A selective and convenient synthesis of gemini surfactants over heterogeneous basic catalyst

Tri-ethanolamine (C₆H₁₅O₃N) and fatty acid (C₁₀H₂₀O₂, C₁₂H₂₄O₂, C₁₄H₂₈O₂ and C₁₆H₃₂O₂) using MgO–ZrO₂ selectively gave the corresponding 2-(bis(2-hydroxyethyl)amino)ethyl alkanoate in good yield. Further the reaction of 2-(bis(2-hydroxyethyl)amino)ethyl alkanoate with epichlorohydrin or 1,2-dichloroethane (in the presence of the 2-(alkanoyloxy)-N,N-bis(2-hydroxyethyl)ethanaminium chloride) over same heterogeneous catalysis to afford novel N,N-bis(2-(alkanoyloxy)ethyl)-N,N,N,N-tetrakis(2-hydroxyethyl) propane-1,3-diaminium or N,N-bis(2-(alkanoyloxy)ethyl)-N,N,N,N-tetrakis(2-hydroxyethyl)ethane-1,2- diaminium (gemini surfactants), respectively. The ease of the diaminium reaction was found to be due to the neighboring-group participation (NGP) in the quaternization step. Results of esterification and diaminium reactions, reported herein were optimized for several catalytic effects to understand the probable mechanism. The catalysts can be easily separated from reaction and showed good recyclability.     

The Identification and Quantification of Phospholipids from Thermus and Meiothermus Bacteria

Structural identities of the major phospholipid (PL-2), minor phospholipid (PL-1) and trace phospholipid (PL-0) from representative strains of the genera Thermus and Meiothermus were established. Phospholipids were quantified using phosphorus-31 nuclear magnetic resonance (³¹P-NMR). The structures of the major phospholipid (PL-2) from Thermus filiformis MOK14.7 and Meiothermus ruber WRG6.9 were identified as 2′-O-(1,2-diacyl-sn-glycero-3-phospho)-3′-O-(α-N-acetylglucosaminyl)-N-glyceroyl alkylamine (GlcNAc-PGAA) and 2′-O-(2-acylalkyldiol-1-O-phospho)-3′-O-(α-N-acetylglucosaminyl)-N-glyceroyl alkylamine (GlcNAc-diolPGAA). Interestingly, M. ruber contained only a diacyl form of GlcNAc-PGAA (87 %), while T. filiformis contained both GlcNAc-PGAA (59 %) and GlcNAc-diolPGAA (18 %). The structures of the minor phospholipid (PL-1) were established as 2′-O-(1,2-diacyl-sn-glycero-3-phospho)-3′-O-(α-glucosaminyl)-N-glyceroyl alkylamine (GlcN-PGAA, 13 %) in T. filiformis and 2′-O-(1,2-diacyl-sn-glycero-3-phospho)-3′-O-(α-galactosaminyl)-N-glyceroyl alkylamine (GalN-PGAA, 19 %) in M. ruber. This is the first reliable discovery of phosphatidylglyceroylalkylamines modified by glucosamine or galactosamine with a free amino group. No signs of diol-based phosphatidylglyceroylalkylamines were found in PL-1 phospholipids. Similar to PL-2, trace phospholipid (PL-0) from T. filiformis contained both unsubstituted diol-based phosphatidylglyceroylalkylamine (diolPGAA) and PGAA, while M. ruber contained only free PGAA. Unlike analysis using TLC, the diol form of phosphatidylglyceroylalkylamines is clearly resolved from the diacyl form via ³¹P-NMR.     

Enzymatic acylation of ether and ester lysophospholipids in rat liver microsomes

The acylation of lysophospholipids by rat liver acyltransferases was studied. A comparison between ester and ether lysophospholipids as substrates revealed large differences in substrate properties. For instance, oleic acid from oleoyl-CoA and arachidonic acid from arachidonoyl-CoA were not incorporated into 1-O-octadecyl-sn-glycero-3-phosphocholine under experimental conditions that allowed an optimal transfer of oleic acid and arachidonic acid to 1-O-palmitoyl-sn-glycero-3-phosphocholine. However, we observed an acyl-CoA-independent transfer of arachidonic acid from 1-O-stearoyl-2-O-arachidonoyl-sn-glycero-3-phosphoinositol to 1-O-octadecyl-sn-glycero-3-phosphocholine.     

