Hemiesters and hemiamides of maleic and succinic acid: synthesis and application of surfactants in emulsion polymerization with styrene and butyl acrylate

Hemiesters and hemiamides of maleic acid with different chain lengths of the hydrophobic alkyl group (R = C8H17, C10H21, C12H25, C16H33) have been synthesized and used as surfactants in the emulsion polymerization of styrene and butyl acrylate. The same polymerization experiments were also carried out using nonreactive surfactants with an analogous succinic structure. The chemical structure of the surfactants was confirmed by 1H nuclear magnetic resonance. The melting point and critical micelle concentration of the reactive surfactants described herein were measured. All of the surfactants studied provided good stability of styrene/butyl acrylate latexes, when compared with a reference late…

Zwitterionic Sulfonates as m/z Shift Reagents for 5-Methylcytosine Detection in Deoxyribonucleic Acids (DNA) Using Flow Injection Analysis and Electrospray Ionisation Mass spectrometry

5-Methylcytosine (5-MC) is an important epigenetic modification of DNA. Abnormally high concentrations of this substance appear because of the hypermethylation of cytosine. Therefore, the measurement of the quantity of this compound in mammals is of great importance. Recently, we reported that several imidazolium-based zwitterionic sulfonates form complexes with 5-MC in solution, which can be studied by electrospray ionisation mass spectrometry (ESI-MS). It is shown in this paper that such an association can be utilised for the detection of 5-MC in a DNA sample using high-throughput a flow injection analysis ESI-MS method. A variety of the sulfonate zwitterions have been tested as m/ z shi…

Immobilized humic substances as sorbents

A new method was developed for the immobilization of humic substances. Humic acids (HA) immobilized onto different carriers were studied as sorbents for organic and inorganic substances. The sorption isotherms of 4-aminoazobenzene, Crystal Violet, Methylene Green, and flavine mononucleotide on immobilized HA show that pH and salt concentration have a significant effect on the sorption process, largely depending on the properties of polymeric matrix. Humic acids from different sources showed differing sorption capacity for the studied groups of substances.

ChemInform Abstract: Dialkylimidazolium Dimethyl Phosphates as Solvents and Catalysts for the Knoevenagel Condensation Reaction.

Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate in the presence of an equimolar amount of 1,3-dialkylimidazolium dimethyl phosphate ionic liquids is investigated.

Structure Effect of Imidazolium-Based Dicationic Ionic Liquids on Claisen Rearrangement

A large group of imidazolium-based dicationic ionic liquids (DILs) has been prepared in good yields. Thermal stability of all DILs has been determined. The effects of the reaction time, cation, imidazolium C2–H acidity, and anion on the Claisen rearrangement of allyl phenyl ether have been investigated. Type of anion and the presence of the acidic C2–H bond in the imidazolium moieties have proven to be essential for this reaction. The simple procedure and the possibility of avoiding the use catalysts and volatile organic solvents make this synthetic method environmentally benign and adaptable for large-scale applications.

Methacrylic maleic bifunctional stabilizer in emulsion polymerization

Behaviour of Nanomaterials in the Environment: A Study of Interaction between Humic Acids and Fullerene C60

Interaction between buckminsterfullerene and humic substances of different origin was investigated using fluorescence spectrometry as function of concentration of humic substances, pH and ionic strength. Binding constants of humic substances and buckminsterfullerene were calculated. It can be suggested that the complexation was driven by hydrophobic interaction depending on properties of the interacting compounds. Hydrophobic interaction model was indicated by linear Stern–Volmer plot, and high Kd values characterized interaction between buckminsterfullerene and humic acids. The results of this study support the development of understanding of fate of nanomaterials in environment as well as…

Hydrophilic Ionic Liquids in the Synthesis of Hantzsch Ester

Hydrophilic Ionic Liquids in the Synthesis of Hantzsch Ester Hantzsch ester synthesis was investigated using (2-hydroxyethyl)-ammonium carboxylates, polar and hydrophilic ionic liquids possessing low toxicity and high biodegradability. The reaction rates and yields of the products in ionic liquids were greater than those in common organic solvents. The relationship between the structure of the ionic liquid used and the structure of the heterocyclic compound was investigated.

