Trimethylammonium Iodide Research Articles

Self-Assembled Organic Functional Nanotubes and Nanorods and Their Sensory Properties

Self-assembled, one-dimensional nanostructures of N,N′-bis(2-(trimethylammonium iodide)ethylene)perylene-3,4,9,10-tetracarboxyldiimide (PTCDI-I) with tunable morphologies were successfully prepared by a facile evaporation method. PTCDI-I nanotubes with diameters of approximately 100−300 nm were obtained by the evaporation of the aqueous solution of PTCDI-I, while long nanorods with diameters of approximately 200−300 nm were produced by slow evaporation of the methanolic solution of PTCDI-I. Studies of the nanostructures formed at different stages suggested that the formation of nanotubes and nanorods could be ascribed to different crystallization processes from different solutions. The PTCDI-I nanostructures were redox-active, and four-probe measurements based on a single nanotube or nanorod exhibited resistance decreased by 2 to 3 orders of magnitude after being exposed to reducing agents such as hydrazine or phenylhydrazine. Such high resistance modulations indicate that these nanostructures will be useful as building blocks for electronic nanodevices and sensors.

PH and salt responsive poly(N,N-dimethylaminoethyl methacrylate) cylindrical brushes and their quaternized derivatives

We present the synthesis and characterization of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) cylindrical brushes, their pH responsiveness, and the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes. PDMAEMA brushes were prepared by atom transfer radical polymerization (ATRP) using the grafting-from strategy. Initiating efficiencies of the ATRP processes were determined by cleaving the side-chains and gel permeation chromatography (GPC) analysis. Due to the slow initiation and steric hindrance, the initiating efficiency is only around 50%. The PDMAEMA brushes show worm-like structures and pH responsiveness, as proven by dynamic light scattering (DLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Strong cationic polyelectrolyte PMETAI brushes were produced by quaternization of the PDMAEMA brushes. AFM and cryo-TEM images showed similar worm-like morphologies for the PMETAI brushes. The PMETAI brushes collapsed in solution with high concentration of monovalent salt, as proven by DLS and AFM results.

Photopolymerization of clay/polyurethane nanocomposites induced by an intercalated photoinitiator through sol–gel modification

An organic silane photoinitiator (1173IPS) was synthesized through the reaction of (3-Isocyanatopropyl)triethoxysilane (IPS) and 2-hydroxy-2-methyl-1-phenylpropane-1-one (1173). The objective of this work was to intercalate photoinitiator 1173IPS into a montmorillonite (MMT) through sol–gel reaction of cationic triethoxysilanepropylamineformylethyl trimethyl ammonium iodide (APS) and 1173IPS. The modified clay was then mixed with urethaneacylate oligomer (CN962) and 1,6-hexanediol diacrylate (HDDA) to form polyurethane–nanoclay composites by photopolymerization. Real-time FTIR (RTIR) results showed the system had almost the same final conversion but different polymerization rates with different ratios of APS/1173IPS modified clay. XRD and TEM results showed that the modified clay was exfoliated and dispersed in parallel alignments as multilayers in the organic matrix.

Preparation of highly exfoliated epoxy–clay nanocomposites by sol–gel modification

The objective of this work is to intercalate epoxy groups into the layered silicates through sol–gel reaction of cationic triethoxysilanepropylamineformylethyl trimethyl ammonium iodide (APS) and 3-glycidoxypropyl trimethoxysilane (GPS). When the ratio of APS to GPS was 1/4 or more, the organoclay was easier to be dispersed in acetone and formed stable slurry. The slurry was then mixed extensively with epoxy resin to form epoxy–nanoclay composites by photopolymerization. The resulting epoxy–nanoclay composites exhibited a high degree of clay exfoliation from ordered exfoliation to highly disordered exfoliation and a better thermal stability property.

