Formation of polymer–colloid complexes of aluminoxane particles with poly(acrylic acid) and its copolymers with acrylamide

Formation of polymer–colloid complexes formed by positively charged aluminoxane particles with a size of ~4.6 nm, which constitute the main part of the dispersed phase in aluminum polyhydroxychloride sols with poly(acrylic acid) and acrylic acid copolymers with acrylamide, is studied. Conditions of preparing water-soluble polymer–colloid complexes are determined. It is shown that water-soluble polycomplexes are obtained through the interaction of aluminoxane particles with acrylic acid–acrylamide copolymers containing no more than 0.8 mol% acrylic acid units. In the polymer–colloid complex, aluminoxane particles are uniformly distributed over polyelectrolyte macromolecules and the optimum composition is attained at the molar ratio of components Z equal to 1:1. In semidilute solutions, the addition of aluminoxane particles to the copolymer brings about formation of the gel featuring viscoelastic properties. For all copolymers, the maximally elastic properties of the gels are attained at Z ≈ 1.     

Study of formation of metal–polymer complexes between copper (I) and polyamic acids by HPLC

Structural, molecular, and hydrodynamic characteristics of thermostable functionalized polymers [polyamic acids (PAAs) with biquinoline chelate groups in the main chain] were studied by high-performance liquid chromatography. Size exclusion mechanism of chromatography in conditions including suppression of polyelectrolyte swelling and ion-exclusion effects was proved. The influence of molecular and structural characteristics of PAAs on their ability to form metal–polymer complexes (MPCs) with copper(I) chloride was studied. The critical polymer concentration at which binding of two PAA macromolecules with Cu⁺ ion takes place to form MPCs was estimated.     

Phase characterization of LC (meth)acrylic monomers based on ω-hexyloxy- and ω-undecyloxy-salicylaldimine groups with different alkoxy tail substitutions

The synthesis and phase characterization of three homologous series of liquid crystalline acrylic and methacrylic monomers, consisting of 21 new compounds are presented. They are based on ω-hexyloxy- and ω-undecyloxysalicylaldimine groups with different alkoxy tail substitutions. The liquid crystalline materials were characterized by polarizing optical microscopy and differential thermal analysis. Smectic A and tilted smectic C phases were observed in the compounds. Near the transition to the isotropic, a narrow nematic phase, coexisting with the smectic A phase, was detected for the pentyloxy and hexyloxy derivatives in the M11 and A11 series. In case of M11R11 and M11R12 only a tilted smectic C phase was detected. The clearing point was comparable for all series, around 100°C.     

Ternary mixed-ligand complexes of copper(II) with α-aminoalkylphosphonic acids and amino acids

Formation of ternary mixed-ligand complexes of copper (II) with 16 -amino acids and -aminophosphonic acids (APA) with a 111 ratio of initial concentrations has been studied by potentiometric titration at 25C and 0.1 M KC1 in aqueous solution. The complexes Cu_pA_nB_sH_q are formed in solution, where A and B are the deprotonated ligands. The stability of the mixed-ligand complexes (log ) increases and the equilibrium is displaced more towards their formation (log K) as the hydrophobic nature of the ligands increases.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 570–575, March, 1991.     

The effects of the molecular weight and structure of poly(acrylic acid) on the formation of “blue silver”

Using UV-spectroscopy and transmittance electron microscopy it was shown that the structure of macromolecules and molecular weight of poly(acrylic acid) can significantly affect the synthesis and stabilization of so-called “blue silver.”     

Influence of α-methyl substitution of proline-based organocatalysts on the asymmetric α-oxidation of aldehydes

The direct asymmetric organocatalytic α-oxidation of aldehydes using trans-2-(p-methylphenylsulfonyl)-3-phenyloxaziridine is reported. This method affords the S isomer of α-hydroxy aldehydes, thereby complementing the selectivity for the R isomer observed using the two-step nitrosobenzene method. Use of α-methylproline and α-methylproline tetrazole significantly increases the enantioselectivity observed for the α-oxidation of aldehydes compared to analogous unsubstituted organocatalysts.     

Novel thiourea derivatives of α-amino acids and their oxorhenium(V) complexes

N-[(Dialkylamino)(thiocarbonyl)]benzimidoyl chlorides react with α-amino acid esters under formation of the corresponding N-[(dialkylamino)(thiocarbonyl)]benzamidines. Derivatives with glycine ethylester, HL(GlyOEt), cysteine methylester and S-benzyl protected cysteine ethylester, HL(S-Bzl-CysOEt), were prepared and isolated in crystalline form. The reaction with cysteine methylester yields the corresponding sulfur-bridged dimeric compound {HL(CysOMe)}₂.     

