New functional polyamides derived from citric acid and L-lysine: Synthesis and characterization

New functional aliphatic polyamides bearing pendant carboxylic acid and tertiary alcohol groups have been synthesized by step-growth polymerization of protected citric acid in the diacyl chloride activated form and protected L-lysine using the interfacial method. It has been found that a secondary reaction occurs during polymerization and leads to the formation of intramolecular imide cycles. Cleavage of protecting groups and partial or total hydrolysis of imide functions were carried out stepwisely. Resulting structural changes are discussed on the basis of IR and ¹³C NMR data.     

Room-temperature polycondensation of β-amino acid derivatives VI. Synthesis of various N-(hydroxyethyl) nylons

Various N-(hydroxyethyl)amino acid esters having a methyl substituent or phenyl group between amine and ester groups have been synthesized and their polycondensation behavior was investigated. These substituted amino acid esters gave amorphous polyamides which were soluble in alcohol. A model reaction between N-(hydroxyethyl)-amine and carboxylic acid ester was carried out in order to elucidate the role of hydroxyethyl group on the polycondensation. It was found that the amidation reaction took place rapidly at room temperature when the alkyl group of the carboxylic acid was small. N-(Hydroxyethyl) polyamides were obtained from N,N′-(bishydroxyethyl)-dicamines and dicarboxylic acid esters. The reaction mechanism of the room-temperature polycondensation reaction is discussed.     

Synthesis and properties of soluble aromatic polyamides derived from 2,2′‐bis(4‐carboxyphenoxy)‐9,9′‐spirobifluorene

The synthesis of a new bis(ether carboxylic acid), 2,2′‐bis(4‐carboxyphenoxy)‐9,9′‐spirobifluorene, in which two orthogonally arranged carboxyphenoxyfluorene entities are connected through an sp³ carbon atom (the spiro center), is reported. The direct phosphorylation polycondensation of this diacid monomer with various aromatic diamines yields aromatic polyamides containing 9,9′‐spirobifluorene moieties in the main chain. The presence of the spiro segment restricts the close packing of the polymer chains and decreases interchain interactions, resulting in amorphous polyamides with enhanced solubility, and high glass‐transition temperatures and good thermal stability are maintained through controlled segmental mobility. The glass‐transition temperatures of these polyamides are in the range of 234–306 °C, with 10% weight losses occurring at temperatures above 530 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1160–1166, 2003     

Synthesis and properties of polyamides of p-phenylenedioxydiacetic acid

Several polyamides of p-phenylenedioxydiacetic acid (PDDA) were synthesized by the low-temperature solution polycondensation techniques. Six different diamines were condensed independently with p-phenylenedioxydiacetyl chloride (PDC) in a mixture of N-methyl pyrolidone (NMP) and hexamethyl phosphoramide (HMPA). The polymers were obtained in 80–95% yield and possessed inherent viscosities in the range 0.32–0.81 dL/g. The polymers were characterized by infrared (IR) and H¹-NMR spectra. The solubility, density, crystallinity, and thermal stability of the polyamides were also determined. A model diamide (MDA-1) was also synthesized from aniline and PDC to confirm the formation of polyamides from diamines.     

Electrogenerated chemiluminescence in mechanistic investigations of electroorganic reactions: Part III. Reduction of some disulfides at the dropping mercury electrode

In the simultaneous cathodic reduction of diphenyl disulfide (Ph?S?S?Ph) or dibenzoyl disulfide (Ph?CO?S?S?CO?Ph) and a series of fluorescent aromatic hydrocarbons A at the dropping mercury electrode in dimethylformamide the emission of A is observed. This electrogenerated chemiluminescence (ECL) originates from the electron transfer between A^? and the radicals Ph?S or Ph?COS, which are formed in a one-electron reductive cleavage of the disulfide bond by A^?. As an intermediate the anion radical Ph?S?S?Ph^? or Ph?CO?S?S?CO?Ph^? is assumed. In the case of Ph?S?S?Ph the ECL intensity is enhanced by proton donors (water or benzoic acid), which increase the cleavage rate of Ph? S?S?Ph^? in an electrophilic attack by the proton. The relatively negative threshold reduction potential of A (?1.4 to ?1.6 V) for the ECL in comparison with the half-wave potential (?0.85 V) supports a mercury-assisted heterogeneous reduction mechanism of Ph?S?S?Ph. The intensity-potential curves and the intensity—time curves at the mercury drop were measured for different concentrations of Ph?S?S?Ph and A and for different mercury pressures. No luminescence could be detected with o,o′-dinitrodiphenyl disulfide and diethyl disulfide.     

