Estimation of the properties of mesoporous aluminosilicates in various environments is important when assessing their sorption capacity. Using inverse liquid chromatography (ILC), Hansen solubility parameters (HSP) and linear free energy relationship (LFER) parameters were calculated to determine the properties of aluminosilicates in a protic and an aprotic system.
Trang 1Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/chroma
K Adamska∗, A Voelkel , M Sandomierski
Poznan University of Technology, Institute of Chemical Technology and Engineering, ul Berdychowo 4, 60-965 Pozna ´n, Poland
a r t i c l e i n f o
Article history:
Received 17 July 2019
Revised 11 September 2019
Accepted 14 September 2019
Available online 14 September 2019
Keywords:
Mesoporous aluminosilicates
Inverse liquid chromatography
Surface characterization
Hansen solubility parameters
Linear free energy relationship
a b s t r a c t
Estimationofthepropertiesofmesoporousaluminosilicatesinvariousenvironmentsisimportantwhen assessingtheirsorptioncapacity.Usinginverseliquidchromatography(ILC),Hansensolubilityparameters (HSP)andlinearfreeenergyrelationship(LFER)parameterswerecalculatedtodeterminetheproperties
ofaluminosilicatesinaproticandanaproticsystem,usingwaterand acetonitrileasthemobilephase, respectively.ThecalculatedHansenparameters,reflectingtheabilityofthematerialunderinvestigation
todifferenttypesofintermolecularinteractions,slightlydifferdependingonthemobilephaseused.It wasfoundthatinthepresenceofwaterthesurfaceofaluminosilicatesshowsaweakerabilitytointeract,
asevidencedbynegativeornear-zeroe, s, a, b, vcoefficients.Additionally,itwasfoundthattheSi/Alratio
inaluminosilicatesstructurehaslittleeffectonthedeterminedparameters
© 2019TheAuthors.PublishedbyElsevierB.V ThisisanopenaccessarticleundertheCCBY-NC-NDlicense
(http://creativecommons.org/licenses/by-nc-nd/4.0/ )
1 Introduction
Applicability of many organic and inorganic solids is often de-
termined by their surface sorption properties Biomaterials and
chromatographic stationary phases should be without a doubt clas-
sified to this group of materials
In 1992 the first information on new family of mesoporous
materials which have an ordered structure was reported [1] These
silica materials with hexagonal, cubic or linear arrangement of
mesopores structure (M41S) were synthesized under hydrother-
mal conditions from silicate/aluminosilicate gels which contain
organic surfactant molecules as templates [1,2] Mesoporous ma-
terials are popular due to their unique properties and application
possibilities in many fields of science and technology Years of
research dedicated to improving the properties of these ordered
materials led to the new low-ordered mesostructures [3] One
of these are MSU materials characterized by higher surface area
and better thermal stability than M41S The abbreviation MSU
refers to mesoporous silica, mesoporous alumina and mesoporous
aluminosilicates [4,5] Initially mesoporous materials were syn-
thesized from “zeolite seeds” of zeolites such as faujastic and
templates (alkyl ammonium bromides) [6,7] Despite many studies
on mesoporous materials there are few reports on their prepa-
ration from a solid silicon source Solid silicon sources provide
∗ Corresponding author
E-mail address: Katarzyna.Adamska@put.poznan.pl (K Adamska)
more silicon to the reaction environment than the most com- monly used sodium silicates The new direction of the synthesis
of mesoporous materials is their preparation from less toxic and less expensive substrates Application during synthesis other sub- strates, templates and various Si/Al ratio has a major impact on the properties (surface area, pore size and volume) of the resulting aluminosilicates what further influences the sorption properties
of the material [8,9] The new procedure of manufacturing alu- minosilicate materials of different Si/Al ratio was proposed [10] Authors suggested the use of Aerosil 200V, sodium aluminate, silicon dioxide as silicon/aluminium sources and hexade- cyltrimethylammonium bromide as crystal template as substrates The surface characteristic and the results of sorption experi- ments for hydrocarbons on studied mesoporous materials allow
