Journal of Molecular Liquids 252 (2018) 1–8

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Adsorption and interactions of the bovine serum albumin-double walled

carbon nanotube system
Turkan Kopac a,⁎, Kadriye Bozgeyik a, Emmanuel Flahaut b
a
Department of Chemistry, Bülent Ecevit University, 67100 Zonguldak, Turkey
b
CIRIMAT, Université de Toulouse, CNRS, INPT, UPS, UMR CNRS-UPS-INP N°5085, Université Toulouse 3 Paul Sabatier, Bât. CIRIMAT, 118, route de Narbonne, 31062 Toulouse cedex 9, France

a r t i c l e i n f o a b s t r a c t

Article history: Adsorption and interactions of Bovine Serum Albumin (BSA) with Double Walled Carbon Nanotubes (DWNT)
Received 21 October 2017 prepared by catalytic chemical vapor deposition (CCVD) synthesis were studied. Adsorption kinetics and equilib-
Received in revised form 11 December 2017 rium were investigated by means of in situ UV-spectroscopy. The extent of adsorption at different temperatures
Accepted 19 December 2017
was determined at the end of a 420-min adsorption period. The adsorption equilibrium experiments were per-
Available online 20 December 2017
formed using various amounts of nanotubes at pH 4 and 40 °C, and the adsorption parameters were evaluated
Keywords:
comparing the experimental data with models such as the Freundlich and Langmuir isotherms. The maximum
Adsorption protein adsorption capacity (Q0) of DWNT was determined as 1221 mg·g−1. The effect of temperature on the ad-
Double walled carbon nanotubes sorption rate experiments was investigated for constant amount of adsorbent at pH 4. Adsorption kinetics follow-
Bovine serum albumin ed the pseudo-first-order rate. Zeta potential measurements were performed with respect to solution pH for
understanding the protein-surface interactions. The interactions between positively charged BSA molecules
with negatively charged DWNT at pH 4 were found to be electrostatic attractions. Thermodynamic parameters,
ΔH0 and ΔS0 were found as 9.40 kJ·mol−1 and 321.5 J·mol−1 K−1, respectively. ΔH0 value indicated that BSA ad-
sorption on DWNT was a physisorption process.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction science [7]. CNTs are in the form of tubular hexagonal carbon structures
which are capped by half fullerene molecules. The main types of CNTs
Adsorption of proteins on solid surfaces is important in natural sci- are single-walled (SWNT), double-walled (DWNT) and multi-walled
ences, medicine and industry, and has an important role in numerous (MWNT) carbon nanotubes [8]. DWNT are at the interface between
applications such as protein chips, biosensors, food industry and medi- SWNT and MWNT with N2 walls, they combine the morphology and
cal implants [1,2]. In many applications related with biomedicine, as the flexibility of the former with the physico-chemical resistance of the lat-
interactions between proteins, implants and cells might have undesir- ter and can thus be considered as a good mode of “carbon nanotubes” in
able effects, inert surfaces should be used. For this reason, such kind of general. The dimensions of their structures range in between 0.4–2 nm
surfaces have been synthesized with various forms of surface modifica- in diameter for SWNT and 2–100 nm for MWNT. Their length typically
tions to inhibit the adsorption on the surfaces [3]. Also, there are appli- ranges from 1 to 50 μm. DWNTs have diameters typically ranging in be-
cations where the surface adsorption and interactions are desired, in tween 1 and 3 nm and lengths from several to tens of micrometers [9].
that case surface modifications are made in order to enhance the ad- DWNTs have a strong tendency to agglomerate and are practically not
sorption. In terms of potential toxicity and biodistribution in the body, soluble in solvents because of their strong hydrophobicity and van der
it is well known that the corona of adsorbed proteins plays a determin- Waals interactions within bundles. However, for potential applications
ing role in the fate of nanoparticles [4], and particles in general. Follow- in the fields of biology and biomedicine, solubility in aqueous solution
ing the discovery of carbon nanotubes (CNT) and because of their many is important [10]. Chen et al. [11] noted that protein adsorption on
potential uses including different biomedical applications, the interac- SWNT field effect transistors led to appreciable changes in the electrical
tion of biomolecules with CNT has been investigated in terms of bio- conductance of the devices that could be utilized for label-free detection
compatibility, usefulness as platforms to support growth of nerve cells of biomolecules. It was also reported that electronic effects occurring at
[5] or bioelectronic sensors [6]. CNTs having unique electronic, mechan- the nanotube-metal interfaces due to protein adsorption constituted a
ical and structural properties are also exploited in the field of materials more significant contribution to the electronic biosensing signal than
adsorption solely along the lengths of CNTs. Salvador-Morales et al.
⁎ Corresponding author. [12] investigated the protein binding to purified CNTs in human plasma
E-mail address: turkan.kopac@beun.edu.tr (T. Kopac). and serum. They reported that when MWNTs were exposed to the

