × S × L)
P= (10) distilled water for 15 min each time. This cycle of use/washing was
A × C0
repeated 5 times.
where θ (s) is the time-lag, and S represents the slope of the curve
obtained by plotting the permeant concentration as a function of time, 2.3.7. TOC
observed at the steady-state condition. Consequently, we determined a The total nitrogen content (TN) was measured in the solution before
coefficient of partition (Kp = P/D), which indicates the affinity of the and after treatment with F2. For this study, Dye 12 was selected due to
permeate to the membrane. its high nitrogen content and because it is the only organometallic dye.
After the permeation analysis, the membranes were dried in a Additionally, Dye 14 was chosen for its relevance in the textile industry.
desiccator and successively used for the fluorescence analysis on both Solutions of both dyes were prepared at a concentration of 50 ppm, and
sides of the membrane: side in contact with vessel "A"-pure water and the total nitrogen content was studied. Subsequently, 3.5 mL of this
vessel "B"-dye solution. solution was taken, and a 10 mm diameter F2 disk was immersed in it at
25 ºC for 12 h. A total of 60 tests were conducted under these conditions

9
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

to obtain a sufficient quantity for the experiment. Finally, the resulting From the perspective of polymer material design, the inclusion of
solutions from the extraction process of each dye were collected and groups susceptible to protonation is crucial for dye removal. These
homogenized for total nitrogen measurement. groups can harbor positive charges, allowing for the exchange of
The remaining F2 disks were used for ICP-MS, PXRD, RAMAN, and anions—specifically, exchanging chlorides for anionic dyes. Addition­
SEM analyses. ally, the presence of other monomers is essential for ensuring the ma­
terial possesses suitable properties, such as manageability. Put
2.3.8. Proof of concept: evaluation of the smart polymer under real-life- differently, if the material were composed entirely of NNDA, its dye
simulated conditions absorption capacity would be much greater. However, this would likely
Our material can be potentially utilized in both industrial and do­ come at the expense of mechanical properties due to the material’s
mestic environments. Therefore, we aimed to assess the efficiency of the significantly increased hydrophilicity. Thus, striking a balance is
smart polymer under conditions akin to those potentially encountered in essential. Furthermore, the dense nature of the material is highly rele­
a household washing machine, considering the composition of the vant, enabling its reuse without sacrificing mechanical properties or dye
washing solution. This assessment aligns with the ’material’s prospec­ extraction capability.
tive applications, such as coating for drainage pipes or purification
membranes. The 10 mm diameter disc of F2 material was immersed in a 3.2. Preliminary results. Removal % and qe
solution of 3.5 mL of tap water, 10 µL of fabric softener, and 10 µL of
laundry detergent. The UV-Vis absorption spectrum (200–900 nm) was Preliminary tests were conducted with 25 different dyes. However,
measured every 15 min for 24 h. dyes 3, 4, 5, and 13 were excluded from the study due to their lack of
solubility in water. Table 1 shows each dye’s chemical structures,
3. Results and discussion common names, CAS numbers, pKa, qe, and removal %.
In Fig. 2c, the solutions of the 21 dyes can be observed both before
3.1. Characterization of the material introducing the material and after the adsorption process. Consistent
with the data presented in Table 1, it becomes evident that the highest
The handleability of a material is a highly significant property, adsorption efficiencies (dye removal % > 90) are associated with dyes 1,
mainly when its final applications are focused on domestic use. From a 2, 7, 8, 12, 14, 18, 21, 23, 24, and 25. Conversely, lower adsorption
theoretical perspective, the handleability of a material is primarily percentages (7 < dye removal % < 63) are observed for dyes 6, 9, 10, 11,
associated with its mechanical and thermal properties. These properties 16, 17, 19, and 20.
must be maintained under the intended working conditions for the As the literature describes, materials with a positive charge, such as
material. For instance, industrial textile washes are conducted at 75 ◦ C. F2, exhibit two potential interaction mechanisms: ion exchange [90]
In this case, the TGA analysis reveals that T5 and T10 (temperatures at and/or electrostatic interaction [13,16,18,22]. In the first scenario, an
which a weight loss of 5 % and 10 % is observed, respectively) have exchange occurs between the H+ ions of the membrane and the dye
values of 265 ◦ C and 342 ◦ C, respectively.[53] These values are components. In the second scenario, the positively charged matrix at­
commonly found in similar acrylic polymers and ensure the polymer’s tracts the dyes in their anionic (deprotonated) state. In both cases, the
thermal stability in industrial applications and processes using steam or pH solution plays an important role. Previous studies have shown that,
even boiling water. Furthermore, characterization through DSC in­ in the case of electrostatic interactions, neutral pH values (7− 8) yield
dicates a glass transition temperature (Tg) of 168 ◦ C, which, combined the most effective adsorption results [22]. In this instance, we are
with the TGA results, confirms the ’material’s suitability for the pro­ dealing with electrostatic interaction behaviour, where the positively
posed application. charged membrane can adsorb dyes in their deprotonated (anionic) form
From a mechanical perspective, the Young’s modulus of F1 was at the working pH. However, the membrane would not work for dye
analyzed immediately after demolding, yielding a value of 435 extraction at pH levels where the NNDA monomer is deprotonated,
± 48 MPa. This result is consistent with the moduli reported in the specifically at pH levels above 8. In this situation, the NNDA monomer
literature for similar materials [54]. would deprotonate and release the dye back into the medium. This
The F2 material was analyzed by FT-IR, which showed typical signals phenomenon has been leveraged as a strategy to design the material’s
for this type of polymer, such as the carbonyl stretching signals of the reuse cycles: in its protonated form, the membrane extracts dyes, and in
ester (1719 cm− 1) corresponding to MMA, NNDA, and 2HEA, the amide its deprotonated form, it releases them.
(1663 cm− 1) corresponding to VP, and the broadband associated with
the -OH stretching band of 2HEA (3428 cm− 1). IR, TGA, and DSC graphs 3.3. Kinetic study
are provided in the Electronic Supplementary Information (ESI-Section
S2). After the preliminary study of dye removal percentages, we pro­
On the other hand, the material, F2 presents a water swelling per­ ceeded with an in-depth investigation, selecting one representative from
centage (WSP) of 54 ± 3 %, derived from its modified composition, each dye family, except for the triarylmethane family, for which two
enabling interaction of the material with the adsorbate and enhancing were chosen. Specifically, the dyes with the highest dye removal per­
its adsorption and retention capabilities. centages were chosen, namely dyes 1 and 18 (triarylmethane family),
It is crucial to note that 3 of the 4 monomers used in the synthesis of dye 7 (anthraquinone family), dye 8 (Xanthene family), dye 12
the material are hydrophilic, thereby producing materials that exhibit (organometallic family), dye 14 (biindolinylidene family), and dye 21
significant swelling in water. This characteristic is beneficial as it facili­ (azo family).
tates the entry of the targets (dyes) into the three-dimensional structure of The adsorption processes in solution can be divided into four stages.
the material, but only up to a certain extent. Excessive swelling of the The comprehension of this phenomenon requires distinguishing be­
material can severely compromise its manageability. This is why the role tween two external regions (outside the membrane): the area that en­
of the cross-linker becomes essential. In our previous studies [55], the circles the material and the remainder of the solution. The initial stage is
amount of cross-linker typically used is 0.1 mol/mol%. In these studies, rapid, and involves the migration of the solute from distant zones to­
the amount of hydrophobic monomers was < 50 mol%, which controls wards the vicinity of F2, while the second stage concerns the migration
water swelling. In this case, since the mol% of hydrophilic monomers from the vicinity of F2 to its surface. The intraparticle diffusion repre­
exceeds 50 mol%, an increase of ethylene glycol dimethacrylate (E) sents the third stage, and the final one involves the solute’s adsorption
cross-linking agent to 2 mol%, to achieve balanced water swelling and onto the adsorbent’s active sites. Various mathematical models exist for
maintain the ’material’s handleability, has been made. interpreting the results of adsorption monitored through UV-Vis

