Synthesis, characterization, interaction with anionic dye, biodegradability, and antimicrobial activity of cationic surfactants: quaternary hydrazinium derivatives

Article abstract of DOI:10.1007/s13738-021-02247-3

A novel cationic surfactant type of N'alkyl N,'N'dimethyl-4-morpholino-4-oxobutanoylhydrazinium iodide (10a–12a) and N'alkyl N', N'dimethyl-4-piperidino-4-oxobutanoylhydrazinium iodide (10b–12b) of quaternary hydrazinium moieties in hydrophilic parts was synthesized. These quaternary hydrazinium surfactants were obtained using a two-step reaction scheme, starting from ring opening of succinic anhydride with a base (morpholine, piperidine), followed by ammonolysis with hydrazine hydrate, then alkylation of the amino group with alkyl bromides (RBr) that have different hydrophobic chain lengths (R, C₁₂H₂₅, C₁₄H₂₉, and C₁₆H₃₇), and ending with the quaternarization of the secondary amino group by two moles of methyl iodide. The chemical composition of the surfactants was analyzed by FTIR, ¹HNMR, mass spectroscopy, and elemental analysis. A variety of surface-active characteristics were achieved by surface calculations, including CMC, γcmc, CMC/C₂₀, Γ_max, pC₂₀, A_min, and Π_cmc. These surface characteristics and foam stability rely on the nature of the hydrophobic chain. Preliminary results showed that an upgrade throughout the CH₂ group in the fatty chain and the morpholine or piperidine ring lowers the CMC and increases the foaming capacity and stability of the quaternary hydrazinium surfactants. Anionic dye (Acid BG) interactions with 12b surfactant (as an example) were studied using the spectrophotometric technique and the binding constant (170.64?dm³.mol^?1) was determined. The results indicate solubilization and binding took place at a large scale. Furthermore, considerable biodegradation of cationic surfactants was observed (68–87%). The antimicrobial activity of these surfactants has also been observed with the minimum inhibitory concentration (MIC) and the size of inhibited growth zone. The smallest MICs were found in 12a (64?μg/mL) and 12b (32?μg/mL) surfactants, indicating the highest antimicrobial activity.

Full text of DOI:10.1007/s13738-021-02247-3

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-021-02247-3
ORIGINAL PAPER
Synthesis, characterization, interaction with anionic dye,
biodegradability, and antimicrobial activity of cationic surfactants:
quaternary hydrazinium derivatives
Nora M. Hilal1 · Entsar. E. Badr2 · Elshimaa H. Gomaa2 · Eman M. Kandeel2 · Rabab A. Ismail3 · Entsar M. Ahmed2
Received: 17 May 2020 / Accepted: 2 April 2021
© Iranian Chemical Society 2021
Abstract
A novel cationic surfactant type of N’alkyl N,’N’dimethyl-4-morpholino-4-oxobutanoylhydrazinium iodide (10a–12a) and
N’alkyl N’, N’dimethyl-4-piperidino-4-oxobutanoylhydrazinium iodide (10b–12b) of quaternary hydrazinium moieties in
hydrophilic parts was synthesized. These quaternary hydrazinium surfactants were obtained using a two-step reaction
scheme, starting from ring opening of succinic anhydride with a base (morpholine, piperidine), followed by ammonolysis
with hydrazine hydrate, then alkylation of the amino group with alkyl bromides (RBr) that have diferent hydrophobic chain
lengths (R, C12H25, C14H29, and C16H37), and ending with the quaternarization of the secondary amino group by two moles
of methyl iodide. The chemical composition of the surfactants was analyzed by FTIR, 1HNMR, mass spectroscopy, and
elemental analysis. A variety of surface-active characteristics were achieved by surface calculations, including CMC, γcmc,
CMC/C20, Γmax, pC20, Amin, and Πcmc. These surface characteristics and foam stability rely on the nature of the hydropho-
bic chain. Preliminary results showed that an upgrade throughout the CH2 group in the fatty chain and the morpholine or
piperidine ring lowers the CMC and increases the foaming capacity and stability of the quaternary hydrazinium surfactants.
Anionic dye (Acid BG) interactions with 12b surfactant (as an example) were studied using the spectrophotometric technique
and the binding constant (170.64 dm3.mol−1) was determined. The results indicate solubilization and binding took place at
a large scale. Furthermore, considerable biodegradation of cationic surfactants was observed (68–87%). The antimicrobial
activity of these surfactants has also been observed with the minimum inhibitory concentration (MIC) and the size of inhib-
ited growth zone. The smallest MICs were found in 12a (64 µg/mL) and 12b (32 µg/mL) surfactants, indicating the highest
antimicrobial activity.
Introduction
cationic surfactants have long been the object of attention
in chemistry [4, 5]. Cationic surfactants/amphiphiles are
widely used in high-tech applications as well as by smooth
models for mesoporous material synthesis [6], corrosion
inhibitors [7], capping agents for nanoparticle synthesis [8],
and biomedical applications such as gene and drug delivery
[9], and antimicrobial activity [11]. The production of these
surfactants should be environmentally acceptable allowing
these components to be soluble and biodegradable. Cationic
surfactants have been given a real consideration because
the increased use of cationic surfactants in industrial, and
household goods have caused ecological difculties due to
low solubility and biodegradability [12–18]. The confgura-
tion of the compounds is the main reason infuencing the
adsorption and micellization properties of cationic sur-
factants since adsorption is the major factor for the diferent
applications [19, 20]. Consequently, structural modifcations
at the molecular stage may enhance surfactant properties.
