Synthesis of 2-(N-Benzylpyrrolyl)-benzimidazoles Using Polyphosphoric Acid Prompted Cyclocondensation

Synthesis of a series of 2-substituted benzimidazoles was carried out for screening anti-inflammatory activities. 2-(N-benzylpyrrolyl)-benzimidazoles 9a-k were synthesized from N-benzyl-2-pyrrole carboxylic acids 8a-d and 4-substituted-1,2-phenylenediamines by cyclocondensation utilizing polyphosphoric acid (PPA) as condensing agent. The N-benzyl-2-pyrrole carboxylic acids were prepared by standard method of N-benzylation of 2-pyrrole carboxylate using NaH/DMF and appropriately substituted benzyl halides followed by alkaline hydrolysis.     

Divergent 2-Chloroquinazolin-4(3H)-one Rearrangement: Twisted-Cyclic Guanidine Formation or Ring-Fused N-Acylguanidines via a Domino Process

A highly efficient 2-chloroquinazolin-4(3H)-one rearrangement was developed that predictably generates either twisted-cyclic or ring-fused guanidines in a single operation, depending on the presence of a primary versus secondary amine in the accompanying diamine reagent. Exclusive formation of twisted-cyclic guanidines results from pairing 2-chloroquinazolinones with secondary diamines. Use of primary amine-containing diamines permits a domino quinazolinone rearrangement/intramolecular cyclization, gated through (E)-twisted-cyclic guanidines, to afford ring-fused N-acylguanidines. This scalable, structurally tolerant transformation generated 55 guanidines and delivered twisted-cyclic guanidines with robust plasma stability and an abbreviated total synthesis of an antitumor ring-fused guanidine (4 steps, 55 % yield).     

Synthesis and Cytotoxic Evaluation of Pyrrole Hetarylazoles Containing Benzimidazole/Pyrazolone/1,3,4‐Oxadiazole Motifs

Azomethine‐linked pyrrole bishetarylazoles containing benzimidazole/pyrazolone/1,3,4‐oxadiazole were synthesized in satisfactory yields. Their structures were confirmed by IR, ¹H‐NMR, ¹³C‐NMR, and elemental analysis. Evaluation for the cytotoxic activities in vitro against a panel of breast cancer cell lines (MDA‐AB‐231, BT‐474, and Ishikawa cells) revealed that the pyrrole–benzimidazole hybrids are more potent than the pyrazolone and 1,3,4‐oxadiazole hybrids in all cell lines. Compound 9 displayed promising cytotoxicity against BT‐474 cell line with IC₅₀ values, 7.7 µM.     

Modeling the Selectivity of Potassium Channels with Synthetic,Ligand‐Assembled π Slides

A supramolecular ion channel model mediates transmembrane ion transport (shown schematically) with a selectivity topology similar to that of K⁺ channels. This supports the biological significance of flexible arene arrays as selective cation binding sites.     

Electrodeposition of polyaniline, poly(2-iodoaniline), and poly(aniline-co-2-iodoaniline) on steel surfaces and corrosion protection of steel

Polyaniline (PANi), poly(2-iodoaniline) (PIANi), and poly(aniline-co-2-iodoaniline) (co-PIANi) were synthesized using cyclic voltammetry in acetonitrile solution containing tetrabuthylammonium perchlorate (TBAP) and perchloric acid (HClO₄) on 304-stainless steel electrodes. Adherent and black polymer films were obtained on the electrodes. The structure and properties of these polymer films were characterized by FTIR and UV-vis spectroscopy and electrochemical method. The corrosion performance of PANi, PIANi, and co-PIANi coated electrodes were investigated in 0.5 M hydrochloric acid (HCl) solutions by potentiodynamic polarization technique, open circuit potential-time curves and electrochemical impedance spectroscopy, EIS. It was found that the PANi film could provide much better protection than PIANi, and co-PIANi and PANi films have barrier property as well as acting as passivator. On the other hand PIANi and co-PIANi films are acting as barrier coatings which were related with the prevention of cathodic reaction taking place at metal\electrolyte interface. EIS measurement shows that every coating gives protection efficiency of greater than 75% after 48 h of immersion time in corrosive test solution.     

