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Molecular Imprinting for
Nanosensors and Other
Sensing Applications

Edited by

Adil Denizli
Hacettepe University, Department of Chemistry,
Beytepe, Ankara, Turkey
Elsevier
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Contributors

Sinan Akgöl, Biochemistry Department, Faculty of Science, Ege University, Bornova,

Izmir, Turkey
Semra Akgönüllü, Hacettepe University, Department of Chemistry, Beytepe, Ankara,
Turkey
Zeynep Altintas, Institute of Chemistry, Technical University of Berlin, Berlin, Germany
Elif Burcu Aydın, Namık Kemal University, Scientific and Technological Research
Center, Tekirdağ-Turkey
Muhammed Aydın, Namık Kemal University, Scientific and Technological Research
Center, Tekirdağ-Turkey
Monireh Bakhshpour, Hacettepe University, Department of Chemistry, Beytepe,
Ankara, Turkey
Nilay Bereli, Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey
M. Iqbal Bhanger, International Center for Chemical and Biological Sciences, H.E.J.
Research Institute of Chemistry, University of Karachi, Pakistan
Nura Brimo, Biomedical Engineering Department, Başkent University, Ankara, Turkey
Duygu Çimen, Hacettepe University, Department of Chemistry, Beytepe, Ankara,
Turkey
Adil Denizli, Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey
Faezeh Ghorbanizamani, Biochemistry Department, Faculty of Science, Ege University,
Bornova, Izmir, Turkey
Emur Henden, Department of Chemistry, Faculty of Science, University of Ege,
Bornova, İzmir, Turkey (Retd)
Neslihan Idil, Department of Biology, Biotechnology Division, Hacettepe University,
Ankara, Turkey
Raif İlktaç, Application and Research Center for Testing and Analysis, University of
Ege, Bornova, İzmir, Turkey
Rüstem Keçili, Anadolu University, Yunus Emre Vocational School of Health Services,
Pharmacy Services Programme, Eskişehir, Turkey
Yiğit Kozalı, Biochemistry Department, Faculty of Science, Ege University, Bornova,
Izmir, Turkey
Kevser Kusat, Turkish Ministry of Health, Turkish Medicines & Medical Devices
Agency, Turkey

xi
xii Contributors

Sakib Hussain Laghari, National Centre of Excellence in Analytical Chemistry,

University of Sindh, Jamshoro, Pakistan
Bo Mattiasson, Devision of Biotechnology, Lund University, Lund, Sweden; Indienz
AB, Annebergs Gård, Billeberga, Lund, Sweden
Najma Memon, National Centre of Excellence in Analytical Chemistry, University of
Sindh, Jamshoro, Pakistan
Arben Merkoçi, Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC
and BIS, Bellaterra, Barcelona, Spain; Catalan Institution for Research and Advanced
Studies (ICREA), Barcelona, Spain
Hichem Moulahoum, Biochemistry Department, Faculty of Science, Ege University,
Bornova, Izmir, Turkey
Işık Perçin, Department of Biology, Molecular Biology Division, Hacettepe University,
Ankara, Turkey
Merve Asena Özbek, Hacettepe University, Department of Chemistry, Beytepe, Ankara,
Turkey
Erdoğan Özgür, Advanced Technologies Application and Research Center, Hacettepe
University, Ankara, Turkey; Department of Chemistry, Faculty of Science, Hacettepe
University, Ankara, Turkey
Muqsit Pirzada, Institute of Chemistry, Technical University of Berlin, Berlin, Germany
Tahira Qureshi, National Centre of Excellence in Analytical Chemistry, University of
Sindh, Jamshoro, Pakistan
Esma Sari, Vocational School of Health Services, Medical Laboratory Techniques,
Yüksek ̇Ihtisas University, Ankara, Turkey
Yeşeren Saylan, Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey
Dilek Çökeliler Serdaroğlu, Biomedical Engineering Department, Başkent University,
Ankara, Turkey
Buse Sevgi, Biochemistry Department, Faculty of Science, Ege University, Bornova,
Izmir, Turkey
Mustafa Kemal Sezgintürk, Çanakkale Onsekiz Mart University, Faculty of
Engineering, Bioengineering Department, Çanakkale-Turkey
Muhammad Raza Shah, International Center for Chemical and Biological Sciences,
H.E.J. Research Institute of Chemistry, University of Karachi, Pakistan
Suna Timur, Biochemistry Department, Faculty of Science, Ege University, Bornova,
Izmir, Turkey; Central Research Testing and Analysis Laboratory Research and
Application Center, Ege University, Bornova, Izmir, Turkey
Aykut Arif Topçu, Aksaray University, Medical Laboratory Program, Vocational School
of Health Service, Aksaray, Turkey
Recep Üzek, Department of Chemistry, Faculty of Science, Hacettepe University,
Ankara, Turkey
Handan Yavuz, Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey
Figen Zihnioglu, Biochemistry Department, Faculty of Science, Ege University,
Bornova, Izmir, Turkey
About the author

