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Methylene Groups (methylene + groups)
Selected AbstractsCross-correlated and conventional dipolar carbon-13 relaxation in methylene groups in small, symmetric moleculesCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2007Leila Ghalebani Abstract A theory for dipolar cross-correlated relaxation processes in AMX or AX2 spin system, with special reference to 13C-methylene groups, is reviewed briefly. Simple experiments and protocols for measuring the transfer rates between the carbon-13 Zeeman order and the three-spin order, and for their analogues in the transverse plane, are discussed using a concentrated solution of the disaccharide trehalose as a model system. Experimental data sets consisting of conventional carbon-13 relaxation parameters (T1, T2, and NOE), along with the cross-correlated relaxation rates, are also presented for some small, rigid, polycyclic molecules. These data are interpreted using spectral density functions appropriate to spherical or symmetric tops reorienting according to small-step rotational diffusion model. The analysis results in a consistent picture of the auto- and cross-correlated spin relaxation processes. © 2007 Wiley Periodicals, Inc. Concepts Magn Reson Part A 30A: 100,115, 2007. [source] CO2 Fixation and Activation by CuII Complexes of 5,5,-Terpyridinophane MacrocyclesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2008Begoña Verdejo Abstract An aza-terpyridinophane receptor containing the polyamine 4,7,10,13-tetraazahexadecane-1,16-diamine linked through methylene groups to the 5,5, positions of a terpyridine unit has been prepared and characterized (L). The acid-base behaviour, CuII speciation and ability to form ternary complexes (CuII -L-carbonate) have been explored by potentiometric titrations in 0.15 M NaClO4 and by UV/Vis and paramagnetic NMR spectroscopy. Comparisons are made with a previously reported terpyridinophane containing the polyamine 4,7,10-triazatridecane-1,13-diamine (L1). For this latter receptor, reductive coupling between indigo and carbon dioxide at indigo-modified electrodes produces carboxylated derivatives via a solid-state reaction under electrochemical activation.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Manifestation of a Chiral Smectic C Phase in Diphenylbutadiene-Cored Bolaamphiphilic Sugars,ADVANCED FUNCTIONAL MATERIALS, Issue 11 2008Suresh Das Abstract A series of symmetrical bolaamphiphiles possessing a diphenylbutadiene core and glucopyranoside head groups linked together by oligomethylene spacers, were synthesized and their thermotropic liquid crystalline properties investigated by polarized light optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optic switching. In spite of the presence of chiral centers, amphiphilic sugars in general do not exhibit macroscopic chirality and this phenomenon is attributed to strong hydrogen bonding between sugar head groups resulting in microphase-segregated layer like arrangements. In the present study all the molecules investigated exhibited the smectic C* phase, i.e., tilted lamellar phase with macroscopic chiral ordering of the molecules. The stability of this phase increased with increase in the length of the oligomethylene spacers. Whereas for derivatives with spacers containing ,4 methylene groups, the smectic C* phase was observed only in the cooling phase, for those containing spacers with ,5 methylene groups this phase was observed both in the heating and cooling cycles. The absorption and fluorescence spectra of these materials suggest that the unusual observation of macroscopic chirality in these bolaamphiphiles containing free hydroxyl groups could be attributed to self-aggregating behavior of the diphenylbutadiene core. [source] Diffusion and distribution of element-labelled surfactants in human hairINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 2 2004F.-J. Wortmann Synopsis To directly follow the diffusion process of cosmetically relevant agents into human hair, a specific methodological approach is presented and elucidated for selected surfactants. For this, practically relevant anionic and cationic surfactants were synthesized with a chlorine atom at the end of their alkyl chain. The property changes of the surfactants through the modification are corresponding to an extension of the alkyl chain by about two methylene groups, thus representing a moderate increase of hydrophobicity. After the application of a modified surfactant to hair, it can be localized and quantified through its chlorine atom in cross-sections by scanning electron microscopy combined with micro X-ray fluorescence analysis. The