Liposome encapsulated electron donor strategy for signal-on CYFRA 21-1 photoelectrochemical analysis.

A novel electron donor controlled-release system is proposed based on liposome encapsulated L-cysteine for the sensitive determination of cytokeratin 19 fragment 21-1 (CYFRA 21-1). On the one hand, a defective TiO2 modified with methylene blue was employed as a photoactive platform which exhibited a high photoelectrochemical (PEC) response owing to the introduction of oxygen vacancies and the high  photosensitivity of the dye. On the other hand, L-cysteine as the sacrificial electron donor was encapsulated in the vesicles of liposomes, and this composite was used as the signal amplification factor, which is labeled on the secondary antibody of CYFRA 21-1 to further improve the photocurrent sensitivity. The excellent electron transfer path in photoactive materials coupled with the skilful electron donor controlled-release system, contributed to the sensitive  PEC analysis of CYFRA 21-1 underoptimum conditions. The PEC immunoassay showed a linear current response in the range 0.0001-100 ng/mL with a detection limitof 37 fg/mL. Enhanced stability and satisfactory reproducibility were also achieved. The proposed concept  provides a novel signal-on strategy for the sensitive detection of other cancer markers in the electrochemical sensing field.

The Contribution of Photodynamic Inactivation vs. Corsodyl Mouthwash to the Control of Streptococcus mutans Biofilms.

This work compared the inhibition effect of the commercially available mouthwash Corsodyl, containing 0.1% chlorhexidine digluconate, and photodynamic inactivation (PDI) employing methylene blue (MB) with irradiation from a red laser on 24-h biofilms formed by Streptococcus mutans strains on hydroxyapatite surfaces. The cytotoxicity of Corsodyl and MB was evaluated by Galleria mellonella surviving assay. The viability of biofilm cells after exposure to mouthwash and PDI was determined by counting colony-forming units. The inhibitory effect of antimicrobial agents was confirmed by confocal scanning laser microscopy. MB did not exhibit a cytotoxic effect on larval survival. Non-diluted Corsodyl slightly decreased the survival of larvae. Using our PDI parameters achieved better inhibition than with non-PDI, proving a significant effect on the eradication of S. mutans biofilms and therefore could be an appropriate supplement for the eradication of dental caries.

Photocatalytic degradation of methylene blue dye by fluorite type Fe2Zr2-xWxO7 system under visible light irradiation.

Nano-sized Fe2Zr2-xWxO7 system was prepared using the Pacini method where x = 0, 0.05, 0.1 and 0.15. All the samples were characterized using chemical analysis, X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), transmission electron microscopy (TEM), UV-vis diffuse reflectance measurements (DRS) and surface area measurements. The undoped Fe2Zr2O7 was crystallised in the cubic fluorite phase as a major phase in addition to rhombohedral phase of Fe2O3 and monoclinic phase of ZrO2 as the minor phases. Meanwhile, single cubic fluorite phase was defined for Fe2Zr0.85W0.15O7 sample. The last has the lowest band gap (1.69 eV) and the highest surface area (106 m2/g). From TEM, the average particle size of the prepared samples was in the range of (3-7 nm). The photocatalytic efficiency of the prepared Fe2Zr2-xWxO7 system was manifested by the degradation of methylene blue and real textile wastewater of blue colour. Ascending degradation efficiency was exhibited with increasing tungsten concentration which is in accordance with their band gap as well as their surface area values. The degradation rate using Fe2Zr0.85W0.15O7 sample obeys the pseudo-first order kinetic at the optimum degradation conditions (1.5 g/L catalyst and pH11). Fe2Zr0.85W0.15O7 showed promising photocatalytic activity for real textile wastewater where the 69% COD removal was obtained under the same conditions used for methylene blue degradation.

A label-free photoelectrochemical aptasensor for facile and ultrasensitive mercury ion assay based on a solution-phase photoactive probe and exonuclease III-assisted amplification.

