Alkyl Chains (alkyl + chain)

Distribution by Scientific Domains
Distribution within Chemistry

Kinds of Alkyl Chains

  • long alkyl chain

  • Terms modified by Alkyl Chains

  • alkyl chain length

  • Selected Abstracts


    Synthesis and Properties of Alkyl Phosphorylcholine Amphiphiles with a Linear and an Asymmetrically Branched Alkyl Chain.

    CHEMINFORM, Issue 51 2005
    Eui-Chul Kang
    No abstract is available for this article. [source]


    Orientation and Arrangement of Octaruthenium Supramolecules with Alkyl Chains on Graphite

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2007
    Dong-Lin Shieh
    Abstract The self-assemblies of octaruthenium grid-type supramolecules, {[Ru2(CO)4(NH2C16H33)2](,-O2CCO2)}4, on highly oriented pyrolytic graphite (HOPG) in air and in 1-phenyloctane were studied by scanning tunneling microscopy (STM). The surface supramolecules are arranged into rows in which the metal cores are linearly packed and the alkyl chains are parallel to the surface. With the aid of theoretical calculations in the framework of density functional theory, the electronic origin of the tunneling in the measured STM images is discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source]


    Tetrathiafulvalene-, 1,5-Dioxynaphthalene-, and Cyclobis(paraquat- p -phenylene)-based [2]Rotaxanes with Cyclohexyl and Alkyl Chains as Spacers: Synthesis, Langmuir,Blodgett Films, and Electrical Bistability,

    ADVANCED FUNCTIONAL MATERIALS, Issue 5 2007
    X. Guo
    Abstract The synthesis and characterization of two new (TTF-DNP-CBPQT4+) [2]rotaxanes 1 and 2 is reported, based on tetrathiafulvalene (TTF), 1,5-dioxynaphthalene (DNP), and cyclobis(paraquat- p -phenylene) (CBPQT4+) with cyclohexyl and alkyl chains as the spacers. Multilayer Langmuir,Blodgett (LB) films of [2]rotaxanes 1 and 2 are prepared. Conducting atomic force microscopy, scanning tunneling microscopy, and two-terminal junction device studies indicate that the LB films of [2]rotaxanes 1 and 2 show electrical bistability behavior. By comparing with the TTF-DNP-CBPQT4+ [2]rotaxanes reported by Stoddart et,al. previously, the present results imply that proper modification of the chemical structures of the TTF unit and the spacer have negligible effect on the electrical bistability behavior of these TTF-DNP-CBPQT4+ [2]rotaxanes. These findings will allow for the design and preparation of new multifunctional TTF-DNP-CBPQT4+ [2]rotaxanes in the future. [source]


    An Unusual , -Oxidation of N -Functionalized Alkyl Chains by 1H- Imidazole

    HELVETICA CHIMICA ACTA, Issue 11 2005
    Heinz Langhals
    The 1H- imidazole-mediated condensation of primary aliphatic amines with perylene-3,4,:,9,10-tetracarboxylic bis-anhydride resulted in by-products where the aliphatic group was functionalized in the , -position by imidazole units. [source]


    Oligo(triacetylene) Derivatives with Pendant Long Alkyl Chains

    HELVETICA CHIMICA ACTA, Issue 6 2004
    Jean-François Nierengarten
    Substituted (E)-2-(ethynyl)but-2-ene and (E)-hex-3-ene-1,5-diyne derivatives 6 and 10, respectively, were prepared by dicyclohexylcarbodiimide(DCC)-mediated esterification of tris(dodecyloxy)benzoic acid (4) with (E)-2-[(triisopropylsilyl)ethynyl]but-2-ene-1,4-diol (3) and (E)-2,3-bis[(trimethylsilyl)ethynyl]but-2-ene-1,4-diol (8), respectively, followed by deprotection with Bu4NF in wet THF (Schemes,1 and 2). Oligomerization reactions of diyne derivative 10 were attempted by treatment with the Hay catalyst in the presence of mono-alkyne 6 as an end-capping reagent. Under these conditions, only compound 7 resulting from the homocoupling of 6 (Scheme,1), and polymers of 10 were obtained due to the difference in reactivity of the alkyne groups in 6 and 10. In contrast, when phenylacetylene was used as the stopper, the oligomerization of 10 afforded a mixture of end-capped oligomers, from which 11,13 were isolated by column chromatography (Scheme,3). The poly(triacetylenes) (PTA) 16,18 were prepared in a similar manner starting from diol 8 and stearic acid (Schemes,4 and 5). Whereas the end-capped monomers and dimers 11, 12, 16, and 17 with pendant long alkyl chains do not exhibit any liquid-crystalline behavior, the trimeric derivatives 13 and 18 show mesomorphic properties, thus demonstrating that the poly(triacetylene) backbone can behave as a mesogenic unit. [source]


    Crystal structure of a polar nematogen 4-(trans- 4-undecylcyclohexyl) isothiocyanatobenzene