determination of the diffusion coefficient D is realized through the application of the Matano-equation to element intensity profiles. Values for D vary within the chosen range of pH and temperature between 10,14 and 10,16 m2 s,1. The diffusion coefficients for the anionic surfactants increase with decreasing pH and increasing temperature, The temperature dependence follows in all cases the Arrhenius relationship with activation energies EA of 50,100 kJ mol,1, which decrease with pH. The pH-related effects, with comparable values for D and EA, are opposite for the cationic surfactant. These observations are consistently interpreted on the basis of ionic and hydrophobic interactions in hair. Résumé Afin de suivre directement le processus de diffusion d'agents cosmétiques pertinents dans le cheveu humain, une approche méthodologique spécifique est présentée et approfondie pour des tensio actifs sélectionnés. En pratique, des tensio actifs pertinents, anioniques et cationiques ont été synthétisés en introduisant un atome de Chlore à l'extrémité de leur chaîne alkyle. Les changements de propriétés de ces tensio actifs, via cette modification, correspondent à un allongement de la chaîne alkyle d'environ deux groupes méthylène, représentant ainsi une augmentation modérée de leur caractère hydrophobe. Suite à l'application sur le cheveu d'un tensio actif modifié, il peut être localisé et quantifié par l'atome de Chlore dans des coupes transverses par microscopie électronique à balayage couplée à l'analyse par micro Fluorescence X. La détermination du coefficient de diffusion D est effectuée par l'application de l'équation de Matano aux profils de l'intensité de l'élément. Les valeurs de D varient, selon l'échelle de pH et de température, entre 10,14 et 10,16 m2 s,1. Les coefficients de diffusion pour les tensio actifs anioniques augmentent avec des pH décroissants et des températures croissantes. La dépendance vis à vis de la température suit, dans tous les cas, la relation d'Arrhenius avec des énergies d'activation EA de 50 à 100 kJ mol,1, qui décroît avec le pH. Les effets liés au pH, avec des valeurs comparables de D et EA, sont opposés pour le tensio actif cationique. Ces observations sont constamment interprétées par les interactions de types ioniques et hydrophobes dans le cheveu. [source] Comparative evaluation of 99mTc-ethylene bis-l-cysteine and 99mTc-ethylene bis-l-,-homocysteine during reversed phase HPLC analysis and electrophoresis at various pH conditionsJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 4 2001K.O. Mang'era Ethylene bis- L -,-homocysteine (L,L -EH) differs from ethylene bis- L -cysteine (L,L -EC) in having an extra methylene group between each pair of amine and carboxyl groups. The objective of this study was to determine the effect of the extra methylene groups on the characteristics of the complex of these compounds with technetium-99m during analysis by reversed phase HPLC and by electrophoresis at various pH values. Up to pH 5.5, 99mTc- L,L -EH exhibits a substantially longer retention time during reversed phase HPLC than 99mTc- L,L -EC, suggesting a more lipophilic character for 99mTc- L,L -EH under these conditions. On the other hand, 99mTc- L,L -EH clearly possesses a higher negative charge in the pH range 3-6.5 as shown by the markedly greater migration towards the anode in electrophoresis experiments. A rational explanation for these seemingly opposing observations can not yet be offered. Copyright © 2001 John Wiley & Sons, Ltd. [source] pH-independent hydrolysis of 4-nitrophenyl 2,2-dichloropropionate in aqueous micellar solutions: relative contributions of hydrophobic and electrostatic interactionsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8 2001Omar A. EI Seoud Abstract The pH-independent hydrolysis of 4-nitrophenyl 2,2-dichloropropionate (NPDCP) in the presence of aqueous micelles of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, alkyltrimethylammonium chlorides, alkyldimethylbenzylammonium chlorides (alkyl,=,cetyl and dodecyl) and polyoxyethylene(9) nonylphenyl ether was studied spectrophotometrically. The observed rate constants, kobs, decrease in the following order: bulk water >cationic micelles >anionic micelles >non-ionic micelles. This order is different from that observed for pH-independent hydrolysis of 4-nitrophenyl chloroformate (NPCF), whose reaction is faster in cationic micelles than in bulk water. A proton NMR study on solubilization of a model ester, 4-nitrophenyl 2-chloropropionate, showed that the methylene groups in the middle of the surfactant hydrophobic chain are most affected by the solubilizate. Lower polarity and high ionic strength of