DOI: 10.1002/slct.

201801504 Full Papers

1
2 z Organic & Supramolecular Chemistry
3
4
5
Nanobubbles from Ethanol-Water Mixtures: Generation and
6 Solute Effects via Solvent Replacement Method
7
8 Jeremiah C. Millare*[a] and Blessie A. Basilia[a, b]
9
10
11 Replacement of ethanol-water solutions (70 – 100% v/v) with showed that the resulting solutions upon exchange have
12 deionized water was performed in a flow cell of a particle size higher particle quantities than the starting ethanol-water
13 analyzer. The resulting alcohol solutions were found to contain solvents with smaller diameters ranging from 80 to 160 nm due
14 bulk nanoscale bubbles due to air supersaturation as can be to nanobubble formation. The claim for air supersaturation
15 induced by the difference in gas solubility of the solvents. The forming nanobubbles that may have resulted to the increase in
16 effect of charged and polar solutes (salt and sugar) that may particle density can also be deduced from the obtained optical
17 influence the formation and surface chemistry of nanobubbles images in a microscope. The electrokinetic potential or zeta
18 was also determined. Dispersion characteristics such as hydro- potential was also higher for the solvent exchange protocols
19 dynamic diameter, particle concentration, along with the entailing for a selective orientation of ethanol molecules in a
20 particle‘s electrokinetic property were measured all at once bubble surface. More importantly, In terms of solute effects, it
21 using light scattering techniques after solution replacement appears that while salt anions promote gaseous diffusion, sugar
22 with and without the solute species. Light scattering results molecules inhibit it.
23
24
nanobubbles last for up to several days are the surrounding
25 Introduction
charged species that can control the surface tension and resist
26
The past decade showed interesting investigations on bubbles the different forces of dissolution.[13–14] Due to these unique
27
with less than 1 μm in diameter. Their skeptical existence characteristics, various fields in nanotechnology can be signifi-
28
before are now vividly reported as advanced characterizations cantly influenced by this new class of nanoscopic domain.[15–19]
29
on nanosystems continuously evolved. Microscopy techniques Generating nano-size bubbles in aqueous and organic
30
used to image nanobubbles on a surface such as Atomic Force solutions through the use of different stimuli like heat, sonic
31
Microscopy (AFM)[1,24,26,35–36,39] Total Internal Reflection energy, electrical potential and gas dissolution along with other
32
Fluorescence Microscopy (TIRF)[2–4] and Freeze–Dried Method techniques have been reported. Commonly used methods like
33
on a Transmission Electron Microscope (TEM)[5] supports the ultrasonication,[6–7] gas supersaturation[19] and baffled agitation
34 [20]
evidence of their possible existence in bulk liquids as detected were able to generate nanobubbles homogeneously in the
35
in Laser Light Scattering Techniques.[6–10,22] Just recently, a liquid phase and can impact applications in environmental,
36
Nanoparticle Tracking Analyzer (NTA) – considered as a new industrial and agricultural fields.[21–25] Other methods such as
37
type of Dynamic Light Scattering, equipped with an ultra- electrolysis,[8,26–28] temperature difference,[29] microwave irradi-
38
microscope and a laser illumination system that calculates the ation[30] and solvent exchange[1,31–36] are known for nanobubble
39
size of analyte on a particle–by particle basis has been nucleation at the surface of a hydrophobic material making
40
successfully used to image nanobubbles in bulk liquids.[9–10] them suitable for more sophisticated systems like micro and
41
Nanobubbles are known initially to form on hydrophobic nano fluidics,[37–39] and, immunoassays[40–42] in the biomedical
42
surfaces in liquids.[11–12] In bulk liquids, their ability to stagnate field.