When Chlorides are the Most Reactive: A Simple Route towards Diverse Mono- and Dicationic Dimethyl Phosphate Ionic Liquids

Structurally diverse aromatic and aliphatic ionic liquids have been prepared via anion metathesis utilizing alkylammonium chlorides and trimethyl phosphate. Excellent oxygen-containing functional-group tolerance in preparation of potentially greener dimethyl phosphate ionic liquids has been demonstrated. For the first time, this method has been employed in the synthesis of dicationic imidazolium-based ionic liquids possessing a dimethyl phosphate counterion, providing a simple, direct route towards structurally novel products of high purity.

Ionic liquids as solvents for the Knoevenagel condensation: understanding the role of solvent–solute interactions

The Knoevenagel condensation in ionic liquids has been demonstrated as a strongly solvent-dependent process. The objective of this study was to establish a simple and descriptive trend of solvent–solute interactions that favour the Knoevenagel condensation in ionic liquid media. The reaction between 4-(dimethylamino)benzaldehyde and ethyl cyanoacetate in several imidazolium- and pyrrolidinium-based ionic liquids and one ionic liquid mixture was studied. The rate constants were rationalised by studying the change in the 1H NMR chemical shift of representative starting materials in the ionic liquids and the measurement and consideration of the Kamlet–Taft descriptors for each solvent. The hyd…

A route to simple nonionic surfactants

AbstractA method for the synthesis of nonionic surfactants – N-alkyl-O-(2-hydroxyethyl) carbamates is proposed by acylation of fatty amines with ethylene carbonate without any solvent or catalyst. The surface tension of the prepared surfactants was measured, toxicity and biodegradability were determined for the surfactant with n-dodecyl as a hydrophobic group and N-monosubstituted amide and hydroxyl groups for their hydrophilic part.

Maleic diamide polymerizable surfactants. Applications in emulsion polymerization

Abstract A series of new polymerizable non-ionic and ionic surfactants (surfmers) with amides groups on both sides of the C=C double bonds have been prepared upon reaction of maleic isoimide carrying a long alkyl chain (or a benzyl group) with a hydrophilic amine derivative. Their critical micellar concentration (CMC) was measured with a surface tensiometer. They have been engaged in batch emulsion polymerization of styrene, and semi-batch seeded copolymerization of styrene and butyl acrylate, giving stable latexes during the polymerization process, and upon extraction with ethanol, showing a high rate of incorporation at the particle surface. However these surfmers do not confer good steri…

Characterization of interaction between tricyclic structures containing pharmaceuticals, their models and humic substances.

Their persistence and wide consumption identify pharmaceuticals as “emerging pollutants”. The complexation of pharmaceuticals containing adamantine ring structures and their model substances with humic acids (HA) of different origins was compared using fluorescence spectroscopy as a function of pH, humic acid concentration, ionic strength, and molecular mass of HA. Binding constants between the studied pharmaceuticals and humic acids were calculated. A combination of dynamic and static quenching processes as indicated by nonlinear Stern-Volmer plots and high Kd values were positively correlated with the concentration of carboxyl groups in the studied humic acids. For basic functional group-…

Electrospray Ionization Mass Spectrometry of Non-Covalent Complexes Formed between N-Alkylimidazolium-Containing Zwitterionic Sulfonates and Protonated Bases

This paper describes non-covalent complexes between zwitterionic 3-(1-alkyl-3 N-imidazolio)-propane-1-sulfonates and different amines. Electrospray ionization (ESI) mass spectrometry and collision-induced dissociation were used to measure the stability of such complexes in solution and in the gas phase. Generally, zwitterionic sulfonates formed more abundant complexes with protonated 5-methylcytosine (5-MCH) than with aliphatic amines. The results show that the association constants and half-dissociation threshold energies of these complexes nonlinearly depend on the alkyl chain length of the zwitterion. It is shown that the complexes with the lowest stability exist in acetonitrile solutio…

Synthesis and NMR characterization of new poly(ethoxyalkyl) maleates

Polymerizable surfactants derived from maleic anhydride have been synthesized. The hydrophilic part is obtained by a controlled ethylene oxide polymerization according to a new heterogeneous catalytic process. Some maleates derivatives have been obtained and fully characterized by 1H and 13C NMR. Their cmc were also measured. Some of them have been engaged in styrene emulsion polymerization in which monodisperse latex particles have been produced.

