Two performance (efficacy and attractiveness) comparisons of neonicotinoid baits QuickBayt® (imidacloprid) and Agita® (thiamethoxam) against filth flies were conducted under field conditions to determine suitability for use outdoors. The first experiment compared bait performance and the second compared effects of different applications on QuickBayt® performance. Applications compared were: (i) scattered in petri dish (SPD); (ii) wet-down in petri dish (WPD); (iii) scattered on cardboard (SCB) and (iv) painted on cardboards (PCB). Efficacy and attractiveness were assessed based on knockdown percentage (KD%) and number of flies feeding on baits, respectively. The KD% of QuickBayt® (34% ± 3.0%) was not significantly higher than Agita® (29% ± 1.3%) (t-test, P>0.05). Agita® (101 ± 5.7 flies) was significantly more attractive to flies than QuickBayt® (76 ± 4.8 flies) and the sugar solution (49 ± 7.2) (one-way ANOVA, P<0.05). The PCB and SCB applications were significantly more attractive to filth flies than WPD and SPD (One-way ANOVA, P<0.05), however differences in KD% were not significantly different (One-way ANOVA, P>0.05). The two baits provided the same level of efficacy in a wide-open area against filth flies of various species. QuickBayt® was more versatile; efficacy was not significantly affected by different applications. Surface area and moisture affects attractiveness of the bait.
Binding of a potent anticancer agent, ponatinib (PTB) to human serum albumin (HSA), main ligand transporter in blood plasma was analyzed with several spectral techniques such as fluorescence, absorption and circular dichroism along with molecular docking studies. Decrease in the KSV value with increasing temperature pointed towards PTB-induced quenching as the static quenching, thus affirming complexation between PTB and HSA. An intermediate binding affinity was found to stabilize the PTB-HSA complex, as suggested by the Ka value. Thermodynamic analysis of the binding phenomenon revealed participation of hydrophobic and van der Waals interactions along with hydrogen bonds, which was also supported by molecular docking analysis. Changes in both secondary and tertiary structures as well as in the microenvironment around Trp and Tyr residues of HSA were anticipated upon PTB binding to the protein, as manifested from circular dichroism and three-dimensional fluorescence spectra, respectively. Binding of PTB to HSA led to protein's thermal stabilization. Competitive ligand displacement experiments using different site markers such as warfarin, indomethacin and ketoprofen disclosed the binding site of PTB as Sudlow's site I in HSA, which was further confirmed by molecular docking analysis.
The bovine milk allergenic protein, 'β-lactoglobulin' is one of the leading causes of milk allergic reaction. In this research, a novel label-free non-faradaic capacitive aptasensor was designed to detect β-lactoglobulin using a Laser Scribed Graphene (LSG) electrode. The graphene was directly engraved into a microgapped (~ 95 µm) capacitor-electrode pattern on a flexible polyimide (PI) film via a simple one-step CO2 laser irradiation. The novel hybrid nanoflower (NF) was synthesized using 1,1'-carbonyldiimidazole (CDI) as the organic molecule and copper (Cu) as the inorganic molecule via one-pot biomineralization by tuning the reaction time and concentration. NF was fixed on the pre-modified PI film at the triangular junction of the LSG microgap specifically for bio-capturing β-lactoglobulin. The fine-tuned CDI-Cu NF revealed the flower-like structures was viewed through field emission scanning electron microscopy. Fourier-transform infrared spectroscopy showed the interactions with PI film, CDI-Cu NF, oligoaptamer and β-lactoglobulin. The non-faradaic sensing of milk allergen β-lactoglobulin corresponds to a higher loading of oligoaptamer on 3D-structured CDI-Cu NF, with a linear range detection from 1 ag/ml to 100 fg/ml and attomolar (1 ag/ml) detection limit (S/N = 3:1). This novel CDI-Cu NF/LSG microgap aptasensor has a great potential for the detection of milk allergen with high-specificity and sensitivity.