O-Demethylation reaction at a diruthenium core: synthesis and structural study of two novel diruthenium compounds

The reaction between Ru₂(OAc)₄Cl and di(o-methoxyphenyl)formamidine led to the unexpected products trans-Ru₂(O₂CCH₃)₂(μ-N,N′-η²-N,O-o-MeOForm)(μ-N,N′-η²-N,O-o-MeOForm′) (1) and Ru₂(O₂CCH₃)(μ-N,N′-o-MeOForm)(μ-N,N′-η²-N,O-o-MeOForm)(μ-N,N′-η²-N,O-o-MeOForm′) (2), where o-MeOForm is di(o-methoxyphenyl)formamidinate, and o-MeOForm′ is the O-demethylation derivative of o-MeOForm, (o-methoxyphenyl)(o-oxyphenyl)formamidinate. Both compounds 1 and 2 were structurally characterized by X-ray diffraction analysis, and are isoelectronic with the previously studied chloro-tetracarboxylatodiruthenium(II,III) and chlorotetrakis(diarylformamidinato)diruthenium(II,III) on the basis of structural and magnetic data.     

The degradation of platelet-activating factor and related lipids: Susceptibility to phospholipases C and D

1-O-Octadecyl-2-O-methyl-rac-glycero-3-phosphocholine (ET-18-OCH₃) is an ether-linked lipid that exhibits selective cytotoxicity toward several types of tumor cells and is relatively inactive toward normal cells under the same conditions of treatment. The mechanism of this selective cytotoxicity is unknown. We conducted studies to determine whether this compound is metabolized by phospholipases C and D and, if so, whether sensitive and resistant cells differ in their ability to degrade ET-18-OCH₃ by these enzymes. We have examined the metabolism of the L-isomer of ET-18-OCH₃, 1-O-octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (L-ET-18-OCH₃), by lysophospholipase D of rat liver microsomes and by a phospholipase D from the marine bacteriumVibrio damsela. The metabolism of L-ET-18-OCH₃ was also examined in cell culture using Madin-Darby canine kidney cells, human promyelocytic leukemia cells and human myelocytic leukemia cells. In these studies, L-ET-18-OCH₃ and related 1-O-alkyl-linked phosphocholine analogs radiolabeled with³H in the 1-O-alkyl chain were used. L-ET-18-OCH₃ was not hydrolyzed by lysophospholipase D from rat liver microsomes under conditions where cleavage of 1-O-alkyl-2-lyso-sn-glycero-3-phosphocholine was observed. However, phospholipase D from the marine bacteriumV. damsela readily hydrolyzed L-ET-18-OCH₃ to 1-O-[³H]octadecyl-2-O-methyl-sn-glycero-3-phosphate, demonstrating that L-ET-18-OCH₃ can be degraded by a phospholipase D. Platelet-activating factor (PAF) and lyso-PAF were also substrates for the bacterial phospholipase D. When intact cells were incubated with radiolabeled L-ET-18-OCH₃ a product was formed that was identified as 1-O-[³H]octadecyl-2-O-methyl-sn-glycerol. There are two mechanisms that could account for the appearance of this product. The first involves cleavage of the compound by a phospholipase C, resulting in direct release of the diglyceride. The second possible mechanism involves cleavage by a phospholipase D to form the phosphatidic acid analog with subsequent hydrolysis to the diglyceride by a phosphohydrolase. Preliminary data support the phospholipase C-type mechanism. Regardless of which mechanism operates in intact cells, the metabolic degradation of L-ET-18-OCH₃ does not appear to be a significant factor in the selective cytotoxicity of this antitumor agent.     

Structure-cytotoxicity studies on alkyl lysophospholipids and some analogs in leukemic blasts of human origin in vitro

Eleven lipids have been tested for cytotoxic (trypan blue dye exclusion) activity in cells from eight freshly explanted human leukemias in vitro. 4-Aminomethyl-1-[2,3-(di-N-decyloxy)N-propyl]-4-phenylpiperidine (CP-46,665), 1-mercapto-hexadecyl-2-methoxymethyl-rac-glycero-3-phosphocholine (BM 41.440), the 2-acetamide analog of platelet-activating factor (PAF) and 1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine (ET-18-OCH₃) were found among the most active compounds. 2-Lysophosphatidylcholine (2-LPC) showed the lowest activity. However, in addition there was variation among the results regarding the activity of the 1-octadecyl-rac-glycero-3-phosphocholine (ET-18-OH) and its D- and L-forms, but a significantly higher cytotoxic activity of D-ET-18-OH compared with L-ET-18-OH on the basis of 2-LPC as control after an incubation time of 48 hr. We conclude that with the limited number of structures available, this type of study is not sufficient to yield further information about the mode of the accumulation and toxicity of this type of lipids.     