https://doi.org/10.1016/j.molliq.2017.12.100
0167-7322/© 2017 Elsevier B.V. All rights reserved.
2 T. Kopac et al. / Journal of Molecular Liquids 252 (2018) 1–8

human plasma and serum, only a few kinds of proteins were able to area of DWNT sample were done using a Quantachrome Automated
bind MWNTs. Roman et al. [13] investigated the amino acids adsorption Gas Sorption Analyzer. Brunauer-Emmett-Teller (BET), Barrett-Joyner-
on graphite sheets and CNTs through density functional theory. They re- Halenda (BJH) and non-local density functional theory (NLDFT) tech-
ported weak binding of the biomolecules on both CNTs and graphite niques were used for the surface area, pore size and pore volume anal-
sheets, but generally favorable adsorption pathways were observed. ysis of the sample. TGA, operated in air atmosphere at 1°/min, was
Zwitterion adsorption through the charged carboxylate and amine performed using a SETARAM TAG24 thermobalance. The morphology
groups were bound stronger to the CNT surface as compared to the non- was observed by transmission electron microscopy (JOEL 2100F) with
ionic counterparts, phenylalanine, histidine, and cysteine side chain a maximum acceleration of 100 kV. Raman spectroscopy was performed
groups. Binding strengths on graphite did not show similar trends for using a Jobin Yvon LABRAM spectrometer (green laser at 532 nm) with
amino acid interactions with the increase in CNT diameter. In order a maximum power of 2 mW.
for CNTs to be used as biosensors or drug delivery carriers, information The effects of working parameters such as adsorbent dosage
regarding whether protein or enzyme biomolecules could bind with (0.2–1.0 g·L−1) and temperature (25, 30, 37, 40 °C) on BSA adsorption
CNT is rather important. were studied in a batch adsorber for a specific period of contact time.
Adsorption of BSA to various surfaces such as gold nanoparticles, Merck grade BSA (12,657, fraction V) was used as received. The BSA so-
gold electrodes, polypyrrole-based adsorbents, neutral and charged hy- lutions were prepared in 0.15 M NaCl solution at 0.60 g·L−1. Adjust-
drophilic and hydrophobic surfaces, silica, ment of solution pH was done using a NaH2PO4·2H2O/H3PO4 buffer
poly(hydroxyethylmethacrylate)-Reactive Green 19 cryogel disks, solution (pH 2.8). For equilibrium and kinetic studies, 100 mL of protein
mica, polymeric nanoparticles, chromium(III) oxide suspension, zirco- solution at constant initial concentration and at constant pH 4 was taken
nia nanoparticles were investigated in some of the reported literature in a 250 mL flask and agitated in a shaking water bath for 420 min con-
studies [14–23]. In recent years, there are only a few studies related tact time at 100 rpm speed. Equilibrium experiments were conducted
with the investigation of the adsorption and the attractions between with different concentrations of DWNT as adsorbent (0.2–1.0 g·L−1)
the proteins and carbon based nanomaterials [5,21–29]. at constant temperature (40 °C). Kinetic experiments were conducted
In our previous works, the kinetics and equilibrium of BSA adsorp- at 25, 30, 37, 40 °C with a constant dose of adsorbent (0.60 g·L−1). At
tion onto several metal oxides (TiO2, Al2O3, ZnO2) and attraction inter- various time intervals, the solution sample was filtered and then ana-
actions of surface-protein by zeta potential measurements were lyzed using the method of Lowry [35] by a Shimadzu 1700-E spectrom-
investigated [30–32]. The adsorption of BSA on MWNTs and SWNTs eter at a wavelength of 720 nm. The BSA concentration of the adsorbent
were also carried out and compared with the results of metal oxide ad- phase (qe, mg·g−1) was determined using,
sorption studies [33,34]. The optimum conditions for protein adsorption
on metal oxides and CNTs were found as pH 4 and 40 °C. In the present ðC o −C ÞV
qe ¼ ð1Þ
study, we focused on the equilibrium and kinetics of adsorption behav- w
ior of BSA on clean DWNTs prepared by a catalytic chemical vapor depo-
where Co is the initial value of BSA concentrations (mg·L−1), C is the
sition (CCVD) synthesis that involved the use of a MgO-based catalyst
BSA concentration (mg·L−1) at any time, V denotes the volume
[9]. The equilibrium and kinetics of BSA on DWNTs were examined at
(L) and w is the amount of DWNT (g). Some of the experiments were re-
optimum solution conditions (pH: 4, T: 40 °C) determined in the previ-
peated in order to check the reproducibility of the measurements, and
ous studies [30–34]. The electrokinetic properties of protein adsorption
the relative errors obtained for the selected runs were found not to be
were also examined to determine the interactions between BSA with
higher than 3%.
DWNTs. The protein capacity of DWNTs, at same experimental condi-
Zeta potentials for DWNT were measured at a concentration of
tions, was compared with protein capacities of metal oxides and other
0.02 wt% in 0.6 mg·mL−1 BSA solution using a ZetaPlus zeta potential
carbon nanotubes.
analyzer (Brookhaven Instruments Corporation) by electrophoresis
light scattering method. All BSA solutions were prepared using
2. Experimental 0.15 mol·L−1 NaCl solution in order to keep the ionic strength constant,
and the adjustment of the pH of the suspension was done using NH4Cl/
DWNTs used in this work were prepared by CCVD synthesis using a NH3 and NaH2PO4·2H2O/H3PO4 buffers, having pH 10 and 2.8, respec-
MgO-based catalyst containing Co and Mo as the active elements. The tively. The electrophoretic mobility (μe) is related to the zeta potential
details of the synthesis and sample processing were described earlier (ζ) as shown by the following Hückel equation:
[9]. Clean CNTs, obtained in gram-scale amounts, contained ca. 80%
DWNTs, the rest of the CNTs corresponding to ca. 5% of SWNT and 15% 2eζ
μe ¼ ð2Þ
of triple-walled CNTs [9]. Pore characterization and specific surface 3η