Laccases, oxidative copper-enzymes found in fungi and bacteria were used as the basis in the design of nona- and tetrapeptides. Laccases are known to be excellent catalysts for the degradation of phenolic xenobiotic waste. However, since solvent extraction of laccases is environmentally-unfriendly and yields obtained are low, they are less preferred compared to synthetic catalysts. The histidine rich peptides were designed based on the active site of laccase extracted from Trametes versicolor through RCSB Protein Data Bank, LOMETS and PyMol software. The peptides were synthesized using Fmoc-solid phase peptide synthesis (SPPS) with 30-40% yield. These peptides were purified and characterized using LC-MS (purities >75%), FTIR and NMR spectroscopy. Synthesized copper(II)-peptides were crystallized and then analyzed spectroscopically. Their structures were elucidated using 1D and 2D NMR. Standards (o,m,p-cresol, 2,4-dichlorophenol) catalysed using laccase from Trametes versicolor (0.66 U/mg) were screened under different temperatures and stirring rate conditions. After optimizing the degradation of the standards with the best reaction conditions reported herein, medications with phenolic and aromatic structures such as ibuprofen, paracetamol (acetaminophen), salbutamol, erythromycin and insulin were screened using laccase (positive control), apo-peptides and copper-peptides. Their activities evaluated using GC-MS, were compared with those of peptide and copper-peptide catalysts. The tetrapeptide was found to have the higher degradation activity towards salbutamol (96.8%) compared with laccase at 42.8%. Ibuprofen (35.1%), salbutamol (52.9%) and erythromycin (49.7%) were reported to have the highest degradation activities using Cu-tetrapeptide as catalyst when compared with the other medications. Consequently, o-cresol (84%) was oxidized by Tp-Cu while the apo-peptides failed to oxidize the cresols. Copper(II)-peptides were observed to have higher catalytic activity compared to their parent peptides and the enzyme laccase for xenobiotic degradation.
The formation of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) was investigated using a kinetic study approach as described by first-order, Arrhenius, and Eyring equations. Chemical model systems with different amino acid precursors (proline, phenylalanine, and glycine) were examined at different times (4, 8, 12, and 16 min) and temperatures (150, 180, 210, 240, and 270 °C). PhIP was detected using high-performance liquid chromatography equipped with fluorescence detector (HPLC-FLD). The good fit in first-order suggested that PhIP formation was influenced by the types of amino acids and PhIP concentration significantly increased with time and temperature (up to 240 °C). PhIP was detected in proline and phenylalanine model systems but not in the glycine model system. The phenylalanine model system demonstrated low activation energy (Ea) of 95.36 kJ/mol that resulted in a high rate of PhIP formation (great amount of PhIP formed). Based on the ∆S‡ values both proline and phenylalanine demonstrated bimolecular rate-limiting steps for PhIP formation. Altogether these kinetic results could provide valuable information in predicting the PhIP formation pathway.
The microwave-assisted three-component reactions of 3,5-bis(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones, acenaphthenequinone and cyclic α-amino acids in an ionic liquid, 1-butyl-3-methylimidazolium bromide, occurred through a domino sequence affording structurally intriguing diazaheptacyclic cage-like compounds in excellent yields.
Nasopharyngeal carcinoma (NPC) is a form of head and neck cancer of multifactorial etiologies that is highly prevalent among men in the population of Southern China and Southeast Asia. NPC has claimed many thousands of lives worldwide; but the low awareness of NPC remains a hindrance in early diagnosis and prevention of the disease. NPC is highly responsive to radiotherapy and chemotherapy, but radiocurable NPC is still dependent on concurrent treatment of megavoltage radiotherapy with chemotherapy. Despite a significant reduction in loco-regional and distant metastases, radiotherapy alone has failed to provide a significant improvement in the overall survival rate of NPC, compared to chemotherapy. In addition, chemo-resistance persists as the major challenge in the management of metastatic NPC although the survival rate of advanced metastatic NPC has significantly improved with the administration of chemotherapy adjunctive to radiotherapy. In this regard, targeted molecular therapy could be explored for the discovery of alternative NPC therapies. Nutlin-3, a small molecule inhibitor that specifically targets p53-Mdm2 interaction offers new therapeutic opportunities by enhancing cancer cell growth arrest and apoptosis through the restoration of the p53-mediated tumor suppression pathway while producing minimal cytotoxicity and side effects. This review discusses the potential use of Nutlin-3 as a p53-activating drug and the future directions of its clinical research for NPC treatment.
