LC-MS/MS method for the simultaneous quantification of pyriproxyfen and bifenthrin and their dissipation kinetics under field conditions in chili and brinjal.

Bifenthrin, a synthetic pyrethroid, and pyriproxyfen, a plant growth regulator, are used extensively in agriculture for controlling the different insect pests. The present study was undertaken to examine the dissipation behavior of a formulation with a combination of pyriproxyfen and bifenthrin on chili and brinjal under field conditions at four different locations. Dissipation study of combination of pyriproxyfen and bifenthrin revealed swift degradation in both crops with a half-life of 2.5-2.6 and 2.0-2.1 days in brinjal and chili, respectively. Also, a simple method for simultaneous quantification of pyriproxyfen and bifenthrin was developed and validated using modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) technique on liquid chromatography with tandem mass spectrometry (LC-MS/MS). Recovery of the method was found to be under an acceptable range of 90.0%-93.5% and 88.7%-94.3% in chili and 92.4%-96.6% and 97.4%-100.9% in brinjal for pyriproxyfen and bifenthrin, respectively. At harvest time, the terminal residues of bifenthrin and pyriproxyfen were below the maximum residue limits set by European Union in chili and brinjal, respectively, suggesting that the use of this pesticide formulation is safe and does not impose harmful effects on human health. PRACTICAL APPLICATION: In this paper, dissipation behavior of a pesticide formulation with a combination of pyriproxyfen and bifenthrin was undertaken under field conditions at four different locations on chili and brinjal in India. The simultaneous quantification of pyriproxyfen and bifenthrin using LC-MS/MS technique has been validated incorporating modified QuEChERS extraction method with limit of detection at 0.005 µg/g and limit of quantification at 0.01 µg/g, which is well below the EU-MRLs (European Union legislation Maximum Residue Level) of pyriproxyfen and bifenthrin in both chili and brinjal. Furthermore, dissipation kinetics of a formulation undertaken under field conditions at four different locations on chili and brinjal suggested that the terminal residues of both bifenthrin and pyriproxyfen were below the maximum residue limits set by European Union in chili and brinjal, respectively, at the time of harvest and that the use of this pesticide formulation is safe.

Extended Release of Metronidazole Drug Using Chitosan/Graphene Oxide Bionanocomposite Beads as the Drug Carrier.

This study depicts the facile approach for the synthesis of chitosan/graphene oxide bionanocomposite (Chi/GO) beads via the gelation process. This is the first-ever study in which these Chi/GO beads have been utilized as a drug carrier for the oral drug delivery of metronidazole (MTD) drug, and investigations were made regarding the release pattern of the MTD drug using these Chi/GO beads as a drug carrier for a prolonged period of 84 h. The MTD is loaded on the surface as well as the cavity of the Chi/GO beads to result in MTD-Chi/GO bionanocomposite beads. The MTD drug loading was found to be 683 mg/g. Furthermore, the in vitro release patterns of pure drug and the drug encapsulated with Chi/GO beads are explored in simulated gastric as well as simulated intestinal fluids with phosphate-buffered saline (PBS) of pH 1.2 and 7.4, respectively. As-synthesized bionanocomposite beads have shown excellent stability and capacity for extended release of the MTD drug as compared to the pure drug in terms of bioavailability in both media. The cumulative release data are fitted with the Korsmeyer-Peppas kinetics and first-order reaction kinetics at pH 1.2 and 7.4. The synthesized bionanocomposite beads have good potential to minimize the multiple-dose frequency with the sustained drug release property and can reduce the side effects due to the drug.

Ruthenium oxide nanoparticles immobilized over Citrus limetta waste derived carbon material for electrochemical detection of hexestrol.

Hexestrol is a non-steroidal estrogen which causes carcinogenic effects in animals. It is therefore important to develop sensitive and selective test methods for its early detection. Herein, we report the development of an electrochemical sensor to detect hexestrol in ultralow concentrations. In order to devise a simple and cost-effective hexestrol sensing electrode, attention is paid to the development of biomass-derived porous carbon (PCB) with large surface area and suitable porosity to immobilize ruthenium oxide nanoparticles (RuO2 NPs, 3-4 nm). The leftover Citrus limetta pulp is chosen as waste biomass since it has N and O based chemical species. Structural, morphological and compositional analysis of PCB and RuO2@PCB revealed well-dispersed RuO2 NPs over the PCB surface. High loading (5.27 at%) of Ru content is achieved due to the large surface area of PCB. Cyclic voltammetry, chronoamperometry and differential pulse voltammetry results suggest that the RuO2@PCB/ITO electrode is capable of detecting hexestrol concentration (in the range of 1 × 10-7-2 × 10-5 M). The practical application of hexestrol detection in milk samples demonstrates the recovery from 96.28 to 101%.

