Carbon dots have great potential to be utilised as an optical sensing probe due to its unique photoluminescence and less toxic properties. This work reports a simple and novel synthesis method of carbon dots via direct acid hydrolysis of bovine serum albumin protein in a one-pot approach. Optimisation of the important synthetic parameters has been performed which consists of temperature effect, acid to protein ratio and kinetics of reaction. Higher temperature has promoted better yield with shorter reaction time. The carbon dots obtained shows a strong emission at the wavelength of 400 nm with an optimum excitation of 305 nm. The potential of the carbon dots as optical sensing probe has been investigated on with different cations that are of environmental and health concern. The fluorescence of the carbon dots was significantly quenched particularly by lead (II) ions in a selective manner. Further analytical study has been performed to leverage the performance of the carbon dots for lead (II) ions sensing using the standard Stern-Volmer relationship. The sensing probe has a dynamic linear range up to 6.0 mM with a Stern-Volmer constant of 605.99 M(-1) and a limit of detection (LOD) of 5.05 μM. The probe performance was highly repeatable with a standard deviation below 3.0%. The probe suggested in this study demonstrates the potential of a more economical and greener approach that uses protein based carbon dots for sensing of heavy metal ions.
The efficiency of Schiff base derived from 4-aminoantipyrine, namely 2-(1,5-dimethyl-4-(2-methylbenzylidene)amino)-2-phenyl-1H-pyrazol-3(2H)-ylidene) hydrazinecarbothioamide as a corrosion inhibitor on mild steel in 1.0 M H2SO4 was investigated using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PD) and electrochemical frequently modulation (EFM) in addition to the adsorption isotherm, corrosion kinetic parameters and scanning electron microscopy (SEM). The results showed that this inhibitor behaved as a good corrosion inhibitor, even at low concentration, with a mean efficiency of 93% and, also, a reduction of the inhibition efficiency as the solution temperature increases. A polarization technique and EIS were tested for different concentrations and different temperatures to reveal that this compound is adsorbed on the mild steel, therefore blocking the active sites, and the adsorption follows the Langmuir adsorption isotherm model. The excellent inhibition effectiveness of 2-(1,5-dimethyl-4-(2-methylbenzylidene)amino)-2-phenyl-1H-pyrazol-3(2H)-ylidene)hydrazinecarbothioamide was also verified by scanning electron microscope (SEM).
Recent years, great interest has been devoted to the conversion of biomass-derived carbohydrate into sugars, such as glucose, mannose and fructose. These are important versatile intermediate products that are easily processed into high value-added biofuels. In this work, microwave-assisted dilute sulfuric acid hydrolysis of deproteinated palm kernel cake (DPKC) was systematically studied using Response Surface Methodology. The highest mannose yield (92.11%) was achieved at the optimized condition of 148°C, 0.75N H2SO4, 10min 31s and substrate to solvent (SS) ratio (w/v) of 1:49.69. Besides that, total fermentable sugars yield (77.11%), was obtained at 170°C, 0.181N H2SO4, 6min 6s and SS ratio (w/v) of 1:40. Ridge analysis was employed to further verify the optimum conditions. Thus, this work provides fundamental data of the practical use of DPKC as low cost, high yield and environmental-friendly material for the production of mannose and other sugars.
The large surface area of highly porous titanium structures produced by additive manufacturing can be modified using biofunctionalizing surface treatments to improve the bone regeneration performance of these otherwise bioinert biomaterials. In this longitudinal study, we applied and compared three types of biofunctionalizing surface treatments, namely acid-alkali (AcAl), alkali-acid-heat treatment (AlAcH), and anodizing-heat treatment (AnH). The effects of treatments on apatite forming ability, cell attachment, cell proliferation, osteogenic gene expression, bone regeneration, biomechanical stability, and bone-biomaterial contact were evaluated using apatite forming ability test, cell culture assays, and animal experiments. It was found that AcAl and AnH work through completely different routes. While AcAl improved the apatite forming ability of as-manufactured (AsM) specimens, it did not have any positive effect on cell attachment, cell proliferation, and osteogenic gene expression. In contrast, AnH did not improve the apatite forming ability of AsM specimens but showed significantly better cell attachment, cell proliferation, and expression of osteogenic markers. The performance of AlAcH in terms of apatite forming ability and cell response was in between both extremes of AnH and AsM. AcAl resulted in significantly larger volumes of newly formed bone within the pores of the scaffold as compared to AnH. Interestingly, larger volumes of regenerated bone did not translate into improved biomechanical stability as AnH exhibited significantly better biomechanical stability as compared to AcAl suggesting that the beneficial effects of cell-nanotopography modulations somehow surpassed the benefits of improved apatite forming ability. In conclusion, the applied surface treatments have considerable effects on apatite forming ability, cell attachment, cell proliferation, and bone ingrowth of the studied biomaterials. The relationship between these properties and the bone-implant biomechanics is, however, not trivial.