Photoreactive polyamides having m- or 1-type dimer moiety derived from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid derivatives

Photoreactive polyamides having m- or 1 -type cyclobutane moiety were prepared via a topochemical photodimerization of 4-(3-oxo-3-phenyl-1-propenyl)benzoic derivatives,⁴ followed by polycondensation of cyclobutane dicarboxylate derivatives with diamines. From the spectral studies of resulted polyamides compared with the corresponding reference diamides, it was concluded that both types of polyamides were depolymerized photochemically to give the same type of amide derivative having chalcone moiety with a small amount of undefined side reaction. The cyclobutane ring of the m-dimer from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid in crystal is severely twisted presumably because of the enhanced steric repulsions between two pairs of adjacent substituents. The higher quantum yield of the m-dimer for the photocleavege, compared with that of the 1 -dimer, has been interpreted in terms of such steric repulsions by the strained structure of the m-dimer.     

Determination and comparison of stability constants of tungsten(VI) and molybdenum(VI) with nitrilotriacetic acid and glutamic acid at different ionic strengths

The formation constants of species formed in the systems H⁺?+?W(VI)?+?nitrilotriacetic acid (NTA) and H⁺?+?NTA have been determined in aqueous solution for pH?=?4–9 at 25°C and different ionic strengths ranging from 0.1 to 1.0?mol?dm^?3 NaClO₄, using potentiometric and spectrophotometric techniques. It was shown that tungsten(VI) forms a mononuclear 1?:?1 complex with NTA of the type WO₃L^3? at pH?=?7.5. The composition of the complex was determined by the continuous variations method. The complexation of molybdenum(VI) with glutamic acid was investigated in aqueous solution ranging in pH from 4 to 9, using polarimetric, potentiometric and spectrophotometric techniques. The composition of the complex was determined by the continuous variations method. It was shown that molybdenum(VI) forms a mononuclear 1?:?1 complex with glutamic acid of the type MoO₃L^2? at pH?=?6.0. The dissociation constants of glutamic acid and the stability constants of the complex were determined at 25°C and at ionic strengths ranging from 0.1 to 1.0?mol?dm^?3 sodium perchlorate. In both complex formation reactions the dependence of the dissociation and stability constants on ionic strength is described by a Debye-Huckel type equation. Finally, a comparison has been made between the patterns of ionic strength dependence for the two complexes and the results have been compared with data previously reported.     

Synthesis and characterization of physically crosslinked N‐vinylcaprolactam,acrylic acid,methacrylic acid,and N,N‐dimethylacrylamide hydrogels

Physically crosslinked hydrogels based on N‐vinylcaprolactam/acrylic acid and N‐vinylcaprolactam/methacrylic acid were prepared via free radical polymerization. These temperature responsive hydrogels were characterized in terms of glass transition, phase separation temperature, potentiometric titration and swelling properties. Results showed that phase transition temperature was dependent on the pH value of the solution; increasing pH led to higher lower critical solution temperature (LCST) values which was related to the dissociative behaviors of the carboxylic group of MAc in the buffered solutions. Additionally, with the incorporation of N,N‐dimethylacrylamide into the system, cloud point measurements and MDSC showed an increased in the LCST. This increase was based on hydrophilicity, the hydrophilic–hydrophobic balance was disturbed, and consequently, the LCST behavior was shifted. The pKa of the copolymers ranged between 5.6 and 6.5, while for the terpolymers pKa ranged between 5.3 and 6. At high pH (>10), the ? COOH group is deprotonated and negatively charged (? COO^?), while at low pH (1–3) the carboxylic group remains protonated which results in hydrogen bonding between the hydroxyl groups (from NaOH) and the excess of HCl. These results correlate with swelling studies where above the pKa value the hydrogels dissolved rapidly compared to below pKa they did not dissolve at all. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1555–1564     