10
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 2
Kinetic parameters obtained through nonlinear least squares fitting to Eq. 2, [Dye]o = 50 mg/L, and parameters obtained through nonlinear least squares fitting of the
Crank-Dual model reported in Eq. 3.
Nonlinear Least Squares Fitting
Dye Nº k1 105, s¡1 qe, mgdye/gF2 R2
18 ±0.03 26.05 ± 0.05 0.999
4.45
14 ±0.05 29.75 ± 0.09 0.998
5.47
7 ±0.02 27.99 ± 0.03 0.999
5.92
21 ±0,03 28.74 ± 0.03 0.999
6.48
1 ±0.04 27.48 ± 0.05 0.999
7.18
8 ±0.20 26.00 ± 0.10 0.984
8.70
12 ±0.04 28.63 ± 0.02 0.999
9.42
Crank-Dual model
Dye Ds 1012, m2/s kf 109, m/s qe, mg/g Bi R2
18 0.87 ± 0.07 2.49 ± 0.02 25.87 ± 0.03 0.143 ± 0.002 0.9996
14 1.04 ± 0.02 3.11 ± 0.03 29.49 ± 0.06 0.149 ± 0.004 0.9993
7 1.19 ± 0.08 3.21 ± 0.02 27.92 ± 0.02 0.134 ± 0.002 0.9998
21 1.29 ± 0,01 3.53 ± 0.02 28.67 ± 0.03 0.137 ± 0.002 0.9996
1 1.54 ± 0.01 3.67 ± 0.04 27.51 ± 0.05 0.119 ± 0.003 0.9990
8 1.00 ± 8.00 5.00 ± 3.00 25.86 ± 0.08 0.200 ± 0.900 0.9900
12 1.94 ± 0.02 4.99 ± 0.04 28.62 ± 0.02 0.128 ± 0.002 0.9993

spectroscopy, such as the pseudo-first-order kinetic and the Crank-Dual figures for the other dyes examined (dyes 1, 7, 8, 12, 18, and 21) can be
models. The former assumes that the fourth stage is the rate-determining found in the ESI-Section S3 (Figures S7-S12).
step, while the latter suggests that the most crucial stages are the second In previous work, we have studied how the size and shape of ad­
and the third, related to diffusion. The first model enables us to deter­ sorbates affect the adsorption process using this same type of material,
mine the percentage of adsorption at any given time, whereas the Crank- which is highly relevant for understanding the differences observed
Dual model allows us to elucidate the kinetic mechanism of adsorption. between the various dyes in this study [42]. Among the dyes studied,
Table 2 displays the results of the kinetic parameters calculated using only dye 14 conforms to a Freundlich isotherm. This compound differs
each model, i.e., the pseudo-first-order kinetic model and the Crank- from the rest because it exhibits a linear structure with charges at ter­
Dual model, respectively (the corresponding graphs can be found in minal groups. Due to this configuration, we believe it shows a preference
the ESI-Section S3 Figures S7c-S12c, and S7d-S12d). for interaction with certain binding sites, causing the adsorbent surface
The values of Bi < < 1 indicates that external diffusion is the domi­ to behave as a heterogeneous surface, where some sites exhibit more
nant factor influencing the overall process rate [91–93]. This finding affinity for adsorption than others. The remaining dyes conform to the
aligns with previous studies on similar materials [42]. model of a favourable Langmuir isotherm (see ESI-Section S3,
Considering that the geometrical dimensions of the membrane are Figures S7e-S10e, S12e). Dye 12, likely due to its high k1 resulting from
strictly controlled, we can observe that k1 and kf follow the same trend, its small size, the isotherm at a concentration of 50 mg L − 1 could not be
confirming that the external diffusion is the dominant step, as also calculated.
justified in the ESI-Section S3. Moreover, since all dyes are studied under Additionally, particular focus has been directed towards dye 14 due
the same conditions, a linear relationship is observed between the values to its prevalent use in dyeing denim pants. Utilizing the isotherm data,
of k1 and kf, with a slope of 1.80 ± 0.1 m⁻1 , representing the propor­ the percentage of adsorption can be delineated concerning the ratio of
tionality constant. This indicates the good agreement between the two grams of adsorbent to grams of dye (Fig. 3 f). Notably, it is discerned that
mathematical approaches used in the kinetic study. with a ratio exceeding 25, removal surpasses 90 %.

3.5. Permeation study

3.4. Isothermal study
The permeation curves analysis is reported in Fig. 4, and their
In this section, we conducted studies on dyes 1, 7, 8, 12, 14, 18, and parameter values are resumed in ESI-Section S4, Table S1. It can be seen
21, particularly emphasizing dye 14, indigo carmine. This decision is that the time-lag, θ, for different dyes follows the order:
well-founded due to its extensive usage in the textile industry, particu­ 18 < 12 < 21 < 7 < 14. An increase in θ indicates the steady-state flux
larly in denim garments such as jeans and jackets. Due to its widespread is attained at longer times and, consequently, permeant affinity to the
application and demand within the fashion market, Indigo carmine membrane follows the same order as θ. These results agree with the
holds significant sway, both environmentally and economically. inverse order of the D values, which show the capacity of the molecules
Hence, we carried out the isotherm study for this specific dye using to pass through the membrane. In other words, considering the dye 14, it
both procedures detailed in the experimental section. We exclusively presents the highest affinity to the membrane but the lowest rate of
followed procedure B for the remaining dyes, maintaining a constant diffusion, suggesting the greatest capacity of the membrane F2 to retain
disk size while varying the dye concentration. Fig. 3 presents compre­ it. On the other hand, dyes 1 and 8 showed no measurable permeation
hensive results for dye 14, encompassing kinetic fittings (pseudo-first- after 14 days.
order model and Crank-Dual model) and isotherm fittings conducted
using the two distinct procedures: procedure A (with constant dye
concentration while altering the F2 disk size) and procedure B (with a
fixed F2 disk size while modifying the dye concentration). Analogous

11
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

30 1.00

25
0.75
20
qt, mg/g

qt/qe
15 0.50

10
0.25
5

0 0.00
0.0 2.0x10
4
4.0x10
4
6.0x10
4
8.0x10
4
0 2 4 6
2 1/2
t, s (Dst/l )

120 100
Isotherm B
100 Isotherm A
80
80
% Absorption

60
qe, mg/g

60
40
40
20 20

0 0
0 5 10 15 20 25 30 0 20 40 60 80 100
Ce, mg/l grAbs/grDye
Fig. 3. a) Dye 14 chemical structure; b) Photograph of the initial dye solution (3.5 mL, 60 mg/L) before (left) and after (right) completion of the adsorption process
using a 10 mm diameter disc of F2; c) kinetic study: pseudo-first-order model, λabs: 607 nm; d) kinetic study: Crank-Dual model, λabs: 607 nm; e) isotherm A + B:
Freundlich model, λabs: 607 nm; f) Variation of the adsorption percentage of dye as a function of the ratio of gram of adsorbent to gram of dye.