43
and become stable for longer periods of time given their high Among the said techniques, several studies have proven
44
internal pressure compared to ordinary bubbles put them at the effectiveness of using solvent exchange for generating
45
the frontier of bubble research. One of the factors why nanobubbles in a hydrophobic substrate. An organic solvent
46
like ethanol has been used[1,31–33,35 36] to be replaced with water
47
in various hydrophobic flat surfaces. Since the former has more
48 [a] Prof. J. C. Millare, Dr. B. A. Basilia dissolved gases in the solid-liquid interface, trapped gases
49 School of Chemical, Biological, Materials Engineering and Sciences, Mapua
comes out of the surface through nanobubbles upon purging
50 University, Muralla Street, Intramuros, Manila, Philippines, 1002
E-mail: jcmillare@mapua.edu.ph of ethanol with water. Solution exchange of salt-water mixtures
51
[b] Dr. B. A. Basilia instead of an organic solvent has also been proven to
52 Materials Science Division, Industrial Technology Development Institute, effectively generate nano-size bubbles on a hydrophobic
53 Department of Science and Technology, General Santos Avenue, Bicutan,
surface.[34] These studies have developed correlated sets of
54 Taguig, Metro Manila, Philippines, 1631
E-mail: basiliablessie@gmail.com properties and optimized conditions to generate stable nano-
55
Supporting information for this article is available on the WWW under bubbles on a surface using solvent exchange. A similar concept
56
https://doi.org/10.1002/slct.201801504 of nanobubble generation based on solvent exchange method
57

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was applied by simply mixing organic solvents of high gas
1
solubility with water. However, this method has undergone
2
issues on whether bulk nanobubbles were really formed or not.
3
A study from Habich et al.[43] proposed that the presence of
4
nano-scale objects in aqueous organic solutions were not
5
gaseous domains but contaminants arising from sample
6
preparation. Moreover, Sedlak et al.,[44] through application of
7
gravitational centrifugal fields suggest that these particles are
8
supramolecular structures. With all these anti-nanobubble
9
postulates, several studies were still able to provide strong
10
evidences of nanobubble presence in the said solutions .[1,8,10,22]
11
The generation of bulk particles in ethanol-water system
12
has already been demonstrated. However, compared to Figure 2. DLS data comparing 20–30% v/v ethanol solutions. (From left to
13
previous works concerning only on whether bulk nanobubbles right) the first two were prepared in a beaker; and the next four samples –
14
were formed or not,[8,43,44] the present work will also determine with final concentrations of about 28, 25, 22 and 20% v/v ethanol
15 respectively, were prepared directly into the flow cell.
the effect of adding solute species like salt and sugar on the
16
formation and surface modification of nano-scale objects in
17
ethanol-water mixtures.
18
concentration and was much higher than the 30% and 20%
19
samples prepared in the beaker. It can be suggested that micro
20
Results and Discussion confinements or the increased in surface area of the pure
21
solvents in the micro-channels of the flow cell increases the
22 1. Concentration and Size of the Generated Particles
contact between the liquids during mixing thereby increasing
23
The ethanol mixtures were replaced with deionized water and the rate of formation of nano-size bubbles. In the other respect,
24
the resulting solutions generate particle concentrations far the dissolution of the initially formed bubbles in the beaker
25
greater than the individual solvents as shown in Figure 1. This samples upon transport to the flow cell may have also
26
contributed to the difference. Meanwhile, the 70 and 80%
27
ethanol to water samples with final concentrations of about 20
28
to 22% ethanol had a much lower particle counts per ml
29
compared to the beaker samples. This can be caused by the
30
initial particles present in the 70 and 80% ethanol starting
31
solvents. In nanobubble formation, these intrinsic particles
32
reported by other groups[45–48] as aggregated ethanol and
33
ethanol-water molecules may limit the encapsulation rate of
34
gaseous domains as they would have to be re-dissolved again
35
