Poly(arylene ether sulfone) multi-block copolymers bearing perfluoroalkylsulfonic acid groups

Poly(arylene ether sulfone) (PAES) multi-block copolymers bearing perfluoroalkylsulfonic acid moieties were prepared from hydrophilic and hydrophobic prepolymers. The latter were synthesized by reaction of N,N-diisopropylethylammonium 2,2-bis(p-hydroxyphenyl)pentafluoropropanesulfonate (HPPS) with bis-(4-fluorophenyl) sulfone (FPS), and biphenol (BP) with FPS, respectively. Prepolymers and multi-block copolymers were prepared at 180 °C in N,N-dimethylacetamide in the presence of K₂CO₃. The prepolymers were reacted overnight; the multi-block copolymers were reacted only 80 min to minimize transetherification. Prepolymers and multi-block copolymers were characterized using ¹H and ¹³C NMR. ¹⁹F NMR provided molecular weight of hydrophilic prepolymers bearing aryl fluoride end groups. GPC was used to characterize the multi-block copolymers. Copolymer block lengths were determined by quantifying ¹³C NMR peak areas of quaternary carbon atoms adjacent to sulfur in FPS moieties. Hydrophilic and hydrophobic block lengths were in the range 9.4-23.4 and 4.4-11.8 repeating units, respectively. AFM showed phase separation for all block lengths. Conductivity at 80 °C and 100% relative humidity ranged from 6.2 to 34.3 mS/cm, with the best value obtained for hydrophilic/hydrophobic block lengths of 13.3/6.0.     

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N′-bis(salicylidene)-1,2-phenylenediamino chromium^III X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium^III (NO₃) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N′-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromium^III (NO₃) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, ¹H NMR, and ¹³C NMR measurements. Almost 100% carbonate content of the resulting polycarbonate were obtained with the help of these effective catalyst systems under facile conditions.     

Insight into Isomeric Diversity of Glycated Amino Acids in Maillard Reaction Mixtures

Maillard reactions generate a wide array of amino acid- and sugar-derived intermediates; the isomeric mixtures of glycated amino acids are of particular interest. Excluding stereoisomers, regioisomers, and various anomers, most amino acids can form two monoglycated and three N,N-diglycated isomers when reacted with sugars during the Maillard reaction. Using synthetic Schiff bases and Amadori compounds as standards, we have demonstrated that diagnostic ions obtained from MS/MS fragmentations in negative ionization mode can be used effectively for the discrimination between glucose-derived Schiff bases and their corresponding Amadori compounds in both mono- and diglycated forms. The utilization of these diagnostic ions and isotopic labeling in the glycine/glucose model system revealed that milling glucose/glycine mixtures for 30 min/30 Hz at ambient temperature produced monoglycated glycine in equal proportions of Amadori and Schiff base forms, whereas diglycated glycine was a mixture of the three isomers: Schiff-Schiff, Schiff-Amadori, or Amadori-Amadori in approximately equal molar proportions. The above results were further corroborated using a synthetic histidine Amadori product, N,N-difructosyl-β-alanine, dipeptides, and ribose. Using mechanochemistry as a convenient synthetic tool in combination with MS/MS diagnostic ions, the isomeric diversity of the early stages of the Maillard reaction can be revealed.     

Reactive green HE‐4BD functionalized supermacroporous poly(hydroxyethyl methacrylate) cryogel for heavy metal removal