Particular attention has been paid to capillary electrophoresis as versatile and environmentally friendly approach for enantioseparations of a wide spectrum of compounds. Cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) is a method of choice to provide effective separation toward hydrophobic and uncharged stereoisomers. The chiral discrimination of the solutes relies upon the partitioning between a given CD in the aqueous phase and micelles formed from a surfactant. Synergistic combinations of chiral selectors, surfactant, and modifier contribute to successful enantioseparations of the enantiomers. In this chapter, an application of CD-MEKC for the enantioseparation of selected imidazole drugs employing a dual CDs system is described.
Unsymmetrically substituted sterically tuned Pd(II)–NHC complexes of the general formula [PdCl2(NHC)2] (NHC = 1-allyl-3-methylimidazolin-2-ylidene, 7; 1-allyl-3-butylimidazol-2-ylidene, 8; 1-benzyl-3-butyl imidazolin-2-ylidene, 9) were prepared through transmetallation from their corresponding Ag(I)–NHC complexes. The Pd complexes were structurally characterized by different spectroscopic and X-ray diffraction methods. Complexes 7 and 9 adopted a trans–anti arrangement of the NHC ligands, whereas complex 8 adopted a cis–syn arrangement. Preliminary antibiogram studies using Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria showed that Ag(I)–NHC complexes demonstrate higher activity compared with Pd(I)–NHC complexes. Furthermore, Pd(II)–NHC complexes were evaluated for their anticancer potential using the human colorectal cancer cell line. A higher anticancer activity was observed for complexes 8 and 9, with 26.5 and 6.6 mM IC50 values, respectively.
A facile electrochemical sandwich immunosensor for the detection of a breast cancer biomarker, the human epidermal growth factor receptor 2 (HER2), was designed, using lead sulfide quantum dots-conjugated secondary HER2 antibody (Ab2-PbS QDs) as a label. Using Ab2-PbS QDs in the development of electrochemical immunoassays leads to many advantages such as straightforward synthesis and well-defined stripping signal of Pb(II) through acid dissolution, which in turn yields better sensing performance for the sandwiched immunosensor. In the bioconjugation of PbS QDs, the available amine and hydroxyl groups from secondary anti-HER2 and capped PbS QDs were bound covalently together via carbonyldiimidazole (CDI) acting as a linker. In order to quantify the biomarker, SWV signal was obtained, where the Pb2+ ions after acid dissolution in HCl was detected. The plated mercury film SPCE was also detected in situ. Under optimal conditions, HER2 was detected in a linear range from 1-100 ng/mL with a limit of detection of 0.28 ng/mL. The measures of satisfactory recoveries were 91.3% to 104.3% for the spiked samples, displaying high selectivity. Therefore, this method can be applied to determine HER2 in human serum.
Small biomolecules play a critical role in the fundamental processes that sustain life and are essential for the proper functioning of the human body. The detection of small biomolecules has garnered significant interest in various fields, including disease diagnosis and medicine. Electrochemical techniques are commonly employed in the detection of critical biomolecules through the principle of redox reactions. It is also a very convenient, cheap, simple, fast, and accurate measurement method in analytical chemistry. Zeolitic imidazolate frameworks (ZIFs) are a unique type of metal-organic framework (MOF) composed of porous crystals with extended three-dimensional structures. These frameworks are made up of metal ions and imidazolate linkers, which form a highly porous and stable structure. In addition to their many advantages in other applications, ZIFs have emerged as promising candidates for electrochemical sensors. Their large surface area, pore diameter, and stability make them ideal for use in sensing applications, particularly in the detection of small molecules and ions. This review summarizes the critical role of small biomolecules in the human body, the standard features of electrochemical analysis, and the utilization of various types of ZIF materials (including carbon composites, metal-based composites, ZIF polymer materials, and ZIF-derived materials) for the detection of important small biomolecules in human body fluids. Lastly, we provide an overview of the current status, challenges, and future outlook for research on ZIF materials.
