Synthesis of porous vinylnaphthalene/divinylnaphthalene copolymers and their sorptive properties towards phenol and its derivatives

Four porous vinylnaphthalene/divinylnaphthalene (VN/DVN) polymers having three different nominal crosslinking degrees (60, 80 and 100 wt.%) have been synthesized using the suspension polymerization method in the presence of toluene and decane.The use of various crosslinking levels and inert diluents was aimed at changing the extent of polymeric network-diluent interactions. The resultant polymers have specific surface area in the range 450-700 m²/g depending on the DVN content. Two sets of pores were detected in all resins: one with the diameter of ≈2 nm and the second one in the range of 30-40 nm. Their sorptive properties have been studied using dilute (0.5 mmol/l) solutions of phenol and its derivatives (o-chlorophenol, 2-methylphenol, o-nitrophenol, m-nitrophenol and p-nitrophenol). It has been found that sorption, at low equilibrium concentration, follows the order: o-nitrophenol > o-chlorophenol > m-nitrophenol > o-methylphenol > p-nitrophenol > phenol. Full characteristics of the porous structure of resultant polymers was obtained by nitrogen adsorption at 77 K and their surface properties analyzed using Inverse Gas Chromatography.     

New N-vinylamide-based polymers for the preconcetration of nitrophenols from aqueous media

New cross-linked copolymer with molecular imprints of 4-nitrophenol have been synthesized by the radical polymerization of cyclic N-vinyl amides and ethylene glycol dimethacrylate. Sorption characteristics of the obtained polymers depend on the nature of the functional monomer, ratio of components in the prepolymerization mixture, pH of solution, and temperature. It has been established that N-vinylpyrrolidone-based copolymers provide higher selectivity of 4-nitrophenol extraction than N-vinylcaprolactam-based products.     

Analysis of Fenitrothion and Metabolites in Stored Wheat

Abstract

A simple and rapid method for the analysis of fenitrothion and its metabolites, fenitrooxon, S-methyl fenitrothion, demethyl fenitrothion, demethyl S-methyl fenitrothion, 3-methyl-4-nitrophenol, and dimethyl phosphorothioic acid in stored wheat has been developed. Simultaneous analysis of the extract was conducted using FPD-GLC after derivatization with diazoethane except for 3-methyl-4-nitrophenol which was analyzed directly by EC-GLC. Recoveries of all compounds from wheat fortified at the levels from 0.1 to 5.0 ppm were greater than 90%.

The developed method was used to quantitatively determine major metabolites found in grain treated with fenitrothion and stored at 20°C for 12 months. Demethyl fenitrothion, 3-methyl-4-nitrophenol, and dimethyl phosphorothioic acid were the major breakdown products of fenitrothion found in stored wheat. Confirmation of these metabolites was carried out by chemical derivatization plus FPD-GLC and by TLC.     

Graphene oxide embedded P(AAm)/PANI cryogel polymer composites for sensor application against pesticide,nitro compound,and organic dyes

Abstract

Graphene oxide (GO) embedded superporous poly(acrylamide) (P(AAm)) cryogel composites (P(AAm)-GO) were prepared and used as conductive sensor materials. For this goal, the GOs flakes within superporous P(AAm) cryogels were reduced in-situ employing hydriodic acid (HI), hydrazine (N₂H₄), and sodium borohydride (NaBH₄) as reducing agents. Amongst all reduced agents\the highest conductivity was observed for HI reduced P(AAm)-GO (P(AAm)-rGO) with 1.7?×?10^?6±9.7?×?10^?8 S.cm^?1. Then again, this P(AAm)-rGO was used for in-situ synthesis of conductive polymers, poly(aniline) (PANI), and poly(pyrrole) (PPy) by using oxidative polymerization technique. The SEM, FT-IR, TGA and conductivity measurements were done for the characterization of prepared cryogel composites. It was found that the conductivity of P(AAm)-rGO increased 70- and 1400-fold with the presence of PANI and PPy, respectively. Furthermore, potential sensor application of P(AAm)-rGO/conductive polymers were tested against herbicides such as paraquat, glyphosphate (G), and a phenolic compound, 4-nitrophenol (4-NP), and some dyes such as methylene blue (MB), methyl orange (MO). Conductivity of P(AAm)-rGO/PANI decreased 5.3 -fold upon reacting with 10?mL 50?ppm G solution. The sensitivity and effect of G amounts were also tested for P(AAm)-rGO/PANI cryogel composite.     