Cationic surfactants are substances that have one or more
hydrophobic groups linked directly or indirectly to posi-
tively charged atoms, frequently nitrogen (QAC quaternary
ammonium compounds) [1, 2], and few phosphorous (QPC
quaternary phosphonium compounds) [3]. Due to its broad
synthesis and unrestricted use in a variety of industrial areas,
* Entsar. E. Badr
entsar@azhar.edu.eg
1
2
3
Taif University, University College of Ranyah, Taif, KSA,
Saudi Arabia
Faculty of Science, Girls Branch, Al-Azhar University,
Nasr City, Cairo, Egypt
Chemistry Department, University of Hafr AlBatin,
Hafr AlBatin, KSA, Saudi Arabia
Vol.:(0123456789)
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Journal of the Iranian Chemical Society
Recently, several reports analyzed and investigated sev-
eral diferent forms of imidazolium [21], pyridinium [22],
piperidineium [23], and pyrrolidinium cationic compounds
[24]. So far, there are few syntheses and studies on cati-
onic surfactants containing morpholine and piperidine rings
attached to the hydrophilic head regarding their properties
and potential use in many applications [25–27]. Asadov.
et al. [28] have shown that morpholine amphiphile has petro-
collecting and dispersing properties. Biocompatibility and
sustainability considerations also have slowly allowed the
production and design of several diferent forms of biocom-
patible surfactants consisting of biodegradable functional
molecules, such as ester [29, 30] and amide groups [31, 32],
which are deemed eco-friendly, to be easily broken down
after usage. Hydrazinium derivatives have a wide range of
applications, such as sourcing anhydrous hydrazine, propel-
lant additives, antineoplastic agents, cancer and Hodgkin ’s
disease drugs, explosives, and ligands for the preparation of
hydrazinium/hydrazine metal complexes[33–35]. Also, due
to their industrial and biological uses, the knowledge of dye
interaction with the surfactants is of great importance to the
scientifc and academic community [36]. Surfactants serve
as solubilizers for water-insoluble dyes, breaking down dye
aggregates to improve processes of adsorption on fber, as
auxiliaries for enhancing dye adsorption and leveling or dif-
fusing agents [37, 38].
unless stated to be otherwise. Water used for experiments
was deionized water.
Structural characterization
Characterizations of cationic surfactants (10a–12b) were
1
performed with the assistance of FTIR, HNMR, and
MALDI MS techniques. Using a Bruker Tensor 27 spec-
trometer, Fourier transform infrared (FTIR) spectra were
obtained within the range of 4000–400 cm-1. 1HNMR was
performed with a Bruker DRX300 NMR spectrometer. With
TMS as an internal standard, the samples were dissolved
in CDCl3. The MALDI mass spectrum was acquired from
the Bruker SolariX XR device in the dithranol matrix in
dichloromethane.
Synthesis
Synthesis of N’alkyl‑4‑morpholino‑4‑oxobutanehydrazide
(7a‑9a) and N’alkyl‑4‑oxo‑4‑piperidinobutanehydrazide
(7b‑9b)
Succinic anhydride (5.0 g, 0.05 mol) was applied to a base
solution (morpholine, piperidine) (0.05 mol) in methanol
after full addition and stirring. The reaction mixture was
heated under refux, and the acid value of hemi amide acid
was measured at diferent reaction time instances. The ester
compound was fully formed when the reactants’ acid value
was less than 1.5mgKOH/gm. Hydrazine hydrate (3.20 g,
0.064 mol) was added to the fask and the mixture contin-
ued to be refuxed until the peak of the ester group disap-
peared from the IR spectra. Then, an alkyl bromide (dodecyl,
tetradecyl, hexadecyl bromide) equivalent mole was intro-
duced to the reaction solution. The experiment proceeded
for another fve hours under the same experimental condi-
tions. The solvent was collected under reduced pressure; the
residual was treated with water and purifed by ethanol for
recrystallization. (7a–9b).
The substantial interest in cationic surfactants has encour-
aged us to prepare six new cationic surfactants including
morpholine or piperidine nucleus attached to 4-oxobutane-
hydrazinium with terminal N-alkyl substitutes (C10–C16)
(10a–12b).
The objective of this research is to determine surface
activity by studying surface tension and study the interaction
of anionic dye (Acid BG) with 12b surfactant by the spec-
trophotometric technique. Biodegradability and the efect of
the introduction of amide units on their chemical nature are
also analyzed. Additionally, microbial activity against both
gram-positive and gram-negative bacteria was examined by
identifying a minimum inhibitory concentration (MIC).
N’‑dodecyl‑4‑morpholino‑4‑oxobutanehydrazide (7a)
White semisolid (yield 87%) IR (KBr, cm−1)3181 (NH) and
1641, (C=O).
Materials and methods
1HNMR of 7a(CDCl3,400 MHz) 0.96(3H,t,CH3CH2),1.2
9[20H,m,CH3(CH2)10], 1.59(2H,t,CH2CH2N)2.38[2H,t,NC
OCH2], 2.71[2H,t,CH2CON],3.27(1H,s,CH2NH),
3.50[4H,t, CH2NCH2],3.77[4H,m, CH2OCH2]
9.81(1H,s,CONH),. 7a Calcd. for C20H39N3O3: C, 65.00;
H, 10.64; N, 11.37. Found: C, 65.10; H, 10.66; N, 11.38 8a.
Calcd. for C22H43 N3O3: C, 66.46; H, 10.9; N, 10.57. Found:
C, 66.49; H, 10.93; N, 10.59 9a.Calcd. for C24H47 N3O3:
C, 67.72; H, 11.13; N, 9.87. Found: C, 67.74; H, 11.15; N,
11.89, %.
