Gene Transfection in High Serum Levels: Case Studies with New Cholesterol Based Cationic Gemini Lipids

Background: Six new cationic gemini lipids based on cholesterol possessing different positional combinations of hydroxyethyl (-CH2CH2OH) and oligo-oxyethylene -(CH2CH2O)(n)- moieties were synthesized. For comparison the corresponding monomeric lipid was also prepared. Each new cationic lipid was found to form stable, clear suspensions in aqueous media. Methodology/Principal Findings: To understand the nature of the individual lipid aggregates, we have studied the aggregation properties using transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential measurements and X-ray diffraction (XRD). We studied the lipid/DNA complex (lipoplex) formation and the release of the DNA from such lipoplexes using ethidium bromide. These gemini lipids in presence of a helper lipid, 1, 2-dioleoyl phophatidyl ethanol amine (DOPE) showed significant enhancements in the gene transfection compared to several commercially available transfection agents. Cholesterol based gemini having -CH2-CH2-OH groups at the head and one oxyethylene spacer was found to be the most effective lipid, which showed transfection activity even in presence of high serum levels (50%) greater than Effectene, one of the potent commercially available transfecting agents. Most of these geminis protected plasmid DNA remarkably against DNase I in serum, although the degree of stability was found to vary with their structural features. Conclusions/Significance: -OH groups present on the cationic headgroups in combination with oxyethylene linkers on cholesterol based geminis, gave an optimized combination of new genera of gemini lipids possessing high transfection efficiency even in presence of very high percentage of serum. This property makes them preferential transfection reagents for possible in vivo studies.

Antitumor and antioxidant status of Terminalia catappa against Ehrlich ascites carcinoma in Swiss albino mice

Objective: The present study was undertaken to evaluate the antitumor and antioxidant status of ethanol extract of Terminalia catappa leaves against Ehrlich ascites carcinoma (EAC) in Swiss albino mice. Materials and Methods: The leaves powder was extracted with Soxhlet apparatus and subjected to hot continuous percolation using ethanol (95% v/v). Tumor bearing animals was treated with 50 and 200 mg/kg of ethanol extract. EAC induced in mice by intraperitoneal injection of EAC cells 1 x 10(6) cells/mice. The study was assed using life span of EAC-bearing hosts, hematological parameters, volume of solid tumor mass and status of antioxidant enzymes such as lipid peroxidation (LPO), reduced glutathione (GSH), superoxide dismutase (SOD) and catalase (CAT) activities. Total phenolics and flavonoids contents from the leaves extract were also determined. Results: Total phenolics and flavonoids contents from the leaves extract were found 354.02 and 51.67 mg/g extract. Oral administration of ethanol extract of T. catappa (50 and 200 mg/kg) increased the life span (27.82% and 60.59%), increased peritoneal cell count (8.85 +/- 0.20 and 10.37 +/- 0.26) and significantly decreased solid tumor mass (1.16 +/- 0.14 cm(2)) at 200 mg/kg as compared with EAC-tumor bearing mice (P < 0.01). Hematological profile including red blood cell count, white blood cell count, hemoglobin (11.91 +/- 0.47 % g) and protein estimation were found to be nearly normal levels in extract-treated mice compared with tumor bearing control mice. Treatment with T. catappa significantly decreased levels of LPO and GSH, and increased levels of SOD and CAT activity (P < 0.01). Conclusion: T. catappa exhibited antitumor effect by modulating LPO and augmenting antioxidant defense systems in EAC bearing mice. The phenolic and flavonoid components in this extract may be responsible for antitumor activity.

Gas sensing response analysis of p-type porous chromium oxide thin films

The ethanol sensing properties of porous Cr2O3 thin films deposited by the ultrasonic nebulized spray pyrolysis of an aqueous combustion mixture is reported. The impact of the precursor selection and various deposition parameters on the film crystallinity, surface morphology and stoichiometry are studied using thermo-gravimetric analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and atomic force microscopy techniques. The film morphology exhibits a highly porous nature, as a result of the exothermic combustion reaction during film deposition. The gas sensing properties of these films are investigated in the temperature range of 200-375 degrees C for ethanol. The films show two different regions of response for ethanol above and below 300 degrees C. A good relationship between the response and the ethanol concentration is observed, and is modeled using an empirical relation. The possible mechanism and the surface chemical reactions of ethanol over the chromium oxide surface are discussed.