A tetraester derivative of fluorescent calix[4]arene bearing a proton-ionizable moiety for highly sensitive extraction-fluorometric determination of sodium ion

In this study, we report the highly sensitive extraction-fluorometric detection system of Na⁺ using flow injection analysis with a tetraester derivative of fluorescent calix[4]arene. In liquid-liquid extraction experiments, the fluorescent intensity of calix[4]arene derivative 1 bearing a p-nitrophenol moiety was highly dependent on pH and the Na⁺ concentration in the aqueous phase. On the other hand, such phenomenon was not observed in the case of calix[4]arene derivative 2, which is almost the same structure as 1 except for a p-nitrophenol moiety. These results show that the proton dissociation of the p-nitrophenol moiety decisively affects the fluorescence intensity of 1. Owing to these fluorescence responsiveness, a calibration graph of the Na⁺ concentration could be successfully prepared using flow injection analysis with good linearity at the tens of nanomolar level. The tetraester scaffold of calix[4]arene was essential to the detection of Na⁺ in such a very low concentration range.     

Novel Polyurethane Multiblock Copolymers and Their Zwitterionomers Using a Polyurethane Macroiniferter

Abstract

Polyurethane-poly(4-vinylpyridine) multiblock copolymers have been prepared by the decomposition of a tetraphenylethane-based polyurethane macroiniferter in the presence of 4-vinylpyridine. The increase in the molecular weight and conversion with an increase in polymerization time proves the “living” radical mechanism. The polyurethane-poly(4-vinylpyridine) multiblock copolymers so obtained were converted into their zwitterionomers by treating with γ-propane sultone. Both block copolymers and their zwitterionomers have been characterized using spectral and thermal techniques.     

Acidic Peroxo Salts: A New Class of Initiators for Vinyl Polymerization. IV. Kinetics of Polymerization of Methyl Methacrylate Initiated by Potassium Monopersulfate Catalyzed by Ag(l)

Abstract

Kinetics of vinyl polymerization of methyl methacrylate (MMA) initiated by an acidic peroxo salt, such as potassium monopersulfate coupled with silver nitrate, have been investigated in aqueous medium over the temperature range from 35 to 50°C. The rates of polymerization (R_p) have been computed for various concentrations of the monomer and initiator. The effectiveness of various metal salts in catalyzing the polymerization reaction has been determined from the observed R_p values. The effects of the catalyst (AgNO₃), initiator, monomer, and various secondary aliphatic and aromatic amines on R_p and percentage conversion have been studied. The endgroups of the resultant polymers have been studied using standard methods. From the observed endgroups and kinetic results, a reaction scheme has been proposed involving initiation by ′OH or SO₄ ^? radicals, generated by the interaction of the initiator with silver nitrate and termination by mutual combination.     

Studies on the Kinetics of Polymerization of Styrene Initiated by Arsenic Trichloride

Abstract

The cationic polymerization of styrene initiated by arsenic trichloride (AsCl₃) in the presence of traces of acetic acid (co-catalyst) at -8, -4, and 0°C for 100 min using the dilatometric technique in an inert atmosphere yielded low molecular weight polymer. The rate of polymerization (R_p) is a direct function of the concentration of AsCl₃, monomer, and polar solvent, but inversely proportional to the polymerization temperature and nonpolar solvent. Hydroquinone has no effect on R_p Various kinetic parameters have been evaluated and a kinetic scheme is proposed.     