in the solvent replacement process. Overall, based on the
36
figures presented, it can be shown that the number of
37
generated particles strictly depends on the concentration of
38
alcohol and was highest at around 20–30% v/v ethanol
39
whether or not the mixing process was done directly in the
40
Figure 1. Light scattering data of sample solutions. Particle concentration flow cell volume. The high particle concentration at these
41 and hydrodynamic diameter determined by Dynamic Light Scattering (DLS). ethanol-water ratios was also reported by other authors.[8,10,43]
42
In terms of particle size, the pure solvents did not exhibit a
43
stable sub-micron hydrodynamic diameter; mostly, molecular
44
phenomenon has also been observed by other studies.[8,10,43] clusters of 1-nm size for deionized water and pure ethanol
45
The cause of particle generation/increase can be attributed to were obtained. The mixing of the pure solvents up to 70%
46
the formation of air nanobubbles when water of low gas ethanol generates bigger particles (∼ 300 nm) which were
47
solubility attempts to carry the gaseous species dissolved in reported to be aggregated molecular clusters.[45–48] On the
48
high-ethanol solutions. other hand, samples obtained from the replacement process
49
The direct mixing of the solvents into a flow cell may have have particles that are much smaller and close to the ∼ 140-nm
50
also enhanced the air dissolution process and eventual objects of the 20 and 30% ethanol–beaker samples. Though
51
formation of bubbles. Figure 2 compares the ethanol-water one may attribute the decrease in particle size upon solvent
52
mixtures of 30% and 20% v/v alcohol prepared in a beaker with exchange to the dissolution or dissociation of particles initially
53
the solvent exchange solutions – roughly 28, 25, 22 and 20% v/ present in the starting solutions (90 – 70%), the high particle
54
v ethanol respectively. concentrations for the 100EtOH to H2O and 20–30% ethanol
55
It appears that the 100%EtOH to H2O sample with a final beaker samples (having started with the pure solvents) suggest
56
ethanol content of about 28%, produced the highest particle it otherwise. The particles contained in the starting solutions
57

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 Full Papers
however may still play a role in the replacement process. If
1
these are aggregated amphiphilic molecules of ethanol as
2
reported, they may scatter or re-dissolve upon water injection
3
and interact with the newly generated particles, or perhaps,
4
even participate in the encapsulation of accumulated gaseous
5
domains. This may have contributed to the bigger particle sizes
6
for the solvent-replaced samples particularly at starting
7
solutions of 80–70% ethanol where the particle concentrations
8
are 103 much higher than pure ethanol. Concentrations of
9
about 1x106 – 1x107 particles/ml were measured for these
10
starting solvents representing only a diminutive fraction of the
11
maximum in Figure 1.
12
13
14 2. Zeta Potential of the Generated Particles Figure 4. Zeta Potential comparison for the 20–30% ethanol solutions.
15
Figures 3 shows that the samples from solution exchange
16
protocols have much higher zeta potentials than the ethanol-
17
water through the –OH group and eventual anion adsorp-
18
tion.[6,49]
19
Take note that we do not exclude the possible concurrence
20
of pure molecular aggregates even at low-ethanol solutions
21
(20-30%) nor the absence of gaseous-object clusters at higher
22
ethanol concentrations. It can be implied based on the earlier
23
results and zeta potential data that the existence of mostly
24
aggregated molecules especially at high-ethanol amounts as
25
reported by other groups can drastically lower the zeta
26
potential since it would be highly difficult for them to have an
27
ordered array of molecules on a surface compared to ethanol
28
aggregation at an air-water interface.[49] This irregularity of
29
surface structure affects the adsorption of negative ions as
30
would have been the case for a bubble surface.[6,8,22]
31
32
33 Figure 3. Zeta Potential of the solvents and solution exchange samples. 2. Microscopic Analysis2.1 Bulk Particle Imaging of Starting
34 The zeta potential was determined by the embedded Phase Analysis Light Solvents
Scattering (PALS) system of the particle size analyzer.