In typical photoelectrochemical (PEC) biosensing assays, electrodes are generally modified with photoactive probes and/or target recognition probes, which makes the processes complicated, time-consuming, and difficult to achieve excellent reproducibility. Hence, to overcome such shortcomings, we propose here an immobilization-free and label-free PEC aptasensor using solution-phase methylene blue (MB) as the PEC signal probe. Based on the unique T-Hg2+-T base pairs, and the diffusivity difference between free MB molecules and the MB/G-quadruplex composite towards the ITO electrode surface with negative charge, the "signal-off" approach for Hg2+ detection is developed. In the presence of target Hg2+, via the T-Hg2+-T bond formation, the two sticky ends of the hairpin DNA probe form a rigid duplex stem, which triggers the exonuclease III-facilitated target cycling amplification, and the formation of multiple G-quadruplexes. Upon the intercalation of MB in G-quadruplexes, significantly decreased photocurrent is obtained owing to the increased electrostatic repulsion between the MB/G-quadruplex composite and the ITO electrode. Therefore, highly sensitive and ultrasensitive Hg2+ determination is achieved, with a low detection limit of 1.2 pM, well below the maximum allowable Hg2+ level in drinking water defined by the WHO, China's Ministry of Health, and the US EPA. Due to the avoidance of sophisticated electrode modification and recognition probe immobilization processes, as well as an expensive labeling procedure, the PEC aptasensor proposed here demonstrates the advantages of simplicity, good reproducibility, rapidness and low cost.

Photosensitizer-Conjugated Bi2Te3 Nanosheets as Theranostic Agent for Synergistic Photothermal and Photodynamic Therapy.

Phototherapy, including photothermal therapy (PTT)/photodynamic therapy (PDT), is usually considered as a promising strategy for cancer treatment due to its noninvasive and selective therapeutic effect by laser irradiation. A light-activatable nanoplatform based on bovine serum albumin (BSA)-coated Bi2Te3 nanosheets conjugated with methylene blue (MB) was successfully designed and constructed for bimodal PTT/PDT combination therapy. The resultant nanoconstruct (BSA-Bi2Te3/MB) exhibited high stability in various physiological solutions and excellent biocompatibility. Especially, the nanoconstruct not only possessed strong near-infrared absorption and high photothermal conversion as a photothermal agent for efficient tumor ablation but also could successfully load photosensitizer for PDT of tumor. When exposed to laser irradiation, tumors in mice with BSA-Bi2Te3/MB injection were completely eliminated without recurrence within 15 d, demonstrating the potential of the nanoconstruct as a bimodal PTT/PDT therapeutic platform for cancer treatment.

Composite nanofibers for highly efficient photocatalytic degradation of organic dyes from contaminated water.

In this study highly efficient photocatalyst based on composite nanofibers containing polyacrylonitrile (PAN), carbon nanotubes (CNT), and surface functionalized TiO2 nanoparticles was developed. The composite nanofibers were fabricated using electrospinning technique followed by chemical crosslinking. The surface modification and morphology changes of the fabricated composite nanofibers were examined through SEM, TEM, and FTIR analysis. The photocatalytic performance of the composite nanofibers for the degradation of model molecules, methylene blue and indigo carmine, under UV irradiation in aqueous solutions was investigated. The results demonstrated that high photodegradation efficiency was obtained in a short time and at low power intensity compared to other reported studies. The effective factors on the degradation of the dyes, such as the amount of catalyst, solution pH and irradiation time were investigated. The experimental kinetic data were fitted using pseudo-first order model. The effect of the composite nanofibers as individual components on the degradation efficiency of MB and IC was evaluated in order to understand the overall photodegradation mechanism. The results obtained showed that all the components possess significant effect on the photodegradation activity of the composite nanofibers. The stability studies demonstrated that the photodegradation efficiency can remain constant at the level of 99% after five consecutive cycles.

Adsorption and Photocatalytic Degradation of Methylene Blue Using Potassium Polytitanate and Solar Simulator.