基于邻香草醛缩2-氨基-4-硝基苯酚的Schiff碱有机锡配合物的合成、晶体结构及生物活性

邻香草醛缩2-氨基4-硝基苯酚(H₂L)分别与二丁基氧化锡、二苄基二氯化锡反应, 合成了二丁基锡Schiff碱配合物(1)和单苄基Schiff碱配合物(2)。配合物经元素分析、¹H NMR、¹³C NMR、IR、UV-Vis表征, 并用X-射线单晶衍射测定了分子结构。研究了配体H₂L及配合物1、2对癌细胞Hela、MCF7、HepG2、Colo205、NCI-H460的抑制活性, 结果表明配合物1对这5种癌细胞的抑制效果优于现有抗癌药物卡铂, 可作为抗癌药物的候选化合物。在Tris缓冲溶液中, 以EB做为荧光探针, 用荧光光谱法研究了配体H₂L及配合物2与鲱鱼精DNA的相互作用, 结果表明配合物与DNA作用主要是由于Schiff碱配体协同效应所致。     

Preparation and lectin binding specificity of polystyrene particles grafted with glycopolymers bearing S-linked carbohydrates

Polystyrene particles bearing ATRP initiating groups, obtained by emulsifier-free emulsion polymerization of styrene (St) and 2-chloropropyloxyethyl methacrylate (CPEM), were subjected to surface-initiated activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) using glycomonomers, i.e., 4-vinylbenzenesulfonamidoethyl 1-thio-β-d-glucopyranoside (1) and 4-vinylbenzenesulfonamidoethyl 1-thio-β-d-lactoside (2). The glycopolymer-grafted polystyrene particles obtained Gp1 and Gp2 were shown to have hydrated graft layers of 15–65 nm in thickness on the cores of 370 nm in diameter. Gp1 and Gp2 coagulated in the presence of concanavalin A (Con A) and that of peanut agglutinin (PNA), respectively, showing highly specific response toward lectins.     

Molecular recognition of amphiphilic p-sulfonatocalix[4]arene with organic ammoniums

The binding abilities and thermodynamic origin for the intermolecular complexation of two water-soluble calixarenes, p-sulfonatocalix[4]arene (SC4A) and 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis(n-butyl)-calix[4]arene (SC4A-Bu), with six organic cations: 1,4-diazabicyclo[2,2,2]octane (G1), 3,5,6,8,-tetrahydropyrazino[1,2,3,4-Imn][1,10]phenanthroline (G2), diquat (G3), paraquat (G4), 1-methylpyridin-1-ium (G5) and 1,3-dimethylimidazolium (G6), have been determined by means of isothermal titration calorimetry in aqueous solutions at pH 7.0, 298.15 K, and their binding modes have been investigated by NMR spectroscopy. The obtained results indicate that the binding modes of SC4A-Bu and SC4A change a little but their binding affinities show great difference, resulting from the distinguishable binding thermodynamics. The binding selectivity of G1 is up to 688 times for the SC4A/SC4A-Bu hosts, and SC4A-Bu prefers to include planer molecules of large π system with low electron density. The aggregation behaviours of SC4A-Bu before and after complexation with G3 were then investigated, showing that G3 is able to induce the aggregation of SC4A-Bu.     

Living Anionic Polymerization of 4-(α-Alkylvinyl)styrene Derivatives

Summary. The anionic polymerization of four bis-functionalized styrene derivatives with α-alkylvinyl groups have been carried out in THF at −78°C with the initiator prepared from oligo(α-methylstyryl)lithium and potassium tert-butoxide. The four monomers herein used are 4-isopropenylstyrene (4), 3-isopropenylstyrene (5), 2-isopropenylstyrene (6), and 4-(α-isopropylvinyl)styrene (7). It was found that under such polymerization conditions, the vinyl groups of both 4 and 7 are selectively polymerized and the isopropenyl and α-isopropylvinyl groups remain completely intact to afford stable living anionic polymers. As expected, the resulting polymers possessed precisely controlled chain lengths and narrow molecular weight distributions. More importantly, they also possessed the pendant isopropenyl and α-isopropylvinyl group in each monomer unit possible for further modification. On the other hand, the anionic polymerization of either 5 or 6 proceeded more or less along with the unwanted side reactions leading to chain-branching, followed by cross-linking. The positional effect of isopropenyl group on the polymerization and the cause of possible side reactions were discussed.     