to indicate the crucial surface parameters for adsorption process However, these materials were characterized as dry solids During separation procedures, e.g extraction process, the particles of the sorbent are surrounded by water, hydrocarbon solvent of water so- lution containing salt molecules It may significantly influence the surface properties of mesoporous species Therefore, it seems to
be vital to estimate mesoporous materials sorption ability in real system i.e in environment where it usually “works” Biomaterial
is surrounded by body fluid, while during the use of mesoporous materials as sorbents the process is carried out by using mobile phase in the form, e.g of dilute water solution of inorganic salts There is a number of techniques, which enable to carry out the characteristic of surface, including FTIR, Raman spectroscopy, https://doi.org/10.1016/j.chroma.2019.460544
0021-9673/© 2019 The Authors Published 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/ )
Trang 2X-ray diffraction, contact angle measurements and others [11–13]
Unfortunately, the measurements methodology of all mentioned
techniques do not allow to observe the influence of environment,
surrounding examined material on sorption properties Depending
on physicochemical properties of liquid environment, the sorption
ability of material will be changed A large number of other analyt-
ical methods can be used to study the sorption properties of nano-
materials in solutions (e.g liquid NMR, analytical ultracentrifuga-
tion, isothermal titration calorimetry [14–16]
Inverse liquid chromatography (ILC) is a method of surface char-
acterization, where an examined material is situated in chromato-
graphic column It allows to examine the changes of surface prop-
erties in diversified environment The principle of measurements is
based on the determination of the retention factors for the test so-
lutes, having specified physicochemical properties These analytes
are introduced into the chromatographic system separately The
column is filled with the examined material, which in this case
would be one of the mesoporous materials The test solutes are
dissolved in specified solvent which is the same as applied mo-
bile phase and then, every individual test compound is introduced
to the chromatographic column Depending on the force of inter-
actions between the test solute and the examined surface, the so-
lutes leave the column with different retention times, which is the
basis for physicochemical characterisation The retention parame-
ter is a result of all occurring interactions in the system i.e solute
– solvent, solute – stationary phase and solvent – stationary phase
There are few procedures, involving inverse liquid chromatog-
raphy usually used for physicochemical characterization of com-
mercially available stationary phases e.g surface excess isotherms
or surface energies, silanol activity and hydrophobicity or using an
aromatic sulphonic acids as a test compounds [17–21] One of the
most relevant and commonly applied mathematical model, that
considers a retention parameter as a result of all interactions oc-
curring in the chromatographic system is known as a linear free
energy relationship [22]
In the condensed phases strong attractive forces arises between
molecules, expressed as molar cohesive energy It is defined as the
molar internal energy and is related to the evaporation energy at
a given temperature or internal pressure:
where: E coh– cohesive energy, U –evaporation energy, H – en-
thalpy of vaporization, R – gas constant, T – temperature
For liquids, assuming that the intramolecular properties are the
same in the gaseous and liquid state, the molar cohesive energy
can be represented as the sum of two factors: (a) molar evap-
oration energy needed to convert a moll of liquid into saturated
vapour, (b) the energy required to transfer saturated vapour to an
infinite volume at a constant temperature, i.e the energy needed
to completely separate the particles:
−E=g
l U +
V=∞
V=V par
∂U
∂V
T
The cohesive energy related to the molar volume is called the
cohesion energy density, expressed as:
c = −E
The concept of the solubility parameter was proposed by
Scatchard, Hildebrand to regular solutions, i.e solutions that do not
show an entropy effect upon mixing In practice, such type of so-
lutions are rare The proposed solubility parameter referred to the
systems in which cohesion resulted only from dispersive forces It
is defined as the square root of cohesive energy density (CED) [23]