Insulin-induced conformational transition of fluorescent copolymers: a perspective of self-assembly between protein and micellar solutions of smart copolymers.

Synthesizing and understanding phase transition behavior of novel block copolymers is very crucial for fabricating next generation of smart materials with foreseeable applications. In this regard, we synthesized three random (r) copolymers of poly(N-vinyl-caprolactam) (PVCL) and poly(2-dimethyl amino ethyl methacrylate) (PDMAEMA) with varying percentages of each block and characterized them using nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) patterns, time-resolved fluorescence spectroscopy, and atomic force microscopy (AFM). Synthesized copolymers i.e. PVCL30-PDMAEMA70, PVCL50-PDMAEMA50 and PVCL70-PDMAEMA30 have fluorescence properties, which were confirmed by time-resolved fluorescence spectra and emission spectra, and emission bands were observed at ∼310, ∼435 and ∼424 nm, respectively. The fluorescence lifetime for PVCL50-PDMAEMA50 is larger than those of the other two copolymers suggesting a slow decay of the excited state. The copolymers have spherical geometry as micelles, which were confirmed by TEM. We observed patterned arrangement of micelles and the arranged micelles appear to be pentagon in shape, creating space in between the arranged micelles; however, for PVCL50-PDMAEMA50, the arranged micelles do not form any particular shape. The thermal phase transition of PVCL-r-PDMAEMA in aqueous solution was studied by differential scanning calorimetry and thermal fluorescence spectroscopy. In order to design a biomimetic polymer for bio-specific applications and to understand novel concepts towards polymer-protein interactions, we studied the effect of insulin on lower critical solution temperature (LCST) of PVCL-r-PDMAEMA using multiple sophisticated techniques. The LCST is finely tuned by incorporation of two blocks with various block compositions and the value falls within the range of human body temperature, making PVCL50-PDMAEMA50 a highly compatible material for bio-medical and bio-material applications. Insulin forms a self-assembly with the monomers of PVCL-r-PDMAEMA, which leads to enhancing the micellar aggregates and the eventual decrease in the LCST of the diblock copolymer aqueous solution. The present study provides new insights into insulin-copolymer interactions and can be used for self-assembling nanocarriers and designing protein resistance surfaces.

NiO nanocomposites/rGO as a heterogeneous catalyst for imidazole scaffolds with applications in inhibiting the DNA binding activity.

Herein, we report a facile approach to synthesize a new highly versatile heterogeneous catalyst by spontaneous aerial oxidation based on nickel oxide nanocomposites immobilized on surface-functionalized reduced graphene oxide sheets. NiO nanocomposite/reduced graphene oxide (rGO-NiO-NC) is a highly efficient, cost-effective, reusable, selective, and eco-friendly nano-catalyst that does not lose any activity even after five reaction cycles. Nickel loading on the rGO-NiO nanocomposite was found to be 3.3 at%, which contributes to the effective and efficient use of rGO-NiO-NCs as a nano-catalyst for the synthesis of imidazole derivatives. Consequently, a series of imidazole derivatives were synthesized, catalyzed by rGO-NiO-NCs, in 60 min with high yields (86% to 96%) under green conditions. Furthermore, the present synthetic methodology was used for the synthesis of highly aromatic imidazole derivatives (B1-B3) whose calf thymus-DNA binding affinities suggest their superior inhibition ability to displace ethidium bromide (EB), which was further confirmed by molecular docking studies. Additionally, the green chemistry matrix of the synthesis reaction was found to be very close to ideal values, such as carbon efficiency (82.32%), E-factor (0.51), atom economy (77.86%), process mass intensity (1.51), and reaction mass efficiency (66.14%).

Sustainable Solvothermal Conversion of Waste Biomass to Functional Carbon Material: Extending Its Utility as a Biocompatible Cosolvent for Lysozyme.