The aim of this study was to investigate the heavy metal adsorption performance of supermacroporous poly(hydroxyethyl methacrylate) [PHEMA] cryogel. The PHEMA cryogel was produced by cryo‐polymerization. The PHEMA cryogel was characterized by scanning electron microscopy (SEM). The PHEMA cryogel containing 385 μmol Reactive Green HE‐4BD/g were used in the adsorption studies. Adsorption capacity of the PHEMA cryogel for the metal ions, i.e., Cu²⁺, Cd²⁺, and Pb²⁺ were investigated in aqueous media containing different amounts of the ions (5–600 mg/L) and at different pH values (3.2–6.9). The maximum adsorption capacities of the PHEMA cryogel were 11.6 mg/g (56 μmol/g) for Pb²⁺, 24.5 mg/g (385 μmol/g) for Cu²⁺ and 29.1 mg/g (256 μmol/g) for Cd²⁺. The competitive adsorption capacities were 10.9 mg/g (52 μmol/g) for Pb²⁺, 22.1 mg/g for Cd²⁺ (196 μmol/g) and 23.2 mg/g (365 μmol/g) for Cu²⁺. The PHEMA/Reactive Green HE‐4BD cryogel exhibited the following metal ion affinity sequence on molar basis: Cu²⁺ > Cd²⁺ > Pb²⁺. The PHEMA/Reactive Green HE‐4BD cryogel can be easily regenerated by 50 mM EDTA with higher effectiveness. These features make the PHEMA/Reactive Green HE‐4BD cryogel a potential adsorbent for heavy metal removal. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Complexation of Titanium Alkoxides with Cis-2-butene-1,4-diol and Hydrolysis of Their Products

Reaction of Ti(OEt)₄ and Ti(OBu ⁿ )₄ with cis-2-butene-1,4-diol (B.diol-2H) in 1:1 molar ratio was studied at room temperature using the sol-gel process. ¹³C{¹H}- and ¹H-NMR data showed that all the B.diol-2H completely reacted with both titanium alkoxides. Each of the products was hydrolyzed by water. The new hydrolyzed products were characterized by ¹³C- and ¹H-NMR spectroscopy and Karl–Fischer Titration. Thermogravimetric and differential thermal analyses (TGA-DTA) of the hydrolyzed-products were also studied.     

Preparation,characterization and the antimicrobial properties of metal ion-doped TiO2 nano-powders

TiO₂ samples doped with lithium, sodium, magnesium, iron or cobalt were prepared by high-energy ball milling for different periods of time. The crystalline phase, chemical composition, crystalline size and photo-absorption were characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS) and Ultraviolet visible diffuse reflectance spectroscopy (UV - Vis - DRS), Fourier transform infrared spectroscopy (FT - IR) and scanning electron microscopy (SEM). The antimicrobial properties of the modified TiO₂ samples were evaluated with E. coli and S.aureus assays. The results of the XRD show that the TiOSO₄, Ti₃O₅, Li₂TiO₃ and NaTi₂O₄ phases appear along with Li, Na and Mg doped TiO₂. However, XPS spectra indicated that Ti exists as both Ti³⁺ and Ti⁴⁺ in Na-doped TiO₂ samples. Ti³⁺, due to its narrow band gap, is highly active in promoting visible light-induced photocatalytic activity. SEM images showed that the crystalline size of TiO₂ is reduced and has a common-round and hexagonal plate morphology after milling. The modified TiO₂ samples had the best antimicrobial activities after 3 h of milling. In particular, the antimicrobial rate of TiO₂ 5% doped with transition metals (Co, Fe) reached 100% against E. coli, but the antibacterial rate against S. aureus for Co and Fe dopants was 98.4% and 98.2%, respectively.     

The Effects of the Organic Groups Attached at the Silicone Atoms of the Organosilane-Based Gemini Nonionic Surfactants on Their Surface Activities