Solar photocatalytic degradation of organic water pollutants can be used to degrade toxic organic pollutants in water. In this study, potassium titanate nanofibres were synthesized by an aqueous peroxide route at high pH and examined as photocatalysts for photodegradation of methylene blue (MB) using a solar simulator. Initially, MB was adsorbed on the surface of potassium polytitanates to achieve adsorption equilibrium before the photocatalysts were illuminated using solar simulator. The results showed that potassium polytitanate nanofibres were effective adsorbents of MB and also facilitated its photocatalytic degradation. Sulphate ion evolution during photocatalysis confirmed that some mineralisation occurred and hence photo-oxidative degradation of MB took place. The optimum operational conditions for the photocatalytic degradation of MB were found at 0.05 g/L of photocatalyst load, 10 mg/L MB and pH 7. The stability and regeneration of the photocatalyst specimen was also studied for 3 degradation cycles using adsorption/photocatalysis model. Morphological structure analysis of potassium titanate showed nanocrystallines structure of longitudinally-oriented isolated fibre with a length up to several micrometres with diameters ranging from 10 to 20 nanometres.

Low Frequency Ultrasonication of Degussa P25 TiO2 and Its Superior Photocatalytic Properties.

We report the simple and effective method for enhancing the photocatalytic properties of Degussa P25 TiO2 by low frequency ultrasonication. The improvement in the crystallinity of ultrasonicated TiO2 was confirmed by the X-ray diffraction and Raman spectroscopy studies. Further, the X-ray photoelectron spectroscopy was utilized to study the changes in chemical nature and band edge due to the effect of ultrasonication and H2O2 solvent. The transmission electron microscope (TEM) was used to analysis the surface distortion. The Moire fringes in TEM were examined to understand the partial transformation of amorphous to crystalline anatase structure and overlapping of rutile over anatase crystal. The photocatalytic results indicated improvement in the degradation of methylene blue dye. The degradation efficiency was estimated to be 86% for ultrasonicated TiO2, which is higher as compared to 40% of P25. The rate constant values revealed four times superior degradation property of ultrasonicated TiO2. The improvement in the photocatalytic efficiency was correlated to the formation of rutile/anatase TiO2 aggregation and its consequences on electron-hole recombination.

Crystal Structure and Photocatalytic Activity of Al-Doped TiO2 Nanofibers for Methylene Blue Dye Degradation.

Al-TiO2 nanofibers were prepared using a sol-gel derived electrospinning by varying the Al/Ti molar ratio from 0 to 0.73 to investigate the effect of Al doping on the crystal structure and the photocatalytic activity of Al-TiO2 for methylene blue (MB) degradation. XRD results indicated that as the Al/Ti molar ratio rose, crystal structure of Al-TiO2 was changed from anatase/rutile (undoped), anatase (0.07-0.18), to amorphous phase (0.38-0.73), which was confirmed by XPS and Raman analysis. The degradation kinetic constant increased from 7.3 x 10(-4) min(-1) to 4.5 x 10(-3) min(-1) with the increase of Al/Ti molar ratios from 0 to 0.38, but decreased to 3.4 x 10(-3) min(-1) when the Al/Ti molar ratio reached 0.73. The Al-TiO2 catalyst doped with 0.38 Al/Ti molar ratio demonstrated the best MB degradation. Experimental results indicated that the Al doping in Al-TiO2 was mainly attributed to the crystal structure of TiO2 and the photocatalytic degradation of MB.

Microwave synthesis of pure and doped cerium (IV) oxide (CeO2) nanoparticles for methylene blue degradation.

Cerium (IV) oxide (CeO2), samarium (Sm) and gadolinium (Gd) doped CeO2 nanoparticles were prepared using microwave technique. The effect of microwave irradiation time, microwave power and pH of the starting solution on the structure and crystallite size were investigated. The prepared nanoparticles were characterized using X-ray diffraction, FT-Raman spectroscopy, and transmission electron microscope. The photocatalytic activity of the as-prepared CeO2, Sm and Gd doped CeO2 toward degradation of methylene blue (MB) dye was investigated under UV light irradiation. The effect of pH, the amount of catalyst and the dye concentration on the degradation extent were studied. The photocatalytic activity of CeO2 was kinetically enhanced by trivalent cation (Gd and Sm) doping. The results revealed that Gd doped CeO2 nanoparticles exhibit the best catalytic degradation activity on MB under UV irradiation. For clarifying the environmental safety of the by products produced from the degradation process, the pathways of MB degradation were followed using liquid chromatography/mass spectroscopy (LC/MS). The total organic carbon content measurements confirmed the results obtained by LC/MS. Compared to the same nanoparticles prepared by another method, it was found that Gd doped CeO2 prepared by hydrothermal process was able to mineralize MB dye completely under UV light irradiation.