Completely Aqueous Procedure for the Growth of Polymer Brushes on Polymeric Substrates

The growth of polymer brushes on polymer substrates is often challenging because of substrate incompatibility with the organic solvents used for initiator attachment. This letter reports the use of layer-by-layer adsorption of macroinitiators and subsequent aqueous ATRP from these immobilized initiators to prepare polymer brushes on polymeric substrates. Polyethersulfone (PES) films and porous membranes were modified with polyelectrolyte multilayer films, and a previously developed polycationic initiator, poly(2-(trimethylammonium iodide)ethyl methacrylate-co-2-(2-bromoisobutyryloxy)ethyl acrylate), was then electrostatically adsorbed onto these polyelectrolyte films. The immobilized macroinitiator is very efficient in initiating the growth of polymer brushes on PES, as demonstrated by aqueous syntheses of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) films. PHEMA (250 nm thick) and PDMAEMA (40 nm thick) brushes were grown in 2 h from surfaces modified with polycationic initiators. Moreover, this procedure is effective for growing brushes in the pores of PES membranes.

Synthesis and Characterization of Star-Shaped Poly(N,N-dimethylaminoethyl methacrylate) and Its Quaternized Ammonium Salts

We report on the synthesis and characterization of star-shaped strong polyelectrolytes and their precursor stars with up to 24 arms. To achieve this we polymerized 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) by atom transfer radical polymerization employing a core-first attempt. Sugar-based scaffolds as well as silsesquioxane nanoparticles were used as oligofunctional initiators. Subsequent quaternization of the obtained poly(DMAEMA) stars yielded star-shaped poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI). The initiation site efficiency was determined both by molecular weight measurements of the cleaved arms and by a statistical method after partial destruction of the inorganic core. The rather low efficiency of the initiation sites (30−75%) leads to a moderate arm number distribution of the prepared polyelectrolyte stars. As expected, the hydrodynamic radii of these polyelectrolyte stars decrease with increasing ionic strength. However, if the ionic strength was adjusted with NaI instead of NaCl, pronounced ion-specific effects were observed; the star polyelectrolyte first strongly shrinks with increasing salt concentration and becomes insoluble at about 0.5 M NaI (“salting out”). Still higher concentrations of NaI lead to a redissolution and a reswelling of the star polyelectrolyte (“salting in”). The measured osmotic coefficients are low and decrease with increasing arm number from φ ∼ 0.12 for a 3-arm star down to φ ∼ 0.04 for an 18-arm star, confirming the expected strong counterion confinement within these objects with high charge density.

Trimethyl(4-Iodophenyl)Ammoniumiodid, Eine Hypervalente Verbindung Des Iods

The crystal structure of trimethyl(4-iodophenyl)ammonium iodide (2), obtained from 4-iodo-N,N-dimethylaniline and methyl iodide, reveals the presence of weak hypervalent bonding of the iodine atom

Products of hydrolysis of (ferrocenylmethyl)trimethylammonium iodide: Synthesis of hydroxymethylferrocene and bis(ferrocenylmethyl) ether

The attempted coupling of (ferrocenylmethyl)trimethylammonium iodide ( 1) with 1,4,7-(triformyl)-1,4,7,10-tetraazacyclododecane ( 2) in water led to the formation of the expected compound 1-(ferrocenemethyl)-4,7,10-(triformyl)-1,4,7,10-tetraazacyclododecane ( 3). In addition, hydrolysis of the ferrocenyl precursor 1 led to the formation of two other known compounds, hydroxymethylferrocene ( 4) and bis(ferrocenylmethyl) ether ( 5). An X-ray crystal structure determination of 4 revealed the presence of H-bonding between the hydroxyl groups of one molecule of 4 and the oxygen atom of an adjacent molecule resulting in a left-handed helical chain of molecules lying along the b-axis direction. The O⋯O distances are significantly shorter than those found in previously reported structures of hydroxymethylferrocene derivatives indicative of moderate strength H-bonding interactions. In the structure of 5, the orientation of the ferrocenyl groups are staggered relative to a vector comprising the two carbons of the C–O–C linker.

First stages of barium ferrite microparticles entrapment in the electrodeposition of CoNi films

Abstract A study of the incorporation of magnetic barium ferrite microparticles into a CoNi matrix by means of electrodeposition over silicon-base substrates has been performed. A cationic surfactant synthesized in our laboratory (4-ethylazobenzene-4′-(oxyethyl)trimethylammonium iodide – AZTMAI) has been selected to favour the inclusion of magnetic particles in the alloy deposit. This surfactant reduces during the cobalt–nickel electrodeposition avoiding its inclusion in the film and favours the inclusion of magnetic particles without damaging the deposits quality. The amount of ferrite incorporated during the electrodeposition increases gradually with the surfactant concentration. A moderate deposition temperature allows greater barium ferrite incorporation. Magnetic properties of CoNi–barium ferrite deposits obtained in the presence of AZTMAI are clearly different of those corresponding to pure-CoNi films obtained in the absence of surfactant. Coercivity is clearly increased.

