Green synthesis of biopolymer-silver nanoparticle nanocomposite: An optical sensor for ammonia detection

Biopolymer used for the production of nanoparticles (NPs) has attracted increasing attention. In the presence article we use aqueous solution of polysaccharide Cyamopsis tetragonaloba commonly known as guar gum (GG), from plants. GG acts as reductive preparation of silver nanoparticles which are found to be <10. nm in size. The uniformity of the NPs size was measured by the SEM and TEM, while a face centered cubic structure of crystalline silver nanoparticles was characterized using powder X-ray diffraction technique. Aqueous ammonia sensing study of polymer/silver nanoparticles nanocomposite (GG/AgNPs NC) was performed by optical method based on surface plasmon resonance (SPR). The performances of optical sensor were investigated which provide the excellent result. The response time of 2-3. s and the detection limit of ammonia solution, 1. ppm were found at room temperature. Thus, in future this room temperature optical ammonia sensor can be used for clinical and medical diagnosis for detecting low ammonia level in biological fluids, such as plasma, sweat, saliva, cerebrospinal liquid or biological samples in general for various biomedical applications in human. © 2012 Elsevier B.V.

Detailed investigation of a gamma-cyclodextrin inclusion complex with L-thyroxine for improved pharmaceutical formulations

Thyroxine is a naturally occurring human hormone produced by the thyroid gland. Clinical applications of thyroxine to treat several chronic disorders are limited by poor water solubility and instability under physiological conditions. An inclusion complex of levo-thyroxine (l-thyroxine), the active form of the hormone with gamma cyclodextrin (gamma-CD) has been obtained and studied with the aim of improving oral delivery rather than the injection formulation of the sodium salt. In addition to greater patient acceptability, inclusion complexes often improve aqueous solubility and bioavailability, stability, and reduce toxicity of drugs, thus providing enhanced pharmaceutical formulations. Physicochemical characterization of the inclusion complex was carried out using Fourier transform infrared spectroscopy, X-ray diffractometry, differential scanning calorimetry, scanning electron microscopy and proton nuclear magnetic resonance spectroscopy. Intermolecular dipolar interactions for the inclusion complex were also studied using 2 dimensional ROESY experiments. Formation of the inclusion complex between the protons H3 and H5 of cyclodextrin with aromatic protons of thyroxine was confirmed by their dipolar interaction. Molecular modelling was used to understand the basis for the complex formation and predict the formation of other complexes. Interestingly, we found that l-thyroxine forms an inclusion complex only with the larger gamma-CD and not with other available alpha and beta forms.

Antibodies against the extracellular domain of human Notch1 receptor reveal the critical role of epidermal-growth-factor-like repeats 25-26 in ligand binding and receptor activation

The Notch signalling pathway is implicated in a wide variety of cellular processes throughout metazoan development. Although the downstream mechanism of Notch signalling has been extensively studied, the details of its ligand-mediated receptor activation are not clearly understood. Although the role of Notch ELRs EGF (epidermal growth factor)-like-repeats] 11-12 in ligand binding is known, recent studies have suggested interactions within different ELRs of the Notch receptor whose significance remains to be understood. Here, we report critical inter-domain interactions between human Notch1 ELRs 21-30 and the ELRs 11-15 that are modulated by calcium. Surface plasmon resonance analysis revealed that the interaction between ELRs 21-30 and ELRs 11-15 is similar to 10-fold stronger than that between ELRs 11-15 and the ligands. Although there was no interaction between Notch 1 ELRs 21-30 and the ligands in vitro, addition of pre-clustered Jagged1Fc resulted in the dissociation of the preformed complex between ELRs 21-30 and 11-15, suggesting that inter-domain interactions compete for ligand binding. Furthermore, the antibodies against ELRs 21-30 inhibited ligand binding to the full-length Notch1 and subsequent receptor activation, with the antibodies against ELRs 25-26 being the most effective. These results suggest that the ELRs 25-26 represent a cryptic ligand-binding site which becomes exposed only upon the presence of the ligand. Thus, using specific antibodies against various domains of the Notch1 receptor, we demonstrate that, although ELRs 11-12 are the principal ligand-binding site, the ELRs 25-26 serve as a secondary binding site and play an important role in receptor activation.