δ= √ c =
E coh
H − RT
where: δ -solubility parameter, R gas constant, T temperature,
H enthalpy of vaporization, V m molar volume
In 1966, Hansen proposed the concept of a solubility parame- ter, referring to the systems in which aside from dispersion inter- actions, polar and hydrogen bonding interactions may exist The basic equation representing Hansen’s assumptions is:
where: d dispersive, p polar, h hydrogen bonding
The total cohesion energy includes the energetic contribution brought by dispersive (non-polar), polar and hydrogen bonding (specific) interactions Dividing the energy by the molar volume:
E coh
V m = E d
V m+ E p
V m+ E h
V m
(6)
a relationship, describing the total solubility parameter (Hildebrand solubility parameter), is obtained as the sum of the dispersive δd, polar δpand hydrogen bonding δhcomponents:
δ2
T= δ2
d+ δ2
p+ δ2
δTis also called the corrected solubility parameter
It is assumed that materials having similar values of Hansen’s parameters show high mutual affinity
In the case of volatile substances the value of the solubility pa- rameter can be determined using the enthalpy of evaporation from the Eq (4)[24,25] However, for more complex systems or non- volatile materials, it was necessary to develop other procedures to determine the solubility parameter One of the methods is to ob- serve the dissolution capacity of a compound (e.g a polymer) in solvents with known value of the Hildebrand solubility parameter [26] It is assumed that the solubility parameter of the tested ma- terial (dissolved substance) is approximately equal to the solubil- ity parameter of the solvent, in which the test material dissolves
or mixes with it in all proportions, without changing the enthalpy and volume A similar procedure is the measurement of polymer swelling e.g for cross-linked polymers, as well as semi-crystalline materials [27] Conducted observations of the studied systems en- able to classify selected solvents for good, i.e those that show a stronger interaction with the tested material causing, for example, dissolution, swelling, suspension and the bad, in which no changes are observed In the case of dye/solvent systems, the analysis is made on the basis of determining the degree of suspension or sed- imentation Such characteristics of the systems studied are based
on relatively strong adsorption by some liquids compared to oth- ers
Based on knowledge of the chemical structure of the com- pound, the solubility parameter can be calculated using the so- called additive methods They are based on the assumption that the total cohesion energy is the sum of energy contributed by each functional group of the compound molecule They enable the esti- mation of the total solubility parameter value and its individual components [28] Additive methods have found wide application [29–33] The calculated solubility parameter values for hydrocar- bons and other compounds are acceptable, however, in many cases, e.g for large functional groups located around a central atom, the obtained data may be affected by a large error In molecules in which, for example, spatial effects or couplings may exist, it can be difficult to clearly determine the total cohesion energy It should
be noted that in molecules in which there are several strongly interacting functional groups (e.g hydroxyl groups) additional in- tramolecular interactions, affecting the total cohesion energy of the molecule, may appear apart from intermolecular interaction [29] There are also other, indirect methods for determining the sol- ubility parameter using, for example, molecular modeling Smidsrod and Guillet [34]were the first to apply the inverse gas chromatography technique in studies of the interaction between
Trang 3the solvent (test compound) and the polymer as the stationary
phase As a result of interaction between them the obtained re-
tention data are used to calculate the solubility parameter δ from
the Flory-Huggins interaction parameter χ∞
1,2 The procedure proposed by Guillet has used Price [35,36] in
his research to determine the solubility parameter for compounds
with low molecular weights According to his assumption, the
total solubility parameter resulted from the shares of two fac-
tors – dispersive δd and polar δp interactions Voelkel and Janas
[37] have extended the group of test compounds to apply the
