Several parts of the world have been facing the problem of nitrite and nitrate contamination in ground and surface water. The acute toxicity of nitrite has been shown to be 10-fold higher than that of nitrate. In the present study, aminated silica carbon nanotube (ASCNT) was synthesised and tested for nitrite removal. The synergistic effects rendered by both amine and silica in ASCNT have significantly improved the nitrite removal efficiency. The IEP increased from 2.91 for pristine carbon nanotube (CNT) to 8.15 for ASCNT, and the surface area also increased from 178.86 to 548.21 m2 g-1. These properties have promoted ASCNT a novel adsorbent to remove nitrite. At optimum conditions of 700 ppm of nitrite concentration at pH 7 and 5 h of contact with 15 mg of adsorbent, the ASCNT achieved the maximal loading capacity of 396 mg/g (85% nitrite removal). The removal data of nitrite onto ASCNT fitted the Langmuir isotherm model better than the Freundlich isotherm model with the highest regression value of 0.98415, and also, the nonlinear analysis of kinetics data showed that the removal of nitrite followed pseudo-second-order kinetic. The positive values of both ΔS° and ΔH° suggested an endothermic reaction and an increase in randomness at the solid-liquid interface. The negative ΔG° values indicated a spontaneous adsorption process. The ASCNT was characterised using FESEM-EDX and FTIR, and the results obtained confirmed the removal of nitrite. Based on the findings, ASCNT can be considered as a novel and promising candidate for the removal of nitrite ions from wastewater.
In this study, hydrothermal carbonization (HTC) of a biomass was used as a means to improve the physicochemical properties of rubber seed shell (RSS) and enhance its reactivity in the char-CO2 gasification reaction, known as the Boudouard reaction (C + CO2 ↔ 2CO). Hydrochar samples were developed by hydrothermal treatment of RSS, without separating the solid residue from the liquid product, at 433, 473, 513, and 553 K under autogenous pressure. The CO2 gasification reactivity of the developed hydrochars was then investigated at different heating rates (5, 10, 20, and 30 K/min) by the non-isothermal thermogravimetric method. The hydrochars revealed higher reactivity and improved gasification characteristics compared to the untreated biomass, while the hydrochar which was filtered from the liquid slurry showed lower reactivity compared to the untreated biomass. This was due to the chemical and structural evolutions of the biomass during hydrothermal treatment as indicated by various analyses. The gasification reactivity of the hydrochar was substantially enhanced by introduction of a catalyst (NaNO3) during HTC. Kinetic analysis of the char-CO2 gasification reaction was carried out by applying Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink isoconversional methods, and thermodynamic parameters were also determined. The activation energy of the Na-loaded RSS hydrochar in CO2 gasification (120-154 kJ/mol) was considerably lower than that of the untreated biomass (153-172 kJ/mol). Thermodynamic studies also confirmed the promoting effect of hydrothermal treatment and catalyst impregnation on enhancement of reactivity of the virgin biomass and reduction of gasification temperature.
In this study, luminescent bio-adsorbent nitrogen-doped carbon dots (N-CDs) was produced and applied for the removal and detection of Hg (II) from aqueous media. N-CDs were synthesized from oil palm empty fruit bunch carboxymethylcellulose (CMC) and urea. According to several analytical techniques used, the obtained N-CDs display graphitic core with an average size of 4.2 nm, are enriched with active sites, stable over a wide range of pH and have great resistance to photobleaching. The N-CDs have bright blue emission with an improved quantum yield (QY) of up to 35.5%. The effect of the variables including pH, adsorbent mass, initial concentration and incubation time on the removal of Hg (II) was investigated using central composite design. The statistical results confirmed that the adsorption process could reach equilibrium within 30 min. The reduced cubic model (R2 = 0.9989) revealed a good correlation between the observed values and predicted data. The optimal variables were pH of 7, dose of 0.1 g, initial concentration of 100 mg/L and duration of 30 min. Under these conditions, adsorption efficiency of 84.6% was obtained. The adsorption kinetic data could be well expressed by pseudo-second-order kinetic and Langmuir isotherm models. The optimal adsorption capacity was 116.3 mg g-1. Furthermore, the adsorbent has a good selectivity towards Hg (II) with a detection limit of 0.01 μM due to the special interaction between Hg (II) and carboxyl/amino groups on the edge of N-CDs. This work provided an alternative direction for constructing low-cost adsorbents with effective sorption and sensing of Hg (II).