Materials
Dodecanyl, tetradecyl, and hexadecyl bromide were bought
from Aldrich (USA) and used without additional purif-
cation. Schuchardt chemically pure products were hydra-
zine hydrate (85%), piperidine, morpholine, and methyl
iodide. Single-azo dye (Acid Red BG) was purchased from
Sigma-Aldrich Chemical Company (Molecular Formula:
C18H14N4Na2O8S2). All other chemicals were reagent grade
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Journal of the Iranian Chemical Society
N’‑tetradecyl‑4‑oxo‑4‑piperidinobutanehydrazide (8b)
5.87[1H,s, NHCO]. 11a.Calcd. for C24H48 IN3O3: C, 52.07;
H, 8.74; N, 7.59. Found: C, 52.12; H, 8.75; N, 7.60%.
MALDI-TOF MS m/z: 426 for [M-I]+.
Yellowish white (yield 89%) IR (KBr, cm−1)3168 (NH) and
1639, (C=O). 1HNMR of 8b (CDCl3,400 MHz) 0.87(3H,t,
CH3CH2),1.24–1.45[24H,m,CH3(CH2)12], 1.61[6H,m, CH2
CH2CH2] 2.29[4H,m,CO(CH2)2CO], 2.55(2H,t,CH2N),
3.21(1H,s,CH2NH) 3.32[4H,t,CH2NCH2]. 9.51(1H, s,
CONH).Elemental analysis:0.7b Calcd. for C21H41N3O2:
C, 68.62; H, 11.24; N, 11.43. Found: C, 68.64; H, 11.26;
N, 11.45 8b Calcd. for C23H45N3O2: C, 69.83; H, 11.46; N,
10.62. Found: C, 69.84; H, 11.49; N, 10.649b Calcd. for
C25H49 N3O2: C, 70.87; H, 11.66; N, 9.92. Found: C, 70.89;
H, 11.68; N, 9.94, %.
N’‑Hexadecyl N’,N’dimethyl‑4‑morpholino‑4‑
oxobutanoylhydrazinium iodide (12a)
1HNMR of 12a (CDCl3, 400 MHz)0. 93(3
H , t , C H 3 C H 2 ) , 1 . 3 3 [ 2 0 H , m , C H 3 ( C H 2 ) 1 4 ] ,
2.42[4H,m,CO(CH2)2CO],2.67[6H,s,N+(CH3)2],3.27[2H
,t,CH2N+],3.47[4H,t,CH2NCH2],3.66[4H,m, CH2OCH2],
5.74[1H,s, NHCO]. 12a.Calcd. for C26H52 IN3O3: C, 53.69;
H, 9.01; N, 7.22. Found: C, 53.75; H, 9.02; N, 7.23%.
MALDI-TOF MS m/z: 454 for [M-I]+.
Synthesis of (N’‑alkyl N’,N’dimethyl‑4‑morpholino‑4‑
oxobutanoylhydrazinium) iodide (10a‑12a)
and (N’‑alkylN’,N’dimethyl‑4‑piperidino‑4‑
oxobutanoylhydrazinium) iodide (10b‑12b)
N’‑DodecylN’,N’dimethyl‑4‑piperidino‑4‑
oxobutanoylhydrazinium iodide (10b)
A sequence of six quaternary hydrazinium surfactants was
produced by quaternaization of N’alkyl-4-(morpholino or
piperidino-4-oxobutanehydrazide (7a,b–9a,b) (0.01 mol)
with two moles of methyl iodide in ethanol as a solvent
under refux over eight hours. The mixtures were left to cool
down, and the products obtained were further fltered by
recrystallization from acetone/isopropanol [18:2 (vol/vol)]
to get (10a–12b).
1HNMR of 10b(CDCl3,400 MHz)0.95(3H,t,CH3CH2),1.23
[20H,m,CH3(CH2)10], 1.41[6H,m, CH2CH2CH2],2.40[4H,
m,CO(CH2)2CO],2.71[6H,s,N+(CH3)2],3.13[2H,t,CH2N+
],3.37[4H,t,CH2NCH2], 7.40[1H,s, NHCO]10b.Calcd. for
C23H46 IN3O2: C, 52.77; H, 8.86; N, 8.03. Found: C, 52.85;
H, 8.93; N, 8.07%. MALDI-TOF MS m/z: 396 for [M-I]+.
N’‑Dodecyl N’,N’dimethyl‑4‑morpholino‑4‑
N’‑TetradecylN’,N’dimethyl‑4‑piperidino‑4‑
oxobutanoylhydrazinium iodide (11b)
oxobutanoylhydrazinium iodide (10a)
IR (KBr, cm−1)3178–3197 (NH) and 1631–1644 (C=O-N).
Their yields were 86, 88, 91, 83, 87, and 94% for 10a–12b,
respectively.
1HNMR of 11b (CDCl3,400 MHz)0.97(3H,t,CH3CH2),1.30-
[20H,m,CH3(CH2)12], 1.43[6H,m, CH2CH2CH2],2.44[4H,
m,CO(CH2)2CO],2.75[6H,s,N+(CH3)2],3.17[2H,t,CH2N+
],3.41[4H,t,CH2NCH2], 7.26[1H,s, NHCO]. 11b.Calcd. for
C25H50 IN3O2: C, 54.44; H, 9.14; N, 7.62. Found: C, 54.56;
H, 9.21; N, 7.71%. MALDI-TOF MS MALDI-TOF MS m/z:
424 for [M-I]+.
1HNMR of 10a (CDCl3,400 MHz)0.95-
( 3 H , t , C H 3 C H 2 ) , 1 . 2 7 [ 2 0 H , m , C H 3 ( C H 2 ) 1 0 ] ,
2.31[4H,m,CO(CH2)2CO],2.77[6H,s,N+(CH3)2],3.17[2H
,t,CH2N+],3.35[4H,t,CH2NCH2],3.55 [4H,m, CH2OCH2],
5.89[1H,s, NHCO]. 10a Calcd. for C22H44IN3O3: C, 50.28;
H, 8.44; N, 8.00. Found: C, 50.33; H, 8.45; N, 8.01%.
MALDI-TOF MS m/z: 398 for [M-I]+.