three-parameter Hansen equation
The solubility parameter found the application in the descrip-
tion of the properties of diluted solutions, especially non-polar
There are a number of relations that combine the solubility param-
eter with other physicochemical quantities, e.g surface tension or
thermal expansion coefficient, so the concept of solubility param-
eter can be used in many fields to interpret some phenomena in-
cluding mixing, adsorption and dissolution processes [38–41] The
Hansen solubility parameter has found wide application in the se-
lection of a solvent or solvent system for a particular material in
the industry coatings industry, cleaning agents or printing inks
[39,42–44] Solubility parameters have been applied extensively in
the pharmaceutical sciences The use of this parameter in the phar-
maceutical industry has been described in detail by Hancock et al
[45], showing how this factor is used to assess the properties of
unknown materials, the impact of technological processes on the
properties of materials, as well as estimation of interactions and
incompatibilities between materials It can be used also to assess
the bioavailability/solubility of various types of active substances
[46–49] The concept of the Hansen Solubility Parameter (HSP) has
been also used in the studies on the affinity between the adsor-
bent and organic solvent [50], a dispersion of carbon fillers and
polymer matrix [51]or to determine the inter-molecular interac-
tions in ionic liquid/solvent system [52]
Karger et al [53] described various chromatographic processes
using the concept of solubility parameter The authors used com-
ponents of solubility parameters, responsible for different types of
intermolecular interactions to describe retention in various types
of chromatography: gas solid, gas liquid, liquid solid and liquid
-liquid The general description of the model was based on evapo-
ration, dissolution, mixing and adsorption processes taking place in
the chromatographic system These considerations gave the back-
ground of our investigations
The energy of interactions between solid adsorbent ( ad) and
sorbate (test solute) ( i) ( E lsc) is given by the Eq (8) [53] One
should take into account also interaction between the molecules
of adsorbing test solute and molecules of mobile phase ( j)
E lsc= −n
E A
j /ad−( E s)i/ j+
E A
i / j+
E A
i /ad (8) where: j= mobile phase; ad – adsorbent; i = solute; E A – energy
of adsorption, E s– solubilization energy
The respective energetic contribution may be expressed in
terms of components of solubility parameter [53]:
( E s)i / j= V i
δj2
− 2 δi
dδj
d− 2 δi
oδj
o− 2 δi
inδj
in− 2 δi
aδj
b− 2 δj
aδi b
(9)
E A
i /ad= V i δi
dδad
d + δi
oδad
o + δad
inδi
d+ δi
inδad
d + δi
aδad
b + δad
a δi b
(10)
E lsc =
E A
i /ad− A i
A j
E A
A i , A j– molecular area of “i ” and “j ”; δiδj– solubility parameter
of “i ” and “j ”; indices d, o, in, a, b – denote component of solubility
parameter corresponding to dispersive, orientation forces, induc- tive, proton donor ability and proton acceptor ability interactions, respectively
E lsc= −RTlnV i
V i
N – net retention volume of the test solute “i ” in ILC experiment
It leads to
V i δi
dδad
d+ δi
oδad
o + δad
inδi
d+ δi
inδad
d + δi
aδad
b + δad
a δi b
−A i
A j V
i δj
dδad
d + δj
oδad
o + δad
inδj
d+ δj
inδad
d + δj
aδad
b + δad
a δj b
= − RT lnV i
N
(13) and finally to
−RT lnV i N
V i = δad
d
δi
d+ δi
in−A i
A j
δj
d+ δj
in + δad
o
δi
o−A i
A jδj o
+ δad in
δi
d−A i
A jδj d
+ δad b
δi
a−A i
A jδj a
+ δad a
δi
b−A i
A jδj b
(14)
−RT lnV i N
V i = δad
d W 1 + δad
o W 2 + δad
in W 3 + δad
b W 4 + δad
a W 5 (15)
Eq.(15)is polynomial where:
W1 =
δi
d+ δi
in−A i
A j
δj
d+ δj in
W2 =
δi
o−A i
A jδj o
W3 =
δi
d−A i
A jδj d
W4 =
δi
a− A i
A jδj a
W5 =
δi
b− A i
A jδj b
However, there is a lack of the respective data for components expressing the ability to inductive and orientation interactions Therefore, we have adapted the idea of Hansen solubility parame- ter to solve this problem For the system in liquid-solid chromatog- raphy (LSC) one obtains:
Eqs.(11)and (12)remain unchanged and
δi
a+ δi b
= δi
δj
a+ δj b
= δj
δi
a+ δi b
·
δj
a+ δj b
= δi
aδj
a+ δi
aδj
b+ δi
bδj
a+ δi
bδj
but δi
aδj
a =0 and δi
bδj
b=0 as the proton donor ability or proton acceptor ability of test solute and mobile phase molecules do not influence the magnitude of their interactions
