Preparation of Some Eco-friendly Corrosion Inhibitors Having Antibacterial Activity from Sea Food Waste

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Preparation of Some Eco-friendly Corrosion Inhibitors Having Antibacterial Activity from Sea Food Waste
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  ORIGINAL ARTICLE Preparation of Some Eco-friendly Corrosion Inhibitors HavingAntibacterial Activity from Sea Food Waste Mohamed H. M. Hussein  • Mohamed F. El-Hady  • Hassan A. H. Shehata  • Mohammad A. Hegazy  • Hassan H. H. Hefni Received: 29 April 2012/Accepted: 17 July 2012/Published online: 24 August 2012   The Author(s) 2012. This article is published with open access at Springerlink.com Abstract  Chitosan is one of the important biopolymersand it is extracted from exoskeletons of crustaceansin sea food waste. It is a suitable eco-friendly carbonsteel corrosion inhibitor in acid media; the deacetylationdegree of prepared chitosan is more than 85.16 %, andthe molecular weight average is 109 kDa. Chitosan wasmodified to 2-  N  ,  N  -diethylbenzene ammonium chloride  N  -oxoethyl chitosan (compound I), and 12-ammoniumchloride  N  -oxododecan chitosan (compound II) as solublewater derivatives. The corrosion inhibition efficiency forcarbon steel of compound (I) in 1 M HCl at varyingtemperature is higher than for chitosan and compound (II).However, the antibacterial activity of chitosan for  Entero-coccusfaecalis , Escherichiacoli , Staphylococcusaureus ,and Candida albicans  is higher than for its derivatives, and theminimum inhibition concentration and minimum bacterialconcentration of chitosan and its derivatives were carried outwith the same strain. Keywords  Chitosan    Corrosion    Eco-friendly   Antibacterial    Sea food waste Introduction Acid solutions are commonly used in the chemical industryto remove mill scales from metallic surfaces. The additionof inhibitors effectively secures the metal against acidattack. And many studies using organic inhibitors havebeen reported [1–7]. The inhibitor adsorption mode is strictly affected by its structure. Most acid inhibitors areorganic compounds containing oxygen, nitrogen and sulfur.These compounds are adsorbed onto the metallic surfaceblocking the active corrosion sites. Although the mosteffective and efficient organic inhibitors are compoundsthat have  p  bonds, the biological toxicity of these products,especially organic phosphate, is documented especiallywith regard to their environmental harmful characteristics[8, 9]. From the standpoint of safety, the development of  non-toxic and effective inhibitors is considered mostimportant and desirable. Chitosan is derived from poly-saccharide chitin which is well known as a low cost,renewable marine polymer coming from the structuralcomponents of the shells of crustaceans, such as shrimps,lobsters, and crabs [10]; it is the most plentiful naturalpolymer next to cellulose. Chitosan is produced at anestimated amount of one billion tons per year [11]. Themolecular structure of chitosan is represented by a beta1–4 linked linear biopolymer consisting of 80 % poly( D -glucosamine) and 20 % poly(  N  -acetyl- D -glucosamine).Chitosan exhibits various biological activities and bio-medical applications including excellent biocompatibility,biodegradability, osteoconductivity, antimicrobial proper-ties, a flocculating agent, a drug delivery vehicle, animmobilization and encapsulation agent of toxic heavymetals, and also in cosmetics [12, 13]. It is a linear poly- base electrolyte having a highly positive (C) charge densitybecause it includes an amine group [14]. With such acationic property together with several hydroxyl groups itis consider a good corrosion inhibitor of steel.Chitosan inhibits the growth of a fairly diverse range of bacteria [15] and thus offers great benefit to a wide variety M. H. M. Hussein    