Prof. Dr. Adil Denizli was born in 1962 in

Ankara. In 1985, he graduated from the De-
partment of Chemical Engineering at Hacette-
pe University, Ankara, Turkey. He received
his Master of Science (MSc) degree with the
thesis on “Controlled Delivery of Anticancer
Drugs from Polymeric Matrices” in 1986 at
Hacettepe University. He got his Doctor of
Philosophy (PhD) degree with the thesis on
“Specific Sorbents for Hemoperfusion” in
1992 at Hacettepe University. He became an
Associate Professor of Chemical Technologies
in 1994. Dr. Denizli is a Professor in the De-
partment of Chemistry, Hacettepe University
since 2000. Dr. Denizli has written over 600 articles and 40 book chapters. He
published more than 150 popular science articles. He has 4 patents. He is one
of the most-cited scientists in the chemistry and engineering field (over 23,000
citations, h-index of 77). He served as an associated member of the Turkish
Academy of Sciences from 1999 to 2007, and as a full member since 2007.
Dr. Denizli has received “The Scientific and Technological Research Council of
Turkey (TUBITAK) Encouragement Award” in 1998 for his studies on “Bio-
medicine, Biotechnology and Environmental Applications of Polymeric Matri-
ces.” He also received the TUBITAK Science Award and Basic Science Award
of Popular Science Magazine in 2006. He was elected as the most publishing
scientist of Hacettepe University between 1995 and 2005 by COMSTECH. He
is an editor of the “Protein Chromatography and New Generation Polymeric
Systems” (2010) and “Affinity Based Biosensors I and II” (2015–16) books
and the writer of “Bioseparation and Polymeric Carriers” (Turkish Academy of
Sciences Press, 2011) and, Turkish translation editor of “Stryer’s Biochemis-
try” (Palme Press, 2014) and “Principles of Chemistry: A Molecular Approach”
(Nobel Press, 2015) books. He is also a chief editor of 15 books of 50th Year of
Hacettepe University. He is an Editorial Board Member of 39 journals. He has
supervised 62 MSc and 47 PhD theses, 5 post-doctoral, and 5 visiting research-
ers up to now. He organized 20 “Chromatography Congress” and 14 “Affinity
Techniques” congress, 6 Graduate Summer Schools, and 4 Graduate Course.

xiii
xiv About the author

His main research fields are molecular imprinting technologies, affinity chro-
matography, biosensors based on synthetic receptor technology, production
of polymers have different surface and bulk properties, shape and geometries,
application of these polymers in medicine and biochemistry. He is married to
Dr. Fatma Denizli and has one child (Alp Denizli).
Preface

I welcome the publication of this book on molecular imprinted nanosensors for

sensing applications. Recently, nanosensors have been used for enormous ap-
plications from environmental monitoring, pharmaceutical analysis, biomarkers
detection, and food quality detection to defense and security fields. The devel-
opment and progress of the nanosensors encompass from electronic materials to
nanotechnology and chemistry. A huge body of information on different types
of nanosensors and applications is already existed and continuing to publish
to create more reliable, selective, sensitive, and economic nanosensors for a
variety of applications although a complicated and time-consuming production
procedure. The development of the molecular imprinting technique provided a
promising opening to solve selectivity and economy problems.
This book contains 14 chapters, which cover different types of nanosensors
prepared by combining nanotechnology and molecular imprinting technology.
In the opening chapter, fundamentals of molecular imprinting method, prepara-
tion methods of molecularly imprinted polymers, applications of molecularly
imprinted polymers based systems, and prospects are reviewed. In Chapter 2,
recent advances in the fabrication of novel molecular imprinting-based smart
nanosensors toward pharmaceutical compounds are highlighted. The develop-
ment strategies and techniques for these nanosensors, their potential for the ef-
ficient target recognition of the pharmaceutical compounds in complex matrices
are also discussed with future perspectives. Theranostics applications of molecu-
lar imprinted polymer-based nanoprobes are evaluated in Chapter 3. An overview
of the synthesis methods was given with a comprehensive highlight of molecular
imprinting-based probing applications. The next chapter, Chapter 4, concentrated
on the detection of metal ions with imprinted nanosensors with recent articles.
Chapter 5 includes molecularly imprinted polymer-based optical nanosensors
for pesticide detection which cause serious environmental and health problems
over the accepted levels. Chapter 6 summarizes the performance and analytical
features of the molecularly imprinted polymer-based nanosensors for different
types of analytes. In Chapter 7, overview of the classification and basic proper-
ties of nano-molecularly imprinted polymers for different types of nanosen-
sors can be found. Electrochemical-based nano-molecularly imprinted polymer
sensors for the detection of proteins, hormones, pesticides, and neurotransmit-
ters are reviewed in Chapter 8. The marked sensing capability of quantum dots
serves new opportunities for the generation of selective and sensitive fluoro-
phores with up to femtomolar level of optical detection. This relatively novel

xv
xvi Preface

use of quantum dots coated imprinted probes is given in Chapter 9. Molecularly

imprinted polymer-based nanosensors for the detection of microorganisms,
which were prepared by different imprinting strategies for the different sensing
platforms were combined in Chapter 10. The next chapter, Chapter 11, gives
details about the application of molecularly imprinted fluorescence nanosen-
sors based on the four types of fluorophores. Another type of analyte of interest
in molecularly imprinted polymer nanosensors is allergens. The efforts on the
preparation of these types of nanosensors are summarized in Chapter 12. An
elucidatory comparison of immunosensing strategies with molecularly imprint-
ed polymer-based mass sensitive nanosensors is given in Chapter 13. Finally,
a challenging task of template removal, which directly affects the performance
of molecularly imprinted polymer materials, is given in detail in Chapter 14.
I believe this book provides an overview and highlights some of the recent
research including the extensively studied topics.
I would like to deeply thank Elsevier and all the contributors to the genera-
tion of this book possible. I hope this book will reach a broad range of readers.
Chapter 1

Fundamentals and Applications

of Molecularly Imprinted
Systems
Yeşeren Saylan and Adil Denizli∗
Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey
∗
Corresponding author