This leads to
δi
h·δj
h= δi
aδj
b+ δi
bδj
V i δi
dδad
d+ δi
pδad
p + δi
hδad h
−A i
A j V
i δj
dδad
d+ δj
pδad
p + δj
hδad h
= −RT lnV i
N
(20)
Trang 4We have introduced the component corresponding to ability to po-
lar interactions ( δi
p) instead of orientation and inductive forces – due to the unavailability of such data in the literature
V i
δad
d
δi
d−A i
A jδj
d
+ δad p
δi
p−A i
A jδj p
+ δad h
δi
h−A i
A jδj h
= −RTlnV i
−RT lnV i
N
V i = δad
d
δi
d−A i
A jδj d
+ δad p
δi
p−A i
A jδj p
+ δad h
δi
h−A i
A jδj h
(22) The values in brackets on the right side of Eq.(22)are constant for
the given adsorbent, the test solute and the mobile phase (molec-
ular area of the molecule of mobile phase is required) The val-
ues of HSP for the adsorbent (examined material) are unknown
and these values might be calculated by using multilinear regres-
sion A more detailed description of HSP determination is given in
Section2.4
The linear free energy relationship (LFER) was used, which in-
volves five independent parameters characterising physiochemical
properties of the examined surface [54]
Since 1980’s the mathematical correlation of the retention pa-
rameters with physicochemistry of solute-sorbent interaction has
attracted more attention Abraham and co-workers adapted Kam-
let and Taft solvatochromic methods to chromatographic analy-
sis, giving it the form of linear free energy relationship (LFER)
[20] In this mathematical relationship, the retention parameter
depends on solute solvation process, which has been identified
and dissected into four types of solute-solvent interaction: cav-
ity formation-dispersive interaction, dipolarity-polarizability inter-
action and acidity or basicity hydrogen bonding interaction In
the case of liquid chromatography, one can observe three types
of interactions: solute-stationary phase, solute-mobile phase and
stationary phase-mobile phase All these interactions have a ma-
jor influence on the observed retention parameter One of more
widely accepted symbolic representations of LFER model in the
form of multiple linear regression equation was presented by
Abraham:
where: log k is the logarithm of the solute retention factor, is
the linear regression coefficient The capital letters E, S, A, B and
V corresponds to the solute descriptors, independent on the mo-
bile/stationary phase used; E is the excess molar refraction, S –
dipolarity/polarizability descriptors, A and B correspond to the so-
lute hydrogen bond acidity and basicity respectively, and V is the
McGowan volume of the solute The lowercase letters e, s, a, b,
v are the system parameters reflecting the difference in solute
interaction between the mobile and stationary phase Therefore,
the value of the above-mentioned parameters might be useful for
description of the physicochemical properties of material surface
(in a given chromatographic conditions: mobile phase composition
and temperature) and estimation of the surface ability to different
types of intermolecular interactions
The aim of the study was to introduce the new procedure for
the estimation of Hansen Solubility Parameters Moreover the goal
of this work was to estimate physicochemical properties of meso- porous materials surface in aquatic and non-aqueous systems To estimate those properties, we planned to use five descriptors ( e, s,
a, b, v) of linear free energy relationship adopted for liquid chro- matography as well as HSPs data
2 Experimental
2.1 Materials
Mesoporous aluminosilicates with a different Si/Al ratio ( Table 1) were prepared according to the following procedure ( Table2): NaOH (A) and NaAlO 2(B) were dissolved in the distilled water (C) Then, a silicon source: silicon dioxide (D) or Aerosil 200V (D) was added to NaOH (E) dissolved in the distilled water (F) Next silicon and aluminum mixtures were mixed in different ratios and stirred (700 rpm) for 1 hour and then heated and stirred
at 100 °C for 24 h Subsequently mixture was mixed with solution
of hexadecyltrimethylammonium bromide (CTAB, 18 g in 572 ml
of distilled water) After 1 h stirring H 2SO 4 was added to obtain
pH = 9–10 and then mixture was stirred for 24 h The samples were crystallized for 48 h at 100 °C The resulting materials were filtered, washed with distilled water and dried The last step was removal of the template by calcination at 540 °C for 7 h A de- tailed analysis of the materials is presented in the following pub- lications [55–57] The real Si/Al ratio, given in Table1, was deter- mined from EDS results obtained using EDS Octane SDD detector made by EDAX The maximum size of agglomerated particles is
