Synthesis of 2-Organylchalcogenopheno[2,3-b]pyridines from Elemental Chalcogen and NaBH4 /PEG-400 as a Reducing System: Antioxidant and Antinociceptive Properties.

An alternative method to prepare 2-organylchalcogenopheno[2,3-b]pyridines was developed by the insertion of chalcogen species (selenium, sulfur or tellurium), generated in situ, into 2-chloro-3-(organylethynyl)pyridines by using the NaBH4 /PEG-400 reducing system, followed by an intramolecular cyclization. It was possible to obtain a series of compounds with up to 93 % yield in short reaction times. Among the synthesized products, 2-organyltelluropheno[2,3-b]pyridines have not been described in the literature so far. Moreover, the compounds 2-phenylthieno[2,3-b]pyridine (3 b) and 2-phenyltelluropheno[2,3-b]pyridine (3 c) exhibited significant antioxidant potential in different in vitro assays. Further studies demonstrated that compound 3 b exerted an antinociceptive effect in acute inflammatory and non-inflammatory pain models, thus indicating the involvement of the central and peripheral nervous systems on its pharmacological action. More specifically, our results suggest that the intrinsic antioxidant property of compound 3 b might contribute to attenuating the nociception and inflammatory process on local injury induced by complete Freund's adjuvant (CFA).

Green synthesis of gold nanoparticles using Artemisia dracunculus extract: control of the shape and size by varying synthesis conditions.

In this study, selective green synthesis of gold nanoparticles (nAu) with the use of Tarragon extract (Artemisia dracunculus) was investigated. Characterization of the synthetized nAu was carried out using several techniques including: UV-Vis, SEM, zeta potential analysis, DLS, and ATR-FTIR. Based on measurements of Tarragon extract by HPLC-MS, significant chemical substances participating as reducing and stabilizing agents were identified. FTIR confirmed typical functional groups that could be found in these acids on the nAu surface, such as O-H, C=O and C-O. The effects of various parameters (concentration of Tarragon extract, Au precursor, and initial pH of the synthesis) on the shape and size of the nanoparticles have been investigated. UV-Vis and SEM confirmed the formation of nAu at various concentrations of the extract and Au precursor and showed correlation between the added extract concentration and shift in maximal absorbance towards higher frequencies, indicating the formation of smaller nanoplates. Zeta potential determined at various pH levels revealed that its value decreased with pH, but for all experiments in the pH range of 2.8 to 5.0, the value is below - 30 mV, an absolute value high enough for long-term nAu stability. In order to evaluate nAu catalytic activity, the reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride was used as a model system. The reaction takes place 1.5 times faster on Au-triangles than on Au-spherical NPs.

Reductive amination derivatization for the quantification of garlic components by isotope dilution analysis.

In this work, we synthesized internal standards for four garlic organosulfur compounds (OSCs) by reductive amination with 13C, D2-formaldehyde, and developed an isotope dilution analysis method to quantitate these organosulfur components in garlic samples. Internal standards were synthesized for internal absolute quantification of S-allylcysteine (SAC), S-allylcysteine sulfoxide (alliin), S-methylcysteine (SMC), and S-ethylcysteine (SEC). We used a multiple reaction monitoring (MRM) to detect 13C, D2-formaldehyde-modified OSCs by ultrahigh-performance liquid phase chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and obtained MS spectra showing different ratios of 13C, D2-formaldehyde-modified and H2-formaldehyde-modified compounds. The resulting labeled and unlabeled OSCs were exhibited correlation coefficient (R2) ranged from 0.9989 to 0.9994, respectively. The average recoveries for four OSCs at three concentration levels ranged from 89% to 105%. By 13C, D2-formaldehyde and sodium cyanoborohydride, the reductive amination-based method can be utilized to generate novel internal standard for isotope dilution and to extend the quantitative application.

Catalytic reduction of 4-nitrophenol and photo inhibition of Pseudomonas aeruginosa using gold nanoparticles as photocatalyst.

