Regular copolyamides. II. Preparation and characterization of regular aliphatic copolyoxamides

Regular copolyoxamides were prepared from diamine-oxamides and aliphatic diacid chlorides by interfacial and solution polymerization. Interfacial polymerization is preferred with diamineoxamides where the diamine portion has two to six methylene groups and the diamine-oxamides are readily soluble in water. Regular aliphatic polyoxamides from diamine-oxamides are readily soluble in water. Regular aliphatic polyoxamides from diamine-oxamides with more than six methylene groups in the diamine portion of the molecule are better prepared by solution polymerization in dimethyl acetamide. Regular aliphatic oxamides are soluble in trifluoroacetic acid and hexafluoroisopropanol and show a considerable alternation of the melting point behavior in the diamine portion of the polyamides with up to five methylene groups. Copolyoxamides with two and four methylene groups melt higher than the copolyoxamides with three and five methylene groups. Aliphatic copolyoxamides/adipamides melt at approximately 260°C and show a steady decrease in melting points to about 220°C for polyoxamides with twelve methylene groups.     

Capillary gas chromatographic separation of urinary organic acids. Retention indices of 101 urinary acids on a 5% phenylmethyl silicone capillary column

Gas chromatographic retention indices (methylene units) are reported for 101 urinary organic acids as their trimethylsilyl and oximated trimethylsilyl derivatives on a 5% phenylmethyl silicone fused silica capillary column. Using anion exchange chromatography, organic acids were extracted from urines of five healthy individuals, seven patients with neuroblastoma, and nine patients with inherited organic acidurias. Separation of the various acids was achieved by capillary gas chromatography and identification was done by mass spectrometry using a computerized library search program. All identifications were confirmed by visual comparison with reference mass spectra. Standard deviations of the retention indices for all acids were less than 0.035 methylene units and for 46 acids less than 0.01 methylene units. Three chromatograms of urine from individuals with neuroblastoma, phenylketonuria, and propionic acidemia and one from a healthy individual are shown.     

Separation of inorganic anions using a series of sulfobetaine exchangers

A set of five new sulfobetaine exchangers with inner quaternary amines and outer sulfonic acids have been prepared. A series of zwitterionic precursors was attached to highly porous divinylbenzene polymer using a grafting reaction, which allows a flexible adjustment of the degree of functionalisation. The resulting materials have identical spacers to the polymeric backbone and differ only in chain length between the charged functional groups. Capacities of the stationary phases were analysed by two different methods based on elemental analysis and the results obtained were found to correlate. The application of combustion elemental analysis proved an identical molar content of sulfur and nitrogen. The distance between the charged functional groups is varied from one to five methylene groups for a better understanding of the retention behaviour of inorganic anions on zwitterionic stationary phases. Inorganic anions were separated using sodium acetate eluents with varying ionic strength and pH and the behaviour of all columns has been compared to each other and to ZIC-HILIC and ZIC-pHILIC columns from Merck SeQuant. The exchangers with two and five methylene groups between the charges showed the highest retention factors. Polarity and accessibility of the anion exchange sites are dependent on the distance between the charged groups and the flexibility of the chains. These properties have a strong influence on anion separations. The exchanger with two methylene groups between the charged functional groups showed the biggest difference as compared to the commercially available ZIC-HILIC and ZIC-pHILIC exchangers.     

Functional polymers and sequential copolymers by phase-transfer catalysis. 16. Influence of sequence distribution on the mesomorphic properties of thermotropic copolyethers containing 4,4′-dihydroxybiphenyl

Random and alternating thermotropic liquid-crystalline copolyethers have been synthesized from 4,4′-dihydroxybiphenyl and a 1/1 mol ratio of 1,5-dibromopentane and α,ω-dibromoalkanes by a two-phase (organic solvent-aqueous NaOH) phase-transfer-catalyzed polyetherification. Random copolyethers were prepared from α,ω-dibromoalkanes having six to twelve methylene units. Their phase behavior was compared with those of the perfectly alternating copolyethers containing five methylene units in one spacer and eight, nine, or eleven methylene units in the other, respectively. An odd-even dependence in thermal transitions has been observed in both oligomeric systems. In all cases, alternating copolyethers, even though comparatively lower in molecular weight, have given rise to higher melting and isotropization temperatures. Since the increase in the melting temperature is larger than the increase in the isotropization temperature, the thermal stability range of the mesophase has narrowed for alternating copolyethers with respect to their random copolyether counterparts.     