Dispersion properties of BaTi4O9/Ba2Ti9O20 colloids with amphoteric polyelectrolytes

An amphoteric water-soluble copolymer, i.e., polyacrylamide/(α-N,N-dimethyl-N-(3-(β-carboxylate)acrylamino)propyl) ammonium ethanate (PAM/DAE) was synthesized and used as a dispersion agent for BaTi₄O₉/Ba₂Ti₉O₂₀ (BT₄/B₂T₉) particles. PAM/DAE was prepared from acrylamide and (α-N,N-dimethyl-N-(3-(β-carboxylate)acrylamino)propyl) ammonium ethanate in a basic condition through a free radical polymerization. The dispersing property of this copolymer was examined by means of rheology, particle size, and leached Ba²⁺ concentration measurements. The results indicate that PAM/DAE could reduce the viscosity of slurries greatly, and cause BT₄/B₂T₉ particle sizes a shift to smaller values. Compared with a commercial dispersant, ammonium salt of poly(methacrylic acid) (PMAA–NH₄), PAM/DAE is as effective in preparing dispersed suspensions. More importantly, PAM/DAE could lessen the leached Ba²⁺ concentration.     

Synthesis and characterization of water-soluble polyaspartamide-ferrocene conjugates for biomedical applications

Polymer-ferrocene conjugates are synthesized from the polyamide1, poly-,-dl-[N-(3-(morpholin-4-yl)propyl)aspartamide-co-N-(2-aminoethyl)aspartamide, through coupling of amino side groups with the carboxyl function in a number of ferrocenylcarboxylic acids, including ferrocenoic acid, ferrocenylacetic acid, 3-ferrocenylpropanoic acid, 3-ferrocenylbutanoic acid, 4-ferrocenylbutanoic acid, and 4-ferrocenyl-4-hydroxypentanoic acid. The ferrocene complex has been chosen for conjugation by virtue of the cytotoxic properties observed with some of its derivatives. The coupling reactions, mediated by HBTU (O-benzotriazolyl-N,N,NN-tetramethyluronium hexafluorophosphate), are brought about inN,N-dimethylformamide solution and lead to degrees of substitution in the range of 25–95%. The resulting conjugates2, fractionated by dialysis in tubing with a 12,000–14,000 molecular mass cutoff and collected in the solid state by freeze-drying, are completely soluble in water after isolation and retain this property in frozen aqueous solutions. Preliminary electrochemical data are reported, indicating a decreasing (i.e., less positive) potential with increasing length of the aliphatic, electron-donating connecting link between the ferrocene and the carboxamide anchoring group. The 4-ferrocenylbutanoyl substituent is associated with the least positive potential of those structures investigated and, hence, should provide conjugates with optimalin vivo stability in the ferricenium state. Selected conjugates will be submitted to screening tests for antineoplastic activity.Metallocene polymers 46. For Part 45, see Ref. 1.     

Anthocyanins Profile of Grape Berries of Vitis amurensis, Its Hybrids and Their Wines

Anthocyanins are responsible for the color of grapes and wine, an important attribute of their quality. Many authors have used anthocyanins profile to classify the grape cultivars and wine authenticity. The anthocyanin profiles of grape berries of Vitis amurensis, its hybrids and their wines were analyzed by HPLC-ESI-MS/MS. The results identified 17 anthocyanins in these grape cultivars, including 11 anthocyanin monoglucosides (five pyranoanthocyanin monoglucosides and one acylated pyranoanthocyanin monoglucoside) and six anthocyanin diglucosides. Likewise, 15 kinds of anthocyanins were detected in wines, including six diglucosides and nine monoglucosides of anthocyanidins, in which four pyranoanthocyanin monoglucosides (Petunidin-3-O-glucoside-4-acetaldehyde, Malvidin-3-O-glucoside-4-pyruvic acid, Malvidin-3-O-glucoside-acetaldehyde and Peonidin-3-O-glucoside-4-pyruvic acid) were detected. In addition, a total of 14 kinds of anthocyanins including six diglucosides and eight monoglucosides of anthocyanidins were identified in skins, in which two pyranoanthocyanin monoglucosides (Peonidin-3-O-glucoside-4-pyruvic acid, Malvidin-3-O-glucoside-4-vinylphenol) and one acylated pyranoanthocyanin monoglucoside (Malvidin-3-O-(6-O-acetyl)-glucoside-4-vinylphenol) were detected. The anthocyanins profile of grape skin of V. amurensis and its hybrids consist of the anthocyanin monoglucosides, diglucosides and pyranoanthocyanins. The wines produced resulted in a slightly different anthocyanin distribution. Pelargonidin-3,5-diglucosides was first found in the skins and wines, however, no acetyl was detected in wines. The principal component analysis results suggest that the anthocyanin profiles were helpful to classify these cultivars of V. amurensis.     