interfacial water decrease the rates of hydrolysis of both NPCF and NPDCP, but the fraction of the former ester that diffuses to the interface is probably higher than that of the latter. Therefore, whereas the (negatively charged) transition state of NPCF is stabilized by cationic interfaces and destabilized by anionic interfaces, that of NPDCP is negligibly affected by ionic interfaces, which explains the observed rate retardation by all ionic micelles. Calculated activation parameters corroborate our explanation. Copyright © 2001 John Wiley & Sons, Ltd. [source] Synthesis and characterization of liquid-crystalline polyphosphonates containing disubstituted ferrocene esters as mesogensJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2002S. Senthil Abstract A series of ferrocene-containing liquid-crystalline polyphosphonates with an even number of methylene groups are reported. All the polymers gave birefringent melts. The mesophase was identified as transparent with an increase in the spacer. The effects of pendant substitution and the spacer were studied with thermogravimetric analysis and differential scanning calorimetry. The effects of the phosphonate group in the spacer and the ferrocene ester group in the mesogen were examined. The presence of a steplike mesogenic structure and a pendant phenyl group in the spacer led to reductions in the glass-transition and melting temperatures. The ferrocene moiety in the mesogen might be one of the reasons for the increased thermal stability and decreased liquid crystallinity. An energy-minimized structure for the mesogenic and spacer segments was created with computer-modeling programs, and it suggested the reason for the reductions in the glass-transition and melting temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2256,2263, 2002 [source] Synthesis, characterization, and in vitro degradation of thermotropic polyesters and copolyesters based on terephthalic acid, 3-(4-hydroxyphenyl)propionic acid, and glycolsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2001Minoru Nagata Abstract A new series of thermotropic liquid-crystalline (LC) polyesters were prepared from a diacyl chloride derivative of 4,4,-(terephthaloyldioxy)-di-4-phenylpropionic acid (PTP) and glycols with a different number of methylene groups (n) [HO(CH2)n OH, n = 6,10, 12] by high-temperature solution polycondensation in diphenyl oxide. PTP6/10 and PTP6/hydroquinone (H) LC copolyesters were also prepared according to a similar procedure. The chemical structure, LC, phase-transition behaviors, thermal stability, and solubility were characterized by elemental analysis, Fourier transform infrared spectroscopy, 1H and 13C NMR spectra, differential scanning calorimetry (DSC), thermogravimetric analysis, and a polarizing light microscope. The melting and isotropization temperatures decreased in a zigzag manner as the number of n increased. All of the polyesters formed a nematic phase with the exception of PTP8. The temperature ranges of the mesophase (,T) were much wider for the polyesters with an odd number of n's than those with an even number. ,T increased markedly for the PTP6/10 and PTP6/H copolyesters. The in vitro degradations of the polymers were ascertained by enzymatic hydrolysis and alkaline hydrolysis. The model compound, PTP dihexylester, was synthesized and found to be degraded into terephthalic acid, 3-(4-hydroxyphenyl)propionic acid, and 1-hexanol by Rhizopus delemar lipase, but PTPn homopolyesters and PTP6/10 and PTP6/H copolyesters were resistant to Rhizopus delemar hydrolysis. They were degradable in a sodium hydroxide buffer solution of pH 12 at 60 °C, depending on the number of n's and the copolymer composition. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3043,3051, 2001 [source] Polyurethanes with Pendant Hydroxyl Groups: Synthesis and CharacterizationMACROMOLECULAR RAPID COMMUNICATIONS, Issue 3 2004Luc Ubaghs Abstract Communication: Phenoxycarbonyloxymethyl ethylene carbonate 4 was synthesized from glycerol carbonate and phenyl chloroformate. Polyurethanes with pendant hydroxyl groups were obtained from polycondensation reactions of this AA* monomer with diamines. These polymers contain primary as well as secondary hydroxyl groups. The obtained polyurethanes are amorphous materials. The glass transition temperature decreases with increasing number of methylene groups between the urethane groups. As the number of methylene groups increases between the urethane groups, the glass transition temperature of the polymer decreases. [source] Piperidone derivative from Dalbergia sympatheticaMAGNETIC RESONANCE IN CHEMISTRY, Issue 3 2005N. Shanmugam Nagarajan Abstract An