Photodegradation of aramids. II. Irradiation in air

A series of isomeric fully aromatic polyamides (aramids) were photodegraded in the presence of oxygen. Films and fibers of these aramids gave carboxylic acids as the major products when measured by infrared spectroscopy and potentiometric titration. These acids probably resulted from the oxygen interception of the radicals generated by photocleavage of the amide bonds. In contrast to results found upon irradiation in the absence of oxygen, carboxylic acid formation was accompanied by a rapid loss in molecular weight, and a decrease in useful mechanical properties. Quantum yields for carboxylic acid formation were ≤5.5 × 10^?5 mole/einstein and decreased along the aramid series roughly in agreement with increases in T_g. The photo-Fries rearrangement product was observed in aramid fibers irradiated in air, whereas no rearrangement product was seen in films irradiated in air.     

Dominant structural factors for complexation and denaturation of proteins using carboxylic acid receptors

Complexation accompanied by denaturation of protein with synthetic carboxylic acid receptors was investigated, to evaluate the key factors for recognition of proteins. The synthetic receptors used were tetraphenylporphyrin (TPP) derivatives and receptors bearing multiple (2–8) carboxylic acid groups. The complexation behavior was quantified from the absorption in the far UV CD spectrum attributed to the secondary structure of the protein. TPP derivatives bearing multiple carboxylic acid groups in the side chains exhibited higher affinity than other receptors that were smaller and had fewer carboxylic acid groups. As the degree of complexation was influenced by the pH and ionic strength in aqueous solution, electrostatic interaction was one of the most important factors for the recognition of proteins. Complexation was also estimated by observation of fluorescence quenching of the TPP derivatives. The stoichiometry of the complexes between lysozyme and the porphyrins was investigated by quantitative analysis of the denaturation using CD spectra. From the results of Job plots and slope analysis for the amount of denatured protein, formation of 1:1 complexes was confirmed. The equilibrium association constants (K_ass) for lysozyme and the TPP receptors ranged from 0.6 × 10⁶ to 1.1 × 10⁶ M⁻¹. The lytic activity of lysozyme was partially lost in the presence of anionic TPP derivatives, due to complexation and denaturation.     

A combined experimental and DFT investigation of the adsorption of humic acid by-products on polypyrrole

This study sheds light on the removal of humic acid by-products (trimellitic and pyromellitic acids; TMA and PMA, respectively) from aqueous solution using conducting polypyrrole (PPy) as an effective adsorbent. The effects of experimental factors including contact time, solution pH, initial concentration, adsorbent dose, and temperature were systematically investigated. The pseudo-second-order kinetic model provides the best correlation with adsorption experimental data. The equilibrium adsorption was well described by the Langmuir model with maximum mono-layer adsorption capacities of 47.62 and 71.43?mg?g^?1 for TMA and PMA, respectively. The analysis of thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. In addition, we investigated the adsorption mechanism using the density functional theory (DFT) calculations. The TMA and PMA were physisorbed on the PPy surface through the formation of hydrogen bonds between carboxylic groups of adsorbate molecules and the amino group of the adsorbent. The calculated theoretical data were in good agreement with experiments.     

High-Energy Phosphonium Compounds and Their Application to Polymer Synthesis

High-energy phosphonium compounds, the N-phosphonium salts of pyridines, were prepared by the oxidation of phosphorous acid and its esters with mercuric salts or halogens in pyridines, or by a hydrolysis-dehydration reaction of diphenyl and triaryl phosphites or phosphonites. These salts are very reactive to nucleophiles, activating carboxyl, amino, or hydroxyl compounds via the corresponding N-phosphonium salts to yield carboxylic amides and esters in high yields on further aminolysis, alcoholysis, and acidolysis. These reactions, especially the hydrolysis-dehydration reactions with phosphites, were successfully extended to the direct polycondensation reaction of dicarboxylic acids with diamines, of free α-amino acids or dipeptides, and of carbon dioxide and disulfide with diamines under mild conditions, yielding linear polymers of high molecular weight (polyamides, polypeptides, polyureas, and polythioureas).     