    CRYSTAL RESEARCH AND TECHNOLOGY, Issue 10 2007
    S. Biswas
    Abstract Crystal and molecular structures of a nematogenic compound 4-(trans- 4-undecylcyclohexyl) isothiocyanatobenzene (11CHBT) have been determined by direct methods using single crystal X-ray diffraction data. The compound (C24H37N1S1) crystallizes in the monoclinic system with the space group P21/c and Z = 4. The unit cell parameters are a = 5.5539(11) Å, b = 8.1341(10) Å, c = 51.494(5) Å, and (= 91.127(14)0. The structure was refined to Rw = 0.051. The molecule is found to be slightly bow-shaped though the alkyl chain is in all- trans conformation. The phenyl ring and the alkyl chain are planar and the cyclohexyl group is in chair conformation. The isothiocyanato groups are almost linear. Parallel imbricated mode of packing of the molecules is found in the crystalline state which is precursor to the nematic phase structure. There are many van der Waals' interactions particularly in the isothiocyanato benzene part of the molecule. Of the various associated pairs of molecules the one having anti-parallel configuration with overlaps in the isothiocyanato phenyl group probably exists in both the crystalline and the nematic phases. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]


    Structure,activity relationships for acute and chronic toxicity of alcohol ether sulfates

    ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2000
    Scott D. Dyer
    Abstract Acoholethersulfates(AES)areanionicsurfactantscommonlyusedinconsumerproducts. Commercial AES alkyl chain lengths range from C12 to C18, with ethoxylate (EO) units ranging from 1 to 5. Alkyl sulfate is a special case of AES with no EO units. Acute and chronic toxicity tests using Ceriodaphnia dubia via a novel flowthrough method were conducted with 18 AES compounds to derive SARs for effects assessment. In general, acute toxicity (48-h LC50) increased with increased alkyl carbon chain length and decreased with increased numbers of EO units. Parabolic structure,chronic (7-d) toxicity relationships were observed for endpoints such as the no-observed-effect concentration, lowest-observed-effect concentration, maximum acceptable toxicant concentration, EC20, and EC50. A linear relationship of the fractional negative-charged surface area (FNSA-3) with acute toxicity was also determined. FNSA-3 refers primarily to the polar head group of AES and secondarily to the alkyl chain. Seventy percent of the variance in the chronic data was addressed with a quadratic equation relating toxicity to alkyl chain length and EO units. Alternatively, the molecular descriptors FNSA-3 and S3P (3,p, which is the simple, third-order path index) were also found to address most of the data nonlinearity. A chronic test conducted with a mixture of four AES components indicated additivity, leading to the support of the performance of an effects assessment of AES as a mixture. [source]


    Potential MRI Contrast Agents Based on Micellar Incorporation of Amphiphilic Bis(alkylamide) Derivatives of [(Gd,DTPA)(H2O)]2,

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2003
    Kristof Kimpe
    Abstract DTPA-bisamide derivatives with alkyl chains containing 14, 16 and 18 carbon atoms were synthesized and complexes of various trivalent lanthanide ions (Ln = Gd, La, Pr, Eu) were formed. Variable temperature proton NMR spectroscopy of paramagnetic praseodymium(III) and europium(III) complexes revealed that long aliphatic substituents considerably increase the energy barrier for the intramolecular rearrangement around the lanthanide ion. The gadolinium(III) complexes were incorporated into mixed micelles, and photon correlation spectroscopy showed that the mean sizes of all the micelles were within the same range. The NMRD curves of all three DTPA-bisamide-gadolinium complexes incorporated in mixed micelles display higher relaxivity values than the commercially available Gd,DTPA contrast agent. The higher relaxivity obtained for the micellar DTPA-bisamide-gadolinium complexes with C14 and C16 chains relative to the micellar DTPA-bisamide-GdIII C18 chain complex could be attributable to the fact that the alkyl chain containing 18 carbon atoms is longer than the alkyl chain of the major component of the micelles, DPPC, in which it is inserted. This would allow increased mobility of the polar head and hence a lower relaxivity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source]


    Asymmetric bolaamphiphiles from vernonia oil designed for drug delivery

    EUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 1 2010
    Sarina Grinberg
    Abstract Throughout the ages, fats, oils and their chemical derivatives have been used in a variety of medical applications, but currently they are becoming important as components in drug delivery systems. Liposomes (vesicles from phospholipids) are among the lipid-based delivery systems that have been most extensively studied. However, targeting of liposomes to specific tissues is still problematic, and attempts to overcome these limitations include developments in nano-sized monolayer vesicles made of bolaamphiphiles (compounds containing two hydrophilic headgroups at each end of an alkyl chain). This paper describes bolaamphiphile synthesis and characterization of the nano-sized vesicles formed from the bolaamphiphiles with potential application for targeted drug delivery to the brain. The starting material for the synthesis is vernonia oil (or its fatty acids or methyl esters), which is a naturally epoxidized triacylglycerol obtained from the seeds of Vernonia galamensis. The targeting mechanism is based on the hydrolysis of the amphiphile's headgroup by an enzyme abundant in the target tissue, with subsequent release of the encapsulated drug at the target site. Preliminary experiments in mice demonstrated that the marker FITC-dextran, which normally does not penetrate the blood brain barrier, is delivered into the brain when encapsulated in these vesicles. [source]


    Synthesis and Anion-Binding Properties of Novel Redox-Active Calixarene Receptors