3.6. Fluorescence analysis permeation analysis, which indicate the slowest rate of diffusion, higher
rate of permeation and strongest affinity to the membrane. Moreover,
It is worth noting that well-defined surfaces are obtained after this shift to higher λemis can also suggest that the dye molecule mainly
permeation experiments. The surface in contact with the dye solution is interacts at the surface of the membranes. This finding aligns with the
colourful and shows a layer-like dye on the surface, which is not results obtained for isotherms, where it was deduced that adsorption
observable on the membrane side in contact with water. This allowed for primarily occurs on the material’s surface.
a fluorescence study of the materials on both sides. Figure S13 (ESI-
Section S5) shows that the membranes for each dye can present emission
peaks and/or a shift of the peaks as function of the excited membrane 3.7. Characterization of the interaction mechanism between dyes and F2
side. In general, peaks with lower λ emission were observed when the
side in contact with pure water was analysed (dashed line) than the λ Due to the significance of Dye 14 in the textile industry, we con­
observed for the side membrane in strict contact with the dye solution ducted SEM experiments to characterize the interaction between Dye 14
(solid line). These changes are noticeable for dyes 1, 8 and 14. In and F2. Additionally, Dye 12 was included in this study because it is the
agreement, dye 14 showed the highest θ, P and K values in the only dye among those tested that contains an iron atom, which we
considered particularly interesting for EDXS analysis of the samples.

12
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

6 The results obtained from RAMAN experiments also confirmed the

interaction between the dye and F2. Once again, the experiments with
5 Dye 12 provided the highest quality information due to the intense band
exhibited by Dye 12 at 2128 cm⁻1 . As shown in Fig. 5 f, F2 does not
4 exhibit any bands at these wavenumbers initially; however, after the
[Dye], mg/L

adsorption process with Dye 12, it displays the characteristic band of the
3 dye.
2 The ICP-MS results were also highly elucidative, particularly in
justifying the ion exchange process. The F2 material initially had a
1 chlorine concentration of 6906 ± 71 ppb, which decreased to 1166
± 315 ppb and 2838 ± 373 ppb after the adsorption process of dyes 12
0 and 14, respectively. This indicates that the chlorides, which acted as
counterions in the NNDA monomer, were released from the material and
5

6
0
10

10

10

10

10

10

10
replaced by anionic dyes. Therefore, assuming the hypothesis that both
0.
0x

0x

0x

0x

0x

2x

4x
dyes entered the three-dimensional network of the polymeric material,
2.

4.

6.

8.

1.

1.

1.
the concentration of Fe (in the case of Dye 12) and the concentration of S
Fig. 4. Permeation analysis curves with dye 7 (green), dye 12 (magenta), dye (in the case of Dye 14) should increase. Indeed, the results confirm this.
14 (blue), dye 18 (red) and dye 21 (purple). Analysis was performed at 25 ◦ C,
The iron concentration increased from 53 ± 28 ppb in the original F2 to
using a membrane thickness = 100 µm, area = 2 cm2, the content of beaker A
4445 ± 27 ppb after the adsorption process of Dye 12. Similarly, the
= 200 mL of MQ water and content of beaker B = 200 mL of dye solution at
sulfur concentration increased from 43 ± 16 ppb in the original F2 to
50 mg/L.
4148 ± 527 ppb after the adsorption process of Dye 14 (ICP-MS data are
means of 2 replicates ± sd).
All materials used in this section were prepared by immersing a
Regarding the total nitrogen measurement, this technique, like the
10 mm diameter disc of F2 in 3.5 mL of a 50 ppm dye solution. In an
others, confirmed the near-complete removal of both dyes (12 and 14)
initial experiment with Dye 12, we observed that our materials are not
from the prepared solutions. In the experiment with Dye 12, the total
perfect and exhibit surface defects in the form of small holes (Fig. 5a).
nitrogen content decreased from 12.05 ± 0.10 ppm to 0.45 ± 0.02 ppm.
These defects are attributable to the imperfections in the glass moulds
In the experiment with Dye 14, the total nitrogen content dropped from
used during the preparation of these materials (Figure S1c). Interest­
1.95 ppm ± 0.03 to 0 (total nitrogen data are means of 3 replicates
ingly, we noted that these defects could act as nucleation sites for the
± sd).
formation of Dye 12 crystals (Fig. 5b).
The anionic exchange process that takes place results in the release of
However, we do not believe that this is the initial process occurring
chloride anions into the water, which, at concentrations expected in
during the adsorption of dyes on F2. In fact, our hypothesis posits that
realistic scenarios, pose no risk. Furthermore, the potential migration of
ion exchange occurs first [94], following a mechanism similar to that of
substances from these materials (with non-significant modifications)
ion exchange resins, as depicted graphically in the diagram in Fig. 5c.
into the water they are submerged in has already been studied in pre­
Following this initial process, a second process becomes apparent in the
vious works [95], where tests were conducted according to the pro­
SEM images. Specifically, after the saturation of the active sites of the
visions of Commission Regulation (EU) No 10/2011 (and its
material, dye crystallization occurs on the surface of F2 rather than
amendments) concerning plastic materials and articles intended to come
within the material, due to its dense nature (Fig. 5d).
into contact with food, and the results were favourable.
In both the Dye 12 and Dye 14 experiments, nanoparticles and mi­
croparticles of the dye can be observed on the surface of the material. At
3.8. Proof of concept
this stage, the EDXS analysis of the Dye 12 particles was extremely
informative, revealing high quantities of iron due to the organometallic
The proof of concept focused exclusively on dye 14. The main aim
nature of the dye, as shown in Fig. 5d.
was to investigate potential interferences for domestic material use,
To further our objective of characterizing the interaction between
specifically assessing whether fabric softeners and detergents affect the
the dye and F2, we conducted PXRD experiments. The spectra shown in
adsorption and kinetics of the material. Essentially, a kinetic assay using
Fig. 5e display typical amorphous halos, which provide the average
a 10 mm diameter disc of F2 was replicated by introducing standard
distance between polymer chains and allow us to observe the effect of
quantities of detergent and fabric softener into the medium (3.5 mL of
chloride ion exchange with Dye 12 and Dye 14. This interchain distance
tap water, 10 µL of fabric softener, and 10 µL of detergent). After fitting
is described by the equation <R> = 5/8(λ/sin θmax), indicating that as
the data to a pseudo-first-order model, the determined values for k1 and
θmax increases, the interchain distance decreases. When chloride ions
qe were (5.8 ± 0.1) × 10− 5 s− 1 and 5.75 ± 0.03 mg/g, respectively.
are present between the chains, the distance is minimal due to chloride
Comparable data were obtained in the assay without fabric softener or
being the smallest anion (7.38 Å). Substituting this chloride with a
detergent ((5.95 ± 0.06) × 10− 5 s− 1 and 6.19 ± 0.02 mg/g). Conse­
larger anion, such as Dye 12 or Dye 14, significantly increases the
quently, it can be inferred that typical quantities of fabric softener or
interchain distance to 7.46 Å and 7.43 Å, respectively, resulting in a
detergent in a household washing machine do not impact the dye
decrease in 2θmax from 15.00 to 14.84 and 14.89, respectively. These
adsorption process.
results also provide insights into how Dye 14 interacts with the material,
Likewise, when analysing the results obtained for the Crank-Dual
as it is a much larger molecule than Dye 12 (Fig. 5 g). However, both
model in the presence of fabric softener or detergent, one observes
dyes produce nearly the same chain separation. In fact, the separation
values of Ds, kf, qe, and Bi as (12.8 ± 0.3) × 10⁻13 m2/s, (2.86 ± 0.08)
between chains with Dye 14 is slightly less. Our hypothesis is that the
× 10− 9 m/s, 5.78 ± 0.03 mg/g, and 0.110 ± 0.006, respectively.
linear and elongated structure of Dye 14, along with the localization of
Similar results were obtained in the experiment conducted without
two charges at the ends of the molecule, facilitates its alignment parallel
fabric softener or detergent (9 ± 3) × 10⁻13 m2/s, (3.5 ± 0.1) × 10⁻9 m/
to the polymeric chains, rather than transversely. Assuming this, the
s, 6.15 ± 0.01 mg/g, and 0.21 ± 0.09). Like the pseudo-first-order
separation between chains would be less than that caused by Dye 12, as
model, it can be inferred that typical quantities of fabric softener or
reflected in the molecular sizes shown in Fig. 5 g and supported by the
detergent in a household washing machine do not significantly influence
experimental results.
the dye adsorption process when employing the Crank-Dual model.