Base Triggered Enhancement of First Hyperpolarizability of a Keto-Enol Tautomer

This work describes the base triggered enhancement of first hyperpolarizability of a tautomeric organic molecule, namely, benzoylacetanilide (BA). We have used the hyper-Rayleigh scattering technique to measure the first hyperpolarizability (beta) of BA which exists in the pure keto form in water and as a keto-enol tautomer in ethanol. Its anion exists in equilibrium with the keto and enol forms at pH 11 in aqueous solution. The beta value of the anion form is 709 X 10(-30) esu, whereas that of the enol is 232 x 10(-3) esu and of the keto is 88 X 10(-30) esu. There is an enhancement of beta by similar to 8 times for the anion and similar to 3 times for the enol compared to the keto form. All these are achieved by altering the equilibrium between the three forms of BA by simple means. MP2 calculations reproduce the experimental trend, but the computed beta values are much lower than the measured values. DFT calculations with the standard B3LYP functional could not predict the right order in the beta values. The difference between experimental and calculated values is, perhaps, due to the fact that electron correlation effects are important in computing optical nonlinearities of large organic molecules and MP2 and B3LYP calculations done here for different forms of BA could not account for such effects adequately.

Remarkable Regioisomer Control in the Hydrogel Formation from a Two-Component Mixture of Pyridine-End Oligo(p-phenylenevinylene)s and N-Decanoyl-L-alanine

N-Decanoyl-L-alanine (DA) was mixed with either colorless 4,4-bipyridine (BP) or various derivatives such as chromogenic oligo(p-phenylenevinylene) (OPV) functionalized with isomeric pyridine termini in specific molar ratios. This mixtures form salt-type gels in a water/ethanol (2:1, v/v) mixture. The gelation properties of these two-component mixtures could be modulated by variation of the position of the N atom of the end pyridyl groups in OPVs. The presence of acid-base interactions in the self-assembly of these two-component systems leading to gelation was probed in detail by using stoichiometry-dependent UV/Vis and FTIR spectroscopy. Furthermore, temperature-dependent UV/Vis and fluorescence spectroscopy clearly demonstrated a J-type aggregation mode of these gelator molecules during the sol-to-gel transition process. Morphological features and the arrangement of the molecules in the gels were examined by using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray diffraction (XRD) techniques. Calculation of the length of each molecular system by energy minimization in its extended conformation and comparison with the XRD patterns revealed that this class of gelator molecules adopts lamellar organizations. Rheological properties of these two-component systems provided clear evidence that the flow behavior could be modulated by varying the acid/amine ratio. Polarized optical microscopy (POM), differential scanning calorimetry (DSC), and XRD results revealed that the solid-phase behavior of such two-component mixtures (acid/base=2:1) varied significantly upon changing the proton-acceptor part from BP to OPV. Interestingly, the XRD pattern of these acid/base mixtures after annealing at their associated isotropic temperature was significantly different from that of their xerogels.

Chemical vapor detection using nonlinear electrical properties of carbon nanotube bundles

We demonstrate the electrical transport behavior of carbon nanotubes (CNTs) upon exposure to organic analytes (namely ethanol, benzene, acetone and toluene). The resulting nonlinear current-voltage characteristics revealed a power law dependence of the differential conductivity on the applied bias voltage. Moreover, suppression of differential conductivity at zero bias is found to be dependent on different selective analytes. The power law exponent values have been monitored before, during and after exposure to the chemicals, which revealed a reversible change in the number of electron conducting channels. Therefore, the reduction in the number of conductive paths can be attributed to the interaction of the chemical analyte on the CNT surfaces, which causes a decrease in the differential conductivity of the CNT sample. These results demonstrate chemical selectivity of CNTs due to varying electronic interaction with different chemical analytes.

Multimodal shape oscillations of droplets excited by an air stream

The shape dynamics of droplets exposed to an air jet at intermediate droplet Reynolds numbers is investigated. High speed imaging and hot-wire anemometry are employed to examine the mechanism of droplet oscillation. The theory that the vortex shedding behind the droplet induces oscillation is examined. In these experiments, no particular dominant frequency is found in the wake region of the droplet. Hence the inherent free-stream disturbances prove to be driving the droplet oscillations. The modes of droplet oscillation show a band of dominant frequencies near the corresponding natural frequency, further proving that there is no particular forcing frequency involved. In the frequency spectrum of the lowest mode of oscillation for glycerol at the highest Reynolds number, no response is observed below the threshold frequency corresponding to the viscous dissipation time scale. This selective suppression of lower frequencies in the case of glycerol is corroborated by scaling arguments. The influence of surface tension on the droplet oscillation is studied using ethanol as a test fluid. Since a lower surface tension reduces the natural frequency, ethanol shows lower excited frequencies. The oscillation levels of different fluids are quantified using the droplet aspect ratio and correlated in terms of Weber number and Ohnesorge number. (C) 2014 Elsevier Ltd. All rights reserved.