Fig. 1. Representative (a). SEM image (b). TEM image of DWNTs.

 T. Kopac et al. / Journal of Molecular Liquids 252 (2018) 1–8 3

Fig. 2. Representative Raman spectrum of DWNTs (532 nm).

where η is the viscosity of the suspending liquid, and e is the dielectric → Co3O4. This combustion of the CNTs is then almost completed at
constant. 600 °C, when the derivative curve becomes flat. The small weight loss
at 932 °C corresponds to the final transformation of Co3O4 into CoO,

3. Results and discussion

(a)
3.1. Characterization of DWNT 1200
Adsorption
Desorption
Characterization of the physical and chemical properties of DWNT is 1000

necessary to correlate the structure of DWNT with the adsorption be-

havior of protein. Fig. 1(a), (b) shows representative SEM and TEM im- 800
V(cc/g)

ages of the DWNT samples, revealing the simultaneous presence of

sections with individual nanotubes, but mainly a bundle organization. 600

Raman spectroscopy (Fig. 2) reveals a low level of defects with a very

low ratio of intensity between the D and G bands (ID / IG = 7%) [36] as 400

well as carbon nanotubes with a diameter range between 1 and 2 nm

(for those visible at 532 nm). The thermogravimetric analysis consists 200

in heating the sample in air and monitoring the weight variation versus
temperature. At a temperature close to 330 °C (as indicated by the de- 0
0,0 0,2 0,4 0,6 0,8 1,0
rivative curve - in red), the combustion of CNTs in air starts to induce
P/P0
some weight loss (combustion of the CNTs in air). Simultaneously, the
oxidation of the small amount of residual Co present in the sample
leads to a very small weight gain (not visible on Fig. 3), due to Co (b)
0,018

0,016

0,014

0,012
Dv(d) [cc/Å/g]

0,010

0,008

0,006

0,004

0,002

0,000

0 50 100 150 200 250 300 350 400 450

Pore Width [Å]

Fig. 4. (a) Adsorption-desorption isotherms of N2 on DWNT (b) pore size distributions of

Fig. 3. TGA of DWNTs in air at 1 °C/min. DWNT.
4 T. Kopac et al. / Journal of Molecular Liquids 252 (2018) 1–8