A novel trisiloxane gemini nonionic surfactant was synthesized by the reaction of 3-(diethoxy(methyl)silyl)propan-1-amine with hexamethyldisiloxane to get 3-(trisiloxane)propan-1-amine, which was further reacted with glutaroyl dichloride to form the surfactant molecule, N ¹,N ⁵-bis(3-(trisiloxane)propyl)glutaramide (3). Some related compounds were also prepared, including N ¹,N ⁵-bis (3-(trimethoxysilyl)propyl) glutaramide (1), and N ¹,N ⁵-bis(3-(diethoxy(methyl)silyl)propyl)glutaramide (2). All prepared compounds were analyzed by IR, ¹H-NMR and ¹³C-NMR to confirm their structures. Their interfacial activities, including surface tension and wetting ability, were measured. These surface activities were compared each other and a discussion was carried out on how the organic groups attached on the silicone atoms affect their surface tension and wetting ability. To explain the superior surface activities of the molecules 3, a hypothesis was proposed about a cyclic hydrophobic core area that could be formed by the two hydrophobic chains and the linker of the gemini molecule due to the dispersion force (Van der Waals force) between the two trisiloxane moieties, which close the hydrophobic cycle inside the molecule.     

Free coating of a Newtonian liquid onto a vertical surface

The entrainment of Newtonian liquid films onto a vertical surface which is continuously withdrawn from a bath of the liquid is considered. A new theoretical treatment is presented which is significantly different from previous theoreis and which predicts accurately the relationship between the dimensionless thickness parameter, T₀, and the Capillary Number, Ca, up to a value of Ca of 2. Experimental results have been obtained using a capacitance technique for film thickness measurement for a variety of Newtonian fluids with viscosities ranging from 0·006 to 2·06 N. sec m^?2.     

An investigation into the synthesis and characterization of new optically active poly(ester-imide) thermoplastic elastomers,derived from N,N′-(pyromellitoyl)-bis-l-leucine,synthetic diols and polyethyleneglycol-diol (PEG-200)

Pyromellitic dianhydride (1) was reacted with l-leucine (2) to result [N,N′-(pyromellitoyl)-bis-l-leucine diacid] (3). This compound (3) was converted to N,N′-(pyromellitoyl)-bis-l-leucine diacid chloride (4) by reaction with thionyl chloride. Polycondensation reaction of this diacid chloride (4) with polyethyleneglycol-diol (PEG-200) and/or three synthetic aromatic diols furnish a series of new PEIs and Co-PEIs. Polycondensation was carried out in the presence of triethylamine (TEA) or pyridine (Py) as a catalyst in different solvents, at different reaction times and temperatures. The resulting polymers and copolymers have inherent viscosities in the range of 0.10–0.33 dl g⁻¹. These polymers are optically active, thermally stable and soluble in polar aprotic solvents such as DMF, DMSO, NMP, DMAc and sulfuric acid. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation and thermal analyses. Some structural characterizations and physical properties of these optically active PEIs and Co-PEIs are reported.     

Silver(I) complexes with 1′-(diphenylphosphino)-1-cyanoferrocene and nitrite or nitrate supporting ligands

The reactions of 1′-(diphenylphosphino)-1-cyanoferrocene (1) and silver(I) salts with common oxoanions, viz. AgNO₃, AgNO₂ and Ag₂SO₄, led to defined products only in the case of AgNO₃ and AgNO₂. Whereas the reactions involving silver(I) nitrate produced the phosphine complex [Ag(NO₃-κ²O,O′)(1-κP)₂] (2) irrespective of the metal-to-ligand ratio, those with AgNO₂ gave rise to the coordination polymer [Ag{μ(P,N)-1}(NO₂-κ²O,O′)]_n (3) and the discrete monosilver complex [Ag(NO₂-κO,O′)(1-κP)₂] (4) at the Ag:1 molar ratios 1:1 and 1:2, respectively. Compounds 2–4 were structural characterized by spectroscopic methods and by single-crystal X-ray diffraction analysis.     

Molecular Rearrangement of Pyrazino[2,3-c]quinolin-5(6H)-ones during Their Reaction with Isocyanic Acid

New tetrahydropyrazino[2,3-c]quinolin-5(6H)-ones were prepared from 3-chloroquinoline-2,4(1H,3H)-diones and ethylene diamine. In their reaction with HNCO, an unprecedented molecular rearrangement produced new types of hydantoin derivatives. All prepared compounds were characterized on the basis of their ¹H, ¹³C, and ¹⁵N NMR and ESI mass spectra and some were authenticated by X-ray analysis of single crystalline material. A proposed mechanism for rearrangement is discussed in this essay. The CDK and ABL inhibition activity as well as in vitro cytotoxicity of the prepared compounds was also tested.     

