Multiplex binding modes of toluidine blue with calf thymus DNA and conformational transition of DNA revealed by spectroscopic studies

It is noteworthy to understand the details of interactions between antitumor drugs and DNA because the binding modes and affinities affect their antitumor activities. Here, The interaction of toluidine blue (TB), a potential antitumor drug for photodynamic therapy of tumor, with calf thymus DNA (ctDNA) was explored by UV-vis, fluorescence, circular dichroism (CD) spectroscopy, UV-rnelting method and surface-enhance Raman spectroscopy (SERS). The experimental results suggest that TB could bind to ctDNA via both electrostatic interaction and partial intercalation.

Blue bottle light: lecture demonstrations of homogeneous and heterogeneous photo-induced electron transfer reactions

The classic, non-photochemical blue bottle experiment involves the reaction of methylene blue (MB) with deprotonated glucose, to form a bleached form of the dye, leuco-methylene blue (LMB), and subsequent colour recovery by shaking with air. This reaction is a popular demonstrator of key principles in kinetics and reaction mechanisms. Here it is modified so as to highlight features of homogenous and heterogeneous photoinduced electron transfer (PET) (Pure Appl. Chem., 2007, 79, 293-465) reactions, i.e. blue bottle light experiments. The homogeneous blue bottle light experiment uses methylene blue, MB, as the photo-sensitizer and triethanolamine as the sacrificial electron donor. Visible light irradiation of this system leads to its rapid bleaching, followed by the ready restoration of its original colour upon shaking away from the light source. The heterogeneous blue bottle light experiment uses titania as the photo-sensitizer, MB as a redox indicator and glucose as the sacrificial electron donor. UVA light irradiation of this system leads to the rapid bleaching of the MB and the gradual restoration of its original colour with shaking and standing. The latter 'dark' step can be made facile and more demonstrator-friendly by using platinised titania particles. These two photochemical versions of the blue bottle experiment are used to explore the factors which underpin homogeneous and heterogeneous PET reactions and provide useful demonstrations of homogeneous and heterogeneous photochemistry.

Mechanical, thermal and colorimetric properties of LLDPE coloured with a blue nanopigment and conventional blue pigments

Purpose – This research deals with a new kind of nanopigment, obtained from the combination of organic dyes and layered nanoclays, that the authors call nanoclay-colorant pigment (NCP). Whilst they have already been employed in inks and coatings, to date these nanopigments have not been used as pigments for polymers. The existing lack of knowledge surrounding them must be redressed in order to bridge the gap between current academic studies and commercial exploitation. Therefore, the main purpose of this paper is to examine the hitherto unknown aspects of the NCP, which relate specifically to their applicability as a new type of colorant for polymers. Design/methodology/approach – A blue NCP has been prepared at the laboratory according to the patented method of synthesis (patent WO0104216), using methylene blue and montmorillonite nanoclay. It has then been applied to a thermoplastic polymer (linear low-density polyethylene – LLDPE) to obtain a coloured sample. Furthermore, samples with the same polymer but using conventional blue colorants have been prepared under the same processing conditions. The mechanical, thermal and colorimetric properties of these materials have been compared. Findings – The thermal stability of the sample coloured with NCP is reduced to some extent, while the mechanical strength is slightly increased. Moreover, this sample has better colour performance than the conventionally pigmented samples. Originality/value – In this paper, a blue NCP has been synthesised and successfully employed with polyethylene and the obtained sample shows better colour performance than polyethylene with conventional pigments.

Integrating efficient filtration and visible-light photocatalysis by loading Ag-doped zeolite Y particles on aluminia nanofiber membrane

Filtration membrane technology has already been employed to remove various organic effluents produced from the textile, paper, plastic, leather, food and mineral processing industries. To improve membrane efficiency and alleviate membrane fouling, an integrated approach is adopted that combines membrane filtration and photocatalysis technology. In this study, alumina nanofiber (AF) membranes with pore size of about 10 nm (determined by the liquid-liquid displacement method) have been synthesized through an in situ hydrothermal reaction, which permitted a large flux and achieved high selectivity. Silver nanoparticles (Ag NPs) are subsequently doped on the nanofibers of the membranes. Silver nanoparticles can strongly absorb visible light due to the surface plasmon resonance (SPR) effect, and thus induce photocatalytic degradation of organic dyes, including anionic, cationic and neutral dyes, under visible light irradiation. In this integrated system, the dyes are retained on the membrane surface, their concentration in the vicinity of the Ag NPs are high and thus can be efficiently decomposed. Meanwhile, the usual flux deterioration caused by the accumulation of the filtered dyes in the passage pores can be avoided. For example, when an aqueous solution containing methylene blue is processed using an integrated membrane, a large flux of 200 L m-2 h-1 and a stable permeating selectivity of 85% were achieved. The combined photocatalysis and filtration function leads to superior performance of the integrated membranes, which have a potential to be used for the removal of organic pollutants in drinking water.