N-(4-amino-7-nitrobenzaoxa-1,3-diazole)-substituted aza crown ethers: complexation with alkali, alkaline earth metal ions and ammonium

Three novel aza-crown ether derivatives incorporating 4-amino-7-nitrobenzaoxa-1,3-diazole (NBD) chromophore were synthesized and their structure confirmed by ¹H-NMR, IR and elemental analysis. The influence of the solvent polarity and protonation on the photophysical properties of NBD-15-crown-5 was studied by UV/Vis and fluorescence methods. The influence of the investigated cations on the absorption spectra of the ligands was negligible, however emission was strongly affected. Complexation and binding stability of NBD-aza-15-crown-5 and NBD-aza-18-crown-6 were studied using fluorescence spectroscopy. NBD-aza-18-crown-6 exhibits strong selectivity toward Ca²⁺ and Sr²⁺ ions with formation constants about 10³ times higher than the formation constants with the other ions included in the study.     

Investigation effect of benzotriazole on the corrosion of brass-MM55 alloy in artificial seawater by dynamic EIS

The electrochemical behavior of brass-MM55 alloy was studied in artificial seawater with benzotriazole by using a novel method called dynamic electrochemical impedance spectroscopy (DEIS). This method gives possibility to investigate the protection of metals in corrosive medium by using inhibitors in galvanostatic conditions for a long time. Instantaneous impedance spectra for brass-MM55 were recorded for 10 h in artificial seawater for different concentration of benzotriazole. It was found that a few hours were not enough for the accurate calculation of corrosion inhibition. Also with this method it is possible to figure out how the charge transfer resistance (R _ct) changes by the time. Usefulness of the DEIS technique in the investigation of non-stationary phenomena has been proved in the field of inhibitor research. All studies clearly show that benzotriazole inhibits the corrosion of brass-MM55 alloy in artificial seawater solution and the value of inhibition efficiency increases with increasing concentration of benzotriazole.     

Crystallization and Melting Behavior of Monodisperse Oligomers of ϵ-Caprolactone

Monodisperse ?-caprolactone (CL) oligomers with different end groups (t-butyldimethylsilyl, benzyl, hydroxyl, and carboxylic acid) and different numbers of repeating units (4–64) have been studied by differential scanning calorimetry and small-angle X-ray scattering (SAXS) in order to gather information regarding the melting temperature, long period, and melting enthalpy. Oligomers crystallized at their maximum temperatures (different for the different oligomers) to full crystallinity yielded extended-chain crystals for oligomers with 4, 8, and 16 repeating units with the important exception of the oligomers with four and eight repeating units and hydroxyl and benzyl end groups that showed double-layer crystals. Oligomers with 32 and 64 repeating units exhibited remarkably stable once-folded (32-mer) and thrice-folded (64-mer) crystals. Only the oligomer with 16 repeating units showed two crystallization temperature regimes resulting in once-folded crystals (low temperatures) and extended-chain crystals (high temperatures). The end groups had a profound effect on the structures. Hydrogen-bonding groups promoted the formation of crystal bilayers and led to a very high melting enthalpy (150 J g^?1) exceeding the melting enthalpy of 100% crystalline poly (?-caprolactone). The bulky end groups, in particular t-butyldimethylsilyl, reduced the crystallinity and favored chain tilting and probably preventing the unfolding of crystal stems in the oligomers with 32 and 64 repeating units. Melting temperatures of mature crystals obeyed a linear relationship with inverse CL stem length. The intercept (equilibrium melting temperature) was in the range of 350 to 357 K.     

Assessing the transport properties of organic penetrants in low‐density polyethylene using free volume models

Three models, two of them relying on free volume—the Cohen–Turnbull–Fujita (CTF) model and the Vrentas–Duda (VD) model, and the third being empirical using an exponential concentration dependence of the diffusivity, were applied to desorption data for a series of alkane penetrants (2,2‐dimethylbutane, cyclohexane, n‐hexane, n‐decane, and n‐tetradecane) in low‐density polyethylene. The CTF model described the desorption data very well and better than the exponential diffusion law. The VD model with the attractive feature of being based on independently determined parameters was unsuccessful in describing the desorption data. Diffusivity data indicated that the three components outside the crystal core were less accessible to n‐tetradecane than to the other penetrants. This indication was further substantiated by solubility data. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 723–734, 2007