Studies of peri-implant soft tissue on in vivo models are commonly based on histological sections prepared using undecalcified or 'fracture' techniques. These techniques require the cutting or removal of implant during the specimen preparation process. The aim of this study is to explore a new impression technique that does not require any cutting or removal of implant for contour analysis of soft tissue around four types of titanium (Ti) surface roughness using an in vitro three-dimensional oral mucosal model (3D OMM).
The electrochemical oxidation of caffeine, a widely over-the-counter stimulant drug, has been investigated in effluent wastewater and deionized water (DIW) using graphite-poly vinyl chloride (PVC) composite electrode as anode. Effects of initial concentration of caffeine, chloride ion (Cl(-)) loading, presence of hydrogen peroxide (H2O2), sample volume, type of sample and applied voltage were determined to test and to validate a kinetic model for the oxidation of caffeine by the electrochemical oxidation process. The results revealed that the electrochemical oxidation rates of caffeine followed pseudo first-order kinetics, with rate constant values ranged from 0.006 to 0.23 min(-1) depending on the operating parameters. The removal efficiency of caffeine increases with applied voltage very significantly, suggesting a very important role of mediated oxidation process. However, the consumption energy was considered during electrochemical oxidation process. In chloride media, removal of caffeine is faster and more efficiently, although occurrence of more intermediates takes place. The study found that the adding H2O2 to the NaCl solution will inhibit slightly the electrochemical oxidation rate in comparison with only NaCl in solution. Liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS) technique was applied to the identification of the by-products generated during electrochemical oxidation, which allowed to construct the proposed structure of by-products.
Artemisinins are peroxidic antimalarial drugs known to be very potent but highly chemically unstable; they degrade in the presence of ferrous iron, Fe(II)-heme, or biological reductants. Less documented is how this translates into chemical stability and antimalarial activity across a range of conditions applying to in vitro testing and clinical situations. Dihydroartemisinin (DHA) is studied here because it is an antimalarial drug on its own and the main metabolite of other artemisinins. The behaviors of DHA in phosphate-buffered saline, plasma, or erythrocyte lysate at different temperatures and pH ranges were examined. The antimalarial activity of the residual drug was evaluated using the chemosensitivity assay on Plasmodium falciparum, and the extent of decomposition of DHA was established through use of high-performance liquid chromatography with electrochemical detection analysis. The role of the Fe(II)-heme was investigated by blocking its reactivity using carbon monoxide (CO). A significant reduction in the antimalarial activity of DHA was seen after incubation in plasma and to a lesser extent in erythrocyte lysate. Activity was reduced by half after 3 h and almost completely abolished after 24 h. Serum-enriched media also affected DHA activity. Effects were temperature and pH dependent and paralleled the increased rate of decomposition of DHA from pH 7 upwards and in plasma. These results suggest that particular care should be taken in conducting and interpreting in vitro studies, prone as their results are to experimental and drug storage conditions. Disorders such as fever, hemolysis, or acidosis associated with malaria severity may contribute to artemisinin instability and reduce their clinical efficacy.
Epizootic ulcerative syndrome (EUS) is a devastating fish disease caused by the fungus, Aphanomyces invadans. Rapid diagnosis of EUS is needed to control and treat this highly invasive disease. The current diagnostic methods for EUS are labor intensive. We have developed a highly sensitive and specific electrochemical genosensor towards the 18S rRNA and internal transcribed spacer regions of A. invadans. Multiple layers of latex were synthesized with the help of polyelectrolytes, and labeled with gold nanoparticles to enhance sensitivity. The gold-latex spheres were functionalized with specific DNA probes. We describe here the novel application of this improved platform for detection of PCR product from real sample of A. invadans using a premix sandwich hybridization assay. The premix assay was easier, more specific and gave higher sensitivity of one log unit when compared to the conventional method of step-by-step hybridization. The limit of detection was 0.5 fM (4.99 zmol) of linear target DNA and 1 fM (10 amol) of PCR product. The binding positions of the probes to the PCR amplicons were optimized for efficient hybridization. Probes that hybridized close to the 5' or 3' terminus of the PCR amplicons gave the highest signal due to minimal steric hindrance for hybridization. The genosensor is highly suitable as a surveillance and diagnostic tool for EUS in the aquaculture industry.