Table 1 BSA/DWNT
Surface area, pore size and pore volume of DWNT. 700
pH 4
o
BJH NLDFT 25 C
600 o
Surface area, m2·g−1 771 780 30 C
Pore diameter, Å 24.36 91.14 o
37 C
Pore volume, cm3·g−1 1.794 1.729 500
o
BET surface area, m2·g−1 790.5 40 C
Total pore volume (P/P0 = 0.995), cm3·g−1 1.82

C (mg/L)
400

300
and can be used to quantify the amount of residual Co present in the
sample. From TGA analysis (Fig. 3) the concentration of residual metals
can be estimated to 1.2 wt%. Adsorption-desorption isotherms of N2 and 200
pore size distributions of DWNT are shown in Fig. 4(a) and (b),
respectively. Table 1 shows the surface properties of DWNT evaluated 100
using the data shown in Fig. 4. According to the International Union of
Pure and Applied Chemistry (IUPAC) classification, the pores may be di- 0
vided in broad terms according to diameter (d) into macropores (d 0 100 200 300 400 500
N 50 nm), mesopores (2 b d b 50 nm) and micropores (d b 2 nm) t (min)
[37–38]. As demonstrated in Table 1 and Fig. 4(b), DWNT correspond
to a mesoporous structure. The specific surface area found was Fig. 6. Change of BSA solution concentration with time for adsorption on DWNT at
790.5 m2·g−1. different temperatures (C0: 581.5–582.6 mg·L−1; pH: 4; w: 0.6 g·L−1; V: 0.1 L).

3.2. Zeta potential results 3.3. Temperature effects

The main driving force for enzyme-solid interactions is an electro- Fig. 6 shows the effect of solution temperature on BSA adsorption
static force [39]. In order to understand the behavior of interactions, in- onto DWNT at constant initial concentration (600 mg·L−1) and
formation about the electrostatic properties of BSA and DWNT are DWNT dosage (0.6 g·L−1). From this figure, it was obvious that BSA ad-
needed. Zeta potential measurements were performed for this purpose. sorption onto DWNT at pH 4 was increased with increasing tempera-
Fig. 5 shows the changes in the zeta potentials of the DWNT, BSA and ture. The BSA adsorption onto DWNT was higher at 40 °C. For this
BSA-DWNT particles with respect to pH. The isoelectric point (pI) of study, the optimum experimental conditions were observed to be at
BSA was determined as 4.7 in our previous studies, and the zeta poten- pH 4 and 40 °C. In our earlier studies, the optimum experimental condi-
tial values of BSA were positive below pI and negative above pI [33,34]. tion for the maximum BSA adsorption onto the TiO2 and the surface area
As shown from the figure, the DWNT particles were negatively charged enhanced TiO2 were also found at pH 4 and 40 °C [30].
at all pH levels, however BSA was positively charged at pH 4 only. The
zeta potentials for the DWNT solution decreased (in absolute value)
upon the addition of BSA, which can be attributed to the interfacial 3.4. Equilibrium analysis
film formed due to the increase in the distance between the
shear and the particle surfaces [40]. The decrease was higher for attrac- Adsorption isotherm data are necessary for the design of adsorbers,
tion interactions between BSA with DWNT particles at pH 4. This result and provide information about the adsorption capacity and the distribu-
shows that the maximum BSA adsorption onto DWNT particles occurs tion of adsorption molecules between solid and liquid phases at equilib-
at pH 4. rium. The equilibrium isotherms were obtained by plotting BSA

1600
5 BSA/DWNT
pH 1400 o
40 C pH 4
0
3 4 5 6 7 8 9 10 11 12 13 14 1200
-5
1000
Zeta Poential (mV)

qe (mg/g)

-10
800

-15
600

-20
400

-25
DWNT 200

-30 BSA
DWNT/BSA 0
0 50 100 150 200 250 300 350 400 450
-35
Ce (mg/L)
Fig. 5. Zeta potential curves for BSA adsorption on DWNT at different pH (w: 5 g·L−1; T: 20
°C). Fig. 7. qe-Ce curve for BSA adsorption on DWNT (pH: 4; w: 0.2–1 g·L−1; V: 0.1 L).
 T. Kopac et al. / Journal of Molecular Liquids 252 (2018) 1–8 5