60 μm for AS4 material [55,56] In the case of others it does not exceed 20 μm
2.2 ILC experiments
ILC experiments were conducted by using Dionex Ultimate
30 0 0 liquid chromatograph equipped with refractive detector (Shodex, Ltd USA) Empty stainless steel column (2.0 mm i.d × 100 mm) were used Columns were filled with materials in the dry state using a semi-automated column packer designed for packing of inverse gas chromatographic columns (Surface Measure- ments System Ltd London, UK) Column ends were sealed with stainless steel frit inserts After packing, the column were condi- tioned at the measuring temperature of 30 °C and with a mobile phase flow of 0.2 ml/min before the experiment started, in order
to stabilize the pressure in the column and the base line of the de- tector The mobile phase used in experiments were acetonitrile for HPLC (Sigma-Aldrich) and distilled water All test compounds were dissolved in proper mobile phase at concentration 10 mg/ml The injection volume was 10 μl Test solutes were injected separately and due to this on ILC chromatograms single peaks were recorded Examples are presented in Fig.1
Retention factor is given as:
k = t R − t 0
t 0 = t R
t 0
(24) where: k is the retention factor, t
R– the corrected retention times,
t0 – the retention time of the non-retained substance
Table 1
Description of the examined materials
Material abbreviation Silicon source Assumed Si/Al ratio Real Si/Al ratio
Trang 5Table 2
The amount of substrates used during the synthesis [g]
Fig 1 Caffeine chromatograms for AS2 material, mobile phase (a) water, (b) ace-
tonitrile
The retention time of the non-retained substance was calcu-
lated according to the equation:
where: V0 – the void volume, F – the flow rate [ml/min]
The void volume of the filled column was determined by the
pycnometric method [58] Using such procedure four different sol-
vents having different densities were used: acetonitrile, dioxane,
heptane and dichloromethane (Sigma-Aldrich) The void volume
was calculated from the following equation:
where: w1, w2 are the mass of the column filled with solvent [g]
with different densities d1and d2
Group of selected test solutes with different chemical struc-
ture and properties i.a polarity, electron donor-acceptor were
chosen for ILC experiments All test solutes were at least of analyti-
cal grade: aniline, butanone, diethyl ether, phenol, pyridine, propy-
lamine (AVANTOR), benzonitrile, cyklohexanol, cyclohexanone,
1,3-diaminopropane, 1,4-dioxane, geraniol, caffeine, acetic acid,
N,N-dimethyloformamide, ethyl acetate, propanol, 1,3-propanediol,
tetrahydrofurane (Sigma-Aldrich), acetophenone (Fluka)
Table 3
Descriptors of the test solutes [59–62] Test
solute
Descriptor
1,3-diaminopropane 0.446 0.610 0.430 1.140 0.731 1,3-propanediol 0.397 0.910 0.770 0.850 0.649 1,4-dioxane 0.329 0.750 0.000 0.640 0.681
Acetonitrile 0.237 0.900 0.070 1.739 0.404 Acetophenone 0.818 1.010 0.000 0.480 1.014
Benzonitrile 0.742 1.110 0.000 0.330 0.871
Cyclohexanone 0.403 0.860 0.000 0.560 0.861 Cyclohexanol 0.460 0.540 0.320 0.570 0.904 Diethyl ether 0.041 0.250 0.000 0.450 0.731 Ethyl acetate 0.106 0.620 0.000 0.450 0.747
N,N-dimethylformamide 0.367 1.310 0.000 0.740 0.647
Propylamine 0.225 0.350 0.160 0.610 0.631
Tetrahydrofuran 0.289 0.520 0.000 0.480 0.622
2.3 LFER calculations
Each test compound was injected five times Q-Dixon Test was applied to reject of outliers The average value of retention time was used to calculate the log k The LFER coefficients were cal- culated according to Eq.(23)using the test compound descriptors given on Table3
2.4 HSP calculations
HSPs parameters were found by solving Eq.(22) One should collect the retention data for series of the test solutes The set of
Eq.(22) equal to the number of applied test solutes is obtained Molar volume of the test solute, molecular area of adsorbing test solute, molecular area of the molecule of mobile phase as well as HSPs data for test solute are collected in Table4
Molecular area of test solutes was calculated using procedure proposed by Diaz et al [63]assuming a spherical molecular shape