13
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

a) b)

c) d)

e) F2 + Dye 14
F2 + Dye 12 2 MAX = 14.89
f) Dye 12
F2 + Dye 12
F2
F2
2 MAX = 14.84

2 MAX = 15.00
6000
Raman Intensity (a.u.)

5000
Intensity

4000 12 13 14 15 16 17 18 2000 2100 2200

3000
2000
1000
10 20 30 40 50 60 70 80
0 1000 2000 3000
2 Wavenumbers (cm-1)

g)

Fig. 5. Characterization of 10 mm diameter discs of F2, both before and after immersion in 3.5 mL of 50 ppm Dye 12 and Dye 14 solutions overnight. a) and b) SEM
images of F2 + dye 12 (1000x and 10,000x magnification, respectively; c) diagram of the Ion Exchange Mechanism Underpinning Dye Removal Using F2; d) SEM
images of F2, F2 +dye 12 and F2 +dye 14 (surface and cross-section); e) PXRD spectra of F2, F2 +dye 12 and F2 +dye 14 showing 2θMAX; f) RAMAN spectra of F2,
dye 12 and F2 +dye 12; g) The molecular sizes of dyes 12 and 14.

14
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

100
6
5
95

Dye Removal %
4 qe

qe (mg/g)
Dye rem. % 90
3
2
85
1
0 80
1 2 3 4 5
Cycle
6 1.00

0.75
4
qt, mg/g

qt/qe
0.50
2
0.25

0 0.00
0.00 4 4 4
2.50x10 5.00x10 7.50x10 1.00x10
5
0 2 4 6 8
t, s (Dst/l2)1/2

Fig. 6. a) Initial dye solution at 10 mg/L (left) and after the completion of the adsorption process (right), conducted using a 10 mm diameter F2 disk, in the presence
of 10 mL detergent and 10 mL fabric softener in tap water (3.5 mL). b) Reuse of a 10 mm diameter F2 disk. The graph depicts the absorbance of a 10 mg/L dye 14
solution in distilled water (3.5 mL) before and after introducing the F2 disk. Following the adsorption process, the disk is washed with a 1 mol/L aqueous solution of
NaOH for 12 h, renewing the washing solution twice. Subsequently, it is reprotonated with a 4 % HCl solution, and the adsorption process is initiated again. This
process was repeated 5 times. Kinetic study of the adsorption of dye 14 using a 10 mm F2 disk, fitting the pseudo-first-order (c) and Crank-Dual (d) models. The study
in distilled water is represented in green, while the study in tap water with detergent and fabric softener is represented in blue.

In the graphs of Fig. 6, it can be observed that the trend remains Furthermore, the desorption process damages neither the material
consistent both with and without detergents. Although the presence of nor the dye, which is recovered in an aqueous solution form as a sodium
detergents introduces some dispersion in the measurements, especially salt. Much of this merit lies in its dense (non-porous) nature, which
in the later points of the kinetics, the values of the constants were withstands the stress exerted on the material during these cycles,
examined (Figs. 4c and 4d), and considering the error, no significant enabling its recovery and reuse. Considering that in the textile industry,
differences were found between the calculated parameters in both pro­ 10 % of the dyes used are discharged with wastewater [2], these reus­
cesses. Therefore, it can be concluded that the adsorption capacities of ability properties represent an outstanding advantage from an industrial
the material are not affected by the presence of co-formulants in com­ and environmental point of view. Herein, the reuse of dyes would lower
mercial detergents and fabric softener formulations. their costs and applied amount, with a reduced environmental impact by
decreasing contamination.

3.9. Reusability study

3.10. Comparative study
The reusability of this material relies on the N,N-dimethylamino
functional group contained in the NNDA monomer, which has a theo­ The contamination by dyes is a real problem. While the literature
retical pKa of approximately 8. In fact, the material is only capable of provides numerous materials capable of extracting dyes from aqueous
interacting with anionic dyes when it has been previously protonated, media (see Table 3), most of these methods present certain in­
and the pH of the medium is below 8. Under these conditions, the N,N- conveniences or disadvantages. These drawbacks include being non-
dimethylamino functional group contained in the NNDA monomer is reusable [13,14,16,17,20,21,96], specific to a single dye [12–14,
protonated, thus possessing a formal positive charge and a chloride 16–20,23], causing dye degradation [13,14,18–21], requiring UV light
counteranion. This chloride anion can be exchanged for molecules of for operation or performance enhancement [13,16,18,21,90], or being
anionic dyes. However, if after adsorption the material is placed in an contingent on specific conditions such as phytoremediation [2], which,
basic aqueous medium, the N,N-dimethylamino functional group while initially a sustainable alternative, depends on plants growing time
deprotonates, loses its positive charge, and therefore, the electrostatic and conditions as well as big implant space. The alternative proposed in
interaction with the anionic dye disappears, leading to the release of the this study does not exhibit any of these disadvantages. Firstly, the ma­
dye into the medium. terial can be synthesized using low-cost commercial reagents. It does not
Thus, the material was subjected to 5 cycles of adsorption/desorp­ require UV light for operation or performance improvement. While not
tion, maintaining its properties and adsorption capacity throughout. biodegradable, its reusability cycles allow for both material reutilization
Fig. 6b illustrates absorbance graphs of dye solutions before and after and the recovery of 100 % of the adsorbed dye. Additionally, it can be
adsorption, accompanied by corresponding images of the material taken employed for more than 20 different dyes. The material remains unaf­
before adsorption and after desorption. These data demonstrate fected by laundry soaps, enabling its use in both industrial and domestic
consistent performance of the material across all cycles. settings.

