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Файл:Ординатура / Хирургия / Библиотека им академика М.И. Перельмана / Книга_5390_Библиотеки_им_академика_М_И_Перельмана.pdf
396 C. Chapa
bioactivity. Mater Today Sustain 26:100710. Available at: https://doi.org/10.1016/J.MTSUST.
2024.100710
Thomas D, Mathew
application. Int
IJBIOMAC.2020.12.227
Tören E et al (2024) Recent advances in biopolymer based electrospun nanomaterials for drug
delivery systems. Polym Adv Technol 35(3):e6309. Available at:
6309
Tudorachi N et al (2017) Studies on the nanocomposites based on carboxymethyl starch-g-lactic
acid-co-glycolic acid copolymer and magnetite. J Therm Anal Calorim:1–14. Available at:
https://doi.org/10.1007/s10973-017-6682-9
Villarreal-Gómez LJ et al (2016) Electrospinning as a powerful technique for biomedical
applications: a critically selected survey. J Biomater Sci Polym Ed 27(2):157–176.
Available at: https://doi.org/10.1080/09205063.2015.1116885
Wang Z, Shang J, Zhang Z (2024) Composite or modified hydroxyapatite microspheres as drug
delivery carrier for bone and tooth tissue engineering. Curr Med Chem 31. Available at: https://
doi.org/10.2174/0109298673303632240320073606
Yasar H et al (2018) Starch-chitosan polyplexes: a versatile carrier system for anti-infectives and
gene delivery. Polymers 10(3). Available at: https://doi.org/10.3390/POLYM10030252
You BC et al (2022) Dielectric and biodegradation properties of biodegradable nano-hydroxyapa-
tite/starch bone scaffold. J Mater Res Technol 18:3215–3226. Available at: https://doi.org/10.
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Zhang D et al (2023) Hydroxyapatite-based nano-drug delivery system for nicotinamide mononu-
cleotide (NMN): significantly enhancing NMN bioavailability and replenishing in vivo nicotinamide adenine dinucleotide (NAD+) levels. J Pharm Pharmacol 75(12):1569–1580.
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N, Nath MS (2021) Starch modified alginate nanoparticles for drug delivery
J Biol Macromol 173:277–284. Available at:
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https://doi.org/10.1002/PAT.
Dr. Christian Chapa is a leading researcher at the Institute of
Engineering and Technology of the Autonomous University of
Ciudad Juarez (Mexico), and head of the NANOMEDICINE
research group. His research interests focus on nanomedicine,
physico-chemical properties of biomaterials and nanomaterials
where teragnostic approach is the main approach. In 2012, he
formed the Nanomedicine Research Group for the proposal and
execution of research projects related to the preclinical investigation of interactions between biomaterials or nanomaterials with
biomolecules, clinical analytes or drugs to develop nanomedicine
systems proposed for the identification of molecular targets for the
diagnosis and treatment of a diverse number of human diseases
and develop activities focused on student learning and innovative
application of knowledge. In 2020, he formed the Laboratory for
Integration of Data and Evidence in Health and Science Reviews,
LIDERSC, to conduct critical reviews of the scientific literature
with the goal of providing robust and reliable evidence to answer
research questions and support decision making in health and
science. Christian Chapa has published more than 30 scientific
articles in scientific journals of international recognition, 7 book
chapters and has more than 50 presentations in scientific
congresses. Christian Chapa was president of the Scientific Committee of the Mexican Society of Biomedical Engineering in
2018–2019 and received recognition from the International Federation for Medical and Biological Engineering for his outstanding
15 Hydroxyapatite-Starch-Based Sustainable Biomaterials 397
work as vice president of the Scientific Committee for the VIII
Latin American Congress of Biomedical Engineering. He is a
researcher of the National Council of Humanities, Science and
Technology of Mexico, participates in programs to promote scientific vocations, such as the Summer of Research. Currently, he
collaborates with other research groups ByNEF and BIOCIM to
propose and execute academic and research projects with social
impact in the areas of nanotechnology
ioengineering.
and b
Surfactant-Free Synthesis of Metal and Metal Oxide Nanomaterials: Sustainable and Eco-Synthesis Methods
Sayali Churi, Ushasi Das, Popat Mohite, Sanchita Mandal,
and Sudarshan Singh
Abstract
Surfactant free synthesis of metallic nanomaterials offers multiple benefits in
medical, pharmaceutical, biological, biomedical, and catalytic application due to
their high surface-to-volume ratio and fascinating physicochemical properties.