Study on surface acid-base property of carboxylic acid-terminated self-assembled monolayers by cyclic voltammetry and electrochemical impedance spectroscopy

Cyclic voltammetry and electrochemical impedance spec-troscopy were used to study the surface acid-base property of carboxylic acid-terminated self-assembled monolayers(SAMs).A carboxylic acid-terminated thiol,such as thioctic acid(1,2-dithiolane-3-pentanoic acid),was self-assembled on gold electrodes.Electron transfer between the bulk solution and the SAM modified electrode was studied at different pH using Fe(CN)63-as a probe.The surface pka of thioctic acid was determined by cyclic voltammetry and electrochemical impedance spectroscopy to be 5.6 ±0.1 and 5.8±0.1,respectively.The method is compared with other methods of monolayer pKa measurement.     

Synthesis and Properties of Polyamides and Polyimides Derived From Diamines Having 2-Phenyl-4,5-Oxazolediyl Units and Polyamide/Montmorillonite Composite

Aromatic polyamides were synthesized from 4,5-bis(4-aminophenyl)-2-phenyloxazole (APO) or 4,5-bis[4(4-aminophenoxy)phenyl]-2-phenyloxazole (APPO) containing 2-phenyl-4,5-oxazolediyl units with several aromatic carboxylic dichlorides by a low-temperature solution polycondensation method. The polyamides were obtained quantitatively, and their inherent viscosities ranged from 0.48 to 1.25 dL g^?1. The glass transition temperatures (T _gs) were displayed between 234 to 311°C, and the residual weight at 600°C (Res.wt₆₀₀) exceeded 52% in nitrogen atmosphere. The polyamides showed good solubility in several aprotic polar solvents, such as N,N-dimethylacetoamide (DMAc), N-methyl-2-pyrrolidone (NMP), and dimethyl sulfoxide (DMSO). Aromatic polyimides were derived from APO or APPO with aromatic carboxylic dianhydrides through polyamic acids. The inherent viscosities of the polyamic acids, which were 0.53 to 1.02 dL g^?1, T _gs of the polyimides were observed between 259 to 361°C and their Res.wts₆₀₀ were above 70%. The polyamides and polyimides were amorphous and afforded thin, flexible and tough films. We also prepared a nanocomposite of the polyamide derived from APPO with organophilic montmorillonite clay.     

Polarographic reduction of 2,4,6-trinitrobenzene-1-sulphonic acid and some 2,4,6-trinitrophenyl-amino acid derivatives

The rapid d.c. polarography of 2,4,6-trinitrobenzene-1-sulphonic acid and its derivatives with serine (I), threonine (II), glycine (III) and histidine (IV) revealed a 3-wave reduction and a marked pH dependence of the reduction potential. The polarographic waves of the derivatives (2.5 × 10^?4 M) showed appreciable changes when sulphite ions were present, with the development of a new wave at more negative potential in ?0.01 M sulphite solutions at pH 7.0. The E_1/2 values of these waves in pH 7.0 supporting electrolyte were: (I) ?1000; (II) ?1007; (III) ?1021; (IV) ?949 mV (vs. Ag/AgCl, sat. KCl). These waves were used to determine the amino acids investigated (1–4 × 10^?4 M) in the presence of excess of 2,4,6-trinitrobenzene-1-sulphonic acid, with good precision (2%).     