N’‑Hexadecyl N’,N’dimethyl‑4‑piperidino‑4‑
oxobutanoylhydrazinium iodide (12b)
N’‑Tetradecyl N’,N’dimethyl‑4‑morpholino‑4‑
oxobutanoylhydrazinium iodide (11a)
1HNMR of 12b(CDCl3,400 MHz)0.99(3H,t,CH3CH2),1.26
[H,m,CH3(CH2)14], 1.45[6H,m, CH2CH2CH2],2.47[4H,m
,CO(CH2)2CO],2.77[6H,s,N+(CH3)2],3.19[2H,t,CH2N+],
3.39[4H,t,CH2NCH2], 7.14[1H,s, NHCO]0.12b.Calcd. for
C27H54 IN3O2: C, 55.95; H, 9.39; N, 7.25. Found: C, 56.07;
H, 9.46; N, 7.31%. MALDI-TOF MS m/z: 452 for [M-I]+.
1HNMR of 11a (CDCl3, 400 MHz)0. 90(3
H , t , C H 3 C H 2 ) , 1 . 2 6 [ 2 0 H , m , C H 3 ( C H 2 ) 1 2 ] ,
2.51[4H,m,CO(CH2)2CO],2.80[6H,s,N+(CH3)2],3.21[2H
,t,CH2N+],3.41[4H,t,CH2NCH2],3.61[4H,m, CH2OCH2],
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Journal of the Iranian Chemical Society
bacterial strains: Escherichia coli (NCTC-10416), Staphy-
lococcus aureus (NCTC-7447), Pseudomonas aeruginosa
(NCIB-9016), and Bacillus subtilis (NCIB-3610) using the
agar difusion method, which is a sterilized disc of flter
paper saturated with a determined sample quantity that is
put on a plate containing a solid bacterial nutrient agar
broth, which has been heavily seeded with the spore sus-
pension of the organism examined. Upon incubation, the
width of the clear inhibition zone around the sample is
taken as a measure of the inhibitory capacity of the sample
against the specifcally tested organism [40]. Minimum
inhibitory concentration is determined by tube dilution
method with inoculum to give 105 microorganisms per mL.
The tested compounds in distilled water were diluted to
provide fnal concentrations from 512 to 2 μg/mL. As the
MIC, the lowest concentration of the antibacterial agent
needed to inhibit the variable growth of the bacteria. This
investigation was carried out at Fermentation Biotechnol-
ogy and Applied Microbiology lab (FBAM, Al Azhar Uni-
versity, Cairo, Egypt).
Measurement of surface‑active properties
Surface tension measurements with a Krüss K 6 Tensi-
ometer were performed at 25 0.2 °C through a Du Nouy
platinum ring technique. Measurements were performed
at the initial concentration of 50 mM for the aqueous
solution; other solutions were collected using the serial
dilution process. CMC (critical micellular concentration)
and γCMC (surface tension at critical micellular concentra-
tion) were measured as the surface tension breakpoint vs.
concentration plot values (semilogarithmic scale). Foam-
ing characteristics were measured at 2 g/dm3 and 25 °C.
Foam stability was calculated by contrasting the level in
the Ross–Miles method after ten minutes with the original
foam point.
Spectrophotometric measurements
Hitachi UV-2800 spectrophotometer was used to meas-
ure the UV–visible spectrophotometric values inside the
UV–visible range. The cells used were square cuvettes
with a thickness of 1.0 cm. Distilled water was kept at the
reference side in simple UV/visible absorption spectra,
while the dye solution was adopted as a reference in dif-
ferential UV/visible spectroscopy. A dye-surfactant-water
ternary solution was taken into the sample cell in both
situations. All the tests occurred at room temperature.
Results and discussion
Preparation of (N’‑alkyl N’,N’dimethyl‑4‑morpholino‑
4‑oxobutanoylhydrazinium) iodide (10a–12a)
and (N’‑alkylN’,N’dimethyl‑4‑piperidino‑4‑
oxobutanoylhydrazinium) bromide (10b–12b)
The synthesized surfactants biodegradability
Cationic surfactants containing amide and hydrazinium
groups and carrying morpholine or piperidine rings have
been synthesized by opening the ring of succinic anhydride
with a base (morpholine or piperidine) using methanol as
solvent. Morpholino or piperidino oxobutanoate, when
reacting with hydrazine hydrazide, produced correspond-
ing 4-morpholino-4-oxobutane hydrazide and 4-oxo-
4-piperidinobutane hydrazide which, when reacting with
fatty alkyl bromide (dodecyl, tetradecyl, and hexadecyl),
produced analogous N’alkyl-4-morpholino-4-oxobutane
hydrazide and N’alkyl-4-oxo-4-piperidinobutane hydrazide,
respectively. Subsequent quaternarization of the respective
N’alkyl (4-morpholino or 4-piperidino) oxobutane hydrazide
(7a–9b) with methyl iodide gave the corresponding cationic
surfactants: (N’-alkyl N, N’dimethyl-4-morpholino-4-ox-
obutanoylhydrazinium) iodide (10a–12a) and (N’-alkyl N,
N’dimethyl-4-piperidino-4-oxobutanoylhydrazinium) iodide
(10b–12b) (Scheme 1).
Biodegradation assessments of the generated surfactants of
cationic hydrazinium were carried out using the river water
die-away technique [39]. River water had been collected
from the Nile River for research. For this procedure, a stir-
ring mixture including the surfactant examined (1000 ppm)
was incubated at 25 °C. Samples were taken regularly, fl-
tered using Whatman flter paper and had their surface ten-
sion measured via a Du-Nouy tensiometer (Kruss type K6).