Inducible <Emphasis Type="Italic">De Novo</Emphasis> Biosynthesis of Isoflavonoids in Soybean Leaves by <Emphasis Type="Italic">Spodoptera litura</Emphasis> Derived Elicitors: Tracer Techniques Aided by High Resolution LCMS

Isoflavonoids are a characteristic family of natural products in legumes known to mediate a range of plant-biotic interactions. For example, in soybean (Glycine max: Fabaceae) multiple isoflavones are induced and accumulate in leaves following attack by Spodoptera litura (Lepidoptera: Noctuidae) larvae. To quantitatively examine patterns of activated de novo biosynthesis, soybean (Var. Enrei) leaves were treated with a combination of plant defense elicitors present in S. litura gut content extracts and L-α-[¹³C₉, ¹⁵N]phenylalanine as a traceable isoflavonoid precursor. Combined treatments promoted significant increases in ¹³C-labeled isoflavone aglycones (daidzein, formononetin, and genistein), ¹³C-labeled isoflavone 7-O-glucosides (daidzin, ononin, and genistin), and ¹³C-labeled isoflavone 7-O-(6″-O-malonyl-β-glucosides) (malonyldaidzin, malonylononin, and malonylgenistin). In contrast levels of ¹³C-labeled flavones and flavonol (4′,7-dihydroxyflavone, kaempferol, and apigenin) were not significantly altered. Curiously, application of fatty acid-amino acid conjugate (FAC) elicitors present in S. litura gut contents, namely N-linolenoyl-L-glutamine and N-linoleoyl-L-glutamine, both promoted the induced accumulation of isoflavone 7-O-glucosides and isoflavone 7-O-(6″-O-malonyl-β-glucosides), but not isoflavone aglycones in the leaves. These results demonstrate that at least two separate reactions are involved in elicitor-induced soybean leaf responses to the S. litura gut contents: one is the de novo biosynthesis of isoflavone conjugates induced by FACs, and the other is the hydrolysis of the isoflavone conjugates to yield isoflavone aglycones. Gut content extracts alone displayed no hydrolytic activity. The quantitative analysis of isoflavone de novo biosynthesis, with respect to both aglycones and conjugates, affords a useful bioassay system for the discovery of additional plant defense elicitor(s) in S. litura gut contents that specifically promote hydrolysis of isoflavone conjugates.     

O-alkyl diolO-,S- andSe-phosphoroamidates of DL-α-tocopherol and their dimethylaminoalkyl derivatives as diester and triester models of phospholipids

Hexamethyltriamide of phosphorous acid, activated by addition of iodine at an optimal molar ratio of 1.05∶0.05, was used as a phosphorylating reagent to synthesize 1-hexadecyloxyethyl-2-O-, 1-hexadecyloxypropyl-3-O-, and 1-hexadecyloxybutyl-4-O-(DL-α-tocopheryl-6-O)-(N,N-dimethylamido)selenophosphate,-thiophosphate and-phosphate derivatives, and some of their 2-dimethyl-aminoethyl-1-O-, and 3-dimethylaminopropyl-1-O-triester analogues in a “one-pot procedure” in overall yields of 69–87%. Activation of the reaction with an equimolar mixture of imidazole and carbon disulfide at the triester formation step permits selective phosphorylation at room temperature. The compounds synthesized represent new diester and triester models containing alkyl ether diolphospholipid structures.     