Synthesis and characterization of polyamides obtained from tartaric acid and L-lysine

Two sets of AA · BB-type polyamides (PLyTA) were synthesized from natural compounds L-lysine and D- or L-tartaric acid via the active ester polycondensation method. The carboxyl and hydroxyl side groups were orthogonally protected as methyl ester and methyl ether, respectively. Direct reaction of methyl L-lysinate dihydrochloride with bis(pentachlorophenyl) di-O-methyl tartaric acid led to the aregic polyamide ar-PLyTA, whereas isoregic (ir-PLyTA) and syndioregic (sr-PLyTA) polyamides were obtained by polycondensation of specifically designed amide–aminoacid and amide–diamine monomeric precursors, respectively. These polyamides have intrinsic viscosities in the 0.50–0.76 dl g⁻¹ range, display optical activity, and are readily soluble in chloroform. They start to decompose well above 200 °C and display glass-transition temperatures at 100–105 °C. DSC and X-ray diffraction results indicated that these polyamides are not crystalline but they seem to adopt a partially ordered phase. No differences in properties other than optical rotation were observed between PLyTA made of D- and L-tartaric acid.     

Simultaneous voltammetric determination of uric acid and ascorbic acid using carbon paste/cobalt Schiff base composite electrode

Differential pulse and cyclic voltammetry were applied for the oxidation of mixture of uric acid and ascorbic acid at the surface of carbon paste/cobalt Schiff base composite electrode. The electrooxidation of these compounds at bare electrode is sluggish, and there is no suitable peak separation between them. However, using cobalt methyl salophen as modifier, two well-defined anodic waves with a considerable enhancement in the peak current and a remarkable peak potential separation near 315 mV are obtained. It can improve the kinetics of electron transfer for both compounds remarkably. All these improvements are created because of the electrocatalytic property of cobalt Schiff base complex. The effect of some parameters such as pH and scan rates were studied. All the anodic peak currents for the oxidation of ascorbic acid and uric acid shifted toward more negative potential with an increase in pH, revealing that protons have taken part in their electrode reaction processes. The best peak separation with appropriate current was obtained for pH 4.0. A linear range of 5.0?×?10^?4 to 1.0?×?10^?8 and 1.0?×?10^?3 to 1.0?×?10^?8 M with detection limit of 8.0?×?10^?9 and 8.0?×?10^?9 M was obtained for ascorbic acid and uric acid using differential pulse voltammetry at the surface of modified electrode, respectively. Analytical utility of the modified electrode has been examined successfully using human urine samples and vitamin C commercial tablets.     

High α transitions of new polyamides based on diamantane

A series of new polyamides were synthesized by direct polycondensation of the 1,6-bis(4-aminophenyl)diamantane with various dicarboxylic acids. The soluble polyamides had high inherent viscosities, ranging from 0.73 to 1.21 dL/g. Polyamides derived from 5-tert-butylisophthalic acid and (±)-1,3-cyclohexanedicarboxylic acid were soluble in N-methyl-2-pyrrolidone (NMP) and pyridine. When NMP and N-dimethylacetamide (DMAc) were added with 3% (w/v) LiCl, the solubilities of polyamides derived from 4,4′-oxybis(benzoic acid) and cis-1,4-cyclohexanedicarboxylic acid were markedly enhanced. Polyamides had tensile strengths of up to 87.8 MPa, elongation to breakage values of up to 19.3%, and initial moduli of up to 2.1 GPa. Dynamic mechanical analysis (DMA) reveals that the polyamides have three relaxations. Their α relaxations occurred at high temperatures, ranging from 380 to 462°C. Three of polyamides exhibited good retention of storage modulus (above 10⁸ Pa) at a temperature exceeding 410°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1257–1263, 1998     

Influence of pH,soil humic acid,ionic strength and temperature on sorption of U(VI) onto attapulgite

The surface property of attapulgite was investigated by N₂-BET surface area and zeta potential analysis in this paper. Solution pH had a remarkable effect on the sorption process, indicated an inner-sphere complexation. Humic acid (HA) in the solution enhanced U(VI) sorption significantly at pH?<?5.0, while decreased U(VI) sorption obviously at pH?>?9.0. The characteristic fluorescence changes of HA indicated that a strong chemical reaction occurred between the functional groups in HA and UO₂²⁺. The sorption was a spontaneous and endothermic process with increased entropy, and the increase in temperature would benefit the sorption.