15
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

Table 3
Comparative study of materials for dye extraction: analysis based on material type, dye removal efficiency, specific dyes utilized, and material reusability.
Technique/Process Material Dye removal Dye Reusabilit of the Ref
(%) material

Ultrafiltration Polyamide + Cetyl(hexadecyl) pyridinium chloride 73.50 Eosin Yes [12]

membrane Polysulfone + Titanium dioxide 97.00 Eosin Yellow No [13]
Polyvinyl alcohol + Zeoliticimidazolate framework (ZIF-8)/ 84.55 Malachite Green (MG) No [14]
chitosan
Cellulose + Graphene oxide > 90.00 Victoria blue B, Methyl Violet Probably* [15]
2B, Rhodamine6G
Polysulfone+ Sulfated nano-titania 90.40 Methylene blue (MB) No [16]
Chitosan + Carboxylated MWCNTs 80.00–90.00 MB, Methyl orange (MO) No [17]
Polysulfone poly + (N-vinylcaprolactam-TiO2-acrylic acid) 93.70 MB Partially [18]
Ion exchange Micro-sized ammonium phosphomolybdate (APM) 94.6 MB, MG, Methyl Red (MR) Yes [90]
Electrocoagulation Anode Fe 96.11 Brilliant green Yes [19]
Advanced oxidation H2O2, and Fe2+ 98.35 Acid Violet 49 No [96]
process 97.25 Acid Red 88
Photocatalytic ZnO 80 MB No [21]
degradation
Coagulation and Moringa oleifera Lam (MO) seeds and subsequently 100 Black 5 No [20]
flocculation ultrafiltration (UF) in TiO2-modified membranes
Phytoremediation Tagetes 59 Textile dye (no specific) Yes [2]
Aster amellus 50
Portulaca grandiflora patula 46
Gaillardia grandiflora 73
Adsorption Multiwall carbon nanotubes 98.7 Acid Scarlet 3 R Yes [22]
97.2 Auramine O
97.6 Basic Violt 2B crystal
Sol-gel immobilized polyurethane foams (sol-gel/PUF) 90.0–100 Eosin yellow Yes [23]
This work > 90 % More than 20 dyes Yes

*The authors explain that this type of material is reusable, but they do not specifically study it in the article.

4. Conclusions organisms, with the potential to disrupt ecosystems and harm aquatic
biodiversity. This paper discusses the development of a novel acrylic
In this work, we developed a novel smart polymer to address the material in film form, engineered to extract toxic anionic dyes. This
escalating environmental threat posed by industrial waste and the sig­ study directly contributes to mitigating the environmental impact
nificant volume of synthetic dyes discharged into water bodies. We associated with the fashion industry and the domestic use of textiles. It
successfully designed and prepared a reusable polyacrylic film with can be implemented on both an industrial and personal scale, thereby
remarkable efficiency in capturing a diverse spectrum of families of encouraging more sustainable practices and promoting collaborative
textile dyes. The polymeric film exhibits specific interactions with dyes citizen science efforts towards
extracting and colouring the material. The textile dye removal efficiency
of the film was high (up to >90 % dye removal efficiency) for anionic- Declaration of Competing Interest
state dyes at the working conditions with external diffusion being the
dominant factor influencing the process rate, as the adsorption of the The authors declare that they have no known competing financial
dye occurs on the material’s surface. Moreover, the presence of fabric interests or personal relationships that could have appeared to influence
detergent and softener does not affect the material adsorption capacity. the work reported in this paper.
Unlike other materials prepared for similar purposes, this membrane
showed durability, enhanced manageability, and good mechanical and Data availability
thermal properties, providing a practical solution for water dye decon­
tamination. These properties, including its ability to minimize waste No data was used for the research described in the article.
generation through reusability (at least 5 cycles of adsorption/desorp­
tion), and the capability of recovering 100 % of the adsorbed dye, make Acknowledgments
it highly suitable for practical applications in both industrial and do­
mestic settings, accessible even to non-specialists. Its versatility extends We gratefully acknowledge the financial support provided by all
to accommodating over 20 different dye types, while remaining unaf­ funders. This work was supported by the Regional Government of Cas­
fected by laundry detergents, further enhancing its usability. The study’s tilla y León (Junta de Castilla y León) and by the Ministry of Science and
findings hold promise for significantly mitigating water pollution Innovation MICIN and the European Union NextGenerationEU PRTR.
stemming from synthetic dyes, offering a comprehensive and sustain­ Author Saul Vallejos received grant BG22/00086 funded by Spanish
able solution that addresses both environmental concerns and practical Ministerio de Universidades. Author Marta Guembe-García received
usability. This inclusive approach, encompassing various dye types funding from the Spanish Ministerio de Universidades-European Union
commonly employed in the textile industry, underscores the material’s under the framework of NextGeneration EU RD 289/2021 for her Post-
adaptability and potential for widespread use in diverse industrial and Doc position. Author Jose Miguel García received grant PID2020-
household settings. Further research and development in this area could 113264RB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by
lead to broader adoption of such innovative materials, fostering sus­ “ERDF A way of making Europe”, and grant TED2021–129419B-C21
tainability in pollution management practices on a global scale. funded by MCIN/AEI/ 10.13039/501100011033 and by the “European
Union NextGenerationEU/PRTR”. The financial support provided by
Environmental implication Fondo Europeo de Desarrollo Regional-European Regional Development
Fund (FEDER, ERDF) and Regional Government of Castilla y León
Dyes released during laundry processes should be classified as -Consejería de Educación, Junta de Castilla y León- (BU025P23) is
"hazardous materials" owing to their significant toxicity towards aquatic gratefully acknowledged. Artur Valente and Gianluca Utzeri thank the