A simple, green method is described for the synthesis of Gold (Au) nanoparticles (NPs) using Cotoneaster horizontalis extract as a phyto-reducer and capping agent with superior photo inhibition activity against Pseudomonas aeruginosa. Different from the other methods used elevated temperatures for nanoparticles synthesis, the novelty of our method lies in its energy saving process and fast synthesis rates (~5min for AuNPs), and its potential to tune the nanoparticles size and afterward their catalytic activity. The starch, fatty acid and reducing sugars present in the extract are mostly responsible for repaid reduction rate Au+3 ions to AuNPs. Strong Plasmon resonance (SPR) of AuNPs was observed at 560nm, which indicates the formation of gold nanoparticles. Uv-visible spectroscopy, high resolution transmission electron microscope (HRTEM) and energy dispersion X-ray diffraction (XRD) were preformed to find out the formation of AuNPs. Proficient reduction of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) in the presence of AuNPs and NaBH4 was observed and was found to depend upon the nanoparticle size or the extract concentration. The AuNPs was also evaluated for antibacterial against P. aeruginosa. Before transferred it into antibacterial activity, it placed under visible light for 120min. The same experiment was performed in dark as control medium. The photo irradiated AuNPs was observed to be more effective against P. aeruginosa. The result showed that diameter of zone of inhibition of visible light irradiated AuNPs against P. aeruginosa was 17 (±0.5) and in dark was 8 (±0.4) mm.

Green synthesis of palladium nanoparticles mediated by black tea leaves (Camellia sinensis) extract: Catalytic activity in the reduction of 4-nitrophenol and Suzuki-Miyaura coupling reaction under ligand-free conditions.

The present study was conducted to synthesize palladium nanoparticles (Pd NPs) through a facile and green route using non-toxic and renewable natural black tea leaves (Camellia sinensis) extract, as the reducing and stabilizing agent. The as-prepared Pd@B.tea NPs catalyst was characterized by UV-vis spectroscopy, X-ray diffraction (XRD), fourier transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The Pd@B.tea NPs catalyst could be used as an efficient and heterogeneous catalyst for Suzuki coupling reactions between phenylboronic acid and a range of aryl halides (X=I, Br, Cl) and also the reduction of 4-nitrophenol (4-NP) using sodium borohydride in an environmental friendly medium. Excellent yields of products were obtained with a wide range of substrates and the catalyst was recycled 7 times without any significant loss of its catalytic activity.

Tyramine-modified pectins via periodate oxidation for soybean hull peroxidase induced hydrogel formation and immobilization.

Pectin was modified by oxidation with sodium periodate at molar ratios of 2.5, 5, 10, 15 and 20 mol% and reductive amination with tyramine and sodium cyanoborohydride afterwards. Concentration of tyramine groups within modified pectin ranged from 54.5 to 538 µmol/g of dry pectin while concentration of ionizable groups ranged from 3.0 to 4.0 mmol/g of dry polymer compared to 1.5 mmol/g before modification due to the introduction of amino group. All tyramine-pectins showed exceptional gelling properties and could form hydrogel both by cross-linking of carboxyl groups with calcium or by cross-linking phenol groups with peroxidase in the presence of hydrogen peroxide. These hydrogels were tested as carriers for soybean hull peroxidase (SHP) immobilization within microbeads formed in an emulsion based enzymatic polymerization reaction. SHP immobilized within tyramine-pectin microbeads had an increased thermal and organic solvent stability compared to the soluble enzyme. Immobilized SHP was more active in acidic pH region and had slightly decreased K m value of 2.61 mM compared to the soluble enzyme. After 7 cycles of repeated use in batch reactor for pyrogallol oxidation microbeads, immobilized SHP retained half of the initial activity.

One-pot green synthesis of reduced graphene oxide (RGO)/Fe3O4 nanocomposites and its catalytic activity toward methylene blue dye degradation.

The reduced graphene oxide (RGO)/Fe3O4 nanocomposites were synthesized through a facile one-pot green synthesis by using solanum trilobatum extract as a reducing agent. Spherical shaped Fe3O4 nanoparticles with the diameter of 18 nm were uniformly anchored over the RGO matrix and the existence of fcc structured Fe3O4 nanoparticles over the RGO matrix was ensured from X-ray diffraction patterns. The amide functional groups exist in the solanum trilobatum extract is directly responsible for the reduction of Fe(3+) ions and GO. The thermal stability of GO was increased by the removal of hydrophilic functional groups via solanum trilobatum extract and was further promoted by the ceramic Fe3O4 nanoparticles. The ID/IG ratio of RGO/Fe3O4 was increased over GO, indicating the extended number of structural defects and disorders in the RGO/Fe3O4 composite. The catalytic efficiency of prepared nanostructures toward methylene blue (MB) dye degradation mediated through the electron transfer process of BH4(-) ions was studied in detail. The π-π stacking, hydrogen bonding and electrostatic interaction exerted between the RGO/Fe3O4 composite and methylene blue, increased the adsorption efficiency of dye molecules and the large surface area and extended number of active sites completely degraded the MB dye within 12 min.

