Synthesis and photophysical study of silver nanoparticles stabilized by unsaturated dicarboxylates

Solution-phase synthesis of nanometer-sized silver particles is reported by sodium borohydride reduction of AgNO_3. Two isomeric dicarboxylates (sodium maleate and sodium fumarate) have been used as stabilizing agents. The dicarboxylate-stabilized silver nanoparticles are characterized by UV-vis spectroscopy, high-resolution transmission electron microscopy (HR-TEM) and fourier transform infrared (FT-IR) spectroscopy. A qualitative comparison is made between the UV-vis spectral characteristic of the SPR band and the simulated curve obtained from modified Mie's theory. Silver nanoparticles prepared using these two isomeric dicarboxylates show intense fluorescence in the visible region. DFT with hybrid functional (B3LYP)-based frequency (IR) calculation of both the dicarboxylates and the respective nanoparticles are in good agreement with the experimental IR frequency. On the basis of this calculation a model has been proposed for the stabilization of silver nanoparticles by these two isomeric dicarboxylate anions.     

HPLC method development and validation of cytotoxic agent phenyl‐heptatriyne in Bidens pilosa with ultrasonic‐assisted cloud point extraction and preconcentration

Extraction and pre‐concentration of a bioactive marker compound, phenyl‐1,3,5‐heptatriyne from Bidens pilosa, prior to HPLC has been demonstrated using both organic and ecofriendly solvents. Non‐ionic surfactants, viz. Triton X‐100, Triton X‐114 and Genapol X‐80, were used for extraction. No back‐extraction or liquid chromatographic steps were required to remove the target phytochemical from the surfactant‐rich extractant phase. The optimized cloud point extraction procedure has been shown to be a potentially useful methodology for the preconcentration of the target analyte, with a preconcentration factor of 4–99. Moreover, the method is simple, sensitive, rapid and consumes lesser solvent than traditional methods. An isocratic chromatographic separation and quantitation was accomplished on a C₁₈ column with acetonitrile–acidified aqueous as mobile phase at a flow rate of 1.0 mL/min, UV detection at 254 nm and specificity with photo diode‐array detector (PDA) and MS. Under the optimum experimental conditions recovery was satisfactory (99.18–100.33%) without interference from the surfactant. The method seems to be reliable with intraday precision and interday precision below 2.0%. Good linearity was obtained in the working range from 7.5 to 30 µg/mL with correlation coefficient >0.99. The limits of detection and quantitation were 1.84 and 6.13 µg/mL, respectively. The method was validated following international guidelines and successfully applied for quantitative assays of cytotoxic compound phenyl‐1,3,5‐heptatriyne in Bidens pilosa. Copyright © 2010 John Wiley & Sons, Ltd.     

An efficient synthesis of 3,4-dihydropyrimidin-2(1H)-ones catalyzed by thiamine hydrochloride in water under ultrasound irradiation

An environmentally benign aqueous Biginelli protocol for the synthesis of substituted 3,4-dihydropyrimidin-2(1H)-ones using thiamine hydrochloride as a catalyst has been achieved. These ultrasound-assisted reactions proceed efficiently in water in the absence of organic solvent. Utilization of ultrasound irradiation, simple reaction conditions, isolation, and purification makes this manipulation very interesting from an economic and environmental perspective.     

Direct analysis in real time (DART) mass spectrometry of nucleotides and nucleosides: elucidation of a novel fragment [C<Subscript>5</Subscript>H<Subscript>5</Subscript>O]<Superscript>+</Superscript> and its in-source adducts

Direct analysis in real time (DART) mass spectrometry is a recently developed innovative technology, which has shown broad applications for fast and convenient analysis of complex samples. Due to the ease of sample preparation, we have recently initiated an investigation of the feasibility of detecting nucleotides and nucleosides using the DART-AccuTOF instrument, which we will refer to as the DART mass spectrometer. Our experimental results reveal that the ions representing the intact molecules of nucleotides are not detectable in either positive-ion or negative-ion mode. Instead, all four natural nucleotides fragment in the DART ion source, and a common fragment ion, [C₅H₅O]⁺ (1), is observed, which is probably formed via multiple-elimination reactions. Interestingly, 1 can form adducts with nucleobases in different molar ratios in the DART ion source. In contrast to nucleotides, the ions representing the intact molecules of nucleosides are detected in both positive-ion and negative-ion mode using DART mass spectrometry. Surprisingly, the fragmentation pattern of nucleosides is different from that of nucleotides in the DART ion source. In the cases of nucleosides (under positive-ion conditions), the production of 1 is not observed, indicating that the phosphate group plays an important role for the multiple eliminations observed in the spectra of nucleotides. The in-source reactions described in the present work show the complexity of the conditions in the DART ion source, and we hope that our results illustrate a better understanding about DART mass spectrometry.     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