Though there are several techniques with different advantageous and challenges
in synthesis metal oxide or metallic nanomaterials have been inves tigated, the
biocompatibility, stability, and purity of such nanomaterials also controllability
with reproducibility are most challenging issue faced by researcher and scientist.
Moreover, the metal oxide and metallic nanoparticles due to variation in size and
shape and percentage of reduction are prone to lose reactivity and ultimately
therapeutic efficacy, as this can precipitate out or form aggregate as bulk metals;
therefore, various stabilizers briefly surfactant or allied materials are typic ally
required. Plant-based is an alternative technique to synthesize stable metal oxide
or metallic nanoparticles, however bench to market of such techniques is not yet
well-setup, thus several surfactant-free strategies such as solvent mediated synthesis, ion-mediated synthesis, and several physical processes have been
introduced for fabrication of oxide and reduced metallic nanoparticles as
16
S. Churi (✉) · P. Mohite
Department Pharmaceutical Chemistry, AETs St. John Institute of Pharmacy and Research,
Palghar, Maharashtra, India
e-mail: sayalic@sjipr.edu.in
U. Das · S. Mandal
Department of Pharmaceutical Technology, Jadavpur University, Kolkata, West Bengal, India
e-mail: smandal.pharmacy@jadavpuruniversity.in
S. Singh
Office of Research Administration, Chiang Mai University, Chiang Mai, Thailand
Faculty of Pharmacy, Chiang Mai University, Chiang Mai, Thailand
#
he Author(s), u
T
R. Malviya, S. Sundram (eds.), Sustainable Green Biomaterials As Drug Delivery
Systems, Biomaterials, Bioengineering and Sustainability 1,
https://doi.org/10.1007/978-3-031-79062-1_16
nder exclusive license to Springer Nature Switzerland AG 2025
399
400 S. Churi et al.
eco-friendly techniques by avoiding use of toxic chemicals. Thus, this chapter
provides a brief on the utilization of surfactant free synthesis process for
manufacturing of metallic nanomaterials with their associated applications and
challenges.
Keywords
Nanoparticles · Surfactant-free synthesis · Sonochemical · Catalysis · Metal
oxides
16.1 Introduction
The typical size range for metal nanoparticles is 1–100 nm. Metal nanoparticles
exhibit distinct physiochemical features concerning optics, magnetism, and specific
chemical reactions as they have large great surface energy, better surface area, and
quantum confinement (Syukri et al.
Ontong et al. 2020; Jayeoye et al. 2021a, b; Kumar et al. 2023; Puri et al. 2023;
Nagime et al. 2023) confinement;.A large surface: volume ratio and intriguing
physicochemical features of metal and metal oxide nanoparticles have generated
great interest in pharmaceutical, biological, medical, biomedical, and catalytic
purposes (Singh et al. 2022 ; Syukri et al. 2024; Kumar et al. 2024; Jayeoye et al.
2024; Shah et al. 2024). Synthesis of nanomaterials including metal and metal-oxide,
numerous methods have been presented to date, each with unique benefits,
drawbacks, and difficulties. Important and difficult problems in this context are the
stability, controllability, and repeatability of synthesis methods in addition to the
purity, stability, and corrosion resistance of nanomaterials. Because metal and metal
oxide nanoparticles can precipitate out or form aggregate as bulk metals, they are
susceptible to losing their reactivity. As a result, various stabilizers, including
functionalized dendrimers, ligands, polymers, inorganic materials (such as carbon,
zeolites, metal oxides, and sol–gel clays), or ionic surfactants, can be used to prevent
it from occurring. In order to synthesize metal and metal oxide nanoparticles with the
advantages of affordability, ease of use, and environmentally benign qualities, a
number of surfactant-free strategies have been introduced recently, such as micro
plasma based, laser synthesis, the Co
techniques. These strategies avoid the use of toxic additives or surfactants (Jiang
et al. 2013)
In compa
.