Fly ash samples from a mixed hazardous waste (MHW) incinerator were subjected to solidification and stabilization (S/S) studies using ordinary Portland cement (OPC) as the binder. Additives (i.e., activated carbon and rice husk) were also homogenized with the binder and waste to determine the effectiveness of the immobilization of heavy metals. The toxicity characteristics leaching procedure (TCLP), Japanese Leaching Test (JLT-13) and the American Nuclear Test 16.1 (modified) ANS 16.1 were used to gauge the leaching of heavy metals from the solidified matrixes. Compressibility strength of the solidified matrixes was also tested using the American Standard Testing Material (ASTM) test procedure for the compressive strength of hydraulic cement mortars.
The objective of this research was to evaluate the treatment ofp-nitrophenol (PNP) as a sole organic carbon source using a sequencing batch reactor (SBR) with the addition of adsorbent. Two types of adsorbents, namely powdered activated carbon (PAC) and pyrolysed rice husk (PRH) were used in this study. Two identical SBRs, each with a working volume of 10 L, were operated with fill, react, settle, draw and idle periods in the ratio of 2:8:1:0.75:0.25 for a cycle time of 12 h. The results showed that, without the addition of adsorbent, increasing the influent PNP concentration to 200 mg/L resulted in the deterioration of chemical oxygen demand (COD) removal efficiency and PNP removal efficiency in the SBRs. Improvement in the performance of the SBR was observed with the addition of PAC. When the dosage of 1.0 g PAC/cycle was applied, COD removal of 95% and almost complete removal of PNP were achieved at the influent PNP concentration of 300 mg/L. The kinetic study showed that the rates of COD and PNP removal can be described by the first-order kinetics. The enhancement of performance in the PAC-supplemented SBR was postulated to be due to the initial adsorption of PNP by the freshly added and the bioregenerated PAC, thus reducing the inhibition on the microorganisms. The PRH was found to be ineffective because of its relatively low adsorption capacity for PNP, compared with that of PAC.
E. coli has been engineered to produce xylitol, but the production faces bottlenecks in terms of production yield and cell viability. In this study, recombinant E. coli (rE. coli) was immobilized on untreated and treated multiwalled carbon nanotubes (MWCNTs) for xylitol production. The immobilized rE. coli on untreated MWCNTs gave the highest xylitol production (5.47 g L-1) and a productivity of 0.22 g L-1 h-1. The doubling time for the immobilized cells increased up to 20.40 h and was higher than that of free cells (3.67 h). Cell lysis of the immobilized cells was reduced by up to 73 %, and plasmid stability improved by up to 17 % compared to those of free cells. Xylitol production using the optimum parameters (pH 7.4, 0.005 mM and 29 °C) achieved a xylitol production and productivity of 6.33 g L-1 and 0.26 g L-1 h-1, respectively. A seven-cycle repeated batch fermentation was carried out for up to 168 h, which showed maximum xylitol production of 7.36 g L-1 during the third cycle. Hence, this new adsorption immobilization system using MWCNTs is an alternative to improve the production of xylitol.
Thiol-functionalized magnetic carbon nanotubes (TMCNTs) were employed as the sorbent in the magnetic micro-solid phase extraction (M-µ-SPE) of sulfonamide antibiotics (SAs) in water, milks and chicken meat products prior to high performance liquid chromatography-diode array detector (HPLC-DAD) analysis. The synthesized sorbent was characterized by several spectroscopic techniques. Optimum conditions were: 20 mg of TMCNTs at pH 4, 2 min extraction time, 10% addition of salt and 30 mL of sample volume. Under the optimized TMCNTs-M-µ-SPE and HPLC-DAD conditions, the method showed good linearity in the range of 0.1-500 µg L-1 (r2 ≥ 0.9950), low limits of detection (0.02-1.5 µg L-1), good analytes recovery (80.7-116.2%) and acceptable RSDs (0.3-7.7%, n = 15). The method was applied to tap water (1), milks (15) and commercial chicken meat products (35), SAs were detected in five chicken meat samples (3.0-25.7 µg L-1). The method is critically compared to those reported in the literature.
The response of trilayer graphene nanoribbon (TGN)-based ion-sensitive field-effect transistor (ISFET) to different pH solutions and adsorption effect on the sensing parameters are analytically studied in this research. The authors propose a TGN-based sensor to electrochemically detect pH. To this end, absorption effect on the sensing area in the form of carrier concentration, carrier velocity, and conductance variations are investigated. Also, the caused electrical response on TGN as a detection element is analytically proposed, in which significant current decrease of the sensor is observed after exposure to high pH values. In order to verify the accuracy of the model, it is compared with recent reports on pH sensors. The TGN-based pH sensor exposes higher current compared to that of carbon nanotube (CNT) counterpart for analogous ambient conditions. While, the comparative results demonstrate that the conductance of proposed model is lower than that of monolayer graphene-counterpart for equivalent pH values. The results confirm that the conductance of the sensor is decreased and Vg-min is obviously right-shifted by increasing value of pH. The authors demonstrate that although there is not the experimental evidence reported in the part of literature for TGN sensor, but the model can assist in comprehending experiments involving nanoscale pH sensors.