Xylitol production by bioconversion of xylose can be economically interesting if the raw material can be recovered from a cheap lignocellulosic biomass (LCB). Meranti wood sawdust (MWS) is a renewable and low-cost LCB that can be used as a promising and economic source of xylose, a starting raw material for the manufacture of several specialty chemicals, especially xylitol. This study aimed to optimize the hydrolysis process of MWS and to determine the influence of temperature, H2SO4 concentration, and residence time on xylose release and on by-product formation (glucose, arabinose, acetic acid, furfural, hydroxymethylfurfural (HMF), and lignin degradation products (LDPs)). Batch hydrolysis was conducted under various operating conditions, and response surface methodology was adopted to achieve the highest xylose yield. Xylose production was highly affected by temperature, acid concentration, and residence time. The optimum temperature, acid concentration, and time were determined to be 124 °C, 3.26 %, and 80 min, respectively. Under these optimum conditions, xylose yield and selectivity were attained at 90.6 % and 4.05 g/g, respectively.
This study was conducted to prepare a mixed matrix membrane (MMM) and to test the performance of the prepared MMM for CO2 and CH4 gas separation. MMM containing polyethersulfone (PES) and multi-walled carbon nanotubes (MWCNTs) was prepared by a dry-wet phase inversion technique using a pneumatically-controlled membrane casting machine. The surface modification was performed on MWCNTs in order to enhance the selectivity of CO2/CH4. The surface modification of MWCNTs using chemical and physical approaches has been adopted. Mixed acid (HNO3/H2SO4) and β-CD were used for chemical and physical approaches, respectively. Effects of surface modification on MWCNTs/PES MMM were investigated. MWCNTs/PES MMMs were characterised using scanning electron microscopy (SEM), the Fourier Transform Infrared (FT-IR) spectroscopy and pure gas permeation test. The permeability and selectivity, which are the parameters describing membrane performance were calculated via the data obtained from pure gas permeation test with the feed pressure difference from 3 to 7 bars. In this study, surface modified MWCNTs/PES MMM using mixed acid and β-CD has successfully enhanced the CO2/CH4 selectivity by 40.6% compared to that of neat PES.
Biodegradable polymeric films, obtained from chitosan/natural rubber latex (CS/NRL) blends with different compositions, have been prepared by wetting process. The blends were characterized by dynamic mechanical thermal analysis (DMTA) and found that the CS/NRL blends are thermodynamically incompatible. This is evident from the presence of two glass transitions, corresponding to CS and NRL phases in the blend. The mechanical properties of the CS/NRL blends were improved with increasing the amount of chitosan and after surface treatment with sulphuric acid due to the sulfonate ionic interaction. The dielectric properties was determined using Precision LCR meter in the frequency range 75 kHz up to 30 MHz. After CS/NRL surface treatment with sulphuric acid at high content of chitosan showed the highest dielectric constant. The surface properties of the CS/NRL blend films before and after surface treatment were confirmed by atomic force microscopy (AFM), respectively.
Different type of fibers which is EFB and KC were liquefied in phenol with the presence of sulphuric acid as a catalyst. The liquefied residue was characterized by using Fourier transform infrared (FTIR) to determine the functional groups presents in both residues, X-ray diffraction (XRD) to determine the degree of crystallinity in the residue, thermogravimetric analysis (TGA) to analyze the thermal properties of the residue and scanning electron microscope (SEM) to investigate the structure and morphology of the residue. Phenol-to-EFB/KC ratio shows great effect on the amount of residue in the liquefaction process. Peak appearance can be observed in the FTIR analysis at 810 and 750 cm-1 which is attributed to the para and meta benzene, respectively or to be specific its associated to the p-alkyl phenol and m-alkyl phenol. In the XRD analysis, CrI of lignocellulosic materials increased after liquefaction process. Liquefaction process caused chemical penetration across the grain of the fiber, thus the fiber bundles started to separate into individual fibers shown in the SEM micrograph and the weights lost curve for both liquefied EFB and KC experienced three region decompositions.