An Efficient Synthesis and Reactions of Novel Indol-ylpyridazinone Derivatives with Expected Biological Activity

Reaction of 4-anthracen-9-yl-4-oxo-but-2-enoic acid (1) with indole gave the corresponding butanoic acid 2. Cyclocondensation of 2 with hydrazine hydrate, phenyl hydrazine, semicarbazide and thiosemicarbazide gave the pyridazinone derivatives 3a-d. Reaction of 3a with POCl(3) for 30 min gave the chloropyridazine derivative 4a, which was used to prepare the corresponding carbohydrate hydrazone derivatives 5a-d. Reaction of chloropyridazine 4a with some aliphatic or aromatic amines and anthranilic acid gave 6a-f and 7, respectively. When the reaction of the pyridazinone derivative 3a with POCl(3) was carried out for 3 hr an unexpected product 4b was obtained. The structure of 4b was confirmed by its reaction with hydrazine hydrate to give hydrazopyridazine derivative 9, which reacted in turn with acetyl acetone to afford 10. Reaction of 4b with methylamine gave 11, which reacted with methyl iodide to give the trimethylammonium iodide derivative 12. The pyridazinone 3a also reacted with benzene- or 4-toluenesulphonyl chloride to give 13a-b and with aliphatic or aromatic aldehydes to give 14a-g. All proposed structures were supported by IR, (1)H-NMR, (13)C-NMR, and MS spectroscopic data. Some of the new products showed antibacterial activity.

Effect of intercalant content of mica on the various properties for the charged nanocomposite poly(N-isopropyl acrylamide) hydrogels

In this study, we intend to adjust the charge properties of the poly(N-isopropylacrylamide) [Poly(NIPAAm)] gel by using anionic clay and cationic monomer. Hence, two series of nanocomposite hydrogels bearing different charges were designed from NIPAAm, intercalated mica (IM) (NIM-series) and NIPAAm, IM, trimethyl (acrylamido propyl) ammonium iodide (TMAAI) (NTIM-series), respectively. The mica was first intercalated with different contents of intercalant, trimethyl (acrylamido propyl) ammonium chloride (TMAACl), based on the cationic exchange capacity (CEC) of mica. The effect of the CEC value of IM and IM content on the charge property, swelling behaviors, mechanical properties, and drug-release behaviors of the present gels were investigated. Results showed that the negative charges for NIM series gels decrease with increase in CEC values of the IM (from −11 to −6 mV), the positive charges for NTIM series gels also decrease with increase in CEC values of the IM (from +36 to +18 mV). The swelling behaviors and mechanical properties for the NTIM gels were significantly enhanced by IM content and CEC values of the IM. The microstructures, morphologies, and drug-release behaviors in these two series gels are also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2277–2287, 2007

Facile Synthesis and Detailed Characterization of a New Ferrocenyl Uracil Peptide Nucleic Acid Monomer

A new ferrocenyl uracil peptide nucleic acid (PNA) monomer, tert-butyl-2-(N-(2-(((9H-floren-9-yl)methoxy)carbonylamino)ethyl)-2-(5-(N-ferrocenylmethylbenzamido)-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)acetamido)acetate (1), has been successfully prepared in good yield by a procedure involving the one-pot reaction of the key synthon, 5-(ferrocenylmethylamino)pyrimidine-2,4(1H,3H)-dione (4), itself prepared from the reaction of (ferrocenylmethyl)trimethylammonium iodide and 5-aminouracil, with benzoyl chloride followed by ethyl bromoacetate. After hydrolysis of the ester, the acid was coupled with a protected PNA backbone to generate 1. NMR spectroscopy showed that 1 hydrogen bonds 9-ethyladenine (EA) in a 1:1 mixture of CD3CN:CDCl3 with an association constant Ka of 70 M(-1) at 30 degrees C. This value is comparable with those observed for model receptors and shows that the ferrocenyl moiety of 1 does not hinder the hydrogen bonding of our new PNA monomer to the complementary DNA base or if it does, not significantly. 1 is oxidized to 1+ with a reversible potential of +538 mV vs the DMFc(0/+) (decamethylferrocene) couple under voltammetric conditions in a 1:1 mixture of CH3CN:CHCl3 (0.1 M Bu4NPF6). For this reversible process, a slightly larger diffusion coefficient of 4.2 x 10(-6) cm(2).s(-1) than usually found for these compounds was determined from these electrochemical studies, which should be analytically useful as it will readily afford submicromolar voltammetric detection limits.