in a hexagonal close-packing configuration [64]:
A = 1 09 × 10 14M
ρN
2/3
(28) where: M – molecular mass, ρ– density, N – Avogadro number
3 Results and discussion
The main purpose of the work was to estimate the physico- chemical characteristic of mesoporous materials surface in aquatic and non-aqueous systems The experiments were carried out in two polar solvents of various chemical nature protic water and aprotic acetonitrile
The physicochemical characteristics were calculated using the values of retention coefficients calculated for a range of the test compounds Application of Hansen solubility parameters concept allowed the determination of the ability of a materials surface to different intermolecular interaction, whereas parameters calculated from Abraham model reflect the behaviour of the materials in dif- ferent systems
Differences in the properties of the examined, materials de- pending on the mobile phase used can be observed by compar- ing the data of retention factors, obtained for a series of test
Trang 6Table 4
Physicochemical data for HSPs calculation
Test solute
Physicochemical parameter ∗
[MPa 0.5 ] [MPa 0.5 ] [MPa 0.5 ] [m 2 ] ∗ 10 −19 [cm 3 mol −1 ]
∗ HSPiP software
Table 5
Values of retention factor - k of test solutes for materials; mobile phase – acetonitrile and water
Test solute
1,3-propanediol 0.790 0.308 nd 0.119 0.632 0.195 0.238 0.014 1,4-dioxane 0.320 0.341 0.212 0.171 0.620 0.256 0.231 0.072
Acetic acid 0.357 0.151 0.103 0.167 0.599 0.222 0.235 0.166
Butanone 0.223 0.263 0.139 0.140 0.660 0.200 0.233 0.115 Caffeine 0.916 0.771 1.152 0.965 0.667 0.350 0.289 0.310 Cyclohexanone 0.241 0.165 0.137 0.154 0.603 0.255 0.212 0.063 Cyclohexanol 0.330 0.618 0.189 0.306 0.615 0.200 0.233 0.255
N,N-dimethylformamide 0.839 0.389 0.863 0.753 0.655 0.206 0.239 0.203
Tetrahydrofuran 0.305 0.298 0.174 0.174 0.661 0.215 0.208 0.112 (nd ∗ ) – no data (no retention data obtained)
solutes in water and acetonitrile ( Table 5) with a standard devi-
ation of 0.001–0.01 Considering water the retention factors val-
ues of the test compounds are very similar, what indicates lower
selectivity of the system In the case of acetonitrile, more var-
ied values of retention factors were obtained The most retained
test solutes in acetonitrile was caffeine This may be due to the
fact that caffeine has two functional groups the tertiary amine
and amide groups They can form hydrogen bonds with hydroxyl
group of aluminosilicates just using the lone pair on the nitro-
gen In water such interactions between caffeine and the surface
of aluminosilicates can be disturbed as a result of the forma-
tion of dimers or higher order aggregates by caffeine in aqueous
media
It can be observed that ability of the materials to a specific type
of interaction, described using the Hansen parameters, slightly dif- fer depending on the mobile phase used ( Tables6and 7) The materials in acetonitrile characterizes slightly higher val- ues of HSP data Higher values for dispersive interactions are ob- served, whereas values for polar and hydrogen bonding are almost the same
Material AS2 exhibits the highest values for polar, hydrogen bonding and total solubility parameter both in water and acetoni- trile as mobile phase from all of the examined materials
In water as mobile phase the ability to interactions is insignif- icantly lover as evidenced by the lower values of the HSP compo- nents, what can be caused by the formation of the hydration layer
Trang 7Table 6
Hansen solubility parameters for examined mesoporous materials (mobile phase –
acetonitrile)
[MPa 0.5 ] [MPa 0.5 ] [MPa 0.5 ] [MPa 0.5 ]
AS1 15.93 ± 0.12 13.19 ± 0.09 12.50 ± 0.12 24.16 ± 0.09
AS2 16.32 ± 0.13 13.68 ± 0.11 12.84 ± 0.12 24.87 ± 0.05
AS4 15.69 ± 0.11 12.25 ± 0.08 12.33 ± 0.12 23.41 ± 0.06
M4 16.66 ± 0.12 12.65 ± 0.19 9.83 ± 0.12 23.12 ± 0.10
Table 7
Hansen solubility parameters for examined mesoporous materials (mobile phase –
water)
[MPa 0.5 ] [MPa 0.5 ] [MPa 0.5 ] [MPa 0.5 ]
AS1 16.52 ± 0.13 12.23 ± 0.08 10.02 ± 0.08 23.52 ± 0.14
AS2 16.27 ± 0.12 13.09 ± 0.10 12.72 ± 0.09 24.45 ± 0.15
AS4 15.62 ± 0.11 12.23 ± 0.05 12.10 ± 0.07 23.23 ± 0.14
M4 15.54 ± 0.18 12.18 ± 0.10 9.33 ± 0.10 21.84 ± 0.22
Table 8
Abraham parameters for examined mesoporous materials (mobile
phase – water)
AS1 0.027 0.037 −0.039 −0.014 −0.031
AS2 0.024 −0.071 −0.046 0.0427 0.008