Characterization of unusual alkenones and alkyl alkenoates by electron ionization gas chromatography/mass spectrometry

Unusual long-chain, diunsaturated alkenones and alkyl alkenoates exhibiting double bonds separated by three methylene units instead of the more usual five were characterized by electron ionization (EI) gas chromatography/mass spectrometry. In a first step, the positions of the double bonds of these compounds (isolated from Holocene Black Sea sediments) were confirmed after OsO4 treatment and silylation. Mass spectra of the resulting tetratrimethylsilyloxy derivatives allowed unambiguous determination of the positions of unsaturations. The EI mass spectra of the non-derivatized compounds were then compared with those of the alkenones and alkyl alkenoates having double bonds separated by five methylene units. Specific fragment ions resulting from gamma-H rearrangements were found to be prominent in EI mass spectra of these unusual 'Black Sea' diunsaturated alkenones and alkyl alkenoates. These fragment ions can be used to characterize these compounds in natural samples without the need for laborious derivatization treatments.     

Kinetic and mechanistic study on the thermal reactivity of stabilized phosphorus ylides,part 3: [(Acetyl)(arylcarbamoyl)methylene]triphenylphosphoranes and [(alkoxycarbonyl)(arylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

A series of five [(acetyl)(arylcarbabmoyl)methylene]triphenyl‐phosphoranes 1a–e and their thiocarbamoyl analogues 2a–e , [(alkoxycarbonyl)(arylcarbamoyl)methylene]triphenylphosphoranes 3a–e and their thiocarbamoyl analogues 4a–e were prepared and fully characterized. All ylides are found under conditions of flash vacuum pyrolysis to fragment giving arylisocyanate or isothiocyanate and acetyl ylides or alkoxy ylides which undergo thermal extrusion of Ph₃PO. A kinetic study shows that these reactions are unimolecular and are of first‐order nature with no significant substituent effect. The thiocarbamoyl ylides 2 react from 4.6 to 42 times faster than their carbamoyl ylides 1 , while the thiocarbamoyl ylides 4 react from 6.6 to 20.9 times faster than their carbamoyl ylides 3 . © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 6–16, 2007     

Effect of lateral substituents on the mesomorphic properties of side-chain liquid crystalline polysiloxanes containing 4-[(S)-2-methyl-1-butoxy]phenyl 4-(alkenyloxy)benzoate side groups

The synthesis of side-chain liquid crystalline polysiloxanes containing either 4-[(S)-2-methyl-1-butoxy]phenyl 4-(alkenyloxy)benzoate or laterally fluoro-, chloro-, bromo-, and methoxy-substituted 4-[(S)-2-methyl-1-butoxy]phenyl 4-(alkenyloxy)benzoate mesogenic side groups is presented. The mesomorphic properties of the synthesized polymers have been characterized by optical polarizing microscopy, differential scanning calorimetry, and X-ray diffraction measurements. The effects of spacer length and lateral substituent on the mesomorphic properties of the obtained polymers are examined. The five polymers which contain three methylene units in the spacers show no mesophase, while the five polymers which contain eleven methylene units in the spacer display smectic mesomorphism. Among the other fifteen polymers which contain respectively four, five, or six methylene units in the spacers, those with small fluoro and chloro substituents reveal respectively an S_A phase, while those with bulky bromo and methoxy substituents show no liquid crystalline behavior. The experimental results demonstrate that introducing a bulky lateral substituent into the mesogenic core of a polymer depresses the tendency to form a mesophase. Furthermore, the technique of thermally stimulated current has been used to study the dipolar relaxation mechanisms in a side-chain liquid crystalline polysiloxane. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2793–2800, 1997     

Stereodivergent Synthesis of N‐Heterocycles by Catalyst‐Controlled,Activity‐Directed Tandem Annulation of Diazo Compounds with Amino Alkynes

A stereodivergent synthesis of five‐membered N‐heterocycles, such as 2,3‐dihydropyrroles, and 2‐methylene and 3‐methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper‐catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium‐catalyzed protocol features a carbenoid insertion into the N? H bond and subsequent Conia‐ene cyclization.     