M. A. Hegazy    H. H. H. Hefni ( & )Petrochemicals Department, Egyptian Petroleum ResearchInstitute (EPRI), Cairo, Egypte-mail: hassanhefni@yahoo.comM. F. El-Hady    H. A. H. ShehataChemistry Department, Faculty of Science, Al-Azhar University,Cairo, Egypt  1 3 J Surfact Deterg (2013) 16:233–242DOI 10.1007/s11743-012-1395-3  of applications, ranging from medical applications [16] toagriculture [17]. The exact mechanism of the antimicro-bial action of chitosan is still ambiguous, although sixmain mechanisms, none of which are mutually exclusive,have been proposed [18, 19] as follows: (1) Interactions between the positively charged moieties on the chitosanmolecules and those negatively charged ones on themicrobial cell outer membranes, lead to changes in thecell membrane structure and permeability. This inducesthe leakage of proteinaceous and other intracellular con-stituents and so challenges the biochemical and physio-logical competency of the bacteria leading to loss of replicative ability and eventual death. (2) Chitosan actsas a chelating agent that selectively binds trace metalsand subsequently inhibits the production of toxins andmicrobial growth. (3) Chitosan activates several defenseprocesses in the host tissue, acts as a water binding agentand inhibits various enzymes. (4) Low molecular weightchitosan penetrates the cytosol of the microorganismsand, through the binding of chitosan with DNA, results inthe interference with the synthesis of mRNA and proteins.(5) Chitosan on the surface of the cell can form animpermeable polymeric layer which alters the cell per-meability and prevents nutrients from entering the cell.(6) Finally, since chitosan can adsorb the electronegativesubstances in the cell and flocculate them, it disturbs thephysiological activities of the microorganism leading totheir death.The aim of this study is to investigate the inhibitionefficiency of chitosan and its derivatives on the carbon steelsurface in 1 M HCl solution, using weight loss measure-ments, and antibacterial activity measurement for differentstrain. Materials and Methods The shrimp shell came as sea food waste from Egyptianshops. Sodium hydroxide, hydrochloric acid, acetone,monochloro acetic acid,  N  ,  N   diethyl aniline and 12-amin-ododecanoic acid were from Sigma Aldrich.Extraction of ChitosanThe shrimp shells were deproteinized, demineralized andsubsequently decolorized as described in the literature[20–22]. The removal of acetyl groups from the prepared chitin was achieved by mixing with NaOH (50 %) withstirring for 2 h at 115   C. The resulting chitosan waswashed until neutrality with running tap water, rinsedwith distilled water, filtered, and then dried at 60   C for24 h.Preparation of Chitosan DerivativesThe two derivatives of chitosan were prepared as shown inScheme 1. Preparation of 2-N,N-Diethylbenzene Ammonium Chloride N-Oxoethyl Chitosan (Compound I) in Two Steps Quaternization of   N  ,  N   diethyl aniline by mono chloroacetic acid to produce  N  -(carboxymethyl)-  N  ,  N  -diethylbenzene ammonium chloride.A mixture of   N  ,  N   diethyl aniline (0.1 mol; 14.9 g),chloro acetic acid (0.1 mol; 9.4 g) and 100 ml acetonewere refluxed for 72 h at 60   C until a dark green solutionwas obtained. The product was then cooled, filtered anddried by vacuum distillation.The structure of this compound was confirmed by FT-IRand  1 H NMR. Preparation of 2-N,N-Diethyl Benzene AmmoniumChloride N-Oxoethyl Chitosan A chitosan sample (2 g) was dissolved in an aqueoussolution of 2 % V/V acetic acid by vigorously stirring toobtain a solution with a concentration of 2 %, filteredthrough polyester cloth to remove residues of insolubleparticles [23]; the desired amount of   N  -(carboxymethyl)-  N  ,  N  -diethylbenzene ammonium chloride (mol/mol aminegroup of chitosan) was added to the chitosan solution. Afteragitating for 2 h at 80   