35
Figure 5 shows the optical images of ejected ethanol solutions
36
and water from the flow cell using bright light. No indication of
37
38
water solutions or solvents used. This was also the case when
39
plotted alongside the 20–30% ethanol beaker samples as
40
presented in Figure 4. Zeta potential measures the stability to
41
particle aggregation through the adsorption of ionic species on
42
the particle’s surface and nanobubbles were known to have a
43
negative zeta potential both on surfaces and in bulk liquids;[8,22]
44
the large difference in zeta potential for the two sample sets in
45
Figure 3 can be an indication that a new type of object was
46
formed giving incentives for nanobubble presence. Figure 5. Optical images upon ejection of samples from flow cell. (a)
47
The available data shows two reasons for obtaining a high Deionized Water (b) 100% Ethanol and (c) 80% Ethanol. Scale bar is 120 μm.
48
negative zeta potential – (1) as reported in previous works[8,10,35]
49
air solubility was much lower in low-ethanol samples and can
50
induce air supersaturation forming nanobubbles, and (2) as
51
discussed earlier, enhanced interaction of the species in the bulk particles within the entire depth of liquid was observed in
52
solvents through solvent replacement in the flow cell. These the samples. Imaged particles from high-ethanol solutions
53
factors can make the particle surface more negative by range mostly from less than 5 μm to 10 μm. These were
54
facilitating the formation of aligned amphiphilic ethanol possibly, trapped micron-size bubbles near the glass substrate
55
molecules at the interface promoting hydrogen bonds with upon ejection of the liquid from the flow cell and were more
56
apparent in 80% sample.
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Accordingly, there have been reports where micron-size Figure 7 was also detected from DLS as shown in Figure 8. In
1
bubbles were imaged along with nanobubbles using solvent comparison to the ethanol-water mixtures prepared in a
2
exchange in ethanol-water[31–32,35] and NaCl-water[34] systems
3
but in smaller populations compared to the latter. Micro-
4
bubbles were also reported to be generated along with
5
nanobubbles in bulk liquids using other techniques.[7–8,22] In the
6
present study, shown in Figure 6 was the DLS detection of
7
8
9
10
11
12
13
14
Figure 7. Optical images upon ejection of samples from flow cell. (a) 100%
15 EtOH to H2O and (b) 80%EtOH to H2O. Fine tuning for bulk movements in
16 sample (b) causes microbubbles trapped near the glass substrate to blur,
17 enlarging the actual size. Scale bar is 120 μm.
18 Figure 6. Sample DLS plot for (a) Deionized Water (b) Pure Ethanol and (c)
80% Ethanol. Micron size objects (< 10 μm) presumed to be microbubbles
19
were also detected in the 80% ethanol sample.
20
21
22
micron-size objects also in very small quantity (less than 4% of
23
the population) compared to its nano-size counterpart. The
24
point here is, although nano-scale objects were hard to be
25
detected using an optical microscope, the emergence of
26
micron-size bubbles can serve as a reference for nanobubble
27
presence negating the possibility that they are purely aggre-
28
gated ethanol-water molecules. It can be observed in the Figure 8. Sample DLS plot for (a) 100%EtOH to H2O and (b) 80%EtOH to
29 H2O. Micron size objects (∼ 10 μm) presumed to be microbubbles were also
images that the particle density was higher for the 80% sample
30 detected in both samples.
or when the ethanol and water solvents were mixed. Therefore,
31
an increase in both concentrations – micron and nano-size
32
bubbles upon mixing would be plausible.
33
Considering the DLS readings, only 1 of about 10 readings beaker, the frequency of micron-size detection increases to
34
was obtained where micron-size particles are detected due to about 5 out of 10 readings substantiating the possible increase
35
the high sub-micron sensitivity of the DLS equipment. Given in the number of nano-size particles. In fact, the higher
36
the very small illuminated part that is viewed by the detectors scattering intensities of nano and micron-size objects in
37
(only < 1 μL), particles bigger than 5 μm could be neglected Figure 8 can further support this claim. This may now explain
38
during DLS measurement giving incentives for microscopic the generation of smaller particles for the solution replacement
39
analysis. samples as was shown in Figures 1 and 2; it disregards the
40
possibility that they are merely dissociated particles from the
41
initial solvents. It should also be noted that given the increase
42 2.2 Bulk Particles from Solution Exchange Samples
in frequency of micron-size detection for the solvent exchange
43
Evidence of improved particle generation upon solution samples, the high sub-micron sensitivity of the DLS equipment
44
replacement can be seen in Figure 3. Increased particle density and greater increase in the number of nano-size objects still
45
and presence of hair-like movements in the bulk liquid prompted smaller particle size measurements compared to the
46
strengthens the claim that the resulting ethanol-water mixtures individual solvents/solutions.