Functional carbon material synthesis from waste biomass by a sustainable method is of prime importance and has wide variety of applications. Herein, functional carbon materials with structural variability are synthesized using a well-known solvothermal method. The leftover pulp waste biomass (PB) of citrus limetta is converted to functional carbon by treatment with a mixture of choline bitartrate (ChBt) and FeCl3 (1:2 mol ratio) as a solvent. The biomass to solvent ratio is varied as 1:1, 0.8:1, and 0.4:1 during solvothermal treatment to obtain PB-1, PB-2, and PB-3 as functional carbon materials, respectively. On characterization, PB carbon materials were found to be rich in oxygen-containing functional groups possessing different morphologies. Furthermore, results suggested the role of solvent as a soft template and catalyst during the synthesis of carbon materials. The feasibility of synthesized carbon materials as a biocompatible cosolvent for lysozyme was evaluated. In the case of PB-2 material (synthesized using 0.8:1 biomass to solvent ratio), results show an enhancement of lysozyme activity by 150%. Besides, spectroscopic and calorimetric data confirm the preservation of thermal and structural stability of lysozyme in the PB-2 solution. Thus, this study stipulates PB-2 as an excellent cosolvent for protein studies. With this work, we aim to delve into an entirely new arena of applications of biomass in the field of biotechnology.

A biophysical strategy to examine the impact of newly synthesized polymerizable ammonium-based ionic liquids on the structural stability and proteolytic activity of stem bromelain.

The present manuscript reports the synthesis and characterization of polymerizable ammonium-based ionic liquids (ILs) and explores their influence on structural stability of stem bromelain (BMN) by using various biophysical techniques. Thermal fluorescence results showed that N-ethyl-2-(methylacryloyloxy)-N,N-dimethylethan-1-ammonium bromide (IL2C) (at lower concentration (0.1 mg/mL)) is found to be increasing the thermal stability of BMN which can be evident from the transition temperature (Tm) for BMN in IL2C (68.51 °C) is higher than BMN in buffer (66.24 °C). Whereas, N-(2-(methacryloyloxy)ethyl)-N,N-dimethylpropan-1-ammonium bromide (IL3C) and N-(2-(methacryloyloxy)ethyl)-N,N-dimethylpentan-1-ammonium bromide (IL5C) are maintaining the Tm values very near to Tm of pure BMN. Though, N-(2-(methacryloyloxy)ethyl)-N,N-dimethylhexan-1-ammonium bromide (IL6C) is found to be destabilizing IL as it significantly decreased the Tm value of BMN at all concentrations. Additionally, consequence of ILs on the proteolytic activity of BMN has also performed for IL2C up to 5 mg/mL while IL3C and IL5C at 0.1 mg/mL and 0.5 mg/mL are enhancing the proteolytic activity of BMN. Later, molecular docking studies are also performed with AutoDock vina and results showed that all ILs have different binding sites on BMN however IL6C is observed to be binding to the catalytic site of the BMN, it turns out to be the most destabilizing IL.

Structure, DNA/proteins binding, docking and cytotoxicity studies of copper(II) complexes with the first quinolone drug nalidixic acid and 2,2'­dipyridylamine.

This work presents the synthesis, structural characterization and biological affinity of the newly synthesized copper(II) complexes with the first antibacterial quinolone drug nalidixic acid (nal) or N-donor ligand 2,2'­dipyridylamine (bipyam). [Cu(II)(nal)(bipyam)Cl], (2) reveals a distorted square pyramidal based geometry in Cu(II) atom confirmed by X-ray crystallography technique. The theoretical stabilities and optimized structures of the complex were obtained from DFT calculations. The ability of the complexes to bind with calf thymus DNA (CT DNA) were investigated by electronic absorption, fluorescence, circular dichroism, and viscosity measurements techniques. The experimental results reveal that the complexes strongly interact with CT DNA via intercalative mode but complex 2 exhibits the highest affinity giving Kb=3.91±0.13×106, M-1. The fluorescence spectroscopy measurements show that both complexes have the superior ability to the replacement of EtBr from DNA-bound EtBr solution and bind to DNA through intercalative mode. Both complex also shows the superior affinity towards proteins with comparatively high binding constant values which have been further revealed by fluorescence spectroscopy measurements. Molecular docking analysis indicates that the interaction of the complexes and proteins are stabilized by hydrogen bonding and hydrophobic interaction. Furthermore, the results of in vitro cytotoxicity reveal that the complex 2 has excellent cytotoxicity than 1 against human breast cancer cell lines (MCF-7).