    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 25 2008
    Estelle Métay
    Abstract A novel synthetic approach towards redox-active calixarene-based receptors is described in which ferrocene fragments were introduced at the lower rim through anion-binding urea or amide connections. These derivatives were prepared in one pot by treating an amine-containing calixarene with ferrocenecarboxylic acid in the presence of diphenylphosphoryl azide and diisopropylethylamine. This method allows a convergent approach to these receptors and is readily adaptable to the introduction of other urea substituents. The anion-binding properties of these artificial receptors have been revealed by NMR spectroscopy and thoroughly investigated by electrochemical methods. We have assessed the importance of the urea,phosphate bonds in the observed electrochemical response by studying receptors in which the ferrocene reporters and binding fragments are closely associated or fully disconnected through a long alkyl chain. The experimental results clearly show the utmost importance of ion-pairing effects in the electrochemical recognition process, which account for most of the transduction signal in organic apolar media. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]


    Towards Efficient Dispersion of Carbon Nanotubes in Thermotropic Liquid Crystals

    ADVANCED FUNCTIONAL MATERIALS, Issue 19 2010
    Stefan Schymura
    Abstract Motivated by numerous recent reports indicating attractive properties of composite materials of carbon nanotubes (CNTs) and liquid crystals (LCs) and a lack of research aimed at optimizing such composites, the process of dispersing CNTs in thermotropic LCs is systematically studied. LC hosts can perform comparably or even better than the best known organic solvents for CNTs such as N -methyl pyrrolidone (NMP), provided that the dispersion process and choice of LC material are optimized. The chemical structure of the molecules in the LC is very important; variations in core as well as in terminal alkyl chain influence the result. Several observations moreover indicate that the anisotropic nematic phase, aligning the nanotubes in the matrix, per se stabilizes the dispersion compared to a host that is isotropic and thus yields random tube orientation. The chemical and physical phenomena governing the preparation of the dispersion and its stability are identified, taking into account enthalpic, entropic, as well as kinetic factors. This allows a guideline on how to best design and prepare CNT,LC composites to be sketched, following which tailored development of new LCs may take the advanced functional material that CNT,LC composites comprise to the stage of commercial application. [source]


    The Influence of Alkyl-Chain Length on Beta-Phase Formation in Polyfluorenes

    ADVANCED FUNCTIONAL MATERIALS, Issue 1 2009
    Daniel W. Bright
    Abstract Di- n -alkyl substituted polyfluorenes with alkyl chain lengths of 6, 7, 8, 9, and 10 carbon atoms (PF6, PF7, PF8, PF9, and PF10) are studied in dilute solution in MCH using optical spectroscopy. Beta-phase is formed upon cooling in solutions (, 7,µg mL,1) of PF7, PF8, and PF9 only, which is observed as an equilibrium absorption peak at , 437,nm and strong changes in the emission spectra. Beta-phase is formed upon thermal cycling to low temperature in solutions (,7,µg mL,1) of PF7, PF8, and PF9, which is observed as an equilibrium absorption peak at , 437,nm and strong changes in the emission spectra. Beta phase is found to occur more favorably in PF8 than in PF7 or PF9, which is attributed to a balance between two factors. The first is the dimer/aggregate formation efficiency, which is poorer for longer (more disordered) alkyl chain lengths, and the second is the Van der Waals bond energy available to overcome the steric repulsion and planarize the conjugated backbone, which is insufficient in the PF6 with a shorter alkyl chain. Beta phase formation is shown to be a result of aggregation, not a precursor to it. A tentative value of the energy required to planarize the fluorene backbone of (15.6,±,2.5) kJ mol,1 monomer is suggested. Excitation spectra of PF6, PF7, PF8, and PF9 in extremely dilute (, 10,ng mL,1) solution show that beta phase can form reversibly in dilute solutions of PF7, PF8 and PF9, which is believed to be a result of chain collapse or well dispersed aggregates being present in solution from dilution of more concentrated solutions. PF7, PF8, and PF9 also form beta phase in thermally cycled solid films spin-cast from MCH. However, in the films the PF7 formed a larger fraction of beta phase than the PF9, in contrast to the case in solutions, because it is less likely that the close-packed chains in the solid state will allow the formation of planarized chains with the longer PF9 side chains. [source]


    Molecular Design of Superabsorbent Polymers for Organic Solvents by Crosslinked Lipophilic Polyelectrolytes,

    ADVANCED FUNCTIONAL MATERIALS, Issue 24 2008
    Toshikazu Ono
    Abstract Molecular design of lipophilic polyelectrolyte gels as superabsorbent polymers that exhibit a high degree of swelling in less-polar and nonpolar organic solvents is demonstrated. A small amount of tetraalkylammonium tetraphenylborate with long alkyl chains as a lipopholic ion pair is incorporated into crosslinked polyacrylates with variable alkyl chain lengths to provide novel lipophilic polyelectrolyte gels. Their swelling degree becomes more than 100 times as much as their dried weights in various organic solvents. The high effectiveness of the swellable solvents shifts to the polar ones by decreasing the length of the alkyl chain. Swelling or collapsing of the lipophilic polyelectrolyte gels originates from both incompatibility of the polymer chains in the media and dissociation of ionic groups. Thus, a unique superabsorbency is observed when the polymer chains have good compatibility with the solvents and the solvents have relatively high polarities enough to dissociate the ionic groups. By varying the polarity of the neutral monomer in these polyelectrolyte gels, the design of gels that can absorb solvents of nearly any polarity is demonstrated. [source]