Physical damage on giant vesicles membrane as a result of methylene blue photoirradiation.

In this study we pursue a closer analysis of the photodamage promoted on giant unilamellar vesicles membranes made of dioleoyl-sn-glycero-3-phosphocholine (DOPC) or 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), by irradiating methylene blue present in the giant unilamellar vesicles solution. By means of optical microscopy and electro-deformation experiments, the physical damage on the vesicle membrane was followed and the phospholipids oxidation was evaluated in terms of changes in the membrane surface area and permeability. As expected, oxidation modifies structural characteristics of the phospholipids that lead to remarkable membrane alterations. By comparing DOPC- with POPC-made membranes, we observed that the rate of pore formation and vesicle degradation as a function of methylene blue concentration follows a diffusion law in the case of DOPC and a linear variation in the case of POPC. We attributed this scenario to the nucleation process of oxidized species following a diffusion-limited growth regime for DOPC and in the case of POPC a homogeneous nucleation process. On the basis of these premises, we constructed models based on reaction-diffusion equations that fit well with the experimental data. This information shows that the outcome of the photosensitization reactions is critically dependent on the type of lipid present in the membrane.

Enhanced photocatalytic efficacy of hetropolyacid pillared TiO2 nanocomposites.

The removal of dye from industrial effluents is prime important, photo-catalysis is a finest method to combat dye from effluents. This study concerns about the investigation of photocatalytic activity of TiO2-HPAs (Hetropolyacids) nanocomposite namely TiO2-Phosphomolybdic nanocomposite [TiO2-HMA] and TiO2-Phosphotungstic nanocomposite [TiO2-HWA] which were prepared by Sol-gel method and the same were characterized by using XRD, SEM-EDAX. The photocatalytic activity of prepared photo-catalysts were evaluated and compared by the degradation of Methylene Blue dye in water solution under UV irradiation. In that TiO2-HMA nanocomposite showed superior photocatalytic activity than TiO2-HWA.

Template-free hydrothermal synthesis different morphologies of visible-light-driven BiVO4 photocatalysts.

Monoclinic BiVO4 nano- and microstructures with a diversity of well-defined morphologies, such as nanoplates, dendrite leaves-like structures, sub-microrods, and microflowers were synthesized via a template-free hydrothermal process with bismuth nitrate and ammonium metavanadate as metal source. The crystal structures, morphologies and optical properties of the as-prepared samples were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and UV-visible absorption spectra (UV-vis). Results showed that the pH value of the solution and the volume of ethylenediamine have great effect on the formation of these unique structures. The photocatalytic activity of these as-prepared samples had been tested by degradation of methylene blue under visible light, indicating that showed good photocatalytic performance.

Engineering bamboo-type TiO2 nanotube arrays to enhance their photocatalytic property.

Bamboo-type TiO2 nanotube arrays with high surface area can be synthesized by alternating voltage (AV) anodization for their important use as photocatalytic medium. Their morphologies are highly dependent on preparation parameters including anodization time and electrolyte composition. Minimum time of high-voltage steps required for forming desired bamboo ridge spacing on these nanotubes can be calculated from current-time profiles recorded during potentiostatic anodization at the voltage. Water content in NH4F-containing ethylene glycol (EG) electrolytes is optimized simply from analyses of current transients or current-voltage relations for anodization in EG electrolytes with different amount of water, in order to achieve efficient electrochemical growth of TiO2 nanotubes for large ridge density and long tube length. Two types of bamboo-type TiO2 nanotubes with the same length of 5.46 microm but different ridge spacing are synthesized for photocatalytic degradation of methylene blue (MB) under UV radiation. Both of the bamboo-type nanotube arrays show improved photo catalysis compared to smooth TiO2 nanotubes of the same length, due to their larger surface area favorable for heterogeneous catalytic processes. In particular, the apparent rate constant of photocatalytic degradation on bamboo-type nanotubes is up to 29.4% higher than that for degradation on smooth ones.

