Removal of methylene blue and azo reactive dyes from aqueous solution and textile effluent via modified pulsed low-frequency ultrasound cavitation process.

Organic dyes in the aqueous solutions and textile effluents cause severe environmental pollution due to their carcinogenic and mutagenic nature. Ultrasound (US) cavitation is one of the promising advanced oxidation processes (AOP) to remove the organic dyes from the aqueous solutions and textile effluents. Nevertheless, the conventional low-frequency US cavitation process exhibits very low efficiency in the dye removal process and demands effective modification to improve its performance. In this investigation, a conventional pulsed low-frequency (22 ± 2 kHz) US cavitation process has been modified by varying the US power (50-150 W), initial solution pH (2-10), and O2 flow rate (1-4 L min-1) to enhance the decomposition of cationic methylene blue (MB) dye in an aqueous solution. The operation of the classic Haber-Weiss reaction, both in the forward and backward directions, and the ozone effect have been observed, for the first time, under the modified US cavitation process, as confirmed via the radical trapping experiments. Moreover, the hydrothermally synthesized hydrogen titanate (H2Ti3O7) nanotubes (HTN) have been utilized as sonocatalyst, for the first time, for 100% dye removal, with effective regeneration obtained via an in-situ thermal activation of persulfate (PS, S2O82-). The most optimum values of US power, initial solution pH, O2 flow rate, HTN, and PS concentrations for 100% MB decomposition are observed to be 150 W, 2, 2 L min-1, 0.3 g L-1, and 10 mM, respectively. The decomposition of industrial azo reactive dyes in an aqueous solution as well as in a textile effluent has also been demonstrated using a modified pulsed low-frequency US cavitation process involving the thermal activation of PS without the use of HTN, which justifies its suitability for a commercial application.

Catalytic dye degradation by novel phytofabricated silver/zinc oxide composites.

Phytofabrication of the nanoparticles with exotic shape and size is an attractive area where nanostructures with noteworthy physicochemical and optoelectronic properties that can be significantly employed for photocatalytic dye degradation. In this study a medicinal plant, Plumbago auriculata leaf extract (PALE) was used to synthesize zinc oxide particles (ZnOPs) and silver mixed zinc oxide particles (ZnOAg1Ps, ZnOAg10Ps, ZnO10Ag1Ps) by varying the concentration of the metal precursor salts, i.e. zinc acetate and silver nitrate. The PALE showed significantly high concentrations of polyphenols, flavonoids, reducing sugar, starch, citric acid and plumbagin up to 314.3 ± 0.33, 960.0 ± 2.88, 121.3 ± 4.60, 150.3 ± 3.17, 109.4 ± 2.36, and 260.4 ± 8.90 µg/ml, respectively which might play an important role for green synthesis and capping of the phytogenic nanoparticles. The resulting particles were polydispersed which were mostly irregular, spherical, hexagonal and rod like in shape. The pristine ZnOPs exhibited a UV absorption band at 352 nm which shifted around 370 in the Ag mixed ZnOPs with concomitant appearance of peaks at 560 and 635 nm in ZnO10Ag1Ps and ZnOAg1Ps, respectively. The majority of the ZnOPs, ZnOAg1Ps, ZnOAg10Ps, and ZnO10Ag1Ps were 407, 98, 231, and 90 nm in size, respectively. Energy dispersive spectra confirmed the elemental composition of the particles while Fourier transform infrared spectra showed the involvement of the peptide and methyl functional groups in the synthesis and capping of the particles. The composites exhibited superior photocatalytic degradation of methylene blue dye, maximum being 95.7% by the ZnOAg10Ps with a rate constant of 0.0463 s-1 following a first order kinetic model. The present result clearly highlights that Ag mixed ZnOPs synthesized using Plumbago auriculata leaf extract (PALE) can play a critical role in removal of hazardous dyes from effluents of textile and dye industries. Further expanding the application of these phytofabricated composites will promote a significant complementary and alternative strategy for treating refractory pollutants from wastewater.

Leucophyllum frutescens mediated synthesis of silver and gold nanoparticles for catalytic dye degradation.