Optimizing the design and synthesis of supported silver nanoparticles for low cost water disinfection.

Silver nanoparticles (AgNPs) were successfully synthesized and impregnated on silica using chemical reduction methods. XPS and Ag K-edge XANES analysis revealed that the impregnation of AgNPs onto silica using a chitosan + sodium borohydride (NaBH4) method results in higher silver loading and Ag(0)/Ag(I) ratio compared to that obtained using NH3 + NaBH4/glucose methods. The effects of the dosage of chitosan on silver loading, Ag(I) release, and bactericidal activities of AgNP-impregnated silica were investigated, with results showing that, at high dosages of chitosan, Ag(I) released from AgNP-impregnated silica plays an important role in disinfection, while AgNP-mediated bactericidal action dominates at low dosages of chitosan. To further decrease the manufacturing cost, partially oxidized "black rice husk ash" containing substantial residual carbon was applied as AgNP support and found to lead to a greater degree of silver impregnation and to exhibit a longer disinfection lifetime than that of lower carbon content silica supports. On the basis of these findings, it is clear that considerable scope exists for careful optimization in the design and production of AgNP-based bactericidal materials for water treatment purposes.

Preparation of gold nanoparticles using Salicornia brachiata plant extract and evaluation of catalytic and antibacterial activity.

The current study deals with the synthesis of gold nanoparticles (AuNPs) using Salicornia brachiata (Sb) and evaluation of their antibacterial and catalytic activity. The SbAuNPs showed purple color with a characteristic surface plasmon resonance peak at 532 nm. Scanning electron microscopy and transmission electron microscopy revealed polydispersed AuNPs with the size range from 22 to 35 nm. Energy dispersive X-ray and thin layer X-ray diffraction analysis clearly shows that SbAuNPs was pure and crystalline in nature. As prepared gold nanoparticles was used as a catalyst for the sodium borohydride reduction of 4-nitro phenol to 4-amino phenol and methylene blue to leucomethylene blue. The green synthesized nanoparticles exhibited potent antibacterial activity against the pathogenic bacteria, as evidenced by their zone of inhibition. In addition, we showed that the SbAuNPs in combination with the regular antibiotic, ofloxacin, exhibit superior antibacterial activity than the individual.

Size effect of gold nanoparticles in catalytic reduction of p-nitrophenol with NaBH4.

Gold nanoparticles (Au NPs) were prepared by reducing HAuCl4 with NaBH4. Their average particle sizes could be tuned in the range of 1.7 and 8.2 nm, by adjusting the amount of NaBH4 used during synthesis. The obtained Au NPs (colloids) were then loaded onto a commercial Al2O3 support to prepare Au/Al2O3 catalysts with tunable Au particle sizes. An optimal pH value (5.9) of the Au colloid solution was found to be essential for loading Au NPs onto Al2O3 while avoiding the growth of Au NPs. Au NPs and Au/Al2O3 catalysts were tested in the reduction of p-nitrophenol with NaBH4. Interestingly, the catalytic activity depended on the size of Au NPs, being the highest when the average size was 3.4 nm. Relevant characterization by UV-Vis, TEM, and XRD was conducted.

Facile one-pot synthesis of gold and silver nanocatalysts using edible coconut oil.

The use of edible oil for the synthesis of metal nanoparticles by wet chemical method is reported for the first time. The paper presents an environmentally benign bottom up approach for the synthesis of gold and silver nanoparticles using edible coconut oil at 373 K. The formation of silver nanoparticles is signaled by the brownish yellow color and that of gold nanoparticles by the purple color. Fine control over the nanoparticle size and shape from triangular to nearly spherical is achieved by varying the quantity of coconut oil. The nanoparticles have been characterized by UV-Visible, Transmission Electron Microscopy and X-ray Diffraction. The chemical interaction of capping agents with metal nanoparticles is manifested using Fourier Transform Infrared Spectroscopy. The stable and crystalline nanoparticles obtained using this simple method show remarkable size-dependent catalytic activity in the reduction of the cationic dye methylene blue (MB) to leuco methylene blue (LMB). The first order rate constants calculated uphold the size dependent catalytic activity of the synthesized nanoparticles.