New Water-Soluble Au(III) Complexes with Xyloside-Based Ligands: Synthesis,Structural Characterization,Solution Studies and Catalytic Evaluation

A short and convenient approach to the original xyloside-based ligands, has been achieved, using d -xylose as a starting material. The complexation properties of these ligands towards Au(III) cations were studied by different methods, such as multinuclear NMR, mass spectrometry, elemental analysis. A preliminary study using protometric titrations has been carried out in aqueous solution under various pH conditions, thus in order to investigate the binding of Au(III) cations to these ligands. Furthermore, molecular calculations were performed to obtain additional structural information. The catalytic activity of the most stable Au(III) complexes was evaluated for the homogeneous reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH₄.     

Side-Chain Type Polysulfates: Their Synthesis,AIE Properties and Applications for p-Nitrophenol Detection in Water

Two small molecular monomers, ph-TPE and ph-TPE-CN, and their homopolymers Poly (ph-TPE) and Poly (ph-TPE-CN) containing tetra phenylethylene and sulfate structures, were synthesized by a sulfur (VI) fluorine exchange click reaction (SuFEx) and radical polymerization. All the monomers and polymers exhibit a typical aggregation-induced emission (AIE) effect both in the solid state and aggregated state. Moreover, based on the intermolecular charge transfer (ICT) effect between the tetra phenylethylene chromophore and p-nitrophenol, both polymers could be used for the selective detection of p-nitrophenol. The detection limit and reactivity coefficient of Poly (ph-TPE) are 0.081 μM and 5.15×10⁴ M⁻¹, respectively, whereas the detection limit and reactivity coefficient of Poly (ph-TPE-CN) are 0.077 μM and 1.81×10⁴ M⁻¹, respectively. This can be attributed to the greater sensitivity of Poly (ph-TPE-CN) to p-nitrophenol than that of Poly (ph-TPE). This work provides a new methodology for the preparation and broadening application of side-chain type AIE-active polysulfate fluorescent probes.     

In situ Polypropylene Nanocomposites: Gas‐Phase Polymerization of Propylene in the Presence of Nanofillers using Nanosilica‐Supported‐Zirconocene Catalyst

This work concentrates on using the gas‐phase polymerization technique for the production of highly loaded nanocomposites. Filler loading levels near the vicinity of 40 wt% have been obtained using different nanofillers. Three different in situ Polypropylene (PP) nanocomposites, i.e., Cloisite‐20A filled polypropylene (CFPP), Kaolin filled polypropylene (KFPP) and nanosilica filled polypropylene (SFPP) have been prepared by gas‐phase polymerization. The catalyst used is Nanosilica‐Supported‐Zirconocene. The fillers used are Closite‐20A, Kaolin and nanosilica, respectively. These were pre‐treated with MAO (Methylaluminoxane) to inhibit their deactivating action on the catalyst because of the presence of either acidic or basic groups on their surfaces; in this way MAO acts as a co‐catalyst for the three polymerization reactions being discussed. Significantly higher molecular weight polypropylene was formed with nanosilica as the filler. The melting temperature and enthalpy is also observed to be comparatively higher in this case. However, in the case of other fillers, the molecular weights, as well as melting points, are comparatively lower. With the catalyst used, a mixture of crystalline and amorphous polypropylene was observed to form. Comparatively lesser amounts of crystalline polypropylene are also observed.     

