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Original Article
a
Institute of Mathematical Sciences and Physics, University of the Philippines Los Ban ~ os College, Laguna, 4031, Philippines
b ~ os College, Laguna, 4031, Philippines
Institute of Biological Sciences, University of the Philippines Los Ban
c
Department of Forest Products and Paper Science, University of the Philippines Los Ban ~ os College, Laguna, 4031, Philippines
a r t i c l e i n f o a b s t r a c t
Article history: Copper-based precipitates were synthesized using a straightforward wet chemical reduction method
Received 18 October 2018 with copper sulfate salts as precursor and L-ascorbic acid as reducing agent. Scanning electron micro-
Received in revised form graphs of the precipitates reveal particle-like structures with edges. The percent age yield was observed
23 December 2018
to increase with the reaction temperature and the reductant-to-precursor concentration ratio. Com-
Accepted 29 December 2018
Available online 5 January 2019
parison of samples prepared at different times showed that the bulk of the precipitates was formed
during the first 24 hours. New yield added to the bulk decreased over time. Here, the ascorbic acid served
as a capping agent, which impeded the oxidation. This capping was not visible in the electron micro-
Keywords:
Wet-chemical method
graphs but may be inferred from the infrared spectra. Faster capping reduced the amount of oxides in the
Capping precipitates. This was seen in samples prepared at a higher temperature and with a lower reductant-to-
Antimicrobial precursor concentration ratio. Antimicrobial testing under dynamic contact conditions showed that the
Staphylococcus aureus copper-based precipitates were more effective against Staphylococcus aureus (a gram-positive bacteria)
Escherichia coli than Escherichia coli (a gram-negative bacteria). Copper-based precipitates collected after the first 24
hours were more potent than those collected after eight days. Furthermore, samples prepared at room
temperature and lower reductant-to-precursor concentration ratios were found to be more effective in
reducing the number of S. aureus after one hour of contact. The synthesized copper-based precipitates
was observed to reduce the population of S. aureus (CFU/mL) by up to 98% after one hour of contact.
© 2019 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
1. Introduction cells. Thus, when placed on different materials and surfaces, anti-
microbial agents can minimize, inhibit, or stop the spread of infec-
Copper is a popular cheaper alternative to silver. Often, it is used tious diseases. Antimicrobial agents may be in the form of liquids,
as a conductor of heat and electricity. Like silver, antimicrobial gels, sheets, and powders. Unlike liquids and gels, powders do not
properties of copper [1e6] are well known. Knowledge of its evaporate and, thus, have longer effective lifetime. Compared to
sanitizing ability dates back to Ancient Egypt, when it was used to sheets, powders have the advantage of being easily integrated,
clean drinking water but it was not until the 19th and early 20th mixed, and incorporated in different materials.
centuries when its applications in the field of medicine became Copper particles or powder may be produced using physical,
prevalent [5]. electrochemical, and chemical means [7e21]. Physical methods
Antimicrobial properties may be attributed to the ability of (e.g., pulse laser ablation or deposition, ball milling method, and
charges (e.g., ions, oxidation states, free electrons, radicals) to pulsed wire discharge method) and electrochemical methods (e.g.,
directly or indirectly disrupt the vital charge transports within the chemical reduction) may be faster. However, these methods usually
require more expensive equipment and/or higher energy cost.
* Corresponding author.
Chemical methods (e.g., chemical reduction) may offer cheaper
E-mail address: muherrera@up.edu.ph (M.U. Herrera). alternatives. But these, at times, use reagents and/or produce by-
Peer review under responsibility of Vietnam National University, Hanoi. products which are harmful to the environment.
https://doi.org/10.1016/j.jsamd.2018.12.009
2468-2179/© 2019 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
A.R. Ramos et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 66e71 67
2. Methodology
Fig. 2. Scanning electron micrographs of the precipitates produced at room temperature (~25 C) after 24 hours using 0.2 M copper sulfate solution and 1.2 M ascorbic acid solution.
The magnifications were (a) 1000, (b) 2000, (c) 5000 and (d) 8000.
68 A.R. Ramos et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 66e71
Table 2
Amount of precipitate collected after 24 hours at different temperatures using 0.2M
copper sulfate solution and 1.2M ascorbic acid solution.
25 0.5072 15.96
85 2.9092 91.56
Table 3
Antimicrobial properties of the precipitates against S. aureus and E.coli under dy-
namic contact conditions. The samples were synthesized at different reaction
temperatures using 0.2M copper sulfate solution and 1.2M ascorbic acid solution.
S. aureus E. coli
25 98 33
85 83 32
Table 6
Amount of precipitate produced at ~25 C using 3:1 reductant-to-precursor con-
centration ratio at different collection times.
have become very small and almost indistinguishable (Fig. 6). After
the first 24 hours, conditions may have favored capping over
further aggregation and improving the yield. Capping may have
continued and become more extensive lessening oxidation and
lowering the antimicrobial property of the precipitates.
In general, the synthesized copper-based particles have better
antimicrobial properties against S. aureus than against E. coli. The
higher percentage reduction observed in S. aureus as compared to
the percentage reduction of E. coli may be attributed to the struc- Fig. 6. X-ray diffraction patterns of precipitates that were taken from the second
tural difference in their cell wall. Gram-positive bacteria such as collection of the samples. The samples were produced at 25 C reaction temperature
S. aureus have abundant pores, which may facilitate foreign parti- using 1.2 M of ascorbic acid solution and (a) 0.4M, (b) 0.2M and (c) 0.1M copper sulfate
solutions. The corresponding reductant-to-precursor ratios are (a) 3:1, (b) 6:1 and (c)
cles to pass through. On the other hand, gram-negative bacteria
12:1, respectively.
such as E. coli have lipopolysaccharide, lipoproteins and phospho-
lipids, which make up a better barrier against foreign particles. The
higher antimicrobial activity of different materials against S. Aureus than in the samples prepared at a higher temperature and using a
than against E.coli is also observed in other works [27e30]. greater reductant-to-precursor concentration ratio.
Comparison of precipitates collected at different times suggests
that about 47% of the total product resulted from reactions occur-
4. Conclusion ring within the first 24 hours. However, in the succeeding days,
these reactions slowed down. The conditions may have favored
A straightforward wet chemical reduction technique was capping thus lowering the amount of oxide in the samples and
employed to produce copper-based particles. Copper sulfate salts decreasing its antimicrobial ability.
and L-ascorbic acid were used as precursor and reducing agent,
respectively. Synthesis of copper-based precipitates was confirmed Acknowledgements
through an X-ray Diffractometer. Scanning electron micrographs of
the precipitates showed particle-like structures with edges. The
This research is funded by Philippine Council for Industry, En-
amount of synthesized copper particles per unit of available copper
ergy, and Emerging Technology Research and Development
ions varied with the reaction temperature and the reactant con-
(PCIEERD), Department of Science and Technology (DOST) with
centration. Greater percent age yield was obtained when the
project number 04013.
sample preparation was performed above room temperature and a
higher reductant-to-precursor concentration ratio was used.
Infrared spectra of the samples suggest formation of networks of References
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