Synthesis and antimicrobial activity of metronidazole containing polymer and copolymers

Homopolymer and copolymers containing metronidazole (MTZ) drug were synthesized. Acryloyl chloride was reacted with MTZ (drug) to produce monomer containing MTZ, and then the monomer was copolymerized with various amounts of methyl methacrylate. The produced monomer, homopolymer, and copolymers were characterized by elemental analysis, IR, and ¹H‐NMR. The antimicrobial activities of the synthesized polymers were tested against Kelpsilic as fungal organisms, and Escherichia coli, Bacillus subitilus, and Pesudomonus areuginosa as bacteria organisms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Unexpected activity of novel 9-oxabispidine zinc complexes in lactide polymerization

The zinc dichlorido and zinc diacetato complexes of the chiral tricyclic 9-oxabispidine (1R,2S,9S)-11-methyl-13-oxa-7,11-diazatricyclo [7.3.1.0^2,7] tridecane were prepared and characterized by X-ray crystallography. The latter complex was found to catalyze the solvent-free polymerization of d,l-lactide to give polylactide.     

Silyl group mediated linkage of closo-C2B10-cage to nido-C2B4-carborane: synthesis of the novel carborane ligand, 1-R-2-[5′-(SiMe2CH2)-2′,3′-(SiMe3)2-2′,3′-C2B4H5]-1,2-C2B10H10 (R=Me,Ph)

The reaction of the sodium salt of the monoanion, nido-[2,3-(Si(CH₃)₃)₂-2,3-C₂B₄H₅]⁻, with (chloromethyl)dimethylchlorosilane in a 1:1 molar ratio produced the B_(cage)-substituted cluster, nido-5-ClCH₂Si(CH₃)₂-2,3-(Si(CH₃)₃)₂-2,3-C₂B₄H₅ (1), in 81% yield. This product (1) was reacted further with the lithium salt of [closo-1-R-1,2-C₂B₁₀H₁₀]⁻ monoanion (R=Me, Ph) to give the novel linked and mixed C₂B₄/C₂B₁₀ carborane species, 1-Me-2-[5^′-SiMe₂CH₂-2^′,3^′-(SiMe₃)₂-2^′,3^′-C₂B₄H₅]-1,2-C₂B₁₀H₁₀ (2), 1-Ph-2-[5^′-SiMe₂CH₂-2^′,3^′-(SiMe₃)₂-2^′,3^′-C₂B₄H₅]-1,2-C₂B₁₀H₁₀ (3), in yields of 76% and 81%, respectively.     

Self-assembled monolayers-based immunosensor for detection of Escherichia coli using electrochemical impedance spectroscopy

An electrochemical impedance immunosensor for the detection of Escherichia coli was developed by immobilizing anti-E. coli antibodies at an Au electrode. The immobilization of antibodies at the Au electrode was carried out through a stable acyl amino ester intermediate generated by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydrosuccinimide (NHS), which could condense antibodies reproducibly and densely on the self-assembled monolayer (SAM). The surface characteristics of the immunosensor before and after the binding reaction of antibodies with E. coli were characterized by atomic force microscopy (AFM). The immobilization of antibodies and the binding of E. coli cells to the electrode could increase the electro-transfer resistance, which was directly detected by electrochemical impedance spectroscopy (EIS) in the presence of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ as a redox probe. A linear relationship between the electron-transfer resistance and the logarithmic value of E. coli concentration was found in the range of E. coli cells from 3.0 × 10³ to 3.0 × 10⁷ cfu mL⁻¹ with the detection limit of 1.0 × 10³ cfu mL⁻¹. With preconcentration and pre-enrichment steps, it was possible to detect E. coli concentration as low as 50 cfu/mL in river water samples.