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Turbidity and light scattering measurements, along with phase contrast microscopy, were used to follow the processes leading to coacervation when aqueous solutions of bovine serum albumin (BSA) and poly-(dimethyldiallylammonium chloride) (PDADMAC) were brought from pH = 4 to 10. The state of macromolecular assembly of complexes formed between BSA and(More)
First examples of stable carbocations are reported from several classes of thia-PAHs with four fused rings, namely, benzo[b]naphtho[2,1-d]thiophene (1) and its 3-methoxy derivative (2), phenanthro[4,3-b]thiophene (3) and its 7-methoxy (4), 10-methoxy (5), and 9-methoxy (6) derivatives, phenanthro[3,4-b]thiophene (7) and its 7-methoxy (8) and 9-methoxy (9)(More)
Reaction of [ArN(2)][BF(4)] salts immobilized in [BMIM][PF(6)] ionic liquid (IL) with TMSX (X = I, Br) and TMSN(3) represents an efficient method for the preparation of iodo-, bromo-, and azido-derivatives via dediazoniation. The reactions can also be effected starting with ArNH(2) by in situ diazotization with [NO][BF(4)] followed by reaction with TMSX or(More)
Mono- and diprotonated carbocations and the two-electron oxidation dications derived from parent pyrene and its nonalternant isomers "azupyrene"(dicyclopenta[ef,kl]heptalene)(DCPH) and dicyclohepta[ed,gh]pentalene (DCHP) were studied by DFT at the B3LYP/6-31G(d) level. The most likely site(s) for mono- and diprotonation were determined based on relative(More)
A mild and efficient process has been developed for the one-pot adamantylation of aromatic substrates employing 1-AdaOH, 1-AdaCl, 1-AdaBr, and 1-Br-3,5,7-trimethyladamantane as adamantylating agents, with triflic acid (TfOH) as promoter and n-butylmethylimidazolium triflate [BMIM][OTf] room temperature ionic liquid (IL) as solvent. The influence of reaction(More)
Tripod-shaped trithiols 1-3, containing CH2SH groups at the three bridgehead positions of the adamantane framework and a halogen-containing group [Br (1), p-BrC6H4 (2), or p-IC6H4 (3)] at the fourth bridgehead, were synthesized, and self-assembled monolayers (SAMs) were prepared on atomically flat Au111 surfaces. The three-point chemisorption of these(More)
Arenediazonium tetrafluoroborate salts undergo metathesis on immobilization in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonato)amide [BMIM][Tf(2)N]. The "noncoordinating", "nonnucleophilic" [Tf(2)N] anion acts as an ambident nucleophile toward the aryl cations, formed via thermal dediazoniation, to give predominantly the oxy anion quenching(More)
A dyad consisting of a tripod-shaped trithiol with an adamantane core and a terminal ferrocenyl group linked through ap-phenyleneethynylene bridge was synthesized. The trithiol formed a stable self-assembled monolayer (SAM) on Au(111), wherein each molecule is bound to the surface by three-point adsorption using all sulfur atoms, with confirmation by(More)
A series of novel carbocations were generated by low-temperature protonation of substituted benzo[c]phenanthrenes, B[c]Phs, and their charge delocalization pathways were elucidated by NMR on the basis of the magnitude of Deltadelta13C values. It has been shown that the protonation regioselectivity is strongly controlled by methoxy and hydroxyl substituents,(More)