1 Introduction
The history of molecular imprinting is started from the introduction of the
conjunction with silica particles in 1931 to organic polymers in 1972 [1].
Although molecular imprinting methods continue to evolve with renewal
in every study, the concept itself has a long history. At the beginning of
the 1970s, Wulff and Klotz independently published their studies about the
preparation of organic polymers with predetermined ligand selectivity prop-
erties [2,3]. After then, many of the researchers from all over the world used
the fascinating features and allow the prospering of this method. The mo-
lecular imprinting method principally depends on the determination interac-
tion reaction that happens at around the target (template molecule) [4]. Tem-
plate molecules are presented during polymerization and recognized by the
resultant polymeric matrix. Molecularly imprinted polymer-based systems
can be synthesized by the different types of template molecules, functional
monomers, cross-linkers, initiators, and solvents combinations for several
applications [5–8]. Besides, the quality of the molecularly imprinted poly-
mer can be changed the monomer mixtures, the experimental conditions,
the interaction mechanisms, and so on [9–12]. The molecularly imprinted
polymers have a lot of important characteristics such as easy preparation,
reusability and cost-friendly, high stability, high affinity, and high selectiv-
ity towards template molecules. According to these properties, the molecu-
larly imprinted polymers can be employed in diverse fields such as sensors,
chromatography, microfluidics, computational modeling systems, and so on
[13–18].

Molecular Imprinting for Nanosensors and Other Sensing Applications.

http://dx.doi.org/10.1016/B978-0-12-822117-4.00001-0 1
Copyright © 2021 Elsevier Inc. All rights reserved.
2 Molecular Imprinting for Nanosensors and Other Sensing Applications

FIGURE 1.1 Steps of molecularly imprinted polymers preparation.

2 Fundamentals of molecular imprinting method

The selected template molecules interact with the suitable functional mono-
mers, cross-linkers, initiators, and solvent mixtures for the preparation of the
molecularly imprinted polymers (Fig. 1.1). At first, the template molecule binds
to the functional monomer and then the obtained pre-complex is copolymerized
in the presence of a cross-linker, initiator, and solvent that create an imprinted
polymeric matrix. Following the removal of the template molecule, specific
cavities are appeared for using recognition, adsorption, separation, and detec-
tion applications [19,20].

3 Preparation methods of molecularly imprinted polymers

There are some key elements (template molecules, functional monomers, cross-
linkers, initiators, and solvents) for the preparation of molecularly imprinted
polymers. The template selection is the most important parameter for all mo-
lecular imprinting methods and applications due to the process are occurred
around the selected templates with crosslinking functional monomers [21,22].
At the end of the polymerization, the template molecule is removed from the
polymeric matrix with suitable desorption agents and elution process. The mo-
lecularly imprinted polymers have template specific binding sites and are ready
to rebind template molecules over and over [23].
The functional monomers are especially needed for a specific interaction with
the template molecule in the binding sites of the polymeric matrix. So, an opti-
mum ratio of the template molecule and functional monomer preparation to obtain
pre-complex is a crucial step. Also, it is an important parameter to figure out the
suitable ratios of the functional monomers to template molecules [24]. In the
polymerization step, the cross-linkers are used for binding the polymeric chains.
 Fundamentals and Applications of Molecularly Imprinted Systems Chapter | 1 3

They play critical roles to determine the properties of imprinted polymers and to
create a rigid polymeric matrix by comprising recognition sides. The high per-
centages of cross-linkers are required to acquire the structural unity of the binding
sites of the polymeric matrix [25]. The initiators are chemical types that affect the
functional monomer to create an intermediate compound by linking a large num-
ber of other functional monomers into a polymeric matrix. The choice of initiators
depends on the type of polymerization and template molecules [26]. Solvents are
employed for increasing or decreasing the polymeric chains of imprinted poly-
mers. The crucial role is that the solvent participates as a porogen maker [27].

3.1 Bulk imprinting

In the bulk imprinting, the template molecules are imprinted completely in
the polymeric matrix and they require to be eluted from the matrix. Then, the
imprinted bulk polymer is generally crushed mechanically and fractionated to
obtain small materials from these bulk polymers [28–30]. In most cases, the
researchers preferred the bulk imprinting to imprinted small molecules because
of the fast and reversible recognition and release of the template molecule [31].
This method has some disadvantages in the case of macromolecules imprinting.
During the polymerization, the conformational durability of a macromolecule
is a big issue [32]. Furthermore, when the huge imprinted sites are formed,
small molecules can also bind to these binding sites that cause cross-reactivity
and decreased selectivity [33]. Because of the dense property of bulk imprinted
polymers, template molecules are attached in the polymeric matrix that brings
about the limitation or no entry to interact with the binding sites. This low ac-
cessibility causes long response times, deviation, and poor regeneration prob-
lems [34]. These drawbacks can overcome with the other imprinting methods.

3.2 Surface imprinting

In the surface imprinting, the mass transfer resistance is reduced in especially
macromolecule imprinted [35]. Recently, the surface imprinting method has
achieved great attention in various applications as a significant alternative to
imprint macromolecules [36–38]. This method can be classified into the sub-
methods including top-down and bottom-up that depends on the polymerization
place. In the top-down method, the template molecule binds a support molecule,
which is removed after formation. So, the interaction sides on the polymeric
matrix surface retreat [39]. In the bottom-up method, the support molecule uses
to immobilize the template molecule to increase the imprinted binding sites and
remove the template molecule completely [40].

3.3 Epitope imprinting

In the epitope imprinting, stronger and more specific interactions can be ac-
quired by employing a region of a macromolecule [41]. A small part of the
4 Molecular Imprinting for Nanosensors and Other Sensing Applications

macromolecule could recognize a whole macromolecule. So, non-specific in-

teractions can be decreased and the affinity can be increased because of various
superiorities [42]. The molecularly imprinted polymers can identify the tem-
plate molecule. Thermodynamic conditions propose to manage of usage a non-
rigid template molecule to fewer clear binding sites in molecularly imprinted
polymers, so this composition contains the molecule in the polymerization by
bordering and also they have drawbacks including insufficient reproducibility
and low specificity [43–45].