    Behenamidopropyl Dimethylamine: unique behaviour in solution and in hair care formulations

    INTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 4 2010
    M. Minguet
    Synopsis The rise of ecological awareness among consumers and industry has impacted the cationic surfactants market. The most used cationic surfactants present some drawbacks in this sense. Therefore, new molecules are being studied and developed which fulfil eco-toxicological requirements without losing performance. One of these surfactants is Behenamidopropyl Dimethylamine (BAPDMA). This biodegradable amidoamine, which converts into a cationic surfactant at acidic pH, shows outstanding water solubility, despite its very long alkyl chain. Its behaviour in solution has been exhaustively studied. The conditioning performance of this product is superior to that of commonly used cationic surfactants, providing a superior sensorial profile and improved combing force reductions on hair. Moreover, other applications for this product in the non-ionic form have been studied, such as conditioning agent in 2 in 1 shampoos, where it also shows colour protection effects, and as gelling agent in hair colouration creams. This multifunctional and high performance profile, together with an improved biodegradation and aquatic toxicity compared with currently used cationic surfactants, make this product a very interesting eco-friendly alternative for the hair care market. Résumé L'essor de la conscience écologique parmi les consommateurs et l'industrie a eu un fort impact dans le marché des tensioactifs cationiques. Les plus employés d'entre eux ont quelques désavantages de ce point de vue. À ce sujet, on est en train d'étudier et développer des nouvelles molécules qui accomplissent les conditions éco-toxicologiques, sans perdre leur efficacité adoucissante. Un de ces tensioactifs c'est la Behenamidopropyl Dimethylamine (BAPDMA). Cette amidoamine, qui est totalement biodégradable et non toxique pour l'environnement, évolue dans un tensioactif cationique à des pHs acides. Dans l'eau le produit montre une solubilité inespérément élevée, malgré qu'il a une chaîne alchilyque très longue. On a étudiéà fond son comportement en dissolution. L'efficacité de conditionnement du produit se montre supérieure à celle des tensioactifs cationiques employés habituellement, en donnant un profil sensoriel supérieur et en améliorant la souplesse de coiffure. En plus, pour ce produit, d'autres applications ont étéétudiées dans la forme non ionique, par exemple, son emploi comme agent conditionneur dans des shampooings 2 en 1, où il montre aussi un effet protecteur de la couleur et comme agent de texture dans des crèmes de coloration capillaire. Ce profil multifonctionnel et de haute efficacité, ainsi que un bon profil éco-toxicologique, en comparaison avec les tensioactifs cationiques employés actuellement, fait que la behenamidopropyl dimethylamine soit une très bonne alternative pour le marché du soin capillaire. [source]


    Use of associating polymers as multifunctional thickeners: studies of Their structure in aqueous solutions via nmr, qels, fluorescence, And rheology measurements

    INTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 5 2007
    Katsunori Yoshida
    The solution properties of an associating polymer were studied by NMR, quasi-elastic light scattering (QELS), fluorescence, and rheology measurements. An associative thickening (AT) polymer was designed having a nonionic poly(ethylene oxide) backbone with long alkyl chains at both ends to achieve high viscosity even at relatively high salt concentrations and over a wide pH range. This study focuses on the associative state of the polymer in aqueous solutions at various polymer concentrations. In a fluorescence probe study using pyrene a spectral change in the I3/I1 ratio was observed for pyrene at a polymer concentration (Cp) of 3 x 10 -4%, indicating an apparent critical concentration (cmc) of the amphiphilic polymer. The viscosity, self-diffusion coefficient (Dsel), and hydrodynamic size (Rh) distribution measurements at various Cp all suggest that there is a second transition at Cp, 0.4%. Although we observed the discontinuity in viscosity, Dsel, and Rh at Cp, 0.4%, no changes in the relaxation times (T1 and T2) were recognized for either the alkyl chain or the ethylene oxide moiety of the polymer at C p= 0.1,1%. These data suggest that there are no structural changes or phase transitions at Cp, 0.4%, but that intermicellar networks are presumably formed by bridging of the end alkyl groups of the polymer, which is driven by hydrophobic forces. Because the polymer forms networks by hydrophobic interaction and the polymer itself is nonionic, the viscosity of the polymer solution was influenced very little by either the addition of salt or a pH change, as would be expected. The dynamic viscoelastic study revealed that the polymer solution exhibits a single mode Maxwell type relaxation behavior with a terminal relaxation time of about 0.61 s, which imparts a unique flow appearance to the polymer solutions. The time course measurements of the dynamic elastic modulus of the stratum corneum revealed that the polymer has excellent potential for skin softening. It was concluded that the associative thickening polymer not only is a useful thickener with a salt and pH tolerance but also has beneficial skincare effects. [source]


    On the Resolution of Chiral Substrates by a retro- Claisenase Enzyme: Biotransformations of Heteroannular Bicyclic ,-Diketones by 6-Oxocamphor Hydrolase

    ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 8-9 2007
    Cheryl
    Abstract The enzyme 6-oxocamphor hydrolase (OCH) from Rhodococcus sp. NCIMB 9784 catalyses the cleavage of a carbon-carbon bond between two carbonyl groups in both mono- and bicyclic non-enolisable ,-diketone substrates. In this mode OCH has been shown to effect the desymmetrisation of both bridged symmetrical bicyclic [2.2.1] and [2.2.2] systems and a series of 1-alkylbicyclo[3.3.0]octane-2,8-diones, yielding chiral substituted cyclopentanone and cyclohexanone products in high optical purity. In the present study, OCH has been challenged with a series of heteroannular substrates including 1-methylbicyclo[4.3.0]nonane-2,9-dione (7a-methylhexahydroindene-1,7-dione) in an effort to assess the competence of the enzyme for kinetic resolutions of asymmetric, racemic substrates. OCH was shown to catalyse the resolution of 1-methylbicyclo[4.3.0]nonane-2,9-dione with an E value of 2.9. The effect of increasing the length of the alkyl chain in the 1-position, or enlarging one of the rings, was to increase the enantioselectivity of the enzyme to 5.7 and 3.1 for the substrates 1-allylbicyclo[4.3.0]nonane-2,9-dione (7a-allylhexahydroindene-1,7-dione) and 1-methylbicyclo[5.3.0]decane-2,10-dione (8a-methyloctahydroazulene-1,8-dione), respectively. 1-Methylbicyclo[5.4.0]undecane-2,10-dione (9a-methyloctahydrobenzocycloheptene-1,9-dione) was not a substrate for OCH. These experiments constitute the first description of the resolution behaviour of such a retro -Claisenase enzyme, and suggest a maximum steric limit for substrate recognition by OCH. [source]


    Oestrogenic activity of isobutylparaben in vitro and in vivo

    JOURNAL OF APPLIED TOXICOLOGY, Issue 4 2002
    P. D. Darbre
    Abstract The alkyl esters of p -hydroxybenzoic acid (parabens) are used widely as preservatives in foods, pharmaceuticals and cosmetics to which the human population is exposed. Recent studies have reported that methylparaben, ethylparaben, n -propylparaben and n -butylparaben all possess oestrogenic activity in several in vitro assays and in animal models in vivo. This study reports on the oestrogenic activity of isobutylparaben in a panel of assays in vitro and in vivo. Isobutylparaben was able to displace [3H]oestradiol from cytosolic oestrogen receptor , of MCF7 human breast cancer cells by 81% at 100 000-fold molar excess. Using a clonal line of MCF7 cells containing a stably transfected oestrogen-responsive ERE-CAT reporter gene, CAT gene expression could be increased by isobutylparaben such that the magnitude of the response was the same at 10,5 M isobutylparaben as with 10,8 M 17,-oestradiol. Isobutylparaben could also increase expression of the endogenous oestrogen-responsive pS2 gene in MCF7 cells and maximal expression at 10,5 M isobutylparaben could be inhibited with the anti-oestrogen ICI 182 780. The proliferation of two oestrogen-dependent human breast cancer cell lines MCF7 and ZR-75-1 could be increased with isobutylparaben such that at concentrations of 10,5 M the proliferation response was of the same magnitude as with 10,8 M 17,-oestradiol. Evidence for oestrogen receptor mediation of proliferation effects was provided by the inability of isobutylparaben to influence the growth of oestrogen-unresponsive MDA-MB-231 human breast cancer cells and by the ability of the anti-oestrogen ICI 182 780 to inhibit the isobutylparaben effects on MCF7 cell growth. The proliferation response to 10,10 M 17,-oestradiol was not antagonized with isobutylparaben at any concentration from 10,9 M to 10,4 M in either MCF7 or ZR-75-1 cells. Finally, subcutaneous administration of isobutylparaben was able to increase the uterine weight in the immature mouse after three daily doses of 1.2 or 12.0 mg per mouse. Previous work using linear-alkyl-chain parabens has shown that oestrogenic activity increases with alkyl chain length from methylparaben to n -butylparaben. The results here show that branching of the alkyl chain to isobutylparaben increases oestrogenic activity beyond that of the equivalent length linear alkyl chain in n -butylparaben. Copyright © 2002 John Wiley & Sons, Ltd. [source]


    Inhibition of acetylcholinesterase by physostigmine analogs: Conformational mobility of cysteine loop due to the steric effect of the alkyl chain

    JOURNAL OF BIOCHEMICAL AND MOLECULAR TOXICOLOGY, Issue 2 2002
    Enrico Gavuzzo
    Abstract The effect of a series of physostigmine analogs on acetylcholinesterase activity was investigated. The second-order rate constant kon of the enzyme,inhibitor complex correlates with the conformational positioning of aromatic residues, especially Trp84, in the transition state complex. The van der Waals interactions are an important structural element of this conformational change. A transient mobility of the cysteine loop (Cys67,Cys94) was confined only to the presence of a significant steric effect. Even with this limitation, however, the steric effect seems to be an appropriate model for future tests on the "back door" hypothesis involving facilitated opening for faster product clearance. © 2002 Wiley Periodicals, Inc. J Biochem Mol Toxicol 16:64,69, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/jbt.10026 [source]


    Synthesis of new imidazole derivatives

    JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 4 2008
    Krystyna Nowak
    The derivatives of 1-propyl- and 1-butyl- of 2-methyl-5-nitroimidazole containing phenylpiperazine, m -chloro- and o -methoxyphenylpiperazine attached at the end of alkyl chain were synthesed. For the obtained new compounds, the biological activity was predicted using the computer program PASS. [source]