The application of nanotechnology is gaining worldwide attention due to attractive physico-chemical and opto-electronic properties of nanoparticles that can be also employed for catalytic dye degradation. This study reports a phytogenic approach for fabrication of silver (AgNPs) and gold nanoparticles (AuNPs) using Leucophyllum frutescens (Berl.) I. M. Johnst (Scrophulariaceae) leaf extract (LFLE). Development of intense dark brown and purple color indicated the synthesis of AgNPs and AuNPs, respectively. Further characterization using UV-visible spectroscopy revealed sharp peak at 460 nm and 540 nm for AgNPs and AuNPs, respectively that were associated to their surface plasmon resonance. High resolution transmission electron microscope (HRTEM) revealed the spherical shape of the AgNPs, whereas anisotropic AuNPs were spherical, triangular and blunt ended hexagons. The majority of the spherical AgNPs and AuNPs were ∼50 ± 15 nm and ∼22 ± 20 nm, respectively. Various reaction parameters such as, metal salt concentration, temperature and concentration of the leaf extract were optimized. Maximum synthesis of AgNPs was obtained when 5 mM for AgNO3 reacted with 10% LFLE for 48 h at 50°C. Likewise, AuNPs synthesis was highest when 2 mM HAuCl4 reacted with 10% LFLE for 5 h at 30°C. Energy dispersive spectroscopy (EDS) showed phase purity of both the nanoparticles and confirmed elemental silver and gold in AgNPs and AuNPs, respectively. The average hydrodynamic particles size of AgNPs was 34.8 nm while AuNPs was 140.8 nm as revealed using dynamic light scattering (DLS) that might be due to agglomeration of smaller nanoparticles into larger clusters. ZETA potential of AgNPs and AuNPs were 0.67 mV and 5.70 mV, respectively. X-ray diffraction (XRD) analysis confirmed the crystallinity of the nanoparticles. Fourier transform infrared spectroscopy (FTIR) confirmed that various functional groups from the phytochemicals present in LFLE played a significant role in reduction and stabilization during the biogenic synthesis of the nanoparticles. The bioreduced AgNPs and AuNPs catalytically degraded Rhodamine B dye (RhB) in presence of UV-light with degradation rate constants of 0.0231 s-1 and 0.00831 s-1, respectively. RhB degradation followed a first order rate kinetics with 23.1 % and 31.7% degradation by AgNPs and AuNPs, respectively.

Autoclave and pulsed ultrasound cavitation based thermal activation of persulfate for regeneration of hydrogen titanate nanotubes as recyclable dye adsorbent.

In the dye removal application, regeneration of hydrogen titanate nanotubes (HTN, H2Ti3O7) has been achieved via thermal activation of persulfate anion (PS, S2O82-) by using the conventional hot plate technique which has limitations from the commercial perspective since it does not provide any precise control over the thermal generation process typically during the scale-up operation. To overcome this drawback, HTN have been synthesized via hydrothermal process which exhibit the methylene blue (MB) adsorption of 93% at the initial dye concentration and solution pH of 90 µM and 10 respectively. HTN have been regenerated via the thermal activation of PS by varying its initial concentration and regeneration temperature, within the range of 0.27-1 wt% and 40-80 °C, under the thermal conditions set by the autoclave and pulsed ultrasound (US) cavitation process. The results of recycling experiments suggest that the optimum values of initial PS concentration and temperature, for the regeneration of HTN under the autoclave conditions, are 1 wt% and 70 °C with the maximum MB adsorption of 92%, while, the corresponding values for the pulsed US cavitation process are 1 wt%, 80 °C, and 91% respectively. Thus, the regeneration and recycling of HTN have been successfully demonstrated by using the autoclave and pulsed US cavitation process. Under the optimum conditions, MB degradation involves the generation and attack of SO4•- for both the thermal generation techniques. The regeneration techniques developed here may be utilized in future during the scale-up operation and also for the regeneration of adsorbents besides HTN.

Hydrophilic 3D Interconnected Network of Bacterial Nanocellulose/Black Titania Photothermal Foams as an Efficient Interfacial Solar Evaporator.