A new poly(4-vinyl pyridine) (P4VP) based cadmium (Cd)-ion selective electrode (ISE) was developed. The 4-vinyl pyridine (4VP) was first polymerized electrochemically on the surface of graphite, later characterized by FTIR, SEM/EDX and then optimized as ISE for Cd. At optimal pH 6.4, slope of 27.7±0.8mVdecade(-1), linear concentration range of 1×10(-7) to 1.0×10(-1)M Cd(2+) and limit of detection (S/N=3) of 2.51×10(-8)M were obtained. The ISE was very selective towards Cd(2+), with K(pot)<1×10(-2) in the presence of the usual cations and anions in water samples. Response time and shelf life of less than 1min and 90 days, respectively, were observed. Its application was tested in various types of samples.
A new method for the simultaneous quantification of 12 mycotoxins was developed and optimized using reverse phase high performance liquid chromatography (RP-HPLC) with a photodiode array (PDA) and fluorescence detector (FLD), a photochemical reactor for enhanced detection (PHRED) and post-column derivatization. The mycotoxins included aflatoxins (AFB(1), AFB(2), AFG(1), and AFG(2)), ochratoxin A (OTA), zearalenone (ZEA), deoxynivalenol (DON), fumonisins (FB(1), FB(2), and FB(3)), T-2 and HT-2 toxins. A double sample extraction with a phosphate-buffered saline solution (PBS) and methanol was used for co-extraction of mycotoxins, and a multifunctional immunoaffinity column was used for cleanup. Optimum conditions for separation of the mycotoxins were obtained to separate 12 mycotoxins in FLD and PDA chromatograms with a high resolution. The method gave recoveries in the range 72-111% when applied to spiked corn samples. The limits of detection (LOD) were 0.025 ng/g for AFB(1) and AFG(1), 0.012 ng/g for AFB(2) and AFG(2), 0.2 ng/g for OTA, 1.5 ng/g for ZEA, 6.2 ng/g for FB(1), FB(3) and HT-2 toxin, 9.4 ng/g for FB(2) and T-2 toxin, and 18.7 ng/g for DON. In addition, the limits of quantification (LOQ) ranged from 0.04 ng/g for AFB(2) and AFG(2) to 62 ng/g for DON. The method was successfully applied to the determination of these mycotoxins in 45 cereal samples obtained from the Malaysian market. The results indicated that the method can be applied for the multi-mycotoxin determination of cereals.
A method is described for the electrochemical determination of squamous cell carcinoma (SCC) antigen, and by testing the effect of 30 nm gold nanoparticles (GNPs). Three comparative studies were performed in the presence and absence of GNPs, and with agglomerated GNPs. The divalent ion Ca(II) was used to induce a strong agglomeration of GNPs, as confirmed by colorimetry and voltammetry. Herein, colorimetry was used to test the best amount of salt needed to aggregate the GNPs. Despite, voltammetry was used to determine the status of biomolecules on the sensor. The topography of the surface of ZnO-coated interdigitated electrodes was analyzed by using 3D-nano profilometry, scanning electron microscopy, atomic force microscopy and high-power microscopy. The interaction between SCC antigen and antibody trigger vibrations on the sensor and cause dipole moment, which was measured using a picoammeter with a linear sweep from 0 to 2 V at 0.01 V step voltage. The sensitivity level was 10 fM by 3σ calculation for the dispersed GNP-conjugated antigen. This indicates a 100-fold enhancement compared to the condition without GNP conjugation. However, the sensitivity level for agglomerated GNPs conjugated antibody was not significant with 100 fM sensitivity. Specificity was tested for other proteins in serum, namely blood clotting factor IX, C-reactive protein, and serum albumin. The SCC antigen was quantified in spiked serum and gave recoveries that ranged between 80 and 90%. Graphical abstractSchematic representation of SCC (squamous cell carcinoma) antigen determination using divalent ion induced agglomerated GNPs. Sensitivity increment depends on the occurrence of more SCC antigen and antibody binding event via GNPs integration. Notably, lower detection limit was achieved at femto molar with proper orientation of biological molecules.
