Search results for "Ionic polymerization"
showing 10 items of 481 documents
Programmed Formation of HCN Oligomers through Organosulfur Catalysis
2021
An efficient, inexpensive, and reliable synthesis of diaminomaleonitrile (DAMN, 1) is described starting from readily available acetone cyanohydrin as the source of hydrogen cyanide (HCN). Diaminomaleonitrile (DAMN) is known to be an important intermediate in heterocyclic and medicinal chemistry as well as being a possible precursor for the origin of life's hypothesis within prebiotic chemistry. The mechanism of its formation through organosulfur catalysis has been investigated by electrospray ionization mass spectrometry (ESI-MS) using two newly synthesized cationic "marker" molecules as a tool that allows for sensitive detection. As a result, the proposed mechanism of a thiocyanate-mediat…
Synthesis, electrochemical and theoretical studies of the Au(i)-Cu(i) heterometallic clusters bearing ferrocenyl groups
2009
Treatment of the polymeric alkynyl compounds (AuC2R)n (R = Fc, C6H4Fc; Fc = ferrocenyl) with the diphosphine PPh2C6H4PPh2 gave complexes (RC2Au)PPh2C6H4PPh2(AuC2R) (1, R = Fc; 2, R = C6H4Fc) with end-capped ferrocenyl groups. The reactions of 1 or 2 with Cu(NCMe)4PF6 result in formation of the heterotrimetallic aggregates [{Au3Cu2(C2R)6}Au3(PPh2C6H4PPh2)3](PF6)2 (3, R = Fc; 4, R = C6H4Fc), which consist of the alkynyl clusters [Au3Cu2(C2R)6]−“wrapped” by the cationic [Au3(PPh2C6H4PPh2)3]3+“belt”. The novel compounds were characterized by NMR spectroscopy and ESI-MS measurements. The solid state structure of 3 is reported. Electrochemical properties of the complexes 1–4 have been studied. Th…
The Use of Polyoxometalates in the Design of Layer‐Like Hybrid Salts Containing Cationic Mn 4 Single‐Molecule Magnets
2013
Herein, we describe the combination of polyoxometalates (POMs) with a polynuclear metallic cluster Mn4 {Mn4 = [Mn4(OAc)2(pdmH)6]2+, (pdmH = deprotonated pyridine-2,6-dimethanol; C7H8NO2)} for the construction of ionic crystals with layered architectures. Choosing a POM with the appropriate charge and size not only allows for the fine tuning of the stacking periodicity, but it also allows modifying the in-plane packing motif and density of the cationic metallic clusters. The isolation of differently layered hybrid crystals with the same Mn4 single-molecule-magnet (SMM) system allowed for the direct comparison of the magnetic properties of such materials. The variation of the slow relaxation …
Extent of the influence of phosphate buffer and ionic liquids on the reduction of the silanol effect in a C18 stationary phase
2017
The presence of anionic free silanols in the silica-based stationary phases gives rise to broad and asymmetrical peaks when cationic basic compounds are chromatographed using hydro-organic mobile phases. The addition to the mobile phase of a reagent with ionic character prevents the access of analytes to the free silanols, improving the peak shape. The silanol activity can be affected by the buffer concentration and mobile phase pH, factors that are not always considered sufficiently in the literature. In this work, the chromatographic behaviour of three basic β-adrenoceptor antagonists (acebutolol, nadolol and timolol), using mobile phases containing acetonitrile, was examined at different…
Solid‐State Anion–Guest Encapsulation by Metallosupramolecular Capsules Made from Two Tetranuclear Copper(II) Complexes
2007
A new cationic tetranuclear copper(II) complex self-assembles from one 1,3-phenylenebis(oxamato) (mpba) bridging ligand and four CuII ions partially blocked with N,N,N′,N′-tetramethylethylenediamine (tmen) terminal ligands. In the solid state, two of these tetracopper(II) oxamato complexes of bowl-like shape and helical conformation then serve as a building block for the generation of either hetero- (MP) or homochiral (MM/PP) dimeric capsules depending on the nature of the encapsulated anion guest, perchlorate or hexafluorophosphate. The overall magnetic behaviour of these metallosupramolecular capsules does not depend on the nature of the encapsulated anion guest, but it is consistent with…
A new palladium(II)-catalyzed [3,3] aza-Claisen rearrangement of 3-allyloxy-5-aryl-1,2,4-oxadiazoles
2011
Abstract A new efficient palladium(II)-catalyzed [3,3] aza-Claisen, formal sigmatropic rearrangement of 3-allyloxy-5-aryl-1,2,4-oxadiazoles was developed. The mechanism was studied by analyzing the regiochemical and stereochemical course of the reaction. The results obtained indicated the intervention of a cationic pallada-cycle similar to the one postulated for the Cope rearrangement of 1,5-dienes.