Effect of substrate texture on the growth of hematite nanowires

The effect of texture of iron foil substrate on the growth of hematite nanowires by annealing method has been investigated in detail. Three substrates of different textures were prepared from a [2 0 0] oriented iron foil by some simple processes. The hematite nanowires on these substrates were synthesized by annealing iron foil at 700 °C in moist oxygen. The growth pattern of nanowires on these substrates showed that the growth of hematite nanowires depends strongly on the iron substrate texture and [1 1 0] oriented iron grains are necessary for their growth. The samples were characterized by Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), X-ray diffraction (XRD), Electron Back Scatter Diffraction (EBSD) and Raman Spectroscopy. We have also tried to explain the various observations on the mechanism of growth. Mainly, the presence of water vapor significantly enhanced the formation of hematite nanowires which resulted in a very dense and aligned growth of nanowires on the substrate areas of favorable texture. Finally, the study proved the substrate texture to be a powerful tool to control growth of nanowires and can be used efficiently for patterning and large scale synthesis of the nanowires.     

Syntheses and characterization of a new class of mono‐ and heterodinuclear derivatives of boron derived from Schiff bases

Reactions of 2‐isopropoxy‐1, 3, 2‐ benzodioxaborole with equivalent amounts of Schiff base ligands having two hydroxyl groups ( 1a–3a ) yield mononuclear derivatives with one residual hydroxy group. The reactions of these mononuclear derivatives with hexamethyldisilazane in a 2:1 ratio yield heterodinuclear derivatives. All these newly synthesized derivatives have been characterized by elemental analyses and molecular weight measurements. Tentative structures have been proposed on the basis of IR and NMR (¹H, ¹³C, ¹¹B,²⁹Si)spectral data and Fab‐mass studies. Schiff bases and their corresponding mono‐ and heterodinuclear derivatives of boron have also been screened for antifungal activities. Copyright © 2010 John Wiley & Sons, Ltd.     

Imprinted silica nanoparticles coated with N‐propylsilylmorpholine‐4‐carboxamide for the determination of m‐cresol in synthetic and real samples

m‐Cresol‐imprinted silica nanoparticles coated with N‐propylsilylmorpholine‐4‐carboxamide have been developed that contain specific pockets for the selective uptake of m‐cresol. Silica nanoparticles were synthesized by a sol–gel process followed by functionalization of their surface with N‐propylsilylmorpholine‐4‐carboxamide. The formation of m‐cresol‐imprinted silica nanoparticles was confirmed by UV‐Vis spectrophotometry, infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy. Electron microscopic studies revealed the formation of monodispersed imprinted silica nanoparticles with spherical shape and an average size of 83 nm. The developed nanoparticles were filled in a syringe and used for the extraction of m‐cresol from aqueous samples followed by quantification using high‐performance liquid chromatography with diode array detection. Various adsorption experiments showed that developed m‐cresol‐imprinted silica nanoparticles exhibited a high adsorption capacity and selectivity and offered a fast kinetics for rebinding m‐cresol. The chromatographic quantification was achieved using mobile phase consisting of acetonitrile/water (70:30 v/v) at an isocratic flow rate of 1.0 mL/min using a reversed‐phase C₁₈ column and detection at λ_max = 275 nm. The limits of detection and quantification were 1.86 and 22.32 ng/mL, respectively, for the developed method. The percent recoveries ranged from 96.66–103.33% in the spiked samples. This combination of this nanotechnique with molecular imprinting was proved as a reliable, sensitive and selective method for determining the target from synthetic and real samples.     

Uncatalyzed synthesis of new substituted dihydro-2H-dipyrimido[1,2-a,4,5-d]pyrimidine-2,4(3H)-dione

Research on Chemical Intermediates - A convenient and new method has been developed for the synthesis of highly substituted dihydro-2H-dipyrimido[1,2-a,4,5-d]pyrimidine-2,4(3H)-dione derivatives by...