[FeFe]-Hydrogenase Abundance and Diversity along a Vertical Redox Gradient in Great Salt Lake,USA

The use of [FeFe]-hydrogenase enzymes for the biotechnological production of H₂ or other reduced products has been limited by their sensitivity to oxygen (O₂). Here, we apply a PCR-directed approach to determine the distribution, abundance, and diversity of hydA gene fragments along co-varying salinity and O₂ gradients in a vertical water column of Great Salt Lake (GSL), UT. The distribution of hydA was constrained to water column transects that had high salt and relatively low O₂ concentrations. Recovered HydA deduced amino acid sequences were enriched in hydrophilic amino acids relative to HydA from less saline environments. In addition, they harbored interesting variations in the amino acid environment of the complex H-cluster metalloenzyme active site and putative gas transfer channels that may be important for both H₂ transfer and O₂ susceptibility. A phylogenetic framework was created to infer the accessory cluster composition and quaternary structure of recovered HydA protein sequences based on phylogenetic relationships and the gene contexts of known complete HydA sequences. Numerous recovered HydA are predicted to harbor multiple N- and C-terminal accessory iron-sulfur cluster binding domains and are likely to exist as multisubunit complexes. This study indicates an important role for [FeFe]-hydrogenases in the functioning of the GSL ecosystem and provides new target genes and variants for use in identifying O₂ tolerant enzymes for biotechnological applications.     

Mechanisms of Enzyme-Catalyzed Reduction of Two Carcinogenic Nitro-Aromatics, 3-Nitrobenzanthrone and Aristolochic Acid I: Experimental and Theoretical Approaches

This review summarizes the results found in studies investigating the enzymatic activation of two genotoxic nitro-aromatics, an environmental pollutant and carcinogen 3-nitrobenzanthrone (3-NBA) and a natural plant nephrotoxin and carcinogen aristolochic acid I (AAI), to reactive species forming covalent DNA adducts. Experimental and theoretical approaches determined the reasons why human NAD(P)H:quinone oxidoreductase (NQO1) and cytochromes P450 (CYP) 1A1 and 1A2 have the potential to reductively activate both nitro-aromatics. The results also contributed to the elucidation of the molecular mechanisms of these reactions. The contribution of conjugation enzymes such as N,O-acetyltransferases (NATs) and sulfotransferases (SULTs) to the activation of 3-NBA and AAI was also examined. The results indicated differences in the abilities of 3-NBA and AAI metabolites to be further activated by these conjugation enzymes. The formation of DNA adducts generated by both carcinogens during their reductive activation by the NOQ1 and CYP1A1/2 enzymes was investigated with pure enzymes, enzymes present in subcellular cytosolic and microsomal fractions, selective inhibitors, and animal models (including knock-out and humanized animals). For the theoretical approaches, flexible in silico docking methods as well as ab initio calculations were employed. The results summarized in this review demonstrate that a combination of experimental and theoretical approaches is a useful tool to study the enzyme-mediated reaction mechanisms of 3-NBA and AAI reduction.     

Fungal Biotransformation of 2′-Methylflavanone and 2′-Methylflavone as a Method to Obtain Glycosylated Derivatives

Methylated flavonoids are promising pharmaceutical agents due to their improved metabolic stability and increased activity compared to unmethylated forms. The biotransformation in cultures of entomopathogenic filamentous fungi is a valuable method to obtain glycosylated flavones and flavanones with increased aqueous solubility and bioavailability. In the present study, we combined chemical synthesis and biotransformation to obtain methylated and glycosylated flavonoid derivatives. In the first step, we synthesized 2′-methylflavanone and 2′-methylflavone. Afterwards, both compounds were biotransformed in the cultures of two strains of entomopathogenic filamentous fungi Beauveria bassiana KCH J1.5 and Isaria fumosorosea KCH J2. We determined the structures of biotransformation products based on NMR spectroscopy. Biotransformations of 2′-methyflavanone in the culture of B. bassiana KCH J1.5 resulted in three glycosylated flavanones: 2′-methylflavanone 6-O-β-d-(4″-O-methyl)-glucopyranoside, 3′-hydroxy-2′-methylflavanone 6-O-β-d-(4″-O-methyl)-glucopyranoside, and 2-(2′-methylphenyl)-chromane 4-O-β-d-(4″-O-methyl)-glucopyranoside, whereas in the culture of I. fumosorosea KCH J2, two other products were obtained: 2′-methylflavanone 3′-O-β-d-(4″-O-methyl)-glucopyranoside and 2-methylbenzoic acid 4-O-β-d-(4′-O-methyl)-glucopyranoside. 2′-Methylflavone was effectively biotransformed only by I. fumosorosea KCH J2 into three derivatives: 2′-methylflavone 3′-O-β-d-(4″-O-methyl)-glucopyranoside, 2′-methylflavone 4′-O-β-d-(4″-O-methyl)-glucopyranoside, and 2′-methylflavone 5′-O-β-d-(4″-O-methyl)-glucopyranoside. All obtained glycosylated flavonoids have not been described in the literature until now and need further research on their biological activity and pharmacological efficacy as potential drugs.     