This work evaluates the performance of ionic liquid in supported liquid membrane (SLM) for the removal of phenol from wastewater. Ionic liquids are organic salts entirely composed of organic cations and either organic or inorganic anions. Due to the fact that the vapor pressure of ionic liquid is not detectable and they are sparingly soluble in most conventional solvents, they can be applied in SLM as the organic phase. In this work, 1-n-alkyl-3-methylimidazolium salts, [C(n)MIM](+)[X](-) have been investigated so as to determine an optimal supported ionic liquid membrane. The effect of operational parameters such as pH, stirring speed and the concentration of stripping agent has been studied, and an evaluation of different membrane supports were also carried out. With a minimal amount of the ionic liquid 1-Butyl-3-methylimidazolium hydrogensulfate, 85% phenol removal could be achieved by using polytetrafluoroethylene hydrophobic membrane filter in the SLM.
Tuning the characteristics of solvents to fit industrial requirements has currently become a major interest in both academic and industrial communities, notably in the field of room temperature ionic liquids (RTILs), which are considered one of the most promising green alternatives to molecular organic solvents. In this work, several sets of imidazolium-based ionic liquids were synthesized, and their toxicities were assessed towards four human pathogens bacteria to investigate how tunability can affect this characteristic. Additionally, the toxicity of particular RTILs bearing an amino acid anion was introduced in this work. EC50 values (50% effective concentration) were established, and significant variations were observed; although all studied ILs displayed an imidazolium moiety, the toxicity values were found to vary between 0.05 mM for the most toxic to 85.57 mM for the least toxic. Linear quantitative structure activity relationship models were then developed using the charge density distribution (σ-profiles) as molecular descriptors, which can yield accuracies as high as 95%.
Imidazolinones as a persistent and active herbicides group have potential risks to non-target organisms in the environment. Biochar is a carbon-rich sorbent used as an amendment to change soil properties and its microbial communities effective on pesticides degradation rate. The present study was the first to compare empty fruit bunch (EFB) of oil palm and rice husk (RH) biomasses as biochar feedstock for remediation of imidazolinones-contaminated soils. Degradations of imazapic, imazapyr, and a mixture of them (Onduty®) was investigated in the presence of the optimized biochars in the soil during a 70-days incubation. Based on the results, the polar herbicides were resistant to hydrolysis degradation. Photolysis rates of the herbicides reduced significantly in the presence of the biochars in the soil. EFB biochar had greater effects due to its chemical compositions and surface functional groups. Photo-degradation of imazapyr was more affected by biochars amendment. The imidazolinones bio-degradation, however, accelerated significantly with the presence of EFB and RH biochars in soil with the greater effects of RH biochar. It was concluded that the application of the optimized EFB and RH biochars as an innovative sustainable strategy has the potential to decrease the persistence of the imidazolinones and minimize their environmental hazards.
The partitioning of β-mannanase derived from Bacillus subtilis ATCC 11774 in aqueous two-phase system (ATPS) was studied. The ATPS containing different molecular weight of polyethylene glycol (PEG) and types of salt were employed in this study. The PEG/salt composition for the partitioning of β-mannanase was optimized using response surface methodology. The study demonstrated that ATPS consists of 25% (w/w) of PEG 6000 and 12.52% (w/w) of potassium citrate is the optimum composition for the purification of β-mannanase with a purification fold (PF) of 2.28 and partition coefficient (K) of 1.14. The study on influences of pH and crude loading showed that ATPS with pH 8.0 and 1.5% (w/w) of crude loading gave highest PF of 3.1. To enhance the partitioning of β-mannanase, four ionic liquids namely 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4), 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF4), 1-butyl-3-methylimidazolium bromide ([Bmim]Br), 1-ethyl-3-methylimidazolium bromide ([Emim]Br) was added into the system as an adjuvant. The highest recovery yield (89.65%) was obtained with addition of 3% (w/w) of [Bmim]BF4. The SDS-PAGE analysis revealed that the β-mannanase was successfully recovered in the top phase of ATPS with the molecular size of 36.7kDa. Therefore, ATPS demonstrated a simple and efficient approach for recovery and purification of β-mannanase from fermentation broth in one single-step strategy.