基于邻香草醛缩2-氨基-4-硝基苯酚的Schiff碱有机锡配合物的合成、晶体结构及生物活性

邻香草醛缩2-氨基4-硝基苯酚(H₂L)分别与二丁基氧化锡、二苄基二氯化锡反应, 合成了二丁基锡Schiff碱配合物(1)和单苄基Schiff碱配合物(2)。配合物经元素分析、¹H NMR、¹³C NMR、IR、UV-Vis表征, 并用X-射线单晶衍射测定了分子结构。研究了配体H₂L及配合物1、2对癌细胞Hela、MCF7、HepG2、Colo205、NCI-H460的抑制活性, 结果表明配合物1对这5种癌细胞的抑制效果优于现有抗癌药物卡铂, 可作为抗癌药物的候选化合物。在Tris缓冲溶液中, 以EB做为荧光探针, 用荧光光谱法研究了配体H₂L及配合物2与鲱鱼精DNA的相互作用, 结果表明配合物与DNA作用主要是由于Schiff碱配体协同效应所致。     

Silver nanocomposite hydrogel of Gum Ghatti with potential antibacterial property

Abstract

A nanocomposite hydrogel based on the polysaccharide Gum ghatti (Gg) has been made by microwave assisted polymerization of N,N-dimethylacrylamide (DMA) in the presence of Gg. Silver nanoparticles have been incorporated into the gel by chemical reduction method. The conditions for obtaining the graft copolymer gel and its nanocomposite have been optimized. The chemical, thermal and morphological characterization of the synthesized materials have been made using FTIR, TGA, SEM, EDS, XRD and TEM techniques. Swelling studies in aqueous media indicated the influence of nanoparticles in enhancing the swelling ability of the gel by three fold. In addition, the presence Ag nanoparticles is found to impart significant antibacterial property to the gel against Gram negative and Gram positive bacteria, the effect being pronounced on the former.     

Enhanced photocatalytic performance of N-doped RGO-FeWO4/Fe3O4 ternary nanocomposite in environmental applications

Nitrogen doped RGO- FeWO₄/Fe₃O₄ (NRGO-FeWO₄/Fe₃O₄) ternary nanocomposite was synthesized by rapid single step microwave irradiation approach using iron acetate, ammonium tungstate and graphene oxide as precursors. The synthesized materials were thoroughly characterized by diffraction, microscopic and spectroscopic techniques. The materials were tested for their catalytic efficiency in photo degradation of Methylene Blue (MB) dye and in reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). MB was mineralized within 100 minutes of visible light irradiation time in the presence of the ternary composite, apart from excellent stability and efficiency even after 10 consecutive cycles. The composite also had the capacity to convert 4-NP into 4-AP within 45 seconds and showed very good catalytic activity even after 20 cycles. The results revealed that ternary composite has way more efficiency than the component materials and can act as a promising catalyst for various environmental and engineering applications.     

Single-walled carbon nanohorn as new solid-phase extraction adsorbent for determination of 4-nitrophenol in water sample

Single-walled carbon nanohorn (SWCNH) was developed as new adsorbent for solid-phase extraction using 4-nitrophenol as representative. The unique exoteric structures and high surface area of SWCNH allow extracting a large amount of 4-nitrophenol over a short time. Highly sensitive determination of 4-nitrophenol was achieved by linear sweep voltammetry after only 120 s extraction. The calibration plot for 4-nitrophenol determination is linear in the range of 5.0 × 10⁻⁸ M-1.0 × 10⁻⁵ M under optimum conditions. The detection limit is 1.1 × 10⁻⁸ M. The proposed method was successfully employed to determine 4-nitrophenol in lake water samples, and the recoveries of the spiked 4-nitrophenol were excellent (92-106%).     

Synthesis of a Novel Type of Aromatic Diamines Containing Both Oxygen and Nitrogen Donors

A novel type of aromatic diamines (20 - 28) containing both oxygen and nitrogen donors were synthesized by Raney nickel-catalyzed hydrazine or amalgamated aluminum reduction of the corresponding nitro-compounds (3,12 - 19), which were prepared by condensation of N-substituted nitrogen mustards (4 - 11) with 2-nitrophenol in the presence of potassium carbonate in DMF at 80 °C for 6 h.