3.4 Micro-contact imprinting

The other alternative solution for the problem of macromolecules imprinted
can be figured out using this method. In the micro-contact imprinting, a little
amount of molecular mass needs to expeditiously obtain a monolayer matrix
[46]. Generally, a stamp applies to obtain the template molecule moiety while
imprinting [47]. One layer of the template molecule with the functional mono-
mer on a slide is fabricated and then adhered to a slide with a cross-linker. In
the end, the slide was removed from the surface, which demonstrates the wanted
recognition sides [48–50].

4 Applications of molecularly imprinted polymers-based

systems
Different technologies of molecularly imprinted polymers-based systems have
achieved rapid growth according to continuous use and development of tra-
ditional techniques. Moreover, several molecularly imprinted polymers-based
systems with excellent performances have fabricated and also more thrilling
and universal applications have recognized [51]. In contrast to the conventional
methods, the molecularly imprinted polymers-based systems have superior ben-
efits including high selectivity, high stability, easy and cheap preparation, high
resistance to extra-ordinary conditions, and also featured utilization to desired
template molecules [52]. Because of these considerations, molecularly imprint-
ed polymers-based systems have found application in various fields such as
sensor [53], chromatography [54], microfluidic [55], computational [56], and
other systems.

4.1 Sensor systems

In molecularly imprinted polymers-based sensor systems, a signal is produced
upon the binding of the template molecule to the recognition molecule and a
transducer converts this signal into an output. The properties of the template
molecule or changes in parameters of the sensor systems upon template mol-
ecule binding are employed for specific and sensitive recognition and detection.
Besides, researchers incorporate into the molecularly imprinted polymers to en-
hance the sensor system’s responses [57–60].
 Fundamentals and Applications of Molecularly Imprinted Systems Chapter | 1 5

For instance, Ma et al. recently reported a study about a piezoelectric sensor

for determining cytochrome c. They used the modified palmitic acid epitope
of cytochrome c as a template and 3-aminopropyl triethoxysilane as a mono-
mer to prepare a polymer by using reverse micro-emulsion polymerization and
then combined the advances of imprinted polymers and quartz crystal micro-
balance sensors. They performed kinetic studies in a range from 0.005 µg/mL
to 0.050 µg/mL and obtained a low limit of detection value as 3.6 ng/mL [61].
Fang et al. prepared a filter paper bases on an imprinted polymer for extract-
ing 3-monochloropropane-1,2-diol which is a food processing contaminant.
They showed that this paper-based system exhibited a high adsorption capacity
(68.97 mg/g), an outstanding selectivity (imprinting factor: 4.5) and a low limit
of detection value (0.6 ng/mL). They also reported the recoveries values ranged
from 97.2% to 105.3% with relative standard deviation values below 5.6% and
obtained a linear correlation to the classic GC-MS method [62]. Alizadeh et al.
introduced an imprinted polymer and multi-walled carbon nanotube-based
potentiometric sensor to detect lactic acid. They used allylamine and ethyl-
ene glycol dimethacrylate as a functional monomer and a cross-linker. They
observed that the imprinted polymer cavities were produced during polymeriza-
tion that affected the electrode potentiometric response. They coated the poten-
tiometric sensor with a membrane consisting of the imprinted nanoparticles,
multi-walled carbon nanotube, dibutyl phthalate, poly-vinyl chloride, and tetra-
phenyl phosphonium bromide. They obtained a slope of 30.3 ± 0.4 mV/decade
in the range of 1.0 × 10−1 to 1.0 × 10−6 mol/L with a low limit of detection
value (7.3 × 10−7 mol/L). They also reported that this sensor showed a stable
potential response in the pH range of 5–8 and a fast response time of less than
a minute [63]. Feng et al. fabricated a fluorescent sensor covering a molecu-
larly imprinted polymer layer onto quantum dots for tetrabromobisphenol-A
detection with modification steps (Fig. 1.2A). Following the characterization
experiments, they optimized experiment conditions and reported that this flu-
orescent sensor displayed linearity with tetrabromobisphenol-A coating the
range of 1.0–60.0 ng/mL with a low limit of detection value (3.6 ng/g). They
also claimed that this imprinted fluorescent sensor was successfully used for
the determination of tetrabromobisphenol-A in electronic waste samples. They
obtained the mean recoveries were in the range from 89.6% to 107.9% with the
relative standard deviation below 6.2% [64].
Erdem et al. also presented a study on Enterococcus faecalis detection by an
imprinted nanoparticle-based optic sensor (Fig. 1.2B). They first prepared bac-
teria imprinted nanoparticles by using micro-emulsion polymerization, charac-
terized these imprinted nanoparticles with several techniques and covered the
optic sensor surface using these imprinted nanoparticles. Then, they performed
a kinetic behavior of optic sensors in the range of 2 × 104–1 × 108 cfu/mL with
a low detection limit value (1.05 × 102 cfu/mL). They also performed selec-
tivity and reusability of the sensor to compare detection performances [65].
Akgönüllü et al. recently published a study about a piezoelectric sensor coated
6 Molecular Imprinting for Nanosensors and Other Sensing Applications

FIGURE 1.2 Steps of imprinted fluorescent (A) and optic (B) sensors preparation [64,65].

with imprinted nanoparticles for the synthetic cannabinoids (JWH-018, JWH-

073, JWH-018 pentanoic acid, and JWH-073 butanoic acid) detection. They
first synthesized imprinted nanoparticles, characterized them by different mea-
surements and then spread onto the nanoparticles for covering a sensor surface.
 Fundamentals and Applications of Molecularly Imprinted Systems Chapter | 1 7

After the sensor surface characterization, they monitored selective rebinding

of synthetic cannabinoids as a frequency shift measuring mass change. They
calculated the limit of detection values as 0.28, 0.3, 0.23, 0.29 pg/mL for these
synthetic cannabinoids in artificial saliva [66].