Engineering solid-state porosity of synthetic supercontainers via modification of exo-cavities

Two new coordination supercontainers have been successfully isolated from the self-assembly reactions of the container precursor p-phenylsulfonylcalix [4]arene, Ni(II) or Co(II) ion, and diphenylmethane-4,4'-dicarboxylic acid. Crystal structure analysis revealed that these two coordination supercontainers possess a similar endo cavity and two deeper exo cavities compared to the related supercontainers based on p-tert-butylsulfonylcalix [4]arene. Gas and vapor adsorption studies indicated that the new compounds are permanently porous and show much better CO₂/O₂ and CO₂/N₂ selectivity and higher vapor adsorption than the tert-butyl analogues.     

Electrostatic immobilization of substrate and polyoxotungstate catalyst at the surface of micelles for enhanced reaction efficiency in water

Polyoxometalate (POM)-based micellar catalysts were prepared by assembling the Keggin tri-anion [PW₁₂O₄₀]^3 − and (L)-N-acetylmethioninate salts of Gemini surfactants in water. Contrary to conventional catalytic systems, we propose a new approach in which the POM catalyst and the substrate to be oxidized ((L)-N-acetylmethioninate) are both localized at the surface of micelles by electrostatic interaction before the reaction. The high local concentration of reactants due to their confinement at the surface of micelles enhances the reaction kinetics. Catalyst recovery experiments showed that, after two cycles of reactions, the activity of the catalysts  was not changed.     

Phytochemicals in Chinese Chive (Allium tuberosum) Induce the Skeletal Muscle Cell Proliferation via PI3K/Akt/mTOR and Smad Pathways in C2C12 Cells

Chinese chive (Allium tuberosum) is a medicinal food that is cultivated and consumed mainly in Asian countries. Its various phytochemicals and physiological effects have been reported, but only a few phytochemicals are available for skeletal muscle cell proliferation. Herein, we isolated a new compound, kaempferol-3-O-(6″-feruloyl)-sophoroside (1), along with one known flavonoid glycoside (2) and six amino acid (3–8) compounds from the water-soluble fraction of the shoot of the Chinese chive. The isolated compounds were identified using extensive spectroscopic methods, including 1D and 2D NMR, and evaluated for their proliferation activity on skeletal muscle cells. Among the tested compounds, newly isolated flavonoid (1) and 5-aminouridine (7) up-regulated PI3K/Akt/mTOR pathways, which implies a positive effect on skeletal muscle growth and differentiation. In particular, compound 1 down-regulated the Smad pathways, which are negative regulators of skeletal muscle growth. Collectively, we suggest that major constituents of Chinese chive, flavonoids and amino acids, might be used in dietary supplements that aid skeletal muscle growth.     

Effect of method of preparation on properties of temperature and pH-sensitive gels: Chemical crosslinking versus irradiation with e-beam

Two problems that have impeded a broader application of polyelectrolytic smart polymers are their low speed of response and their faulty behavior in the presence of salts. To contribute to the solution of those problems we prepared two series of gels based on N-isopropylacrylamide (NIPAAm) containing ampholytic units using chemical crosslinking methods and electron beam irradiation. In the first method, the gels prepared contain NIPAAm, N-N′-dimethylaminoethylmethacrylate (DMAEM) and a methacrylate of the ortho-, meta- or para-benzoic acid, respectively, to impart amphoteric behavior. They were crosslinked using N-N′-methylenebisacrylamide (BIS) as crosslinker by standard free-radical techniques. In the second method aqueous solutions containing mixtures of polyNIPAAm and charge balanced copolymers of DMAEM with the methacrylates of the ortho-, meta- and para-benzoic acid, respectively, prepared previously, were irradiated by e-beam. Both series were characterized by DSC, mechanical compression and swelling–shrinking tests in deionized water, buffers solutions at different pH-values and in water having different salt concentrations. The results show that the gels prepared by irradiation have a swelling degree up to four times higher than that of the gels prepared by chemical crosslinking, furthermore, their shrinking velocity is up to twenty times higher than that of gels prepared by chemical crosslinking. The results also showed that the gels prepared by chemical crosslinking using monomers show only polyelectrolyte behavior, while those prepared by e-beam irradiation of polymer solutions show in fact amphoteric behavior; while all gels retained their temperature sensitivity between 32 and 39 °C.     