Mycotoxins are the secondary toxic metabolites produced naturally by fungi. Analysis of mycotoxins is essential to minimize the consumption of contaminated food and feed. In this present work, an ultrasensitive electrochemical immunosensor for the detection of aflatoxin B₁ (AFB₁) was successfully developed based on an indirect competitive enzyme-linked immunosorbent assay (ELISA). Various parameters of ELISA, including antigen⁻antibody concentration, blocking agents, incubation time, temperature and pH of reagents, were first optimized in a 96-well microtiter plate to study the antigen⁻antibody interaction and optimize the optimum parameters of the assay. The optimized assay was transferred onto the multi-walled carbon nanotubes/chitosan/screen-printed carbon electrode (MWCNTs/CS/SPCE) by covalent attachment with the aid of 1-Ethyl-3-(3-dimetylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS). Competition occurred between aflatoxin B₁-bovine serum albumin (AFB₁⁻BSA) and free AFB₁ (in peanut sample and standard) for the binding site of a fixed amount of anti-AFB₁ antibody. Differential pulse voltammetry (DPV) analysis was used for the detection based on the reduction peak of TMB(ox). The developed immunosensor showed a linear range of 0.0001 to 10 ng/mL with detection limit of 0.3 pg/mL. AFB₁ analysis in spiked peanut samples resulted in recoveries between 80% and 127%. The precision of the developed immunosensor was evaluated by RSD values (n = 5) as 4.78% and 2.71% for reproducibility and repeatability, respectively.
Palm oil mill effluent (POME) is highly polluting wastewater generated from the palm oil milling process. Palm oil mill effluent was used as an electrolyte without any additive or pretreatment to perform electrocoagulation (EC) using electricity (direct current) ranging from 2 to 4 volts in the presence of aluminum electrodes with a reactor volume of 20 L. The production of hydrogen gas, removal of chemical oxygen demand (COD), and turbidity as a result of electrocoagulation of POME were determined. The results show that EC can reduce the COD and turbidity of POME by 57 and 62%, respectively, in addition to the 42% hydrogen production. Hydrogen production was also helpful to remove the lighter suspended solids toward the surface. The production of Al(OH)XHO at the aluminum electrode (anode) was responsible for the flocculation-coagulation process of suspended solids followed by sedimentation under gravity. The production of hydrogen gas from POME during EC was also compared with hydrogen gas production by electrolysis of tap water at pH 4 and tap water without pH adjustment under the same conditions. The main advantage of this study is to produce hydrogen gas while treating POME with EC to reduce COD and turbidity effectively.
The effects of azide on electron transport of exoelectrogens were investigated using air-cathode MFCs. These MFCs enriched with azide at the concentration higher than 0.5mM generated lower current and coulomb efficiency (CE) than the control reactors, but at the concentration lower than 0.2mM MFCs generated higher current and CE. Power density curves showed overshoot at higher azide concentrations, with power and current density decreasing simultaneously. Electrochemical impedance spectroscopy (EIS) showed that azide at high concentration increased the charge transfer resistance. These analyses might reflect that a part of electrons were consumed by the anode microbial population rather than transferred to the anode. Bacterial population analyses showed azide-enriched anodes were dominated by Deltaproteobacteria compared with the controls. Based on these results it is hypothesized that azide can eliminate the growth of aerobic respiratory bacteria, and at the same time is used as an electron acceptor/sink.
A simple single-stage approach, based on the hydrothermal technique, has been introduced to synthesize reduced graphene oxide/titanium dioxide nanocomposites. The titanium dioxide nanoparticles are formed at the same time as the graphene oxide is reduced to graphene. The triethanolamine used in the process has two roles. It acts as a reducing agent for the graphene oxide as well as a capping agent, allowing the formation of titanium dioxide nanoparticles with a narrow size distribution (~20 nm). Transmission electron micrographs show that the nanoparticles are uniformly distributed on the reduced graphene oxide nanosheet. Thermogravimetric analysis shows the nanocomposites have an enhanced thermal stability over the original components. The potential applications for this technology were demonstrated by the use of a reduced graphene oxide/titanium dioxide nanocomposite-modified glassy carbon electrode, which enhanced the electrochemical performance compared to a conventional glassy carbon electrode when interacting with mercury(II) ions in potassium chloride electrolyte.