4.2 Chromatography systems

In molecularly imprinted polymers-based chromatographic systems is a major
area of application of imprinted polymers wherein it is used as a sorbent in
chromatographic columns due to its selectivity for template molecule, favorable
molecular recognition capabilities and stability [26]. Especially, solid-phase
extraction is the most developed application of molecularly imprinted poly-
mers that supplies an effective and simple pretreatment method in complicated
samples and opens a new window for extraction and recognition of template
molecules from the complex matrix [67–69].
For example, Zhang et al. prepared an efficient and selective chromatographic
resin to determine and purify different hemoglobin variants. They demonstrated
that the hemoglobin-imprinted polymers can directly recognize and purify from
either crude Escherichia coli (E. coli) extracts or human body fluids in one-step.
They calculated the binding capacity as around 7.4 mg/mL resin at 10% break-
through for adult hemoglobin and fetal hemoglobin. They also observed that this
chromatographic polymer allowed the identification of changes related to amino
acid substitutions on the hemoglobin protein surface [70]. Bashir et al. designed
a dispersive solid-phase extraction sorbent for combining with HPLC to ana-
lyze of griseofulvin that is clinically important due to treating fungal infections
in humans and animals in surface water samples. Following the optimization
experiments, they established a linear data over the range of 0.1–100 g/mL
of griseofulvin. They obtained limits of detection and quantification values as
0.01 and 0.03 g/mL and achieved high recovery values (91.6%–98.8%). Also,
a high good removal efficiency (91.6%) was performed as compared to pow-
der activated carbon (67.7%) with 10 times the reusable performance for water
samples [71]. Wang et al. developed core-shell molecularly imprinted polymers
employing methyl methacrylate as a monomer in seed core and acrylamide as
a shell functional monomer, ethylene glycol dimethacrylate as a cross-linker,
ammonium persulfate as an initiator and lincomycin A as a template molecule.
After the characterization experiments, lincomycin A purification condition was
optimized and they obtained a maximum adsorption capacity as 62.66 mg/g.
As depicted in Fig. 1.3A, they also performed a high purification by column
chromatography and the recovery values of lincomycin A reached 97.57% and
93.3% [72]. Çetin et al. produced a uniform-sized microcryogels employing
2-hydroxyethyl methacrylate and glycidyl methacrylate for purification of trans-
ferrin for immunoaffinity chromatography applications. They first performed
several characterization experiments, explored optimization conditions and
found the maximum adsorption capacity of 9.82 mg/g at pH 6.0. They calculated
8 Molecular Imprinting for Nanosensors and Other Sensing Applications

FIGURE 1.3 Chromatographic separation of lincomycin A (A) and transferrin (B) [72,73].

mathematical coefficients and observed that the experimental capacity values

are very close to the calculated Langmuir isotherm capacity value (11.27 mg/g).
They also observed only 20% capacity decrease after the tenth use of the same
microcryogels. They yielded a purity of the eluted transferrin from plasma as
about 84% (Fig. 1.3B) [73]. Aşır et al. prepared a dopamine-imprinted mono-
lithic column as a stationary phase and applied in capillary electrochromatog-
raphy. They investigated the effect of the content of the mobile phase, applied
pressure and pH of the mobile phase and evaluated the selectivity coefficients.
According to the results, the dopamine-imprinted column has outstanding sepa-
ration of dopamine from structurally related competitor molecule (norepineph-
rine), which is similar in size and shape to the template molecule [74].

4.3 Microfluidic systems

In the molecularly imprinted polymers-based microfluidics systems demon-
strate more exciting benefits with more helpful components in different applica-
tions [75–77]. Furthermore, diversified molecularly imprinted polymers-based
microfluidic systems with excellent performances have been prepared for ex-
citing and universal applications due to the high performance, exceeding the
conventional methods and supplying a more cost-effective approach [78,79].
Especially, the paper-based systems have been admitted as charming detection
platforms due to their incomparable properties, such as low cost and sample
consumption, and, also pump-free transportation [80].
Takimoto et al. prepared microgels using water-soluble monomers in
water-in-oil droplets produced by the microchannels. Following the optimiza-
tion experiments (flow rate selection, suitable surfactants, and concentrations),
they managed the size of microgels by the oil phase flow rate for human serum
albumin detection. Moreover, they described these microgels showed a highly
 Fundamentals and Applications of Molecularly Imprinted Systems Chapter | 1 9

selective and affinity binding behaviors toward human serum albumin [81].
Shiraki et al. synthesized a hydrogel with a microfluidic system for detecting
bisphenol A. They prepared molecule-responsive hydrogels with β-cyclodextrin
as ligands by photopolymerization. The hydrogels depicted ultra-quick shrink-
age in response to bisphenol A. Furthermore, the flow rate is autonomously
adjusted by the shrinking of the hydrogels as smart microvalves [82]. Kellens
et al. reported a molecularly imprinted polymers-based microfluidic system with
the functionalized diamond substrates. They showed that this system can detect
testosterone in urine, saliva, and buffer samples. As demonstrated in Fig. 1.4A,
they characterized this microfluidic system and also modified to a system and
obtained a low limit of detection value (0.5 nM) under a range of testosterone
concentrations [83].
Kong et al. originated a paper-based microfluidic system to determine
bisphenol A employing magnetic nanoparticle peroxidase activity and adsorp-
tion capacities. They first characterized the polymers (Fig. 1.4B) and utilized
the adsorption isotherm models of molecularly imprinted membranes to indi-
cate the interaction between the template molecule and system. They found
a low limit of detection value (6.18 nM) in the range of 10–1000 nM [84].
Li et al. progressed a paper-based microfluidic system using quantum dots to
recognize of phycocyanin. They realized that the quantum dots liquid phase
being transferred to the solid-phase paper base and achieved easy portability.