alcoholic extract of Dalbergia sympathetica, on column chromatography, yielded a compound which analyzed for C6H11NO3 (M+ 145). The IR spectrum of the compound showed the presence of carbonyl and hydroxyl groups. PMR, 13C and DEPT NMR spectral studies of the compound showed the presence of one N -methyl, two methine and two methylene groups. A quaternary carbon signal at , 172.88 ppm was assigned to C-2 carbonyl of the compound. From all the above observations and also from the HMQC 2D NMR spectrum, the compound was identified as 3, 6-dihydroxy- N -methyl-2-piperidone. This is the first report of the natural occurrence of this compound from plant sources. Copyright © 2004 John Wiley & Sons, Ltd. [source] Recombinant decorsin: Dynamics of the RGD recognition sitePROTEIN SCIENCE, Issue 8 2000Andrzej M. Krezel Abstract Decorsin is an antagonist of integrin ,IIb,3 and a potent platelet aggregation inhibitor. A synthetic gene encoding decorsin, originally isolated from the leech Macrobdella decora, was designed, constructed, and expressed in Escherichia coli. The synthetic gene was fused to the stII signal sequence and expressed under the transcriptional control of the E. coli alkaline phosphatase promoter. The protein was purified by size-exclusion filtration of the periplasmic contents followed by reversed-phase high-performance liquid chromatography. Purified recombinant decorsin was found to be indistinguishable from leech-derived decorsin based on amino acid composition, mass spectral analysis, and biological activity assays. Complete sequential assignments of 1H and proton bound 13C resonances were established. Stereospecific assignments of 21 of 25 nondegenerate ,-methylene groups were determined. The RGD adhesion site recognized by integrin receptors was found at the apex of a most exposed hairpin loop. The dynamic behavior of decorsin was analyzed using several independent NMR parameters. Although the loop containing the RGD sequence is the most flexible one in decorsin, the conformation of the RGD site itself is more restricted than in other proteins with similar activities. [source] Identification of lysophosphatidylcholine (LPC) and platelet activating factor (PAF) from PC12 cells and mouse cortex using liquid chromatography/multi-stage mass spectrometry (LC/MS3)RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 22 2008Jeffrey C. Smith Lipids play essential roles in cellular structural support, energy storage and signal transduction. Recently, mass spectrometry (MS) has been used to produce three-dimensional maps that elucidate the lipid composition of complex cellular lysates. The identification of individual lipids within these maps is slow and requires the synthesis and spiking of each candidate lipid. We present a novel MS-based technique that rapidly elucidates the atomic connectivity of the fatty acid/alcohol substituent on the sn -1 position of several different families of glycerophosphocholine-containing lipids within the confines of a chromatographic separation. Sodiated lipid species were fragmented to produce radical cations which lost successive methylene groups upon further collisional activation to reveal the identity of the parent molecule. This approach was demonstrated to be effective on isobaric members of the lysophosphatidylcholine (LPC) and platelet activating factor (PAF) families of glycerophospholipids. We demonstrate the application of this technique to unambiguously identify these species within complex cellular lysates and tissue extracts. Copyright © 2008 John Wiley & Sons, Ltd. [source] 1,3,5-Triphenyladamantane and 1,3,5,7-tetraphenyladamantaneACTA CRYSTALLOGRAPHICA SECTION C, Issue 5 2009Ishtvan Boldog In 1,3,5-triphenyladamantane, C28H28, (I), and 1,3,5,7-tetraphenyladamantane, C34H32, (II), the molecules possess symmetries 3 and , and are situated across threefold and fourfold improper axes, respectively. The molecules aggregate by means of extensive C,H..., interactions. In (I), the pyramidal shape of the molecules dictates the formation of dimers through a `sixfold phenyl embrace' pattern. The dimers are linked to six close neighbors and constitute a primitive cubic net [H..., = 2.95,(2) and 3.02,(2),Å]. Compound (II) is isomorphous with tetraphenyl derivatives EPh4 of group 14 (E = C,Pb) and ionic salts [EPh4][BPh4] (E = P, As and Sb). The multiple C,H..., interactions arrange the molecules into chains, with a concerted action of CH (phenyl) and CH2 (adamantane) groups as donors [H..., = 3.15,(2) and 3.44,(2),Å, respectively]. The additional interactions with the methylene groups (four per molecule) are presumably important for explaining the high melting point and