Cobalt titanate-titania composite oxide films have been grown on FTO-coated glass substrates using a single-source heterometallic complex [Co2Ti4(μ-O)6(TFA)8(THF)6]·THF () which was obtained in quantitative yield from the reaction of diacetatocobalt(ii) tetrahydrate, tetraisopropoxytitanium(iv), and trifluoroacetic acid from a tetrahydrofuran solution. Physicochemical investigations of complex have been carried out by melting point, FT-IR, thermogravimetric and single-crystal X-ray diffraction analyses. CoTiO3-TiO2 films composed of spherical objects of various sizes have been grown from by aerosol-assisted chemical vapor deposition at different temperatures of 500, 550 and 600 °C. Thin films characterized by XRD, Raman and X-ray photoelectron spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis have been explored for electrochemical detection of dopamine (DA). The cyclic voltammetry with the CoTiO3-TiO2 electrode showed a DA oxidation peak at +0.215 V while linear sweep voltammetry displayed a detection limit (LoD) of 0.083 μM and a linear concentration range of 20-300 μM for DA. Thus, the CoTiO3-TiO2 electrode is a potential candidate for the sensitive and selective detection of DA.
Graphene (GR) and its derivatives are promising materials on the horizon of nanotechnology and material science and have attracted a tremendous amount of research interest in recent years. The unique atom-thick 2D structure with sp(2) hybridization and large specific surface area, high thermal conductivity, superior electron mobility, and chemical stability have made GR and its derivatives extremely attractive components for composite materials for solar energy conversion, energy storage, environmental purification, and biosensor applications. This review gives a brief introduction of GR's unique structure, band structure engineering, physical and chemical properties, and recent energy-related progress of GR-based materials in the fields of energy conversion (e.g., photocatalysis, photoelectrochemical water splitting, CO2 reduction, dye-sensitized and organic solar cells, and photosensitizers in photovoltaic devices) and energy storage (batteries, fuel cells, and supercapacitors). The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing, and removal of heavy-metal ions is presented. Additionally, the use of graphene composites in the biosensing field is discussed. We conclude the review with remarks on the challenges, prospects, and further development of GR-based materials in the exciting fields of energy, environment, and bioscience.
PEDOT was synthesized by chemical polymerisation and characterised for its electrochemical insights. Three different anode configuration, namely graphite plate (GP), carbon cloth (CC) and graphite felt (GF) were then loaded with a fixed amount of PEDOT (2.5 mg/m(2)) denoted as GP-P, CC-P and GF-P respectively. The PEDOT coating improved the electrochemical characteristics and electron transfer capabilities of the anodes. They also contributed for enhanced MFC performances with maximum energy generation along with coulombic efficiency than the unmodified anodes. The morphological characteristics like higher surface area and open structure of felt material promoted both microbial formation and electrochemical active area. A maximum current density of 3.5A/m(2) was achieved for GF-P with CE and COD of 51% and 86% respectively. Thus, the GF-P anode excelled among the studied anodes with synergetic effect of PEDOT coating and structural configuration, making it as a potential optimum anode for MFC application.
Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram.
Effective regulation of p-phenylenediamine (PPD), a widely used precursor of hair dye that is harmful to human health in large concentration, relies upon an accurate yet simple detection of PPD. In this context, amperometric electrode sensor based on perovskite oxide becomes attractive given its portability, low cost, high sensitivity, and rapid processing time. This work reports the systematic characterization of a series of Sr-doped PrCoO3-δ perovskite oxides with composition of Pr1-xSrxCoO3-δ(x = 0, 0.2, 0.4, 0.6, 0.8, and 1) for PPD detection in an alkaline solution. PSC82 deposited onto glassy carbon electrode (PSC82/GCE) generates the highest redox currents which correlates with the highest hydrogen peroxide intermediates (HO2-) yield and the σ*-orbital (eg) filling of Co that is closest to unity for PSC82. PSC82/GCE provides the highest sensitivities of 655 and 308 μA mM-1 cm-2 in PPD concentration range of 0.5-2,900 and 2,900-10,400 μM, respectively, with a limit of detection of 0.17 μM. PSC82/GCE additionally demonstrates high selectivity to PPD and long term stability during 50 consecutive cyclic voltammetry scans and over 1-month storage period. The potential applicability of PSC82/GCE was also demonstrated by confirming the presence of very low concentration of PPD of below 0.5% in real hair dyes.
