Adsorption and structure formation of the weak polyelectrolytic diblock copolymer,PVP-<Emphasis Type="Italic">b</Emphasis>-PDMAEMA

This paper reports on the pH-dependent adsorption of weak the polyelectrolytic diblock copolymer poly(2-vinylpyridine)-block-poly(dimethylaminoethyl methacrylate), (PVP-b-PDMAEMA). Aqueous PVP-b-PDMAEMA solutions have been adsorbed on alkaline pretreated silicon substrates. Altogether two copolymers differing in block ratio and molecular weight were used for the investigations. While the electrical charge of both samples in solution was investigated by electrophoretic measurements, the adsorbed polymer layers were studied with ellipsometry and atomic force microscopy (AFM). Depending on pH the electrical charge of both blocks of the diblock copolymer varied. Three different regimes have been identified. Under acidic conditions at pH<5, both blocks are mainly positively charged. At medium pH between 5 and 8, only the PDMAEMA block is positively charged. At pH>8, both blocks are nearly uncharged and a polymer precipitation occurred in solution. Each of these pH regimes was characterized by a specific adsorption behaviour leading to two adsorption maxima at acidic and alkaline pH values, while at medium pH a plateau in the adsorbed amount was observed. Moreover, the structures of the polyelectrolytes formed on the substrate after adsorption were specific to each of the three pH regimes.     

Synthesis,structure, and thermal decomposition of a novel one-dimensional chain complex of manganese(II) with 2,2-diphenic acid and 1,10-phenanthroline

A novel one-dimensional (1D) chain coordination polymer [Mn₂(2,2′-dipha)₂(phen)]_n has been synthesized by hydrothermal reaction, and characterized by elemental analysis, IR spectroscopy, TGA, and X-ray diffraction. Orange crystals crystallized in the monoclinic system, space group C2/c with a = 19.393(7) Å, b = 19.183(7) Å, c = 19.729(7) Å, β = 90.826(6)°, V = 7338(5) ų, Z = 8. In the crystal structure, one manganese atom is six-coordinated with four carboxylate oxygen atoms from one pentadentate 2,2′-dipha ligand and two tetradentate 2,2′-dipha ligands, and with two nitrogen atoms of one phen ligand, giving a slightly distorted octahedral geometry. The other manganese atom is five-coordinated with five oxygen atoms from two tetradentate 2,2′-dipha ligands and two pentadentate 2,2′-dipha ligands and has a trigonal bipyramidal environment. The TGA curve shows that the compound is stable below 310°.     

Swelling behavior of ionically cross-linked polyampholytic hydrogels in varied salt solutions

Ionically cross-linked polyampholytic hydrogels were synthesized by redox copolymerization of acrylamide and an ionic complex of (N,N-diethylamino)ethyl methacrylate and acrylic acid (designated as PADA hydrogel). The swelling behavior of the hydrogels in water indicated that a minimal equilibrium swelling ratio is found when the molar ratio of anionic/cationic monomers was 1.55. In NaCl solution, the hydrogels exhibited the typical swelling behavior of conventional polyampholytic gels. Their equilibrium swelling ratios increased with an increase in the NaCl concentration. In solutions of multivalent ions (CaCl₂ and trisodium citrate solutions), the equilibrium swelling ratios of the hydrogels increased first and were then followed by a decrease with an increase in salt concentration. Interestingly, an unexpected abrupt swelling phenomenon was observed when the fully swollen hydrogels in salt solution were transmitted to pure water. The unique swelling behavior of PADA hydrogels depends not only on the molar ratio of the anionic/cationic monomers but also on the valency of the ions.     

Bioaccumulation study of acrylates in algae (<Emphasis Type="Italic">Chlorella kessleri</Emphasis>) by Py-GC and Py-GC/MS

Acrylate monomers methylmethacrylate (MMA) and cyclohexylmethacrylate (CHMA) bioaccumulation has been determined in aquatic organism, algae (Chlorella kessleri). Algae were collected in amount of 0.4 mg and directly injected to the pyrolytical cell. In algae bodies accumulated monomers were analysed by pyrolysis gas chromatography (Py-GC) and pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS). Traces of the accumulated monomers in algae body can be determined after 1-, 2-, 3-weeks of incubation. Maximum content of MMA was determined after 3-week of experiment, contrariwise in the case of CHMA after 2-week exposition. Relationship with pyrolysis temperature has also been studied.     

Intramolecular cyclization of 5-aryl-3-arylamino-4-benzoyl-1h-3-pyrrolin-2-ones to pyrrolo[3,4-<Emphasis Type="Italic">b</Emphasis>]quinolines

It has been shown that 5-aryl-3-arylamino-4-benzoyl-1H-3-pyrrolin-2-ones cyclize in the presence of conc. H₂SO₄ to give pyrrolo[3,4-b]quinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1543–1545, October, 2004.     