16
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

financial support from The Coimbra Chemistry Centre through Projects [19] Mariah, G.K., Pak, K.S., 2020. Removal of brilliant green dye from aqueous
solution by electrocoagulation using response surface methodology. Mater Today
UIDB/00313/2020 and UIDP/00313/2020 (FCT).
Proc 20, 488–492. [Link]
[20] Beluci, N. de C.L., Mateus, G.A.P., Miyashiro, C.S., Homem, N.C., Gomes, R.G.,
Supplementary material Fagundes-Klen, M.R., et al., 2019. Hybrid treatment of coagulation/flocculation
process followed by ultrafiltration in TIO 2 -modified membranes to improve the
removal of reactive black 5 dye. Sci Total Environ 664, 222–229. [Link]
Materials; characterization of the material; adsorption of dyes: more 10.1016/[Link].2019.01.199.
information about the kinetic, isotherm, and fluorescence study; and [21] Tabrizi Hafez Moghaddas, S.M., Elahi, B., Javanbakht, V., 2020. Biosynthesis of
permeation study. pure zinc oxide nanoparticles using Quince seed mucilage for photocatalytic dye
degradation. J Alloy Compd 821, 153519. [Link]
jallcom.2019.153519.
Open data [22] Shabaan, O.A., Jahin, H.S., Mohamed, G.G., 2020. Removal of anionic and cationic
dyes from wastewater by adsorption using multiwall carbon nanotubes. Arab J
Chem 13, 4797–4810. [Link]
Open Data is available at [Link] [23] Ghandourah, M.A., Orif, M.I., Al-Farawati, R.K., El-Shahawi, M.S., Abu-Zied, R.H.,
under the name "UBU-Polymers Research Group 13022024". 2023. Sol-Gel functionalized polyurethane foam-packed mini-column as an
efficient solid extractor for the rapid and ultra-trace detection of textile dyes in
water. Gels 9, 1–13. [Link]
Appendix A. Supporting information [24] Pandey, S., Makhado, E., Kim, S., Kang, M., 2023. Recent developments of
polysaccharide based superabsorbent nanocomposite for organic dye
Supplementary data associated with this article can be found in the contamination removal from wastewater — A review. Environ Res 217, 114909.
[Link]
online version at doi:10.1016/[Link].2024.135006. [25] Ibrahim, I.M., Radwan, M.A., Sadek, M.A., Darwish, S.A., Mostafa, N.Y., 2023.
Effect of electrostatic interactions on the dye removal behavior of different
References hydrogel based materials. Egypt J Chem 66, 257–261. [Link]
EJCHEM.2022.176630.7228.
[26] Bhattacharya, S., Shunmugam, R., 2020. Polymer based gels and their applications
[1] Cao, D., Niu, K., Yu, F., 2011. Economic analysis on pollution control for textile
in remediation of dyes from textile effluents. J Macromol Sci Part A 57, 906–926.
industry. Adv Mater Res 332–334, 1087–1092. [Link]
[Link]
[Link]/AMR.332-334.1087.
[27] Ruan, C., Ma, Y., Shi, G., He, C., Du, C., Jin, X., et al., 2022. Self-assembly cellulose
[2] Chandanshive, V.V., Kadam, S.K., Khandare, R.V., Kurade, M.B., Jeon, B.H.,
nanocrystals/SiO2 composite aerogel under freeze-drying: adsorption towards dye
Jadhav, J.P., et al., 2018. In situ phytoremediation of dyes from textile wastewater
contaminant. Appl Surf Sci 592, 153280. [Link]
using garden ornamental plants, effect on soil quality and plant growth.
APSUSC.2022.153280.
Chemosphere 210, 968–976. [Link]
[28] Utzeri, G., Guirado-Moreno, J.C., Cova, T.F.G.G., Pais, A.A.A.C., De Carvalho, L.A.
chemosphere.2018.07.064.
E.B., Ibeas, S., et al., 2024. Reusable and effective polyacrylic membranes for
[3] Ulson de Souza, S.M.A.G., Forgiarini, E., Ulson de Souza, A.A., 2007. Toxicity of
mecoprop and bentazon extraction. NPJ Clean Water 7. [Link]
textile dyes and their degradation by the enzyme horseradish peroxidase (HRP).
s41545-024-00328-3.
J Hazard Mater 147, 1073–1078. [Link]
[29] A.N. Alsulami, A.S. Alharthi, F.M. Alshareef, H. Alwael, E.A. Bahaidarah, M.
JHAZMAT.2007.06.003.
Oubaha, An innovative sol-gel functionalized polyurethane foams as dispersed
[4] Al-Tohamy, R., Ali, S.S., Li, F., Okasha, K.M., Mahmoud, Y.A.G., Elsamahy, T.,
solid phase microextractor ( d-µ SPME) for removal of selected textile dyes in water
et al., 2022. A critical review on the treatment of dye-containing wastewater:
prior to their spectrophotometric analysis: kinetics, thermodynamics, and
ecotoxicological and health concerns of textile dyes and possible remediation
reusability studies, (2022).
approaches for environmental safety. Ecotoxicol Environ Saf 231, 113160. https://
[30] Pandey, S., Son, N., Kang, M., 2022. Synergistic sorption performance of karaya
[Link]/10.1016/[Link].2021.113160.
gum crosslink poly(acrylamide-co-acrylonitrile) @ metal nanoparticle for organic
[5] M. Hassan, C.C.- Chemosphere, undefined 2018, A critical review on recent
pollutants. Int J Biol Macromol 210, 300–314. [Link]
advancements of the removal of reactive dyes from dyehouse effluent by ion-
IJBIOMAC.2022.05.019.
exchange adsorbents, ElsevierMM Hassan, C. CarrChemosphere, 2018•Elsevier (n.
[31] Makhado, E., Motshabi, B.R., Allouss, D., Ramohlola, K.E., Modibane, K.D.,
d.).
Hato, M.J., et al., 2022. Development of a ghatti gum/poly (acrylic acid)/TiO2
[6] Imran, M., Crowley, D.E., Khalid, A., Hussain, S., Mumtaz, M.W., Arshad, M., 2015.
hydrogel nanocomposite for malachite green adsorption from aqueous media:
Microbial biotechnology for decolorization of textile wastewaters. Rev Environ Sci
statistical optimization using response surface methodology. Chemosphere 306,
Biotechnol 14, 73–92. [Link]
135524. [Link]
[7] Lellis, B., Fávaro-Polonio, C.Z., Pamphile, J.A., Polonio, J.C., 2019. Effects of
[32] Bhattacharya, S., Shunmugam, R., 2020. Polymer based gels and their applications
textile dyes on health and the environment and bioremediation potential of living
in remediation of dyes from textile effluents. J Macromol Sci Part A 57, 906–926.
organisms. Biotechnol Res Innov 3, 275–290. [Link]
[Link]
BIORI.2019.09.001.
[33] Zhu, H., Chen, S., Luo, Y., 2023. Adsorption mechanisms of hydrogels for heavy
[8] Maheshwari, K., Agrawal, M., Gupta, A.B., 2021. Dye Pollut Water Wastewater BT -
metal and organic dyes removal: a short review. J Agric Food Res 12, 100552.
Nov Mater Dye-Contain Wastewater Treat.
[Link]
[9] Clark, M., 2011. Handb Text Ind dyeing: Princ, Process Types Dyes.
[34] Hu, X.S., Liang, R., Sun, G., 2018. Super-adsorbent hydrogel for removal of
[10] Christie, R., 2007. Environ Asp Text dyeing. [Link]
methylene blue dye from aqueous solution. J Mater Chem A 6, 17612–17624.
9781845693091.
[Link]
[11] Hunger, K., 2007. Ind dyes: Chem, Prop, Appl.
[35] Shalla, A.H., Bhat, M.A., Yaseen, Z., 2018. Hydrogels for removal of recalcitrant
[12] Purkait, M.K., DasGupta, S., De, S., 2004. Removal of dye from wastewater using
organic dyes: a conceptual overview. J Environ Chem Eng 6, 5938–5949. https://
micellar-enhanced ultrafiltration and recovery of surfactant. Sep Purif Technol 37,
[Link]/10.1016/[Link].2018.08.063.
81–92. [Link]
[36] Vallejos, S., Muñoz, A., García, F.C., Serna, F., Ibeas, S., García, J.M., 2012.
[13] Kuvarega, A.T., Khumalo, N., Dlamini, D., Mamba, B.B., 2018. Polysulfone/N,Pd
Methacrylate copolymers with pendant piperazinedione-sensing motifs as
co-doped TiO2 composite membranes for photocatalytic dye degradation. Sep Purif
fluorescent chemosensory materials for the detection of Cr(VI) in aqueous media.
Technol 191, 122–133. [Link]
J Hazard Mater 227–228, 480–483. [Link]
[14] Khajavian, M., Salehi, E., Vatanpour, V., 2020. Chitosan/polyvinyl alcohol thin
jhazmat.2012.05.047.
membrane adsorbents modified with zeolitic imidazolate framework (ZIF-8)
[37] Pascual, B.S., Vallejos, S., Reglero Ruiz, J.A., Bertolín, J.C., Represa, C., García, F.
nanostructures: batch adsorption and optimization. Sep Purif Technol 241,
C., et al., 2019. Easy and inexpensive method for the visual and electronic
116759. [Link]
detection of oxidants in air by using vinylic films with embedded aniline. J Hazard
[15] Liu, P., Zhu, C., Mathew, A.P., 2019. Mechanically robust high flux graphene oxide
Mater 364, 238–243. [Link]
- nanocellulose membranes for dye removal from water. J Hazard Mater 371,
[38] Vallejos, S., Muñoz, A., Ibeas, S., Serna, F., García, F.C., García, J.M., 2014.
484–493. [Link]
Selective and sensitive detection of aluminium ions in water via fluorescence “turn-
[16] Pereira, V.R., Isloor, A.M., Bhat, U.K., Ismail, A.F., Obaid, A., Fun, H.K., 2015.
on” with both solid and water soluble sensory polymer substrates. J Hazard Mater
Preparation and performance studies of polysulfone-sulfated nano-titania (S-TiO2)
276, 52–57. [Link]
nanofiltration membranes for dye removal. RSC Adv 5, 53874–53885. [Link]
[39] Bustamante, S.E., Vallejos, S., Pascual-Portal, B.S., Muñoz, A., Mendia, A., Rivas, B.
org/10.1039/c5ra07994b.
L., et al., 2019. Polymer films containing chemically anchored diazonium salts with
[17] Shi, J., Wu, T., Teng, K., Wang, W., Shan, M., Xu, Z., et al., 2016. Simultaneous
long-term stability as colorimetric sensors. J Hazard Mater 365, 725–732. https://
electrospinning and spraying toward branch-like nanofibrous membranes
[Link]/10.1016/[Link].2018.11.066.
functionalised with carboxylated MWCNTs for dye removal. Mater Lett 166,
[40] García Pérez, J.M., García García, F.C., Vallejos, S., Trigo, M., Reglero-Ruiz, J.A.,
26–29. [Link]
2022. Smart polymers. Principles and Applications. De Gruyter,, Boston. https://
[18] Singh, R., Sinha, M.K., Purkait, M.K., 2020. Stimuli responsive mixed matrix
[Link]/10.1515/9781501522468.
polysulfone ultrafiltration membrane for humic acid and photocatalytic dye
[41] Vallejos, S., Muñoz, A., Ibeas, S., Serna, F., García, F.C., García, J.M., 2013. Solid
removal applications. Sep Purif Technol 250, 117247. [Link]
sensory polymer substrates for the quantification of iron in blood, wine and water
seppur.2020.117247.

