Tunable helical assemblies of L-alanine methyl ester-containing polyphenylacetylene

The self-assemblying behaviors of L-alanine methyl ester-containing polyphenylacetylene (PPA-Ala, in Chart 1 ) were investigated upon the evaporation of its solvent on mica and on air/water interfaces. The introduction of chiral amino acid attachments to the polyphenylacetylene backbone induced a helical conformation of the backbone, which was stabilized by various noncovalent interactions, especially hydrophobic effect and hydrogen bonds. The helicity of the polymer was further amplified in its higher-order self-assemblies as the formation of helical fibers on the surface of mica upon natural evaporation of its THF solution. By LB technique, the polymer chains were guided to form ordered parallel ridges and highly aligned, with their helical conformation still remaining. The reorganization of the chiral polymer chains on air/water interface was associated with the additional hydrophobic effect of PPA-Ala on an air/water interface. The polymer backbones had to adopt different arrangements to minimize their contact with water, and this adjustment led to the formation of aligned polymer ridges under proper surface pressure.     

Complex surface chemistry of 4-mercaptopyridine self-assembled monolayers on Au(111)

The adsorption of 4-mercaptopyridine on Au(111) from aqueous or ethanolic solutions is studied by different surface characterization techniques and density functional theory calculations (DFT) including van der Waals interactions. X-ray photoelectron spectroscopy and electrochemical data indicate that self-assembly from 4-mercaptopyridine-containing aqueous 0.1 M NaOH solutions for short immersion times (few minutes) results in a 4-mercaptopyridine (PyS) self-assembled monolayer (SAM) with surface coverage 0.2. Scanning tunneling microscopy images show an island-covered Au surface. The increase in the immersion time from minutes to hours results in a complete SAM degradation yielding adsorbed sulfur and a heavily pitted Au surface. Adsorbed sulfur is also the main product when the self-assembly process is made in ethanolic solutions irrespective of the immersion time. We demonstrate for the first time that a surface reaction is involved in PyS SAM decomposition in ethanol, a surface process not favored in water. DFT calculations suggest that the surface reaction takes place via disulfide formation driven by the higher stability of the S-Au(111) system. Other reactions that contribute to sulfidization are also detected and discussed.     

Viscoelastic phase diagram of fluorinated and grafted polymer films and proton‐exchange membranes for fuel cell applications

The influence of temperature and moisture activity on the viscoelastic behavior of fluorinated membranes for fuel cell applications was investigated. Uncrosslinked and crosslinked ethylene tetrafluoroethylene (ETFE)‐based proton‐conducting membranes were prepared by radiation grafting and subsequent sulfonation and their behavior was compared with ETFE base film and commercial Nafion^® NR212 membrane. Uniaxial tensile tests and stress relaxation tests at controlled temperature and relative humidity (RH) were carried out at 30 and 50 °C for 10% < RH < 90%. Grafted films were stiffer and exhibited stronger strain hardening when compared with ETFE. Similarly, both uncrosslinked and crosslinked membranes were stiffer and stronger than Nafion^®. Yield stress was found to decrease and moisture sensitivity to increase on sulfonation. The viscoelastic relaxation of the grafted films was found to obey a power‐law behavior with exponent equal to ?0.04 ± 0.01, a factor of almost 2 lower than ETFE, weakly influenced by moisture and temperature. Moreover, the grafted films presented a higher hygrothermal stability when compared with their membranes counterparts. In the case of membranes, a power‐law behavior at RH < 60% was also observed. However, a markedly different behavior was evident at RH > 60%, with an almost single relaxation time exponential. An exponential decrease of relaxation time with RH from 60 s to 10 s was obtained at RH ≥ 70% and 30 °C. The general behavior of grafted films observed at 30 °C was also obtained at 50 °C. However, an anomalous result was noticed for the membranes, with a higher modulus at 50 °C when compared with 30 °C. This behavior was explained by solvation of the sulfonic acid groups by water absorption creating hydrogen bonding within the clusters. A viscoelastic phase diagram was elaborated to map critical conditions (temperature and RH) for transitions in time‐dependent behavior, from power‐law scaling to exponential scaling. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1139–1148     

Potassium Fluoride on Alumina: Condensation of 1,4-Diacetylpiperazine-2,5-Dione with Aldehydes. Dry Condensation Under Microwave Irradiation. Synthesis of Albonursin and Analogues

1,4-Diacetylpiperazine-2,5-dione (1) was condensated with aldehydes (2) with KF on alumina without solvent under microwaves or in at room temperature in the presence of DMF. The reaction was stereoselective and some natural products (4a-c) like albonursin(4c) were synthesized.     

Stereoselective Synthesis of Some Dialkyl (E)-2-Bromomethylene Glutarates

Reaction of 2-bromo-2-bromomethyl glutaric acid esters with tetraalkylammonium fluoride in HMPA, conveniently provides the corresponding dialkyl (E)-2-bromomethylene derivatives in good yields.     

Synthesis of 4-Benzidinyl Butyric Acid: A Key Intermediate for Antibodies Production Against Benzidin

a four-step synthesis of monoalkylated benzidin is reported for immunogen preparation against benzidin dye. Use of 10% H₂SO₄/ dioxan for N-Boc cleavage avoids the cyclisation of 4-benzidinyl butyric acid into the corresponding lactam observed with the classical TFA/ CH₂Cl₂ system.     

Facile Synthesis of Novel Aminopyrrolobenzimidazole System via Regioselective Amination

A new series of substituted pryrrolobenzimidazoles have been prepared via regioselective displacement of chlorine atom from dichloropyrrolobenzimidazoles with various amine nucleophiles. The dichloro compounds were obtained from the reaction of ortho phenylene diamine compounds with dichloromaleic anhydride.     

Synthesis,characterization, and transport properties of Nafion-polypyrrole membrane for direct methanol fuel cell (DMFC) application

Journal of Solid State Electrochemistry - Due to their distinctive chemical, electronic, and environmental properties, polypyrrole is used as a blocking barrier for methanol leakage in direct...