on the surface, blocking the active group and reducing the ability
to interaction in the presence of water In water as mobile phase
together with the decrease Si/Al ratio (materials AS1-AS4, M4), the
decrease of δdis observed
According to ref [65] e, s, a, b, v parameters reflect the dif-
ference in interaction in solute/mobile phase and solute/stationary
phase systems A positive values of the parameters indicate that
given type of interaction, described by Abraham parameters, is
more favorable for the stationary phase However, if the given type
of interaction is more significant between solute and mobile phase,
the values are negative Therefore, a positive values are taken to
consideration to characterize the properties of the stationary phase
(investigated material)
Considering the data received for water, given in Table8it can
be concluded, that OH groups on the surface of materials can form
hydrogen bonds with a protic solvent As a result, the aluminosil-
icate surface in these conditions has a limited ability to interact
with the test solutes, as shown by close to zero or negative values
of Abraham parameters For M4 the highest values for s, a and v
parameter are observed This indicates that such surface is involved
in dipole-dipol ( ) interactions Additionally the highest value of
a coefficient ( a = 0.424) indicates higher basicity of the surface,
which may affect stronger interaction with hydrogen-bond donor
solutes A positive value of v term indicates, that the test solute
will preferentially transfer from the mobile phase to the stationary
phase
Comparing the data obtained for acetonitrile ( Table9), they are
higher than for water In addition, positive values of Abraham pa-
rameters are not close to zero, as in the case of water This denotes
the greater ability of the surface for interaction with test solutes
The positive value of a coefficient indicates higher basicity of alu-
minosilicates surface in the presence of acetonitrile, which should
reflect stronger interactions with hydrogen-bond donor solutes For
almost all materials its acidic properties (parameter b) are little
higher than basic (parameter a) Based on this, the ability of the
surface to interaction with basic solutes should be stronger
Table 9
Abraham parameters for examined mesoporous materials (mobile phase – acetonitrile)
AS1 −0.141 0.530 0.039 0.329 −0.317 AS2 0.151 −0.264 0.362 0.291 0.348 AS4 −0.464 0.878 0.251 0.561 −0.078
4 Conclusions
Mesoporous materials were examined by means of inverse liq- uid chromatography Hansen solubility parameters and Abraham parameters were used to express the ability of mesoporous alu- minosilicates to interact with different environment The relatively weak influence of the composition (Si/Al ratio) of these materi- als on the presented characteristics was found Much more impor- tant was the influence of the environment of material (the mo- bile phase used) The comparison of the values of both groups of estimated parameters showed that the presence of protic solvent decreases the activity of examined material The findings of this paper are important as they present the ability to characterize the material which may change their properties in changing surround- ing Calculated parameters may be useful in assessing the suitabil- ity of mesoporous materials in sorption processes during the solid- phase extraction process from various solutions
Declaration of Competing Interest
The authors declare that they have no known competing finan- cial interests or personal relationships that could have appeared to influence the work reported in this paper
Acknowledgement
This work was supported by the NationalScienceCentre,Poland under research project no UMO-2015/17/B/ST8/02388
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... ConclusionsMesoporous materials were examined by means of inverse liq- uid chromatography Hansen solubility parameters and Abraham parameters were used to express the ability of mesoporous alu-... behaviour of the materials in dif- ferent systems
Differences in the properties of the examined, materials de- pending on the mobile phase used can be observed by compar- ing the data of retention... using the values of retention coefficients calculated for a range of the test compounds Application of Hansen solubility parameters concept allowed the determination of the ability of a materials surface