rison to their bulk counterparts, these nanoparticles also exhibit lower
melting points and electrical/thermal conductivity. As metal nanoparticles get
smaller and have a measurable number of atoms on their surfaces, their physicochemical characteristics alter. The morphology (i.e., shape and dimensionality),
composition (i.e., whether the nanoparticles are of an alloy or a metal), and agglomeration of the nanoparticles are important in addition to these size-based effects, as
are the physical and chemical properties of the nanoparticles.
2020, 2021; Nwabor et al. 2020, 2021a, b;
Cat process, and mono-alcohol fabrication,
4
16 Surfactant-Free Synthesis of Metal and Metal Oxide Nanomateria ls:… 401
Scientific interest in metal nanoparticle research is growing as a result of the
discovery of controllable-solution-based methods for producing metal nanoparticles
(Khan et al.
2019).
16.2 Metal and Metal Oxide Nanomaterial Synthesis Devoid
of Surfactants
In colloidal synthesis without surfactants, the solvent functions as a stabilizer,
reducing agent, and reaction media. Forming valuable metallic nanop articles (NPs)
that don’t include any molecules with a molar mass higher than 100 g mol
-1
by this
process shows promise. Numerous surfactant-free methods for formulating NPs
have been documented, such as those utilizing alkaline mono-alcohols, plasma,
alkaline polyols, DMF, or lasers. Although most catalysis research still involves
surfactants with/without direct deposition of NPs on confirms in one-pot syntheses,
these approaches provide control over the chemical structure and size of surfactantdevoid NPs. The greatest source for examining and explaining the role of ligands and
surfactants in NP formation and catalysis are those that are surfactant-free.
16.2.1 Solvent-Assisted Synthesis
16.2.1.1 N,N-Dimethylformamide (DMF) Assisted Synthesis
Dimethylamine or DMF is a polar, aprotic, organic solvent that was originally
produced in 1893 by the French scientist Albert Verley. It is generated either by
treating dimethylamine coupled with carbon monoxide or by distilling a combination of dimethylamine hydrochloride and potassium formate (Amooref and Hautala
1983) Pastoriza-Santos’s team (Pastorizo-Santos and Liz-Marzán 2009) published
the first study on the metal nanoparticles synthesis using DMF in 1999. Since then, it
has been demonstrated that this technique is adaptable for producing different kinds
of metallic nanoparticles with monitored surface treatment, dimension, and structure.
DMF plays three distinct functions as a reductant, solvent, and protectant. Strong
and adaptable, DMF finds usage in a versatile range of processes, including the
production of block copolymers, the fabrication of colloids, and organic synthesis
including non-solvent- hydrolysis, allylation, decarboxylation, and polymerization
(Muzart 2009).
Moreover, it finds application in the production of films, fibers,
adhesives, surface coatings, and synthetic leathers. DMF is utilized as an initial
component utilized for reactions in the dye making process. Additionally, it serves as
a catalyst in significant organic processes such as the Beckmann rearrangement,
Friedel–Crafts reaction, and Vilsmeier–Haack reaction (Kumar et al. 2010). DMF
serves as an origin of important precursors in a variety of processes because it has the
ability to react as an nucleophilic or electrophilic mediator (Kawasaki
2013;
Heravi
et al. 2018). Distinct from surfactant-free metallic nanoparticles made using methyl
isobutyl ketone and ethylene glycol as reductants, the DMF-reduction technique
yields thermally stable metal nanoparticles or nanoclusters with a limited variability