Comparative study on adsorption of two cationic dyes by milled sugarcane bagasse

Adsorptions of Rhodamine B (RhB) and Basic Blue 9 (BB9, also known as methylene blue) by sugarcane bagasse of different surface areas were compared in this study. There was a small gain in the amount of dye removed by increasing bagasse surface area from 0.57 m2/g to 1.81 m2/g. BB9 adsorption was less sensitive to surface area change than RhB adsorption. Adsorption capacity of 250 mg/L RhB on 1 g/L bagasse was 65.5 mg/g compared to a value of 30.7 mg/g obtained with BB9 under the same conditions. Increasing adsorption temperature (from 30 °C to 50 °C) while having no effect on RhB adsorption, slightly decreased BB9 adsorption by ~4%. The differences in adsorption performances between these dyes have been related to the molecular structure of the dyes and the surface chemistry of bagasse.

Titania nanowires as substrates for sensing and photocatalysis of common textile industry effluents

Sensing and photocatalysis of textile industry effluents such as dyes using mesoporous anatase titania nanowires are discussed here.Spectroscopic investigations show that the titania nanowires preferentially sense cationic (e.g. Methylene Blue, Rhodamine B) over anionic (e.g. Orange G, Remazol Brilliant Blue R) dyes. The adsorbed dye concentration on titania nanowires increased with increase in nanowire dimensions and dye solution pH. Electrochemical sensing directly corroborated spectroscopic findings. Electrochemical detection sensitivity for Methylene Blue increased by more than two times in magnitude with tripling of nanowire average length. Photodegradation of Methylene Blue using titania nanowires is also more efficient than the commercial P25-TiO2 nanopowders. Keeping illumination protocol and observation times constant, the Methylene Blue concentration in solution decreased by only 50% in case of P25-TiO2 nanoparticles compared to a 100% decrease for titania nanowires. Photodegradation was also found to be function of exposure times and dye solution pH.Excellent sensing ability and photocatalytic activity of the titania nanowires is attributed to increased effective reaction area of the controlled nanostructured morphology. (C) 2010 Elsevier B.V. All rights reserved.

Vesicle and Stable Monolayer Formation from Simple ``Click'' Chemistry Adducts in Water

Click chemistry has been successfully extended into the field of molecular design of novel amphiphatic adducts. After their syntheses and characterizations, we have studied their aggregation properties in aqueous medium. Each of these adducts forms stable suspensions in water. These suspensions have been characterized by dynamic light scattering (DLS) studies and transmission electron microscopy (TEM). The presence of inner aqueous compartments in such aggregates has been demonstrated using dye (methylene blue) entrapment studies. These aggregates have been further characterized using X-ray diffraction (XRD), which indicates the existence of bilayer structures in them. Therefore, the resulting aggregates could be described as vesicles. The temperature-induced order-to-disorder transitions of the vesicular aggregates and the accompanying changes in their packing and hydration have been examined using high-sensitivity differential scanning calorimetry, fluorescence anisotropy, and generalized polarization measurements using appropriate membrane-soluble probe, 1,6-diphenylhexatriene, and Paldan, respectively. The findings of these studies are consistent with each other in terms of the apparent phase transition temperatures. Langmuir monolayer studies confirmed that these click adducts also form stable monolayers on buffered aqueous subphase at the air-water interface.