17
M. Guembe-García et al. Journal of Hazardous Materials 476 (2024) 135006

by a scalable RGB technique. J Mater Chem A 1, 15435–15441. [Link] [71] MolGpKa, (n.d.).
10.1039/c3ta12703f. [72] Vyavahare, G., Gurav, R., Patil, R., Sutar, S., Jadhav, P., Patil, D., et al., 2021.
[42] Guembe-García, M., Peredo-Guzmán, P.D., Santaolalla-García, V., Moradillo- Sorption of brilliant green dye using soybean straw-derived biochar:
Renuncio, N., Ibeas, S., Mendía, A., et al., 2020. Why is the sensory response of characterization, kinetics, thermodynamics and toxicity studies. Environ Geochem
organic probes within a polymer film different in solution and in the solid-state? Health 43, 2913–2926. [Link]
Evidence and application to the detection of amino acids in human chronic 6.
wounds. Polym (Basel) 12. [Link] [73] Abbas, M., 2020. Removal of brilliant green (BG) by activated carbon derived from
[43] Do, D.D., 1998. Adsorption analysis: equilibria and kinetics. Chem Eng 2, 913. medlar nucleus (ACMN) – Kinetic, isotherms and thermodynamic aspects of
[44] Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and adsorption. Adsorpt Sci Technol 38, 464–482. [Link]
platinum. J Am Chem Soc 40, 1361–1403. [Link] 0263617420957829/ASSET/IMAGES/LARGE/10.1177_0263617420957829-FIG9.
JA02242A004/ASSET/[Link].PNG_V03. JPEG.
[45] Freundlich, H., 1907. Over the adsorption in solution. J Phys Chem 57U, 385–470. [74] Pearce, J., 1994. Studies of any toxicological effects of Prussian blue compounds in
[Link] mammals—A review. Food Chem Toxicol 32, 577–582. [Link]
[46] Valente, A.J.M., Polishchuk, A.Y., Lobo, V.M.M., Burrows, H.D., 2000. Transport 0278-6915(94)90116-3.
properties of concentrated aqueous sodium dodecyl sulfate solutions in polymer [75] Steingruber, E., 2004. Indigo and indigo colorants. Ullmann’s Encycl Ind Chem.
membranes derived from cellulose esters. Langmuir 16, 6475–6479. [Link] [Link]
org/10.1021/LA000286L/ASSET/IMAGES/MEDIUM/[Link]. [76] Ristea, M.E., Zarnescu, O., 2023. Indigo carmine: between necessity and concern.
[47] Yadav, H.K.S., Raizaday, A., 2016. Inorganic nanobiomaterials for medical J Xenobiotics 13, 509–528. [Link]
imaging. Nanobiomater Med Imaging Appl Nanobiomater 365–401. [Link] [77] Malik, P.K., 2003. Use of activated carbons prepared from sawdust and rice-husk
org/10.1016/B978-0-323-41736-5.00012-1. for adsorption of acid dyes: a case study of Acid Yellow 36. Dye Pigment 56,
[48] Tuzimski, T., 2015. Advanced spectroscopic detectors for identification and 239–249. [Link]
quantification. UV–Visible, Fluoresc, Infrared Spectrosc, Instrum Thin-Layer [78] Bistas, E., Sanghavi, D.K., 2023. Methylene Blue. Hist Mod Clin Toxicol 231–241.
Chromatogr 239–248. [Link] [Link]
[49] Niwa, M., 2019. Derivatization and labeling techniques. Encycl Anal Sci 210–213. [79] Sousa, H.R., Silva, L.S., Sousa, P.A.A., Sousa, R.R.M., Fonseca, M.G., Osajima, J.A.,
[Link] et al., 2019. Evaluation of methylene blue removal by plasma activated
[50] Myers, D.N., 2019. Innovations in monitoring with water-quality sensors with case palygorskites. J Mater Res Technol 8, 5432–5442. [Link]
studies on floods, hurricanes, and harmful algal blooms. Sep Sci Technol 11, JMRT.2019.09.011.
219–283. [Link] [80] Merck KGaA, Pinacyanol chloride, (n.d.).
[51] Christie, R.M., 2011. Fluorescent dyes. Handb Text Ind Dye Princ Process Types [81] Shapovalov, S.A., 2022. The first century of successful applications of pinacyanol:
Dye 1, 562–587. [Link] some noteworthy results. Colorants 1, 165–192. [Link]
[52] Singh, V., Lalitha, K., Maheswari, C.U., Sridharan, V., Pradhan, D., Batra, S., et al., colorants1020011.
2024. Remediation of dyes using supramolecular material derived from [82] Garrudo-Guirado, M.I., Blanco-Flores, A., Toledo-Jaldin, H.P., Sánchez-
carbohydrate based π-gelator using the bottom-up assembly approach. ACS Omega Mendieta, V., Vilchis-Néstor, A.R., 2018. Reuse of sustainable materials for xylenol
9, 5695–5704. [Link] orange dye and copper (II) ion ammoniacal removal. J Environ Manag 206,
LARGE/AO3C08179_0007.JPEG. 920–928. [Link]
[53] Pablos, J.L., Vallejos, S., Ibeas, S., Muñoz, A., Serna, F., García, F.C., et al., 2015. [83] Mani, S., Bharagava, R.N., 2016. Exposure to crystal violet, its toxic, genotoxic and
Acrylic polymers with pendant phenylboronic acid moieties as “turn-off” and carcinogenic effects on environment and its degradation and detoxification for
“turn-on” fluorescence solid sensors for detection of dopamine, glucose, and environmental safety. in: Rev. Environ. Contam. Toxicol. Springer,, Cham,
fructose in water. ACS Macro Lett 4, 979–983. [Link] pp. 71–104. [Link]
ACSMACROLETT.5B00465/SUPPL_FILE/MZ5B00465_SI_001.PDF. [84] Robens, J.F., Dill, G.S., Ward, J.M., Joiner, J.R., Griesemer, R.A., Douglas, J.F.,
[54] Guirado-Moreno, J.C., Carreira-Barral, I., Ibeas, S., García, J.M., Granès, D., 1980. Thirteen-week subchronic toxicity studies of Direct Blue 6, Direct Black 38,
Marchet, N., et al., 2023. Democratization of copper analysis in grape must and Direct Brown 95 dyes. Toxicol Appl Pharmacol 54, 431–442. [Link]
following a polymer-based lab-on-a-chip approach. ACS Appl Mater Interfaces 15, 10.1016/0041-008X(80)90170-2.