0,0024
7,5 Freundlich Model
Langmuir Model
BSA/DWNT BSA/DWNT
0,0020
7,2

0,0016
6,9
1/qe (g/mg)

lnqe
0,0012
6,6

0,0008
6,3

0,0004 6,0

0,000 0,003 0,006 0,009 0,012 0,015 0,018 0,021 0,024 0,027
3,5 4,0 4,5 5,0 5,5 6,0 6,5
1/Ce (L/mg)
lnCe
Fig. 8. Langmuir isotherm model curve for adsorption of BSA on DWNT (pH: 4; T: 40 °C; w:
0.2–1 g·L−1). Fig. 9. Freundlich isotherm model curve for adsorption of BSA on DWNT (pH: 4; T: 40 °C;
w: 0.2–1 g·L−1).

adsorbed (qe) against the BSA concentration left in solution (Ce) at equi-
librium for various adsorbent dosages at pH 4 and 40 °C (Fig. 7). Table 2, it can be seen that the adsorption data gave a better fit with
The most frequently employed models, the Langmuir and the the Langmuir equation than the Freundlich model.
Freundlich equations, were used to express the equilibrium relationship The comparison of the BSA adsorption capacities of different adsor-
during adsorption. The experimental equilibrium data at constant tem- bents reported in our previously published articles [30–31], are also
perature and pH were compared with the model equations. The applica- listed in Table 3. The DWNT samples used in this work exhibited the
bility of the isotherms for describing the process was judged by the largest BSA adsorption capacity of 1221 mg·g−1, when compared to
values of the square of the correlation coefficient, r2. The Langmuir's iso- our previously reported data regarding other kinds of CNTs.
therm [41] model is given below:

1 1 1 1 3.5. Kinetic analysis

¼ þ ð3Þ
qe Q o Q b b C e
In order to investigate the temperature effects on the adsorption ki-
netic, the temperature was varied from 25 °C to 40 °C, while the initial
where Qo and b are the constants related to adsorption capacity and the
BSA concentration held constant at 600 mg·L−1 at the adsorbent dosage
affinity of the binding sites, respectively. Plotting 1 / qe versus 1 / Ce for
of 0.6 g·L−1 (Fig. 6). The BSA adsorption efficiency values were found as
the Langmuir isotherm, a straight line with a slope of 1 / Qo was obtain-
27%, 32%, 53% and 72% for the solution temperatures 25, 30, 37 and 40
ed (Fig. 8). From the figure, the adsorption capacity of DWNT was found
°C, respectively. This showed that the adsorbate onto DWNT increased
as 1221 mg·g−1. Table 2 shows the model constants evaluated.
with increasing temperature at pH 4, which can be attributed to the
The linearized form of the Freundlich model is [42],
availability of more adsorption sites and an increase in the sorptive sur-
  face area.
1 In order to search the rate controlling mechanism of BSA adsorption
logqe ¼ logK f þ logC e ð4Þ
n on DWNT samples, the pseudo-first-order and the pseudo-second-
order equations were applied. The integrated equation of the pseudo-
where Kf and n are model constants. 1 / n gives an indication of how fa- first-order rate [43] is given below,
vorable the adsorption process is, and Kf is the adsorption or distribution
coefficient representing the amount of BSA adsorbed by DWNT at equi-
librium. The slope (1 / n) of the linearized equation ranging between 0 k1 t
log ðqe −qÞ ¼ logqe − ð5Þ
and 1 indicates the adsorption intensity or surface heterogeneity. As 1 2:303
/ n approaches to zero, the adsorbent surface gets more heterogeneous.
1 / n b 1 indicates a normal Langmuir isotherm, while 1 / n N 1 shows co-
where q (mg·g−1) is the amount of BSA adsorbed on DWNT at time t,
operative adsorption. The plot of log qe against log Ce gave a straight line,
and k1 (min−1) is the rate constant.
and Kf was evaluated from the intercept (Fig. 9). The constants of Kf and
1 / n together with r2 values are also listed in Table 2. 1 / n was found as
0.360, indicating a favorable adsorption. From the values of r2 given in Table 3
Comparison of maximum BSA adsorption capacity onto different adsorbents at pH 4 and
40 °C.
Table 2 Adsorbents Maximum BSA adsorption capacity Reference
Langmuir and Freundlich model parameters for BSA adsorption onto DWNT at pH 4. (mg·g−1)
Temperature Langmuir Freundlich TiO2 42.6 Kopac et al. [27]
MWNT 139.5 Bozgeyik and Kopac [31]
Q 0 (mg·g−1) b r2 Kf 1/n r2
SWNT 609.8 Kopac and Bozgeyik [30]
40 °C 1221 0.00163 0.81 137.0 0.360 0.79 DWNT 1221 This work
6 T. Kopac et al. / Journal of Molecular Liquids 252 (2018) 1–8

