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a
Centro de Graduados e Investigación en Quı´mica, Instituto Tecnológico de Tijuana, Blvd. Alberto Limón Padilla S/N,
Mesa de Otay, C.P. 22500 Tijuana, B.C., Mexico
b
Universidad Autónoma de Baja California, Facultad de Ciencias Quimicas e Ingenieria, Calzada Universidad 14418
Parque Industrial Internacional, C.P. 22390 Tijuana, B.C., Mexico
c
Centro de Nanociencia y Nanotecnologı´a de la Universidad Nacional Autónoma de Me´xico, km. 107 Carretera
Tijuana-Ensenada, Ensenada C.P. 22860, B.C., Mexico
CHEMICAL COM- Abstract In this work, a comparative study of the effect of the NCD size as a stabilizing agent, on
POUNDS STUDIED IN the synthesis of copper nanoparticles (Cu-NPs) by an easy green method was reported. The
THIS ARTICLE
nanoparticles were synthesized through the chemical reduction of aqueous solutions of copper
Copper (II) Sulfate Pentahy- (II) sulfate with ascorbic acid, using different native cyclodextrins (NCDs) (a-, b-, or c-NCD) as
drate (CuSO4.5H2O, Pub- stabilizing agents. Cu-NPs were characterized by scanning electron microscopy–energy dispersive
Chem CID: 24463); spectroscopy (SEM–EDX), powder X-ray diffraction (XRD) and transmission electron microscopy
a-NCD (C36H60O30, Pub- (TEM). The pattern showed in the typical selected area electron diffraction (SAED) and lattice
Chem CID: 444913); fringes, evidence that the crystalline structure of Cu-NPs is face-centered cubic (FCC) with a
b-NCD (C42H70O35, Pub- (1 1 1), (2 0 0) and (2 2 0) lattice planes of Cu. The analysis of the TEM images show that the size
Chem CID: 444041);
of the Cu-NPs depends on the type of native cyclodextrin (NCD), also it was observed that the
c-NCD (C48H80O40, Pub-
Chem CID: 86575);
nanoparticles are spherical and with a size between 2 and 33 nm. The smaller Cu-NPs were
Ascorbic Acid (C6H8O6, obtained with a-NCD (mode 4 nm), while the nanoparticles obtained with b-NCD show the narrow
PubChem CID: 54670067) size distribution (mode 6.5 nm). The average particle size and particle size distribution of Cu-NPs
depend upon the type of CDs.
KEYWORDS Ó 2016 King Saud University. Production and hosting by Elsevier B.V. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Copper-nanoparticles;
Green chemistry method;
Cyclodextrins as stabilizing
agents
* Corresponding author.
E-mail addresses: hespinoza@uabc.edu.mx (H. Espinoza-Gómez), lzflores@hotmail.com (L.Z. Flores-López).
Peer review under responsibility of King Saud University.
http://dx.doi.org/10.1016/j.jscs.2016.10.005
1319-6103 Ó 2016 King Saud University. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
342 J. Suárez-Cerda et al.
Scheme 1 General reaction for the synthesis and stabilization of Cu-NPs with NCDs.
Figure 2 ATR-FTIR spectra of (a) b-NCD, and Cu-NPs synthesized with (b) a-NCD, (c) b-NCD, and (d) c-NCD.
ols (e.g., ethylene glycol) [25,26]; which they can be ‘‘caught” on ous solution was poured in a round bottom flask, and heated
the surface of Cu-NPs increasing nanoparticle toxicity [27]. at 80 °C. Later, the mixture of aqueous solutions of ascorbic
Therefore, green chemistry synthesis of Cu-NPs is an alter- acid and NCD was added drop wise to the metallic solution
native method for its preparation, due to some advantages: it is with magnetic vigorous agitation (700 rpm). The color of the
eco-friendly, environmentally benign and non-toxic solvents
are used [28–30].
Native cyclodextrins (NCDs) have a large number of pri-
mary and secondary hydroxyl groups, which can be used as
coordination sites for metal chelation, forming covalent bonds
at basic pH. Due to those groups, NCDs are water-soluble mole-
cules. These cyclic oligosaccharides possess a non-toxic nature,
so they have applications in the pharmaceutical, food, and cos-
metic industry, as well as in analytical separations [31–35].
The aim of this study is to determine the effect of the NCDs
size used as stabilizing agent, in the characteristics of Cu-NPs
synthesized (shape and size) by a green chemistry method, in
order to determine which one is the best stabilizing agent. This
work is part of a responsible green approach for the develop-
ment of nanotechnology.
2. Methodology
3500
3500 (a) (b) 3500 (c)
111
3000 3000 3000
111 111
2500 2500 2500
0 0 0
30 40 50 60 70 80 30 40 50 60 70 80 30 40 50 60 70 80
2 theta 2 theta 2 theta
Figure 4 XRD of Cu-NPs synthesized with (a) a-NCD, (b) b-NCD, (c) c-NCD.
solution changed, from light blue to light green, and finally to The structural characterization using XRD of Cu-NPs was
a dark yellow; after 5 min the formation of a brown precipitate studied using a Philips X0 pertMPD. The morphology and size
began. The reaction conditions were maintained for 5 h and of the as-synthesized Cu-NPs were characterized by transmis-
then cooled to room temperature. After that, the solution with sion electron microscopy (TEM, JEM-2100F, JEOL), at an
the brown precipitate was centrifuged for 10 min at 4000 rpm. accelerating voltage of 200 kV and fitted with a CCD camera.
The precipitate was washed two times with distilled water
(5 mL) and once with ethanol anhydrous (5 mL), to remove 3. Results and discussion
any unreacted reagent. Finally, the brown powder was dried
at room temperature to obtain the Cu-NPs. Cu-NPs are very The methodology for synthesizing Cu-NPs, using NCDs as
sensible to oxidation and tend to form copper oxide nanopar- stabilizing agent in water, is very simple. However, no reports
ticles. However, the formation of the Cu-NPs was achieved have been found in the literature concerning the study of the
due to the reducing and stabilizing properties of ascorbic acid effect of the NCD size, as a stabilizing agent, on the colloidal
and NCDs, respectively. The formations of Cu-NPs were cor- synthesis of Cu-NPs at room temperature by a green chemistry
roborated by ATR-FTIR, SEM-EDX, XRD and TEM method. In Scheme 1 the proposed mechanism of nanoparticle
analyses. formation is shown, which considers that the characteristics of
the stabilizing agent used influence, the size and shape of the
2.3. Characterization of Cu-NPs nanoparticles.
Copper (II) sulfate dissolved in water, dissociates into Cu2+
The interaction between NCD and synthesized Cu-NPs was and SO2 4 . Cu
2+
is reduced to Cu0 by reduction action of
studied using a PerkinElmer Spectrum 400 FT-IR/FT-NIR ascorbic acid, forming metallic copper nuclei, which initiate
Spectrometer with Universal ATR Sampling Accessory. The the growth stage. Growing nanoparticles are stabilized by sev-
presence of elemental copper was determined using a VEGA eral molecules of cyclodextrins distributed around them (Cu-
3 Tescan scanning microscope equipped with EDX capability. NPs-NCD). These agglomerates grow to a certain size and,
Green synthesis of copper nanoparticles 345
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