FIGURE 1.4 Electron microscope images of channels (A) and membranes (A: pure cellulose
paper, B: imprinted membranes, C: magnetic imprinted membranes and D: non-imprinted) (B)
[83,84].
10 Molecular Imprinting for Nanosensors and Other Sensing Applications

They reported that their three-dimensional paper-based microfluidic system can

assign phycocyanin in a range of 10–50 mg/L with a low limit of detection
value (2 mg/L) [85]. Ge et al. also invented a paper-based microfluidic system
applying electropolymerization of molecularly imprinted polymers in the modi-
fied gold nanoparticle. They composed the growth of a gold nanoparticle layer
on the fiber surfaces in the electrode and investigated a system that comprised
of a pad surrounded by sample tabs to recognize D-glutamic acid in a different
range with a low limit of detection value (0.2 nM) [86].

4.4 Computational modeling systems

In computational modeling systems, the foundation of suitable design is a usual
procedure in the molecularly imprinted polymers productions, and has led to
major developments in functional monomer screening, cross-linker and solvent
selection, functional monomer and template molecule ratio optimization, and
also selectivity analysis. Application of molecular modeling in the molecularly
imprinted polymer’s progress process provides solutions to several problems.
Appropriate simulations and computations assist the definition of the nature of
the interaction between the reagents [56,87,88].
Viveiros et al. designed a molecularly imprinted polymer for acetamide
recognition using a computational application to optimize synthesis in super-
critical carbon dioxide. They used SYBYL™ software for molecular modeling
introducing carbon dioxide as a solvent in the design of the imprinted poly-
mer (Fig. 1.5A). They first create an essential library of functional monomers,
screened against acetamide, selected the monomers giving the highest binding
energy and employed in a simulated annealing process to study their interac-
tion with acetamide in the presence of carbon dioxide. They finally performed
binding and selectivity experiments to estimate the affinity performance of the
imprinted polymers [89].
Martins et al. addressed to design of molecularly imprinted polymer-based
computational systems for deltamethrin recognition to produce a suitable sor-
bent. They investigated the complexity of the mechanistic basis to recognize
deltamethrin and attempted the use of a quantum chemical application. They cor-
roborated the DFT calculations with experimental assays enabling one to select
the most suitable imprinting system for extraction technique, which encom-
passes acrylamide and ethylene glycol dimethacrylate (Fig. 1.5B). In addition,
they successfully applied the solid-phase extraction methodology for the clean
up of spiked olive oil samples [90]. Munawar et al. originated a nanoparticle-
based assay to replace the primary antibody for ELISA method comparison.
They used computational modeling to design the imprinted nanoparticle select-
ing monomers that interact with fumonisin B1. They tested in model samples
is for selectivity experiments and observed that no cross-reactivity with other
mycotoxins. They also performed that the detection of fumonisin B1 in the
range of 10 pM–10 nM with a low detection limit (1.9 pM) and a high recovery
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Title: Seven daughters

Author: Amanda M. Douglas

Release date: September 25, 2023 [eBook #71729]

Language: English

Original publication: Boston: Lee and Shepard, 1874

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*** START OF THE PROJECT GUTENBERG EBOOK SEVEN

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 BOOKS FOR “OUR GIRLS.”

THE MAIDENHOOD SERIES.

By Popular Authors.

SEVEN DAUGHTERS.
By Miss A. M. Douglas, Author of “In Trust,” “Stephen Dane,”
“Claudia,” “Sydnie Adriance,” “Home Nook,” “Nelly Kennard’s
Kingdom.” 12mo, cloth, illustrated. $1.50.
“A charming romance of Girlhood,” full of incident and humor. The
“Seven Daughters” are characters which reappear in some of Miss
Douglas’ later books. In this book they form a delightful group,
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By Sophie May, Author of “The Doctor’s Daughter,” “Our Helen,” &c.
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“Has the ring of genuine genius, and the sparkle of a gem of the
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 THAT QUEER GIRL.
By Miss Virginia F. Townsend, Author of “Only Girls,” &c. 12mo,
cloth, illustrated. $1.50.
Queer only in being unconventional, brave and frank, an “old-
fashioned girl,” and very sweet and charming. As indicated in the
title, is a little out of the common track, and the wooing and the
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The above six books are furnished in a handsome box for $9.00,
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LEE AND SHEPARD, Publishers, Boston.
SEVEN DAUGHTERS.
Seven Daughters.
 THE MAIDENHOOD SERIES.

Seven Daughters.
BY
AMANDA M. DOUGLAS,
Author of “In Trust,” “Home Nook,” “Katie’s Stories,” &c.

BOSTON:
LEE AND SHEPARD, PUBLISHERS.
NEW YORK:
CHARLES T. DILLINGHAM.
Entered, according to Act of Congress, in the year 1874,
By LEE AND SHEPARD,
In the Office of the Librarian of Congress, at Washington.
 TO

KATE ISABELLE HIBBARD.

In thy book, oh Lord, are written all that do what they can, though
they cannot do what they would.
St. Bernard.
Belvidere, N. J.
SEVEN DAUGHTERS.
 CHAPTER I.

“‘How many? Seven in all,’ she said,

And wondering looked at me.”
Wordsworth.