Nowadays, sensitive biosensors with high selectivity, lower costs and short response time are required for detection of DNA. The most preferred materials in DNA sensor designing are nanomaterials such as carbon and Au nanoparticles, because of their very high surface area and biocompatibility which lead to performance and sensitivity improvements in DNA sensors. Carbon nanomaterials such as carbon nanotubes (CNTs) can be considered as a suitable DNA sensor platform due to their high surface-to-volume ratio, favourable electronic properties and fast electron transfer rate. Therefore, in this study, the CNTs which are synthesised by pulsed AC arc discharge method on a high-density polyethylene substrate are used as conducting channels in a chemiresistor for the electrochemical detection of double stranded DNA. Moreover, the response of the proposed sensor is investigated experimentally and analytically in different temperatures, which confirm good agreement between the presented model and experimental data.
Three strains of Spirulina platensis isolated from different locations showed capability of synthesizing poly(3-hydroxybutyrate) [P(3HB)] under nitrogen-starved conditions with a maximum accumulation of up to 10 wt.% of the cell dry weight (CDW) under mixotrophic culture conditions. Intracellular degradation (mobilization) of P(3HB) granules by S. platensis was initiated by the restoration of nitrogen source. This mobilization process was affected by both illumination and culture pH. The mobilization of P(3HB) was better under illumination (80% degradation) than in dark conditions (40% degradation) over a period of 4 days. Alkaline conditions (pH 10-11) were optimal for both biosynthesis and mobilization of P(3HB) at which 90% of the accumulated P(3HB) was mobilized. Transmission electron microscopy (TEM) revealed that the mobilization of P(3HB) involved changes in granule quantity and morphology. The P(3HB) granules became irregular in shape and the boundary region was less defined. In contrast to bacteria, in S. platensis the intracellular mobilization of P(3HB) seems to be faster than the biosynthesis process. This is because in cyanobacteria chlorosis delays the P(3HB) accumulation process.
A moderately halophilic bacterium isolated from fermenting shrimp paste, Salinivibrio sp. M318 was found capable of using fish sauce and mixtures of waste fish oil and glycerol as nitrogen and carbon sources, respectively, for poly(3-hydroxybutyrate) (PHB) production. A cell dry weight (CDW) of up to 10 g/L and PHB content of 51.7 wt% were obtained after 48 h of cultivation in flask experiment. Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] was synthesized when 1,4-butanediol, γ-butyrolactone, or sodium 4-hydroxybutyrate was added as precursors to the culture medium. The biosynthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] was achieved by supplying precursors such as sodium valerate, sodium propionate, and sodium heptanoate. Salinivibrio sp. M318 was able to accumulate the above mentioned PHAs during the growth phase. High CDW of 69.1 g/L and PHB content of 51.5 wt% were obtained by strain Salinivibrio sp. M318 after 78 h of cultivation in fed-batch culture. The results demonstrate Salinivibrio sp. M318 to be a promising wild-type bacterium for the production of PHA from aquaculture residues.
Interaction between split RNA aptamer and the clinically important target, HIV-1 Tat was investigated on a biosensing surface transduced by functionally choreographed multiwall carbon nanotubes (MWCNTs). Acid oxidation was performed to functionalize MWCNTs with carboxyl functional groups. X-ray photoelectron spectroscopy analysis had profound ~2.91% increment in overall oxygen group and ~1% increment was noticed with a specific carboxyl content owing to CO and OCO bonding. The interaction between split RNA aptamer and HIV-1 Tat protein was quantified by electrical measurements with the current signal (Ids) over a gate voltage (Vgs). Initially, 34.4 mV gate voltage shift was observed by the immobilization of aptamer on MWCNT. With aptamer and HIV-1 Tat interaction, the current flow was decreased with the concomitant gate voltage shift of 23.5 mV. The attainment of sensitivity with split aptamer and HIV-1 Tat interaction on the fabricated device was 600 pM. To ensure the genuine interaction of aptamer with HIV-1 Tat, other HIV-1 proteins, Nef and p24 were interacted with aptamer and they displayed the negligible interferences with gate voltage shift of 3.5 mV and 5.7 mV, which shows 4 and 2.5 folds lesser than HIV-1 Tat interaction, respectively.