47
were supersaturated with air causing air bubbles to come out
48
of the solution. Bulk particle movements can be considered in
49
the sub-micron range as those detected in DLS and are stable 3. Solute Effects
50
upon continuous observation in the microscope. It should be
51 3.1 Effect of Salt Addition on Bubble Generation and
noted that if these bulk movements were just purely
52 Properties
aggregated molecules, they should also transpire in the bulk of
53
80 and 100% ethanol samples. Perhaps, as being suggested, Salts are compounds that can play an important role on
54
the particles were influenced by gaseous domains. different reactions and processes that occur in liquids. They are
55
The particle generation at the micron level causing high instantly solvated by water in an aqueous organic solution
56
particle densities for the solution replacement samples in which causes the water molecules to be “salted out”.
57

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Alternatively, when aqueous solutions of salt are mixed with a We now explain these changes theoretically and in
1
polar solvent like ethanol, the alcohol easily solvates the water accordance to previous reports[50–51] regarding the interaction
2
causing a “salting in” phenomenon. The present work applies of salts with amphiphiles, H2O molecules and other species in
3
this effect to observe how ionic species may affect the liquids. This can be rooted out in two ways – (1) the anion of
4
formation and dispersion properties of the presumed nano- salt (Cl and SO32 ) can interact through ion-dipole forces with
5
bubbles in ethanol-water solutions. Shown in Figures 9 and 10 the polar H group of amphiphilic ethanol molecules[51] making
6
it hard for them to stabilize or encapsulate gaseous domains.
7
This can lead to accumulation of gas molecules readily
8
increasing the bubble size and may decrease the number of
9
stable bubbles formed, and (2) the Na + ions interferes with
10
the H2O molecules and OH ions on the surface of the
11
proposed micelle-encapsulated nanobubbles giving a lower
12
zeta potential. This adsorption of Na + ions on the outer
13
surface (that is, on top and/or in place of H2O and/or OH–
14
species) becomes more pronounce at higher salt concentra-
15
tions and could lead to a higher rate of bubble coalescence.
16
In this experiment, for all samples, a small macrobubble can
17
be seen on top of the flow cell glass surface after light
18
scattering measurements (see Supporting Information Fig-
19
ure S1) and its size increases at increasing amounts of salt. This
20
can support the postulate of gas diffusion or accumulation due
21
Figure 9. DLS data of 100% Ethanol replaced with aqueous solutions of salts to encapsulation inhibition, and, bubble coalescence through
22
(NaCl and NaSO3). time as possibly caused by the low zeta potentials.
23
But what about the higher particle concentrations and
24
smaller average sizes formed up to 3% NaCl sample? It has
25
been reported that the cation Na + can lower the surface
26
tension of bubbles in surfactant solutions through its direct
27
interaction with the polar head of surrounding amphiphilic
28
molecules.[52] The cations pull them together making the
29
bubble rigid and smaller. It appears that the 3% NaCl in water
30
(or much smaller after the exchange process) was small enough
31
to regulate the interaction between Cl ions and ethanol
32
molecules while allowing the Na + ions to participate in the
33
encapsulation of gaseous domains. As previously reported,
34
these cations can hold the amphiphilic molecules through their
35
polar group allowing more bubbles to be stabilized while
36
making the overall diameter smaller.