Stereodivergent Synthesis of N‐Heterocycles by Catalyst‐Controlled,Activity‐Directed Tandem Annulation of Diazo Compounds with Amino Alkynes

A stereodivergent synthesis of five‐membered N‐heterocycles, such as 2,3‐dihydropyrroles, and 2‐methylene and 3‐methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper‐catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium‐catalyzed protocol features a carbenoid insertion into the N H bond and subsequent Conia‐ene cyclization.     

Separation of -amino acids using a series of zwitterionic sulfobetaine exchangers

A set of five new covalently bond sulfobetaine exchangers with inner quaternary amines and outer sulfonic acids have been prepared by attachment of a series of zwitterionic precursors to hyperporous divinylbenzene polymers using a grafting reaction. The series of zwitterionic exchangers have the same backbone and identical spacers to the polymeric backbone, as well as comparable capacities. The only difference is the chain length for one to five methylene groups between the charged functional groups. Chromatographic properties are examined by separation of α-amino acids using sodium acetate and nitric acid eluents. The separation mechanism is explored by varying eluent ionic strength and eluent pH, resulting in the conclusion that amino acids are separated due to cation exchange interactions. This is a behavior never before observed using zwitterionic exchangers. It contradicts the fact that sulfobetaine-type materials used in zwitterionic ion chromatography (ZIC) usually are well suited for anion separation and only poorly for cation separation. Contrary to anion separations using the identical set of exchangers, the materials with three and four methylene groups between the charges give the highest retention factors. Materials showing the high potential in ZIC separations of inorganic anions give low retention factors for amino acids and vice versa.     

Activated carbon blended with grape stalks powder: Properties modification and its application in a dye adsorption

In this study, activated carbon was blended with grape stalks powder to adsorb methylene blue (MB) dye with various concentrations from a wastewater. For this purpose, five independent variables involving pH (2–13), contact time (5–270 min), grape stalks powder dosage (0.1–10 g/l), methylene blue initial concentration (20–300 mg/l), and activated carbon dosage (0.1–10 g/l) for methylene blue adsorption were studied. The Central Composite Design (CCD) under Response Surface Methodology (RSM) was applied to estimate the independent variables effects on the methylene blue adsorption. The pseudo- first order, pseudo-second order, Elovich and intraparticle diffusion models were employed to study the adsorption kinetics and isotherm. The Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models were applied to investigate the adsorption isotherm. It was concluded that the intraparticle diffusion isotherm and pseudo-second order kinetic models could show the best results. Furthermore, some data such as physical adsorption (by analyzing FTR and applying some standard equations) and mean free energy (E) were discovered in this research. Finally, activated carbon blended with grape stalks powder as an effective bio-adsorbent for the methylene blue reduction from a wastewater was introduced.     

The binding of human carbonic anhydrase II by functionalized folded polypeptide receptors

Several receptors for human carbonic anhydrase II (HCAII) have been prepared by covalently attaching benzenesulfonamide carboxylates via aliphatic aminocarboxylic acid spacers of variable length to the side chain of a lysine residue in a designed 42 residue helix-loop-helix motif. The sulfonamide group binds to the active site zinc ion of human carbonic anhydrase II located in a 15 A deep cleft. The dissociation constants of the receptor-HCAII complexes were found to be in the range from low micromolar to better than 20 nM, with the lowest affinities found for spacers with less than five methylene groups and the highest affinity found for the spacer with seven methylene groups. The results suggest that the binding is a cooperative event in which both the sulfonamide residue and the helix-loop-helix motif contribute to the overall affinity.     