Infrared and Raman spectra of poly(α-methyl styrene)

Assignments are proposed for the i.r. and Raman spectra of poly(α-methyl styrene) and the D₅-chain-deuterated analogue.     

Study on formation of poly(β-hydroxybutyrate-co-hydroxyvalerate) (PHBV) fiber

In this paper, the crystallization behavior, thermal degradation properties, rheological behavior and the spinnability of poly(β-hydroxybutyrate-co-hydroxyvalerate) (PHBV) fiber were studied. Experimental results indicated that the spherulite growth rate of PHBV was very slow and its size was very large. PHBV began to degrade above 170°C. The flowing curve indicated that the processing temperature and the residential time had important effects on PHBV melts. When the equipment of melting spinning was improved and processing conditions were strictly controlled, the mechanical properties of the PHBV filament can comply with the requirements of the American Pharmacopoeia. __________ Translated from Journal of Donghua University (Natural Science Edition), 2007, 33(4): 425–430     

UV-light and visible-light photochromism of inorganic–organic multilayer films based on polyoxometalate and poly(acrylamide)

Novel UV-light and visible-light photochromic inorganic–organic multilayers composed of polyoxometalates (phosphomolybdic acid (PMoA)) and poly(acrylamide) (PAM) were prepared by the layer-by-layer (LbL) self-assembly method. The grown process, composition, surface topography, and photochromic properties and mechanism of the multilayer films were investigated by ultraviolet–visible (UV–vis) spectra, Fourier transform infrared spectra (FT-IR), atomic force microscopy (AFM), electron resonance spectra (ESR), and X-ray photoelectron spectra (XPS). Irradiation with UV-light or visible-light, the transparent films changed from colorless to blue and showed reversible photochromism. PMoA/PAM LbL films had higher photochromic efficiency under UV-light irradiation than visible-light irradiation. The bleaching process occurred when the films were in contact with O₂ in the dark or heated in air. The photochromic process of PMoA/PAM LbL film was in accordance with radical mechanism.     

Influence of γ-radiation on iodine-doped poly (3-pentylthiophene)

The influence of -radiation on iodinedoped poly (3-pentylthiophene) has been studied. Doping accompanied by -radiation brings about a decrease of iodine release rate. An increased dopant concentration in the poly (3-pentylthiophene) leads to an increased conductivity, which may be accounted for by the formation of bipolarons in the irradiated and doped samples.     

Study of behaviour on simulated daylight ageing of artists�� acrylic and poly(vinyl acetate) paint films

This work proposes a multi-method approach that combines advanced microscopy (SEM/EDX, AFM) and spectroscopy (UV-vis and FTIR) techniques. This approach not only characterises the behaviour of the additives of two commercial poly(vinyl acetate) (PVAc) and acrylic emulsion paints but also simultaneously characterises the changes in chemical composition and morphology observed in the paint films as a result of ageing due to the paints being exposed to an intense source of simulated daylight. In parallel, a series of mechanical tests were performed that correlate the chemical changes in composition and the changes observed in the films' mechanical properties. This work was a comparative study between both types of acrylic and PVAc paints. The results obtained are of great interest for the modern paint conservation field as they provide valuable information on the mid- and long-term behaviours of these synthetic paints.     

The formation of host–guest complexes between surfactants and cyclodextrins

Cyclodextrins are able to act as host molecules in supramolecular chemistry with applications ranging from pharmaceutics to detergency. Among guest molecules surfactants play an important role with both fundamental and practical applications. The formation of cyclodextrin/surfactant host–guest compounds leads to an increase in the critical micelle concentration and in the solubility of surfactants. The possibility of changing the balance between several intermolecular forces, and thus allowing the study of, e.g., dehydration and steric hindrance effects upon association, makes surfactants ideal guest molecules for fundamental studies. Therefore, these systems allow for obtaining a deep insight into the host–guest association mechanism. In this paper, we review the influence on the thermodynamic properties of CD–surfactant association by highlighting the effect of different surfactant architectures (single tail, double-tailed, gemini and bolaform), with special emphasis on cationic surfactants. This is complemented with an assessment of the most common analytical techniques used to follow the association process. The applied methods for computation of the association stoichiometry and stability constants are also reviewed and discussed; this is an important point since there are significant discrepancies and scattered data for similar systems in the literature.     