The procedure was replicated for seven days. The biodeg-
radation percentage D % was determined in terms of the
surface tension measured as shown by Eq. 1:
[(
) (
)]
D = ꢀt − ꢀ0 ∕ ꢀbt − ꢀ0 × 100
(1)
where γt surface tension exists at t, period zero is the sur-
face tension γ0 (initial surface tension), and γbt is the blank
experiment surface tension at period t.
Chemical structure confrmation
Measurement of antimicrobial activity
The progress in the reaction formation of hydrazide was
detected by examining a small portion of the reaction mix-
ture every 60 min until the rate of disappearance of the
Cationic hydrazinium surfactants were examined for anti-
microbial activity against the reference of the following
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Journal of the Iranian Chemical Society
O
O
H
N
R
N H
i-CH3OH
ii
O
+
H2N
N
NH2NH2
O
R
1a, b
O
2
3a, b
CH3(CH2)nBr
4-6
O
H
N
H3C
O
H
N
H
Isopropanol
N
N
CH3 (CH2)n
I-
CH3 (CH2)n
H3C
N
N
CH3I \ Na2CO3
O
R
O
R
7a--9b
10a-12a
( R = O ; n= 11,13, 15)
10b-12b ( R = CH2 ; n = 11,13,15)
Scheme 1 Synthesis of quaternary hydrazinium-functionalized surfactants
The resonance of the two methyl protons immediately
bound to the positive charge quaternary nitrogen that was
detected as a singlet δ within 2.79–2.85 ppm for the cati-
onic surfactants. A typical resonance signal for the hydro-
gen protons of the methylene group was directly bound to
the positively charged quaternary nitrogen, which is a part
of the fatty chain, and was within δ 3.13–3.21 ppm for the
cationic amphiphiles. The methylene proton’s signals were
next to the oxygen of the morpholine group, which are part
of the hydrophilic part and were observed between δ 3.55
and 3.67 ppm for cationic surfactants. The resonance of one
proton attached to nitrogen attached to the carbonyl group
was shifted to the downfeld afected by the adjacent quater-
nary nitrogen atom, which was observed for morpholino and
piperidino cationic surfactants as a singlet at 5.71–7.19 ppm
(Fig. 3a and b). The MS data obtained for all these current
cationic surfactants confrmed a chemical construction. The
parent-ion value for the surfactants was identifed for both
the positive ion without iodide ion for each surfactant atom.
The calculated MALDI-TOF MS m/z values for morpholino
surfactants 10a–12a were 398.338, 426.369, and 454. 401
and piperidino surfactants 10b–12b were 396.358, 424.390,
and 452.421 for M-I which strictly matched the practical
values for morpholino surfactants 10a–12a values of 398,
426, and 454 and for pipredino surfactants 10a–12b values
of 396,424, and 452.
CO-ester
2835
c
3322
2919
CO-amide
T %
CO-ester
2835
2919
3322
b
CO-amide
CO-amide
a
2835
CO-ester
3322
2919
4000
3000
2000
-1
1000
Wave number (cm )
Fig. 1 a FTIR spectrum of hydrazide formation reaction progress
after 2hrs (a); 3hrs (b); 4hrs (c)
characteristic absorption band of the ester group increased.
The FTIR spectrum was used to confrm the progress of the
hydrazide formation reaction (Fig. 1a).
The structural verifcation is exemplifed for N’-hexade-
cyl-4-morpholino-4-oxobutanehydrazide and N’-dodecyl-
4-piperidine-4-oxobutanehydrazide derivatives (Fig. 2a, b).
In the study, 1HNMR was developed according to the
chemical structures of the modern cationic surfactants.
Chemical shifts for methyl protons of the fatty alkyl chain
of hydrazinium surfactants occurred as a triplet between
0.90 and 0.99 ppm. The four butane protons of the two
methylenes among carbonyl groups were found as a tri-
plet of δ 2.63–2.68 ppm for, 10b, and 10a, respectively.
Surface activity
The surface properties of the new quaternary hydrazinium
surfactant derived from morpholine and piperidine were
examined via measuring the surface tension. CMC refers
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Journal of the Iranian Chemical Society
Fig. 2 a 1HNMR of N’-hexadecyl l-4-morpholino-4-oxobutanehydrazide, b 1HNMR of N’-dodecyl-4-piperidino-4-oxobutanehydrazide
to the stage where a signifcant shift in slope happens on
the curve. After the slope shift, the resulting lines and the
corresponding slope lines indicate a decrease in the surface
tension intersecting after a defnite point, showing the CMC
quantities for the surfactants (Fig. 4).