Insight into impact of choline-based ionic liquids on bovine ß-lactoglobulin structural analysis: Unexpected high thermal stability of protein.

In this present work, we report the effects of different concentrations of various cholinium-based ionic liquids (ILs) on the structural and thermal stability of ß-lactoglobulin (ß-LG). Results indicated that anions in ILs have played an important role in affecting the thermal and structural stability of ß-LG. Biomolecular interactions between ß-LG and ILs are carried out by differential scanning calorimetry (DSC), different spectroscopic and dynamic light scattering (DLS). Analysis of experimental data revealed that an excellent thermal stability of ß-LG is obtained in presence of choline dihydrogen phosphate [Chn][Dhp] and choline bitartrate [Chn][Bit] where Tm value of ß-LG increased to 93.58 and 93.22 °C, respectively, as compared to Tm of ß-LG in buffer at 72.48 °C. Similarly, in presence of choline acetate [Chn][Ac] and choline chloride [Chn][Cl] thermal stability of ß-LG also increased, however, it was not possible to calculate Tm values in case of choline iodide [Chn][I], because of obtaining two endothermic peaks in DSC curves. On the other hand, choline hydroxide [Chn][OH] acts as complete destabilizer for ß-LG native structure as no Tm is obtained in its presence. The obtained results are further confirmed by estimating the thermodynamic parameters such as Gibbs free energy of unfolding (ΔuG), enthalpy of unfolding (ΔuH), heat capacity change (ΔCp) and total entropy change during protein unfolding (ΔuS). Molecular docking studies of ß-LG and various choline-based ILs are also performed to know the probable binding conformations using AutoDock Vina and AutoDock tools 1.5.6, results obtained are in correlation with spectroscopic and biothermodynamic data. The combined study by DSC, spectroscopy techniques and molecular docking studies suggest that some of these ILs can be used as industrial green solvents for different biocatalytic processes and also can help in resolving the problems involving protein unfolding and thermal stability studies.

Effect of Imidazolium-Based Ionic Liquids on the Structure and Stability of Stem Bromelain: Concentration and Alkyl Chain Length Effect.

In the present work, changes in the structure and stability of stem bromelain (BM) are observed in the presence of a set of four imidazolium-based ionic liquids (ILs) such as 1-ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), 1-hexyl-3-methylimidazolium chloride ([Hmim][Cl]), and 1-decyl-3-methylimidazolium chloride ([Dmim][Cl]), using various biophysical techniques. Fluorescence spectroscopy is used to observe the changes taking place in the microenvironment around the tryptophan (Trp) residues of BM and its thermal stability because of its interactions with the ILs at different concentrations. Near-UV circular dichroism results showed that the native structure of BM remained preserved only at lower concentrations of ILs. In agreement with these results, dynamic light scattering revealed the formation of large aggregates of BM at higher concentrations of ILs, indicating the unfolding of BM. In addition to this, the results also show that higher alkyl chain length imidazolium-based ILs have a more denaturing effect on the BM structure as compared to the lower alkyl chain length ILs because of the increased hydrophobic interaction between the ILs and the BM structure. Interestingly, it is noted that low concentrations (0.01-0.10 M) of short alkyl chain ILs only alter the structural arrangement of the protein without any significant effect on its stability. However, high concentrations of all five ILs are found to disrupt the structural stability of BM.

Reduced graphene oxide nanoribbon immobilized gold nanoparticle based electrochemical DNA biosensor for the detection of Mycobacterium tuberculosis.