    N -[3-[4-(2-methoxyphenyl) piperaziny-1-yl]propyl]cyclam: synthesized as a potential 5-HT1A receptor ligand and labelled with 99mTc-nitrido core

    JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 10 2008
    Fenglong Wang
    Abstract This paper reports the synthesis of new potential 5-HT1A receptor ligand N -[3-[4-(2-methoxyphenyl)piperaziny-1-yl]propyl]cyclam (MPPC) and radiolabelling of it with 99mTc-nitrido core. The novel neutral complex 99mTcN-MPPC combines 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand as chelate moiety for 99mTc-nitrido with a 1-(2-methoxyphenyl)piperazine moiety derived from WAY 100635 via a 3-carbon alkyl chain. This provided a reliable and reproducible method for attaching the technetium to the pharmacophore moiety of WAY 100635. 99mTcN-MPPC was prepared by a two-step procedure and the radiochemical purity was found to be greater than 95%. It was hydrophilic and stable for at least 4,h at room temperature. In vivo stability study in normal rats showed that no degradation of 99mTcN-MPPC was found in deproteinated blood samples at 2,h post-injection. This effective 99mTc-labelling strategy for obtaining neutral 99mTc nitrido complexes would be a useful tool to prepare new SPECT agents to image 5-HT1A receptor with cyclam conjugated ligands. Copyright © 2008 John Wiley & Sons, Ltd. [source]


    Mechanistic studies of branched-chain alkanols as skin permeation enhancers

    JOURNAL OF PHARMACEUTICAL SCIENCES, Issue 3 2004
    Doungdaw Chantasart
    Abstract As part of a long-term effort to understand the structure/function relationship between chemical permeation enhancers and skin permeation enhancement, the present study examined the influence of hydrocarbon chain branching on the effectiveness of skin permeation enhancers of the type that possesses a polar group (e.g., the hydroxyl group) attached to a hydrocarbon chain(s). The effects of x -hexanol, x -heptanol, x -octanol, and x -nonanol (where x is the position of the hydroxyl group ranging from 1 up to 5) on the transport of a probe permeant, corticosterone, across hairless mouse skin (HMS) were investigated. Isoenhancement concentrations are defined as the aqueous concentrations for which different enhancers induce the same extent of permeant transport enhancement, E, across the lipoidal pathway of stratum corneum (SC). The isoenhancement concentrations of 2-alkanol, 3-alkanol, 4-alkanol, and 5-alkanol to induce E,=,10 were approximately 1.9-, 2.6-, 3.1-, and 3.9-fold higher, respectively, than those of the 1-alkanols of the same molecular formula. This suggested that the branched-chain alkanols have lower enhancer potency than the 1-alkanols of the same molecular formula; the potency decreases as the hydroxyl group moves from the end of the chain towards the center of the enhancer alkyl chain. To further investigate the mechanism(s) of action of the branched-chain alkanols as skin permeation enhancers, the equilibrium uptake of the enhancers into the hairless mouse skin stratum corneum (HMS SC) from aqueous enhancer solutions of E,=,10 was determined. The data from these experiments provided a direct measure of the "intrinsic" potency of the enhancer. In the same experiments, the equilibrium partitioning (distribution) of a surrogate permeant, estradiol (E2,), into the HMS SC was also determined and compared to the partitioning from PBS (no enhancer present). The uptake amounts (micromole/mg SC) for 1-alkanols into the intercellular lipids of the SC were found to be essentially the same at their isoenhancement concentrations. However, at their isoenhancement concentrations, the uptake amounts of the branched-chain alkanols into the intercellular lipids of HMS SC were higher than those of the 1-alkanols. These results support the view that: (1) the intrinsic potencies of the 1-alkanols are essentially the same and independent of their 1-alkyl chain length at their isoenhancement concentrations, (2) the intrinsic potencies of the branched-chain alkanols are lower than those of the normal alkanols, and (3) branching of the alkyl chain reduces the ability of the enhancer to effect lipid fluidization in the SC lipid lamellae at the target site(s). The enhancement effects of the branched-chain alkanols and the 1-alkanols at their isoenhancement concentrations upon E2, partitioning into the SC intercellular lipids were found to be approximately the same and in the range of five- to eight-fold enhancement. The constancy of this enhancement for E2, partitioning suggests that the mechanism of enhancement action for the branched-chain alkanols and the 1-alkanols are the same. Additionally, a good correlation of the intercellular lipid/PBS partition coefficients of both the branched-chain alkanols and the 1-alkanols with the n -octanol/PBS partition coefficients was found. This supports the view that the chemical microenvironment of the polar head group and the alkyl group of the studied enhancers at the site of skin permeation enhancer action in the SC lipid lamellae can be represented by water-saturated n -octanol for both the branched-chain alkanols and the 1-alkanols. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93:762,779, 2004 [source]


    Bile acid sequestrants based on cationic dextran hydrogel microspheres.