Photocatalytic degradation of methylene blue under UV light irradiation on prepared carbonaceous TiO2.

This study involves the investigation of altering the photocatalytic activity of TiO2 using composite materials. Three different forms of modified TiO2, namely, TiO2/activated carbon (AC), TiO2/carbon (C), and TiO2/PANi, were compared. The TiO2/carbon composite was obtained by pyrolysis of TiO2/PANi prepared by in situ polymerization method, while the TiO2/activated carbon (TiO2/AC) was obtained after treating TiO2/carbon with 1.0 M KOH solution, followed by calcination at a temperature of 450°C. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermogravimetric analysis (TG-DTA), Brunauer-Emmet-Teller (BET), and UV-Vis spectroscopy were used to characterize and evaluate the prepared samples. The specific surface area was determined to be in the following order: TiO2/AC > TiO2/C > TiO2/PANi > TiO2 (179 > 134 > 54 > 9 m(2) g(-1)). The evaluation of photocatalytic performance for the degradation of methylene blue under UV light irradiation was also of the same order, with 98 > 84.7 > 69% conversion rate, which is likely to be attributed to the porosity and synergistic effect in the prepared samples.

Targeted oxidation of Torpedo californica acetylcholinesterase by singlet oxygen: identification of N-formylkynurenine tryptophan derivatives within the active-site gorge of its complex with the photosensitizer methylene blue.

The principal role of AChE (acetylcholinesterase) is termination of impulse transmission at cholinergic synapses by rapid hydrolysis of the neurotransmitter acetylcholine. The active site of AChE is near the bottom of a long and narrow gorge lined with aromatic residues. It contains a CAS (catalytic 'anionic' subsite) and a second PAS (peripheral 'anionic' site), the gorge mouth, both of which bind acetylcholine via π-cation interactions, primarily with two conserved tryptophan residues. It was shown previously that generation of (1)O(2) by illumination of MB (Methylene Blue) causes irreversible inactivation of TcAChE (Torpedo californica AChE), and suggested that photo-oxidation of tryptophan residues might be responsible. In the present study, structural modification of the TcAChE tryptophan residues induced by MB-sensitized oxidation was investigated using anti-N-formylkynurenine antibodies and MS. From these analyses, we determined that N-formylkynurenine derivatives were specifically produced from Trp(84) and Trp(279), present at the CAS and PAS respectively. Peptides containing these two oxidized tryptophan residues were not detected when the competitive inhibitors, edrophonium and propidium (which should displace MB from the gorge) were present during illumination, in agreement with their efficient protection against the MB-induced photo-inactivation. Thus the bound MB elicited selective action of (1)O(2) on the tryptophan residues facing on to the water-filled active-site gorge. The findings of the present study thus demonstrate the localized action and high specificity of MB-sensitized photo-oxidation of TcAChE, as well as the value of this enzyme as a model system for studying the mechanism of action and specificity of photosensitizing agents.

Design and synthesis of metal complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide and their photocatalytic degradation of methylene blue.

The photocatalytic degradation has been considered to be an efficient process for the degradation of organic pollutants, which are present in the effluents released by industries. The photocatalytic bleaching of cationic dye methylene blue was carried out spectrometrically on irradiation of UV light using Cu(II), Ni(II), and Co(II) complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide (HL). The effects of pH and metal ion were studied on the efficiency of the reaction. Cu(II) complex shows better catalytic activity and the highest percentage degradation (~88.8%) of methylene blue was observed at pH 12. A tentative mechanism has also been proposed for the photocatalytic degradation of methylene blue.