Cationic and Zwitterionic Polymerizable SurfactantsQuaternary Ammonium Dialkyl Maleates. 2. Emulsion Polymerization of Styrene and Butyl Acrylate

Polymerizable cationic and zwitterionic dialkyl maleates with different hydrophobic chain lengths (R = C10H21, C12H25, C16H33, C18H37) and different counterions (I, Br, HSO4) for the cationic hydrophilic part, as well as some similar surfactants, dialkyl succinates, were used in batch and seeded emulsion polymerization of styrene and butyl acrylate. All surfactants, when used in emulsion polymerization, provide good stability to the styrene/butyl acrylate latices. A styrene/butyl acrylate latex prepared with sodium dodecyl sulfate (SDS) was used as a reference. Some stability tests for latices were performed, and the glass transition temperatures, as well as the molecular weights of the pol…

Nonionic Maleic Surfmers

ABSTRACT A set of nonionic maleic surfactants have been prepared, all coming from the derivatization of maleic hemiesters with a long alkyl chain. They are either amidoesters or diester products. In the case of amidoesters, the acid group was first activated and then reacted with primary or secondary or tertiary ethanolamine compounds. In the case of diesters, the hemiester was reacted directly with glycidol, in acid or basic conditions. These surfactants were characterized for their structure by 1H NMR, and for their surface active properties, by surface tension measurements. They were also used in batch emulsion polymerisation of styrene, and seeded core-shell copolymerisation of a 1/1 mi…

ChemInform Abstract: Imidazolium and Pyridinium Salts - Solvents Influencing the Rate and Direction of the Fries, Beckmann, and Claisen Rearrangements.

The effects of the structural elements of the ionic liquid media on the direction of these rearrangements and the product yields are studied.

Catalytic condensation of aromatic aldehydes with acetone on activated Mg-Al mixed oxides

Abstract The factors affecting the aldol condensation of some model aromatic aldehydes (benzaldehyde, the three isomers of F-benzaldehyde and 2-naphthaldeyde) with acetone have been investigated using heterogeneous catalysts obtained by the calcination of hydrotalcite-type (HT) precursors at 773 K for 8 h, followed by rehydration at room temperature for 7 h under a flow of N 2 saturated with water vapour. At 273 K the main product was the β-hydroxy-ketone, while at 318 K it mainly dehydrated to the corresponding trans -arylideneacetone, with small amounts ( cis -arylideneacetone, 1,3-diarylideneacetone and 4-hydroxy-4-methyl-2-pentanone. High reaction times favoured the formation of trans -…

Synthesis of Polymer Colloids Using Polymerizable Surfactants

A series of new anionic surfactants were prepared by reacting a polymerizable alcohol with either maleic or succinic anhydride, as well as sulfosuccinic anhydride, resulting in either bireactive or monoreactive surfactants, either carboxylated or sulfonated. The synthesis presented and the critical micelle concentration (CMC) determined. These compounds were engaged in the emulsion polymerization of styrene in batch and also in semi-batch seeded copolymerization producing core-shell latexes. The core was a polystyrene seed prepared using sodium dodecyl sulfate (SDS), thoroughly purified through ion exchange resins. The seed was then swollen overnight with a small amount of a 1 : 1 mixture o…

Cationic and Zwitterionic Polymerizable Surfactants:  Quaternary Ammonium Dialkyl Maleates. 1. Synthesis and Characterization

Cationic and zwitterionic reactive dialkyl maleates with different hydrophobic chain lengths (R = C10H21, C12H25, C16H33, and C18H37), and some similar surfactants without double bonds were synthesized with an aim to use them as stabilizers in the batch and seeded emulsion copolymerization of styrene and butyl acrylate (part 2 of this series). Surfactants are obtained in a three-step synthesis, starting from ring opening of maleic anhydride, followed by O alkylation with an aminoalkyl compound, and finishing with quaternization of the amino group in the hydrophilic part of the molecule. The chemical structure of surfactants was confirmed by 1H NMR. Melting points and critical micelle concen…

Lewis acid-catalyzed Beckmann rearrangement of ketoximes in ionic liquids

Abstract The Beckmann rearrangement of five ketoximes was done in 17 different ionic liquids by using four Lewis acids. The effect of the type of cation and the type of anion in the ionic liquid on the rate of the rearrangement reaction and product composition is compared and discussed. The effects of the hydrophobicity and the hydrogen bonding ability of ionic liquids on the rearrangement of ketoximes were investigated, as well as the catalytical activity of the Lewis acids.