Pretreatments with different types of alkali and acid were compared to determine their effects on gelatin extraction from African catfish (Clarias gariepinus) skin. The study was divided into three parts. In the first part, the skins were only treated with alkaline (Ca(OH)2 or NaOH) solution or pretreated with acetic acid solution. For second part, combination of alkali and acid pretreatment was carried out. For the third part, the skins were first treated with NaOH solution, followed by the treatment with acetic acid, citric acid or sulfuric acid solution. Functional properties including the yield of protein recovery, gel strength, viscosity, pH and viscoelastic properties were determined on gelatins obtained with different pretreatment conditions. Pretreatment with alkali removed noncollagenous proteins effectively, whilst acid pretreatment induced some loss of collagenous proteins. Combination of alkali and acid pretreatment not only removed the noncollagenous proteins and caused a significant amount of swelling, but also provided the proper pH condition for extraction, during which some cross-linkages could be further destroyed but with less breakage of intramolecular peptide chains. Pretreatment of catfish skins with 0.2 N NaOH followed by 0.05 M acetic acid improved yield of protein recovery, gel strength, viscosity, melting temperature and gelling temperature of gelatin extract.
The kitchen waste fraction in municipal solid waste contains high organic matter particularly carbohydrate that can contribute to fermentable sugar production for subsequent conversion to bioethanol. This study was carried out to evaluate the influence of single and combination pretreatments of kitchen waste by liquid hot water, mild acid pretreatment of hydrochloric acid (HCl) and sulphuric acid (H2SO4) and enzymatic hydrolysis (glucoamylase). The maximum total fermentable sugar produced after combination pretreatment by 1.5% HCl and glucoamylase consisted of 93.25 g/L glucose, 0.542 g/L sucrose, 0.348 g/L maltose, and 0.321 g/L fructose. The glucose released by the combination pretreatment method was 0.79 g glucose/g KW equivalent to 79% of glucose conversion. The effects of the pre-treatment on kitchen waste indicated that the highest solubilization was 40% by the combination method of 1.5% HCl and glucoamylase. The best combination pre-treatment gave concentrations of lactic acid, acetic acid, and propionic acid of 11.74 g/L, 6.77 g/L, and 1.02 g/L, respectively. The decrease of aliphatic absorbance bands of polysaccharides at 2851 and 2923 cm(-1) and the increase on structures of carbonyl absorbance bands at 1600 cm(-1) reflects the progress of the kitchen waste hydrolysis to fermentable sugars. Overall, 1.5% HCl and glucoamylase treatment was the most profitable process as the minimum selling price of glucose was USD 0.101/g kitchen waste. Therefore, the combination pretreatment method was proposed to enhance the production of fermentable sugar, particularly glucose from kitchen waste as the feedstock for bioethanol production.
Bleached kenaf core pulps (BKC) were hydrolyzed in H2SO4 (0.5M) at different time (0min to 90min) at room temperature. After the hydrolysis process, the viscosity average molecular weight (Mŋ) for BKC sample has reduced from 14.5×10(4) to 2.55×10(4). The hydrolyzed BKC was then dissolved in NaOH:urea:water and in LiOH:urea:water mixed solvent at the ratio of 7:12:81 and 4.6:15:80.4, respectively. The increased in hydrolysis time has decreased Mŋ of cellulose leading to easy dissolution process. Higher porosity and transparency with lower crystallinity index (CrI) of regenerated membrane produced can be achieved as the Mŋ reduced. The properties of membrane were observed through FESEM, UV-vis spectrophotometer and XRD. This study has proven that acid hydrolysis has reduced the Mŋ of cellulose, thus, enhanced the properties of regenerated membrane produced with assisted by alkaline/urea system.
The aim of this study is to investigate the technical feasibility of converting macroalgae cellulosic residue (MCR) into bioethanol. An attempt was made to present a novel, environmental friendly and economical pretreatment process that enhances enzymatic conversion of MCR to sugars using Dowex (TM) Dr-G8 as catalyst. The optimum yield of glucose reached 99.8% under the optimal condition for solid acid pretreatment (10%, w/v biomass loading, 4%, w/v catalyst loading, 30min, 120°C) followed by enzymatic hydrolysis (45FPU/g of cellulase, 52CBU/g of β-glucosidase, 50°C, pH 4.8, 30h). The yield of sugar obtained was found more superior than conventional pretreatment process using H2SO4 and NaOH. Biomass loading for the subsequent simultaneous saccharification and fermentation (SSF) of the pretreated MCR was then optimized, giving an optimum bioethanol yield of 81.5%. The catalyst was separated and reused for six times, with only a slight drop in glucose yield.