402 S. Churi et al.
Fig. 16.1 N, N-dimethylformamide (DMF) based reduction synthesis method and reaction
pathway
in size (<7 nm) (Nagata and Obora 2020). When synthesizing acyl halides and acyl
chlorides from carboxylic acids, this chemical compound is frequently utilized as a
catalyst (Dubey et al. 2010; Nagata and Obora 2020
formed as part
of its catalytic process. In addition, it helps in the synthesis of azepine,
). Imidoyl chloride is reversibly
condensation processes, cyclo-addition reactions, cyclic carbonates, reductive ringcleavage, allylation of aldehydes, alcohol conversion to bromides, and acylation of
aromatic compounds. Various processes have been suggested to explain the methods
by which DMF reduces gold and silver ions. Nonetheless, the production of H
+
ions
and carbamic acid is a component of each of these reactions (Fig. 16.1). In DMF
(Nagata and
down into (CH
Obora 2020), the resulting carbamic acid is weak and quickly breaks
NH and CO2. Several metals and bimetallic compounds may be
3)2
synthesized as quantum dots, clusters, and nanoparticles using the surfactant-free
form of the ingredient. Since DMF protection reduces considerably at elevated
temperatures, DMF-stabilized clusters are the perfect choice for unconventional
catalysts composed of untreated NPs. In DMF, colloids an remain stable for several
en a
weeks, ev
solutions (Qu
fter being redispersed in a variety of solvents, such as water-based
inson et al. 2023).
Reduction of a metal source in dimethyl acetamide (DMF) in the atmosphere and
reflux reaction yields colloids. The presence of DMF on the NP surface is confirmed
16 Surfactant-Free Synthesis of Metal and Metal Oxide Nanomateria ls:… 403
by experimental data, and the stabilization is achieved by the interaction with the
amide groups of DM F. Because of the tiny size of these produced clusters, size
management might be difficult. As the reaction time rises, Ag nanoparticles with a
size control of 4–10 nm may be generated. An extensive investigation of the effects
of reaction duration, temperature, water content, and metal precursor salt were
conducted for Pt nanoparticles. By adjusting reactivity paramet
synthesis, cubic
(Kawasaki et al.
or truncated octahedral nanopar ticles successfully synthesized
2010; Da Costa et al. 2011).
ers with autoclave
The optical characteristics of Au nanoparticles (AuNPs), such as fluorescence and
plasmon resonance that are formed by DMF synthesis have been the subject of
investigations. The impact of ligand functionalizations on these characteristics was
assessed by the investigators using surfactant-free Au NPs as an instance. Several
ligands, such as 11-mercaptoundecanoic acid, thioctic acid, 1-dodecanethiol, PVP,
dodecylamine, poly(amido) amine, triphenylphosphine, and thiocholine bromide,
were used to functionalize the same batch of Au NPs. PVP was added, and this had a
considerable impact on the emission wavelengths, whereas the absorp tion
wavelengths did not alter at varied concentration levels. According to the authors,
the ligand concentration impact is a result of cross-linking (Liu et al.
2008; Duchesne
and Zhang 2012; Maman et al. 2019).
Capping a
ot only stabilize nanoparticle dispersion but also influence
gents n
particle morphology, as seen with ethyleneglycol or higher polyols. Although PVP
is frequently used to modify the shape of nanoparticles, other substances are equally
interesting. This is focuses on synthesizing nanoparticles using other capping agents
and discusses the use of PVP as a stabilizer and morphology control, both in the
presence and absence of preformed seed. DMF is a flexible catalyst that may be used
to create Au and Ag nanoparticles with specific optical characteristics. As different
capping agents offer different surface functions, they can be utilized as stabilizers
during particle synthesis. PVP enables adaptable particle size and shape adjustment.
The primary element affecting the ultimate particle shape is the crystallinity of the
original seeds, perhaps in combination with PVP. PVP modifies the development
process by preferentially interacting using the seeds’ crystallographic features. The
benefit of DMF is that it may provide a variety of particle morphologies in a broad
size range and with narrow size distributions, including triangles, decahedra,
octahedrons, and spheres. This method provides a more adaptable way to synthesize
metallic particles (Pastorizo-Santos and Liz-Marzán 2009)
DMF synth
esis has opened up new perspectives for electrocatalysis and hetero-
.
geneous catalysis, especially uncontrolled heterogeneous catalytic reactions. This
creates the opportunity to investigate further reactions using supported catalysts,
such electrocatalytic processes. Strong metallic surface contact, the non-ecofriendly
solvent DMF, the high boiling point, and the restricted potential for scale-up are
some of the constraints of the synthesis. A lengthy synthesis duration and an elevated
temperature are necessary for the reaction, and a metal quantity of approximately
1 mM is the ideal (Prat et al.