The effects of structural changes on the anti-microbial and anti-proliferative activities of diimidazolium salts
2017
An array of diimidazolium salts has been synthesized and used to investigate their anti-microbial and anti-proliferative activities. In particular, salts based on the 3,30-di-n-alkyl-1,10-(1,n-phenylenedimethylene)- diimidazolium cation and differing in the alkyl chain length on the imidazolium ion, the isomeric substitution on the aromatic spacer and in the anion nature were used. The anti-proliferative activity was evaluated against cervical (HeLa), colon adenocarcinoma (HT-29) and breast (SKBR3) cancer cell lines. In the latter case, also a morphological assessment after treatment with salts was performed. All salts were tested for their hemolytic activity against human erythrocytes. On …
Bioresponsive poly(amidoamine)s designed for intracellular protein delivery.
2013
Poly(amidoamine)s with bioreducible disulfide linkages in the main chain (SS-PAAs) and pH-responsive, negatively charged citraconate groups in the sidechain have been designed for effective intracellular delivery and release of proteins with a net positive charge at neutral pH. Using lysozyme as a cationic model protein these water soluble polymers efficiently self-assemble into nanocomplexes by charge attraction. At pH 5 (the endosomal pH) the amide linkages connecting the citraconate groups in the sidechains of the SS-PAAs are hydrolyzed by intramolecular catalysis, resulting in expulsion of the negative citraconate groups and formation of protonated amine groups, resulting in charge reve…
The introduction of fluorine atoms or trifluoromethyl groups in short cationic peptides enhances their antimicrobial activity
2006
The effect of introducing fluorine atoms or trifluoromethyl groups in either the peptidic chain or the C-terminal end of cationic pentapeptides is reported. Three series of amide and ester peptides were synthesised and their antimicrobial properties evaluated. An enhanced activity was found in those derivatives whose structure contained fluorine, suggesting an increase in their hydrophobicity.
Synthesis and Reactivity toward Isonitriles of (2-Aminoaryl)palladium(II) Complexes
2001
Mixtures of “Pd(dba)2” (dba = dibenzylideneacetone) and 2,2‘-bipyridine (bpy; 1:2) or N,N,N‘,N‘-tetramethylethylenediamine (tmeda; 1:1) react with 2-bromo-4-nitroaniline to give [Pd{C6H3NH2-2-NO2-5}Br(N−N)] (N−N = bpy (1b), tmeda (1b‘)). Reactions of 2-iodoaniline with mixtures of “Pd(dba)2” and isonitriles RNC (R = C6H3Me2-2,6 (Xy), 2:1:2 molar ratios; R = tBu, 2.9:1:2 molar ratios) result in the formation of the complexes [Pd{κ2C,N-C(NXy)C6H4NH2-2}I(CNXy)] (2a) and trans-[Pd{C(NtBu)C6H4NH2-2}I(CNtBu)2] (3a*). The reactions of [Pd{C6H4NH2-2}I(bpy)] and 1b‘ with RNC give the complexes trans-[Pd{C(NR)C6H3NH2-2-Y-5}}X(CNR)2] (Y = H, X = I, R = Xy (3a), tBu (3a*); Y = NO2, X = Br, R = Xy (3b),…