Collision-Induced Dissociation of Imidazolium-Based Zwitterionic Liquids

Fragmentation pathways of some imidazolium based zwitterionic liquids—3-(3-alkyl-1-imidazolio)-propane sulfonates and 3-(2-methyl-3-alkyl-1-imidazolio)-propane sulfonates—have been studied by tandem electrospray mass spectrometry and collision-induced dissociation. The relative abundances of the lowest energy fragment ions depend on the length of the alkyl chain at the IIN of the imidazolium ring and the cone voltage. The first fragment ions originate from the scission of Cnon aromatic–N bond of compounds investigated, but with increasing collision energy, scission of C–C bonds occurs. Aggregates of the general formula [(M + H) x + (M) y]+ ( x;y = 1–2) formed. Methyl substituted zwitterion…

Positive and negative electrospray ionization-collision-induced dissociation of sulfur- containing zwitterionic liquids.

The mass spectrometric properties of several (1,2-dimethyl-1 H-imidazol-3-ium-3-yl)-alkane-1-sulfonates (alkane=ethyl, propyl and butyl) are investigated in this study. These substances, named zwitterionic liquids (ZILs), were synthesized using classical transformations and analyzed in positive and negative electrospray ionization mode using collision-induced dissociation (0–50 eV). We have also performed regioselective deuterium labeling of the alkyl chain of 3-(1,2-dimethyl-1 H-imidazol-3-ium-3-yl)-propane-1-sulfonates. Thus, the mass spectra of isotopically-labeled compounds were used for the confirmation of fragmentation pathways of ZILs. Briefly, the data obtained in this study show t…

Reactions of Maleisomides with Alcohols

Abstract New surfactants (surfmers) with various amide and ester groups next to C˭C double bonds have been obtained. Maleic acid amidesters (AE) with different hydrophobic groups at the nitrogen atom and hydrophilic substituents at oxygen atoms were synthesized starting with maleic isoimides. 1H KMR and IR spectra were used for their characterization. Some were further characterized for their critical micellar concentration (CMC). A few cationic and zwitterionic surfmers were also prepared from isoimide precursors and characterized. All these surfmers were applied in batch emulsion polymerization of styrene, and in core‐shell seeded copolymerization of styrene and butylacrylate to give late…

Alkylation of ambident indole anion in ionic liquids

AbstractAlkylation of indole salts in different ionic liquids is reported. Ionic liquids increase the alkylation reaction rate of ambident indole anion and reduce the effects of counter ions and/or additives, the alkylation reaction rates being independent of the presence of small amounts of protic solvents or water.

Dialkylimidazolium dimethyl phosphates as solvents and catalysts for the Knoevenagel condensation reaction

Abstract The reaction between benzaldehyde and ethyl cyanoacetate is investigated in 1,3-dialkylimidazolium salts as solvents. The impact of both ions in these ionic liquids on the yield of the condensation reaction product is examined. Potentiometric titrations are employed for quantitative analyses of the best ionic liquids, revealing these to be 1,3-dialkylimidazolium dimethyl phosphates.

Structural characterization and chemical classification of some bryophytes found in Latvia.

Bryophytes are the second largest taxonomic group in the plant kingdom; yet, studies conducted to better understand their chemical composition are rare. The aim of this study was to characterize the chemical composition of bryophytes common in Northern Europe by using elemental, spectral, and non-destructive analytical methods, such as Fourier transform IR spectrometry (FT-IR), solid-phase (13) C-NMR spectrometry, and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), for the purpose of investigating their chemotaxonomic relationships on the basis of chemical-composition data. The results of all these analyses showed that bryophytes consist mainly of carbohydrates. Judging by FT-IR …