2015).
404 S. Churi et al.
16.2.1.2 Ethylene Glycol Assisted Synthesis
Charles-Adolphe Wurtz, a French scientist, discovered ethylene glycol (EG), the
most basic diol, in 1859 by saponifying ethylene glycol diacetate with potassium
hydroxide.Ethylene glycol serves as a reducing ingredient in methods as well as a
solvent for precursor molecules.Large-scale nanostructure synthesis may be easily
accomplished at an affordable price and with great versatility using the ethylene
glycol-mediated synthesis methodology, also known as the polyol process (Yue
et al. 2012; Soni et al. 2020). Fiévet et al. (2018) initially presented the polyol
process in the late 1980s. It is a liquid-phase synthesis method that yields finely split
metals from their salts in polyalcohols, hydroxides, or oxides. Polyalcohols like
α-diols and ethylene glycols are examples of liquid organic compounds that may be
used in this procedure as both a reducing substance and a solvent. Copper, electropositive metals like nickel and cobalt, and noble metals can all be reduced to zerovalent state ions by polyols. For the purpose of forming metal and alloy powders
with non-agglomerated nanoparticles that have a precise form, a restricted variation
in size, and a monitored size in the micrometer or submicrometer range, the polyol
process was thought to be a flexible and intriguing technique (Li et al. 2007, 2008).
Because ethylene glycol-mediated synthesis works in an enclosed framework and
reduces metallic prerequisites to their zero-valence state, it is a sustainably beneficial
and energy-conscious approach (Fig. 16.2).
A class
of glycols known as polyols is chelation-based and water-compara ble,
providing adequate command on size of particles, dispersity, and variations.
Propanediol, butanediol, pentanediol, glycerol, pentaerythritol, and certain
carbohydrates are representatives of this group of compounds. A viable method
for producing homogeneous magnetic iron oxide nanoparticles that may be applied
to magnetic resonance imaging is polyol. The polyol approach performs because of
their capacity to interact with the nuclei developed, which makes post-synthesis
intervention simple. Thermal anneal ing, carboxylates, amines, and other coordination exchangers, as well as repeated washing with plain water are effective postsynthesis treatments for eliminating polyols (Watt et al.
Niederberger 2017; Gul et al. 2019).
Polyol functions as a stabilizing agent, reducing
2017;
Deshmukh and
agent, and solvent that manages particle development and inhibits aggregation. A
polyol is used to dissolve or suspend precursor chemicals such as hydroxides,
oxides, nitrates, sulfates, and acetates. The resulting product is subsequently heated
to reflux. In order to generate polyols, a soluble metal precursor must first be reduced
to metal nuclei, which then nucleate into metal nanoparticles. This process provides
an intermediate molecule. The reagent polyvinylpyrrolide (PVP) functions as a
shape-controlling and stabilizing substance facilitating both heat degradation and
diverse nucleation (Bhattarai et al.
Alkaline EG was used by Wang et al. to
2015).
decrease metal ions such as ruthenium, rhodium, and platinum in order to formulate
metal nanoparticles without incorporating surfactants. They synthesized robust
noble metal nanoparticles (Pt, Rh, and Ru) with an average diameter of 1–2 nm by
using metal solutions in EG that contained NaOH and had concentrations ranging
from 0.3 to 3.7 g/l. Despite the use of natural stabilizing agents, the stability of these
nanoparticles was ascribed to the adsorption of EG and OH-ions on their surfaces,
16 Surfactant-Free Synthesis of Metal and Metal Oxide Nanomateria ls:… 405
Fig. 16.2 Ethylene glycol mediated synthesis pathway
which prevented aggregation. Pt/Ru and Pt/Rh bimetallic nanoparticles have also
been synthesized using the alkaline EG synthesis technique (Wang et al. 2000).