37
In spite of this, the allowance for bubble stabilization seems
38
to be outweighed at further increase of NaCl concentration. As
39 Figure 10. Zeta Potentials of 100% Ethanol replaced with aqueous solutions
of salts (NaCl and NaSO3)
posited earlier, the Cl- ions may decrease the degree of
40
amphiphilic encapsulation allowing more time for gases to
41
diffuse in, forming fewer bubbles with bigger average sizes. By
42
are the light scattering results when salt was added in the considering also the type of salt used, the effects were more
43
replacing liquid. apparent for the Na2SO3 solutions since it contains twice Na +
44
For the 100%EtOH to %Salt samples, the resulting solutions ions, and, a much bigger and more negatively charged SO32
45
have a final salt concentration much lesser than the provided ion. It shows that the Na2SO3 resulting solutions had even
46
water-salt ratios but were surely of increasing amounts. In skipped the stage of particle concentration increase and
47
Figure 9, increased particle concentrations and smaller bubble bubble size reduction due to the apparent ionic effect improve-
48
diameters can be observed at initial additions of NaCl followed ment.
49
by an inversion at the highest ionic concentration; this was in Salt addition was also performed for the 80%EtOH to H2O
50
contrast to the NaSO3 samples where a single transition of samples and light scattering results in Figures 11 and 12
51
decreasing particle quantity and increasing particle diameter provided a trend similar to the 100%EtOH to %Salt solutions.
52
were obtained. The only difference was the sudden decrease in concentration
53
In Figure 10, for both NaCl and Na2SO3 solution samples, a and zeta potential of the presumed nano-scale gaseous objects
54
decrease or much less negative zeta potentials can be noticed for the two sets of salted solutions. This may have been caused
55
and were more apparent for the latter. by the additional water moieties in the starting solution that
56
can increase the chemical activity of the ions present and lack
57

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1
2
3
4
5
6
7
8
9
10
11
12
13
14 Figure 11. DLS data of 80% Ethanol replaced with aqueous solutions of salts Figure 13. DLS data of 100% Ethanol replaced with aqueous solutions of
15 (NaCl and NaSO3). sugar (Glucose and Sucrose).
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Figure 12. Zeta Potentials of 80% Ethanol replaced with aqueous solutions of Figure 14. Zeta Potentials of 100% Ethanol replaced with aqueous solutions
32 salts (NaCl and NaSO3) of sugar (Glucose and Sucrose).
33
34
35
of ethanol molecules for encapsulation. A small macrobubble
36
caused by the reduced air solubility of salt addition was also and still be utilized in forming the air-water interface. All these
37
observed for this set of solutions after the measurements. will favor the results presented in Figures 13 and 14.
38
The slight decrease or a less negative zeta potential at
39
initial glucose additions may have been caused by a perceived
40 3.2 Effect of Sugar Addition on Bubble Generation and
irregularity of ethanol-glucose structure on a bubble surface.
41 Properties
Nevertheless, at higher concentrations, enough glucose mole-
42
In the same way, a non-electrolyte like sugar may have an cules may form a much organized interaction while also
43
effect on bubble formation and properties due to its polar improving anion adsorption. Accordingly, it appears that the
44
molecular structure. It is also quite interesting how a bulkier much bigger sugar molecule (sucrose) may readily form a more
45
sugar molecule may play a role in nanobubble generation. stable air-water interface enhancing the corresponding
46
Shown in Figures 13 and 14 are the light scattering data for changes in bubble properties.
47
the 100%EtOH to %Sugar solutions. The results greatly differ In Figures 15 and 16, the same trend were obtained for the
48
from the previous nanobubble salt solutions. Collectively, the 80% ethanol starting solvent in terms of the changes in
49
number of particles generated increases significantly, the quantity, size and zeta potential of the presumed bulk nano-
50
bubble size decreases, and the zeta potential increases upon bubbles. Nevertheless, as one may expect, the percent decrease
51
glucose and sucrose addition. The reason for this was unlike in average diameter of the detected particles upon sugar
52
salt, sugar molecules have a hydrophobic backbone that can addition was higher due to a much significant increase in
53
promote the stabilization of gaseous phases, and, polar groups number of species for bubble encapsulation; that is, unlike the
54
for hydrogen bonding with the H2O molecules and OH– ions. previous solution exchange protocol, smaller number of
55
They can also interact with the amphiphilic ethanol molecules ethanol molecules is present (only 80%v/v), which was also
56
57

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 Full Papers
causes anions to interact with ethanol molecules allowing gas
1
phase accumulation resulting to an increase in bubble size.