cationic surfactants was estimated to rely on the size of
the hydrophobic chain and the nature of the cationic head
unit. Based on the data seen in Table 1, an increase in
the fatty chain length (nonpolar tail) reduces the CMC
of an investigated amphiphiles at 25 °C. The CMC val-
ues obtained for the quaternary hydrazinium piperidine
series of 10b–12b at the same length of the hydrocarbon
chain were lower than those obtained for the quaternary
It became clear that the molecular design of these qua-
ternary hydrazinium surfactants should have a signifcant
efect upon their surface behaviors. A CMC value for such
1 3

Journal of the Iranian Chemical Society
1
1
Fig. 3 a HNMR of N’-hexadecyl N’, N’dimethyl-4-morpholino-4-oxobutanehydrazonium) iodide, b HNMR of N’-dodecyl N’, N’dimethyl-
4-piperidino-4-oxobutanehydrazonium) iodide
hydrazinium morpholine series of 10a–12a described
here. Besides, the CMC values for these new quaternary
hydrazinium-related cationic surfactants contradict with
some other surfactants that depend on morpholine, piperi-
dine, and traditional quaternary ammonium surfactants,
which are equally efcient as other cationic compounds
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Journal of the Iranian Chemical Society
Fig. 4 Variation in the surface tension of surfactants 10a–12a, 10b–12b vs. the concentration at 25 °C. For confgurations, it includes scheme 1
Table1 Surface-active
properties of cationic
hydrazinium surfactants
(N’-alkyl N’,N’dimethyl-
4-morpholino-4-
oxobutanoylhydrazinium)
iodide (10a–12a) and
(N’-alkylN’,N’dimethyl-
4-piperidino-4-
Surfactanta CMC γCMC
Πcmc 106Γmax Amin pC20 CMC/ C20 Foam
Foam stability
V10/V0
0 min
10 min *100
mM
0.89
mN/m mN/m mol/m2 nm2
40.15 32.35 1.87
ml
125
80
%
64
10a
11a
12a
10b
11b
12b
0.89
0.86
0.77
0.84
0.81
0.74
3.52 2.94
3.83 4.12
4.15 5.22
3.67 1.87
3.93 2.38
4.29 3.70
0. 61 38.12 34.28 1.93
143
105
159
125
142
91
165
125
184
143
73
78
67
75
80
oxobutanoylhydrazinium) iodide
(10b–12b)
0.37
0.40
0.28
0.19
36.50 35.90 2.14
38.91 33.49 1.98
36.45 35.95 2.06
34.60 37.80 2.25
aFor confgurations, it includes Scheme 1. CMC(critical micelle concentration), CMC surface tension,
CMC surface pressure, CMC surface pressure, maximum excess surface concentration, Amin (Total Area
per Molecule)
[25, 26]. γCMC is the highest surfactant capable of reduc-
ing water surface tension to be equal to the CMC value.
Lowering the surface tension of the water happens as the
surfactant monomers adsorb the air–water interface. That
after a certain stage, the whole interface is flled by the
monomers of the surfactant; therefore, there is no fur-
ther decrease in the surface tension of the aqueous solu-
tion that will result from increasing the concentration of
the surfactant. During this particular stage, the trend of
the surface tension graph varies rapidly and is constant,
and the resulting value is known as γmin. Values of γCMC
were 40.15, 38.12, and 36.50 mN/m for the quaternary
hydrazinium morpholine series 10a–12a and in the case of
quaternary hydrazinium piperidine series 10b–12b, 38.91,
36.45, and 34.60 mN/m. The small variations in the γCMC
values for the two series may be related to the design of
the head group.
Certain surface parameters, i.e., surface excess concen-
tration (Γmax), air–water interface molecular surface area
(Amin), and surface tension decrease efciency of 20 mN
m−1 (C20) were derived from the quaternary hydrazinium
surfactants surface tension graph (Table 1). Using the Gibbs
adsorption isotherm Eq. 2, the maximum surface excess con-
centration at the air/water interface, i.e., Γmax, is calculated
as follows:
Γmax = − (1∕2.304 nRT) (dꢀ∕d logC)
(2)
From the previous equation, the gas constant R
(8.31 J mol−1 K‐1), the absolute temp of T, the surfactant
C, and (dγ/d log C)T the slope of surface tension sections are
1 3

Journal of the Iranian Chemical Society
below the CMC. The n is a fxed value determined by the
number of singular ions which make up the adsorbed sur-
factant at the interface. The value of n would then be taken
for cationic surfactants 2 as there is one counter ion linked
to the ionic head group. Consistent adsorption of surfactant
particles at the air–water interface with increasing surfactant
concentrations induces a progressive reduction of the aque-
ous solution’s surface tension. Continuous surfactant adsorp-
tion leads to high interface aggregation, and the surfactant
monomer concentration at an interface is more concentrated
than at the bulk solution. Γmax determines the region associ-
ated with the air–water interface concentration of quaternary
hydrazinium surfactants and their value is dependent on the
length of the hydrophobic chains and the size of the cationic
head groups.
is the lowest concentration arising from complete surface
adsorption saturation [43]. Therefore, C20 can be used to
test the adsorption potential of surfactant molecules at the
air–water interface. Therefore, the higher the pC20 value,
the higher the surfactant’s adsorption performance. ΠCMC is
the surface pressure at CMC, and this parameter measures
the surfactant’s efect on the surface tension of the pure sol-
vent, i.e., water, as defned in Eq. 5:
pC20 = − log C20
⋅
(5)
(5) where γ0 is the surface tension of pure solvent and γCMC
is the solution surface tension at CMC. ΠCMC establishes
the maximum surface tension decrease and can be used to
determine surfactant efectiveness to reduce water surface
tension [44, 45]. So, the greater the surfactant’s interest, the
higher the surfactant’s efectiveness. The pC20 and ΠCMC
values are reported in Table 1. The variability of pC20 and
ΠCMC suggested that both pC20 and ΠCMC increased as the
hydrocarbon chain increased. The CMC/C20 ratio value
is used to evaluate the main features of the adsorption and
micellization process. A surfactant with a higher CMC/C20
ratio tends to adsorb more on the air–water interface than to
form micelles in solutions. Table 1 shows that the surfactant
with a longer fatty chain was easier to accumulate at the
air–water interface than to self-assemble in a solution.
The data were consistent with the interpretation of the
value pC20.
Using Eq. 3, the minimal area at the air–water interface
occupied per surfactant molecule (Amin) has been calcu-
lated [41]:
Amin = 1∕N Γmax
(3)
where N is the number for Avogadro and where Amin is
in nm2 (Table 1). Amin values for both the quaternary
hydrazinium surfactants (10a–12b) synthesized through-
out this study were found to be similar to those reported
earlier for morpholine and piperidine surfactants [42]. A
higher value of Γmax and a lower value of Amin indicate
a denser structure of the surfactant particles on the surface
of the solution [43]. It is evident from Table 1 that qua-
ternary hydrazinium surfactants piperidine series 10b–12b
have a signifcantly higher Γmax value and a prominent
smaller Amin value than quaternary hydrazinium surfactants
morpholine series 10a–12a, suggesting a denser structure
of quaternary hydrazinium surfactants piperidine series
10b–12b at the air–water interface. This can be clarifed
by the conformational changes in the air–water interface
owing to the repulsive force between the two lone pairs of
electrons on the oxygen atom in the morpholine ring. A con-
trast between the values of Amin in both series shows that
changes in the slopes are primarily due to the nature of the
base ring infuenced by the hydrazinuim head [41]. This was
well recognized that the hydrophilic head group was a major
inducer throughout the infuence of the Γmax and Amin values
of surfactants.