Preparation of modified semi-coke by microwave heating and adsorption kinetics of methylene blue.

Preparation of modified semi-coke has been achieved, using phosphoric acid as the modifying agent, by microwave heating from virgin semi-coke. Process optimization using a Central Composite Design (CCD) design of Response Surface Methodology (RSM) technique for the preparation of modifies semi-coke is presented in this paper. The optimum conditions for producing modified semi-coke were: concentration of phosphoric acid 2.04, heating time 20 minutes and temperature 587 degrees C, with the optimum iodine of 862 mg/g and yield of 47.48%. The textural characteristics of modified semi-coke were analyzed using scanning electron microscopy (SEM) and nitrogen adsorption isotherm. The BET surface area of modified semi-coke was estimated to be 989.60 m2/g, with the pore volume of 0.74 cm3/g and a pore diameter of 3.009 nm, with micro-pore volume contributing to 62.44%. The Methylene Blue monolayer adsorption capacity was found to be mg/g at K. The adsorption capacity of the modified semi-coke highlights its suitability for liquid phase adsorption application with a potential usage in waste water treatment.

Reduction of methylene green by EDTA: a relation between dielectric constant of medium and activated state.

Kinetics of an alkaline reduction of the methylene green with ethylenediaminetetraaceticacid (EDTA) as a role of dielectric constant of the medium with anecdotal ionic strength in a diverse solvent system (aqueous mixtures of methanol) (10-30%) was studied by measuring the specific rate constant of the reaction spectrophotometrically at λ (max) = 660nm. An effort has been made to give an elucidation of vital role of dielectric constant of the medium captivating into reflection of single sphere and double sphere complex in reaction assortment. This investigation leads to disclose that single sphere complex of the dye and reductant was found to be the most suitable complex existed in a varied organic solvent. The deviation of the theoretical values from experimental results for single sphere and double sphere complex model in the presence of an alkali and nitrate ions were justified through HPLC analysis. HPLC analysis recommended that a considerable amount of the dye degrades in the existence of nitrate ion and alkali and additional peaks which may be of by-product were obtained. This leads to confirm the non identical values of single sphere and double sphere model in the occurrence of nitrate and an alkali. Rate of deletion of color showed a linear liaison with respect to water content below 30% and temperature between 20-40(o)C whereas an increase in the concentration of organic solvent showed the inhibition of dye decoloration at given optimum condition. Therefore study was restricted up to 30% of methanol binary mixtures. A mechanism of reduction of dye has been proposed based on verdict.

Synthesis, property characterization and photocatalytic activity of the novel composite polymer polyaniline/Bi2SnTiO7.

A novel polyaniline/Bi(2)SnTiO(7 )composite polymer was synthesized by chemical oxidation in-situ polymerization method and sol-gel method for the first time. The structural properties of novel polyaniline/Bi(2)SnTiO(7) have been characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray spectrometry. The lattice parameter of Bi(2)SnTiO(7) was found to be a = 10.52582(8) Å. The photocatalytic degradation of methylene blue was realized under visible light irradiation with the novel polyaniline/Bi(2)SnTiO(7) as catalyst. The results showed that novel polyaniline/Bi(2)SnTiO(7 )possessed higher catalytic activity compared with Bi(2)InTaO(7) or pure TiO(2) or N-doped TiO(2) for photocatalytic degradation of methylene blue under visible light irradiation. The photocatalytic degradation of methylene blue with the novel polyaniline/Bi(2)SnTiO(7) or N-doped TiO(2) as catalyst followed first-order reaction kinetics, and the first-order rate constant was 0.01504 or 0.00333 min(-1). After visible light irradiation for 220 minutes with novel polyaniline/Bi(2)SnTiO(7 )as catalyst, complete removal and mineralization of methylene blue was observed. The reduction of the total organic carbon, the formation of inorganic products, SO(4)2- and NO(3-), and the evolution of CO(2) revealed the continuous mineralization of methylene blue during the photocatalytic process. The possible photocatalytic degradation pathway of methylene blue was obtained under visible light irradiation.