C the 2-  N  ,  N  -diethylbenzene ammo-nium chloride  N  -oxoethyl chitosan was precipitated byacetone, filtered, washed several times with acetone, anddried in a desiccator for 24 h. HamONH 2 HOOOHONHHOOOH+ R 2% Acetic acid \ 80 o C2h stirrer Acetone\ -   H 2 OCH 2 CCH 2 H 2 CCH 2 H 2 CCH 2 H 2 CCH 22 CCH 2 H 2 CONH 3+ Cl - 11-carboxyundecan-1-ammonium chlorideRCompound (II); R =Compound (I); R = NH 2 CCH 3 H 2 CCH 3 CH 2 COClN-(carboxymethyl)-N,N-diethylbenzene monium chloride Scheme 1  Preparation of chitosan derivatives234 J Surfact Deterg (2013) 16:233–242  1 3  Preparation of 12-Ammonium Chloride N-oxododecanChitosan (Compound II) The desired amount of 12-aminododecanoic acid (mol/molamine group of chitosan) was dissolved in 60 ml of 0.1 MHCl and added to the 2 % chitosan solution with stirringfor 2 h at 80   C, the 12-ammonium chloride  N  -oxododecanchitosan was precipitated by acetone, filtered, washedseveral times with acetone, and dried in a desiccator for24 h.Characterization of the Prepared CompoundsFT-IR measurement was carried out using a ShimadzuFTIR-4200 spectrometer with a wave number range of 400–4,200 cm - 1 and resolution 100 cm - 1 .The elemental analyses were carried out for all preparedcompound using a CHNS/O analyzer (Perkin-Elmer,USA), and lasted in Table 1.The molecular weight determinations were carried outby gel permeation chromatography (GPC) using aSupremamax 3000 column (Polymer Standard Service,Mainz, Germany) with 2 % CH 3 COOH/0.2 M buffer(CH 3 COONa) as an eluent (1 ml/min). The standardpullulans (  M  w  of 11,800, 47,300, 112,000, and 780,000)were used for calibration.Determination of degree of deacetylation of chitosan(DD) by infrared spectroscopy (FT-IR) and elementalanalysis.Weight Loss MeasurementsThe carbon steel specimens have a composition of (wt%):0.21 C, 0.035 Si, 0.25 Mn, 0.082 P, with the remain-der being Fe. The carbon steel sheets of 2.5 cm  9 2.0 cm  9  0.6 cm were abraded with emery papers (grades320, 500, 800 and 1200) and then washed with distilledwater and acetone. After weighing accurately, the speci-mens were immersed in 250-mL beakers containing200 mL of 1 M hydrochloric acid in the absence and in thepresence of 10 - 8 , 10 - 7 , 10 - 6 , 10 - 5 and 10 - 4 molar units(monomer) of the inhibitors at 25   C. After immersiontime intervals of 18 h, the specimens were taken out,washed, dried, and weighed accurately. The tests wererepeated at 35, 45 and 55   C. The corrosion rate ( C  R ) andthe inhibition efficiency ( g  %) were calculated using Eqs.(1–2) [24]: C  R  ¼ W St  ð 1 Þ g % ¼ C  R  C  R ð inh Þ C  R  100  ð 2 Þ where  W   is the average weight loss of three parallel carbonsteel sheets (one specimen in each beaker),  S   is the totalarea of the steel specimen, and  t   is immersion time,  C  R  and C  R(inh)  are the corrosion rates obtained in the absence andthe presence of inhibitors, respectively.The degree of surface coverage  h  for different concen-trations of the inhibitor in acidic media was evaluated fromthe weight loss using the equation: h ¼ 1  C  R ð inh Þ C  R ð 3 Þ Antibacterial Activity of Chitosan and Its Derivatives  Bacterial Strain and Inoculum Preparation Overnight cultures of the following micro-organisms wereused throughout the study:  Enterococcus faecalis  as Gram-negative bacteria,  Escherichia coli  as Gram-positive bac-teria  , Staphylococcus aureus  as antibiotic resistant bacteria and Candida albicans  as yeast. Long term maintenance of the microbial strains was at  - 20   C using glycerol andshort term maintenance was on nutrient agar plates andSabarouds dextrose agar at 4   C. Preparation of Solutions Stock solutions of final concentrations of 2 % chitosansolution, 2 % compound (I) and 2 % of compound (II)were prepared and sterilized. Formation of Clear Zone Preliminary screening of antimicrobial activity of com-pounds