Study interaction of acid red BG with 12b cationic
surfactant using the spectrophotometric technique
Figure 5a shows the UV/visible spectra of acid red BG
in the absence (curve 1) and the presence of 12b (curves
2 to 13). In this case, (1.0 × 10 − 5 mol/L Red BG) the
dye showed maximum absorption at 512.5 nm. The
efect of various concentrations (0.1 to 4.5 × 10–4 mol/L)
of 12b cationic surfactants (as an example) on Red BG
fxed concentration absorption spectrum solubilization
was analyzed and shown in Fig. 5a ( curves 2 to 13).
Although the concentration of 12b slowly increased (0.1
to 0.17 × 10–4 mol/L), the size of the red BG band frstly
decreases by the rise in the concentration of 12b well
below the CMC (0.00019 mol/L) and reaches the mini-
mum value and then increases for again with an additional
rise in the surfactant beyond the CMC. Concentration is
interpreted as CMC at the minimum observed (Fig. 5b).
Red BG relates the initial decrease in intensity to the ion-
pair interaction of red BG with the 12b. Once the 12b
concentration rises to 0.00019 mol/L, a redshift with
548.7 nm bands is observed. This switch is likely a result
of the red BG/12b micelles association [46]. A substantial
increase in absorbance was found when the concentration
Certain signifcant surface-active parameters, like adsorp-
tion efciency (pC20) and surface tension reduction ef-
ciency (ΠCMC), also can be calculated from the surface ten-
sion chart. The pC20 is measured using Eq. 4:
pC20 = − log C20
⋅
(4)
In the equation, C is the surfactant’s molar concentration
and C20 is the surfactant concentration by which the pure
solvent’s surface tension is decreased by 20 mN m−1. C20
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Journal of the Iranian Chemical Society
Fig. 5 a Visible absorption spectra of acid red BG (1) in the presence
of various 12b cationic surfactant concentrations (1 to 13). b The
absorbance change of 1×10–5 mol/ L ( below and above the CMC)
with the concentration of 12b surfactant. c The plot of DT/ A-Ao
against 1/CM for acid red BG in 12b cationic surfactant
of 12b (2.50 to 4.50× 10–4 mol/L) was further added. The
increase in absorbance in 12b above the CMC concentra-
tion can be due to the introduction of the red BG mol-
ecules into 12b micelles [47].
via dye and surfactant molecules, while the latter combine
their hydrophobic elements in parallelly:
D
ꢀ− + S+ ←→ DS
(6)
The penetration of dye particles into micelles is encour-
aged since cationic 12b attracts anionic dyes. Between the
hydrated micelle surfaces up to the nonpolar heart, there is
a continuum of climate. The solubilized components may
be adsorbed to the surface and positioned there or become
trapped in the center of hydrocarbons. Its polar and/or non-
polar groups are associated diferently with the surfactant,
based on their substituents. First, the dye-surfactant com-
plex is produced and then adsorbed onto the surfaces of
the micelle, gradually leading to the realignment of the dye
molecules into the micelle. Long-range electrostatic forces
and short-range hydrophobic forces work together to create a
dye-surfactant matrix. The former are brought close together
By time, these complexes undergo self-aggregation (as
shown below), and subsequently, an increase in absorbance
in the premicellar region is witnessed:
(DS) ←→ (DS)
(7)
Once all the CMC dye molecules are interconnected as
normal monomers in micelles, the absorbance reaches its
limiting value:
(DS)ꢀ + M ←→ DM
(8)
In Eq. 8, DM is the refection of dye monomers interca-
lated into the micelles. Solubilization is a dynamic process,
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Journal of the Iranian Chemical Society
and solubilization can lapse diferent instances of time of
residence between core and surface at diferent rates. The
hydrophilic and hydrophobic forces’ imbalances make the
solubilized components in the micelle somehow unpredict-
able, thus giving random absorbance values [48–50].
The dye–micelle complexes’ binding constant Kb can be
determined from the Benesi-Hildebrand equation (Eq. 9),
as follows:
DT
1
1
=
+
(
)
(
)
(9)
ΔA
ꢀM − ꢀo
Kb ꢀM − ꢀo CM
(9)
where DT is the dye concentration, ΔA=A-A0 is the dif-
ference between the absorption of the dye in the presence
and the absence of the surfactant, ꢀM is the molar extinguish-
ing coefcient of dye that is completely bound to micelles
(ꢀo = 4126.32 L∕mol cm),ꢀo is the molar extinguishing
coefcient of acid red BG (ꢀM = 82100 L∕mol cm), Kb
is the binding constant, an CM is the micellized surfactant
concentration.
Fig. 6 Biodegradation of cationic surfactants based on morpholine
and piperidine investigated by the river die-away method using a sur-
face-tension technique. For structures, see scheme 1
breaks very easily, and these categories of surfactants were
found to be partially or readily biodegradable when reviewed
[53]. Thus, the results obtained show that these new cati-
onic components can potentially be used to formulate large-
performance cleaning products, stain remover, adhesives,
fabric softeners, etc.
CM = Cs−CMC
(10)
The binding constant (Kb) was calculated from the results
of spectral measurements to be equal to 170.64 dm3 mol−1
DT
(Fig. 5c) from the linear relationship between against 1/
Antimicrobial activity of cationic hydrazinium
surfactants
ΔA
CM.