Redetermination of trimethylammonium iodide at 93 K

The crystal structure of the title compound, C3H10N+·I−, originally determined by Sheldrick & Sheldrick [Acta Cryst. (1970), B26, 1334–1338], has been redetermined at 93 K. Both ions lie on a mirror plane. They form N—H⋯I hydrogen-bonded units in the crystal structure.

Preparation, single-crystal X-ray diffraction and high-resolution NMR spectroscopic analyses of N-[(1,4-anhydro-5-deoxy-2,3- O-isopropylidene- d, l-ribitol)-5-yl]trimethylammonium iodide

The synthesis and isolation of 1,4-anhydro-5-deoxy-5-iodo-2,3- O-isopropylidene- d, l-ribitol and N-[(1,4-anhydro-5-deoxy-2,3- O-isopropylidene- d, l-ribitol)-5-yl]trimethylammonium iodide are described. The products were examined by 1H, 13C NMR spectroscopy, and N-[(1,4-anhydro-5-deoxy-2,3- O-isopropylidene- d, l-ribitol)-5-yl]trimethylammonium iodide was additionally analyzed by X-ray crystallography.

Cell separation in microcanal coated with electrically charged phospholipid polymers

To separate the cell population in whole blood using microcanal, the surface was covered with a polyion complex (PIC) composed of electrically charged phospholipid polymers. The phospholipids polymers were prepared by the polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and n-butyl methacrylate with 3-(methacryloyloxypropyl)-trimethyl ammonium iodide as the cationic unit or potassium 3-methacryloyloxypropyl sulfonate as the anionic unit. The PIC was formed at the solid-liquid interface, that is, first, the cationic polymer was coated on the substrate and an aqueous solution containing the anionic polymer with different concentrations was applied to the polymer-coated substrate. The formation of the PIC was followed using a quartz crystal microbalance (QCM), and the PIC surfaces were analyzed by both ζ-potential measurement and X-ray photoelectron spectroscopic measurement. The surface electrical potential on the PIC was controllable from +40 to −40 mV by increasing the amount of the adsorbed anionic polymer. The PIC surface was prepared in microcanal. The surface electrical potential was sequentially changed. When the whole blood was introduced into the microcanal, the cells adhered on the positively charged surface, but could not adhere to the negatively charged surface. Even when the cells adhere to the surface, the morphology of cells was maintained. This is due to MPC units at the surface, which show a good biocompatibility. These results indicated that the change in the surface electrical potential will be a useful method to separate the cells from whole blood.

Crystal Structure of (1-Adamantylmethyl)trimethyl-ammonium Iodide

The title compound, (1-adamantylmetyl)trimethyl-ammonium iodide (AdMeNMe3I), was synthesized, and its structure was investigated by X-ray crystallography. It was crystallized in the monoclinic space group P21/n with the following cell parameters: a = 7.573(2)A, b = 13.935(3)A, c = 14.1095(18)A, β = 99.792(15)°, and Z = 4. The final residual factor was 0.0984. The compound exhibited a warped cavity of the adamantyl group due to an interaction with a quaternary ammonium group.

Normal and shear forces between a polyelectrolyte brush and a solid surface

AbstractThe diblock copolymer poly(methyl methacrylate)‐b‐poly(sodium sulfonated glycidyl methacrylate) (PMMA‐b‐PSGMA) was end‐attached by its hydrophobic block (PMMA) onto mica hydrophobized by a stearic trimethylammonium iodide (STAI) layer, to form a polyelectrolyte brush immersed in water. With a surface force balance (SFB), we extended earlier measurements between two such brush layers for the case of normal and shear forces at different shear rates, surface separation, and compressions between one mica surface coated with STAI or a STAI‐diblock layer against a bare mica surface. After coating one of the surfaces with STAI, a long range attraction that results in a jump into an adhesive flat contact between the hydrophobic and hydrophilic surfaces was observed. A very different behavior was seen after forming the polyelectrolyte brush on the STAI‐coated surface. The long range attraction was replaced by repulsion, accompanied by very low friction during shear (ca. three orders of magnitude lower than with adsorbed polyelectrolytes). On further compression, a weak attraction to the adhesive contact was observed. From the final surface–surface contact separation, we deduce that most of the polyelectrolyte diblock brush layer was squeezed out from the gap, leaving the STAI layer and a small amount of the polymer attached to the surface. Stick‐sliding behavior was seen while applying shear, suggesting a dissipation mechanism caused by the trapped polyelectrolyte. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 193–204, 2005