16055–16062. [Link] [85] Pan, H., Feng, J., Cerniglia, C.E., Chen, H., 2011. Effects of Orange II and Sudan III
[55] Vallejo-García, J.L., Arnaiz, A., Busto, M.D., García, J.M., Vallejos, S., 2023. Film- azo dyes and their metabolites on Staphylococcus aureus. J Ind Microbiol
shaped reusable smart polymer to produce lactose-free milk by simple immersion. Biotechnol 38, 1729–1738. [Link]
Eur Polym J 200, 112495. [Link] [86] Khayyat, L.I., Essawy, A.E., Sorour, J.M., Soffar, A., 2018. Sunset Yellow and Allura
[56] Mordant Blue 29 | C23H13Cl2Na3O9S | CID 54682456 - PubChem, (n.d.). Red modulate Bcl2 and COX2 expression levels and confer oxidative stress-
[57] Pytlakowska, K., Zerzucha, P., Czoik, R., 2011. Influence of mixed cationic- mediated renal and hepatic toxicity in male rats. PeerJ 6. [Link]
nonionic surfactant systems on the spectral properties of C.I. Mordant Blue 29 and PEERJ.5689.
its complexes with Iron(III). Anal Sci 27, 555–560. [Link] [87] Hashem, E.Y., Saleh, M.S., Al-Salahi, N.O.A., Youssef, A.K., 2017. Advanced
analsci.27.555. spectrophotometric analysis of sunset yellow dye E110 in commercial food
[58] Mordant Blue 3 | 3564–18-9, (n.d.). samples. Food Anal Methods 10, 865–875. [Link]
[59] Fagan, C., Kiernan, J.A., 2020. Certification procedures used by the biological stain 0630-3.
commission for eriochrome cyanine R (C.I. 43820, Mordant blue 3). Biotech [88] John, E., Ashitha, V.C., 2010. Acute toxic effects of the textile dye, acid blue 113,
Histochem 95, 396–402. [Link] on the biochemicals of teleost fish, Tilapia mossambica (Peteres) (Pisces:Teleostei,
[60] Poulios, I., Micropoulou, E., Panou, R., Kostopoulou, E., 2003. Photooxidation of Cichlidae). Biosci. Biotechnol. Res. Asia. 7, 395–400.
eosin Y in the presence of semiconducting oxides. Appl Catal B Environ 41, [89] Scientific Committee on Consumer Safety, Revision of the opinion on Acid Orange
345–355. [Link] 7 - SCCS/1536/14, 2014. [Link]
[61] HanOfAciInd, (n.d.). [90] Joseph, J., Radhakrishnan, R.C., Johnson, J.K., Joy, S.P., Thomas, J., 2020. Ion-
[62] Christie, R.M., 2011. Fluorescent dyes. in: Handb. Text. Ind. Dye. Elsevier,, exchange mediated removal of cationic dye-stuffs from water using ammonium
pp. 562–587. [Link] phosphomolybdate. Mater Chem Phys 242, 122488. [Link]
[63] Kumar, A., Raorane, C.J., Syed, A., Bahkali, A.H., Elgorban, A.M., Raj, V., et al., matchemphys.2019.122488.
2023. Synthesis of TiO2, TiO2/PAni, TiO2/PAni/GO nanocomposites and [91] Sun, X., Chen, J.H., Su, Z., Huang, Y., Dong, X., 2016. Highly effective removal of
photodegradation of anionic dyes Rose Bengal and thymol blue in visible light. Cu(II) by a novel 3-aminopropyltriethoxysilane functionalized polyethyleneimine/
Environ Res 216, 114741. [Link] sodium alginate porous membrane adsorbent. Chem Eng J 290, 1–11. [Link]
[64] Reshetnyak, E.A., Rysukhina, A.I., Kamneva, N.N., Goloviznina, K.V., 2017. org/10.1016/[Link].2015.12.106.
Influence of tetrabutylammonium bromide and sodium bromide on acid-base [92] Dávila-Guzman, N.E., Cerino-Córdova, F.J., Diaz-Flores, P.E., Rangel-Mendez, J.R.,
properties of thymol blue in water-ethanol medium. Period Karazin Ua 29, 46–52. Sánchez-González, M.N., Soto-Regalado, E., 2012. Equilibrium and kinetic studies
[Link] of ferulic acid adsorption by Amberlite XAD-16. Chem Eng J 183, 112–116.
[65] Skjolding, L.M., Jørgensen, L. v G., Dyhr, K.S., Köppl, C.J., McKnight, U.S., Bauer- [Link]
Gottwein, P., et al., 2021. Assessing the aquatic toxicity and environmental safety [93] Illanes, C.O., Ochoa, N.A., Marchese, J., 2009. Kinetic sorption of Cr(VI) into
of tracer compounds Rhodamine B and Rhodamine WT. Water Res 197, 117109. solvent impregnated porous microspheres. Chem Eng J 136, 92–98. [Link]
[Link] org/10.1016/[Link].2007.03.008.
[66] Zamouche, M., Hamdaoui, O., 2012. Sorption of Rhodamine B by Cedar Cone: [94] Üzüm, G., Özmen, B.A., Akgül, E.T., Yavuz, E., 2022. Emulsion-templated porous
effect of Ph and ionic strength. Energy Procedia 18, 1228–1239. [Link] polymers for efficient dye removal. ACS Omega 7, 16127–16140. [Link]
10.1016/[Link].2012.05.138. 10.1021/ACSOMEGA.2C01472/ASSET/IMAGES/LARGE/AO2C01472_0011.JPEG.
[67] EPA, 2019. Provisional peer reviewed toxicity values for acenaphthylene. Public [95] Vallejos, S., Reglero, J.A., García, F.C., García, J.M., 2017. Direct visual detection
Health,. and quantification of mercury in fresh fish meat using facilely prepared polymeric
[68] Sabnis, R.W., 2010. Handbook of biological dyes and stains: Synthesis and sensory labels. J Mater Chem A 5, 13710–13716. [Link]
industrial applications. John Wiley & Sons,. c7ta03902f.
[69] Siddiqui, S.I., Allehyani, E.S., Al-Harbi, S.A., Hasan, Z., Abomuti, M.A., Rajor, H.K., [96] Deshannavar, U.B., Kumar Singa, P., Gaonkar, D., Gayathri, A., Patil, A., Malade, L.
et al., 2023. Investigation of congo red toxicity towards different living organisms: V., 2020. Removal of acid violet 49 and acid red 88 dyes from aqueous solutions
a review. Processes 11, 807. [Link] using advanced oxidation process. Mater Today Proc 24, 1011–1019. [Link]
[70] Thioflavin T. | C17H19ClN2S | CID 16953 - PubChem, (n.d.). org/10.1016/[Link].2020.04.414.

18