A novel powdering material that utilizes acid-modified Imperata cylindrica (IC) powder for the development of fingermarks was studied. Experiments were carried out to determine the suitability, adherence quality and sensitivity of the acid-modified IC powder. Fingermarks of different constituents (eccrine, sebaceous and natural fingermarks) on different types of surfaces were used. Acid-modified IC powder was also used to develop fingermarks of different ages as well as aged fingermarks recovered from the water. From the visual inspection, acid-modified IC powder was able to interact with different fingermark constituents and produced distinct ridge details on the examined surfaces. It was also able to develop aged fingermarks and fingermarks that were submerged in water. A statistical comparison was made against the Sirchie® Hi-Fi black powder in terms of the powders' sensitivity and quality of the developed natural fingermarks. The image quality was analyzed using MITRE's Image Quality of Fingerprint (IQF) software. From the experiments, acid-modified IC powder has the potential as a fingermark development powder, although natural fingermarks developed by Sirchie® black powder showed better quality and sensitivity based on the results of the statistical comparison.
The chemical production of methyl oleate using chemically synthesized fatty acid alcohols and other toxic chemicals may lead to significant environmental hazards to mankind. Being a highly valuable fatty acid replacement raw material in oleochemical industry, the mass production of methyl oleate via environmentally favorable processes is of concern. In this context, an alternative technique utilizing Candida rugosa lipase (CRL) physically adsorbed on multi-walled carbon nanotubes (MWCNTs) has been suggested. In this study, the acid-functionalized MWCNTs prepared using a mixture of HNO3 and H2SO4 (1:3 v/v) was used as support for immobilizing CRL onto MWCNTs (CRL-MWCNTs) as biocatalysts. Enzymatic esterification was performed and the efficiency of CRL-MWCNTs was evaluated against the free CRL under varying conditions, viz. temperature, molar ratio of acid/alcohol, solvent log P, and enzyme loading. The CRL-MWCNTs resulted in 30-110 % improvement in the production of methyl oleate over the free CRL. The CRL-MWCNTs attained its highest yield (84.17 %) at 50 °C, molar ratio of acid/alcohol of 1:3, 3 mg/mL of enzyme loading, and iso-octane (log P 4.5) as solvent. Consequently, physical adsorption of CRL onto acid-functionalized MWCNTs has improved the activity and stability of CRL and hence provides an environmentally friendly means for the production of methyl oleate.
In this study, cellulose nanocrystals (CNC) were produced using acid hydrolysis method. Kenaf core was pretreated with 4
wt. % sodium hydroxide (NaOH), followed by bleaching using 1.7 wt. % sodium chlorite (NaClO2
) in acetate buffer. The
bleached fiber was acid hydrolyzed for 45 and 55 min using 64 wt. % sulfuric acid (H2
SO4
). The size distribution of the
CNC segregated via differential centrifugation with different speed was also investigated. The CNC suspension obtained
was centrifuged at 3000, 6000, 9000 and 12000 rpm. The resultant CNC suspension collected was characterized using
Fourier transform infrared (FTIR) analysis, X-ray diffraction (XRD) and transmission electron microscopy (TEM). FTIR
results showed the progressive removal of non-cellulosic constituents for each subsequent treatment. It also showed that
the CNC produced after hydrolysing for 55 min has the highest degree of crystallinity (81.15%). CNC produced from acid
hydrolysis process of 45 min have lengths between 50 and 270 nm while CNC produced from acid hydrolysis process of
55 min have length around 40 to 370 nm.
In this work, fractionation of empty fruit bunch (EFB) by bisulfite pretreatment was studied for the production of bioethanol and high value products to achieve biorefinery of EFB. EFB was fractionated to solid and liquor components by bisulfite process. The solid components were used for bioethanol production by quasi-simultaneous saccharification and fermentation. The liquor components were then converted to furfural by hydrolysis with sulfuric acid. Preliminary results showed that the concentration of furfural was highest at 18.8g/L with 0.75% sulfuric acid and reaction time of 25min. The conversion of xylose to furfural was 82.5%. Furthermore, we attempted to fractionate the liquor into hemicellulose sugars and lignin by different methods for producing potential chemicals, such as xylose, xylooligosaccharide, and lignosulfonate. Our research showed that the combination of bisulfite pretreatment and resin separation could effectively fractionate EFB components to produce bioethanol and other high value chemicals.