A novel disposable electrochemical biosensor based on immobilized calf thymus double-stranded DNA (dsDNA) on the carbon-based screen-printed electrode (SPE) is developed for rapid biorecognition of carrageenan by using methylene blue (MB) redox indicator. The biosensor protocol for the detection of carrageenan is based on the concept of competitive binding of positively charged MB to the negatively charged dsDNA and carrageenan. The decrement in the MB cathodic peak current (ipc) signal as a result of the released MB from the immobilized dsDNA, and attracted to the carrageenan can be monitored via differential pulse voltammetry (DPV). The biosensor showed high sensitivity and selectivity to carrageenan at low concentration without interference from other polyanions such as alginate, gum arabic and starch. Calibration of the biosensor with carrageenan exhibited an excellent linear dependence from 1-10 mg L-1 (R2 = 0.98) with a detection limit of 0.08 mg L-1. The DNA-based carrageenan biosensor showed satisfactory reproducibility with 5.6-6.9% (n = 3) relative standard deviations (RSD), and possessing several advantages such as simplicity, fast and direct application to real sample analysis without any prior extensive sample treatments, particularly for seaweeds and food analyses.
In this study, the potential of electrohydrodynamic atomization or electrospraying to produce nanometer-order CGTase particles from aqueous suspension was demonstrated. CGTase enzyme was prepared in acetate buffer solution (1% v/v), followed by electrospraying in stable Taylor cone-jet mode. The deposits were collected on aluminium foil (collector) at variable distances from the tip of spraying needle, ranging from 10 to 25 cm. The Coulomb fission that occurs during electrospraying process successfully transformed the enzyme to the solid state without any functional group deterioration. The functional group verification was conducted by FTIR analysis. Comparison between the deposit and the as-received enzyme in dry state indicates almost identical spectra. By increasing the distance of the collector from the needle tip, the average particle size of the solidified enzyme was reduced from 200±117 nm to 75±34 nm. The average particle sizes produced from the droplet fission were in agreement with the scaling law models. Enzyme activity analysis showed that the enzyme retained its initial activity after the electrospraying process. The enzyme particles collected at the longest distance (25 cm) demonstrated the highest enzyme activity, which indicates that the activity was controlled by the enzyme particle size.
A high-performance interdigitated electrode (IDE) biosensing surface was reported here by utilizing self-assembled silica nanoparticle (SiNP). The modified surface was used to evaluate the complementation of hairpin forming region from Mitoxantrone resistance gene 7 (MXR7; liver cancer-related short gene). The conjugated SiNPs on 3-aminopropyl triethoxysilane functionalization were captured with probe sequence on IDE biosensing surface. The physical and chemically modified surface was used to quantify MXR7 and an increment in the current response upon complementation was noticed. Limit of target DNA detection was calculated (1-10 fM) and this label-free detection is at the comparable level to the fluorescent-based sensing. A linear regression was calculated [y = 0.243x - 0.0773; R² = 0.9336] and the sensitivity was 1 fM on the linear range of 1 fM to 10 pM. With the strong attachment of capture DNA on IDE through SiNP, the surface clearly discriminates the specificity (complementary) versus nonspecificity (complete-, single-, and triple-mismatched sequences). This detection strategy helps to determine liver cancer progression and the similar strategy can be followed for other gene sequence complementation.
A new technique was accepted to fill the porosity of Al coating applied by arc thermal spray process to enhance corrosion resistance performance in artificial ocean water. The porosity is the inherent property of arc thermal spray coating process. In this study, applied coating was treated with different concentrations of ammonium phosphate mono basic (NH4H2PO4: AP) solution thereafter dried at room temperature and kept in humidity chamber for 7d to deposit uniform film. The corrosion resistance of Al coating and treated samples have been evaluated using electrochemical impedance spectroscopy (EIS) and potentiodynamic techniques with exposure periods in artificial ocean water. Electrochemical techniques, X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM) and field emission-scanning electron microscopy (FE-SEM) indicated that phosphate ion would have been retarding corrosion of Al coating effectively. The formation of AHP (Ammonium Aluminum Hydrogen Phosphate Hydrate: NH4)3Al5H6(PO4)8.18H2O) on Al coating surface after treatment with AP is nano sized, crystalline and uniformly deposited but after exposure them in artificial ocean water, they form AHPH (Aluminum hydroxide phosphate hydrate Al3(PO4)2(OH)3(H2O)5) that is very protective, adherent, uniform and plate like morphology of corrosion products. The AHPH is sparingly soluble and adherent to surface and imparted improved corrosion resistance.