Substituent effect on fluorescence signaling of the cell permeable HSO4- receptors through single point to ratiometric response in green solvent

Two new 2-(2-aminophenyl)benzimidazole-based HSO4- ion selective receptors, 6-(4-nitrophenyl)-5,6-dihydrobenzo4,5]imidazo1,2-c]quinazoline (L1H) and 6-(4-methoxyphenyl)-5,6-dihydrobenzo4,5]imidazo1,2-c] quinazoline (L2H), and their 1 : 1 molecular complexes with HSO4- were prepared in a facile synthetic method and characterized by physicochemical and spectroscopic techniques along with the detailed structural analysis of L1H by single crystal X-ray crystallography. Both receptors (L1H and L2H) behave as highly selective chemosensor for HSO4- ions at biological pH in ethanol-water HEPES buffer (1/5) (v/v) medium over other anions such as F-, Cl-, Br-, I-, AcO-, H2PO4-, N-3(-) and ClO4-. Theoretical and experimental studies showed that the emission efficiency of the receptors (L1H and L2H) was tuned successfully through single point to ratiometric detection by employing the substituent effects. Using 3 sigma method the LOD for HSO4- ions were found to be 18.08 nM and 14.11 nM for L1H and L2H, respectively, within a very short responsive time (15-20 s) in 100 mM HEPES buffer (ethanol-water: 1/5, v/v). Comparison of the utility of the probes (L1H and L2H) as biomarkers for the detection of intracellular HSO4- ions concentrations under a fluorescence microscope has also been included and both probes showed no cytotoxic effect.

Digestive ripening and green synthesis of ultra-small (r < 2 nm) stable ZnO quantum dots

Given the recent reports pertaining to novel optical properties of ultra-small quantum dots (QDs) (r <2 nm), this nanomaterial is of relevance to both technology and science. However it is well known that in these size regimes most chalocogenide QD dispersions are unstable. Since applications often require use of QD dispersions (e.g. for deployment on a substrate), stabilizing these ultra-small particles is of practical relevance. In this work we demonstrate a facile, green, solution approach for synthesis of stable, ultra-small ZnO QDs having radius less than 2 nm. The particle size is calculated using Brits' equation and confirmed by transmission electron micrographs. ZnO QDs reported remain stable for > 120 days in ethanol (at similar to 298-303 K). We report digestive ripening (DR) in TEA capped ZnO QDs; this occurs rapidly over a short duration of 5 min. To explain this observation we propose a suitable mechanism based on the Lee's theory, which correlates the tendency of DR with the observed zeta potentials of the dispersed medium. To the best of our knowledge this is the (i) first report on DR in oxide QDs, as well as the first direct experimental verification of Lee's theory, and (ii) most rapid DR reported so far. The facile nature of the method presented here makes ultra-small ZnO readily accessible for fundamental exploration and technologically relevant applications. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Effect of evaporation and agglomeration on droplet shape oscillations

The effects of evaporation and the presence of agglomerating nanoparticles on the oscillation characteristics of pendant droplets are studied experimentally using ethanol and aqueous nanoalumina suspension, respectively. Axisymmetric oscillations induced by a round air jet are considered. Wavelet transform of the time evolution of the 2nd modal coefficient revealed that while a continuous increase in the natural frequency of the droplet occurs with time due to the diameter regression induced by vaporization in the case of ethanol droplet, no such change in resonant frequency occurs in the case of the agglomerating droplet. However, a gradual reduction in the oscillation amplitude ensues as the agglomeration becomes dominant. (C) 2014 Elsevier Ltd. All rights reserved.

Role of degree of saturation in denitrification of unsaturated sand specimens

Nitrate contamination of groundwater arises from anthropogenic activities, such as, fertilizer and animal manure applications and infiltration of wastewater/leachates. During migration of wastewater and leachates, the vadose zone (zone residing above the groundwater table), is considered to facilitate microbial denitrification. Particle voids in vadose zone are deficient in dissolved oxygen as the voids are partially filled by water and the remainder by air. Discontinuities in liquid phase would also restrict oxygen diffusion and therefore facilitate denitrification in the vadose/unsaturated soil zone. The degree of saturation of soil specimen (S (r)) quantifies the relative volume of voids filled with air and water. Unsaturated specimens have S (r) values ranging between 0 and 100 %. Earlier studies from naturally occurring nitrate losses in groundwater aquifers in Mulbagal town, Kolar District, Karnataka, showed that the sub-surface soils composed of residually derived sandy soil; hence, natural sand was chosen in the laboratory denitrification experiments. With a view to understand the role of vadose zone in denitrification process, experiments are performed with unsaturated sand specimens (S (r) = 73-90 %) whose pore water was spiked with nitrate and ethanol solutions. Experimental results revealed 73 % S (r) specimen facilitates nitrate reduction to 45 mg/L in relatively short durations of 5.5-7.5 h using the available natural organic matter (0.41 % on mass basis of sand); consequently, ethanol addition did not impact rate of denitrification. However, at higher S (r) values of 81 and 90 %, extraneous ethanol addition (C/N = 0.5-3) was needed to accelerate the denitrification rates.