Uranium(IV) amido-borohydrides as highly active diene polymerisation catalysts.

The synthesis and structural characterisation of the uranium(IV) amido-borohydrides (N'')2U{κ(2)-N(SiMe3)SiMe2CH2BBN-H} and U{κ(2)-N(SiMe3)SiMe2CH2BBN-H}2, and their activity as pre-catalysts for the polymerisation of isoprene are described.

Catalytic reduction of 4-nitrophenol using biogenic gold and silver nanoparticles derived from Breynia rhamnoides.

A simple, green method is described for the synthesis of Gold (Au) and Silver (Ag) nanoparticles (NPs) from the stem extract of Breynia rhamnoides. Unlike other biological methods for NP synthesis, the uniqueness of our method lies in its fast synthesis rates (~7 min for AuNPs) and the ability to tune the nanoparticle size (and subsequently their catalytic activity) via the extract concentration used in the experiment. The phenolic glycosides and reducing sugars present in the extract are largely responsible for the rapid reduction rates of Au(3+) ions to AuNPs. Efficient reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of AuNPs (or AgNPs) and NaBH(4) was observed and was found to depend upon the nanoparticle size or the stem extract concentration used for synthesis.

Enhancing the stability of colloidal silver nanoparticles using polyhydroxyalkanoates (PHA) from Bacillus circulans (MTCC 8167) isolated from crude oil contaminated soil.

Polyhydroxyalkanoate (PHA) was produced by growing Bacillus circulans (MTCC 8167) in the specific detection medium. The identification of the polymer as PHA was confirmed by fluorescence microscopy. The PHA was purified and characterized using FT-IR. The silver nanoparticles (SNP) were synthesized from AgNO3 in the dispersed colloids of PHA (0.085%) using NaBH4 (sodium borohydrate as reducing agent). The stability was tested using wave length scanning with a UV-Vis spectrophotometer and finally with transmission electron microscopy. The PHA stabilized solution was found to be stable for 30 days as against the low stability of silver nanoparticles (SNP) solution alone.

Selenium speciation in flue desulfurization residues.

Flue gas from coal combustion contains significant amounts of volatile selenium (Se). The capture of Se in the flue gas desulfurization (FGD) scrubber unit has resulted in a generation of metal-laden residues. It is important to determine Se speciation to understand the environmental impact of its disposal. A simple method has been developed for selective inorganic Se(IV), Se(VI) and organic Se determination in the liquid-phase FGD residues by hydride generation atomic fluorescence spectrometry (AFS). It has been determined that Se(IV), Se(VI) and organic Se can be accurately determined with detection limits (DL) of 0.05, 0.06 and 0.06 microg/L, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1632c, and also by analyzing spiked tap-water samples. Analysis indicates that the concentration of Se is high in FGD liquid residues and primarily exists in a reduced state as selenite (Se(IV)). The toxicity of Se(IV) is the strongest of all Se species. Flue gas desulfurization residues pose a serious environmental risk.

Boron carbon nitride nanostructures from salt melts: tunable water-soluble phosphors.

A simple, high yield, chemical process is developed to fabricate layered h-BN nanosheets and BCNO nanoparticles with a diameter of ca. 5 nm at 700 °C. The use of the eutectic LiCl/KCl salt melt medium enhances the kinetics of the reaction between sodium borohydride and urea or guanidine as well as the dispersion of the nanoparticles in water. The carbon content can be tuned from 0 to 50 mol % by adjusting the reactant ratio, thus providing precise control of the light emission of the particles in the range 440-528 nm while reaching a quantum yield of 26%. Because of their green synthesis, low toxicity, small size, and stability against aggregation in water, the as-obtained photoluminescent BCNO nanoparticles show promise for diagnostics and optoelectronics.

Headspace trapping of the hydrides on a Pd(II)-coated graphite adsorptive bar as a microextraction method for ETV-ICP-MS determination of Se, Te and Bi in seawater and human hair samples.