Hydrophobicity modification of woven cotton fabric by hydrophobic fumed silica coating

Water repellency of woven cotton fabric was achieved by coating with the aqueous dispersion containing organosilane agent (HDTMS) and fumed silica. The coating agents were applied using padding method and then followed by batching the coated fabric at the ambient temperature for 24 h to allow the condensation reaction between HDTMS silanol group and fumed silica silanol group, rendering silica particles hydrophobic. An ultrasonicator was employed to prepare the homogenous coating dispersion. The water repellency evaluated by water contact angle determination which showed the contact angle over 110° was obtained with low amount of applied HDTMS of 1 wt%. The effect of fumed silica addition on an increase in fiber surface roughness geometry showed the influential result in improving the water contact angle. From durability to washing test, the hydrophobic coatings evidenced from SEM and ATR/FTIR remained adhering to fiber surface, indicating the durability. After washing, the coating on the fabric with fumed silica addition appeared to be scatter particles which made a contribution to the higher contact angle value when compared to sheet-like layer coating in case of HDTMS coating alone.     

Comparison of the fragility index of different eudragit polymers determined by activation enthalpies

The present study aimed to apply fragility index (m) of polymers in the determination of the optimal amount of plasticizer in polymer films. The fragility index of different Eudragit polymers (RS, RL, EPO) was assessed by differential scanning calorimerty (DSC), applying the Arrhenius connection (logq–1/T _g). The fragility of Eudragit EPO films proved to be the highest, while in the case of RS and RL, the increase of the alkyl-chain length caused the increase of fragility. Studying the effect of plasticizer (triethyl citrate, TEC) on the m value of Eudragit RL and RS films, a near linear reduction of the fragility index could be observed between 5–30% TEC concentration, but above 30%, this value leveled out to constant.     

Physicochemical characterization of degradable thermosensitive polymeric micelles

Amphiphilic AB block copolymers consisting of thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) and poly(ethylene glycol), pHPMAmDL-b-PEG, were synthesized via a macroinitiator route. Dynamic light scattering measurements showed that these block copolymers form polymeric micelles in water with a size of around 50 nm by heating of an aqueous polymer solution from below to above the critical micelle temperature (cmt). The critical micelle concentration as well as the cmt decreased with increasing pHPMAmDL block lengths, which can be attributed to the greater hydrophobicity of the thermosensitive block with increasing molecular weight. Cryogenic transmission electron microscopy analysis revealed that the micelles have a spherical shape with a narrow size distribution. 1H NMR measurements in D2O showed that the intensity of the peaks of the protons from the pHPMAmDL block significantly decreased above the cmt, indicating that the thermosensitive blocks indeed form the solidlike core of the micelles. Static light scattering measurements demonstrated that pHPMAmDL-b-PEG micelles with relatively large pHPMAmDL blocks possess a highly packed core that is stabilized by a dense layer of swollen PEG chains. FT-IR analysis indicated that dehydration of amide bonds in the pHPMAmDL block occurs when the polymer dissolved in water is heated from below to above its cmt. The micelles were stable when an aqueous solution of micelles was incubated at 37 degrees C and at pH 5.0, where the hydrolysis rate of lactate side groups is minimized. On the other hand, at pH 9.0, where hydrolysis of the lactic acid side groups occurs, the micelles started to swell after 1.5 h of incubation and complete dissolution of micelles was observed after 4 h as a result of hydrophilization of the thermosensitive block. Fluorescence spectroscopy measurements with pyrene loaded in the hydrophobic core of the micelles showed that when these micelles were incubated at pH 8.6 and at 37 degrees C the microenvironment of pyrene became increasingly hydrated in time during this swelling phase. The results demonstrate the potential applicability of pHPMAmDL-b-PEG block copolymer micelles for the controlled delivery of hydrophobic drugs.     

Interfacial and micellar properties of binary mixtures of surfactant and phospholipid in an aqueous medium

Mixed micelles formed by zwitterionic surfactant dimethyldodecylammniopropane sulfonate and short-chain phospholipid 1,2-diheptanoyl-sn-glycero-3-phosphocholine in different proportions in an aqueous medium have been studied physicochemically at an air/water interface and in the bulk by using interfacial tension and pyrene fluorescence intensity measurements, respectively. The critical micellar concentration and free energies of micellization and of interfacial adsorption have been determined. The interfacial study reveals that a mixed monolayer is formed at the air/water interface by the adsorption of surfactant and phospholipid monomers. This has been confirmed by evaluating the interfacial parameters; the maximum surface excess, the minimum area per molecule of a surface-active compound, and the Gibbs surface excess related to surface pressure. The nonideality of mixing, expressed in the terms of the regular solution interaction parameter, #, has negative values over the whole mole fraction range. The negative # values indicate the mutual synergism between the surfactant and phospholipid monomers. The equilibrium distribution of components between micelle and monomer phases was evaluated using a theoretical treatment based on excess thermodynamics quantities evaluated by Motomura's formulation.     

Configuration of MFI-type zeolite interacting with the probe molecule P(CH<Subscript>3</Subscript>)<Subscript>3</Subscript> – a theoretical study

With P(CH₃)₃ as the probe molecule adsorbed on titanium silicalite (TS-1) zeolite, the special and important role of T12 site in MFI-type zeolite was clearly elucidated. There are altogether three active sites present in TS-1 zeolite with Ti at the T12 site. Owing to the preferential adsorption of probe molecules on the first Brönsted acidic site, the Ti12 center will probably fail to show Lewis acidity. The ionic [HP(CH₃)₃]⁺ species can be stabilized by the first or second Brönsted acidic site, with the former energetically favored. The latter was formed through the transfer of the ionic [HP(CH₃)₃]⁺ species from the first to the second Brönsted acidic site.