Stabilization of Co-3 - Oxoclusters in a pcu Net: Synthesis, Structure, Solvent Exchange (Single Crystal to Single Crystal) and Magnetic Studies

The solvothermal reaction of CoCl(2)4H(2)O and 4,4-sulfonyldibenzoic acid (H(2)SDBA) resulted in the formation of a three-dimensional coordination polymer Co-3(C14H8O6S)(3)(DMA)(2)(MeOH)].DMA (Ia) consisting of trinuclear Co-3 oxo-cluster units. The Co-3 trimeric units are connected by SDBA(2-) anions leading to a three dimensional structure with a pcu topology. The terminal methanol molecules could be exchanged in a single crystal to single crystal (SCSC) fashion by other similar solvent molecules (ethanol, acetonitrile, water, ethyleneglycol). Magnetic studies on the parent compound, Ia, indicate antiferromagnetic interactions between the central metal atoms.

Porous wide band gap BiNbO4 ceramic nanopowder synthesised by low temperature solution-based method for gas sensing applications

In this study, we report the gas sensing behavior of BiNbO4 nanopowder prepared by a low temperature simple solution-based method. Before the sensing behaviour study, the as-synthesized nanopowder was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-diffuse reflectance spectroscopy, impedance analysis, and surface area measurement. The NH3 sensing behavior of BiNbO4 was then studied by temperature modulation (50-350 degrees C) as well as concentration modulation (20-140 ppm). At the optimum operating temperature of 325 degrees C, the sensitivity was measured to be 90%. The cross-sensitivity of as-synthesized BiNbO4 sensor was also investigated by assessing the sensing behavior toward other gases such as hydrogen sulphide (H2S), ethanol (C2H5OH), and liquid petroleum gas (LPG). Finally, selectivity of the sensing material toward NH3 was characterized by observing the sensor response with gas concentrations in the range 20-140 ppm. The response and recovery time for NH3 sensing at 120 ppm were about 16 s and about 17 s, respectively.

Throwing light on platinized carbon nanostructured composites for hydrogen generation

In the present study, we have synthesised carbon nanoparticles (CNPs) through a relatively simple process using a hydrocarbon precursor. These synthesised CNPs in the form of elongated spherules and/or agglomerates of 30-55 nm were further used as a support to anchor platinum nanoparticles. The broad light absorption (300-700 nm) and a facile charge transfer property of CNPs in addition to the plasmonic property of Pt make these platinized carbon nanostructures (CNPs/Pt) a promising candidate in photocatalytic water splitting. The photocatalytic activity was evaluated using ethanol as the sacrificial donor. The photocatalyst has shown remarkable activity for hydrogen production under UV-visible light while retaining its stability for nearly 70 h. The broadband absorption of CNPs, along with the Surface Plasmon Resonance (SPR) effect of PtNPs singly and in composites has pronounced influence on the photocatalytic activity, which has not been explored earlier. The steady rate of hydrogen was observed to be 20 mu mol h(-1) with an exceptional cumulative hydrogen yield of 32.16 mmol h(-1) g(-1) observed for CNPs/Pt, which is significantly higher than that reported for carbon-based systems.

Covalent assembly-disassembly of poly(ether imine) dendritic macromolecular monomers and megamers

Poly(ether imine) dendritic macromolecules were undertaken to study the reversible dendrimer monomer-megamer assembly-disassembly in aqueous solutions. Synthesis of thiol functionalized poly(ether imine) (PETIM) dendrimers and their covalent aggregation behavior in the aqueous solution of ethanol/water (2:1) is demonstrated. The dendritic megamers were characterized using microscopic techniques. Kinetics of the aggregation behavior was followed using turbidity measurements, light-scattering and atomic force microscopic techniques. Inherent luminescence behavior of PETIM dendrimer monomers was retained in the dendrimer megamers also, which allowed visualization of the megamers through confocal microscopy. Extent of thiol functionalities that remained after the megamer assembly was estimated through Ellman's assay. Subsequent to megamer assembly, disassembly of megamers to dendrimer monomers was conducted, using dithiothreitol reagent. Water-insoluble sudan I dye was encapsulated in dendrimer megamer and subsequent release profile was assessed during the disassembly in aqueous solutions. The studies were conducted using first, second and third generations, representing 4, 8 and 16 sulfhydryl groups at their peripheries of dendrimers, respectively. (C) 2014 Elsevier Ltd. All rights reserved.