Cleavage of alkylsilanes by strong acids : IV. The reactions of alkyldimethylfluorosilanes with fluorosulfonic acid

The kinetics of cleavage of alkyl groups and fluorine from five alkyldimethylfluorosilanes by fluorosulfonic acid dissolved in methylene chloride has been studied with proton magnetic resonance. Competitive cleavage of alkyl, methyl and fluoro occurs to form three products. A mechanism is proposed based on the third order kinetics which involves the formation of a pentacoordinate intermediate through nucleophilic attack of fluorosulfonic acid at silicon followed by electrophilic attack α to silicon.     

Production of pyrans, pyridazines, pyrimidines, pyrazines and triazine compounds using benzoylacetonitriles as a precursor

Benzoylacetonitriles are easily available and have high chemical reactivity due to the presence of three active moieties; nitrile, carbonyl, and active methylene functions. This review article represents a survey covering the synthetic strategies leading to five six-membered heterocycles; pyrans, pyridazines, pyrimidines, pyrazines, and triazine compounds; utilizing benzoylacetonitriles as starting precursor since 1985. The reactions are subdivided into groups that cover the synthetic methods of these heterocycles.     

Liquid-crystalline behaviour of 4-(ω-aminoalkyloxy)-4'-cyanobiphenyls and their side chain epoxy polymers

Liquid-crystalline side chain polymers were obtained from the ring-opening reaction of epoxy resin with mesogenic amines, 4-(ω-aminoalkyloxy)-4'-cyanobiphenyl. The amines with the alkyl group ranging from five to nine methylene units were synthesized, and were found to exhibit an enantiotropic nematic phase. Polymerization of these amines with ethylene glycol diglycidyl ether at 100°C yielded the polymers of low glass transition and melting temperatures. The mesomorphic properties of the amines and the resulting epoxy polymers are reported.     

2-Halogeno-N-phenacylimidazolium salts and their reactions with active methylene species,arylamines and thiocyanate ions

This study describes the reactivity of 2-halogeno-N-phenacylimidazolium salts towards active methylene species, arylamines and thiocyanate ions. The 2-chloro-N-phenacylimidazolium salt undergoes unexpected reactions in the presence of active methylene species and a tertiary amine as the base. The reaction of 2-bromo-N-phenacylimidazolium salts with arylamines led to a mixture of the corresponding 2-(arylamino)-N-phenacylimidazolium salts and imidazolone. The reaction of 2-bromo-N-phenacylimidazolium bromide with KSCN led to the corresponding imidazole-2-thione. The crystal structures of five compounds are reported.     