Novel water soluble copolymers based on thioxanthone: photochemistry and photoinitiation activity

The absorption, luminescence and photoreduction properties of five novel water soluble thioxanthone copolymers are reported. The new polymers have been prepared by copolymerization of 1-methyl-4-(3-acryloxypropoxy) thioxanthone (TX3), 1-chloro-4-acryloxy thioxanthone (TX4), 1-chloro-4-oxyethylacrylate thioxanthone (TX5), and 1-chloro-4-allyloxy thioxanthone (TX6), with two water soluble comonomers, acrylamide (AAm) and 2-acryloxyethyl trimethylammonium iodide (MI). The photoinitiation effectiveness of these new copolymers was studied by photocalorimetry and photodilatometry for acrylamide photopolymerization in aqueous solution and in the presence of a tertiary amine. The results compared to those of the corresponding low molecular weight model compounds, (TX1), 1-methyl-4-(2-hydroxy-3- N, N, N-trimethylammoniumpropoxy) thioxanthone chloride salt, and TX2, 1-chloro-4-(2-hydroxy-3- N, N, N-trimethylammoniumpropoxy) thioxanthone chloride salt. The new copolymers show high polymerisation rates under the experimental conditions used, and confirm that these compounds operate as effective photoinitiators of polymerization. The data are discussed in relation to their photophysical and photochemical properties.

Electroencephalographic effects induced by choline pivaloyl esters in scopolamine-treated or nucleus basalis magnocellularis lesioned rats

The electroencephalographic (EEG) effects of two choline pivaloyl esters, [2-(2,2-dimethylpropionyloxy)ethyl]trimethylammonium iodide (1) and [2-(2,2-dimethylpropionyloxy)ethyl]trimethylammonium 2,2-dimethylpropionate (2), were evaluated in scopolamine-treated or nucleus basalis magnocellularis (NBM) lesioned rats. In scopolamine-treated animals, Compounds 1 and 2 prevented or reduced EEG effects, such as increased amplitude of total spectra and high-voltage spindle (HVS) activity as well. Furthermore, choline esters showed a noticeable effectiveness in reversing the EEG changes produced in rats by AMPA-induced lesion of NBM. Indeed, Compounds 1 and 2 were able to induce EEG desynchronisation, a significant decrease in the total EEG power (0.25–16 Hz) and in the lower frequency delta and theta bands (0.25–3 and 3–6 Hz, respectively). The EEG effects produced by Compounds 1 and 2 were well comparable with that evoked by Tacrine, used as a reference compound. The results of the present work allow us to put forward the hypothesis that the EEG effects observed are most likely mediated through the stimulation of the cholinergic neurotransmission ensuing from enhanced cerebral levels of acetylcholine (ACh) consequent upon acetylcholinesterase (AChE) inhibition by choline pivaloyl esters.

Choline pivaloyl esters improve in rats cognitive and memory performances impaired by scopolamine treatment or lesions of the nucleus basalis of Meynert

The effects of two choline pivaloyl esters, [2-(2,2-dimethylpropionyloxy)ethyl]trimethylammonium iodide ( 1) and [2-(2,2-dimethylpropionyloxy)ethyl]trimethylammonium 2,2-dimethylpropionate ( 2), on learning and memory impairments induced in rats by scopolamine or lesions of nucleus basalis magnocellularis (NBM) have been evaluated by object recognition and Morris water maze tests in comparison with Tacrine (THA). Both 1 and 2 restored discrimination in object recognition test for assessing working-episodic memory and improved spatial memory in scopolamine or NBM-lesioned rats as well. The positive effects produced by 1 and 2 on cognitive and memory deficits were well comparable with those evoked by THA, used as reference compound.