Trapping of Dioxygen Dissolved in Water by Alkylhydroxylamines: A Comparison of Hydroquinone, Gallic Acid and Aminophenols as Organocatalysts

One of the most usual methods used to deoxygenate water and prevent the corrosion of industrial boilers is based on the reduction of dioxygen in aqueous alkaline solution with an hydroxylamine in the presence of catalytic amounts of hydroquinone (H₂Q). In order to improve the effectiveness and the “greenness” of this process, the influence of the nature of the hydroxylamine and of the catalyst has been investigated. With H₂Q as a catalyst, the efficiency of various hydroxylamines was found to be in the following order: methylhydroxylamine > dimethylhydroxylamine > hydroxylamine > tert-butylhydroxylamine > diethylhydroxylamine (DEHA). To replace the potentially carcinogenic hydroquinone, a natural polyphenol, i.e. gallic acid, which was previously shown to be safer and more robust that H₂Q to trap O₂ in the presence of DEHA, was used. Methylhydroxylamine was still by far the most active partner, but DEHA was almost as efficient as the other hydroxylamines, free hydroxylamine being the least active oxygen scavenger. As only a catalytic amount of dioxygen scavenger is required in the presence of appropriate hydroxylamines, compounds having a bit more acute toxicity but higher reactivity than hydroquinone may also be alternative catalytic systems. Hence, five aminophenols, i.e. 4-aminophenol, 4-amino-2,5-dichlorophenol, 5-amino-salicylic acid, 4-N-methylaminophenol and 4-N,N-dimethylaminophenol, were also investigated. Among them, 4-N-methylaminophenol was found to be the most efficient although much slower than H₂Q.     

Synthesis of PAA-g-PNIPAM well-defined graft polymer by sequential RAFT and SET-LRP and its application in preparing size-controlled super-paramagnetic Fe3O4 nanoparticles as a stabilizer

A series of well-defined double hydrophilic graft copolymers, poly(acrylic acid)-g-poly(N-isopropylacrylamide) (PAA-g-PNIPAM), was employed as a novel water-soluble coating for constructing superparamagnetic iron oxide nanoparticles. The copolymer was synthesized via a three-step procedure: firstly, a well-defined hydrophobic PtBA-based backbone, poly(tert-butyl 2-((2-chloropropanoyloxy)-methyl)acrylate)-co-poly(tert-butyl acrylate), (PtBCPMA₁₉-co-PtBA₁₈), was prepared through RAFT copolymerization of a new trifunctional acrylic monomer, tert-butyl 2-((2-chloropropanoyloxy)methyl)acrylate and tert-butyl acrylate; secondly, taking this backbone as a macroinitiator to initiate SET-LRP of N-isopropylacrylamide resulted in well-defined (poly(tert-butyl 2-((2-chloropropanoyloxy)methyl)-acrylate)-co-poly(tert-butyl acrylate))-g-poly(N-isopropylacrylamide) ((PtBCPMA-co-PtBA)-g-PNIPAM) amphiphilic graft copolymers with relatively narrow polydispersities (M_w/M_n ≤ 1.31); thirdly, handling (PtBCPMA-co-PtBA)-g-PNIPAM in acidic conditions afforded PAA-g-PNIPAM graft copolymers. The resulting PAA-g-PNIPAM copolymers were directly utilized as a polymeric stabilizer in the preparation of superparamagnetic Fe₃O₄ nanoparticles. The particle size can be readily tuned in the range of 12.1–23.2 nm by varying the amount of PAA-g-PNIPAM copolymer or the length of PNIPAM side chain. Besides, the structure and properties of prepared Fe₃O₄/polymer nanocomposites were characterized by XRD, FT-IR, TGA, TEM, and magnetic measurement in detail.