The aim of this study was to investigate and apply supported ionic liquid membrane (SILM) in two-phase micro-electrodriven membrane extraction combined with high performance liquid chromatography-ultraviolet detection (HPLC-UV) for pre-concentration and determination of three selected antidepressant drugs in water samples. A thin agarose film impregnated with 1-hexyl-3-methylimidazolium hexafluorophosphate, [C6MIM] [PF6], was prepared and used as supported ionic liquid membrane between aqueous sample solution and acceptor phase for extraction of imipramine, amitriptyline and chlorpromazine. Under the optimized extraction conditions, the method provided good linearity in the range of 1.0-1000μgL(-1), good coefficients of determination (r(2)=0.9974-0.9992) and low limits of detection (0.1-0.4μgL(-1)). The method showed high enrichment factors in the range of 110-150 and high relative recoveries in the range of 88.2-111.4% and 90.9-107.0%, for river water and tap water samples, respectively with RSDs of ≤7.6 (n=3). This method was successfully applied to the determination of the drugs in river and tap water samples. It is envisaged that the SILM improved the perm-selectivity by providing a pathway for targeted analytes which resulted in rapid extraction with high degree of selectivity and high enrichment factor.
Hepatitis B core antigen (HBcAg) is used as a diagnostic reagent for the detection of hepatitis B virus infection. In this study, immobilized metal affinity-expanded bed adsorption chromatography (IMA-EBAC) was employed to purify N-terminally His-tagged HBcAg from unclarified bacterial homogenate. Streamline Chelating was used as the adsorbent and the batch adsorption experiment showed that the optimal binding pH of His-tagged HBcAg was 8.0 with a binding capacity of 1.8 mg per ml of adsorbent. The optimal elution condition for the elution of His-tagged HBcAg from the adsorbent was at pH 7 in the presence of 500 mM imidazole and 1.5 M NaCl. The IMA-EBAC has successfully recovered 56% of His-tagged HBcAg from the unclarified E. coli homogenate with a purification factor of 3.64. Enzyme-linked immunosorbent assay (ELISA) showed that the antigenicity of the recovered His-tagged HBcAg was not affected throughout the IMA-EBAC purification process and electron microscopy revealed that the protein assembled into virus-like particles (VLP).
Sildenafil and its analogues (tadalafil and vardenafil) are phosphodiesterase type 5 inhibitors used in the treatment of male erectile dysfunction. Some dietary supplements, herbal preparations and food products which claim to enhance male sexual function have been found to be adulterated with these drugs. In this study, a gas chromatograph-mass spectrometer (GC-MS) assay was developed for identification of the drugs. In addition to good and short chromatographic separation that can be achieved within 6 min by using a short 10 m capillary column, no prior sample clean-up before GC-MS analysis was required, thus making this assay a cost saving and rapid method. Furthermore, the assay is specific as the identification of sildenafil, tadalafil and vardenafil were done by detection of molecular ions; m/z 474, 389 and 488, [corrected] respectively, and several other characteristic ions resulted from the mass fragmentation of individual molecules. Using our currently developed assay, sildenafil and its analogues were successfully identified in food and herbal matrices.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
In this study, novel nanocomposite films based on regenerated cellulose/halloysite nanotube (RC/HNT) have been prepared using an environmentally friendly ionic liquid 1-butyl-3-methylimidazolium chloride (BMIMCl) through a simple green method. The structural, morphological, thermal and mechanical properties of the RC/HNT nanocomposites were investigated using X-ray diffraction (XRD), Fourier transform infrared (FTIR), field emission scanning electron microscopy (FESEM), thermal analysis and tensile strength measurements. The results obtained revealed interactions between the halloysite nanotubes and regenerated cellulose matrix. The thermal stability and mechanical properties of the nanocomposite films, compared with pure regenerated cellulose film, were significantly improved When the halloysite nanotube (HNT) loading was only 2 wt.%, the 20% weight loss temperature (T20) increased 20°C. The Young's modulus increased from 1.8 to 4.1 GPa, while tensile strength increased from 35.30 to 60.50 MPa when 8 wt.% halloysite nanotube (HNT) was incorporated, interestingly without loss of ductility. The nanocomposite films exhibited improved oxygen barrier properties and water absorption resistance compared to regenerated cellulose.