Synthesis and characterization of inclusion complexes of aliphatic-aromatic poly(Schiff base)s with β-cyclodextrin (highlight)

This paper describes the formation of polymer inclusion complexes(polymer-CD-ICs) between β-cyclodextrin(β-CD) and aliphatic-aromatic poly(Schiff base)s. Fourier transform infrared(FTIR) spectroscopy, ¹H nuclear magnetic resonance spectroscopy(¹H-NMR), thermogravimetric analysis(TGA) and X-ray diffraction(XRD) have been used to observe the formation of polymer-CD-ICs. In FTIR spectra, the characteristic peaks of β-CD at 3391 cm⁻¹ shifted to 3418 cm⁻¹ and the intense peak at 1602 cm⁻¹ due to the –C = N– stretching vibration diminished after formation of inclusion complexes. Compared the ¹H-NMR of polymer-CD-ICs with β-CD, the chemical shift of the protons H-3, H-5 have shifted to higher field after the formation of inclusion complexes, which is perhaps due to the interaction of these protons with polymers. The TGA analysis revealed that the polymer-CD-ICs had better thermal stability than β-CD, suggesting that the polymer increased the stability of β-CD. The X-ray diffraction patterns displayed that the strong peak for both polymer-CD-ICs at approximately 20.0° (2θ) may confirm their IC formation.     

Influence of gelator structures on formation and stability of supramolecular hydrogels

A supramolecular hydrogel(defined as G1) formed from 1,2,4,5-benzene tetracarboxylic acid (BTCA) and 2-amino-3- hydroxypyridine possessed higher T_(gel) than that of another hydrogel(defined as G2) formed from BTCA and 3-hydroxypyridine. Based on the analysis of their xerogels by ~1H NMR,IR and XRD,the higher stability of G1 was attributed to the formation of stronger hydrogen binding enhanced by the ortho amino group of 2-amino-3-hydroxypyridine.     

Kinetic study of the protonations and substitutions of different cobalt(III)–nta complexes

The behaviour of the Cobalt(III)–nta (nta = nitrilotriacetate) system in an acidic medium was investigated. The acid dissociation constant, pK _a1, of [(nta)(H₂O)Co(-OH)Co(H₂O)(nta)]^– was determined as 3.09(3) and the pK _a of the cis-[Co(nta)(H₂O)₂]/[Co(nta)(H₂O)(OH)]^– equilibrium was determined as 6.71(1). cis-[Co(nta)(H₂O)₂] undergoes ring-opening upon acidification below pH = 2.0. The formation of [Co( ³-nta)(H₂O)₃]⁺ was also studied. The substitutions between cis-[Co(nta)(H₂O)₂] and NCS^– ions were investigated in the pH = 2–7 ranges. [Co(nta) (H₂O)(OH)]^– reacts ca. 70 times faster at 24.7 °C with NCS^– ions than cis-[Co(nta)(H₂O)₂], indicating a cis-labilising effect of the OH^– ligand.     

Copper(II) and oxovanadium(IV) complexes of α-hydroxymethylserine

Summary Potentiometric and spectroscopic measurements were used to characterize the binding ability of -hydroxy-methylserine (Hms) with copper(II) and oxovanadium(IV) ions. The ligand was found to be generally a more efficient chelating agent than serine. Both of the deprotonated hydroxyl groups of Hms can be involved in coordination to vanadyl ions, whereas copper(II) binds in the same way as with serine.     

Synthesis of electroactive multinuclear dipyrrinato complexes and Fe(III) assisted formation of α-alkoxy substituted 5-ferrocenyldipyrromethenes

The synthesis and characterization of multinuclear complexes [Pd(acac)(fcdpm)] (1), [Pd(fcdpm)(2)] (2), [Co(acac)(fcdpm)(2)] (3), [Co(fcdpm)(3)] (4) and α-alkoxy derivatives [α-OMe-fcdpm] (5), [α-OEt-fcdpm] (6), [α-OPr(n)-fcdpm] (7) and [α-OBu(n)-fcdpm] (8) (fcdpm = 5-ferrocenyldipyrromethene; acac = acetylacetone) have been described. Formation of alkoxy derivatives 5-8 takes place from highly selective Fe(III) mediated alkoxylation of fcdpm in alcohol. It has been established that yield of α-alkoxy derivatives depend on the alcohol chain length. The compounds under study have been characterized by elemental analyses, spectral (IR, (1)H, (13)C NMR, ESI-MS, UV-vis) and electrochemical studies (CV and DPV). Structures of 1, 3 and 5 have been verified by X-ray single crystal analyses. Structural studies revealed distorted square planar and octahedral geometry about Pd(II) and Co(III) centres. All the compounds exhibited oxidation wave due to Fc/Fc(+) redox couple (0.34-0.36, 1-4; 0.24-0.25 V, 5-8).