16.2.1.3 Benzyl Alcohol Assisted Synthesis
Benzyl alcohol is a colorless, transparent liquid with minimal vapor pressure,
excellent polarity, solubility in water and solvents, and a subtle aromatic fragrance.
It also has mild toxicity. It is frequently employed as a solvent and textile dye
assistance, as well as in industrial processes and perfumes. In nature it is noti ced in
plants, fruits, tea, and wines, it is a constituent in commercial and pharmaceutical
products (Corcoran and Ray 201 4 ). Without the use of surfactants, binary, ternary,
and doped metal oxide nanocrystals as well as oxide-based hybrid materials may be
produced by the benzyl alcohol approach. Using an autoclave set to 180–230 °C,
benzyl alcohol is reacted with precursors such as metal chloride, alkoxide, acetate, or
acetylacetonate. Excellent quality crystallized metal oxide nanoparticles may be
continuously synthesized using this easy, time- and energy-efficient approach. The
406 S. Churi et al.
initial concentration of the precursor and the duration of the irradiation process
control the crystal size. Tert-butanol can serve as a substitute if oxygen particles
are being targeted without chelating surface ligands (Bilecka and Niederberger
2010;
Mutin and Vioux 2016).
A typical alcohol to react with metal chlorides was benzyl alcohol (BZOH).
Because of the p-π conjugation, BZOH is an aromatic alcohol with a benzene ring
on the α-carbon, which efficiently distributes the positive charge of the carbocation
onto the big benzyl group. This renders it more vulnerable to ionization and
nucleophilic agent damage. Because metal chlorides are inexpensive, oxygen-free
precursors that supply metal resources and prevent oxygen from interfering with the
production of oxides, they enable a deeper understanding of reaction processes
(Hu et al. 2013). Because the carbon–oxygen dissociative interaction is endothermic,
raising the temperature can increase the reactivity of benzyl alcohol. Based on this
property, it was discovered that several metal chlorides might react with benzyl
alcohol by varying the reaction temperature.
In this study, metal chlorides, metallic alkoxides, acetates, acetylacetonates, and
other metal organic groups are reacted using benzyl alcohol as a solvent to investigate the synthesis of various metal oxides (Niederberger et al. 2002;Baetal. 2005).
Prior research has mostly focused on high-valence metal chlorides, with little
attention paid to low-valence metal chlorides that include benzyl alcohol. This
work continues to employ benzyl alcohol because to its distinct reactivity, great
thermal stability, low toxicity, and ability to dissolve inorganic ions. The investigation intends to further understand and categorize the reaction process in addition to
broadening the reaction’s field of use. Metal chloride-based benzyl alcohol-related
interactions are known to be one type of alcohol-driven synthesis that uses alcoholic
solvents with an elevated hydroxyl group ionization potential and can readily
provide oxygen supplies. It has also been discovered that tertiary alcohol can supply
oxygen donors for the manufacture of metal oxides through studies into tertiary
alcohol-derived reactivity with metal chlorides. The E1 reaction, however, is the
main reaction that drives the production of metal oxides in tertiary alcohol-based
synthesis because tertiary carbocation is easier to eradicate a proton from and
convert to an alkene. For benzyl alcohol, the SN1 reaction pathw ay is the one that
matters. The purpose of this work is to extend the idea of organic to inorganic
synthesis and demonstrate the validity and application of the SN1 reaction principle
in explaining this benzyl alcohol-based synthesis (Pinna et al. 2004; Bilecka et al.
2009; Szeifert et al. 2010).
16.2.1.4 Methyl Isobutyl Ketone Assisted Synthesis
Acetone is an outcome of the manufacturing of cumene. Because of its poor
miscibility with water, it may be converted into methyl isobutyl ketone (MIBK), a
solvent used in paints, rubbers, medicines, and liquid-liquid extraction of valuable
metals. The three stages involved in producing MIBK in a batch reactor are acetone
coupling to make diacetone alcohol, diacetone alcohol dehydration to form mesityl
oxide, and mesityl oxide hydrogenation to form MIBK via a metal catalyst. This
process is the conventional method. Recent studies, however, have demonstrated