Hermetia illucens larvae by nature are a decomposer which fed on organic wastes. This study explores the potential of producing biodiesel using lipids from H. illucens larvae. Three types of organic wastes (sewage sludge, fruit waste and palm decanter cake from oil palm mill) were selected based on considerable generation and disposal concern in the area of study as well as lack of investigations as feed for Hermetia illucens larvae in current literatures. Growth rate of the larvae was determined with studying the changes in the biomass per day. H. illucens larvae fed with fruit waste and palm decanter cake have shown growth rates of 0.52±0.02 and 0.23±0.09 g d(-1), respectively. No positive sign of growth were observed in the larvae fed with treated sewage sludge (-0.04±0.01 g d(-1)). Biodiesel as fatty acid methyl ester (FAME) was synthesized by transesterification of the larvae lipid using sulphuric acid as catalyst in methanol. FAME produced was ascertained using ATR-FTIR spectroscopy and GC-MS. The main compositions of fatty acid were found to be C12:0, C16:0 and C18:1n9c. Fatty acid composition of C12:0 fed with fruit waste, sewage sludge and palm decanter was found to be most abundant in the larvae lipid. The amount of C12:0 obtained was 76.13%, 58.31% and 48.06%, respectively. In addition, fatty acid of C16:0 was attained at 16.48% and 25.48% fed with sewage sludge and palm decanter, respectively. Based on the findings, FAME derived from larvae lipids is feasible to be used for biodiesel production.
Recently, a great attention has been paid to advanced microwave technology that can be used to markedly enhance the biodiesel production process. Ceiba pentandra Seed Oil containing high free fatty acids (FFA) was utilized as a non-edible feedstock for biodiesel production. Microwave-assisted esterification pretreatment was conducted to reduce the FFA content for promoting a high-quality product in the next step. At optimum condition, the conversion was achieved 94.43% using 2wt% of sulfuric acid as catalyst where as 20.83% conversion was attained without catalyst. The kinetics of this esterification reaction was also studied to determine the influence of factors on the rate of reaction and reaction mechanisms. The results indicated that microwave-assisted esterification was of endothermic second-order reaction with the activation energy of 53.717kJ/mol.
Halloysite (HNT) is treated with sulfuric acid and the physico-chemical properties of its morphology, surface activity, physical and chemical properties have been investigated when HNT is exposed to sulfuric acid with treatment periods of 1 h (H1), 3 h (H3), 8 h (H8), and 21 h (H21). The significance of this and similar work lies in the importance of using HNT as a functional material in nanocomposites. The chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR). The spectrum demonstrates that the hydroxyl groups were active for grafting modification using sulfuric acid, promoting a promising potential use for halloysite in ceramic applications as filler for novel clay-polymer nanocomposites. From the X-ray diffraction (XRD) spectrum, it can be seen that the sulfuric acid breaks down the HNT crystal structure and alters it into amorphous silica. In addition, the FESEM images reveal that the sulfuric acid treatment dissolves the AlO₆ octahedral layers and induces the disintegration of SiO₄ tetrahedral layers, resulting in porous nanorods. The Bruncher-Emmett-Teller (BET) surface area and total pore volume of HNTs showed an increase. The reaction of the acid with both the outer and inner surfaces of the nanotubes causes the AlO₆ octahedral layers to dissolve, which leads to the breakdown and collapse of the tetrahedral layers of SiO₄. The multi-fold results presented in this paper serve as a guide for further HNT functional treatment for producing new and advanced nanocomposites.
Waste water treatment reservoirs are contaminated with many hazardous chemicals and acids. Reservoirs typically comprise concrete and reinforcement steel bars, and the main elements responsible for their deterioration are hazardous chemicals, acids, and ozone. Currently, a variety of techniques are being used to protect reservoirs from exposure to these elements. The most widely used techniques are stainless steel plating and polymeric coating. In this study, a technique known as arc thermal spraying was used. It is a more convenient and economical method for protecting both concrete and reinforcement steel bar from deterioration in waste water treatment reservoirs. In this study, 316L stainless steel coating was applied to a concrete surface, and different electrochemical experiments were performed to evaluate the performance of coatings in different acidic pH solutions. The coating generated from the arc thermal spraying process significantly protected the concrete surface from corrosion in acidic pH solutions, owing to the formation of a double layer capacitance-a mixture of Cr3+ enriched with Cr₂O₃ and Cr-hydroxide in inner and Fe3+ oxide on the outer layer of the coating. The formation of this passive film is defective owing to the non-homogeneous 316L stainless steel coating surface. In the pH 5 solution, the growth of a passive film is adequate due to the presence of un-dissociated water molecules in the aqueous sulfuric acid solution. The coated surface is sealed with alkyl epoxide, which acts as a barrier against the penetration of acidic solutions. This coating exhibits higher impedance values among the three studied acidic pH solutions.