Synthesis, structural analysis and solvatochromic behaviour of 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile mesogen

In this communication, we report the synthesis and characterisation of a new luminescent liquid crystalline material, 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile (3). We have confirmed its structure by Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy, elemental analysis and X-ray single crystal diffraction studies. The newly synthesised compound crystallises in a monoclinic system with the space group C2/c and its cell parameters are found to be a?=?25.181(4) angstrom, b?=?15.651(4)angstrom, c?=?12.703(19) angstrom, V?=?4880.4 (16) angstrom, Z?=?8. The results indicate that the presence of weak CH center dot center dot center dot O and CH center dot center dot center dot N hydrogen bonding as short-range intermolecular interactions are responsible for the formation of its crystal assembly. The measured torsion angle shows the existence of a distorted structure for the molecule wherein 4-butoxyphenylene ring substituent at the fourth position of the central pyridine ring forms a torsion angle chiC(4), C(3), C(10), C(19)] of 40.55 degrees. Its liquid crystalline behaviour was investigated with the aid of polarised optical microscopy and differential scanning calorimetry. The study reveals that the compound displays a broad nematic phase in the range of 78112 degrees C. Further, solution phase optical studies indicate that it is a blue light emitter in different non-polar and polar organic solvents at a concentration of 10-5M.

Metabolites of PPI-2458, a selective, irreversible inhibitor of methionine aminopeptidase-2: structure determination and In vivo activity

The natural product fumagillin exhibits potent antiproliferative and antiangiogenic properties. The semisynthetic analog PPI-2458, (3R,4S,5S,6R)-5-methoxy-4-(2R,3R)-2-methyl-3-(3-methylbut-2-enyl) oxiran-2-yl]-1-oxaspiro2.5]octan-6-yl] N-(2R)-1-amino-3-methyl-1-oxobutan-2-yl]carbamate, demonstrates rapid inactivation of its molecular target, methionine aminopeptidase-2 (MetAP2), and good efficacy in several rodent models of cancer and inflammation with oral dosing despite low apparent oral bioavailability. To probe the basis of its in vivo efficacy, the metabolism of PPI-2458 was studied in detail. Reaction phenotyping identified CYP3A4/5 as the major source of metabolism in humans. Six metabolites were isolated from liver microsomes and characterized by mass spectrometry and nuclear resonance spectroscopy, and their structures were confirmed by chemical synthesis. The synthetic metabolites showed correlated inhibition of MetAP2 enzymatic activity and vascular endothelial cell growth. In an ex vivo experiment, MetAP2 inhibition in white blood cells, thymus, and lymph nodes in rats after single dosing with PPI-2458 and the isolated metabolites was found to correlate with the in vitro activity of the individual species. In a phase 1 clinical study, PPI-2458 was administered to patients with non-Hodgkin lymphoma. At 15 mg administered orally every other day, MetAP2 in whole blood was 80% inactivated for up to 48 hours, although the exposure of the parent compound was only similar to 10% that of the summed cytochrome P450 metabolites. Taken together, the data confirm the participation of active metabolites in the in vivo efficacy of PPI-2458. The structures define a metabolic pathway for PPI-2458 that is distinct from that of TNP-470 ((3R, 4S, 5S, 6R)-5-methoxy-4-(2R, 3R)-2-methyl-3-(3-methylbut-2-enyl)oxiran-2-yl]-1-oxaspiro2.5]octan-6 -yl] N-(2-chloroacetyl)carbamate). The high level of MetAP2 inhibition achieved in vivo supports the value of fumagillin-derived therapeutics for angiogenic diseases.

Heat mediated synthesis of silver nanoparticles using citrus limon (lemon) extract

In the present study, silver nanoparticles were rapidly synthesized by treating silver ions with Citrus limon (lemon) extract at higher temperature. The effect of process parameters like reductant concentration, mixing ratio of the reactants, concentration of silver nitrate and heating time period were studied. The formation of silver nanoparticles was confirmed by surface plasmon resonance as determined by UV-visible spectra in the range of 400-500 nm. X-ray diffraction analysis revealed the distinctive facets (111, 200, 220, 222 and 311 planes) of silver nanoparticles. Nanoparticles below 50 nm with spherical and spheroidal shape were observed from microscopic studies. The study offers a rapid method to synthesize silver nanoparticles within ten minutes of interaction with the bio-reductant.