Tuberculosis is one of the most dreadful diseases caused by Mycobacterium tuberculosis with more than 9 million individuals suffering from it in 2014. Traditional methods of detection are not efficient enough for its quick and reliable detection; therefore, it is imperative to develop methods of its detection in the early stages. Consequently, we report a highly sensitive and selective biosensor for detection of Mycobacterium tuberculosis. In this work, gold nanoparticles (AuNPs, dia. ∼6 nm, 1.81 wt% loading) are immobilized over reduced graphene oxide nanoribbons (RGONRs). An ssDNA/Au/RGONR electrode is prepared by immobilizing Au nanoparticles followed by covalent modification of Au nanoparticles with 5'SH-ssDNA. As per the best knowledge of the authors, the target DNA of Mycobacterium tuberculosis is detected using a ssDNA/Au/RGONR bioelectrode by cyclic voltammetry and chronoamperometric methods for the first time. With high detection efficiency (0.1 fM), the ssDNA/Au/RGONR bioelectrode exhibited better signal amplification and electrochemical response as compared to bare Au and RGONR electrodes. Additionally, the ssDNA/Au/RGONR bioelectrode displayed good linear response to different concentrations of target M. tuberculosis DNA. The ssDNA/Au/RGONR has shown excellent specificity (92%) to Mycobacterium tuberculosis target DNA as compared with non-complementary DNA. The Au/RGONR matrix has the potential to be used as an immobilization platform for single-stranded probe DNAs of different diseases other than tuberculosis reported here.

Fur-Imine-Functionalized Graphene Oxide-Immobilized Copper Oxide Nanoparticle Catalyst for the Synthesis of Xanthene Derivatives.

Fur-imine-functionalized graphene oxide-immobilized copper oxide nanoparticles (Cu(II)-Fur-APTES/GO) are synthesized and found to be a cost-effective, efficient, and reusable heterogeneous nanocatalyst for the preparation of pharmaceutically important xanthene derivatives under greener solvent conditions. Cu(II)-Fur-APTES/GO exhibits excellent result in the synthesis of xanthenes with reduced reaction time (25-50 min) and higher yields (up to 95%) and has a simple procedure, ease of product separation, and no byproducts. Moreover, the nanocatalyst has a Cu loading of 13.5 at. % over functionalized GO which is far superior than the already known metal-based heterogeneous catalysts. The newly synthesized catalyst has been characterized by various physiochemical techniques such as X-ray photoelectron spectroscopy, X-ray diffraction, energy-dispersive X-ray, Raman spectroscopy for structural characterization, field emission scanning electron microscopy and high-resolution transmission electron microscopy for morphological characterization. The catalyst showed admirable recyclability up to five consecutive runs, and there was no appreciable loss in catalytic efficiency.

La2O3/Reduced Graphene Oxide Nanocomposite: A Highly Efficient, Reusable Heterogeneous Catalyst for the Synthesis of Biologically Important Bis(indolyl)methanes Under Solvent Free Conditions.

Synthesis and characterization of Lanthanum Oxide-reduced graphene oxide (La2O3/RGO) nanocomposite and its application as heterogeneous, reusable catalyst has been reported in this article. Biologically important molecules bis(indolyl)methanes are synthesized in mild reaction condition with excellent yield under solvent free condition. Catalyst was reused for four times without any significant changes in the yields obtained. Reusability, green synthesis and environmentally benign nature makes La2O3/RGO one of the best catalyst for the synthesis of biologically important bis(indolyl)methanes.

Metal complex of the first-generation quinolone antimicrobial drug nalidixic acid: structure and its biological evaluation.

A novel binuclear squire planar complex of nalidixic acid with Ag(I) metal ion with the formula [Ag(Nal)2] has been synthesized. The synthesized metal complex was characterized using CHN analysis, Fourier-transformed infra-red (FT-IR), thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), ultra violet-visible (Uv-vis) and single-crystal X-ray diffraction (XRD). The newly synthesized complex shows more advanced antifungal activity compared to the parent quinolone against four fungi, namely Pythium aphanidermatum, Sclerotinia rolfsii, Rhizoctonia solani and Rhizoctonia bataticola.

Sensitive and reliable ascorbic acid sensing by lanthanum oxide/reduced graphene oxide nanocomposite.

A simple strategy for the detection and estimation of ascorbic acid (AA), using lanthanum oxide-reduced graphene oxide nanocomposite (LO/RGO) on indium tin oxide (ITO) substrate, is reported. LO/RGO displays high catalytic activity toward the oxidation of AA, and the synergism between lanthanum oxide and reduced graphene oxide was attributed to the successful and efficient detection. Detection mechanism and sensing efficacy of LO/RGO nanocomposite are investigated by electrochemical techniques. Chronoamperometric results under optimal conditions show a linear response range from 14 to 100 µM for AA detection. Commercially available vitamin C tablets were also analyzed using the proposed LO/RGO sensor, and the remarkable recovery percentage (97.64-99.7) shows the potential application in AA detection.