under investigation was determined by the agardiffusion method, using the cub plate method (II). The petridishes were incubated at 35   C for 24 h, except for C. albicans  cases which were incubated at 27   C for 48 h.The inhibition zones were measured and recorded as amean diameter of 3 mm. Table 1  The elemental analysis of chitosan and its derivativesCompounds C % H % N % Cl %ChitosanCalculated 44.02 7.10 7.96 –Found 43.92 7.25 8.11 –Compound (I)Calculated 35.42 3.80 3.55 5.15Found 35.62 3.82 5.62 5.32Compound (II)Calculated 32.10 3.98 5.01 12.25Found 32.52 4.40 5.33 12.78J Surfact Deterg (2013) 16:233–242 235  1 3   Minimum Inhibitory Concentration (MIC) Determination The lowest concentration of antimicrobial activity thatinhibits the growth of microorganism being tested asdetected by lack of visual turbidity, is known as the min-imum inhibitory concentration (MIC). The MIC values of chitosan and its derivatives were determined in duplicateusing the twofold broth micro dilution method according tothe Clinical and Laboratory Standards Institute (CLSI)[25].  Minimum Bacterial Concentration (MBC) Determination After MIC testing, the microtiter plates setup for the MICdetermination was used to determine the MBC. For eachsample, 100  l l was transferred and added to 100  l l of saline or 1 % CaCl 2  solution to neutralize chitosan and itsderivatives by dilution and chelation respectively. Theentire volume was spread over nutrient agar plate. TheMBC point is defined as the lowest concentration showingno growth after incubation. Results and Discussion Chemical Structures Conformation of PreparedCompounds FTIR Data FTIR analysis is proposed in many references as a possibleway to investigate the interaction between substances[26–28]. In this study, dried chitosan was analyzed by FTIR toobserve the possible interaction of the functional groups of both molecules. Figure 1 shows the main bands of chitosanand its derivatives. Chitosan exhibits main characteristicbands of carbonyl (RC=O) and amine group (–NH 2 ) at1,654 and 1,540 cm - 1 , respectively [29, 30]. The broad band due to the stretching vibration of –NH 2  and –OHgroup can be observed at 3,400–3,500 cm - 1 [31, 32]. The bands at 1,000–1,200 cm - 1 are attributed to the glucosidicring of chitosan [33]. In the FTIR spectra of compound(I) the same band as found in chitosan, except that the bandat 3,450 cm - 1 is sharp and the band at 1,650 cm - 1 moreintensive. The (NH 2 ) group band was shifted to3,230 cm - 1 due to the interaction of the amino group. Thequaternary ammonium group was observed at 2,615 cm - 1 .In the case of compound (II) the high intensity band isfound at 2,920 and 2,880 cm - 1 related to (CH 2 ) of thehydrocarbon chain; the carbonyl group binding amide isobserved at 1,650 cm - 1 , and the other bands are the samein chitosan and compound (I).  Determination of Degree of Deacetylation (DD) The degree of deacetylation (DD) of prepared chitosan canbe calculated by: FTIR Spectroscopy  By applying [34, 35] the following Eq. (4) the DD equal to 88.15 %.DD ¼ 97 : 67   26 : 486  A 1 ; 655  A 3 ; 450     ð 4 Þ where  A 1,655  and  A 3,450  is the tow absorbance bands at1,655 and 3,450 cm - 1 which related to amide and aminegroups respectively. Elemental Analysis  The DD equal to 82.17 % accordingto Eq. (5)DD ¼  6 : 857  C = N1 : 743    100  ð 5 Þ where C/N is the ratio carbon/nitrogen [36] as determinedby elemental analysis.The average degree of deacetylation (DD) [36] of pre-pared chitosan can be calculated from Eq. (6).DD % ¼ DD IR þ DD CHN 2 ¼ 85 : 16 %  ð 6 Þ GPC Data  From the GPC data, we found that the mole-cular weights of chitosan, compound (I) and compound(II) are 109.050, 118.81, and 137.26 kDa respectively.The increase in molecular weight of these compounds Fig. 1  FT-IR spectra of chitosan and its derivatives236 J Surfact Deterg (2013) 16:233–242  