A new, simple and sensitive method by combining headspace Pd(II)-coated graphite bar microextraction (GBME) with electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the determination of trace Se, Te and Bi in seawater and human hair. In this method, the graphite bar was coated with Pd(II) and then used for headspace trapping of the hydrides of Se(IV), Te(IV) and Bi(III). The graphite bar with enriched hydrides of analytes was inserted directly into the graphite tube and subsequently determined by ETV-ICP-MS according to the established temperature program. The experimental parameters, which may affect the extraction and vaporization of target analytes, were systematically investigated and the optimal experimental conditions were established. Under the optimal conditions, the detection limits of the method were 8.6, 2.6 and 0.2 ng l(-1) and the relative standard deviations (RSDs) were 7.0%, 6.2% and 8.0% (C=0.20 microg l(-1), n=7) for Se, Te and Bi, respectively. Linearity was obtained over the range of 0.05-20.00, 0.01-5.00 and 0.01-20.00 microg l(-1) with the correlation coefficients of 0.9942, 0.9997 and 0.9976 for Se, Te and Bi, respectively. The proposed method was successfully applied for the determination of trace Se, Te and Bi in seawater and human hair samples. In order to validate the method, the proposed method has also been applied for the determination of trace Se, Te and Bi in the certified material of GBW07601 human hair, and the determined values were in good agreement with the certified values.

Sodium borohydride/chloranil-based assay for quantifying total flavonoids.

A novel sodium borohydride/chloranil-based (SBC) assay for quantifying total flavonoids, including flavones, flavonols, flavonones, flavononols, isoflavonoids, flavanols, and anthocyanins, has been developed. Flavonoids with a 4-carbonyl group were reduced to flavanols using sodium borohydride catalyzed with aluminum chloride. Then the flavan-4-ols were oxidized to anthocyanins by chloranil in an acetic acid solution. The anthocyanins were reacted with vanillin in concentrated hydrochloric acid and then quantified spectrophotometrically at 490 nm. A representative of each common flavonoid class including flavones (baicalein), flavonols (quercetin), flavonones (hesperetin), flavononols (silibinin), isoflavonoids (biochanin A), and flavanols (catechin) showed excellent linear dose-responses in the general range of 0.1-10.0 mM. For most flavonoids, the detection limit was about 0.1 mM in this assay. The recoveries of quercetin from spiked samples of apples and red peppers were 96.5 +/- 1.4% (CV = 1.4%, n = 4) and 99.0 +/- 4.2% (CV = 4.2%, n = 4), respectively. The recovery of catechin from spiked samples of cranberry extracts was 97.9 +/- 2.0% (CV = 2.0%, n = 4). The total flavonoids of selected common fruits and vegetables were measured using this assay. Among the samples tested, blueberry had the highest total flavonoid content (689.5 +/- 10.7 mg of catechin equiv per 100 g of sample), followed by cranberry, apple, broccoli, and red pepper. This novel SBC total flavonoid assay can be widely used to measure the total flavonoid content of fruits, vegetables, whole grains, herbal products, dietary supplements, and nutraceutical products.

[Total selenium and se species in vegetables measured with hydride generation-atomic fluorescence spectrometry].

The amounts of total selenium and Se-species including organic and inorganic selenium in vegetables were measured with the method of hydride generation-atomic fluorescence spectrometry. The instrumental parameters and analytical conditions were optimized. In order to obtain the maximum fluorescence signal, the effects of the concentrations of HCI and KBH4 in carrier solution, the concentrations of HCl and HNO3 in sample medium, and the interference from foreign ion (Cu) on the signal were mainly investigated. Under the optimum conditions, the detection limit estimated with 3-fold standard deviation by 11 replicates of procedure blank was 0.35 ng x g(-1). The recovery tested by adding standards ranged from 97.6% to 101%. After being digested with HNO3 by microwave, selenium in several kinds of vegetables was measured. The results indicated that the total amounts of Se in the vegetable samples were low except straw mushroom, in which the content of Se was 0.151 microg x g(-1) (dry weight). In addition, the species of organic selenium were the main existing forms in vegetables.

[Determination of trace bismuth in traditional Chinese medicines by hydride generation atomic fluorescence spectrometry].

A method is reported for the determination of trace bismuth in traditional chinese medicine by hydride generation atomic fluorescence spectrometry. The effect of different means of digestion, the medium amounts of acid and reducing agent on the determination of Bi is investigated. In the given conditions, the linear range of determination is 0.1-200 microg x L(-1), and the detection limit is 0.0946 microg x L(-1). The instrumental relative standard deviation is about 0.55% and the recovery is about 94%-107%. The method is accurate, rapid and convenient with satisfactory results.