Tuning ultrafast photoresponse of gold nanorods

Nondegenerate pump probe differential transmission experiments on gold nanorods with varying longitudinal surface plasmon resonance have revealed a new phenomenon where the polarity of the transient transmission signal can be reversibly switched between photo bleaching and photo-induced absorption by controlling probe fluence. Under the usual case where probe fluences are nominal, photo bleaching effect is observed for the nanorods with longitudinal surface plasmon resonance energy smaller than the probe photon energy. The laser-induced melting of the nanorods or change in their shape is ruled out for the observed optical switching effect. A quantitative understanding of the results is attempted by invoking a cascaded two-photon absorption dominant beyond a threshold probe fluence of similar to 75 mu J/cm(2).

Spontaneous assembly of iridium nanochain-like structures: surface enhanced Raman scattering activity using visible light

A facile, environmentally friendly approach to synthesize branched Ir nanochain-like structures under mild conditions, using polyfunctional capping molecules in an aqueous medium is reported; the nanostructures exhibit a surface plasmon resonance peak (SPR) in the visible region and serve as an active substrate for surface enhanced Raman scattering studies.

Metallic Nanoparticles Arranged in a Helical Geometry: Route Towards Strong and Broadband Chiro-optical Response

Recent advances in nanotechnology have paved ways to various techniques for designing and fabricating novel nanostructures incorporating noble metal nanoparticles, for a wide range of applications. The interaction of light with metal nanoparticles (NPs) can generate strongly localized electromagnetic fields (Localized Surface Plasmon Resonance, LSPR) at certain wavelengths of the incident beam. In assemblies or structures where the nanoparticles are placed in close proximity, the plasmons of individual metallic NPs can be strongly coupled to each other via Coulomb interactions. By arranging the metallic NPs in a chiral (e.g. helical) geometry, it is possible to induce collective excitations, which lead to differential optical response of the structures to right-and left circularly polarized light (e.g. Circular Dichroism - CD). Earlier reports in this field include novel techniques of synthesizing metallic nanoparticles on biological helical templates made from DNA, proteins etc. In the present work, we have developed new ways of fabricating chiral complexes made of metallic NPs, which demonstrate a very strong chiro-optical response in the visible region of the electromagnetic spectrum. Using DDA (Discrete Dipole Approximation) simulations, we theoretically studied the conditions responsible for large and broadband chiro-optical response. This system may be used for various applications, for example those related to polarization control of visible light, sensing of proteins and other chiral bio-molecules, and many more.

Long range emission enhancement and anisotropy in coupled quantum dots induced by aligned gold nanoantenna

Quantum dot arrays have been projected as the material of choice for next generation displays and photodetectors. Extensive ongoing research aims at improving optical and electrical efficiencies of such devices. We report experimental results on non-local long range emission intensity enhancement and anisotropy in quantum dot assemblies induced by isolated and partially aligned gold nanoantennas. Spatially resolved photoluminescence clearly demonstrate that the effect is maximum, when the longitudinal surface plasmon resonance of the nanoantenna is resonant with the emission maxima of the quantum dots. We estimated the decay length of this enhancement to be similar to 2.6 mu m, which is considerably larger than the range of near field interaction of metal nanoantenna. Numerical simulations qualitatively capture the near field behavior of the nanorods but fail to match the experimentally observed non-local effects. We have suggested how strong interactions of quantum dots in the close packed assemblies, mediated by the nanoantennas, could lead to such observed behavior. (C) 2014 AIP Publishing LLC.

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.