Nanoscale ZnO/CdS heterostructures with engineered interfaces for high photocatalytic activity under solar radiation

Semiconductor based nanoscale heterostructures are promising candidates for photocatalytic and photovoltaic applications with the sensitization of a wide bandgap semiconductor with a narrow bandgap material being the most viable strategy to maximize the utilization of the solar spectrum. Here, we present a simple wet chemical route to obtain nanoscale heterostructures of ZnO/CdS without using any molecular linker. Our method involves the nucleation of a Cd-precursor on ZnO nanorods with a subsequent sulfidation step leading to the formation of the ZnO/CdS nanoscale heterostructures. Excellent control over the loading of CdS and the microstructure is realized by merely changing the initial concentration of the sulfiding agent. We show that the heterostructures with the lowest CdS loading exhibit an exceptionally high activity for the degradation of methylene blue (MB) under solar irradiation conditions; microstructural and surface analysis reveals that the higher activity in this case is related to the dispersion of the CdS nanoparticles on the ZnO nanorod surface and to the higher concentration of surface hydroxyl species. Detailed analysis of the mechanism of formation of the nanoscale heterostructures reveals that it is possible to obtain deterministic control over the nature of the interfaces. Our synthesis method is general and applicable for other heterostructures where the interfaces need to be engineered for optimal properties. In particular, the absence of any molecular linker at the interface makes our method appealing for photovoltaic applications where faster rates of electron transfer at the heterojunctions are highly desirable.

Graphene and graphene oxide as effective adsorbents toward anionic and cationic dyes

In the present study, exfoliated graphene oxide (EGO) and reduced graphene oxide (rGO) have been used for the adsorption of various charged dyes such as methylene blue, methyl violet, rhodamine B, and orange G from aqueous solutions. EGO consists of single layer of graphite decorated with oxygen containing functional groups such as carboxyl, epoxy, ketone, and hydroxyl groups in its basal and edge planes. Consequently, the large negative charge density available in aqueous solutions helps in the effective adsorption of cationic dyes on EGO while the adsorption is negligible for anionic dyes. On the other hand, rGO that has high surface area does not possess as high a negative charge and is found to be very good adsorbent for anionic dyes. The adsorption process is followed using UV-Visible spectroscopy, while the material before and after adsorption has been characterized using physicochemical and spectroscopic techniques. Various isotherms have been used to fit the data, and kinetic parameters were evaluated. Raman and FT-IR spectroscopic data yield information on the interactions of dyes with the adsorbent. (C) 2011 Elsevier Inc. All rights reserved.

Vasomodulatory effect of novel peroxovanadate compounds on rat aorta: Role of rho kinase and nitric oxide/cGMP pathway

The present study was undertaken to assess the role of reactive oxygen species (ROS) in rat aortic ring vasoreactivity and integrity by using various peroxovanadate (pV) compounds. All the pV compounds (1 nM-300 mu M) used in the present study exerted concentration-dependent contractions on endothelium intact rat aortic rings. All compounds with an exception of DPV-asparagine (DPV-asn) significantly altered vascular integrity as shown by diminished KCl responses. Phenylephrine (PE)-mediated contractions (3 nM-300 mu M) were unaltered in the presence of these compounds. Acetylcholine (Ach)-mediated relaxation in PE (1 mu M) pre-contracted rings was significantly reduced in presence of diperoxovanadate (DPV), poly (sodium styrene sulfonate-co-maleate)-pV (PSS-CoM-pV) and poly (sodium styrene 4-sulfonate)-pV (PSS-pV). However, no significant change in Ach-mediated responses was observed in the presence of poly (acrylate)-pV (PM-pV) and DPV-asn. DPV-asn was thus chosen to further elucidate mechanism involved in peroxide mediated modulation of vasoreactivity. DPV-asn (30 nM-300 mu M) exerted significantly more stable contractions, that was found to be catalase (100 U/ml) resistant in comparison with H(2)O(2) (30 nM-300 mu M) in endothelium intact aortic rings. These contractile responses were found to be dependent on extracellular Ca(2+) and were significantly inhibited in presence of ROS scavenger N-acetylcysteine (100 mu M). Intracellular calcium chelation by BAPTA-AM (10 mu M) had no significant effect on DPV-asn (30 nM-300 mu M) mediated contraction. Pretreatment of aortic rings by rho-kinase inhibitor Y-27632 (10 mu M) significantly inhibited DPV-asn-mediated vasoconstriction indicating role of voltage-dependent Ca(2+) influx and downstream activation of rho-kinase. The small initial relaxant effect obtained on addition of DPV-asn (30 nM-1 mu M) in PE (1 mu M) pre-contracted endothelium intact rings, was prevented in the presence of guanylate cyclase inhibitor, methylene blue (10 mu M) and/or nitric oxide synthase (NOS) inhibitor, L-NAME (100 mu M) suggesting involvement of nitric oxide and cGMP. DPV-asn, like H(2)O(2), exerted a response of vasoconstriction in normal arteries and vasodilation at low concentrations (30 nM-1 mu M) in PE-pre contracted rings with overlapping mechanisms. These findings suggest usefulness of DPV-asn having low toxicity, in exploring the peroxide-mediated effects on various vascular beds. The present study also convincingly demonstrates role of H(2)O(2) in the modulation of vasoreactivity by using stable peroxide DPV-asn and warrants future studies on peroxide mediated signaling from a newer perspective. (C) 2011 Published by Elsevier Ltd.