多尺度结构Ag/PA6纳米纤维膜的制备及其催化性能

随着工业的进步,废水处理特别是印染废水的处理成为亟待解决的问题.银纳米粒子因其特殊的物理化学性能而表现出催化活性,但银纳米粒子的团聚限制了其使用,所以出现了一系列新的载体材料,如微球、薄膜和纤维等.其中电纺纳米纤维由于具有高比表面积,作为载体材料具有非常大的优势,而将常规电纺纳米纤维作为载体也已有报道.但是,将具有更高比表面积的电纺纳米纤维作为载体,特别是一种类似于树枝状结构的多尺度纳米纤维作为载体还鲜有报道.本文制备了一种多尺度结构的PA6纳米纤维膜,该纳米纤维膜由直径为50?120 nm的主纤维和10?50 nm的分支纤维构成;由于分支纤维的出现,多尺度结构纳米纤维膜的比表面积得到了提高,可以为银纳米粒子的负载提供更多附着位点.制备的多尺度结构纳米纤维膜通过银胶溶液浸渍成功地负载银纳米粒子,对制备的纳米纤维膜的形态、化学结构以及对亚甲基蓝的催化性能进行了探讨.SEM,EDS和TEM结果表明,银纳米粒子成功地负载在多尺度结构纳米纤维的表面,并且银纳米粒子的粒径以及负载量可以通过变换银胶溶液的浓度合理调控.此外,与常规PA6纳米纤维膜相比,多尺度结构纳米纤维膜更有利于银纳米粒子的分散,同样通过银胶溶液A浸渍,负载在多尺度结构纳米纤维上银纳米粒子粒径为8.6 nm,而负载在普通PA6纳米纤维上银纳米粒子粒径为11.2 nm.XPS分析表明,银纳米粒子成功地负载到多尺度结构纳米纤维上,并且经不同银胶溶液处理,纳米纤维膜的载银量不同.通过O的高能XPS分析发现,银纳米粒子与PA6分子间形成了配位键,这在一定程度上有利于Ag纳米粒子的固定,阻止了Ag纳米粒子的团聚.Ag/PA6纳米纤维膜以及多尺度结构Ag/PA6纳米纤维膜催化降解实验表明,多尺度结构Ag/PA6纳米纤维膜具有较高的催化活性,反应2 h后对10 mg/L亚甲基蓝的降解率达到98.13%,并且降解过程符合伪一级动力学.不同浸渍液浓度处理纳米纤维膜催化实验表明,Ag纳米粒子的大小以及含量都会影响纳米纤维的催化活性,纳米粒子粒径越小,其催化活性越高;不同NaBH4加入量催化体系催化实验表明,随着NaBH4加入量的增大,催化体系的降解率增高,其对催化体系的催化性能起着至关重要的作用;其他条件一定,随着染料初始浓度的增大,催化体系的催化性能下降;循环实验表明,经5次循环之后,其降解率仍高达83.5%,该纳米纤维膜具有一定的循环使用性能.     

The crystalline state of methylene blue: a zoo of hydrates

A re-investigation of the crystalline state of methylene blue has led to the identification of five different hydrates with clearly distinct structures. These include the already known pentahydrate, a hydrate with 2.2-2.3 equivalents of water, two dihydrates, and a monohydrate. Contrary to older reports, no trihydrate was found. The preparation and characterization of the hydrates as well as the transformations between them are reported. The applied analytical methods include X-ray powder diffraction (XRPD), infrared spectroscopy (ATR-IR), thermogravimetry (TGA), differential scanning calorimetry (DSC), dynamic water vapor sorption (DVS) and solution calorimetry (SolCal). A phase diagram of temperature vs. composition has been established, and the stability domains of the different hydrates as a function of water activity and temperature have been determined based on data from DSC, SolCal and suspension equilibration experiments. Four out of the five hydrates are thermodynamically stable within a certain range of temperature and humidity.     

Solvent effect on chemical shift non-equivalence of methylene protons in dibenzyl-, diphenacyl- and benzyl phenacyl sulphoxides

The methylene protons of dibenzyl sulphoxide are magnetically equivalent in low dielectric and non-equivalent in high dielectric constant solvents, while for diphenacyl sulphoxide this behaviour is reversed. In both cases, the variation in the magnitude of the non-equivalence reflects a greater downfield shift of one methylene proton than the other on passing from non-polar to polar solvents. By contrast, the chemical shift difference between the benzyl methylene protons or between the phenacyl methylene protons of benzyl phenacyl sulphoxide varies only slightly with solvent polarity.     

Electrochemical Polymerization of Methylene Green

The electrochemical polymerization of methylene green has been carried out using cyclic voltammetry. The electrolytic solution consisted of 4° 10^?3 mol/L methylene green, 0.1 mol/L NaNO₃ and 1 × 10^?2 mol/L sodium tetraborate with pH 11.0. The temperature for polymerization is controlled at 60°C. The scan potential is set between ?0.2 and 1.2 V (vs. Ag/AgCl with saturated KCl solution). There are an anodic peak and a cathodic peak on the cyclic voltammogram of poly (methylene green) at pH≤3.8. Both peak potentials shift towards negative potentials with increasing pH value, and their peak currents decrease with increasing pH value. Poly (methylene green) has a good electrochemical activity and stability in aqueous solutions with pH≤3.8. The UV‐Visible spectrum and FTIR spectrum of poly (methylene green) are different from those of methylene green.