Inter molecular azide-diisocyanate coupling: new insights for energetic solid propellants

Hydroxyl terminated azide binders can undergo a spurious reaction with diisocyanates to form tetrazoline-5-one via an inter molecular 1,3-dipolar cycloaddition reaction apart from urethane/allophanate groups which has been overlooked. This has serious implications on solid propellants. The computed activation barrier using density functional theory (DFT) for urethane formation reaction is 28.4 kJ mol(-1) and that for tetrazoline-5-one formation reaction is 108.0 kJ mol(-1). DFT studies reveal that the rate limiting step of the reaction is 1,3-dipolar cycloaddition between azide and isocyanate. A dual cure was observed in the temperature ranges 42-77 degrees C and 78-146 degrees C by differential scanning calorimetry (DSC) and rheological studies, confirming multiple reactions. Tetrazoline-5-one formation was confirmed by Fourier transform infrared spectroscopy (FTIR) and solid state nuclear magnetic resonance spectroscopy (NMR).

Graphene scavenges free radicals to synergistically enhance structural properties in a gamma-irradiated polyethylene composite through enhanced interfacial interactions

A unique strategy for scavenging free radicals in situ on exposure to gamma irradiation in polyethylene (PE) nanocomposites is presented. Blends of ultra-high molecular weight PE and linear low-density PE (PEB) and their nanocomposites with graphene (GPEB) were prepared by melt mixing to develop materials for biomedical implants. The effect of gamma irradiation on the microstructure and mechanical properties was systematically investigated. The neat blend and the nanocomposite were subjected to gamma-ray irradiation in order to improve the interfacial adhesion between PE and graphene sheets. Structural and thermal characterization revealed that irradiation induced crosslinking and increased the crystallinity of the polymer blend. The presence of graphene further enhanced the crystallinity via crosslinks between the polymer matrix and the filler on irradiation. Graphene was found to scavenge free radicals as confirmed by electron paramagnetic resonance spectroscopy. Irradiation of graphene-containing polymer composites resulted in the largest increase in modulus and hardness compared to either irradiation or addition of graphene to PEB alone. This study provides new insight into the role of graphene in polymer matrices during irradiation and suggests that irradiated graphene-polymer composites could emerge as promising materials for use as articulating surfaces in biomedical implants.

Plasmonic Lipid Bilayer Membranes for Enhanced Detection Sensitivity of Biolabeling Fluorophores

Plasmonics based sensing, using the surface plasmon resonance of metal nanoparticles, has been effectively demonstrated in various applications. Extending this methodology to cell and artificial lipid bilayer membranes is extremely beneficial in enhancing the sensitivity of the detection of binding and cellular transport of molecules across such membranes. Here, the creation of an artificial plasmonic biomembrane template is demonstrated and used to show the enhanced detection sensitivity of certain widely used biomarker molecules. The efficacy of these templates is explained in terms of the ability of the hydrophobic polymer grafted gold nanoparticles used to organize, penetrate, and fluidize the membranes. The enhancement of photoluminescence of the dye molecules used occurs over a reasonably large spectral range as compared to the plasmon resonance of gold nanoparticles. The results could, possibly, be extended to cellular membranes with relevant modifications, as well as to the detection of any other biological molecule appropriately labeled with fluorescent dye molecules, and demonstrate the versatility of these plasmonic bioinspired platforms as potential biochemical sensors.

Enhanced nonlinear optical properties of graphene oxide-silver nanocomposites measured by Z-scan technique

Nonlinear optical properties (NLO) of a graphene oxide-silver (GO-Ag) nanocomposite have been investigated by the Z-scan setup at Q-switched Nd:YAG laser second harmonic radiation i.e., at 532 nm excitation in a nanosecond regime. A noteworthy enhancement in the NLO properties in the GO-Ag nanocomposite has been reported in comparison with those of the synthesized GO nanosheet. The extracted value of third order nonlinear susceptibility (chi(3)), at a peak intensity of I-0 = 0.2 GW cm(-2), for GO-Ag has been found to be 2.8 times larger than that of GO. The enhancement in NLO properties in the GO-Ag nanocomposite may be attributed to the complex energy band structures formed during the synthesis which promote resonant transition to the conduction band via surface plasmon resonance (SPR) at low laser intensities and excited state transition (ESA) to the conduction band of GO at higher intensities. Along with this photogenerated charge carriers in the conduction band of silver or the increase in defect states during the formation of the GO-Ag nanocomposite may contribute to ESA. Open aperture Z-scan measurement indicates reverse saturable absorption (RSA) behavior of the synthesized nanocomposite which is a clear indication of the optical limiting (OL) ability of the nanocomposite.