The design and development of scalable, efficient photothermal evaporator systems that reduce microplastic pollution are highly desirable. Herein, a sustainable bacterial nanocellulose (BNC)-based self-floating bilayer photothermal foam (PTFb) is designed that eases the effective confinement of solar light for efficient freshwater production via interfacial heating. The sandwich nanoarchitectured porous bilayer solar evaporator consists of a top solar-harvesting blackbody layer composed of broad-spectrum active black titania (BT) nanoparticles embedded in the BNC matrix and a thick bottom layer of pristine BNC for agile thermal management, the efficient wicking of bulk water, and staying afloat. A decisive advantage of the BNC network is that it enables the fabrication of a lightweight photothermal foam with reduced thermal conductivity and high wet strength. Additionally, the hydrophilic three-dimensional (3D) interconnected porous network of BNC contributes to the fast evaporation of water under ambient solar conditions with reduced vaporization enthalpy by virtue of intermediated water generated via a BNC-water interaction. The fabricated PTFb is found to yield a water evaporation efficiency of 84.3% (under 1054 W m-2) with 4 wt % BT loading. Furthermore, scalable PTFb realized a water production rate of 1.26 L m-2 h-1 under real-time conditions. The developed eco-friendly BNC-supported BT foams could be used in applications such as solar desalination, contaminated water purification, extraction of water from moisture, etc., and thus could address one of the major present-day global concerns of drinking water scarcity.

Quinoline appended pillar[5]arene (QPA) as Fe3+ sensor and complex of Fe3+ (FeQPA) as a selective sensor for F-, arginine and lysine in the aqueous medium.

A quinoline functionalized pillar[5]arene, QPA has been prepared and its interaction with biologically relevant ions and molecules in aqueous solution has been demonstrated. The sensor molecule, QPA has shown selectivity towards Fe3+ among eleven metal ions studied. The Fe3+ complex of QPA (FeQPA) selectively interacts with F- among halides by ∼4 fold fluorescence enhancement. Further, FeQPA has shown selectivity towards arginine and lysine among twenty naturally occurring amino acids. The binding of QPA with Fe3+ has been confirmed by MALDI-TOF and 1H NMR titrations.

Multifunctional Photostable Nanocomplex of ZnO Quantum Dots and Avobenzone via the Promotion of Enolate Tautomer.

Ideal multifunctional ultraviolet radiation (UVR) absorbents with excellent photostability, high molar absorptivity, broadband UVR screening, and desired skin sensorial properties remain a significant challenge for the sunscreen industry. The potential of the nanocomplex (NCx) formed by microwave synthesis of ZnO quantum dots (QDs) in the presence of Avobenzone (Av) for achieving these goals is reported. The NCx exhibits unique synergy between ZnO QD and Av components, which enhances the photostability and molar absorptivity, extends UVA filtering range, and provides a visible emission that matches the typical human in vivo skin emission color. Density functional theory (DFT) and time-dependent DFT calculations of ZnO-Av hybrid structures and comparison of their spectroscopic features with experiments suggest that ZnO QDs catalyze the formation of highly photostable surface enolate species via aldol condensation reaction. The combination of experiments and computations used in this study can advance the science and technology of photoprotection.

Surface defect rich ZnO quantum dots as antioxidants inhibiting α-amylase and α-glucosidase: a potential anti-diabetic nanomedicine.

Preventing chronic hyperglycaemia and associated oxidative stress is utmost important for the treatment and management of Type 2 Diabetes Mellitus (T2DM). Here we report the role of different size surface defect rich ZnO quantum dots (D-QDs) for inhibiting metabolic enzymes and scavenging free radicals, which plays a key role in reducing hyperglycaemia and oxidative stress. Quantitative analysis of radical scavenging and metabolic enzyme inhibition activity of D-QDs demonstrates a size dependent behaviour, where D-QDs with a smaller diameter shows superior activity compared to larger size D-QDs. Considering the size dependence in surface defect formation, the increased surface defect density in smaller size D-QDs can be considered as the reason behind this enhancement. Detailed studies establishing the underlying mechanism behind potent free radical scavenging and enzyme inhibition provides an intense scientific rationale for considering D-QDs to design safe and effective nanomedicine for T2DM.