insolubility of (II) compared with the EPh4 analogs. [source] Structural Diversity in the Self-Assembly of Pseudopeptidic MacrocyclesCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2010Ignacio Alfonso Dr. Abstract The self-assembling abilities of several pseudopeptidic macrocycles have been thoroughly studied both in the solid (SEM, TEM, FTIR) and in solution (NMR, UV, CD, FTIR) states. Detailed microscopy revealed large differences in the morphology of the self-assembling micro/nanostructures depending on the macrocyclic chemical structures. Self-assembly was triggered by the presence of additional methylene groups or by changing from para to meta geometry of the aromatic phenylene backbone moiety. More interestingly, the nature of the side chain also plays a fundamental role in some of the obtained nanostructures, thus producing structures from long fibers to hollow spheres. These nanostructures were obtained in different solvents and on different surfaces, thus implying that the chemical information for the self-assembly is contained in the molecular structure. Dilution NMR studies (chemical shift and self-diffusion rates) suggest the formation of incipient aggregates in solution by a combination of hydrogen-bonding and ,,, interactions, thus implicating amide and aryl groups, respectively. Electronic spectroscopy further supports the ,,, interactions because the compounds that lead to fibers show large hypochromic shifts in the UV spectra. Moreover, the fiber-forming macrocycles also showed a more intense CD signature. The hydrogen-bonding interactions within the nanostructures were also characterized by attenuated total-reflectance FTIR spectroscopy, which allowed us to monitor the complete transition from the solution to the dried nanostructure. Overall, we concluded that the self-assembly of this family of pseudopeptidic macrocycles is dictated by a synergic action of hydrogen-bonding and ,,, interactions. The feasibility and geometrical disposition of these interactions finally render a hierarchical organization, which has been rationalized with a proposal of a model. The understanding of the process at the molecular level has allowed us to prepare hybrid soft materials. [source] Progress in the Understanding of Drug,Receptor Interactions, Part,2: Experimental and Theoretical Electrostatic Moments and Interaction Energies of an Angiotensin II Receptor Antagonist (C30H30N6O3S)CHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2007Raffaella Soave Dr. Abstract A combined experimental and theoretical charge density study of an angiotensin II receptor antagonist (1) is presented focusing on electrostatic properties such as atomic charges, molecular electric moments up to the fourth rank and energies of the intermolecular interactions, to gain an insight into the physical nature of the drug,receptor interaction. Electrostatic properties were derived from both the experimental electron density (multipole refinement of X-ray data collected at T=17,K) and the ab initio wavefunction (single molecule and fully periodic calculations at the DFT level). The relevance of S,,,O and S,,,N intramolecular interactions on the activity of 1 is highlighted by using both the crystal and gas-phase geometries and their electrostatic nature is documented by means of QTAIM atomic charges. The derived electrostatic properties are consistent with a nearly spherical electron density distribution, characterised by an intermingling of electropositive and -negative zones rather than by a unique electrophilic region opposed to a nucleophilic area. This makes the first molecular moment scarcely significant and ill-determined, whereas the second moment is large, significant and highly reliable. A comparison between experimental and theoretical components of the third electric moment shows a few discrepancies, whereas the agreement for the fourth electric moment is excellent. The most favourable intermolecular bond is show to be an NH,,,N hydrogen bond with an energy of about 50,kJ,mol,1. Key pharmacophoric features responsible for attractive electrostatic interactions include CH,,,X hydrogen bonds. It is shown that methyl and methylene groups, known to be essential for the biological activity of the drug, provide a significant energetic contribution to the total binding energy. Dispersive interactions are important at the thiophene and at both the phenyl fragments. The experimental estimates of the electrostatic contribution to the intermolecular interaction energies of six molecular pairs, obtained by a new model proposed by Spackman, predict the correct relative electrostatic energies with no exceptions. [source] | ||||||||||||||||