1 3  over that of chitosan indicated the formation of newproducts.Corrosion Results Effect of Temperature From corrosion rate values which listed in Table 2, wefound that the corrosion rates decrease with increasingconcentration of inhibitors, and increased by increasing thetemperature, as a result of decreasing the apparent activa-tion energy ( E  a ) of the charge transfer reaction.The increase in temperature will enhance the rate of H ? diffusion to the metal surface as well as ionic mobility. Atlower temperatures, the adsorbed hydrogen atoms block thecathodic area, while the increase in the solution tempera-ture causes desorption of hydrogen. Such hydrogendesorption leads to an increase in the cathodic area andconsequently increases the corrosion rate. This behavior isrepeated for all compounds. These results showed that theprepared compounds act as efficient inhibitors at lowertemperatures rather than at high temperatures.This behavior was the same for all the prepared inhibitorcompounds.  Inhibition Efficiency of Inhibitors However, the data in Table 2 describe that the inhibitionefficiency increases with increasing concentration of prepared inhibitors, and decreases with increasing tem-perature, while in the case of compounds (I) and (II), thevalues of inhibition efficiencies are higher at 308 K than at298 K, a trend that could be due to the higher solubility of these compounds at 308 K.  Adsorption Isotherms The prepared compounds inhibit the corrosion process byadsorption on the metal surface. As it is known, theadsorption of inhibitor (  I  ads ) is always a displacementreaction involving removal of ‘‘  x ’’ number of the absorbedwater molecules from the metal surface, according to theEq. (7):I aq þ  x H 2 O ads  !  I  ads þ  x H 2 O aq  ð 7 Þ The adsorption depends on the structure of the inhibitor,the type of the metal and the nature of its surface, pH of thecorrosion medium, the temperature, and theelectrochemical potential of the metal–solution interface.The mathematical relationship for the adsorption iso-therms suggested that the experimental data of the presentwork fit the Langmuir model [37, 38] in the Eq. (8). C  h  ¼  1 K  ads þ C   ð 8 Þ where ‘‘ K  ads ’’ is the equilibrium constant of the adsorptionreaction, and  C   is the concentration of inhibitors in thesolution bulk. Table 2  Weight loss data of carbon steel corrosion in 1 M HCl in absence and presence of different concentrations of the prepared inhibitors atdifferent temperaturesCompounds Conc.of inhi.(M)298 K 308 K 318 K 328 K  C  R (g cm - 2 h - 1 ) h g  %  C  R (g cm - 2 h - 1 ) h g  %  C  R (g cm - 2 h - 1 ) h g  %  C  R (g cm - 2 h - 1 ) h g  %Blank 0.00 0.35 0.51 0.93 1.52Chitosan 10 - 8 0.21 0.40 40.15 0.33 0.35 34.91 0.68 0.27 26.61 1.27 0.16 16.4110 - 7 0.17 0.50 50.32 0.28 0.44 44.44 0.60 0.27 26.61 1.13 0.25 25.3910 - 6 0.13 0.64 63.57 0.21 0.58 58.22 0.46 0.35 34.91 1.04 0.31 31.4910 - 5 0.04 0.88 88.50 0.10 0.80 80.12 0.27 0.73 73.66 0.53 0.65 65.0810 - 4 0.05 0.86 85.52 0.10 0.80 79.91 0.30 0.71 70.91 0.60 0.60 60.41Compound(I)10 - 8 0.20 0.43 43.45 0.32 0.37 36.66 0.68 0.26 26.16 1.23 0.19 19.1510 - 7 0.16 0.55 55.00 0.28 0.45 45.16 0.56 0.40 39.95 1.06 0.30 30.2810 - 6 0.10 0.71 71.31 0.15 0.70 70.38 0.39 0.58 57.96 0.80 0.48 47.5110 - 5 0.05 0.86 86.39 0.06 0.87 87.91 0.16 0.83 83.10 0.50 0.67 67.0410 - 4 0.06 0.85 84.83 0.07 0.88 88.50 0.19 0.79 79.39 0.54 0.64 64.19Compound(II)10 - 8 0.24 0.31 31.44 0.36 0.29 28.97 0.74 0.20 20.24 1.30 0.14 14.2410 - 7 0.22 0.38 38.31 0.33 0.35 35.12 0.69 0.26 25.68 1.18 0.22 21.8910 - 6 0.15 0.57 56.97 0.20 0.61 60.75 0.50 0.46 45.92 1.05 0.31 30.8110 - 5 0.08 0.77 77.18 0.11 0.79 79.03 0.29 0.69 69.14 0.57 0.62 62.1910 - 4 0.09 0.75 75.48 0.12 0.77 76.78 0.29 0.69 68.54 0.61 0.59 59.45J Surfact Deterg (2013) 16:233–242 237  1 3
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