3,6 0,10
BSA/DWNT BSA/DWNT
3,2 pH 4 pH 4
o
25 C 0,08
o
25 C
2,8 o
30 C o
30 C
o
2,4 37 C o
37 C
o
40 C 0,06 o
40 C

1/(qe-q) (g/mg)
2,0
log(qe-q)

1,6
0,04
1,2

0,8
0,02

0,4

0,0 0,00
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450

t (min) t (min)

Fig. 10. Pseudo-first order rate curves obtained from adsorption of BSA on DWNT at Fig. 11. Pseudo-second order rate curves obtained from adsorption of BSA on DWNT at
different temperatures (C0: 581.5–582.6 mg·L−1; pH: 4; w: 0.6 g·L−1; V: 0.1 L). different temperatures (C0: 581.5–582.6 mg·L−1; pH: 4; w: 0.6.g L−1; V: 0.1 L).

An expression of the pseudo-second-order rate equation is given as evaluated from the plots of lnKC versus 1 / T (Fig. 12) considering
[44], Eqs. (6)–(8) [45].

1 1 qe
¼ þ k2 t ð6Þ KC ¼ ð7Þ
ðqe −qÞ qe Ce

where k2 is the pseudo-second-order rate constant. ΔG0 ¼ −R T lnK C ð8Þ

The slopes and intercepts of plots of log (qe − q) versus t were ob-
tained to determine the first-order rate constant k1 (Fig. 10). r2 values ΔS0 ΔH0
ln K C ¼ − ð9Þ
for the first-order model at pH 4 for 0.6 g·L−1 of adsorbent dose were R RT
found as 0.85, 0.98, 0.88 and 0.90 for 25, 30, 37 and 40 °C, respectively.
The evaluated parameters are all detailed in Table 4. where KC and R are the equilibrium and ideal gas constants.
The slopes and the intercepts of plots of 1 / (qe − q) versus t were ob- The thermodynamic parameters calculated are presented in Table 5.
tained to evaluate the rate constant k2 (Fig. 11). In Table 4, values of k2 ΔG0 values estimated for adsorption of BSA onto DWNT were 1.22, 0.61,
and r2 with respect to temperature are also presented. The r2 values −1.64 and −3.80 kJ·mol−1, respectively, at 298, 303, 310, and 313 K,
for the model at pH 4 for 0.6 g·L−1 of DWNT amount are 0.82, 0.93, indicating a spontaneous physisorption process [46]. As temperature in-
0.54 and 0.59 for 25, 30, 37 and 40 °C, respectively. From the results it creased from 298 to 310 K, ΔG0 values decreased to negative values,
can be concluded that the pseudo first-order model was a better repre-
sentative of the BSA adsorption onto DWNT. Further concerning rate
constants, it was observed that k1 values increased with an increase in
temperature. This shows a change in the adsorption mechanism with
an increase in temperature. 1,5 DWNT/BSA
pH 4
3.6. Thermodynamic analysis
1,0

Based on the basic concepts of the 1st and the 2nd laws of thermody-
namics, energy of the system can neither be created nor destroyed and 0,5
the only driving force is the entropy change. In order to gain insight into
lnKC

the adsorption mechanism, parameters such as changes in standard

0,0
Gibbs free energy (ΔG0), enthalpy (ΔH0) and entropy (ΔS0) were

-0,5

Table 4 -1,0
The values of k1 and k2 for BSA adsorption onto DWNT at pH 4 (w: 0.6 g·L−1).

Temperature (°C) pH 4
-1,5
k1 (min−1) r2 k2 (g·mg−1·min−1) r2 0,00320 0,00324 0,00328 0,00332 0,00336 0,00340
-1
25 0.0062 0.85 0.00014 0.82 1/T (K )
30 0.0079 0.98 0.00016 0.93
37 0.0082 0.88 0.00015 0.54
Fig. 12. The thermodynamic curve for BSA adsorption onto DWNT (pH: 4; w: 0.6 g·L−1; V:
40 0.0083 0.90 0.000093 0.59
0.1 L).
 T. Kopac et al. / Journal of Molecular Liquids 252 (2018) 1–8 7

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