Long carbon chain alkanediols are used in the production of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)], however these substrates possess high toxicity towards bacterial cells. This study demonstrated the effective utilisation of a long carbon chain alkanediol, namely 1,8-octanediol, to enhance the yield and production of a copolymer with a high molecular weight of over 1000 kDa, which is desirable for novel applications in medical and biopharmaceuticals. The increased PHA content (47-61 wt%) and concentration (1.7-4.5 g/L) was achieved by additional feeding of a combination of C4 substrates at C/N 10, with 1,8-octanediol + γ-butyrolactone producing P(3HB-co-22 mol% 4HB) with a high molecular weight (1060 kDa) and elongation at break of 970%. The DO-stat feeding strategy of C/N 10 has shown an increment of PHA concentration for both carbon combination, 0.45-4.27 g/L and 0.32-3.36 g/L for 1,8-octanediol + sodium 4-hydroxybutyrate (4HB-Na) and 1,8-octanediol + γ-butyrolactone, but with a slight reduction on molecular weight and mechanical strength. Nonetheless, further study revealed that a nitrogen-absence feeding strategy could retain the high molecular weight and elongation at break of the copolymer, and simultaneously improving the overall P(3HB-co-4HB) production.
A novel third generation H2O2 biosensor is fabricated using multiporous SnO2 nanofiber/carbon nanotubes (CNTs) composite as a matrix for the immobilization of redox protein onto glassy carbon electrode. The multiporous nanofiber (MPNFs) of SnO2 is synthesized by electrospinning technique from the tin precursor. This nanofiber shows high surface area and good electrical conductivity. The SnO2 nanofiber/CNT composite increases the efficiency of biomolecule loading due to its high surface area. The morphology of the nanofiber has been evaluated by scanning electron microscopy (SEM). Cyclic Voltammetry and amperometry technique are employed to study and optimize the performance of the fabricated electrode. A direct electron transfer between the protein's redox centre and the glassy carbon electrode is established after fabrication of the electrode. The fabricated electrode shows excellent electrocatalytic reduction to H2O2. The catalysis currents increases linearly to the H2O2 concentration in a wide range of 1.0 10-6-1.4×10-4M and the lowest detection limit was 30nM (S/N=3). Moreover, the biosensor showed a rapid response to H2O2, a good stability and reproducibility.
Magnetic beads (AO-γ-Fe2O3) of alginate (A) impregnated with citrate coated maghemite nanoparticles (γ-Fe2O3) and oxidized multiwalled carbon nanotubes (OMWCNTs) were synthesized and used as adsorbent for the removal of methylene blue from water. The XRD analysis revealed that the diameter of γ-Fe2O3 is 10.24 nm. The mass saturation magnetization of AO-γ-Fe2O3 and γ-Fe2O3 were found to be 27.16 and 42.63 emu·g-1, respectively. The adsorption studies revealed that the data of MB isotherm were well fitted to the Freundlich model. The Langmuir isotherm model exhibited a maximum adsorption capacity of 905.5 mg·g-1. The adsorption was very dependent on initial concentration, adsorbent dose, and temperature. The beads exhibited high adsorption stability in large domain of pH (4-10). The thermodynamic parameters determined at 283, 293, 303, and 313 K revealed that the adsorption occurring was spontaneous and endothermic in nature. Adsorption kinetic data followed the intraparticle diffusion model. The AO-γ-Fe2O3 beads were used for six cycles without significant adsorptive performance loss. Therefore, the eco-friendly prepared AO-γ-Fe2O3 beads were considered as highly recyclable and efficient adsorbent for methylene blue as they can be easily separated from water after treatment.
Mixed matrix membranes (MMMs) of cellulose acetate/poly(vinylpyrrolidone) (CA/PVP) infused with acid functionalized multiwall carbon nanotubes (f-MWCNTs) were fabricated by an immersion phase separation technique for hemodialysis application. Membranes were characterized using FTIR, water uptake, contact angle, TGA, DMA and SEM analysis. The FTIR was used to confirm the bonding interaction between CA/PVP membrane matrix and f-MWCNTs. Upon addition of f-MWCNTs, TGA thermograms and glass transition temperature indicated improved thermal stability of MMMs. The surface morphological analysis demonstrated revealed uniform distribution of f-MWCNTs and asymmetric membrane structure. The water uptake and contact angle confirmed that hydrophilicity was increased after incorporation of f-MWCNTs. The membranes demonstrated enhancement in water permeate flux, bovine serum albumin (BSA) rejection with the infusion of f-MWCNTs; whereas BSA based anti-fouling analysis using flux recovery ratio test shown up to 8.4% improvement. The urea and creatinine clearance performance of MMMs were evaluated by dialysis experiment. It has been found that f-MWCNTs integrated membranes demonstrated the higher urea and creatinine clearance with increase of 12.6% and 10.5% in comparison to the neat CA/PVP membrane. Thus, the prepared CA/PVP membranes embedded with f-MWCNTs can be employed for wide range of dialysis applications.