2
Cations on the other hand are said to be adsorbed on the
3
bubble surface decreasing the zeta potential and may also
4
participate, to a certain extent, in bubble stabilization. Con-
5
versely, sugar molecules were observed to prevent gaseous
6
diffusion by participating in the encapsulation process through
7
their hydrophobic backbone; this increases the number of
8
generated nano-scale bubbles with smaller diameters. The
9
polar groups on the other hand were suggested to form
10
hydrogen bonds with the H2O and OH components of the
11
liquid based on the increased zeta potentials.
12
These heterogeneous effects caused by the interference
13
Figure 15. DLS data of 80% Ethanol replaced with aqueous solutions of sugar and property alterations of nanobubbles in the said solutions
14
(Glucose and Sucrose) can greatly influence the extensive applications of ethanol-
15
water systems in micro/nano-fluidic reactions, protein purifica-
16
tion, and other microbiological interactions.
17
18
19 Supporting Information Summary
20
Details on the materials, chemicals and methods conducted
21
can be found in the supporting information file. This includes
22
the purification and preparation of the sample solutions, as
23
well as the parameters and equipments utilized for nanobubble
24
characterization.
25
26
27 Acknowledgement
28
The authors greatly acknowledged the Engineering Research and
29
Development for Technology (ERDT) Scholarship Program of the
30
Figure 16. Zeta Potentials of 80% Ethanol replaced with aqueous solutions of Department of Science and Technology - Science Education
31
sugar (Glucose and Sucrose). Institute (DOST-SEI) for funding this research work.
32
33
34 Conflict of Interest
35
possibly aggravated by the intially formed particles in the The authors declare no conflict of interest.
36
starting solution.
37
38 Keywords: alcohol · light scattering · nanoscale bubbles ·
39 Conclusions solute effects · surface chemistry
40
The effect of solvent replacement method and addition of ionic
41
and polar solutes in the generation of nanobubbles from
42 [1] T. Lou, J. Gao, X. Xiao, X. Li, G. Li, Y. Zhang, M. Li, J. Sun, X. Li, J. Hu,
ethanol-water mixtures has been successfully investigated
43 Mater. Charact. 2002, 48, 211–214.
through Dynamic Light Scattering (DLS) and Phase Analysis [2] C. Chan, C. Ohl, Phys. Rev. Lett. 2012, 109, 174501.
44
Light Scattering (PALS) techniques. The solvent replacement [3] C. Chan, M. Arora, C. Ohl, Langmuir. 2015, 31, 7041–7046.
45 [4] B. Tan, H. An, C. Ohl, Phys. Rev. Lett. 2017, 118.
procedure enhances the nucleation of sub-micron bubbles in
46 [5] T. Uchida, S. Oshita, M. Ohmori, T. Tsuno, K. Soejima, S. Shinozaki, Y.
the said solutions especially for the 100%EtOH to H2O–
47 Take, Y. Mitsuda, Nanoscale Res. Lett., 2011, 6, 295.
exchange sample. It can be concluded based on the light [6] J. Kim, M. Song, J. Kim, J. Colloid Interface Sci. 2000, 223, 285–291.
48
scattering and microscopic analyses, that the optimum concen- [7] S. Cho, J. Kim, J. Chun, J. Kim, Colloids Surf., A. 2005, 269, 28–34.
49 [8] F. Jin, J. Li, X. Ye, C. Wu, J. Phys. Chem. B. 2007, 111, 11745–11749.
tration of ethanol for an ample gneration of gaseous-objects
50 [9] J. Zhu, H. An, M. Alheshibri, L. Liu, P. Terpstra, G. Liu, V. S. J. Craig,
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