    JOURNAL OF PHARMACEUTICAL SCIENCES, Issue 6 2001

    Abstract Cationic dextran hydrogel microspheres with pendant quaternary ammonium groups having alkyl substituents (C2,C12) at quaternary nitrogen were synthesized. The in vitro sorption of sodium salts of four bile acids (glycocholic, cholic, taurocholic, and deoxycholic acids) with these hydrogels was studied as a function of substituent alkyl chain length and bile acid hydrophobicity. Sorption experiments were performed in phosphate buffer solutions (pH 7.4) containing one bile salt (individual sorption) or mixtures of several bile salts (competitive sorption). Parameters for individual sorption were calculated taking into consideration the stoichiometric and cooperative binding of bile salts to oppositely charged polymer hydrogels. The results show that the increase in the length of the alkyl chain of the substituent leads to an increase in both ionization constant K0 and overall stability constant of binding K, but decreases the cooperativity parameter u. The competitive sorption studies indicate that the hydrogels display a good affinity for both dihydroxylic and trihydroxylic bile salts. The molar ratio of maximum amounts bound for the two types of bile acid is 2 to 1, which is much lower than those reported for other cationic polymers recommended as bile acid sequestrants. The binding constants for the sorption of bile salts by some dextran hydrogels are 20,30 times higher than those obtained for cholestyramine under similar sorption conditions. © 2001 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 90:681,689, 2001 [source]


    In-vitro transdermal penetration of cytarabine and its N4-alkylamide derivatives

    JOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 6 2010
    Lesetja J. Legoabe
    Abstract Objectives The aim of this study was to synthesise and determine the transdermal penetration of cytarabine alkylamide derivatives and assess the correlation of flux with physicochemical properties. Methods The alkylamide derivatives of cytarabine were synthesised by acylation at the N4-amino group by the mixed anhydride method. The in-vitro permeation studies were performed using the Franz diffusion cell methodology. Furthermore, partition coefficients (n -octanol,water) and aqueous solubility of the N4-alkylamide derivatives of cytarabine were determined in order to obtain information about their lipophilicity and hydrophilicity. Key findings The N4-alkylamides of cytarabine (acetyl, butanoyl, hexanoyl, octanoyl, and decanoyl derivatives) showed decreased hydrophilicity and increased lipophilicity. The log D values of the alkylamides were higher than that of the parent compound and increased linearly as the alkyl chain lengthened. N4-hexanoyl-4-amino-1-[(2R,3S,4R,5R)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl] pyrimidin-2-one) showed the highest median steady-state flux (Jss) of 89.0 nmol/cm2 per h in the series, which shows a high statistical difference with the parent compound flux value (3.70 nmol/cm2 per h). Conclusions The prodrug approach appears to be a promising strategy for the enhancement of transdermal penetration of cytarabine. [source]


    Experimental and theoretical investigation of a new rapid switching near-infrared electrochromic conjugated polymer

    JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2010
    Han-Yu Wu
    Abstract A new rapid switching near-IR electrochromic conjugated propeller-shape polymer (PBTPAFL) with lower oxidation potential containing a di-triarylamine group was synthesized via Suzuki coupling approach. The observed UV-vis-NIR absorption changes in the PBTPAFL film at various potentials are fully reversible and associated with strong color changes from the original light green to dark green and then to a Prussian blue. Excellent continuous cyclic stability of the electrochromic characteristics with a rapid color switching time 2.58 s and bleaching time 1.76 s was found as well. Compared with P1 and P2, the introduction of more electron-donating propyl phenyl group in the para position of PBTPAFL lowered the oxidative potential and prevented coupling reaction during the electrochromic procedure. The high molecular weight conjugated polymer having high thermal stability with Td10 more than 450 °C has excellent solubility in common organic solvents such as NMP, THF, chloroform, toluene, xylene, and benzene at room temperature (25 °C) due to the propeller-shape structure and long alkyl chain on fluorene. Herein, from the combination of the experimental and computational study, we proposed a mechanism on the basis of the molecular orbital theory to explain the electrochromic oxidation behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3913,3923, 2010. [source]


    Synthesis and liquid crystalline properties of poly(1-alkyne)s carrying triphenylene discogens

    JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2008
    Changmin Xing
    Abstract Triphenylene-containing 1-decynes with different alkyl chain lengths and their polymers are synthesized and the effects of the structural variables on their mesomorphic properties are investigated. The monomers [HCC(CH2)8CO2C18H6 (OCmH2m+1)5; m = 4,9] are prepared by consecutive etherization, coupling, and esterification reactions. The monomers form columnar phases at room temperature. The polymerizations of the monomers are effected by [Rh(nbd)Cl]2, producing soluble polymers in high yields (up to 84%). The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, DSC, POM, and XRD analyses. All the polymers are thermally stable, losing little of their weights when heated to 300 °C. The isotropization temperature of the polymers increases initially with the length of alkyl chain but decreases on further extension. Although the polymers with shorter and longer alkyl chain lengths adopt a homogeneous hexagonal columnar structure, those with intermediate ones form mesophases with mixed structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2960,2974, 2008 [source]


    Synthesis and characterization of alkylated N -vinylformamide monomers and their polymers

    JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2004
    Lianjun Shi
    Abstract N -alkyl- N -vinylformamide monomers (alkyl: n -butyl, hexyl, decyl, and dodecyl) are synthesized in two steps: first, preparation of N -vinylformamide potassium salt by the reaction of N -vinylformamide (NVF) with potassium t -butoxide, then reaction with alkyl bromide. All four monomers are liquid and are characterized by IR, 1H NMR, 13C NMR, and mass spectra. They exist as rotomers in solution and a 2D NOE experiment on the N -hexyl containing polymer shows the E isomer to be favored. The polymerizability of the four monomers is from good to fair, depending upon the length of alkyl chain on the N -atom--the longer the chain length, the lower lower the polymerizability of monomer. The hydrolysis of poly(N -hexyl- N -vinylformamide) and poly(N -dodecyl- N -vinylformamide) under acidic and basic conditions was examined. Studies show that hydrolytic cleavage of formyl groups of poly (N -alkylated- N -vinylformamide) depends on the hydrophobicity of the alkyl substituent on the N -atom under acidic conditions; both polymers were hydrolyzed to only a minor extent under alkaline conditions. The N -alkylated monomers can copolymerize with NVF and demonstrate amphiphilic properties. The copolymers demonstrate a critical aggregation concentration above which they can solubilize a water insoluble dye; the N -hexyl containing copolymer stabilizes a castor oil-in-water emulsion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4994,5004, 2004 [source]


    Continuous Distribution Kinetics for Photopolymerization of Alkyl Methacrylates

    MACROMOLECULAR REACTION ENGINEERING, Issue 9 2009
    Ravikrishnan Vinu
    Abstract The photopolymerization of methyl, ethyl, butyl, and hexyl methacrylates in solution was studied. The effect of initial initiator and monomer concentrations on the time evolution of polymer concentration, , and PDI was examined. The reversible chain addition and , -scission, and primary radical termination steps were included in the mechanism along with the classical steps. The rate equations were derived using continuous distribution kinetics and solved numerically to fit the experimental data. The regressed rate coefficients compared well with the literature data. The model predicted the instantaneous increase in and PDI to steady state values. The rate coefficients exhibited a linear increase with the size of alkyl chain of the alkyl methacrylates. [source]


    Comparisons of Photo-Fries Rearrangements of 4-Dodecylphenyl Phenylacetate and Two Structurally Related Esters in Hexane and Polyethylene Cages.

    PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2006
    How Important Are Anchoring Chains?
    ABSTRACT Photo-Fries rearrangements of 4-dodecylphenyl phenylacetate have been investigated in polyethylene films with 0,71% crystallinity and in hexane over a range of temperatures. The results are compared to those reported previously from phenyl phenylacetate and 1-naphthyl tetradecanoate to assess the influence of a long alkyl chain on the in-cage motions of the intermediate singlet radical pairs. It is demonstrated that the reactivity and selectivity of intimate singlet radical pairs can be tuned by judicious placement of long-chain substituents and selection of a specific polyethylene type as the reaction matrix. [source]


    Columnar liquid-crystalline assemblies composed of spiropyran derivatives and sulfonic acids,

    POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10 2008
    Boon-Hooi Tan
    Abstract A series of fan-shaped spiropyran derivatives with different length of alkyl chains has been synthesized. Liquid-crystalline (LC) assemblies of spiropyran derivatives have been formed by the addition of organic sulfonic acids such as trifluoromethylsulfonic acid, 10-camphorsulfonic acid, 4-methylbenzenesulfonic acid, and imidazolium-based ionic liquids (ILs) having a sulfonic acid group. Equimolar mixtures of a fan-shaped spiropyran derivative with the acidic imidazolium-based ILs exhibit columnar phases with wider LC temperature ranges as compared to those of other mixtures. The ionic interactions formed by the ionic imidazolium moieties should contribute to the stabilization of the columnar phases. On the other hand, equimolar mixtures of the spiropyran derivative with decane-1-sulfonic acid having a long alkyl chain and poly(4-styrenesulfonic acid) do not show mesomorphism. The chemical structure of organic sulfonic acids is a key factor for the induction and stabilization of the LC phases. Copyright © 2008 John Wiley & Sons, Ltd. [source]


    Thiophene-based ionic liquids: synthesis, physical properties, self-assembly, and oxidative polymerization,

    POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10 2008
    Christopher T. Burns
    Abstract Preparation and polymerization of methylimidazolium-based ionic liquids (ILs) that incorporate a thiophene moiety at the terminus of a C10 alkyl chain are described. Both a bromide and nitrate salt of the amphiphilic thiophene IL self-assembles in water (albeit the nitrate to a lesser extent), adopting columnar mesophases. Polarized optical microscopy and small-angle X-ray scattering (SAXS) studies show that at low water content the IL,water binary mixtures form liquid crystalline mesophases possessing significant short-range ordering due to strong , interactions between adjacent thiophene moieties. At higher water content, the short-range ordering is lost, but long-range ordering persists up to ca. 45% (w/w) water. The chemical oxidative coupling of the nitrate monomer yields a highly water-soluble polymer. Electrochemical studies show that the polymer possesses a high oxidation potential (1.95,V) and thus, is resistant to chemical doping. In dilute aqueous solution, electronic absorption spectroscopy and X-ray scattering show the polymer adopts a random, coil-like conformational state. Slight improvement in the polymer conformation can be achieved by exchange of the counter anion. Copyright © 2008 John Wiley & Sons, Ltd. [source]