The cell membrane of microorganisms consists of various
lipids (building units) and protein layers, in bilayer form,
which imparts a hydrophobic character. Membrane perme-
ability is the main function, namely the control of biological
reactions in the cell. Any factor afecting the selective per-
meability of the cell membrane may signifcantly damage the
microorganism. Cationic surfactants have a distinct ability to
adsorb the most negatively charged cell membrane interface.
The potential antimicrobial activity of (N’-alkyl N’,
N’dimethyl-4-morpholino-4-oxobutanoylhydrazinium)
iodide (10a–12a)and (N’-alkylN’, N’dimethyl-4-piperi-
dino-4-oxobutanoylhydrazinium) iodide (10b–12b) on
gram-positive and gram-negative bacteria was evaluated
in vitro by the determination of the inhibition zone (Fig. 7)
and the minimum inhibitory concentration MIC (μg/mL)
as shown in Table 2. The change in the biological activ-
ity (growth of the inhibition zone) cationic hydrazinium
compounds depends on the nature of the hydrophobic tail
connected to the quaternary nitrogen atom as well as the
type of base (morpholine or piperidine) which forms the
amide group [54]. The comparison of the sizes of inhibited
growth zones calculated for the surfactants studied with
those assessed for gentamycin used as control indicates
that the newly developed cationic surfactants are highly
active. Generally, compounds with long hydrocarbon
Biodegradability
Biodegradation is the potential of living microorganisms for
the biological degradation of organic materials. As surface-
active agents are subject to biodegradation and to test their
impact on the environment, the river die-away was used
to investigate the biodegradability of the new quaternary
hydrazinium–functionalized surfactants using the surface-
tension technique as an analytical tool [39]. Surfactants can
be classifed as readily biodegradable if they can achieve
60% biodegradation under the Organization for Economic
Co-operation and Development OECD guidelines [51]. The
biodegradability results are described in Fig. 6. Under the
experiment’s precision, all developed cationic surfactants
tended to degrade quickly, and the level of biodegradation
of various cationic surfactant solutions slowly increased
by time, reaching maximum values in the river water after
14 days. The progressive increase in biodegradation is attrib-
uted to the reduction of the surface activity of the dissolved
surfactants in river water. When biodegradation increased
with hydrophobic chain lengths (fatty chains), the group
showed increased linearity, and these data were consist-
ent with the earlier study [52]. Furthermore, quaternary
hydrazinium surfactants containing hydrazinium connec-
tion were investigated as amphiphiles containing a bond that
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Journal of the Iranian Chemical Society
Fig. 7 Bar graph for zone of
inhibition vs. the synthesized
cationic surfactants. For struc-
tures, see scheme 1
30
25
20
15
10
5
B.subꢀlis
E.coli
S.aureus
P. aeruginosa
0
Synthesized Caꢀonic Surfactants
Table 2 The minimal inhibitory concentration (μ g/ml) values for cat-
cytoplasmic membrane to the surfactants and on the con-
tact between the positive head group of surfactants and the
negatively charged membrane in which the fatty chain tail
enters and interrupts the specifc permeability of the cell
wall resulting in cell damage [58, 59].
ionic hydrazinium surfactants (10a–12b)
Test organ-
ism
Gram-positive bacteria Gram-negative bacteria
B
S
E
P. aerugi-
nosa NCIB-
9016
aureus
coli
Compound
subtilis
NCIB-
3610
NCTC-7447 NCTC-10416
Conclusion
10a
11a
12a
10b
11b
12b
512
256
64
256
128
32
256
128
64
128
128
32
>512
>512
256
>512
>512
128
512
New cationic surfactants decrease the surface tension,
interaction with dyes, are biodegradable, and inhibit the
growth of microorganisms even when applied at low con-
centrations. The surface properties, as well as the antibac-
terial activity of the surfactants, depend on their structure
and the length of the hydrophobic chain attached to the
quaternary nitrogen atom. Surfactants, both morpholine
and piperidine derivatives, with the highest carbon con-
tent in the alkyl chain (12a and b) were found to have
the highest antimicrobial activity as well as the lowest
CMC and the highest adsorption efectiveness among all
surfactants considered. It is concluded that the anionic
dyes acid red BG interacted with cationic surfactant 12b
in aqueous media forming pairs of ions in the premicellar
area despite the results obtained. The new complex was
formed in the post micellar area of the surfactant due to
the solubilization of the dye into a micelle. These catego-
ries of surfactants were found to be partially biodegradable
and can be used to formulate high-performance cleaning
products, stain removers, adhesives, softeners, etc.
>512
>512
512
>512
>512
chains and piperidine as a base showed lower MIC values
against tested strains, similar to the piperidine derivatives
study [55]. Moreover, it was shown that a compound with
16 carbon chains 12a and b has the strongest efect against
S.aureus and B. Subtilis. Compared to conventional qua-
ternary ammonium surfactants (QAS), these compounds
display a medium degree of activity against bacteria with
MIC values of 32–512 μg/mL[56]. Gram-negative P. aer-
uginosa was more resistant to the tested compounds, but
by decreasing the chain length within compounds10a and
b, an increase in their sensitivity was caused (MIC = 512).
This could be explained by the diferent structure of the
cell membrane of the two bacterial types. The external sur-
face of the gram-negative bacteria is almost mainly com-
posed of lipopolysaccharides and proteins which restrict
the entrance of biocides as well as amphiphilic compounds
[57]. The expected action of the synthetic cationic sur-
factant as an antibiotic focuses on the adhesion of the cell
Acknowledgements Our appreciation and deep gratitude to Prof. Dr.
M.S. Taher (Chemistry Department, Faculty of Science, Al-Azhar
University,Nasr City, Cairo , Egypt) for his involvement and valuable
discussions.
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Journal of the Iranian Chemical Society
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