A novel synthesis and characterization of cellulose, hydroxyapatite and chemically-modified carbon electrode (Cellulose-HAp-CME) composite was reported for the analysis of trace Pb(II) ions detection and its validation in blood serum. The Field Emission Scanning Electron Microscopy (FESEM) analyses showed that the composite retained the orderly porous structure but with scattered particle size agglomeration. The Fourier Transform Infrared Spectroscopy (FTIR) spectra suggested the presence of functional groups associated with the bending and stretching of carbon bonds and intermolecular H-bonding. X-ray Diffraction (XRD) analyses further elucidated that the crystallite size could have influenced the properties of the electrode. Based on Thermo-gravimetric Analysis (TGA/DTG), the composites showed thermal stability with more than 60% residual content at 700°C. The sensor was successfully developed for trace Pb(II) ions detection in complex medium such as blood serum, in the physiologically relevant range of 10-60ppb, with resulting Limit of Detection (LOD) of 0.11±0.36ppb and Limit of Quantification (LOQ) of 0.36±0.36ppb. The newly fabricated electrode could be advantageous as a sensing platform with favourable electrochemical characteristics for robust, in situ and rapid environmental and clinical analyses of heavy metal ions.
Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by calcination of LDHs at 800 °C for 5 h. Nitrogen and hexane were used as the carrier gas and carbon source respectively, for preparation of MWCNTs using CVD methods at 800 °C. MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a quartz tube. The materials were subsequently characterized through X-ray diffraction, Fourier transform infrared spectroscopy, surface area analysis, field emission scanning electron microscopy and transmission electron microscopy. It was determined that size and yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.
The effects of multi-walled carbon nanotube (MWNT) concentration on the structural, optical and electrical properties of conjugated polymer-carbon nanotube composite are discussed. Multi-walled carbon nanotube-polypyrrole nanocomposites were synthesized by electrochemical polymerization of monomers in the presence of different amounts of MWNTs using sodium dodecylbenzensulfonate (SDBS) as surfactant at room temperature and normal pressure. Field emission scanning electron microscopy (FESEM) indicates that the polymer is wrapped around the nanotubes. Measurement of the nonlinear refractive indices (n(2)) and the nonlinear absorption (β) of the samples with different MWNT concentrations measurements were performed by a single Z-scan method using continuous wave (CW) laser beam excitation wavelength of λ = 532 nm. The results show that both nonlinear optical parameters increased with increasing the concentration of MWNTs. The third order nonlinear susceptibilities were also calculated and found to follow the same trend as n(2) and β. In addition, the conductivity of the composite film was found to increase rapidly with the increase in the MWNT concentration.
A split plot 3 by 4 experiment was designed to examine the impact of 15-week variable levels of nitrogen fertilization (0, 90, 180 and 270 kg N/ha) on the characteristics of total flavonoids (TF), total phenolics (TP), total non structurable carbohydrate (TNC), net assimilation rate, leaf chlorophyll content, carbon to nitrogen ratio (C/N), phenyl alanine lyase activity (PAL) and protein content, and their relationships, in three varieties of Labisia pumila Blume (alata, pumila and lanceolata). The treatment effects were solely contributed by nitrogen application; there was neither varietal nor interaction effect observed. As nitrogen levels increased from 0 to 270 kg N/ha, the production of TNC was found to decrease steadily. Production of TF and TP reached their peaks under 0 followed by 90, 180 and 270 kg N/ha treatment. However, net assimilation rate was enhanced as nitrogen fertilization increased from 0 to 270 kg N/ha. The increase in production of TP and TF under low nitrogen levels (0 and 90 kg N/ha) was found to be correlated with enhanced PAL activity. The enhancement in PAL activity was followed by reduction in production of soluble protein under low nitrogen fertilization indicating more availability of amino acid phenyl alanine (phe) under low nitrogen content that stimulate the production of carbon based secondary metabolites (CBSM). The latter was manifested by high C/N ratio in L. pumila plants.