Development of micro-shock wave assisted dry particle and fluid jet delivery system

Small quantity of energetic material coated on the inner wall of a polymer tube is proposed as a new method to generate micro-shock waves in the laboratory. These micro-shock waves have been harnessed to develop a novel method of delivering dry particle and liquid jet into the target. We have generated micro-shock waves with the help of reactive explosive compound high melting explosive (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and traces of aluminium] coated polymer tube, utilising 9 J of energy. The detonation process is initiated electrically from one end of the tube, while the micro-shock wave followed by the products of detonation escape from the open end of the polymer tube. The energy available at the open end of the polymer tube is used to accelerate tungsten micro-particles coated on the other side of the diaphragm or force a liquid jet out of a small cavity filled with the liquid. The micro-particles deposited on a thin metal diaphragm (typically 100-mu m thick) were accelerated to high velocity using micro-shock waves to penetrate the target. Tungsten particles of 0.7 mu m diameter have been successfully delivered into agarose gel targets of various strengths (0.6-1.0 %). The device has been tested by delivering micro-particles into potato tuber and Arachis hypogaea Linnaeus (ground nut) stem tissue. Along similar lines, liquid jets of diameter 200-250 mu m (methylene blue, water and oils) have been successfully delivered into agarose gel targets of various strengths. Successful vaccination against murine salmonellosis was demonstrated as a biological application of this device. The penetration depths achieved in the experimental targets are very encouraging to develop a future device for biological and biomedical applications.

Electrochemical sensing and photocatalysis using Ag-TiO2 microwires

Anatase Ag-TiO2 microwires with high sensitivity and photocatalytic activity were synthesized via polyol synthesis route followed by a simple surface modification and chemical reduction approach for attachment of silver. The superior performance of the Ag-TiO2 composite microwires is attributed to improved surface reactivity, mass transport and catalytic property as a result of wiring the TiO2 surface with Ag nanoparticles. Compared to the TiO2 microwires, Ag-TiO2 microwires exhibited three times higher sensitivity in the detection of cationic dye such as methylene blue. Photocatalytic degradation efficiency was also found to be significantly enhanced at constant illumination protocols and observation times. The improved performance is attributed to the formation of a Schottky barrier between TiO2 and Ag nanoparticles leading to a fast transport of photogenerated electrons to the Ag nanoparticles.

Photocatalytic degradation with combustion synthesized WO3 and WO3-TiO2 mixed oxides under UV and visible light

The photocatalytic activity of commercial titanium dioxide under UV and visible radiation was improved by composites of tungsten trioxide (WO3) with TiO2. WO3 was prepared by solution combustion synthesis and the mixed oxides/composites of WO3-TiO2 were prepared in different weight ratios (0, 0.10, 0.15, 0.20, 0.25, 0.50, 0.75, and 1) by physical mixing. These catalysts were characterized by XRD, DRS, BET, SEM, TEM, pH drift method, TGA and photoluminescence. The photocatalytic activity varies with the WO3 loading in the composites. The optimum loading of WO3 in the composites was found to be 15 wt% for both UV and visible radiation. This loading showed faster dye degradation rate than commercial TiO2 (TiO2-C) and WO3 (WO3-C). The effect of initial concentrations of methylene blue (MB) and orange G (OG) and the effect of the functional group on dye degradation was studied with both anionic and cationic dyes with 15 wt% WO3-TiO2. (C) 2012 Elsevier B.V. All rights reserved.