Diosgenin from Dioscorea bulbifera: novel hit for treatment of type II diabetes mellitus with inhibitory activity against α-amylase and α-glucosidase.

Diabetes mellitus is a multifactorial metabolic disease characterized by post-prandial hyperglycemia (PPHG). α-amylase and α-glucosidase inhibitors aim to explore novel therapeutic agents. Herein we report the promises of Dioscorea bulbifera and its bioactive principle, diosgenin as novel α-amylase and α-glucosidase inhibitor. Among petroleum ether, ethyl acetate, methanol and 70% ethanol (v/v) extracts of bulbs of D. bulbifera, ethyl acetate extract showed highest inhibition upto 72.06 ± 0.51% and 82.64 ± 2.32% against α-amylase and α-glucosidase respectively. GC-TOF-MS analysis of ethyl acetate extract indicated presence of high diosgenin content. Diosgenin was isolated and identified by FTIR, 1H NMR and 13C NMR and confirmed by HPLC which showed an α-amylase and α-glucosidase inhibition upto 70.94 ± 1.24% and 81.71 ± 3.39%, respectively. Kinetic studies confirmed the uncompetitive mode of binding of diosgenin to α-amylase indicated by lowering of both Km and Vm. Interaction studies revealed the quenching of intrinsic fluorescence of α-amylase in presence of diosgenin. Similarly, circular dichroism spectrometry showed diminished negative humped peaks at 208 nm and 222 nm. Molecular docking indicated hydrogen bonding between carboxyl group of Asp300, while hydrophobic interactions between Tyr62, Trp58, Trp59, Val163, His305 and Gln63 residues of α-amylase. Diosgenin interacted with two catalytic residues (Asp352 and Glu411) from α-glucosidase. This is the first report of its kind that provides an intense scientific rationale for use of diosgenin as novel drug candidate for type II diabetes mellitus.

Enhanced visible photoluminescence in ZnO quantum dots by promotion of oxygen vacancy formation.

We report on the synthesis of ZnO quantum dots (QDs) rich in oxygen vacancies by inducing an oxygen deficient environment. The precise tunability of particle size is achieved by counter ion capping of the precursor used for synthesis. The prepared QDs show size tunable visible emission with high quantum yield.

Folate receptor targeted, rare-earth oxide nanocrystals for bi-modal fluorescence and magnetic imaging of cancer cells.

Targeted cancer imaging using rare-earth oxide nanocrystals, free from heavy metals (Cd, Se, Te, Hg and Pb), showing bright red-fluorescence and magnetic resonance imaging (MRI) is presented. Y(2)O(3) nanocrystals (YO NC) doped in situ with fluorescent (Eu(3+)) and paramagnetic (Gd(3+)) impurities and conjugated with a potential cancer targeting ligand, folic acid (FA), were prepared using an all-aqueous wet-chemical process. Structural, optical and magnetic properties of these multifunctional nanocrystals were investigated by X-ray diffraction, electron microscopy, photoluminescence and magnetization studies. Highly monodisperse nanocrystals of size approximately 20 nm with cubic bixbyite crystal structure showed bright red-fluorescence when doped with Eu(3+). Co-doping with Gd(3+) and mild air drying resulted significantly enhanced fluorescence quantum efficiency of approximately 60% together with paramagnetic functionality, enabling T(1)-weighted MR contrast with approximately 5 times higher spin-lattice relaxivity compared to the clinically used Gd(3+) contrast agent. Cytotoxicity and reactive oxygen stress studies show no toxicity by YO NC in both normal and cancer cells up to higher doses of 500 microm and longer incubation time, 48h. Cancer targeting capability of FA conjugated NCs was demonstrated on folate receptor positive (FR+) human nasopharyngeal carcinoma cells (KB) with FR depressed KB (FRd) and FR negative (FR-) lung cancer cells A549 as controls. Fluorescence microscopy and flow-cytometry data show highly specific binding and cellular uptake of large concentration of FA conjugated NCs on FR+ve cells compared to the controls. Thus, the present study reveals, unique bi-modal contrast imaging capability, non-toxicity and cancer targeting capability of multiple impurities doped rare-earth oxide nanocrystals that can find promising application in molecular imaging.