NOTHER girl!”
“Seven of ’em!”
“What a pity!”
“The land sakes alive! Brother Endicott will have to buy calico by
the piece for their gowns! He might get a little throwed off, or a spool
of cotton extry. He, he! ho, ho! Well, children are a great risk! You
don’t s’pose there’ll be a donation party right away—do you!”
“There is donation enough for the present, I think; and the sewing
society will not be called upon.”
I liked that soft, silvery voice of Mrs. Whitcomb. It was just like her
pretty light hair, beginning to be plentifully sprinkled with silver, and
her clear peachy skin, that was just a little wrinkled. Her touch was
so gentle, her motions so graceful and pleasing!
“I was only joking about it. They’ll miss her in the s’ciety—that’s
what they will.”
Aunt Letty Perkins was—dreadful! a thorn in the flesh; a sort of
bitter, puckery presence, as if you had just tasted an unripe
persimmon.
“And it’ll be a puzzle to get husbands for ’em all. That’s the most
unfort’net thing about girls.”
I suppose she meant us, not the society. My face was in a blaze of
indignation. Then the door was shut, and I went on with my dusting.
 It was a sunny April morning, and a pair of swallows were
twittering about the windows.
Another girl and there were seven of us. Some one in the parish
had said that Mrs. Endicott would always be sure of a Sunday school
class, for she could fill it up with her own children. I couldn’t help
wishing that there was just one boy among us, even if it were that
wee bairnie they had been discussing. Boys are nice—in some
ways.
I don’t know that I should have modified my opinion so suddenly
but for two things. My eye happened to fall on my pretty pearl paper-
cutter, that had been sent to me at Christmas. On one side of the
handle was my monogram, done in scarlet and gold, on the other a
little trail of blue forget-me-nots. A few weeks ago Harry Denham
had been in spending the evening with us,—that means Fan and I,
the elders. He and Fanny were having a little scrimmage, and, in a
half tragic manner, he seized my pretty gift, pretending to arm
himself with a dagger, and, somehow, in the melee, the poor thing
snapped in twain.
Hal was very sorry. Then he had such great, beseeching brown
eyes, that when he turned them so appealingly to me, I pitied him
more than I did myself. It was very foolish, I know. I ought to have
scolded. I should have said,—
“You great, rough, careless boy! now see what you have done! I
wish you would never come here again!”
“I can get it mended, I know. There is some beautiful white cement
used for such articles. O, Rose, I am so sorry! I’d get you another
one, only it wouldn’t be it.”
“Never mind,” I said, meekly, with a wonderful tendency towards
tears, though whether they would have been for Harry, or the knife,
or myself, I could not exactly tell.
So he had it mended, and it looked as good as new. But little
Frank Mortimer came to call with his mother, and brought it to grief
again.
 The other event that reconciled me to the advent of my little sister,
whom I had not yet seen, was Tabby, who sprang up on the window
sill, with her cunning salutation, like three or four n’s, strung together
in a prolonged musical fashion, not quite a mew. I don’t want you to
think the word back there was meant for a pun, for it wasn’t. I’ll tell
you in the beginning that I am not a bit bright, or sharp, or funny. I
have even heard jokes that I did not see the point of until the next
day.
Tabby is just as beautiful as she can be. A Maltese cat, with a
white nose and two white front paws. She is very cunning, and
knows almost everything within the domain of cat knowledge. If there
is one thing I do love better than another, in the way of pets, it is
cats. A clean-faced, sleek cat, sitting on the hearth-rug before the
grate, is enough to give the whole household a feeling of
contentment. Then the kittens are always so funny and frolicksome!
“Tabby,” I said, as she arched her back and rubbed her head
against my sleeve,—“Tabby, you wouldn’t be half so happy if there
was a boy in the house. He would lift you by the tail, turn your ears
back, put walnut shells on your feet, and make you dance on your
hind legs. Then he would be forever tormenting your kittens. Boys
are bad naturally. Maybe they are born so, and can’t help it,” I
continued, reflectively. “I suppose they do have a good deal more of
the old Adam in them than girls, because, you see, we inherit Eve’s
propensity to curiosity; but then boys are fully as curious—aren’t
they, Tabby? and as full of curiosity!”
“Yes,” answered Tabby.
She says it as plainly as you do. In fact, we sometimes hold quite
lengthy conversations.
“So we don’t care—do we? If Aunt Letty Perkins would not make
such a row about it! How would she like to have a lot of boys, I
wonder?”
Tabby shook her head sagely, and scratched her left ear. I knew
she felt just the same as I did.
 I finished the parlor, and shut down the windows. Then I went to
papa’s study, took the ashes softly out of the grate, and laid another
fire, in case the evening should be cool, picked up papers and
magazines, and dusted with the very lightest of touches. It was my
part of the work to look after the study. I was so glad to be able to
suit papa!
Just then the door opened. It was papa himself, fresh from a walk.
I think him ever and ever so handsome, though sometimes I wish he
was not quite so thin. He is rather tall, has a fine chest and
shoulders; but it is his sweet, dear old face that I like so much. It’s a
little wrinkled, to be sure, and may be his mouth is a trifle wide. I
never considered it any defect, however, for he shuts his lips
together with such a cordial smile! He has lovely deep-gray eyes,
and his hair, which was once a bright brown, begins to be toned with
silvery threads, as well as his soft brown beard, which he wears full,
except a mustache.
“O, papa!” I cried, clasping my arms around his neck, “are you
very sorry?”
“Sorry for what, my daughter?” And he looked a good deal
surprised.
“That we haven’t a boy. There are so many of us girls!”
“My dear, I have always had a great fancy for little girls, as you
know. And we take whatever God sends. She is very pretty.”
“O, you dear, blessed papa!”
“You will have to be the mother now, for a little while, Rose. You
must try to manage the children nicely.”
“Indeed, I will do my best. Papa, do you not believe that I could go
in and see her? Aunt Letty Perkins is there.”
“O, how could Mrs. Whitcomb! Yes; come along, child.”
I followed him to the sitting-room. The Rectory was a great,
rambling old house, with a wide hall through the middle. Back of the
parlor, quite shut off, indeed, were the dining-room and the two
kitchens; on the other side, study, sitting-room, nursery, and
mamma’s sleeping apartment.
Mamma’s door was shut. Mrs. Whitcomb was wise enough to
keep guard over that. There was a little fire in the Franklin stove, and
before it sat Mrs. Perkins, though everybody called her Aunt Letty.
Her feet were on the fender, her brown stuff dress turned up over her
knees, her black alpaca skirt not quite so high, and a faded quilted
petticoat taking the heat of the fire. She always wore substantial gray
yarn stockings in the winter, and lead-colored cotton in summer,
except on state occasions. Her bonnet was always a little awry, and
the parting of her hair invariably crooked. I’m sure I don’t know what
she did, except to attend to other people’s affairs.
Mrs. Downs was beside her, a helpless-looking little fat woman,
who, Fan declared, looked like a feather pillow with a checked apron
tied around it. She was always out of breath, had always just left her
work, and was never going to stay more than a moment.
“O, brother Endicott!” exclaimed Aunt Letty, reaching her hand out
so far that she nearly tipped her chair over; “I s’spose you ought to
be congratyourlated.” (She always put your in the word, and always
said equinomical, regardless of Noah Webster.) “What does the
Bible say about a man having his quiver full of olive branches? or is
it that they sit round the table? now I disremember. I don’t go much
according to Old Testament. It was well enough for them heathenish
Jews and the old times; but I want the livin’ breathin’ gospel. What
you goin’ to call her?”
Papa smiled, at the absurd transition, I suppose. Fan said Aunt
Letty had only one resemblance to a dictionary—she changed her
subjects without any warning.
“Would Keren-happuch do?” papa asked, with a droll twinkle in his
eye.
“O, now, Mr. Endicott!”
“It’s a nice little thing,” put in Mrs. Downs. “Favors its mar I think.”
“Come and see it, Rose.—May we, Mrs. Whitcomb?”
 “O, yes, indeed,” with her sweet smile.
She led me to the corner of the room, between the stove and
mamma’s door. There, on two chairs, was a tiny bed, and under the
blanket a tiny baby with a broad forehead, black, silky hair, a cunning
little mouth, but no nose to speak of. Yet she was pretty. I thought I
should like to squeeze her to a jelly, and cover her with kisses,
though I don’t know as that would be orthodox jelly-cake for any but
a cannibal.
Papa glanced at her with a tender smile, then sighed. Perhaps he
was thinking of the long way the little feet would have to travel. It is a
great journey, after all, from the City of Destruction to the New
Jerusalem. Something in the baby-face brought to mind Christiana
and the children.
“Great pity ’tisn’t a boy,” persisted Aunt Letty.
“O, I don’t know about that. They are so handy to take one
another’s clothes,” said papa, humorously.
“To be sure. But yours could be cut over,” returned the literal
woman.
“I am afraid that I shall always need mine to the last thread. I have
lost the trick of outgrowing them. O, have you heard that Mrs.
Bowers’s sister has come from the west? Arrived last evening.”
“Land sakes alive! Why, I guess I’ll run right over. Sally and me
was thick as peas in our young days. And her husband’s been a
what you call it out there, senate, or constitution, or something.”
“Member of the legislature,” corrected father, quietly.
“O, yes. Some folks do get along. There’s the middle of my
needle. I should knit there if the house was afire!”
She brushed down her skirts, put her knitting in her satchel, jerked
her shawl up, and pinned it, and settled her old black bonnet more
askew than ever. Mrs. Whitcomb kindly pulled it straight for her.
“Thank’ee. If you want any help, Mrs. Whitcomb, send right
straight over. Ministers are always the chosen of the Lord, and I feel
as if one ought to come at their call.”
“I am much obliged,” returned Mrs. Whitcomb, in her quiet, lady-
like way.
Mrs. Downs took her departure at the same moment. There was a
great bustle, and talking; but father finally succeeded in getting them
to the porch. When Aunt Letty was safely off the steps, she turned
and said,—
“I’m glad you are so well satisfied, Mr. Endicott. It’s a sure sign of
grace to take thankfully what the Lord sends.”
“O, dear,” said papa, with a sigh; “I am afraid I don’t give thanks for
quite everything. ‘Tribulation worketh patience.’ But didn’t those
women almost set you crazy? If I thought another sermon on bridling
the tongue would do any good; I should preach it next Sunday.”
Mrs. Whitcomb smiled and said, in her cool, silvery voice,—
“It takes a great deal of powder and shot to kill a man in battle, and
it takes a great deal of preaching to save a soul.”
“Yes. I get almost discouraged when I find how strong the old
Adam is in human souls.”
I looked at papa rather reproachfully; but just then he opened the
door of mamma’s room, and called me thither.
Mamma was very sweet and lovely. She kissed me many times,
and hoped I would prove a trusty house-keeper, and see that papa
had everything he needed, especially to notice that his cuffs and
handkerchiefs were clean, and that he was in nice order on Sunday.
“And—did I like the baby?” She asked it almost bashfully.
“It is just as sweet as it can be. I only wish it was large enough to
hold and to carry about.”
“Thank you, dear.”
Years afterwards I knew what that meant.
I went out to the kitchen to see about the dinner. We never had
regular servants like other people. It was the lame, and the halt, and